WO2020005760A1 - Phosphore de biocharbon ozonisé durable et solisation de sable - Google Patents

Phosphore de biocharbon ozonisé durable et solisation de sable Download PDF

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Publication number
WO2020005760A1
WO2020005760A1 PCT/US2019/038491 US2019038491W WO2020005760A1 WO 2020005760 A1 WO2020005760 A1 WO 2020005760A1 US 2019038491 W US2019038491 W US 2019038491W WO 2020005760 A1 WO2020005760 A1 WO 2020005760A1
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biochar
reactor
oxygenated
ozonization
ozone
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PCT/US2019/038491
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English (en)
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James Lee
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James Lee
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Priority claimed from US16/104,892 external-priority patent/US20190002764A1/en
Application filed by James Lee filed Critical James Lee
Priority to US17/058,131 priority Critical patent/US20210198162A1/en
Publication of WO2020005760A1 publication Critical patent/WO2020005760A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00—Other organic fertilisers
    • C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
    • C05F11/06—Apparatus for the manufacture
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • C05G3/44—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility for affecting solubility

Definitions

  • the present invention is directed to sonicated and ozonized biochar compositions and methods for creating surface-oxygenated biochar materials with higher cation exchange capacity that are also free of potential toxic components for use as phosphorus solubilization reagents, filtration materials, soil amendments and carbon sequestration agents to help control climate change for energy and environmental sustainability on Earth.
  • the capacity of carbon sequestration by application of biochar fertilizer in soils can be used in croplands, grasslands and a fraction of forest lands.
  • the maximum capacity of carbon sequestration through biochar soil amendment in croplands alone is estimated to be about 428 GtC globally. This maximum capacity is estimated using the maximal amount of biochar carbon that could be cumulatively placed into soil while still beneficial to soil environment and plant growth and the arable land area suitable for biochar agricultural use.
  • Gt gigatons
  • dry matter waste biomass e.g., crop stovers, dead leaves, waste woods, and rice straws
  • Deployment of an advanced biomass pyrolysis technology can turn waste biomass into valuable biochar, bio-syngas, and biofuel products.
  • this approach can produce a net reduction of greenhouse-gas emissions of about 1.8 Gt of CO2-C equivalent emissions per year, which is about 12% of the current global anthropogenic emissions.
  • Advanced biomass pyrolysis coupled with biochar soil amendment is unique among carbon sequestration strategies in that it can simultaneously offset gigatons of CO2 emissions and build sustainability into agricultural systems. This is a unique “carbon-negative” bioenergy system approach, which on a life-cycle basis could not only reduce but also reverse human effects on climate change.
  • Organic species including possible inhibitory and benign (or stimulatory) chemicals are produced as part of the biomass pyrolysis process.
  • a number of organic compounds belonging to various chemical classes, including n-alkanoic acids, hydroxyl and acetoxy acids, benzoic acids, diols, triols, and phenols were recently identified in organic solvent extracts of biochar.
  • Some of these biochar chemicals, including polycyclic aromatic hydrocarbons (PAHs), are potentially phytotoxic or biocidal, especially at high concentrations.
  • biochar were to be globally used as a soil amendment and carbon sequestration agent at GtC scales, the release of potentially toxic compounds into soil and associated hydrologic systems might have unpredictable negative consequences in the environment. Therefore, it is essential to address some of these undesirable effects in order for biochar to be used as a soil amendment and carbon sequestration agent at gigaton scales. Any new technology that could produce an advanced biochar product that has high cation exchange capacity without any undesirable side effects is highly desirable for using biochar soil carbon sequestration to control climate change towards sustainability on Earth.
  • the wet route typically requires the use of strong industrial acids such as sulfuric acid, nitric acid, and/or hydrochloric acid to solubilize phosphate from phosphate rock materials (Jiang et al (1990) Fert Res 26 (1-3): 11-20; Fayiga, Nwoke (2016) Environ Rev 24 (4):403-4l5; Khan et al (2013) J Chem Soc Pakistan 35 (1): 144-146; Skut et al (2010) Przem Chem 89 (4):534-539).
  • the thermal route is represented by thermophosphate (Fageria, Santos (2008) Commun Soil Sci Plan 39 (5-6):873-889).
  • the present invention discloses a systematic method for producing and utilizing a surface-oxygenated biochar composition through ozonization in combination with sonication is the method that comprises: treating a biochar source composition with sonication and an ozone- containing gas stream in a biochar sonication-ozonization treatment reactor system using a sonication-ozonization-enabled biochar-surface oxygenation operational process, wherein treating the source biochar composition comprises: a) contacting the source biochar with the ozone-containing gas stream; b) enabling biochar-surface oxygenation; c) destroying a potential biochar toxin; d) producing a surface-oxygenated biochar composition having enhanced cation exchange capacity; e) producing a special surface-oxygenated biochar composition for phosphorus solubilization from insoluble phosphate materials for producing phosphate fertilizers without using strong industrial acids; f) producing a special surface-oxygenated biochar paste composition for sands soilization; and g
  • Exemplary embodiments are directed to improved methods employing the techniques of sonication and ozonization for producing surface-oxygenated biochar compositions.
  • These sonicated and/or ozonized biochar compositions including surface-oxygenated biochar paste products are used for a number of innovative applications including: 1) as filtration materials for clean water and air including odor removal; 2) as phosphorus solubilizing reagents to mix with phosphate rock materials such as hydroxyapatite or fluorapatite to make a slow-releasing phosphate fertilizer; 3) as biochar soil additives to help solubilize phosphorus from the insoluble phosphate materials found in certain soils, reducing phosphorus fertilizer additions required to achieve desired soil phosphorus activity, crop uptake, and yield goals; 4) as sand soilization reagents by utilizing their liquid gel-forming activity in the spaces among sand particles to better retain water and nutrients and hold the sand particles together; 5) as plant growth stimulants by using the surface-oxy
  • an ozonizati on-based method is employed as a post-production biochar-surface oxygenation process to improve biochar properties.
  • the ozonization-enabled biochar surface oxygenation process creates a new generation of advanced hydrophilic and clean biochar materials with higher cation exchange capacity, optimized pH and optimized hydrophilicity, and that are free of undesirable potential toxic components, which represents a significant technological improvement.
  • Exemplary embodiments use a single ozonization-enabled biochar surface oxygenation process to achieve at least one of four improvements in the resulting biochar, i.e., enhanced biochar cation exchange capacity, reduced alkaline biochar pH, improved biochar wetability and destruction of potential biochar toxins.
  • Exemplary embodiments can be practiced in a distributed manner at certain biochar-production facilities, biochar-utilizing farm sites, and other industrial sites to convert tons of conventional biochar materials into surface-oxygenated biochar products for use as soil amendment and other industrial applications.
  • a method for production of an ozonized biochar composition includes reacting a biochar source with an ozone-containing gas stream in a biochar ozonization treatment reactor system using an ozonization-enabled biochar-surface oxygenation operational process.
  • the biochar source is contacted with ozone to (a) enable biochar-surface oxygenation; (b) destruct potential biochar toxins; and (c) produce an ozonized biochar composition having optimal characteristics or an optimal group of characteristics.
  • CEC enhanced cation exchange capacity
  • optimal pH value optimal carboxyl content
  • optimal hydrophilicity and wettability optimal water-holding field capacity
  • optimal oxygen-to-carbon molar ratio surface area, composition, nutrient contents, biochar particle size, uniformity, and any combination thereof.
  • Exemplary embodiments are also directed to a method for producing an ozonized biochar material having a super high cation-exchanging property with CEC value over 50 cmol/kg, 100 cmol/kg, 150 cmol/kg and as high as about 200 cmol/kg.
  • the cation-exchanging ability of a biochar is predominantly dependent on the density of cation-exchanging groups, mainly carboxyl (-COOH) groups on biochar surface.
  • a biochar source is reacted with an injected ozone (Chj-containing stream in a controlled manner such that the biochar source homogeneously acquires carboxy- containing cation-exchanging groups in a post-production biochar-surface oxygenation process that creates carboxyl groups on biochar surfaces even at ambient pressure and temperature.
  • Exemplary embodiments are also directed to a biochar ozonization treatment reactor system having an air inlet pump or valve, an ozone generator system, an ozone air inlet or tube passing through the biochar ozonization reactor wall near its botom, an ozone air space at the bottom of the reactor, a porous metal plate, a biochar ozonization reactor chamber space above the porous metal plate, a biochar inlet passing through the biochar ozonization reactor wall at the upper part of the reactor, an ozonized biochar outlet passing through the reactor wall at the lower part of the reactor, a tail gas vent valve and filter at the top of the reactor, a flexible tail gas recycling tube equipped with its filter and valve and pump and valve connecting from the tail gas vent tube to the air inlet, a heat-smoke-sensing sprinkler system passing through the biochar ozonization reactor wall at the upper part of the reactor, and a flexible inlet and outlet valve at the bottom of the reactor.
  • the biochar ozonization treatment reactor system comprises an O2/CO2 air inlet pump or valve, an ozone generator system, an ozone air inlet or tube passing through the biochar ozonization reactor wall near its bottom, an ozone O3/CO2 air space at the bottom of the reactor, a W-conical-shaped porous metal plate, a biochar ozonization reactor chamber space above the porous metal plate, a biochar inlet passing through the biochar ozonization reactor wall at the upper part of the reactor, an O3/CO2 gas flowing from O3/CO2 air space at the bottom through the W-conical-shaped porous metal plate and the biochar materials toward the upper part of the reactor, an ozonized biochar outlet passing through the reactor wall at the lower part of the reactor, tail gas vent valve and filter at the top of the reactor, a flexible tail gas recycling tube equipped with its filter and valve and pump and valve connecting from the tail gas vent tube to the air inlet, a heat-smoke-sensing sprinkle
  • Exemplary embodiments are directed to a double-wall coolant-jacketed ozone gas biochar reactor system having a heat-conducting reactor inner wall, a reactor outer wall, a coolant chamber space formed between the inner wall and outer wall, a coolant inlet connected with the coolant chamber space at the bottom part of the reactor, a hot coolant outlet connected with the coolant chamber space at the top part of the reactor, an O2/CO2 air inlet pump and valve, an ozone generator system, an ozone air inlet or tube passing through the biochar ozonization reactor wall near its bottom, an ozone O3/CO2 air space at the bottom of the reactor, an inverted- V conical-shaped porous metal plate, a biochar ozonization reactor chamber space above the porous metal plate, a hot biochar inlet passing through the biochar ozonization reactor wall at the upper part of the reactor, an O3/CO2 gas flowing from O3/CO2 air space at the bottom through the conical-shaped porous metal plate and the biochar materials
  • the biochar ozonization treatment reactor system is constructed from special ozone-compatible materials selected from the group consisting of stainless steel, titanium, silicone, glass, polytetrafluoroethylene (PTFE), a perfluoroelastomer polymer, polyether ether ketone (PEEK), polychlorotrifluoroethylene (PCTFE), chlorinated polyvinyl chloride (CPVC), a silicon cast iron, chromium and molybdenum alloy, filled PTFE gasket material, a nickel, molybdenum, chromium and iron alloy, polycarbonate, polyurethane, polyvinylidene difluoride (PVDF), butyl, a heat- and chemical-resistant ethylene acrylic elastomer, a synthetic rubber and fluoropolymer elastomer, ethylene-propylene, a thermoplastic vulcanizate (TPV), flexible polyethylene tubing, commercially available as Flexelene from Eldon James Corporation of Denver, CO
  • TPV thermoplastic
  • Exemplary embodiments are directed to an ozone-enabled biochar-surface oxygenation operational process that is a wet-moisture biochar ozonization treatment operational process that includes the following process steps that may be operated in combination with the use of hydrogen peroxide: a) Loading biochar materials into the reactor through the biochar inlet; b) Monitoring and adjusting (as necessary) biochar temperature; c) Monitoring biochar water content and relative humidity in the reactor, d) Based on the required biochar water content and relative humidity, properly adding water into biochar materials by use of a heat-smoke-sensing sprinkler system with water inlet and water spray system at the upper part of the reactor, and/or introducing at least one of water, steam and water vapor by use of a flexible water inlet and outlet valve and optional water level for vapor and moisture generation at the bottom of the reactor; e) Pumping an oxygen-containing source gas stream such as ambient air oxygen through the ozone generator system to generate ozone; f) Feed
  • the biochar-surface oxygenation and destruction of toxins are accomplished simultaneously by use of an Cb-containing gas stream flowing through the biochar ozonization treatment reactor at ambient pressure and temperature with minimal cost.
  • the optimized biochar pH value is accomplished through the formation of acidic carboxyl groups at biochar surfaces and by the formation and adsorption of nitrogen oxides/nitric acid during a biochar ozonization process in the presence of N2.
  • the ozonized biochar composition has a cation exchange capacity of at least about 200% of that of the untreated biochar and is free of biochar toxins.
  • Exemplary embodiments are directed to ozonized biochar compositions having a given, exceptional, or optimal set of characteristics, such as enhanced cation exchange capacity, optimal pH value, optimal carboxyl content, optimal hydrophilicity and wettability, optimal water holding field capacity, optimal oxygen-to-carbon molar ratio, surface area, composition, nutrient contents, biochar particle size, zero toxin content, and/or uniformity in any of these or other characteristics.
  • Exemplary embodiments of methods disclosed herein are suitable for producing these types of advanced hydrophilic biochar products with higher cation exchange capacity and free of potential toxic components, which can be used in many practical applications such as the use of the ozonized biochars as filtration materials and as a biochar soil amendment and carbon sequestration agent.
  • a method for industrial production of surface-oxygenated biochar composition through ozonization in combination with sonication is the method that comprises treating a biochar source with sonication and an ozone-containing gas stream in a biochar sonication-ozonization treatment reactor system using a sonication- ozonization-enabled biochar-surface oxygenation operational process; wherein the treating of the biochar source comprises: a) contacting the biochar source with the ozone-containing gas stream; b) enabling biochar-surface oxygenation; c) destroying a potential biochar toxin; d) producing a surface-oxygenated biochar composition having enhanced cation exchange capacity; e) producing a special surface-oxygenated biochar composition for solubilizing phosphorus from insoluble phosphate materials for producing phosphate fertilizers without using strong industrial acids; f) producing a special surface-oxygenated biochar paste composition for sand soilization; and g)
  • the biochar sonication-ozonization treatment reactor system is a sonication-enhanced biochar ozonization treatment reactor system comprising: a sonication control unit which comprises an input end in contact with ultrasonic transducer and a sonication output head in contact with liquid in a biochar ozonization reactor chamber space, a heat-conducting reactor inner wall, a reactor outer wall, a coolant chamber space formed between the inner wall and outer wall, a coolant inlet connected with the coolant chamber space at the bottom part of the reactor, a hot coolant outlet connected with the coolant chamber space at the top part of the reactor, an O2 air inlet pump and valve, an ozone generator system, an ozone air inlet and tube passing through the biochar ozonization reactor out wall and inner wall near its bottom, an ozone 03/water space at the bottom of the reactor, a porous metal plate, a biochar sonication-ozonization reactor chamber
  • the sonication-ozonization-enabled biochar-surface oxygenation operational process comprises a liquid biochar sonication- ozonization treatment operational process comprises the following process steps that may be operated in combination with the use of hydrogen peroxide: a) loading biochar materials into a reactor through a biochar inlet; b) monitoring and adjusting biochar temperature; c) monitoring biochar water content and liquid level in the reactor; d) based on a required biochar water content and liquid level, adding at least one of water, steam and vapor into the biochar materials using at least one of a heat-smoke-sensing sprinkler system with a water inlet and water spray system located at a top of the reactor and a flexible water inlet and outlet valve at a bottom of the reactor; e) performing sonication using the sonication control unit which comprises an input end in contact with ultrasonic transducer and a sonication output head in contact with liquid in a bio
  • the sonication enhances biochar ozonization process through at least one of the following mechanisms: 1) Sonication force may physically loose up and/or break up biochar materials such as exfoliating graphite-type biochar materials (including graphite and/or graphite oxides) to produce graphene-type of biochar molecules such as fragmented graphene and graphene oxides; 2) Sonication process enhances mixing and mass transfer of ozone gas with liquid water and biochar particles; and 3) Ultra sonication at a frequency of above 15 kHz producing reactive oxygen radical, hydroxyl and peroxyl radicals from the sonochemistry of C -dissolved water that may also enhance biochar surface oxygenation.
