WO2017210609A1 - Charbons de biomasse infusés par des micro-organismes de solubilisation de minéraux - Google Patents

Charbons de biomasse infusés par des micro-organismes de solubilisation de minéraux Download PDF

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Publication number
WO2017210609A1
WO2017210609A1 PCT/US2017/035759 US2017035759W WO2017210609A1 WO 2017210609 A1 WO2017210609 A1 WO 2017210609A1 US 2017035759 W US2017035759 W US 2017035759W WO 2017210609 A1 WO2017210609 A1 WO 2017210609A1
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Prior art keywords
biochar
treated
pores
microbes
infused
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PCT/US2017/035759
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English (en)
Inventor
Richard Wilson BELCHER
Han Suk KIM
Brian Buege
Ronald A. SILLS
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Cool Planet Energy Systems, Inc.
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Priority claimed from US15/393,176 external-priority patent/US10118870B2/en
Priority claimed from US15/393,214 external-priority patent/US10173937B2/en
Priority claimed from US15/419,976 external-priority patent/US9980912B2/en
Application filed by Cool Planet Energy Systems, Inc. filed Critical Cool Planet Energy Systems, Inc.
Publication of WO2017210609A1 publication Critical patent/WO2017210609A1/fr

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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G2/00—Vegetative propagation
    • 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
    • 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
    • C05F11/08—Organic fertilisers containing added bacterial cultures, mycelia or the like

Definitions

  • Patent Application Serial No.14/385,986 filed on May 29, 2012, titled METHOD FOR ENHANCING SOIL GROWTH USING BIO-CHAR (now U.S. Patent No. 9,493,380 that issued on November 15, 2016), which is a 371 national stage filing of PCT US12/39862 filed May 29, 2012 titled METHOD FOR ENHANCING SOIL GROWTH USING BIO-CHAR, which is a continuation of U.S. Patent Application Serial No. 13/154,213 filed on June 6, 2011, titled METHOD FOR ENHANCING SOIL GROWTH USING BIO-CHAR (now U.S. Patent No. 8,317,891 that issued on November 27, 2012); this application is also a continuation-in-part of U.S. Patent Application No.
  • the invention relates to the use of porous carbonaceous structures that have increased capabilities to retain additives, and in particular to biochars, that have been infused with microbial additives to enable or enhance the solubility of minerals that are beneficial for both plant and animal health and growth.
  • biochar In the agronomical field, among the known types of soil enhancers are biochar. It contains highly porous, high carbon content material similar to the type of very dark, fertile anthropogenic soil found in the Amazon Basin known as Terra Preta, which has very high carbon content and historically has been made from a mixture of charcoal, bone, and manure.
  • Biochar is created by the pyrolysis of biomass, which generally involves heating and/or burning of organic matter, in a reduced oxygen environment, at a predetermined rate. Such heating and/or burning is stopped when the matter reaches a charcoal like stage.
  • the highly porous material of biochar is suited to host beneficial microbes, retain nutrients, hold water, and act as a delivery system for a range of beneficial compounds and additives suited to specific applications.
  • Raw biochar while known for its soil enhancing characteristics, does not always benefit soil and, depending upon the biomass from which the biochar is produced and the method of production, can potentially be harmful to the soil, making it unsuitable for various types of crops or other productive uses.
  • biochar can be detrimental, or even toxic, to 1) soil microbes involved in nutrient transport to the plant; 2) plants and 3) humans.
  • Biochar having pH levels too high, containing too much ash, inorganics, or containing toxins or heavy metal content too high can be harmful and/or have minimal benefit to the soil and the plant life it supports.
  • Biochar can also contain unacceptable levels of residual organic compounds such as acids, esters, ethers, ketones, alcohols, sugars, phenyls, alkanes, alkenes, phenols, polychlorinated biphenyls or poly or mono aromatic hydrocarbons which are either toxic or not beneficial to plant or animal life.
  • biochar Due to the unpredictable performance of biochar and its potential to be detrimental to plant life and growth, it has mostly been a scientific curiosity, not found wide spread use, not found large scale commercial application, and has been relegated to small niche applications. It is, however, known, as noted above, that biochar, having certain characteristics can host beneficial microbes, retain nutrients, hold water, and act as a delivery system for a range of beneficial compounds suited to specific applications. Thus, it has been a continued desire to capture the beneficial soil enhancing characteristics of biochar in a more consistent, predictable way. Biochar research has continued in an attempt to harness biochar having predictable, controllable, and beneficial results as a soil amendment for large scale applications.
  • Minerals are an essential nutrient for both plants and animals, including phosphorus and potassium for plants and minerals such as iron, calcium, copper, zinc, magnesium and manganese for animals.
  • minerals for these minerals to be available for efficient uptake by plant roots or animal ruminant and digestive systems they must be present in soils, fertilizers and animal feed in bioavailable forms. Further, making such minerals and other nutrients and supplements readily available for ingestion by animals to provide proper animal nutrition is key for successful livestock production and aquaculture. Good nutrition can increase feed efficiency and the growth rate of animals and help prevent diseases and ailments. Certain of these nutrients are readily available for plant and animal use, but, in the current environment, are not easily accessible by the plants or animals.
  • the present invention relates to the use of biochar infused with beneficial additives, including both beneficial microbes and minerals that promote the solubility of such minerals. Furthermore, this invention relates to methods of infusing biochars with such additives that allow for more effective storage and delivery of and a more gradual, prolonged release of the compounds (including mineral solubilizing microorganisms (“MSM”)) either into the soil or during animal rumination or digestion.
  • MSM mineral solubilizing microorganisms
  • the characteristics of the infused material, as well as additives that may also be infused, can allow for much better survivability, propagation, and establishment of certain microorganisms in their intended applications.