  • 1) Sonication force may physically loose up and/or break up biochar materials such as exfoliating graphite-type biochar materials (including graphite and/or graphite oxides) to produce graphene-type of biochar molecules such as fragmented graphene and graphene oxides
  • Sonication process enhances mixing and mass transfer of ozone gas
  • the surface-oxygenated biochar composition is a biochar paste product that comprises humic-substances-like surface-oxygenated biochar materials that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments, partially oxygenated linear hydrocarbons, partially oxygenated aromatic compounds, partially oxygenated polycyclic aromatic hydrocarbons, dissolved organic carbons including organic acids, and combinations thereof.
  • humic-substances-like surface-oxygenated biochar materials that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments,
  • the surface-oxygenated biochar composition may be used to solubilize phosphorous from insoluble phosphate materials such as hydroxyapatite or fluorapatite for phosphorous sustainability by at least one of the following molecular mechanisms: a) The effect of protons from the organic acid groups of ozonized biochar which can kick phosphate out of the insoluble phosphate materials, resulting in solubilized phosphate; b) The effect of calcium complexation with the deprotonated biochar carboxylate groups that takes calcium away and thus thermodynamically favors the release of phosphate from the insoluble calcium phosphate materials; c) the anion exchange of the deprotonated biochar dissolved organic carboxylate groups (organic anions) with the phosphate in the insoluble phosphate materials favors the release of phosphate from the insoluble phosphate materials; and d) combinations thereof.
  • insoluble phosphate materials such as hydroxyapatite or fluorapatite for phosphorous sustainability by at least one of
  • the surface-oxygenated biochar compositions including the biochar paste product may be used for sands soilization by their liquid gel-forming activity in the spaces among sand particles that can retain water and nutrients and hold the sand particles together through at least one of the following noncovalent interactions: 1) the ionic (Coulombic) interactions that are the electrostatic interactions between charged species; 2) the hydrogen bond effects of the surface-oxygenated biochar molecular species with water and sands; 3) the p-p interactions between aromatic structures; and 4) the van der Waals interactions among sands and surface-oxygenated biochar molecular species with water.
  • the surface-oxygenated biochar compositions contain certain amounts of beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate green plant growth when used at a proper DOC concentration selected from the group consisting of: 0.1 ppm, 0.2 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 5 ppm, 8 ppm 10 ppm, 12 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, 1000 ppm or a concentration within a particular range bounded by any two of the foregoing values.
  • DOC partially oxygenated dissolved organic carbons
  • FIG. 1 illustrates, from left to right, lOg biochar from pyrolysis of cornstover, lOg soil, and lOg mixture of biochar (10% W) and soil (90% W).
  • the soil sample is a surface soil from 0- 15 cm deep at the University of Tennessee's Research and Education Center, Milan, Tennessee, USA (358560N latitude, 888430W longitude), which is also known as the Carbon Sequestration in Terrestrial Ecosystems site (CSiTE) supported by the U.S. Department of Energy.
  • CSiTE Carbon Sequestration in Terrestrial Ecosystems site
  • FIG. 2 is a process schematic for post-production biochar ozonization to create oxygen- containing functional groups on biochar surfaces.
  • FIG. 3 is a schematic representation of an embodiment of the biochar ozonization treatment reactor system with a flat porous metal plate using an air ozone generator system, a biochar inlet and a heat-smoke-sensing sprinkler system at the upper part of the reactor, flexible tail gas circulating loop, and a biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • FIG. 4 is a schematic representation of an embodiment of the biochar ozonization treatment reactor system with a conical shaped porous metal plate using an O2/CO2 air inlet, a flexible tail gas circulating loop, a biochar inlet and a heat-smoke-sensing sprinkler system with water spray at the upper part of the reactor, a flexible water inlet and outlet at the bottom of the reactor, and an biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • FIG. 5 is a schematic representation of an embodiment of the biochar ozonization treatment reactor system with a W-conical shaped porous metal plate using an O2/CO2 air inlet, a flexible tail gas circulating loop, a recycling water pump connected from a flexible water inlet and outlet at the bottom of the reactor to a heat-smoke-sensing sprinkler system with water spray at the upper part of the reactor, and an biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • FIG. 6 is a schematic representation of an embodiment of the biochar ozonization treatment reactor system with a V-conical shaped porous metal plate using an air inlet, an ozone generator, a flexible tail gas circulating loop, a flexible inlet and outlet at the bottom of the reactor, a heat-smoke-sensing sprinkler system and a biochar inlet at the upper part of the reactor, and an biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • Fig. 7 is a schematic representation of an embodiment of the double-wall-coolant- jacketed biochar ozonization treatment reactor system with coolant inlet and hot coolant outlet, using an inverted-V-conical shaped porous metal plate, an O2/CO2 air inlet, an ozone generator, a flexible tail gas circulating loop, a flexible water inlet and outlet at the bottom of the reactor, a heat-smoke-sensing sprinkler system and a hot biochar inlet at the upper part of the reactor, and an biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • FIG. 8 is a schematic representation of an embodiment of the double-wall-coolant- jacketed biochar liquid-ozonization treatment reactor system with coolant inlet and hot coolant outlet, using a flat porous metal plate, a water liquid fully immersing biochar material at the upper part of the reactor, an O2 air inlet, an ozone generator, a flexible tail gas circulating loop, a 03/water space and a flexible water inlet and outlet at the bottom of the reactor, a heat-smoke- sensing sprinkler system and a hot biochar inlet at the upper part of the reactor, and an biochar outlet at the bottom part of the reactor for harvesting ozonized biochar by use of gravity.
  • Fig. 9 is a graph illustrating Fourier Transformed Infrared-Attenuated Total Reflectance (FTIR-ATR) spectra of biochar samples treated with ozone for 30 min, 60 min and 90 min in comparison with that of untreated biochar.
  • FTIR-ATR Fourier Transformed Infrared-Attenuated Total Reflectance
  • Fig. 10 is a graph illustrating Raman spectra of biochar samples treated with ozone for 60 min in comparison with that of untreated biochar.
  • Fig. 12 is a photograph showing an example of the black viscos biochar paste product in a white jar, which was produced from the biochar liquid sonication-ozonization process.
  • Fig. l3a presents the ion chromatography showing the phosphate peak from the mixture of wet-ozonized biochar and non-ozonized biochar, their respective filtrate and the
  • the phosphate peak appeared at 15.6-16.0 min.
  • the height of the phosphate peak from the mixture with the ozonized biochar was significantly higher compared to that with the non-ozonized biochar.
  • the data represented here were from the sample collected after 30 minutes of incubation time.
  • Fig. l3b shows an example of solubilized phosphorus (P) concentrations measured in the liquid phase after 30 minutes, 2 days, and 2 weeks of hydroxyapatite water incubation with non-ozonized biochar, wet-ozonized biochar, dry-ozonized biochar, and without any biochar (hydroxyapatite with Milli-Q water only).
  • P solubilized phosphorus
  • l4a presents the Ion Chromatograms of B-Soil phosphorus solubilization assay showing the phosphate peak from a 14-day incubation treatment of wet-ozonized Biochar + B- Soil + Water (solid line) in comparison with control-l (dashed line): Biochar + B-Soil + Water; and control-2 (dotted line): B-Soil + Water.
  • Fig. l4b presents the Ion Chromatograms of P-Soil phosphorus solubilization assay showing the phosphate peak from a 14-day incubation treatment of wet-ozonized Biochar + P- Soil + Water (solid line) in comparison with control-l (dashed line): Biochar + P-Soil + Water; and control-2 (dotted line): P-Soil + Water.
  • Fig. 15 presents a photograph showing flocculation of liquid filtrate DOC from the wet- ozonized P400 90W biochar by adding 2.5 mM CaCk;
  • Fig. l6a shows 10 g of sands mixed with 4 ml of water solution containing wet- ozonized biochar dissolved organic carbon (DOC, 940 ppm) compounds and 25 mM CaCk in a plate after 5 hours leaving on laboratory bench with room air stays together when the plate was inclined.
  • DOC wet- ozonized biochar dissolved organic carbon
  • Fig. l6b shows 10 g of sands mixed with 4 ml of water in a plate after 5 hours leaving on laboratory bench with room air falls apart when the plate was inclined.
  • Fig. l7a presents an example of the liquid filtrates collected from the un-hydrolyzed corn stover residue.
  • On the left (darker brown) is 50 mL filtrate resulted from washing 3 g of non-ozonized un-hydrolyzed com stover residue. Its DOC concentration was measured to be 2440 ppm;
  • On the right (yellow) is 50 mL filtrate collected from the wet-ozone treatment of 3 g of un-hydrolyzed corn stover residue.
  • the DOC concentration in the filtrate of the wet-ozonized un-hydrolyzed corn stover residue was measured to be 2928 ppm.
  • Fig. l7b shows the plates in which the silicon dioxide particles were mixed with the filtrate from the un-hydrolyzed com stover residue.
  • 10 g of sands was mixed with 3 mL of the respective liquid.
  • Control 1 sand mixed with 3 mL of milli-Q water.
  • Control 2 sand mixed with 3 mL of milli-Q water with 2.5 mM calcium.
  • Fig. l7c shows the plates in which the silicon dioxide sands were mixed with the un hydrolyzed com stover residue and the filtrate from the un-hydrolyzed corn stover residue.
  • E 9 g of sands mixed with 1 g of the non-ozonized un-hydrolyzed corn stover residue and 4mL of the filtrate from the non-ozonized un-hydrolyzed corn stover residue;
  • F similar to E except that the non-ozonized filtrate contained 2.5 mM of calcium;
  • G 9 g of sands mixed with 1 g of the ozonized un-hydrolyzed corn stover residue and 4mL of the filtrate from the wet ozonized un- hydrolyzed com stover residue.
  • H similar to G except that the wet-ozonized filtrate contained 2.5 mM of calcium.
  • Control 1 10 g sand mixed with 3 mL of milli-Q water.
  • Control 2 10 g sand mixed with 3 mL of milli-Q water with 2.5mM of calcium. After mixture, the plates were left at room temperature overnight. The plates were then slowly tilted to 45 degrees and then to 90 degrees. All treated sand piles did not fall apart except that Controls 1 and 2 collapsed after being tilted at 45 degrees and 90 degrees, respectively.
  • Fig. l8a presents an example of liquid culture growth curves of cyanobacteria
  • Synechococcus elongatus PCC 7942 measured as chlorophyll Absorbance at 680 nm when incubated in multi-well bioassay plates with dissolved organic carbon (DOC) of wet-ozonized P500 biochar filtrates.
  • DOC dissolved organic carbon
  • Fig. 18b presents an example of liquid culture growth curves of Synechococcus elongatus PCC 7942 measured as chlorophyll Absorbance at 680 nm when incubated in multi well bioassay plates with 0 ppm, 10 ppm, 25 ppm, and 75 ppm of dissolved organic carbon (DOC) of the hydrochar (HTC) liquid from a hydrothermal conversion process using un- hydrolyzed com stover residues.
  • DOC dissolved organic carbon
  • HTC hydrochar
  • Fig. 19 presents bioassay results demonstrating that the surface-oxygenated biochar compositions contain certain amounts of beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate higher plant crop seed germination and seedling elongation (growth) such as Sorghum, Lepidium, and Sinapis when used at a proper DOC concentration such as 75 ppm and 150 ppm.
  • beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate higher plant crop seed germination and seedling elongation (growth) such as Sorghum, Lepidium, and Sinapis when used at a proper DOC concentration such as 75 ppm and 150 ppm.
  • DOC partially oxygenated dissolved organic carbons
  • DOC dissolved organic carbon
  • Described herein are a series of improved methods for producing and utilizing surface- oxygenated biochar compositions with special sonication-ozonization methods for creating advanced hydrophilic biochar materials are provided with higher cation exchange capacity, optimized pH, improved wettability, and free of potential toxic components.
  • biochar compositions including surface-oxygenated biochar paste products are used for a number of innovative applications including: 1) as filtration materials for clean water and air such as pig manure odor smell removal; 2) as phosphorus solubilizing reagents to mix with phosphate rock materials such as hydroxyapatite or fluorapatite to make a slow-releasing phosphate fertilizer; 3) as biochar soil additives to help solubilize phosphorus (to make it available for plant growth) from the insoluble phosphate materials existed already in certain soils and thus reduce phosphorus fertilizer additions required to achieve desired soil phosphorus activity, crop uptake, and yield goals; 4) as sand soilization reagent by utilizing their liquid gel- forming activity in the spaces among sand particles to retain water and nutrients and hold the sand particles together; 5) as plant growth stimulants by using the humic acids-like surface- oxygenated biochar substances at a proper concentration; and 6) as carbon sequestration
  • Exemplary embodiments are directed to a systematic method for producing and utilizing a surface-oxygenated biochar composition through ozonization in combination with sonication, the method comprising: treating a biochar source composition with sonication and an ozone-containing gas stream in a biochar sonication-ozonization treatment reactor system using a sonication-ozonization-enabled biochar-surface oxygenation operational process, wherein treating the source biochar composition comprises: a) contacting the source biochar with the ozone-containing gas stream; b) enabling biochar-surface oxygenation; c) destroying a potential biochar toxin; d) producing a surface-oxygenated biochar composition having enhanced cation exchange capacity; e) producing a special surface-oxygenated biochar composition for phosphorus solubilization from insoluble phosphate materials for producing phosphate fertilizers without using strong industrial acids; f) producing a special surface-oxygenated biochar paste composition for sands soilization; and
  • ozonized biochar compositions with unique properties for use as soil amendment or soil additives and as filtration materials, for example, for industrial filtration applications.
  • the methods described herein apply a series of ozone-enhanced biochar-surface oxygenation and cleaning processes to create a new generation of clean biochar materials with super high cation exchange capacity over 50 cmol/kg, 100 cmol/kg, 150 cmol/kg and as high as about 200 cmol/kg.
  • These clean biochar materials are free of undesirable and potentially toxic substances and represent a major technological
  • ozonization chemistry and technologies are employed as a post-production biochar-surface oxygenation process to convert biochar compositions to unique ozonized compositions.
  • Various aspects and embodiments of the methods herein are disclosed below.
  • biochar materials with high surface area may be advantageous to interact with ozone molecules for biochar surface oxygenation to create super high cation exchange capacity. Therefore, it is a preferred practice for certain biochar ozonization process to use source biochar material with high specific surface area (SSA), as commonly determined by BET analysis.
  • SSA specific surface area
  • the BET surface areas of source biochar feedstocks for certain biochar ozonization process are selected a group consisting of 0.5, 1, 2, 3,
  • a method for industrial production of an ozonized biochar composition involves reacting a biochar source with an ozone-containing gas stream in a special biochar ozonization treatment reactor system using a specific ozone-enabled biochar-surface oxygenation operational process.
  • the method utilizes a biochar ozonization treatment reactor system, and the biochar ozonization treatment reactor system in combination with the use of hydrogen peroxide.