  • beneficial additive including, but not limited to, nutrients, beneficial fungi, plant growth producing bacteria (PGPB), hormones, bio pesticides, herbicides, fungicides, nematicides, bacteriacides, fumigants among others additives, as will be described more fully below, it is also well suited to permit the juxtaposition of both minerals and MSM.
  • the method includes producing an additive infused biochar that may contain biochar, minerals and other nutrients, MSM, beneficial fungi, PGPB and/or other additives.
  • the method includes impregnating at least some of the pores of the biochar with liquid additives or additives in liquid solution through an infusion process.
  • the resulting infused biochar provides for gradual and/or steady delivery of the additives to the soil and plants or animals.
  • the utilization of additive infused biochar allows the delivery of more nutrients or additive per unit of biochar and also provides for a more gradual release of the additives to the surrounding soil or during rumination or digestion. In turn, this enables different soils to provide an environment well suited to the long term success of the desired plant, as well as a healthier animal.
  • biochar When used as an enhancement to animal feed, biochar may increase the animals’ uptake of foodstuffs and the energy contained within them, reducing the amount of nutrients lost into excrement and manure. The biochar may also act to detoxify the animal while enriching the beneficial microbes in the digestive track that are key to maintaining an animal’s metabolism and helping them to resist dangerous pathogens.
  • the present invention teaches treating the biochar in a manner that forces, accelerates or assists the infusion of additives into the pores of the biochar. Treatment in this manner allows for the impregnation or inoculation of the pores of the biochar with additives, which can be beneficial for the intended use of the biochar.
  • the invention also includes the treatment of the surfaces of the biochar to make it better suited to carry precipitated nutrients (or beneficial substances) to be delivered, microbes targeted to solubilize nutrients or both.
  • the method for treating the biochar includes placing porous carbonaceous materials in a tank or chamber; adding an additive solution to the tank; and changing the pressure in the tank by, for example, placing the contents of the tank under a partial vacuum.
  • the additive solution may be added to the tank either before the pressure change is applied or while the pressure change is being applied.
  • the pores of the biochar may be impregnated with the additive solution using a surfactant solution (e.g., a liquid solution containing 0.1 - 20% surfactant) or ultrasonic treatment, as will be further described below.
  • a surfactant solution e.g., a liquid solution containing 0.1 - 20% surfactant
  • ultrasonic treatment as will be further described below.
  • a method of solubilizing minerals comprising the steps of infusing biochars that are already impregnated with minerals (e.g. after having been used to purify water containing, among other things, such minerals) with MSM or juxtaposing biochars containing MSM with a mineral-rich environment, such as soil. Additionally, a process can be performed in phases, where a mineral is applied and deposited in to the pores of the biochar, then fixed in place, and then a MSM is added, such that when the MSM is activated, it begins to solubilize the minerals previously fixed or sorbed to the biochar.
  • Figure 1 illustrates a cross-section of one example of a raw biochar particle.
  • Figure 2a is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of treated biochar made from pine.
  • Figure 2b is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of treated biochar made from birch.
  • Figure 2c is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of treated biochar made from coconut shells.
  • Figure 3 is a chart showing porosity distribution of various biochars.
  • Figure 4 is a flow chart process diagram of one implementation of a process for treating the raw biochar in accordance with the invention.
  • Figure 4a illustrates a schematic of one example of an implementation of a biochar treat processes that that includes washing, pH adjustment and moisture adjustment.
  • Figure 4b illustrates yet another example of an implementation of a biochar treatment processing that includes inoculation.
  • Figure 5 is a schematic flow diagram of one example of a treatment system for use in accordance with the present invention.
  • Figure 6 is a chart showing the water holding capacities of treated biochar as compared to raw biochar and sandy clay loam soil and as compared to raw biochar and sunshine potting soil.
  • Figure 7 illustrates the different water retention capacities of raw biochar versus treated biochar measured gravimetrically.
  • Figure 8 is a chart showing the retained water in vacuum impregnated biochar over other biochars after a seven week period.
  • Figure 9 is a chart showing the weight loss of treated biochars versus raw biochar samples when heated at varying temperatures using a TGA testing method.
  • Figure 10 illustrates the plant available water in raw biochar, versus treated biochar and treated dried biochar.
  • Figure 11 is a graph showing the pH of various starting biochars that were made from different starting materials and pyrolysis process temperatures.
  • Figure 12 is a chart showing various pH ranges and germination for treated biochars.
  • Figure 13 is a Thermogravimetric Analysis (TGA) plot showing the measurement of water content, heavy organics and light organics in a sample.
  • Figure 14 is a chart showing the impact of treatment on pores sizes of biochar derived from coconut.
  • Figure 15 is a chart showing the impact of treatment on pores sizes of biochar derived from pine.
  • Figure 16 is a chart showing the measured hydrophobicity index raw biochar, vacuum treated biochar and surfactant treated biochar.
  • Figure 17 is a flow diagram showing one example of a method for infusing biochar.
  • Figure 18 illustrates the improved liquid content of biochar using vacuum impregnation as against soaking the biochar in liquid.
  • Figure 19a is a chart comparing total retained water of treated biochar after soaking and after vacuum impregnation.
  • Figure 19b is a chart comparing water on the surface, interstitially and in the pores of biochar after soaking and after vacuum impregnation.
  • Figure 20 illustrates how the amount of water or other liquid in the pores of vacuum processed biochars can be increased varied based upon the applied pressure.
  • Figure 21 illustrates the effects of NPK impregnation of biochar on lettuce yield.
  • Figure 22 is a chart showing nitrate release curves of treated biochars infused with nitrate fertilizer.
  • Figure 23 is a chart comparing examples of biochars.
  • Figures 24a, 24b, 24c are charts comparing different examples of biochars.
  • Figure 25 contains charts illustrating improved results obtained through the use of biochars.