  • the biochar source is contacted with ozone to (a) enable biochar-surface oxygenation; (b) destruct a potential biochar toxin; (c) produce an ozonized biochar composition having an optimal set of characteristics selected from the group consisting of enhanced cation exchange capacity, optimal pH value, optimal carboxyl content, optimal hydrophilicity and wettability, optimal water-holding field capacity, optimal oxygen-to-carbon molar ratio, surface area, composition, nutrient contents, biochar particle size, uniformity, and any combination thereof; and (d) produce a special ozonized biochar
  • composition having an enhanced filtration property for removing at least one contaminant from a medium selected from the group consisting of water and air.
  • One exemplary embodiment is directed to a method for producing an ozonized biochar material possessing a higher cation-exchanging property.
  • the cation-exchanging ability of a biochar is known to be predominantly dependent on the density of cation-exchanging groups mainly carboxyl (-COOH) groups in the biochar.
  • FIG. 2 an exemplary embodiment of a process is illustrated for reacting a biochar source with an injected ozone (O3) stream, which is a ozonizing agent useful herein, in a controlled manner such that the biochar source homogeneously acquires carboxy-containing cation-exchanging groups in a post-production biochar-surface oxygenation process that can create carboxyl groups on biochar surfaces even at ambient pressure and temperature.
  • O3 injected ozone
  • a suitable biomass is subject to a pyrolysis process that results in biofuels such a H2 and biochar materials, i.e., substrate.
  • the carboxyl groups in pH neutral water are mostly deprotonated to form negatively charged species, which may represent the cation binding and exchanging sites on the biochar surfaces.
  • the biochar ozonization treatment reactor system 100 is a controlled ozone gas biochar reactor system that comprises: an air inlet pump and valve 101, an ozone generator system 102, an ozone air inlet and tube 116 passing through the biochar ozonization reactor wall 105 near its bottom, an ozone air space 103 at the bottom of the reactor, a porous metal plate 104 on top of the ozone air space, a biochar ozonization reactor chamber space 107 above the porous metal plate 104, a biochar inlet 108 passing through the biochar ozonization reactor wall 105 at the upper part of the reactor, an ozonized biochar outlet 109 passing through the reactor wall at the lower part of the reactor, a tail gas vent valve and filter 110 at the top of the reactor, a flexible tail gas recycling tube 111 equipped with its filter and valve 112 and pump and valve 113 connecting from
  • Cast iron, Steel Mod, High-strength low-alloy (HSLA)
  • Zinc Zinc
  • Magnesium Zinc
  • Polypropylene and Nylon are also sensitive to ozone corrosion.
  • Those types of ozone-sensitive materials are not recommended for use in building the reactor and associated parts and joints that may be in contact with ozone. It is a preferred practice to use special ozone-compatible materials that can tolerate the reactive ozone in constructing the ozone biochar reactor system including the associated parts and joints that will be in contact with ozone.
  • the ozone-compatible materials for use in the construction of the reactor system are selected from the group consisting of stainless steel, titanium, silicone, glass,
  • PTFE polytetrafluoroethylene
  • PCTFE poly chi orotrifluoroethylene
  • CPVC chlorinated polyvinyl chloride
  • CPVC chlorinated polyvinyl chloride
  • chromium and molybdenum alloy commercially available as Durachlor-5l from Duriron Company of Dayton, Ohio
  • filled PTFE gasket material commercially available as Durlon ® 9000 from Gasket Resources Inc. of Downingtown, PA
  • nickel, molybdenum, chromium and iron alloy commercially available as Kel-F® from 3M Corporation of St. Paul, MN
  • CPVC chlorinated polyvinyl chloride
  • chromium and molybdenum alloy commercially available as Durachlor-5l from Duriron Company of Dayton, Ohio
  • filled PTFE gasket material commercially available as Durlon ® 9000 from Gasket Resources Inc. of Downingtown, PA
  • nickel, molybdenum, chromium and iron alloy commercially available as Kel-F® from 3M Corporation of St. Paul, MN
  • Ozone is an inorganic trioxygen molecule with the chemical formula O3, and is a pale blue gas with a distinctively pungent smell.
  • Suitable methods for ozone generation include, but are not limited to, the corona discharge method, the cold plasma method, ultraviolet light ozone generation, and electrolytic ozone generation.
  • an ozone generator utilizing the corona discharge method with a corona discharge tube is employed as the ozone generator system 102 in the biochar ozonization treatment reactor system 100 illustrated in Fig. 3, or in any of the illustrated reactor embodiments utilizing an ozone generator system.
  • the corona discharge tube-based ozone generators are cost- effective and do not require an oxygen source other than the ambient air to produce ozone concentrations of 3-6%. Else of an oxygen concentrator in combination with the corona discharge ozone generator increases the ozone concentrations produced.
  • the corona discharge tube-based ozone generators also produce nitrogen oxides from the air (21% O2 and 79% N2) as a by-product, which in the presence of water and vapor can form nitric acid that may be absorbed, to some degree, by biochar materials.
  • Certain conventional biochar materials in particular those made from high-temperature pyrolysis or gasification processes, typically have an alkaline pH ranging from about pH 8.5 up to about pH 12. The adsorption of nitrogen oxides/nitric acid may beneficially reduce the alkaline pH of biochar.
  • air (21% O2 and 79% N2) is used through the ozone generator system 102 to create both ozone and nitrogen oxides with moisture to treat dry biochars or wet biochars.
  • at least one of water and steam is optionally introduced into the biochar ozonization reactor through a flexible inlet and outlet valve 106 at the bottom of the reactor.
  • FIG. 4 another exemplary embodiment of a biochar ozonization treatment reactor system 200 is illustrated in which water is optionally introduced into the biochar ozonization reactor through a heat-smoke-sensing sprinkler system 214 equipped with water inlet 217 and water spray 218 system at the upper part of the reactor for a“wet biochar” treatment process.
  • a heat-smoke-sensing sprinkler system 214 equipped with water inlet 217 and water spray 218 system at the upper part of the reactor for a“wet biochar” treatment process.
  • the formation of carboxyl groups on biochar surfaces through ozonization also reduces the alkaline biochar pH. Consequently, the air ozonization process results in a nitric nutrient-enriched biochar product with a better pH value more desirable for use as an agricultural soil amendment or additive.
  • the nitrogen oxides and nitric acid formation and adsorption is reduced by use of an air dryer that reduces or eliminates nitric acid formation by removing water vapor, increasing overall ozone production.
  • Use of an oxygen concentrator further increases the ozone production and further reduces the risk of nitric acid formation by removing not only the water vapor, but also the bulk of the nitrogen.
  • at least one of pure oxygen and a mixed oxygen gas such as O2/CO2 gas mixtures (that are completely devoid of N2) are used to generate ozone for the biochar treatment process.
  • an ozone generator based on the cold plasma method is utilized as the ozone generator system 102 in the biochar ozonization treatment reactor system 100 illustrated in Fig. 3 or in any illustrated embodiment of the reactor system utilizing an ozone generator system.
  • pure oxygen gas is exposed to plasma created by dielectric barrier discharge.
  • the diatomic oxygen is split into single atoms, which then recombine in triplets to form ozone.
  • Cold plasma machines utilize pure oxygen as the input source and produce a maximum concentration of about 5% ozone.
  • the regime of applied ozone concentrations ranges from about 1% to about 5% in air and from about 6% to about 14% in oxygen for older generation methods.
  • New electrolytic methods achieve up about 20% to about 30% dissolved ozone concentrations in output water for biochar treatment.
  • biochar materials are loaded through the inlet 108, 208, 308, 408, 508 into the reactor chamber space 107, 207, 307, 407, 507 above the porous metal plate 104, 204, 30, 404, 504 for ozonization treatment.
  • the temperature of biochar materials is monitored and adjusted as necessary or desired.
  • the biochar water content and relative humidity in the reactor are monitored and adjusted as necessary or desired.
  • water is added into the biochar materials by use of a heat-smoke-sensing sprinkler system 214 with water inlet 217 and water spray 218 system at the upper part of the reactor, or at least one of water and steam is introduced by use of a flexible water inlet and outlet valve 206 and optional water level 219 at the bottom of the reactor (Fig. 4).
  • Ozone gas is generated from air oxygen through an ozone generator system 102, 202, 302, 402, 502 and fed into the ozone air space 103, 203, 303, 403, 503 at the bottom of the reactor.
  • a dry treating gas stream is used without any water or steam in the reactor.
  • the ozone gas 115, 215, 315, 415, 515 stream passing through the porous metal plate 104, 204, 304, 404, 504 flows and diffuses through the biochar materials upwards.
  • the ozone gas encounters the biochar surfaces during this process, it reacts with certain biochar surface atoms, forming oxygen-containing functional groups on biochar surfaces as illustrated, for example, in Fig. 2.
  • the ozonized biochar product will: 1) become more hydrophilic since both carbonyl and carboxyl groups can attract water molecules; and 2) have higher cation exchange capacity since the carboxyl groups readily deprotonate in water and result in more negative charge (Biochar-COO-) on the ozonized biochar surfaces:
  • the sources of oxygen gas to generate ozone through the ozone generator system are selected from the group consisting of ambient air oxygen, pure oxygen gas, mixed oxygen and carbon dioxide gas, mixed oxygen and nitrogen gas, residual oxygen-containing flue gas, and combination thereof.
  • Use of pure oxygen gas through the ozone generator can create higher concentration of ozone in the gas stream so that the biochar ozonization reactions are enhanced.
  • use of pure oxygen system is limited to well- controlled smaller reactors to ensure operational safety. For better safety and economic considerations, use of ambient air oxygen to generate ozone for biochar ozonization is preferred.
  • Biochar can also be quite reactive and can ignite itself ; therefore, as shown in Fig. 3, a well-equipped heat-smoke-sensing sprinkler system 114 is utilized to extinguish any potential fire with a water spray within the reactor.
  • Liquid water can be injected into the reactor through the use of a flexible inlet and outlet valve 106 at the bottom of the reactor.
  • liquid water can also be discharged from the reactor through the use of the flexible inlet and outlet valve 106 or recycled using a recycling water pump 320 with a flexible water recycling tube 321 connected with the flexible water inlet and outlet 306 and the water inlet 317 to re-use the liquid through water spray 318 as shown in Fig 5.
  • a potential biochar reactor fire can be stopped also by shutting off any air oxygen supply to the reactor such as by closing the air inlet valve 101 (Fig. 3).
  • the biochar ozonization process reactions were somewhat exothermic. Therefore, it is preferred to control the biochar ozonization process speed and heat dissipation so that the temperature of the biochar ozonization reactor can be maintained near the ambient temperature.
  • the reactor wall is preferably made of metals such as stainless steel that tolerate ozone and dissipate heat as necessary or desired.
  • the biochar ozonization process speed is controlled by adjusting compositions including the ozone concentration and the feeding rate and compositions of the treating gas stream.
  • Use of the flexible inlet and outlet valve 106 at the bottom of the reactor enables the introduction of steam and other gases of choice into the ozone-treating gas stream to achieve a more desirable result.
  • Use of the flexible tail gas recycling tube 111 with its filter and valve 112 and pump and valve 113 provides the option to re-use part or all of the tail gas in the process.
  • the tail gas is released through the vent or re-used through the flexible tail gas recycling tube 111 with its filter and valve 112 and pump and valve 113 if the tail gas still contains ozone and/or other gas components that may have a value for re-use.
  • the biochar is desirably ozonized
  • the ozonized biochar product is harvested through the use of ozonized biochar outlet 109 at the lower part of the reactor by use of gravity as illustrated in Fig. 3.
  • a dry biochar ozonization treatment operational process includes the following specific process steps: a) Loading biochar materials into the reactor through the biochar inlet; b) Monitoring and adjusting (if/when necessary) biochar temperature, c) Monitoring and adjusting (if/when necessary) biochar water content and relative humidity in the reactor, d) Pumping dry oxygen-containing source gas such as ambient air oxygen with an air dryer through the ozone generator system to generate ozone; e) Feeding dry ozone-containing gas stream into the reactor chamber space through the porous metal plate above the ozone air space by controlling the air pump fan speed without using any water; f) If/when necessary, using the flexible inlet and outlet valve at the bottom of the reactor to introduce other gas component(s) of choice into the treating gas stream to manipulate the biochar ozonization process; g) If/when necessary, using the flexible tail gas recycling tube with its filter and valve and pump and valve to re-use part and/or all of the tail gas for
  • an exemplary processes in accordance with the present invention uses the biochar ozonization treatment process system for a plurality or series of operational cycles to achieve more desirable results. Any one of the steps a) through j) of this process can be adjusted or modified as desired for certain specific operational conditions.
  • the biochar temperature monitoring and adjusting step of b) is modified by adding additional steps of using a double-wall coolant- jacketed ozone gas biochar reactor system, 505 (reactor outer wall), 522 (reactor inner wall), 523 (coolant chamber space), 524 (coolant inlet), 525 (hot coolant outlet) with a coolant to cool down hot biochar and to utilize the waste heat energy through a heat exchange system to preheat and/or to dry biomass.
  • Any one of the steps a) through i) of the process of the present invention can be applied in whole or in part and in any adjusted combination for enhanced biochar-surface oxygenation in accordance of this invention.
  • a biochar ozonization treatment reactor system 200 is illustrated.
  • the biochar ozonization treatment reactor system 200 is a controlled ozone gas biochar reactor system that comprises: an O2/CO2 air inlet pump and valve 201, an ozone generator system 202, an ozone air inlet and tube 216 passing through the biochar ozonization reactor wall 205 near its bottom, an O3/CO2 air space 203 at the bottom of the reactor, a conical shaped porous metal plate 204, a biochar ozonization reactor chamber space 207 above the porous metal plate 204, a biochar inlet 208 passing through the biochar ozonization reactor wall 205 at the upper part of the reactor, an O3/CO2 air flow 215 from the O3/CO2 air space 203 at the bottom through the conical-shaped porous metal plate and the biochar materials toward the upper part of the reactor, an ozonized biochar outlet 209 passing through the reactor wall at the lower part of the reactor,
  • This biochar ozonization treatment reactor system 200 illustrated in Fig. 4 is similar to the system illustrated in Fig. 3 with the exception of the following additional features.
  • the embodiment of Fig. 4 employs a conical-shaped porous metal plate 204 that provides more surface area for the ozone containing gas stream to pass through into the biochar ozonization reactor chamber space 207 for better efficiency.
  • water inlet 217 and water spray 218 are used to optionally add water into the materials to optimize the biochar ozonization process and to prevent any possible biochar fire or combustion.
  • the embodiment of Fig. 4 utilizes an optional water level 219 and flexible water inlet and outlet 206 to provide moisture for the O3/CO2 air space and to either discharge or to collect and reuse the liquid.
  • the biochar ozonization treatment reactor system 300 is a controlled ozone gas biochar reactor system that includes and O2/CO2 air inlet pump and valve 301, an ozone generator system 302, an ozone air inlet and tube 316 passing through the biochar ozonization reactor wall 305 near its bottom, an ozone O3/CO2 air space 303 at the bottom of the reactor, a W-conical-shaped porous metal plate 304, a biochar ozonization reactor chamber space 307 above the porous metal plate 304, a biochar inlet 308 passing through the biochar ozonization reactor wall 305 at the upper part of the reactor, an O3/CO2 gas 315 flowing from O3/CO2 air space 303 at the bottom through the W-conical-shaped porous metal plate and the biochar materials toward the upper part of the reactor, an ozonized biochar outlet 309 passing through the reactor wall at the lower part of
  • This embodiment of the biochar ozonization treatment reactor system 300 illustrated in Fig. 5 is similar to the embodiment of Fig. 4 with the exception of the following additional features.