  • Figure 26 is an example of carbon dioxide production captured as a continuous gas bubble in BGB (left two tubes) and LTB (right two tubes) growth medium.
  • Figures 27 and 28 illustrate improved growth rates of colonies of Streptomyces lydicus using biochars.
  • Figures 29 and 30 are images that show how different sized bacteria will fit in different biochar pore size structures.
  • Figure 31 illustrates release rate data verse total pore volume data for both coconut shell and pine based treated biochars inoculated with a releasable bacteria.
  • Figure 32 is a chart comparing examples of biochars.
  • Figures 33a, 33b, 33c are charts comparing different examples of biochars.
  • Figure 34 is a chart comparing shoot biomass when the biochar added to a soilless mix containing soybean seeds is treated with microbial product containing bradyrhizobium japonicum. and when it is untreated.
  • Figure 35 shows the comparison of root biomass in a treated verses an untreated environment.
  • Figure 36 is a chart comparing the nitrogen levels when the biochar is inoculated with the rhizobial inoculant verses when it is not inoculated.
  • Figure 37 illustrates the three day release rates of water infused biochar compared to other types of biochar.
  • Figure 38a is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of raw biochar.
  • Figure 38b is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of raw biochar of Figure 38a after it has been infused with microbial species.
  • Figure 38c is a SEM (10KV x 3.00K 10.0 ⁇ m) of a pore morphology of another example of raw biochar of Figure 38a after it has been infused with microbial species.
  • Figure 39 contains charts illustrating improved results obtained through the use of biochars.
  • the present invention relates to additive infused biochars and methods for infusing biochars with additives.
  • the infused biochars allow for the release of the additives into the soil gradually, resulting in an increase of plant growth, vigor, or survivability, while minimizing the loss of beneficial compounds in the root zone.
  • infused biochars allow for the release of additives into the ruminant and digestive system gradually as well, which promotes animal growth and results in healthier animals.
  • the term“animal” is used in its broadest sense, to include all living organisms other than plants and bacteria, whether vertebrate or invertebrate, including, in appropriate circumstances, even human beings. Specific examples include animals raised as livestock (dairy and beef cattle, sheep, goats and swine), poultry and other birds, farm-raised wild animals (e.g. bison, deer and elk), farm-raised fish and other aquatic animals, horses and other members of the horse family, animals commonly found as domestic pets, reptiles, amphibians, birds, insects, and humans.
  • livestock unairy and beef cattle, sheep, goats and swine
  • farm-raised wild animals e.g. bison, deer and elk
  • farm-raised fish and other aquatic animals horses and other members of the horse family
  • horses and other members of the horse family animals commonly found as domestic pets, reptiles, amphibians, birds, insects, and humans.
  • the properties of the raw biochar can be modified to significantly increase the biochar’s ability to retain water, nutrients and additives useful for an end application while also, in many cases, creating an environment beneficial to microorganisms.
  • such enhanced abilities could include holding water and nutrients, e.g. fertilizer, or removing compounds, such as volatile organic compounds (VOCs), dioxins, or other toxins that may react with or negatively impact either the additive itself or microbial or plant life in general.
  • VOCs volatile organic compounds
  • dioxins dioxins
  • other toxins such as volatile organic compounds (VOCs), dioxins, or other toxins that may react with or negatively impact either the additive itself or microbial or plant life in general.
  • VOCs volatile organic compounds
  • dioxins dioxins
  • other toxins such as volatile organic compounds (VOCs), dioxins, or other toxins that may react with or negatively impact either the additive itself or microbial or plant life in general.
  • additives such as liquids, nutrients (e.
  • biochar For example, through treatment, in addition to nutrients, other material additives, e.g., beneficial fungi, PGPB, MSM, herbicides and pesticides, can be utilized and benefit from the increased holding and retention capacities of the treated biochar.
  • other material additives e.g., beneficial fungi, PGPB, MSM, herbicides and pesticides
  • the processing can also ensure that the pH of biochar used in the present application is suitable for creating conditions beneficial for plant or microbial growth, which has been a known challenge for raw biochars.
  • treated biochar of the present invention can be used throughout the world, in numerous soil types, applications involving either agriculture or the raising of animals, horticultural applications, large and small scale farming, organic farming, for the culture of fish or other aquatic animals, for raising, caring for and maintaining farm-raised wild animals, such as bison, deer or elk; for raising, caring for and maintaining horses and other members of the horse family, such as donkeys, mules and burros; for veterinary use; in zoos; at home with pets; for wild animals; and in a variety of soil management applications and systems, and combinations and variations of these.
  • farm-raised wild animals such as bison, deer or elk
  • horses and other members of the horse family such as donkeys, mules and burros
  • veterinary use in zoos; at home with pets; for wild animals; and in a variety of soil management applications and systems, and combinations and variations of these.
  • Examples of some of these agricultural applications include for example, use in acidic and highly weathered tropical field soils, use in temperate soils of higher fertility, use in large commercial applications, use for the production of large scale crops such as, soybean, corn, sugarcane and rice, in forestry applications, for golf courses (e.g., greens, fairways), for general purpose turf grasses, wine grapes, table grapes, raisin grapes, fruit and nut trees, ground fruits (e.g., strawberries, blueberries, blackberries), row crops (e.g., tomatoes, celery, lettuce, leafy greens), root crops (e.g., tubers, potatoes, beets, carrots), mushrooms, and combinations and variations of these and other agricultural applications.
  • biochar treated in this way may also be used in other applications, such as animal feed, composting, water treatment, heavy metal remediation and mineral solubility, to name a few.
  • Treated biochar is also useful in improving the overall environment of animal stalls, pens, cages and swine lagoons, as well as paddocks, corrals, fish tanks, aquaria and other animal enclosures, by promoting beneficial effects such as odor control, ammonia and nitrate management, and moisture absorption. It may also be used in other applications potentially related to the maintenance, care and raising of animals, for example, mixing with manure in holding ponds to, among other things, potentially reduce gaseous nitrogen losses, soil remediation (for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components), ground water remediation, other bioremediations, and storm water runoff remediation.
  • soil remediation for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components
  • ground water remediation for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components
  • storm water runoff remediation for example absorption and
  • biochar shall be given its broadest possible meaning and shall include any solid carbonaceous materials obtained from the pyrolysis, torrefaction, gasification or any other thermal and/or chemical conversion of a biomass.
  • the solid carbonaceous material may include, but not be limited to, BMF char disclosed and taught by U.S. Patent 8,317,891, which is incorporated into this application by reference, and other known methods for production of biochar.
  • Pyrolysis is generally defined as a thermochemical decomposition of organic material at elevated temperatures in the absence of, or with reduced levels of oxygen.
  • the biochar is referred to as“treated” or undergoes“treatment,” it shall mean raw, pyrolyzed biochar that has undergone additional physical, biological, and/or chemical processing.
  • room temperature is 25°C.
  • standard temperature and pressure is 25°C and 1 atmosphere.
  • the term "about” is meant to encompass a variance or range of ⁇ 10%, the experimental or instrument error associated with obtaining the stated value, and preferably the larger of these.
  • biochars typically include porous carbonaceous materials, such as charcoal, that are used as soil amendments or other suitable applications.
  • Biochar most commonly is created by pyrolysis of a biomass.
  • CO 2 carbon dioxide
  • biochar provides the benefit of reducing carbon dioxide (CO 2 ) in the atmosphere by serving as a method of carbon sequestration.
  • CO 2 carbon dioxide
  • biochar has the potential to help mitigate climate change, via carbon sequestration.
  • biochar has the potential to help mitigate climate change, via carbon sequestration.
  • the use of biochar in agricultural and animal related applications must become widely accepted, e.g., ubiquitous. Unfortunately, because of the prior failings in the biochar arts, this has not occurred.
  • one advantage of putting biochar in soil includes long term carbon sequestration. It is theorized that as worldwide carbon dioxide emissions continue to mount, benefits may be obtained by, controlling, mitigating and reducing the amount of carbon dioxide in the atmosphere and the oceans. It is further theorized that increased carbon dioxide emissions are associated with the increasing industrial development of developing nations, and are also associated with the increase in the world's population. In addition to requiring more energy, the increasing world population will require more food. Thus, rising carbon dioxide emissions can be viewed as linked to the increasing use of natural resources by an ever increasing global population.
  • Biochar uniquely addresses both of these issues by providing an effective carbon sink, e.g., carbon sequestration agent, as well as, an agent for improving and increasing agricultural output.
  • an effective carbon sink e.g., carbon sequestration agent
  • biochar is unique in its ability to increase agricultural production, without increasing carbon dioxide emission, and preferably reducing the amount of carbon dioxide in the atmosphere.
  • this unique ability of biochar has not been realized, or seen, because of the inherent problems and failings of prior biochars including, for example, high pH, phytotoxicity due to high metals content and/or residual organics, and dramatic product inconsistencies.
  • Biochar can be made from basically any source of carbon, for example, from hydrocarbons (e.g., petroleum based materials, coal, lignite, peat) and from a biomass (e.g., woods, hardwoods, softwoods, waste paper, coconut shell, manure, chaff, food waste, etc.). Combinations and variations of these starting materials, and various and different members of each group of starting materials can be, and are, used. Thus, the large number of vastly different starting materials leads to biochars having different properties.
  • hydrocarbons e.g., petroleum based materials, coal, lignite, peat
  • a biomass e.g., woods, hardwoods, softwoods, waste paper, coconut shell, manure, chaff, food waste, etc.
  • pyrolysis or carbonization processes can be, and are used, to create biochars.
  • these processes involve heating the starting material under positive pressure, reduced pressure, vacuum, inert atmosphere, or flowing inert atmosphere, through one or more heating cycles where the temperature of the material is generally brought above about 400°C, and can range from about 300°C to about 900°C.
  • the percentage of residual carbon formed and several other initial properties are strong functions of the temperature and time history of the heating cycles. In general, the faster the heating rate and the higher the final temperature the lower the char yield. Conversely, in general, the slower the heating rate or the lower the final temperature the greater the char yield.
  • the higher final temperatures also lead to modifying the char properties by changing the inorganic mineral matter compositions, which in turn, modify the char properties.
  • Ramp, or heating rates, hold times, cooling profiles, pressures, flow rates, and type of atmosphere can all be controlled, and typically are different from one biochar supplier to the next. These differences potentially lead to a biochar having different properties, further framing the substantial nature of one of the problems that the present inventions address and solve.
  • hydrogen and oxygen are first removed in gaseous form by the pyrolytic decomposition of the starting materials, e.g., the biomass.
  • the free carbon atoms group or arrange into crystallographic formations known as elementary graphite crystallites.
  • pyrolysis involves thermal decomposition of carbonaceous material, e.g., the biomass, eliminating non-carbon species, and producing a fixed carbon structure.
  • raw or untreated biochar is generally produced by subjecting biomass to either a uniform or varying pyrolysis temperature (e.g., 300° C to 550° C to 750° C or more) for a prescribed period of time in a reduced oxygen environment. This process may either occur quickly, with high reactor temperature and short residence times, slowly with lower reactor temperatures and longer residence times, or anywhere in between.
  • a uniform or varying pyrolysis temperature e.g. 300° C to 550° C to 750° C or more
  • This process may either occur quickly, with high reactor temperature and short residence times, slowly with lower reactor temperatures and longer residence times, or anywhere in between.