  • the embodiment of Fig. 5 employs a W-shaped or a W-conical-shaped porous metal plate 304 that provides even greater surface area for the ozone containing gas stream to pass through into the biochar ozonization reactor chamber space 307 for better efficiency.
  • This embodiment also utilizes a recycling water pump 320 with a flexible water recycling tube 321 connected with the flexible water inlet and outlet 306 and the water inlet 317 to re-use the liquid for the biochar ozonization process.
  • This biochar ozonization treatment reactor system 400 is a controlled ozone gas biochar reactor system that includes an air inlet pump and valve 401, an ozone generator system 402, an ozone air inlet and tube 416 passing through the biochar ozonization reactor wall 405 near its bottom, an ozone air space 403 at the bottom of the reactor, a V-shaped or V-conical-shaped porous metal plate 404, a biochar ozonization reactor chamber space 407 above the porous metal plate 404, a biochar inlet 408 passing through the biochar ozonization reactor wall 405 at the upper part of the reactor, an ozone gas 415 flowing from ozone air space 403 at the bottom through the V-conical-shaped porous metal plate and the biochar materials toward the upper part of the reactor, an ozonized biochar outlet 409 passing through the reactor wall at the lower part of the reactor, a tail
  • the embodiment of the biochar ozonization treatment reactor system 400 illustrated in Fig. 6 is similar to the embodiment illustrated in Fig. 3. However, this embodiment utilizes a V- conical-shaped porous metal plate 404 that provides greater surface area for the ozone containing gas stream to pass through into the biochar ozonization reactor chamber space 407. This shaped porous metal plate also provides a convenient way for improved harvest of the treated biochar products through the ozonized biochar outlet 409 by use of gravity with minimal energy consumption.
  • FIG. 7 another embodiment of a biochar ozonization treatment reactor system 500 is illustrated.
  • This is a double-wall coolant-jacketed ozone gas biochar reactor system that includes a heat-conducting reactor inner wall 522, a reactor outer wall 505, a coolant chamber space 523 formed between the inner wall 522 and outer wall 505, a coolant inlet 524 connected with the coolant chamber space at the bottom part of the reactor, a hot coolant outlet 525 connected with the coolant chamber space at the top part of the reactor, an O2/CO2 air inlet pump and valve 501, an ozone generator system 552, an ozone air inlet and tube 516 passing through the biochar ozonization reactor outer wall 505 and inner wall 522 near its bottom, an ozone O3/CO2 air space 503 at the bottom of the reactor, an inverted-V conical-shaped porous metal plate 504, a biochar ozonization reactor chamber space 507 above the porous metal plate 504, a hot biochar in
  • the embodiment of the biochar ozonization treatment reactor system 500 of Fig. 7 is similar to the embodiment illustrated in Fig. 6, with the following additional features.
  • the embodiment of Fig. 7 employs a double-wall coolant-jacketed ozone gas biochar reactor system to enable cooling of hot biochar by use of a coolant and the outputting of hot coolant for waste heat energy recovery and utilization such as the utilization of waste heat through a heat exchange system to preheat or to dry biomass.
  • This embodiment also utilizes an inverted-V-conical-shaped porous metal plate 504 that facilitates cooling of the biochar materials within the double-wall coolant-jacketed reactor.
  • this embodiment utilizes well-controlled Cb concentration levels under a CO2 (and/or N2) atmosphere to prevent any possible biochar combustion especially during the loading of hot biochars from a biomass pyrolysis or gasification reactor.
  • the coolant utilized in this embodiment is a fluid that flows through or around a biochar reactor to prevent its overheating, transferring the heat produced by the biochar reactor to other devices that utilize the waste heat to pre-heat or dry biomass or to dissipate the heat.
  • Suitable coolants have a high thermal capacity, low viscosity and are low-cost.
  • the coolants are preferably non-toxic and chemically inert, neither causing nor promoting corrosion of the cooling system.
  • Suitable coolants are selected from the group consisting of water, antifreeze liquid, polyalkylene glycol, oils, mineral oils, silicone oils such as
  • polydimethylsiloxane polydimethylsiloxane, fluorocarbon oils, transformer (insulating) oil, refrigerants, and
  • FIG. 8 another embodiment of a biochar liquid-ozonization treatment reactor system 600 is illustrated.
  • This embodiment of a biochar ozonization treatment reactor system 600 is a double-wall coolant-jacketed ozone gas biochar reactor system that includes a heat-conducting reactor inner wall 622, a reactor outer wall 605, a coolant chamber space 623 formed between the inner wall 622 and outer wall 605, a coolant inlet 624 connected with the coolant chamber space at the bottom part of the reactor, a hot coolant outlet 625 connected with the coolant chamber space at the top part of the reactor, an O2 air inlet pump and valve 601, an ozone generator system 652, an ozone air inlet and tube 616 passing through the biochar ozonization reactor out wall 605 and inner wall 622 near its bottom, an ozone 03/water space 603 at the bottom of the reactor, a porous metal plate 604, a biochar ozonization reactor chamber space 607 above the porous metal plate 604, a bio
  • the biochar ozonization treatment reactor system 600 embodiment of Fig. 8 is similar to the embodiment illustrated in Fig. 7 with the following additional features.
  • the embodiment of Fig. 8 uses a water liquid level 619 that completely immerses biochar materials, and this embodiment takes the advantage of a flat porous metal plate 604 that holds biochar materials and allows Cb gas to bubble through.
  • the feeding of an Cb-containing gas stream is performed preferably with nearly 30% or above 1% of Cb under a pressure of from about 1 to about 30 atmospheres (atm).
  • the Cb-containing gas stream can be an 03/water steam stream, an O3- C02/water steam stream, an 0 3- 02-C02/water steam stream, an 0 3- 02-C02-N2/water steam stream, an artificial gas mixture stream including an O3-CO2 mixture, an oxygen (02)-ozone (O3) mixture, an O3-O2-CO2 mixture, an 0 3- nitrogen (N2) mixture, an O3-O2-CO2-N2 mixture, an O3-CO2-N2 mixture, an 0 3 -argon mixture, an 0 3 -helium mixture, and any combination thereof.
  • one of the 0 3 -containing gas streams listed above is selectively applied in combination with a liquid water spray 218 (Fig. 4) into biochar materials to perform“wet biochar ozonization” to achieve more desirable results.
  • Liquid water mediates the biochar ozonization process in a number of ways, for example, by extracting water-soluble biochar substances including the dissolvable organic content (DOC) that may contain the potential phytotoxins to react with the ozone (see equation [3] below) in the liquid phase to make the biochar product cleaner.
  • the residual ozonized liquid may be discharged at the bottom of the reactor through the flexible water inlet and outlet 206.
  • the residual ozonized liquid stream is recycled through the use of a recycling water pump 320 with a flexible water recycling tube 321 connected with the flexible water inlet and outlet 306 and the water inlet 317 to re-use the liquid for the biochar ozonization process as illustrated, for example, in Fig. 5.
  • a wet-moisture biochar ozonization treatment operational process includes the following process steps that are performed in combination with the use of hydrogen peroxide: a) Loading biochar materials into the reactor through the biochar inlet; b) Monitoring and adjusting (if/when necessary) biochar temperature; c) Monitoring biochar water content and relative humidity in the reactor, d) Based on the required biochar water content and relative humidity, properly adding water into the biochar materials by use of a heat-smoke-sensing sprinkler system with water inlet and water spray system at the upper part of the reactor, and/or introducing water and/or steam/vapor by use of a flexible water inlet and outlet valve and optional water level for vapor/moisture generation at the bottom of the reactor (Fig.
  • an exemplary process in accordance with the present invention uses the wet biochar ozonization treatment process system for a plurality or series of operational cycles to achieve more desirable results.
  • Any one of the steps a) through k) of the processes as described herein can be adjusted or modified as desired for certain specific operational conditions. For example, as shown in Fig 7, when a hot biochar source from a biomass pyrolysis and/or gasification reactor is used with this treatment process, the biochar temperature monitoring and adjusting step of b) is modified by adding additional steps of using a double-wall coolant-jacketed ozone gas biochar reactor system with a coolant to cool down hot biochar and to utilize the waste heat energy through a heat exchange system to preheat and/or to dry biomass. Any one of the steps a) through k) of the embodiments of process of the present invention are described herein can be applied in whole or in part and in any adjusted combination for enhanced biochar-surface oxygenation in accordance of this invention.
  • the biochar ozonization treatment process is operated in combination with the use of hydrogen peroxide (H2O2).
  • H2O2 hydrogen peroxide
  • Suitable overall amounts of hydrogen peroxide include, but are not limited to, about 1, 3, 10, 20, and 30% w/w treatments of H2O2 with or without the use of ozone.
  • biochar treated with H2O2 show an increase in CEC. This increase in CEC is attributed to an increase in the presence of acidic oxygen functional groups on the surface of the biochar materials.
  • H2O2 treatment causes an overall drop in biochar’s capacity for the removal of methylene blue from solution, likely resulting from the weakening of p-p dispersive forces brought about by the introduction of oxygen functionality, which disrupts the overall aromatic structure of the biochar sample.
  • the use of hydrogen peroxide (H2O2) is beneficial especially in combination with the wet biochar ozonization reactor process as illustrated, for example, in Fig. 8.
  • the wet biochar ozonization treatment process is operated with biochar completely immersed in liquid water as shown, for example, in Fig. 8.
  • An ozone-treating gas stream for example, 03/air, is bubbled from the bottom of the reactor through the biochar materials.
  • the presence of excess liquid water allows the biochar particles to move up and down as the bubbling ozone-treating gas stream passes through them, which effectively extracts any water soluble substances such as biochar toxins, other dissolved organic compounds (DOC), and ash salt.
  • Some of the O3 gas can dissolve into the liquid water where it can destruct DOC including the potential biochar toxins while oxygenating the surfaces of biochar particles. As shown, for example, in Fig.
  • the water liquid is discharged through the flexible water inlet and outlet 606 and replenished through a water spray 618 at the upper part of the reactor for continued ozonization and cleaning of the biochar materials until the desired results are achieved. Therefore, use of this biochar liquid ozonization treatment process creates an ultraclean ozonized specialty biochar product used for special industrial applications such as making air and water filters to clean air and water. Suitable applications for these filters include, for are not limited to, home applications, office and industrial applications in addition to biochar soil applications.
  • an 03-containing gas stream either with or without the use of water spray as shown, for example, in Figs. 4, 5 and 6 is performed in either a continuous or a pulsed mode to optimize the operation effects when desirable.
  • the 0 3 - containing gas stream cleans the biochar materials so that small organic molecules (typically at a molecular mass of about 500 Dalton or smaller) are removed from the biochar products by ozone’s reactions with the small aromatic organic molecules. It was recently identified in Smith, Buzan, Lee 2013 ACS Sustainable Chem. Eng.
  • PAHs polycyclic aromatic hydrocarbons
  • the potential biochar toxins (which as tested at a dissolved organic carbon (DOC) concentration of about 75 mg per liter with blue-green alga are toxic to plant cells) are typically soluble organic matter that include residual pyrolysis bio-oils, small organic molecules at a molecular mass of about 500 Dalton (Da) or smaller that are co- produced during biomass pyrolysis, polycyclic aromatic hydrocarbons, degraded lignin-like species rich in oxygen containing functionalities, phenolic type of phytotoxins that are now known to contain at least one carboxyl group per toxin molecule, and combinations thereof.
  • the term“degraded lignin-like species” here and throughout the specification means “degraded lignin species and/or polycyclic aromatic species with structure similar to lignin.”
  • the post-production biochar surface-oxygenation-treatment process with ozone can be used, as shown, for example, in Fig. 6, to convert tons of conventional biochar materials currently available in the market quickly to clean hydrophilic products free of biochar toxin or with minimized potential biochar toxins.
  • “free of biochar toxin” means that the content of the potential biochar toxin (if any) is reduced to such a lower level to eliminate any toxic effect to algal culture growth when tested with a standard concentration of biochar water- extracted substances measured as 0.189 grams of dissolved organic carbon (DOC) per liter.
  • DOC dissolved organic carbon
  • exemplary embodiments of systems and methods produces a substantially uniform (i.e., substantially homogeneous) surface-oxygenated biochar.
  • substantially uniform i.e., substantially homogeneous surface-oxygenated biochar.
  • the resulting biochar contains an absence of regions of non-oxygenated biochar (as commonly found in biochar material formed under uncontrolled conditions, such as in open pits) in the surface- oxygenated biochar.
  • a substantially uniform surface-oxygenated biochar possesses different macroscopic regions, e.g., of at least about 100 pm 2 , 1 mm 2 , 10 mm 2 , or 1 cm 2 in size, that vary by no more than about 10%, 5%, 2%, 1%, 0.5%, or 0.1% in at least one characteristic, such as CEC, oxygen to carbon molar ratio, and surface area.
  • the substantial uniformity of the surface-oxygenated biochar advantageously provides a user with a biochar material that provides a consistent result when distributed into soil, either packaged or in the ground.
  • a substantial uniformity of the surface-oxygenated biochar ensures that a tested characteristic of the biochar is indicative of the entire batch of biochar.
  • a substantially uniform biochar is obtained by an effective level of mixing of the biochar during the surface-oxygenation process.
  • the biochar is agitated, shaken, or stirred either manually or mechanically during the ozonization and purging process.
  • the biochar is reacted with ozone in a reactor containing a tumbling mechanism such that the biochar is tumbled during the ozonization reaction.
  • Suitable biochar sources for use in embodiments of the systems and methods described herein include any biochar material that could benefit by the ozonization process of the inventive method.
  • the biochar source could be, for example, a byproduct of a pyrolysis or gasification process, a material acquired from a biochar deposit and natural coal materials, for example, from coal mines.
  • the biochar is plant-derived, i.e., derived from cellulosic biomass or vegetation.
  • Suitable biomass materials include, but are not limited to, cornstover, e.g., the leaves, husks, stalks, or cobs of corn plants, grasses, e.g., switchgrass, miscanthus, wheat straw, rice straw, barley straw, alfalfa, bamboo and hemp, sugarcane, hull or shell material, e.g., peanut, rice, and walnut hulls, any woody biomasses including dead trees such as dead pine and dead oak, Douglas fir, woodchips, saw dust, waste cardboard, paper or wood pulp, algae, aquatic plants, food waste, spent mushroom substrate, chicken litters, heifer and cow manure, horse manure, pig manure, agricultural waste, and forest waste.
  • cornstover e.g., the leaves, husks, stalks, or cobs of corn plants
  • grasses e.g., switchgrass, miscanthus, wheat straw, rice straw, barley straw, alfalfa, bamboo and hemp
  • the biomass material is in its native form, i.e., unmodified except for natural degradation processes, before being converted to biochar.
  • the biomass material is modified by, for example, adulteration with a non-biomass material, e.g., plastic- or rubber-based materials, or by physical modification, e.g., mashing, grinding, compacting, blending, heating, steaming, bleaching, nitrogenating, oxygenating, or sulfurating, before being converted to biochar.
  • the one or more surface-oxygenation agents considered herein are ozone and ozone- related compounds or materials known in the art that tend to be reactive by imparting oxygen- containing functional groups into organic materials (including any of the O2 plasma, CO2 plasma, and CO plasma that have been disclosed before).
  • An example of a surface-oxygenating agent is O3 in the gas form in addition to the 03/water vapor stream, 03/water liquid, 03/water liquid-peroxide (H2O2), and 03/carbonated water liquid form.
  • the O3 gas may also be in the form of an artificial gas mixture, such as an 0 3 -oxygen (02)-carbon dioxide (CO2), O3-CO2, 0 3 -C02-peroxide (H2O2), O3-CO2-CO (carbon monoxide), 0 3 -02-nitrogen (N2), 0 3 -02-C02-argon, 0 3 -02-C02-helium, or O3-O2-CO2-CO mixture.
  • An artificial gas mixture can be advantageous for the purposes of the invention in that the level of O3 can be precisely controlled, thereby further controlling the pyrolysis and ozonization reactions to optimize the density and kind of oxygen-containing functional groups in the biochar.
  • an 0 3 -C02-containing gas mixture having at least, less than, or about, for example, 0.1%, 0.5%, 1%, 2%, 3%, 5%, 7%, 10%, 15%, 20%, 30%, 40%,
  • the biochar source can be treated with O3 for“oxygen- implantation” onto the surfaces of the biochar materials as shown in Equation 1 above.
  • the O3 treatment increases the 0:C molar ratios or carboxyl groups at biochar surfaces.
  • the cation exchange capacity increases with the 0:C ratio of the biochar materials. Accordingly, use of O3 treatment can enable molecular re-engineering of biochar materials to impart unique surface properties such as the cation exchange capacity, without affecting the bulk properties of the biochar.
  • the O3 treatment is conducted at low or ambient temperature, e.g., from about l5°C to about 30°C.
  • the O3 treatment process entails subjecting the biochar at ambient pressure to a source of 0 3 -containing gas or liquid.
  • the O3 is typically produced by pumping at least one of pure O2 and ambient air (containing about 21% O2 and 79% N2) through an ozone generator system that utilizes a special electric field under which O2 is converted into O3, which is then fed into the biochar ozone treatment reactor.
  • the particular O3 generating and feeding conditions depend on several factors including the type of ozone generators, gas composition, power source capability and characteristics, operating pressure and temperature, the degree of ozonization required, and characteristics of the particular biochar being treated, i.e., its susceptibility or resistance to oxygenation.
  • the biochar can be exposed to the ozone treatment for at least about 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 4, or 5 minutes and up to 6, 8, 10, 12, 15, 20, 30, 40, 50, 60, 90 or 180 minutes.
  • the biochar can be ozone treated within a temperature range of about l5°C to about 30°C, a lower temperature, e.g., less than l5°C, or a higher temperature, e.g., greater than about 30°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, l00°C, H0°C, l20°C, l30°C, l40°C, l50°C, l60°C, l70°C, l80°C, l90°C, 200°C, 2lO°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, and 300°C, 350°C, 400°C, or a range bounded by any two of the foregoing values, may also be used under controlled conditions where the possibility of combustion is adequately suppressed in the presence of at least one of
  • biochar ozonization treatment reactor system 500 that employs a double-wall coolant-jacketed ozone gas biochar reactor system to enable cooling of hot biochar by use of a coolant and outputting hot coolant for the waste heat energy recovery and utilization such as the utilization of waste heat through a heat exchange system to preheat or to dry biomass.
  • This system also takes advantage of an inverted- V-conical-shaped porous metal plate 504 that facilitates cooling of the biochar materials within the double-wall coolant-jacketed reactor.
  • this biochar ozonization system 500 (Fig. 7) may be integrated with an existing biomass pyrolysis or gasification reactor to produce advanced hydrophilic biochar products.
  • the hot biochar is cooled down to a temperature below about 120 °C in the double-wall coolant-jacketed reactor system to recover the heat from hot biochar to generate hot coolant output for waste heat utilization through a heat exchange system to dry biomass and/or biochar products.
  • This operational feature results in not only better energy efficiency through utilization of biochar waste heat but also lowering the potential biochar fire risks when in contact with the ozone-containing gas treatment stream.
  • the biochar ozonization treatment reactor process is operated at a pressure selected from the group consisting of ambient pressure, 0.1 atm, 0.2, 0.5,
  • the organic contaminants, i.e., potential toxins, adsorbed on biochar surfaces are removed by oxygenation chemical reactions with highly reactive Cb.
  • certain Cb-enabled oxygenation chemical reactions promote surface carboxylation and sometimes hydroxylation (possibly forming carboxyl COOH groups and hydroxyl OH on the biochar carbon surfaces), which increases surface wettability and cation exchange capacity (CEC).
  • CEC surface wettability and CEC are important properties for biochar soil applications to better retain water and nutrients for improved soil fertility as well as reduction of agricultural chemical runoff.
  • ozone is reacted with biochar in a closed system, i.e., a closed container, to ensure that the intended amount of ozonization reactants as measured, and no less and no more, is reacted with the biochar.
  • a closed system i.e., a closed container
  • an ozonizing gas or liquid or a solution thereof
  • a selected volume of the gas or liquid corresponding to a calculated weight or moles of the ozone can be charged into the closed container (reactor) along with the biochar source and the contents homogeneously mixed or blended under conditions suitable for ozonization of the biochar to take place.
  • the temperature of the mixed reactants in the container can be controlled along with proper agitation until the ozone gas or liquid flows and diffuses fully through the biochar materials to promote its reaction with the biochar in a uniform, i.e., homogeneous, manner.
  • the moisture level in the ozone treatment reactor can be suitably adjusted, for example, to a humidity level of about, at least, or no more than 1%, 2%, 5%, 10%, 15, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%, or a humidity level within a range bounded by any two of these values.
  • ozonization/carboxylation of biochar materials is attained by conducting the ozonization/carboxylation reactions in an open or closed container and by rapidly quenching hot biochar with Cb/CCh-containing water (Fig. 7).
  • the extremely hot and reacting biochar from a biomass pyrolysis or gasification reactor can be quenched by, for example, contacting the reacting biochar with an excessive amount of Cb/CCh-containing water such as Cb/CCb/carbonated water, and/or an inert substance, preferably when the biochar material is still hot, e.g., at a temperature of at least about 800°C, 750°C, 700°C, 650°C 600°C 550°C 500°C, 450°C, 400°C, 350°C, 300°C, 250°C, 200°C, l50°C, l00°C, 50°C, or within a range bounded by any two of these values, as produced from a biomass-to-biochar process.
  • Cb/CCh-containing water such as Cb/CCb/carbonated water
  • an inert substance preferably when the biochar material is still hot, e.g., at a temperature of at least about 800°C, 750°C
  • the inert substance can be, for example, carbonates, bicarbonate or a form of biomass (e.g., soil, plant-material, or the like).
  • An excessive amount of Cb/CCb/carbonated water, 03/water liquid, 03/water liquid- peroxide (H2O2), 03/carbonated water liquid, 03/carbonated water liquid-peroxide (H2O2), and/or 03/carbonates/inert substance is an amount that preferably covers all of the reacting biochar, or alternatively, functions as a bulk surface shield of the biochar, with the result that the
  • the ozonization/carboxylation process is facilitated due to the addition of the excess O3/CO2 to the hot biochar preferably at a pressure higher than the ambient atmospheric pressure in the reactor as shown in Fig 7. If an elevated temperature is being used in the ozonization/carboxylation process, the quenching step also has the effect of rapidly reducing the temperature of the biochar.
  • the methods described herein can also include one or more preliminary steps for producing biochar, i.e., the biochar source or "produced biochar", from biomass before the biochar is oxygenated/carboxylated.
  • the biomass-to-biochar process can be conducted within any suitable time frame before the produced biochar is oxygenated/carboxylated.
  • a biomass-to-biochar process is conducted in a non-integrated manner with the biochar ozonization process as shown, for example, in Fig. 6.
  • biochar produced by a biomass-to-biochar process is transported to a separate location where the biochar ozonization process is conducted.
  • the transport process generally results in the cooling of the biochar to ambient temperature conditions, e.g., l5-40°C, before ozonization occurs.
  • the produced biochar is packaged and/or stored in the non- integrated process before ozonization of the biochar.
  • a biomass-to-biochar process is conducted in an integrated manner with a biochar ozonization process.
  • biochar produced by a biomass-to-biochar process is treated in situ using the double-wall coolant-jacketed ozone gas biochar reactor system 500 (Fig. 7) when the biochar is still very hot.
  • freshly produced biochar can have a temperature of, for example, about or at least 700°C, 650°C, 600°C, 550°C, 500°C, 450°C, 450°C, 400°C, 350°C, 300°C, 250°C, 200°C, l50°C, l00°C, or 50°C, or a temperature within a range bounded by any two of these values, before being subjected to the ozonization/carboxylation process.
  • the freshly produced biochar can be subjected to additional cooling and/or heating to adjust and/or maintain its temperature before the ozonization step.
  • the biochar ozonization process can be integrated with, for example, a biomass-to-fuel process, such as a low temperature or high temperature pyrolysis/gasification process.
  • a biomass-to-fuel process such as a low temperature or high temperature pyrolysis/gasification process.
  • typically about 40%, 50%, or 60% of the biomass carbon is converted into biochar while the remaining 60%, 50%, or 40% of carbon is converted to fuel (syngas and bio-oils).
  • the biochar ozonization process is integrated with a biomass pyrolysis/gasification process conducted at a temperature of about 800°C, 750°C, 700°C, 650°C, 600°C, 550°C, 500°C, 450°C, 400°C, 350°C, or 300°C or a temperature within a range bounded by any two of these values.
  • the biochar ozonization process is integrated with a biomass pyrolysis process operated at a temperature of about 500°C to produce a clean hydrophilic biochar product with higher CEC value and minimized potential biochar toxins.
  • Biochar produced from biomass pyrolysis process at around 500°C is typically already quite clean (with minimized potential biochar toxins); however, its CEC value is often very low due to the loss of its carboxyl groups at such a high pyrolysis temperature (500°C).
  • the use of the biochar ozonization process enables creation of oxygen-containing functional groups on biochar surfaces at ambient temperature under ambient pressure, resulting in a better hydrophilic biochar product with higher CEC value and minimized potential toxins.
  • an integrated process is configured as a batch process wherein separate batches of produced biochar are ozonized at different times.
  • the integrated process is configured as a continuous process wherein biochar produced by the biomass-to-biochar process is continuously subjected to an ozonization process as it is produced.
  • produced biochar can be continuously transported either manually or by an automated conveyor mechanism through a biochar ozonization zone.
  • the automated conveyor mechanism can be, for example, a conveyor belt, a gravity-fed mechanism, or an air pressure mechanism.
  • the ozonized biochar produced herein has a particular, exceptional, or optimal set of characteristics, such as a particular, exceptional, or optimal cation exchange capacity, optimal pH value, optimal carboxyl content, optimal hydrophilicity and wettability, optimal water-holding field capacity, optimal oxygen-to-carbon molar ratio, surface area, nutrient contents, biochar particle size, composition, zero toxin content, and/or uniformity in any of these or other characteristics.
  • the methods described herein are particularly suitable for producing these types of advanced hydrophilic biochars.
  • the biochar ozonization treatment process has a feature that significantly increases the CEC value of biochars often by more than a factor of 2.
  • the biochar ozonization treatment can improve the CEC value of a biochar from its initial value of 80 mmol/kg to as high as 230 mmol/kg after an ozone treatment.
  • the CEC of the ozonized biochar is at least moderate, e.g., about or at least 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 mmol/kg, or within a particular range bounded by any two of the foregoing values.
  • the CEC of the ozonized biochar is atypically or exceptionally high, e.g., about or at least 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500 mmol/kg, or within a particular range bounded by any two of the foregoing values.
  • the CEC of the ozonized biochar is within a range having a minimum value selected from any of the exemplary moderate CEC values given above and a maximum value selected from any of the exemplary atypically high CEC values given above (for example, 100-1000 mmol/kg or 200-1200 mmol/kg).
  • the CEC value is substantially uniform throughout the biochar material.
  • the density of carboxy-containing cation-exchanging groups is typically proportional to the measured oxygen-to-carbon molar ratio of the biochar, wherein the higher the oxygen-to- carbon molar ratio, the greater the density of cation-exchanging groups in the biochar.
  • the oxygen-to-carbon molar ratio of the ozonized biochar surface is at least 0.1 : 1, 0.15: 1, 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1, 0.4: 1, 0.45: 1, 0.50: 1, 0.60: 1, 0.70: 1, or within a range bounded by any two of the foregoing ratios.
  • the ozonized biochar contains a substantially uniform density of the carboxy-containing cation-exchanging groups and a substantially uniform oxygen-to-carbon molar ratio throughout the biochar surface material.
  • the ozone-enabled molecular implantation of oxygen atoms into biochar carbon materials can be used also as a mechanism to remove potential biochar toxins through molecular structural destruction by the ozone-assisted implantation of oxygen atoms into the toxic organic molecules such as phenolic-type phytotoxins and polycyclic aromatic hydrocarbons (PAHs). Therefore, the destruction of potential biochar toxins, the enhancement of biochar cation exchange capacity and hydrophilicity, and the optimization of biochar pH are accomplished simultaneously through the ozone-enabled oxygenation into both the potential toxin molecules and biochar surfaces.
  • PAHs polycyclic aromatic hydrocarbons
  • the ozonized biochar can have any suitable specific surface area (SSA), as commonly determined by BET analysis.
  • SSA specific surface area
  • the ozonized biochar has an SSA value of about, or at least, or no more than 0.1, 0.5, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 80, 100, 200, 400, 600, or 800 m 2 /g, or an SSA value within a range bounded by any two of the foregoing values.
  • the ozonized biochar can also have any suitable charge density.
  • the ozonized biochar can also have any suitable charge density.
  • the ozonized biochar has a surface charge density of about, or at least, or no more than 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, or 120 mmol/m 2 , or a charge density within a range bounded by any two of the foregoing values.
  • use of a biochar ozonization process can achieve biochar-surface oxygenation to significantly functionalize biochar surface properties such as its cation exchange value and pH without significantly affecting some of the biochar bulk properties such as the biochar core carbon stability and elemental compositions.
  • biochar surface atomic layer that is accessible to ozone represents only a very small fraction of the total biochar mass. Therefore, a significant biochar- surface oxygenation by ozonization may not significantly alter the bulk properties of the biochar core carbon materials, which is desirable in maintaining biochar carbon stability for biochar soil amendment and carbon sequestration applications.
  • the ozonized biochar can also have any suitable carbon, nitrogen, oxygen, hydrogen, phosphorous, calcium, sulfur, ash, and volatile matter content.
  • the carbon content can be about, at least, or no more than, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 mole percent, or within a particular range therein.
  • the nitrogen content can be about, at least, or no more than, for example, 0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.5, 5.0, 6.0, 7.0, or 8.0 mole percent, or within a particular range therein.
  • the oxygen content can be about, at least, or no more than, for example, 1, 2, 5, 10, 15, 20, 25, or 30 mole percent, or within a particular range therein.
  • the hydrogen content can be about, at least, or no more than, for example, 1, 2, 5, 10,
  • the phosphorus or calcium content can independently be about, at least, or no more than, for example, 5, 10, 25, 50, 100,
  • the sulfur content can be about, at least, or no more than, for example, 50, 100, 200,
  • the ash content can be about, at least, or no more than, for example, 1, 2.5, 5, 10, 15, 20, 30, 40, 50, 60, or 70%, or within a particular range therein.
  • the volatile matter content can be about, at least, or no more than, for example, 1, 2.5, 5, 10, 15, 20, 25, 30, 35, or 40%, or within a particular range therein.
  • the ozonized biochar can also have any suitable particle size.
  • the ozonized biochar can have a particle size of about, at least, or no more than, for example, 50, 100, 250, 500, 750, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000 pm, or a particle size within a particular range bounded by any two of the foregoing values.
  • biochar particle sizes such as 6000, 7000, 8000, 9000, 10,000, 20,000, 30,000, 40,000, 50,000 pm, or higher (for example, up to 100,000 pm), or a particle size within a particular range bounded by any two of the foregoing values, may be preferred.
  • the biochar materials may also be in the form of an agglomeration, compaction, or fusion of biochar particles, e.g., pellets or cakes, for this type of application as well.