  • the biomass from which the char is obtained may be first stripped of debris, such as bark, leaves and small branches, although this is not necessary.
  • the biomass may further include feedstock to help adjust the pH and particle size distribution in the resulting raw biochar.
  • biomass that is fresh, less than six months old, and with an ash content of less than 3%.
  • This ash content often contains minerals including but not limited to phosphorous, nitrate, and potassium.
  • the desired minerals can be added to the biomass via simple mixing or through an infusion process prior to pyrolysis or injected into the pyrolysis system during pyrolysis.
  • biochar derived from different biomass e.g., pine, oak, hickory, birch and coconut shells from different regions, and understanding the starting properties of the raw biochar, the treatment methods can be tailored to ultimately yield a treated biochar with predetermined, predictable physical and chemical properties.
  • biochar particles can have a very wide variety of particle sizes and distributions, usually reflecting the sizes occurring in the input biomass. Additionally, biochar can be ground or crushed after pyrolysis to further modify the particle sizes. Typically, for agricultural uses, biochars with consistent, predictable particle sizes are more desirable.
  • the biochar particles can have particle sizes as shown or measured in Table 1below. When referring to a batch having 1 ⁇ 4 inch particles, the batch would have particles that will pass through a 3 mesh sieve, but will not pass through (i.e., are caught by or sit atop) a 4 mesh sieve.
  • biochar particles having particle sizes from about 3/4 mesh to about 60/70 mesh, about 4/5 mesh to about 20/25 mesh, or about 4/5 mesh to about 30/35 mesh. It being understood that the desired mesh size, and mesh size distribution can vary depending upon a particular application for which the biochar is intended.
  • FIG. 1 illustrates a cross-section of one example of a raw biochar particle.
  • a biochar particle 100 is a porous structure that has an outer surface 100a and a pore structure 101 formed within the biochar particle 100.
  • the terms "porosity”, “porous”, “porous structure”, and “porous morphology” and similar such terms are to be given their broadest possible meaning, and would include materials having open pores, closed pores, and combinations of open and closed pores, and would also include macropores, mesopores, and micropores and combinations, variations and continuums of these morphologies.
  • the term“pore volume” is the total volume occupied by the pores in a particle or collection of particles;
  • the term“inter- particle void volume” is the volume that exists between a collection of particle;
  • the term“solid volume or volume of solid means” is the volume occupied by the solid material and does not include any free volume that may be associated with the pore or inter-particle void volumes;
  • the term“bulk volume” is the apparent volume of the material including the particle volume, the inter-particle void volume, and the internal pore volume.
  • the pore structure 101 forms an opening 121 in the outer surface 100a of the biochar particle 100.
  • the pore structure 101 has a macropore 102, which has a macropore surface 102a, and which surface 102a has an area, i.e., the macropore surface area. (In this diagram only a single micropore is shown. If multiple micropores are present than the sum of their surface areas would equal the total macropore surface area for the biochar particle.) From the macropore 102, several mesopores 105, 106, 107, 108 and 109 are present, each having its respective surfaces 105a, 106a, 107a, 108a and 109a.
  • each mesopore has its respective surface area; and the sum of all mesopore surface areas would be the total mesopore surface area for the particle.
  • the mesopores e.g., 107
  • each micropore has its respective surface area and the sum of all micropore surface areas would be the total micropore surface area for the particle.
  • the sum of the macropore surface area, the mesopore surface area and the micropore surface area would be the total pore surface area for the particle.
  • Macropores are typically defined as pores having a diameter greater than 300 nm, mesopores are typically defined as diameter from about 1-300 nm, and micropores are typically defined as diameter of less than about 1 nm, and combinations, variations and continuums of these morphologies.
  • the macropores each have a macropore volume, and the sum of these volumes would be the total macropore volume.
  • the mesopores each have a mesopore volume, and the sum of these volumes would be the total mesopore volume.
  • the micropores each have a micropore volume, and the sum of these volumes would be the total micropore volume. The sum of the macropore volume, the mesopore volume and the micropore volume would be the total pore volume for the particle.
  • the total pore surface area, volume, mesopore volume, etc., for a batch of biochar would be the actual, estimated, and preferably calculated sum of all of the individual properties for each biochar particle in the batch.
  • the pore morphology in a biochar particle may have several of the pore structures shown, it may have mesopores opening to the particle surface, it may have micropores opening to particle surface, it may have micropores opening to macropore surfaces, or other combinations or variations of interrelationship and structure between the pores. It should further be understood that the pore morphology may be a continuum, where moving inwardly along the pore from the surface of the particle, the pore transitions, e.g., its diameter becomes smaller, from a macropore, to a mesopore, to a micropore, e.g., macropore 102 to mesopore 109 to micropore 114.
  • the pores can be terminal as depicted in Figure 1, where the pore ends somewhere in the particle or open-ended where the pore ends at one or more other pore openings.
  • terminal pores have only one opening to the external surface of the particle and open-ended pores have two or more openings to the external surface of the particle.
  • the biochars have porosities that can range from 0.2 cm 3 /cm 3 to about 0.8 cm 3 /cm 3 and more preferably about 0.2 cm 3 /cm 3 to about 0.5 cm 3 /cm 3 .
  • porosity is provided as the ratio of the total pore volumes (the sum of the micro + meso + macro pore volumes) to the solid volume of the biochar. Porosity of the biochar particles can be determined, or measured, by measuring the micro-, meso-, and macro pore volumes, the bulk volume, and the inter particle volumes to determine the solid volume by difference. The porosity is then calculated from the total pore volume and the solid volume.
  • FIGS. 2A, 2B and 2C illustrate Scanning Electron Microscope (“SEM”) images of various types of treated biochars showing the different nature of their pore morphology.
  • Figure 2A is biochar derived from pine.