  • the size of the pellets or cakes can correspond, for example, to any of the larger particle sizes given above.
  • particle size as used above for a particular value can mean a precise or substantially monodispersed particle size, e.g., within ⁇ 0-5% of the value, or a more dispersed particle size, e.g., greater than 5% and up to, for example, about 50% or 100% of the value.
  • the biochar particles may have a size distribution that is monomodal, bimodal, or higher modal.
  • the term “particle size” may also refer to an average particle size.
  • the particle size of the ozonized biochar can be appropriately modified by techniques known in the art. For example, the biochar particles may be ground, agglomerated, or sieved by any of the techniques known in the art.
  • the above exemplary particle or pellet sizes refer to the diameter of the particles or pellets.
  • the above exemplary particle or pellet sizes can refer to at least one, two, or three of the dimensional axes of the particles or pellets.
  • the ozonized biochar can also have any suitable pore size.
  • the ozonized biochar can have a pore size of about, at least, or no more than, for example, 0.5, 1, 1.5,
  • the ozonized biochar can also have any suitable pH value.
  • Some of the conventional biochar materials typically have an alkaline pH ranged from about pH 8.5 up to about pH 12, which are not ideal for use in many regions such as those in the western regions of the United States where the soil pH is already above pH 8.0.
  • use of the ozonization treatment can reduce the pH value of biochar through the formation of acidic carboxyl groups at biochar surfaces and/or by the formation and adsorption of nitrogen oxides/nitric acid during a biochar ozonization process in the presence of N2.
  • the ozonized biochar can have an optimized pH value of about, at least, or no more than, for example, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, or a pH value within a particular range bounded by any two of the foregoing values.
  • the ozonized biochar such as produced by the method described above, may also be admixed, i.e., enriched, with one or more soil-fertilizing compounds or materials for use as a fertilizing biochar soil amendment or additive and carbon sequestration agent.
  • the soil-fertilizing compounds or materials can be, for example, nitrogen-based, e.g., ammonium-based, carbonate- based, e.g., CaCCb, phosphate-based, e.g., the known phosphate minerals, such as in rock phosphate or triple superphosphate, and potassium-based, e.g., KC1.
  • the one or more soil-fertilizing compounds or materials include at least one nitrogen-containing, for example, NH 4 + -containing, compound or material.
  • nitrogen-containing fertilizing compounds or materials include, for example, (NFL ⁇ CCb, NH4HCO3, NH4NO3, (NH4)2S04, (NH 2 )2CO, biuret, triazine-based materials, e.g., melamine or cyanuric acid, urea- formaldehyde resin, and polyamine or polyimine polymers.
  • the fertilizer material may be inorganic, as above, or alternatively, organic.
  • organic fertilizer materials include peat moss, manure, insect material, seaweed, sewage, and guano.
  • the biochar material can be treated by any of the methods known in the art in order to combine the biochar material with a fertilizer.
  • the biochar material is treated with a gas stream of hydrated ammonia to saturate the biochar material.
  • the biochar material may also be coated with fertilizer compounds or materials. The coating may also be suitably modified or optimized as known in the art to adjust the rate of release of one or more fertilizer compounds or materials into soil.
  • one or more of the above generic or specific soil-fertilizing compounds or materials are excluded from the ozonized biochar composition.
  • the invention is directed to a soil formulation containing, at a minimum, soil admixed with the biochar composition described above.
  • the soil can be of any type and composition.
  • the soil can have any of the numerous and diverse proportions of clay, sand, and silt.
  • the sand, silt, and clay components can be independently present in an amount ranging from substantially absent, i.e., zero weight percent or in trace amounts, up to about 100 weight percent, e.g., exactly 100% or at least 98 or 99%.
  • one or more of the sand, silt, and clay components are in an amount of, independently, about, at least, or no more than, for example, 0.1, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 weight percent of the total weight of the soil absent the biochar.
  • the soil may also preferably have one or more of the sand, silt, and clay components present in an amount within a range bounded by any two of the foregoing exemplary weight percentages.
  • the soil can also contain any amount of humus and humic substances, i.e., organic matter, humic acid, fulvic acid, cellulose, lignin, peat, or other such component, in any of the exemplary amounts or ranges given above.
  • humus and humic substances i.e., organic matter, humic acid, fulvic acid, cellulose, lignin, peat, or other such component, in any of the exemplary amounts or ranges given above.
  • an ozonized biochar can remove certain industrial organic molecules such as methylene blue dye 5 times better than the untreated biochar.
  • the ozonized biochar can be used as filtration materials to remove various cations and pollutants from fluid streams including water and air.
  • This embodiment is also directed to the use of certain ozonized biochar materials for other environmental or industrial applications such as the formulation and production of ozonized biochar columns or filters for filtration of fluids, including, for example, water, air and other solvents.
  • various cations and/or pollutants in the medium such as water and air will be in contact with the ozonized biochars in the columns and filters thereby are removed through cation exchange binding and/or physical chemistry adsorption on the ozonized biochar materials.
  • the used biochar columns and filters can be readily disposed by combustion cleanly back to air CO2 and H2O.
  • certain biochar columns and filters after used in removal of certain heavy metal ions such as, for example, Cu 2+ they can also be combusted to retain their adsorbed heavy metal content in a relatively small amount of the resultant ash that can also be readily disposed by other proper ways as well.
  • the biochar materials may be disposed by burying into soil at certain proper locations consistent with the practices of both waste disposal and biochar carbon sequestration.
  • ozonized biochar columns and filters may be used to remove various cations, contaminants, and pollutants selected from the group consisting of ammonium (NH 4 + ), Li + , Ba 2+ , Fe 2+ , Fe 3+ , Cu + , Cu 2+ , Cd 2+ , Cs + , Sr 2+ , Ni 2+ , Zn 2+ , Cr 3+ , Pb 2+ , Hg 2+ , other metal ions including uranium ions, plutonium ions, osmium ions, platinum ions, gold ions, iridium ions, ruthenium ions, rhodium ions, cobalt ions, titanium ions, thallium ions, tin ions, indium ions,
  • NH 4 + ammonium
  • the present invention here further comprises an improved method for industrial production and utilization of surface-oxygenated biochar composition through ozonization in combination with sonication.
  • the improved method comprises at least one of the following steps: 1) treating a biochar source with sonication and an ozone-containing gas stream in a biochar sonication-ozonization treatment reactor system using a sonication-ozonization-enabled biochar-surface oxygenation operational process, wherein treating the biochar source comprises: 2) contacting the biochar source with the ozone-containing gas stream; 3) enabling biochar- surface oxygenation; 3) destroying a potential biochar toxin; 5) producing a surface-oxygenated biochar composition having enhanced cation exchange capacity; 6) producing a special surface- oxygenated biochar composition for solubilizing phosphorus from insoluble phosphate materials for producing phosphate fertilizers without using strong industrial acids; 7) producing a special surface-oxygenated biochar paste composition for sand soilization; and 8) producing a special surface
  • the biochar source composition comprises a carbon product or recalcitrant biomass material selected from the group consisting of charcoals from a slow biomass pyrolysis process, charcoals from a fast biomass pyrolysis process, biochar from flash pyrolysis (typically, 815-871 °C, residence time about 30 seconds) of biomass, charcoals from a biomass gasification (typically, >700 °C) process, hydrochars from a biomass hydrothermal carbonization process, a material acquired from a biochar deposit, natural coal materials, lignin residues, lignin cellulosic materials, carboxymethyl cellulose, un hydrolyzed biomass residues such as un-hydrolyzed corn stover residues, recalcitrant biomasses, and a combination thereof.
  • a carbon product or recalcitrant biomass material selected from the group consisting of charcoals from a slow biomass pyrolysis process, charcoals from a fast biomass pyrolysis process, biochar from flash pyrolysis (typically, 815-871
  • this embodiment of a sonicati on-enhanced biochar ozonization treatment reactor system 700 comprises a sonication control unit 730 which comprises an input end in contact with ultrasonic transducer and a sonication output head 731 in contact with liquid in a biochar ozonization reactor chamber space 707, a heat-conducting reactor inner wall 722, a reactor outer wall 705, a coolant chamber space 723 formed between the inner wall 722 and outer wall 705, a coolant inlet 724 connected with the coolant chamber space at the bottom part of the reactor, a hot coolant outlet 725 connected with the coolant chamber space at the top part of the reactor, an O2 air inlet pump and valve 701, an ozone generator system 752, an ozone air inlet and tube 716 passing through the biochar sonicati on-ozonizati on reactor out wall 705 and inner wall 722
  • the sonication-ozonization-enabled biochar-surface oxygenation system (Fig. 11) operational process comprises a liquid biochar sonication-ozonization treatment operational process with the following process steps that may be operated in combination with the use of hydrogen peroxide: a) loading biochar materials into a reactor through a biochar inlet; b) monitoring and adjusting biochar temperature; c) monitoring biochar water content and liquid level in the reactor; d) based on a required biochar water content and liquid level, adding at least one of water, steam and vapor into the biochar materials using at least one of a heat-smoke-sensing sprinkler system with a water inlet and water spray system located at a top of the reactor and a flexible water inlet and outlet valve at a bottom of the reactor; e) performing sonication using the sonication control unit which comprises an input end in contact with ultrasonic transducer and a sonication output head in contact with liquid
  • an exemplary process of the sonication- ozonization-enabled biochar-surface oxygenation system uses the steps a) through 1) of the liquid biochar sonication-ozonization treatment operational process for a plurality or series of operational cycles to achieve more desirable results in accordance of the present invention. Any one of the steps a) through 1) of this process can be adjusted or modified as desired for certain specific operational conditions. For example, as shown in Fig 11, after the steps of performing sonication-ozonization e) through j), these steps may be repeated for a number of times to ensure the biochar feedstocks are fully sonicated and ozonized before k) discharging and 1) harvesting.
  • Any one of the steps a) through 1) of the process can be applied in whole or in part and in any adjusted combination for production of the desired surface-oxygenated biochar compositions including biochar paste products, which may be valuable to a number of innovative applications such as phosphorous solubilization from“insoluble” phosphate materials and/or sand soilization for agricultural and environmental sustainability.
  • treating the source biochar composition with sonication comprises using a sonication control unit comprising an input end in contact with an ultrasonic transducer and a sonication output head in communication with the ultrasonic transducer and disposed in the volume of liquid to expose the biochar composition to ultrasonic frequencies.
  • sonication enhances biochar ozonization process through at least one of the following three mechanisms: 1) Sonication force may physically loose up and/or break up biochar materials such as exfoliating graphite-type biochar materials (including graphite and/or graphite oxides) to produce biochar-derived organic matters such as the graphene-types of biochar molecules such as fragmented graphene and graphene oxides; 2) Sonication process enhances mixing and mass transfer of ozone gas with liquid water and biochar particles; and 3) Ultra sonication at a frequency of above 15 kHz producing reactive oxygen radical, hydroxyl and peroxyl radicals from the sonochemistry of Ck-dissolved water that may also enhance biochar surface oxygenation.
  • biochar materials such as exfoliating graphite-type biochar materials (including graphite and/or graphite oxides) to produce biochar-derived organic matters such as the graphene-types of biochar molecules such as fragmented graphene and graphene oxides
  • Sonication process enhances mixing and
  • ozonization of fragmented graphene and graphene oxides generates partially oxygenated poly aromatic carbon molecules similar to humic acids. Therefore, the sonication-enhanced biochar ozonization process can convert conventional biochar materials into“humic-acids-like” substances and/or biochar paste materials.
  • the humic-acids-like substances that are produced from this process are partially oxygenated graphene-like molecules and/or partially oxygenated graphene molecular fragments.
  • the biochar“humic-acids-like substances” here are defined as surface-oxygenated biochar derived organic matters that are similar to humic acids in their structures and functions.
  • the processing technology of surface-oxygenation through ozonization in combination with sonication may be applied also to other recalcitrant biomass materials selected from the group consisting of lignin residues, lignin cellulosic materials, carboxymethyl cellulose, un-hydrolyzed biomass residues such as un-hydrolyzed com stover residues, recalcitrant biomass residues, and combinations thereof.
  • the sonication-ozonization process can be used to treat many different carbon materials including but not limited to hydrochar, slow- pyrolysis biochar, fast pyrolysis biochar, and gasification char.
  • the liquid sonication of biochar materials produces a biochar paste, which is a black viscous fluid of the sonicated fine (mostly sub- millimeter) surface-oxygenated amorphous carbon particles and biochar molecular species including dissolved organic molecular carbons and organic acids in the presence of water.
  • the biochar paste may be ozonized to generate partially oxygenated biochar molecules including biochar molecular carboxylic acids.
  • the sonication-enhanced biochar ozonization process can convert tons of conventional biochar materials into surface-oxygenated biochar-derived organic matters including“humic acids like” substances and/or biochar paste materials that can be immediately applied into soil for agriculture and environmental sustainability.
  • the surface-oxygenated biochar composition produced from the biochar sonication-ozonization reactor process is a biochar paste product which comprises surface-oxygenated biochar-derived organic matters including humic-like substances that are selected from the group consisting of surface- oxygenated biochar particles, surface-oxygenated amorphous carbon particles, surface- oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments, partially oxygenated linear hydrocarbons, partially oxygenated aromatic compounds, partially oxygenated polycyclic aromatic hydrocarbons, dissolved organic carbons including organic acids, and combinations thereof.
  • a significant beneficial feature of the surface-oxygenated biochar paste product is that it is a highly functionalized biochar molecular material which is much more powerful than the conventional biochar for agricultural application.
  • a conventional biochar material in the current market is typically a solid carbon material with a grain size in a range from a few mm to tens of mm, which often has a quite limited cation exchange capacity often not much higher than that of a typical soil. Consequently, it often requires more than ten tons of conventional biochar materials per acre for use as soil amendment since most of the conventional biochar materials as solid carbon grains just sitting there in soil with quite limited functionality to improving soil fertility properties.
  • the sonicated surface-oxygenated biochar paste product as a highly functionalized biochar molecular material can provide much more functionality per carbon mass to improve soil fertility properties. Therefore, the sonicated biochar paste product with fine (mostly sub-millimeter) surface-oxygenated amorphous carbon particles and dissolved organic molecular carbons can significantly reduce the required amount of biochar carbon usage per acre by more than a factor of ten while providing better benefits for sustainable agricultural productivity. This can translate to a significant cost reduction while providing better benefits for the end users such as farmers.
  • the surface-oxygenated biochar paste/liquid is used as part of irrigation into the crop root zones so that it needs less a ton of biochar carbon material per acre to help solubilizing phosphorus from the“insoluble” phosphate material in certain soils for crop to uptake (see more details on surface oxygenated biochar for phosphorous sustainability below).
  • Phosphorus sustainability has recently been identified as one of the major issues for long-term agricultural and environmental sustainability on Earth.
  • the wet route typically requires the use of strong industrial acids such as sulfuric acid, nitric acid, and/or hydrochloric acid to solubilize phosphate from phosphate rock materials such as hydroxyapatite: Caio(P0 4 ) 6 (OH)2 and fluorapatite: CaTPOifF
  • the thermal route is represented by thermophosphate. Both routes are quite energy intensive and not very environmentally friendly.
  • the present invention here discloses a method on using the green chemistry with ozonized biochar to provide a novel approach to solubilize phosphorus from calcium phosphate rock materials and/or insoluble soil phosphate mineral phases, which may lead to a new technological pathway for producing phosphate fertilizers or making phosphorus available in soils for crop plants to uptake without using strong industrial acids.