  • Figure 2B is biochar derived from birch.
  • Figure 2C is biochar derived from coconut shells.
  • the surface area and pore volume for each type of pore can be determined by direct measurement using CO 2 adsorption for micro-, N 2 adsorption for meso- and macro pores and standard analytical surface area analyzers and methods, for example, particle analyzers such as Micrometrics instruments for meso- and micro pores and impregnation capacity for macro pore volume.
  • particle analyzers such as Micrometrics instruments for meso- and micro pores and impregnation capacity for macro pore volume.
  • Mercury porosimetry which measures the macroporosity by applying pressure to a sample immersed in mercury at a pressure calibrated for the minimum pore diameter to be measured, may also be used to measure pore volume.
  • the total micropore volume can be from about 2% to about 25% of the total pore volume.
  • the total mesopore volume can be from about 4% to about 35% of the total pore volume.
  • the total macropore volume can be from about 40% to about 95% of the total pore volume.
  • Figure 3 shows a bar chart setting out examples of the pore volumes for sample biochars made from peach pits 201, juniper wood 202, a first hard wood 203, a second hard wood 204, fir and pine waste wood 205, a first pine 206, a second pine 207, birch 208 and coconut shells 209.
  • treatment can increase usable pore volumes and, among other things, remove obstructions in the pores, which leads to increased retention properties and promotes further performance characteristics of the biochar. Knowing the properties of the starting raw biochar, one can treat the biochar to produce controlled, predictable and optimal resulting physical and chemical properties.
  • treating and/or washing the biochar in accordance with the present invention involves more than a simple wash or soak, which generally only impacts the exterior surfaces and a small percentage of the interior surface area.
  • “Washing” or“treating” in accordance with the present invention involves treatment of the biochar in a manner that causes the forced, accelerated or assisted infusion and/or diffusion of liquids and/or additivities into and/or out of the biochar pores (through mechanical, physical, or chemical means) such that certain properties of the biochar can be altered or improved over and above simply contacting these liquids with the biochar or so that treatment becomes more efficient or rapid from a time standpoint over simple contact or immersion.
  • effective treatment processes can mitigate deleterious pore surface properties, remove undesirable substances from pore surfaces or volume, and impact anywhere from between 10% to 99% or more of pore surface area of a biochar particle.
  • the treated biochars can exhibit a greater capacity to retain water and/or other nutrients as well as being more suitable habitats for some forms of microbial life.
  • agricultural applications can realize increased moisture control, increased nutrient retention, reduced water usage, reduced water requirements, reduced runoff or leaching, increased nutrient efficiency, reduced nutrient usage, increased yields, increased yields with lower water requirements and/or nutrient requirements, increases in beneficial microbial life, improved performance and/or shelf life for inoculated bacteria, and any combination and variation of these and other benefits.
  • Treatment further allows the biochar to be modified to possess certain known properties that enhance the benefits received from the use of biochar. While the selection of feedstock, raw biochar and/or pyrolysis conditions under which the biochar was manufactured can make treatment processes less cumbersome, more efficient and further controlled, treatment processes can be utilized that provide for the biochar to have desired and generally sustainable resulting properties regardless of the biochar source or pyrolysis conditions.
  • treatment can (i) repurpose problematic biochars, (ii) handle changing biochar material sources, e.g., seasonal and regional changes in the source of biomass, (iii) provide for custom features and functions of biochar for particular soils, regions or agricultural purposes; (iv) increase the retention properties of biochar, (v) provide for large volumes of biochar having desired and predictable properties, (vi) provide for biochar having custom properties, (vii) handle differences in biochar caused by variations in pyrolysis conditions or manufacturing of the “raw” biochar; and (viii) address the majority, if not all, of the problems that have, prior to the present invention, stifled the large scale adoption and use of biochars.
  • Treatment can wash both the interior and exterior pore surfaces, remove harmful chemicals, introduce beneficial substances, and alter certain properties of the biochar and the pore surfaces and volumes. This is in stark contrast to simple washing which generally only impacts the exterior surfaces and a small percentage of the interior surface area. Treatment can further be used to coat substantially all of the biochar pore surfaces with a surface modifying agent or impregnate the pore volume with additives or treatment to provide a predetermined feature to the biochar, e.g., surface charge and charge density, surface species and distribution, targeted nutrient addition, magnetic modifications, root growth facilitator, and water absorptivity and water retention properties.
  • treatment can also be used to remove undesirable substances from the biochar, such as dioxins or other toxins either through physical removal or through chemical reactions causing neutralization.
  • FIG. 4 is a schematic flow diagram of one example treatment process 400 for use in accordance with the present invention.
  • the treatment process 400 starts with raw biochar 402 that may be subjected to one or more reactors or treatment processes prior to bagging 420 the treated biochar for resale.
  • 404 represents reactor 1, which may be used to treat the biochar.
  • the treatment may be a simple water wash or may be an acid wash used for the purpose of altering the pH of the raw biochar particles 402.
  • the treatment may also contain a surfactant or detergent to aid the penetration of the treatment solution into the pores of the biochar.
  • the treatment may optionally be heated, cooled, or may be used at ambient temperature or any combination of the three.
  • the treatment may include liquids or solids targeted to react with residual substances or biology on the surfaces of the biochar.
  • a water and/or acid/alkaline wash 404 (the latter for pH adjustment) may be the only necessary treatment prior to bagging the biochar 420. If, however, the moisture content of the biochar needs to be adjusted, the treated biochar may then be put into a second reactor 406 for purposes of reducing the moisture content in the washed biochar. From there, the treated and moisture adjusted biochar may be bagged 420.
  • the treated moisture adjusted biochar may then be passed to a third reactor 408 for inoculation, which may include the impregnation of biochar with beneficial additives, such as nutrients, bacteria, microbes, fertilizers or other additives.