  • ozonized biochar may be used to help solubilize phosphate from “insoluble” phosphate rock materials such as hydroxyapatite, Caio(P0 4 ) 6 (OH)2, through a phosphorous solubilization reaction such as:
  • the surface-oxygenated biochar composition may be used to solubilize phosphorous from“insoluble” phosphate materials such as hydroxyapatite or fluorapatite for phosphorous sustainability by at least one of the following molecular mechanisms: a) Protonic effect including the effect of protons from the organic acid groups such as carboxylic acids of ozonized biochar on“insoluble” phosphate rock materials, which for example can kick phosphate out of the hydroxyapatite structure resulting in solubilized phosphate; b) Cation exchange including the effect of calcium complexation with the
  • deprotonated biochar carboxylate groups such as Biochar-(COOCa) + and/or Biochar- (COO)2Ca
  • biochar surfaces and/or biochar molecules and its associated dissolved organic acids that takes calcium away from the“insoluble” phosphate rock materials such as hydroxyapatite structure and thus thermodynamically favors the release of phosphate from the “insoluble” phosphate rock materials
  • Anion exchange including the effect of anions such as the deprotonated biochar carboxylate groups and its associated dissolved organic acids in exchange with the phosphate (anion) of the insoluble phosphate materials
  • the surface-oxygenated biochar composition may help solubilizing phosphorus from at least one of the“insoluble” phosphate rock materials that comprise: ground soft rock phosphate, Caio(P0 4 ) 6 (OH)2 (hydroxyapatite), Ca5(POs)3F (fluorapatite), and phosphorite (also known as phosphate rock or rock phosphate) which typically is a non-detrital sedimentary rock which contains high amounts of phosphate minerals such as the peloidal phosphorite (Phosphoria Formation, Simplot Mine, Idaho) and the fossiliferous peloidal phosphorite (Yunnan province, China).
  • the“insoluble” phosphate rock materials that comprise: ground soft rock phosphate, Caio(P0 4 ) 6 (OH)2 (hydroxyapatite), Ca5(POs)3F (fluorapatite), and phosphorite (also known as phosphate rock or rock phosphate) which typically is a non-detrital sedimentary
  • the phosphate content of phosphorite (or grade of phosphate rock) varies greatly, from 4% to 20% phosphorus pentoxide (P2O5). Marketed phosphate rock is enriched ("beneficiated") to at least 28%, often more than 30% P2O5. This is achieved typically through washing, screening, de-liming, magnetic separation or flotation.
  • the surface-oxygenated biochar composition may be used to mix with phosphate rock powders and/or ground soft rock phosphate to make slow-releasing phosphorus and calcium fertilizers with surface-oxygenated biochar; wherein the content of phosphate rock powders in the mixture of phosphate rock powers and surface-oxygenated biochar composition can be about, at least, or no more than, for example, 0.00001%, 0.00005%, 0.0001%, 0.0005%, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% weight percent, or within a particular range therein.
  • the approach of ozonized biochar for phosphorous sustainability works better than the conventional technology such as the use of strong industrial acids such as chloric acid (HC1) because of the following three reasons. 1) Production and use of ozonized biochar derived from waste biomass represents a renewable green-chemistry process; whereas production and use of strong industrial acids such as HC1 is energy intensive and highly hazardous (corrosive); 2) The use of strong industrial acids such as chloric acid (HC1) does not provide the benefit of calcium complexation with an organic acid ligand (deprotonated biochar carboxylate group) on biochar surfaces and/or biochar molecules; And 3) strong industrial acids such as chloric acid (HC1) are so corrosive that typically are not environmentally friendly to use in agriculture soil environment whereas ozonized biochar (Biochar-COOH) that carries gentle carboxyl acid groups are more suitable to agriculture soil application.
  • strong industrial acids such as chloric acid (HC1) because of the following three reasons. 1) Production and use of ozonized biochar derived from waste biomass represents a renewable green-
  • the“insoluble” phosphate materials in soils include (but are not limited to): phosphorus containing minerals (mostly apatites:
  • Ca(H2P04)2-H20 monocalcium phosphate
  • the surface-oxygenated biochar composition may be applied into the root zone of agricultural soils to help unlock phosphorus from the“insoluble” phosphate material there for crop to uptake with a number of application techniques selected from the group consisting of: 1) mixing surface-oxygenated biochar with soils under wet and calm (non-windy) conditions during plowing of a field and/or tillage practices; 2) mixing and/or coating certain seeds such as wheat, soybean, and peanuts with certain surface-oxygenated biochar composition so that the seeds and surface-oxygenated biochar composition are co-inserted into soil during sowing; 3) placing surface-oxygenated biochar composition into soil during planting of seedlings; 4) using surface-oxygenated biochar paste and/or liquid as an irrigation into the crop root zones; and 5) combinations thereof.
  • application techniques selected from the group consisting of: 1) mixing surface-oxygenated biochar with soils under wet and calm (non-windy) conditions during plowing of a field and/or tillage practices; 2) mixing and/or
  • the content of the applied surface- oxygenated biochar composition in a soil mixture can be about, at least, or no more than, for example, 0.00001%, 0.00005%, 0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% weight percent, or within a particular range therein.
  • inorganic phosphorus in highly weathered acidic soils rich in Al- and Fe-oxides (e.g., Ferralsols that pre-dominate in subtropical and tropical regions), inorganic phosphorus (Pi) is strongly sorbed onto the edges of silicate clay minerals and to pedogenic Al- and Fe-oxides. Over time, the inorganic phosphorus sorption may become gradually stronger by a slow diffusion of phosphate into micropores forming“occluded P” or even transitions to precipitated Al- and Fe-phosphates.
  • Si inorganic phosphorus
  • This process contributing to the low efficiency of fertilizer P in low pH soils, may be partly avoided or reversed by application of surface-oxygenated biochar composition and its dissolved organic carbons including biochar organic acids, low molecular organic anions and higher molecular organic anions such as anions of surface-oxygenated biochar derived fulvic and humic-like acids that can compete with phosphate anions through anion exchange for positively charged binding sites thus favoring phosphorus release.
  • Chelating biochar organic anions may also contribute to the phosphate desorption.
  • phosphorus solubilization in certain acidic soils is accomplished through anion exchange by mixing the soils with surface-oxygenated biochar paste product which comprises surface-oxygenated biochar-derived organic anions such as humic-like substances that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments, partially oxygenated linear hydrocarbons, partially oxygenated aromatic compounds, partially oxygenated polycyclic aromatic hydrocarbons, dissolved organic carbons including organic acids, and combinations thereof.
  • surface-oxygenated biochar paste product which comprises surface-oxygenated biochar-derived organic anions such as humic-like substances that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygen
  • phosphorus solubilization may be accomplished by application of the surface-oxygenated biochar composition in various soils including certain alkaline soils, pH neutral soils and acidic soils through the effect selected from the group consisting of the protonic effect, cation exchange, anion exchange and combinations thereof.
  • the application of surface-oxygenated biochar composition by mixing with certain soils can result in a solubilized phosphorus concentration that is, at least, 100% higher than the critical P concentration of 0.15 ppm, which is the P concentration in soil solution that is required for crop plant growth (Matula 2011 Plant Soil and Environment, 57(7): p. 307-314).
  • the surface-oxygenated biochar paste materials including the“humic acids like” substances produced from the sonication-enhanced biochar ozonization process can be used to convert desert sands into useful soil, which can help better retain water and nutrients.
  • Sand (silica, silicon dioxide) particles typically have negative surface charges.
  • the principal mechanism by which sand (silica) surfaces acquire a negative charge is the dissociation (deprotonation) of silanol groups:
  • humic acids like surface-oxygenated biochar organic molecular species that have at least two carboxyl groups per molecule (XOO-R-COO-) in combination with other biomass materials selected from the group consisting of lignin cellulosic materials, carboxymethyl cellulose, un-hydrolyzed biomass residues such as un-hydrolyzed cornstover residues, lignin residues, recalcitrant biomass residues, humic substances, and combinations thereof; and in combination with certain cations selected from the group consisting of Ca 2+ , Mg 2+ , Fe 2+ , and Fe 3+ can form a type of ionic cross-linking structures that may create a type of jelly state to better retain water and nutrients and hold sand particles together:
  • the surface-oxygenated biochar paste products may act like a gelator or a liquid gel-forming material in the spaces among sand particles that can help to retain much more water (and nutrients) and hold sand particles together, resulting in a novel“sand soilization” effect.
  • the liquid gel-forming activity of surface-oxygenated biochar paste compositions in the spaces among sand particles can retain water and nutrients and hold the sand particles together through at least one of the noncovalent interactions selected from the group consisting of: 1) the ionic (Coulombic) interactions that are the electrostatic interactions between charged species as shown in equation 5 above for example; 2) the hydrogen bond effects of the surface-oxygenated biochar molecular species with water and sands; 3) the p-p interactions between aromatic structures; and 4) the van der Waals interactions among sands and surface-oxygenated biochar molecular species with water.
  • the noncovalent interactions selected from the group consisting of: 1) the ionic (Coulombic) interactions that are the electrostatic interactions between charged species as shown in equation 5 above for example; 2) the hydrogen bond effects of the surface-oxygenated biochar molecular species with water and sands; 3) the p-p interactions between aromatic structures; and 4) the van der Waals interactions among sands and surface-oxy
  • the surface-oxygenated biochar compositions including the biochar paste product may be used for sand soilization by their liquid gel-forming activity in the spaces among sand particles that can retain water and nutrients and hold the sand particles together through at least one of the following noncovalent interactions: 1) the ionic (Coulombic) interactions that are the electrostatic interactions between charged species; 2) the hydrogen bond effects of the surface-oxygenated biochar molecular species with water and sands; 3) the p-p interactions between aromatic structures; and 4) the van der Waals interactions among sands and surface- oxygenated biochar molecular species with water.
  • the surface-oxygenated biochar compositions including the biochar paste product typically has high cation exchange capacity which is the key property that is central to help retain soil water and nutrients. Therefore, the use of surface-oxygenated biochar compositions in mixing with sands for sand soilization also help to better retain water and plant nutrients is fundamentally important to agricultural and environmental sustainability. This“sand soilization” effect, which helps in retaining water and holding sand particles together, may be used as a way to reduce the likelihood of sands becoming airborne with winds and thus may be used also as a way to help minimize desert sand storms.
  • divalent cation solutions such as CaCb and/or MgCh solution may be used to spray on the surface of sands to anchor the sands and/or soils with and/or without surface-oxygenated biochar paste compositions depending on the consideration of specific environmental conditions.
  • the surface-oxygenated biochar compositions-enhanced sand soilization has a special characteristic that the mixture of sands and surface-oxygenated biochar materials retains much more water and nutrients and hold the sand particles together so that the sands will less likely become airborne with winds than the control sands.
  • the surface-oxygenated biochar composition treated sands retain water for much longer time than the control sands so that the surface-oxygenated biochar treated sands will less likely to flow with gravity than the control sands when the sand plates are tilted up to 90 degrees.
  • the content of surface-oxygenated biochar composition in the sands mixture for sand soilization can be about, at least, or no more than, for example, 0.00001%, 0.00005%, 0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.8%, 0.9%, 1%,
  • the surface-oxygenated biochar compositions comprise certain amounts of beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate green plant growth when used at a proper DOC concentration selected from the group consisting of: 0.1 ppm, 0.2 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 5 ppm, 8 ppm 10 ppm, 12 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, 1000 ppm or a DOC
  • the surface-oxygenated biochar compositions may be used to reduce and/or remove the offensive odor associated with manure applications and to reduce agriculture chemical runoff.
  • the surface-oxygenated biochar compositions can absorb the offensive odor from manures significantly better than conventional biochar.
  • surface-oxygenated biochar can absorb the ammonia (NFE) gas odor through its reaction with the biochar molecular carboxylic acid (Biochar-COOH) to form ammonium carboxylate on ozonized biochar surface (Biochar-COONFE).
  • the surface- oxygenated biochar compositions can be used to reduce the offensive odor associated with manures selected from the group consisting of pig manure, cow manure, buffalo manure, sheep manure, horse manure, donkey manure, camel manure, chicken manure, duke manure, goose manure, turkey manure, human manure, and dog manure, zoo animal manures, and combinations thereof.
  • the raw biochar pieces are often too large for practical use so that they are resized at a crushing and screening workstation.
  • the output produces typically five sizes: Chip (size 1" to 3 mm), Medium (grain size: 3 mm to US Standard 25 mesh (0.71 mm)), Small (25 mesh (0.71 mm) to 50 mesh (0.300 mm)), Powder (50 mesh (0.300 mm) and under), and Fine Power (140 mesh (0.105 mm) and under).
  • any of these biochar particle sizes may be used in a biochar-surface oxygenation process through sonication and ozonization.
  • Biochar liquid ozonization in combination with sonication can produce liquid biochar paste with fine surface-oxygenated amorphous carbon particles (sizes well below 0.105 mm) plus significant amounts of dissolved organic carbons (DOC) in the presence of water.
  • DOC dissolved organic carbons
  • Table lb shows the changed in pH of the biochar samples brought about by treatment with ozone. Overall there is a dramatic decrease in the pH of the biochar samples from untreated at 7.30 ⁇ 0.39 to the sample treated with 90 minutes of ozone at 5.28 ⁇ 0.33. This sharp decrease in pH results from, for example, the addition of acidic functional groups, primarily carboxyl groups on the surface of the biochar. The trend of the drop in pH illustrates a relationship between treatment time and increasing acidity of the biochar samples. This drop in pH is an important characteristic when considering using biochar as a soil amendment. Therefore, exemplary embodiments for ozone treatment of biochar can be used to adjust or to“tune” biochar pH to a desired value for a given soil.
  • Table lb Summary data for pH, CEC, and Methylene blue adsorption.
  • Example 2 Ozone Treatment Enhancing Biochar Cation Exchange Capacity by a factor of more than 2 times.
  • Table lb also illustrates a significant increase in the measured CEC values of biochar processed in accordance with exemplary embodiments of the ozone treatment.
  • the untreated biochar sample had a CEC of 153.9 ⁇ 15.9, and the sample treated with 90 minutes of ozone had a value of 326.9 ⁇ 25.1 (in units of mmol/kg biochar).
  • there is only a small difference between the 30, 60, and 90 minute ozone treated samples which is potentially due to a saturation of the sites available for alteration by ozone treatment.
  • the increase in CEC is due to an increase in oxygen functionality, as discussed, for example, in Lee et al., Environ. Sci. Technol.
  • cation exchange capacity correlates to the availability of oxygen function groups, predominately carboxylic acid groups which carry a negative charge in basic and neutral solutions, making them electrostatically attracted to cations.
  • Table 1 also lists the CEC value of a reference soil sample of 131.8 ⁇ 9.6. From this, it is clear that even untreated biochar has a higher CEC, and treated samples more than double the native CEC of the reference soil sample.
  • Example 3 Ozone Treatment Improving Biochar Methylene Blue Adsorption Capability by a factor of more than 5 times.
  • Methylene blue adsorption capacity was measured to evaluate the viability of the biochar for dye-contaminant removal in water systems. As shown in Table lb, there is a dramatic increase in methylene blue removal capacity resulting from ozone treatment, with the untreated biochar sample only removing 1.79 ⁇ 0.18 mg dye/kg biochar while the 90 minute ozone treated sample removed 9.35 ⁇ 0.04. This significant increase shows the usefulness of ozone treatment when considering biochar amendment for use in contaminated water systems. It is believed that the increase in methylene blue adsorption capacity results from the increase of oxygen functionality on the surface of the biochar, which makes the biochar overall more negatively charged. Methylene blue is natively positive in solution, and therefore is more electrostatically attracted to biochar that has been treated with ozone.