  • beneficial additives such as nutrients, bacteria, microbes, fertilizers or other additives.
  • the inoculated biochar may be bagged 420, or may be yet further processed, for example, in a fourth reactor 410 to have further moisture removed from or added to the biochar. Further moisture adjustment may be accomplished by placing the inoculated biochar in a fourth moisture adjustment reactor 410 or circulating the biochar back to a previous moisture adjustment reactor (e.g.
  • Figure 4a illustrates a schematic of one example of an implementation of biochar processing that includes washing the pores and both pH and moisture adjustment.
  • Figure 4b illustrates yet another example of an implementation of biochar processing that includes inoculation.
  • raw biochar 402 is placed into a reactor or tank 404.
  • a washing or treatment liquid 403 is then added to a tank and a partial vacuum, using a vacuum pump, 405 is pulled on the tank.
  • the treating or washing liquid 403 may be used to clean or wash the pores of the biochar 402 or adjust the chemical or physical properties of the surface area or pore volume, such as pH level, usable pore volume, or VOC content, among other things.
  • the vacuum can be applied after the treatment liquid 403 is added or while the treatment liquid 403 is added.
  • the washed/ adjusted biochar 410 may be moisture adjusted by vacuum exfiltration 406 to pull the extra liquid from the washed/moisture adjusted biochar 410 or may be placed in a centrifuge 407, heated or subjected to pressure gradient changes (e.g., blowing air) for moisture adjustment.
  • the moisture adjusted biochar 412 may then be bagged or subject to further treatment. Any excess liquids 415 collected from the moisture adjustment step may be disposed of or recycled, as desired.
  • biochar fines may be collected from the excess liquids 415 for further processing, for example, to create a slurry, cakes, or biochar extrudates.
  • a positive pressure pump may be used to apply positive pressure to the tank 404.
  • applying positive pressure to the tank may also function to force or accelerate the washing or treating liquid 403 into the pores of the biochar 402.
  • Any change in pressure in the tank 404 or across the surface of the biochar could facilitate the exchange of gas and/or moisture into and out of the pores of the biochar with the washing or treating liquid 403 in the tank.
  • changing the pressure in the tank and across the surface of the biochar, whether positive or negative is within the scope of this invention.
  • Changing pressure in the tank can be done by reducing or increasing the pressure from a starting pressure and then returning it to the starting pressure or atmospheric pressure after at least 5 seconds. Additionally, during the pressure change, the pressure can be held at a set pressure, fluctuated between pressures, or be sequentially held and fluctuated. If the pressure change is to create a vacuum, the vacuum can be created by applying an absolute pressure below 760 Torr.
  • the washed/ adjusted biochar 410 or the washed/ adjusted and moisture adjusted biochar 412 may be further treated by inoculating or impregnating the pores of the biochar with an additive 425.
  • the biochar can be further moisture adjusted by vacuum filtration 406 to pull the extra liquid from the washed/moisture adjusted biochar 410 or may be placed in a centrifuge 407 for moisture adjustment.
  • the resulting biochar 430 can then be bagged. Any excess liquids 415 collected from the moisture adjustment step may be disposed of or recycled, as desired.
  • biochar particulates or“fines” which easily are suspended in liquid may be collected from the excess liquids 415 for further processing, for example, to create a slurry, biochar extrudates, or merely a biochar product of a consistently smaller particle size.
  • both processes of the Figure 4a and 4b can be performed with a surfactant solution in place of, or in conjunction with, the vacuum 405.
  • the biochar can optionally be cooled or heated to affect the materials used to adjust/inoculate or to inspire some planned reactivity.
  • the treatment process can be geared to treat different forms of raw biochar to achieve treated biochar properties known to enhance these characteristics.
  • the treatment may be the infusion of an acid solution into the pores of the biochar using vacuum, surfactant, or other treatment means.
  • This treatment of pore infusion through, for example, the rapid, forced infusion of liquid into and out the pores of the biochar, has further been proven to sustain the adjusted pH levels of the treated biochar for much longer periods than biochar that is simply immersed in an acid solution for the same period of time.
  • excess liquid and other selected substances e.g. chlorides, dioxins, and other chemicals, to include those previously deposited by treatment to catalyze or otherwise react with substances on the interior or exterior surfaces of the biochar
  • excess liquid and other selected substances e.g. chlorides, dioxins, and other chemicals, to include those previously deposited by treatment to catalyze or otherwise react with substances on the interior or exterior surfaces of the biochar
  • FIG. 5 illustrates one example of a system 500 that utilizes vacuum impregnation to treat raw biochar.
  • raw biochar particles and preferably a batch of biochar particles, are placed in a reactor, which is connected to a vacuum pump, and a source of treating liquid (i.e. water or acidic/basis solution).
  • a source of treating liquid i.e. water or acidic/basis solution.
  • the valve to the reactor is closed, the pressure in the reactor is reduced to values ranging from 750 Torr to 400 Torr to 10 Torr or less.
  • the biochar is maintained under vacuum (“vacuum hold time”) for anywhere from seconds to 1 minute to 10 minutes, to 100 minutes, or possibly longer.
  • a vacuum hold time of from about 1 to about 5 minutes can be used if the reactor is of sufficient size and sufficient infiltrate is available to adjust the necessary properties.
  • the treating liquid may then be introduced into the vacuum chamber containing the biochar.
  • the treating liquid may be introduced into the vacuum chamber before the biochar is placed under a vacuum.
  • treatment may also include subjecting the biochar to elevated temperatures from ambient to about 250 oC or reduced temperatures to about -25° C or below, with the limiting factor being the temperature and time at which the infiltrate can remain flowable as a liquid or semi-liquid.
  • the infiltrate or treating liquid is drawn into the biochar pore, and preferably drawn into the macropores and mesopores.