  • Example 4 Elemental Analysis Measurement Showing Biochar Bulk Properties such as Elemental Composition Not Significantly Altered by Ozonization
  • Elemental analysis measures the bulk composition of the biochar and is useful in determining the degree of change brought about by ozone treatments. Overall, there is not a dramatic change through the use of ozone treatments as shown in Table 2, However, there is a clear drop in carbon content from the untreated sample (73.90% ⁇ 0.06) and the 30 minute ozone treated sample (66.76% ⁇ 2.77). Additionally, there appears to be an increase in oxygen content of the biochar samples as measured by the difference from the untreated (22.78%) to the 30 minute ozone treated sample (30.07). This data correlates well with the concurrent drop in pH of these samples, as well as the increase in CEC, both owing the change in their properties due to an increase in oxygen functionality.
  • biochar was produced from pinewood biomass by pyrolysis at a highest treatment temperature (HTT) of 400 °C. This biochar was then treated with varying
  • biochar methylene blue adsorption decreased with higher H2O2 concentration treatments. This is believed to be due to the addition of oxygen groups onto the aromatic ring structure of the biochar which in turn weakens the overall dispersive forces of p-p interactions that are mainly responsible for the adsorption of the dye onto the surface of the biochar.
  • the elemental analysis revealed that there was no general augmentation of the elemental composition of the biochar samples through the treatment with H2O2, which suggests that the bulk property of biochar remains unchanged through the treatment.
  • the FTIR-ATR spectra as shown in Figure 9 reveals information about the functional group changes brought about by ozone treatment.
  • Two peaks appearing at 1590 cm 1 and 1440 cm 1 correspond to elastic and inelastic stretching of carbon-carbon double bonds in an aromatic ring structure. These two peaks primarily appear only in the untreated sample, and are greatly reduced in the ozone treated samples, revealing that the ozone selectively reacts with the double bonded carbon throughout the biochar substrate.
  • a peak at 875 cm 1 on the untreated sample spectra corresponding to C-H out of plane stretching from an aromatic carbon ring is also greatly reduced with ozone treatment, showing further evidence of the reaction of ozone selectively with carbon-carbon double bonds.
  • Example 8 Production of surface-oxygenated biochar through sonication in combination with wet ozonization
  • the ozone generator was set to optimum condition for the generation of ozone.
  • the ozone gas stream was bubbled into the liquid sample mixture for 90 min. After 90 min, the mixture was transferred into a Buchner funnel and the filtrate was collected in a vessel for further analysis.
  • the biochar product was then washed with 600 mL of ultrapure water and kept in oven maintained at l05°C for drying.
  • the biochar was then washed with 1800 mL of ultrapure water and kept in oven maintained at l05°C for drying. This sonicated-ozonized biochar product is designated as P400 90W+S.
  • liquid sonication was done to the biochar material two times during ozonization treatment.
  • this double-sonication treatment in combination with wet ozonization, 9.0 g of oven dried biochar was weighed and placed into an ozone treatment vessel and 50.0 mL of ultrapure water was added to it.
  • the sample mixture was sonicated for 15 minutes with the Ultrasonic Processor set at 50% amplitude.
  • the ozone generator was set to optimum condition for the generation of ozone.
  • the ozone was bubbled into the liquid sample mixture for 45 min.
  • the sample mixture was again sonicated for 15 minutes and ozone was bubbled into the sample liquid mixture for next 45 min.
  • biochar liquid-sonication-ozonization reactor (Fig. 11) process generated a black viscos biochar paste product as shown in Fig.
  • biochar derived organic matters including humic-like substances that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments, partially oxygenated linear hydrocarbons, partially oxygenated aromatic compounds, partially oxygenated polycyclic aromatic hydrocarbons, dissolved organic carbons including organic acids, and combinations thereof.
  • biochar derived organic matters including humic-like substances that are selected from the group consisting of surface-oxygenated biochar particles, surface-oxygenated biochar-derived organic matters, surface-oxygenated amorphous carbon particles, surface-oxygenated graphite particles, partially oxygenated graphene, partially oxygenated graphene-like molecules, partially oxygenated graphene molecular fragments, partially oxygenated linear hydrocarbons, partially oxygenated aromatic compounds, partially oxygenated polycyclic aromatic hydrocarbons,
  • Example 9 Solubilization of phosphorus from hydroxyapatite with surface-oxygenated biochar composition
  • the pH of the biochar showed a two units decrease when treated with ozone (pH 5.64 for the non-ozonized control biochar versus 3.60 and 3.96 for the wet and dry-ozonized biochar respectively).
  • the biochar cation exchange capacity increased by 50% when the biochar is treated with ozone (14.4 cmol/kg and 13.2 cmol/kg for wet and dry-ozonized biochar
  • Table 5 present the results from a l4-day hydroxyapatite solubilization assay with surface-oxygenated biochar as measured at the end of the incubation experiment.
  • the biochar materials including wet-ozonized biochar and dry-ozonized biochar were washed with water to remove any dissolved organic carbon (DOC) before used in this experiment.
  • the washed clean biochar material is designated as“biochar” to use in the experiment.
  • the DOC liquid resulted from the washing of biochars was designated as“filtrate”.
  • the concentration of Ca ++ in the liquid phase was lowered, which is favorable for P solubilization from hydroxyapatite.
  • the deprotonated carboxylate groups (anions) of the partially oxygenated DOC in the biochar filtrates may exchange with phosphate (anions) out of the hydroxyapatite surfaces, which could also explain the observed low molar ratio ( 0.1 ⁇ 0.3) of Ca/P in the incubation solutions with surface-oxygenated biochars and filtrates.
  • the data listed in Table 5 indicated that the phosphorous solubilization with surface-oxygenated biochar is accomplished through at least one of the following molecular mechanisms: a) Protonic effect including the effect of protons from the organic acid groups of ozonized biochar which can kick phosphate out of the insoluble phosphate materials, resulting in solubilized phosphate; b) Cation exchange including the effect of calcium complexation with the deprotonated biochar carboxylate groups on biochar surfaces and/or biochar molecules and its associated dissolved organic acids that takes calcium away and thus thermodynamically favors the release of phosphate from the insoluble phosphate materials; c) Anion exchange including the effect of anions such as the deprotonated biochar molecular carboxylate groups and its associated dissolved organic acids in exchange with the phosphate (anion) of the insoluble phosphate materials thus thermodynamically favors its phosphorus release; and d) combinations thereof.
  • Example 11 Utilization of surface-oxygenated biochar composition for phosphorus solubilization from soil insoluble phosphate mineral phases
  • the soil samples tested included the Portneuf Soil (P-Soil) collected from South Central Idaho and the Bennett Soil (B-Soil) collected from Eastern Colorado. Tests were conducted by mixing 0.5 g of surface-oxygenated biochar with 1 g of soil plus 12 ml of water to incubate for 30 minutes, 2 days, and 14 days and then measuring the solubilized phosphate concentration in the liquid phase using an Ion Chromatograph IPS 5000 Dionex SP. As shown in the ion chromatogram of Fig.
  • Example 12 Flocculation of certain partially oxygenated dissolved organic carbons (DOC) from liquid biochar ozonization process
  • liquid filtrate samples comprising certain partially oxygenated dissolved organic carbons (DOC) were made from liquid ozonization of P400 biochar materials for 90 min.
  • the liquid filtrate DOC concentration was determined to be about 940 ppm.
  • flocculation of the filtrate DOC from the wet-ozonized P400 90W was demonstrated by adding 2.5 mM CaCb into the liquid sample.
  • the flocculated DOC materials sink down to the bottom of the test tube likely as a result from the complexation of the wet- ozonized P400 90W DOC organic acids with divalent cation Ca ++ .
  • Example 13 Utilization of surface-oxygenated biochar composition for sand soilization
  • sand soilization was experimentally demonstrated by mixing 10 g of silicon dioxide sand particles with 4 ml of wet-ozonized P400 90W liquid filtrate (shown in Fig. 15, DOC concentration 940 ppm) plus 25 mM CaCb in a petri dish plate. After leaving the sand piles on petri dish plates for 5 hours under room temperature and air humidity, the treated sand pile (mixed with 4 ml of the liquid filtrate +25 mM CaCb) remained wet while the control plate of sands (mixed with 4 ml of pure water) became dry.
  • Example 15 Utilization of wet-ozonized un-hydrolyzed corn stover residue for sand soilization
  • ozonized biochar composition may be used in combination with recalcitrant biomasses such as un-hydrolyzed corn stover residue and its filtrate, and in combination with divalent cations such as Ca 2+ to enhance sand soilization to better retain water and nutrients and hold the sand particles together.
  • Example 14 Utilization of surface-oxygenated biochar composition for stimulation of algal culture growth
  • the blue-green algae (cyanobacteria) growth assays demonstrated that the surface-oxygenated biochar compositions contain certain amounts of beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate plant cell growth such as cyanobacteria when used in liquid culture medium such as BG-l 1 medium at a proper DOC concentration such as 2 ppm, 7.5 ppm, and/or 10 ppm.
  • beneficial humic acids-like substances including certain partially oxygenated dissolved organic carbons (DOC) that can stimulate plant cell growth such as cyanobacteria when used in liquid culture medium such as BG-l 1 medium at a proper DOC concentration such as 2 ppm, 7.5 ppm, and/or 10 ppm.
  • DOC partially oxygenated dissolved organic carbons
  • the liquid culture of cyanobacteria Synechococcus elongatus PCC 7942 was incubated in multi-well bioassay plates with wet-ozonized P500 biochar filtrate at a series of DOC concentration of 0 ppm, 2 ppm, 7.5 ppm and 10 ppm.
  • the multi-well bioassay plates were placed on a shaker platform shaking at lOOrpm at room temperature under continuous actinic illumination light intensity of 15.8 pmol/m 2 s.
  • Example 15 Utilization of surface-oxygenated biochar composition for stimulation of higher plant seed germination and growth
  • DOC partially oxygenated dissolved organic carbons
  • Soil was saturated with 35 ml of UHCSR HTC liquid (4.87 ml UHCSR HTC liquid in 200 ml volumetric flask), was then covered with black filter paper, and followed by the placement of 2 seeds per kind (Sorghum, Lepidium, and Sinapis). The plate was then incubated in the dark for germination.
  • the surface-oxygenated biochar compositions contain certain amounts of beneficial humic acids-like substances including certain partially oxygenated biochar dissolved organic carbons (DOC) that can stimulate higher plant seed germination and seedling elongation (growth) such as Sorghum, Lepidium, and Sinapis when used at a proper DOC concentration such as 75 ppm and 150 ppm.
  • beneficial humic acids-like substances including certain partially oxygenated biochar dissolved organic carbons (DOC) that can stimulate higher plant seed germination and seedling elongation (growth) such as Sorghum, Lepidium, and Sinapis when used at a proper DOC concentration such as 75 ppm and 150 ppm.
  • Example 16 Comparative experiments of dairy manure gasification biochar, 815-871 °C Flash Pyrolysis woody biochar and Pine 400 biochar before and after ozonization for CEC, pH, methylene blue adsorption and its effect on Synechococcus elongatus PCC 7942
  • 3 types of biochar were used to compare in the tests are: 1) Pine 400 biochar which was produced from Pinewood biomass through pyrolysis with a high pyrolysis temperature of 400 degrees Celsius (400 °C for 30 min); 2) Dairy manure gasification (>700 °C) biochar (Company biochar 1); and 3) Flash Pyrolysis woody biochar (Company biochar 2) which was produced by 815-871 °C Flash (30 seconds) Pyrolysis using chopped 2-inch chips of softwood including Douglas fir (Oregon pine) and sugar pine with 35% water content.
  • the three different types of biochar were treated with ozone under dry condition (without water) and wet condition (with water) for 90 minutes.
  • the biochar samples were then tested for BET surface area measurements.
  • the Company biochar 2 had a type of“steam activation” effect from the 815-871 °C Flash (30 seconds) Pyrolysis using 35% water content of the chopped softwood (the water content in the biomass quickly turned into steam upon sudden contacting with the high pyrolysis temperature of 815-871 °C) so that its BET surface area was as high as 434.9 m 2 /g before ozonization.
  • the Pine 400 biochar before ozonization had the lowest BET surface area of 0.7616 m 2 /g.
  • Ozonization slightly increased the BET surface area under wet conditions for Company biochar 2 giving a BET surface area of 452.7 m 2 /g.
  • Ozonization caused a drop in pH for all 3 types of biochars; a dramatic pH drop was observed in the Company biochar 2 going from pH 9.835 +/-0.028 to 4.65 +/- 0.071 upon dry ozonization.
  • CEC cation exchange capacity
  • DOC dissolved organic carbon
  • Company Biochar 2 is among the best for use with ozonization, which upon dry ozonization yielded the greatest reduction in pH, greatest increase in CEC (by a factor of nearly 5), and greater production of biochar DOC (part of the biochar-derived organic matters).
  • the commercial production capacity of Company Biochar 2 recently reached 3500 tons per year in conjunction with the operation of a 30 MW boiler-based electricity generation power plant, annually utilizing about 250,000 tons of chopped softwood with 35% moisture through 815-871 °C Flash Pyrolysis.
  • the syngas produced from the biomass Flash Pyrolysis was utilized through its clean combustion to heat the boiler for steam turbine electricity generation.
  • Example 17 Production of dissolved organic carbon (DOC) matters from Pine 400 biochar through sonication, dry ozonization, wet ozonization, and sonication combination with wet ozonization
  • wet biochar ozonization treatment along with sonication resulted in the highest DOC concentration (2413.3 ppm) and production yield (40.22 g /kg biochar).

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Abstract

La présente invention concerne des compositions de biocharbon oxygénées en surface et des procédés de sonication-ozonation permettant de créer des matériaux hydrophiles avancés à base de biocharbon présentant une plus grande capacité d'échange de cations, un pH optimisé, une meilleure mouillabilité et qui sont dépourvus de composants toxiques. Les compositions de biocharbon ayant subies une sonication-ozonation sont utilisées comme matériaux de filtration pour le nettoyage de l'eau et de l'air, comme réactifs de solubilisation de phosphore pour se mélanger avec des matériaux de roche phosphatés pour la fabrication d'engrais à base de phosphate à libération prolongée, comme additifs de sol biocharbonnés pour aider à solubiliser le phosphore et à réduire les additions d'engrais au phosphore requises pour obtenir une activité souhaitée de phosphore au sol, une absorption de récolte et des objectifs de rendement, comme réactifs de solisation de sable par utilisation de leur activité de formation de gel liquide dans les espaces entre les particules de sable afin de retenir l'eau et les nutriments et maintenir les particules de sable ensemble, comme stimulants de la croissance des plantes par l'utilisation des substances de biocharbon oxygénées en surface de type acides humiques à une concentration en ppm appropriée et comme agents de séquestration de carbone pour aider à réguler le changement climatique afin d'assurer une durabilité énergétique et environnementale sur terre.
PCT/US2019/038491 2018-06-24 2019-06-21 Phosphore de biocharbon ozonisé durable et solisation de sable WO2020005760A1 (fr)

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WO2021047111A1 (fr) * 2019-09-11 2021-03-18 东北农业大学 Procédé associé à la disponibilité de phosphore insoluble
CN116584332A (zh) * 2023-07-13 2023-08-15 北京建工环境修复股份有限公司 一种适用于风沙地区光伏电站沙地中中药种植方法
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EP4025535A4 (fr) * 2019-09-03 2023-09-27 Pure Life Carbon Inc. Unité et système de traitement
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CN116584332A (zh) * 2023-07-13 2023-08-15 北京建工环境修复股份有限公司 一种适用于风沙地区光伏电站沙地中中药种植方法
CN116584332B (zh) * 2023-07-13 2023-10-27 北京建工环境修复股份有限公司 一种适用于风沙地区光伏电站沙地中中药种植方法

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