  • the infiltrate can coat anywhere from 10% to 50% to 100% of the total macropore and mesopore surface area and can fill or coat anywhere from a portion to nearly all (10% - 100%) of the total macropore and mesopore volume.
  • the treating liquid can be left in the biochar, with the batch being a treated biochar batch ready for packaging, shipment and use in an agricultural or other application.
  • the treating liquid may also be removed through drying, subsequent vacuum processing, centrifugal force (e.g., cyclone drying machines or centrifuges), with the batch being a treated biochar batch ready for packaging, shipment and use in an agricultural application.
  • centrifugal force e.g., cyclone drying machines or centrifuges
  • a second, third or more infiltration, removal, infiltration and removal, and combinations and variations of these may also be performed on the biochar with optional drying steps between infiltrations to remove residual liquid from and reintroduce gasses to the pore structure if needed.
  • the liquid may contain organic or inorganic surfactants to assist with the penetration of the treating liquid.
  • a system 500 for providing a biochar preferably having predetermined and uniform properties.
  • the system 500 has a vacuum infiltration tank 501.
  • the vacuum infiltration tank 501 has an inlet line 503 that has a valve 504 that seals the inlet line 503.
  • the starting biochar is added to vacuum infiltration tank 501 as shown by arrow 540.
  • a vacuum is pulled on the tank, by a vacuum pump connected to vacuum line 506, which also has valve 507.
  • the starting biochar is held in the vacuum for a vacuum hold time.
  • Infiltrate, as shown by arrow 548 is added to the tank 501 by line 508 having valve 509.
  • the infiltrate is mixed with the biochar in the tank 501 by agitator 502.
  • the mixing process is done under vacuum for a period of time sufficient to have the infiltrate fill the desired amount of pore volume, e.g., up to 100% of the macropores and mesopores.
  • a vacuum can be applied at an absolute pressure below 760 Torr.
  • the vacuum mixing period is at least 5 seconds between the time the pressure is reduced from a starting pressure to when it is returned to the starting pressure or atmospheric pressure.
  • the pressure can be held at a set pressure, fluctuated between pressures, or be sequentially held and fluctuated.
  • the mixture can also, optionally be agitated by mixing, shaking or stir or causing movement to the biochar mixture.
  • the infiltrate may be added to the vacuum infiltration tank 501 before vacuum is pulled on the tank.
  • infiltrate is added in the tank in an amount that can be impregnated into the biochar.
  • the biochar is circulated in the tank to cause the infiltrate to fill the pore volume.
  • the agitation of the biochar during this process can be performed through various means, such as a rotating tank, rotating agitator, pressure variation in the tank itself, or other means.
  • the biochar may be dried using conventional means before even the first treatment. This optional pre-drying can remove liquid from the pores and in some situations may increase the efficiency of impregnation due to pressure changes in the tank.
  • the infiltrated biochar can be moved by conveyor 514, as shown by arrow 542, to a drying apparatus 516, e.g., a centrifugal dryer or heater, where water, infiltrate or other liquid is removed by way of line 517, and the dried biochar leaves the dryer through discharge line 518 as shown by arrow 545, and is collected in bin 519.
  • the biochar is removed from the bin by discharge 520.
  • the biochar may be shipped as a treated biochar for use in an agriculture application, as shown by arrow 547.
  • the biochar may also be further processed, as shown by 546.
  • the biochar could be returned to tank 501 (or a second vacuum infiltration tank) for a further infiltration step.
  • the drying step may be repeated either by returning the dry biochar to the drying apparatus 516, or by running the biochar through a series of drying apparatus, until the predetermined dryness of the biochar is obtained, e.g., between 50% to less than 1% moisture.
  • the system 500 is illustrative of the system, equipment and processes that can be used for, and to carry out the present inventions. Various other implementations and types of equipment can be used.
  • the vacuum infiltration tank can be a sealable off-axis rotating vessel, chamber or tank.
  • washing equipment may be added or utilized at various points in the process, or may be carried out in the vacuum tank, or drier, (e.g., wash fluid added to biochar as it is placed into the drier for removal). Other steps, such as bagging, weighing, the mixing of the biochar with other materials, e.g., fertilized, peat, soil, etc. can be carried out.
  • positive pressure can be applied, if needed, to enhance the penetration of the infiltrate or to assist with re-infusion of gaseous vapors into the treated char.
  • the infiltrate may have soluble gasses added which then can assist with removal of liquid from the pores, or gaseous treatment of the pores upon equalization of pressure.
  • the biochar may also be treated using a surfactant.
  • a surfactant such as yucca extract
  • the vacuum infiltration tank or any other rotating vessel, chamber or tank can be used.
  • a surfactant such as yucca extract
  • the quantity of the surfactant added to the infiltrate may vary depending upon the surfactant used. For example, organic yucca extract can be added at a rate of between 0.1 - 20%, but more preferably 1-5% by volume of the infiltrate.
  • the infiltrate with surfactant is then mixed with the biochar in a tumbler for several minutes, e.g., 3-5 minutes, without applied vacuum.
  • a vacuum or positive pressure may be applied with the surfactant to improve efficiency, but is not necessary.
  • infiltrate to which the surfactant or detergent is added may be heated or may be ambient temperature or less.
  • the mixture of the surfactant or detergent, as well as the char being treated may be heated, or may be ambient temperature, or less.
  • excess free liquid can be removed in the same manner as described above in connection with the vacuum infiltration process. Drying, also as described above in connection with the vacuum infiltration process, is an optional additional step.
  • surfactant treatment a number of other surfactants may be used for surfactant treatment, which include, but are not limited to, the following: nonionic types, such as, ethoxylated alcohols, phenols- lauryl alcohol ethoxylates, Fatty acid esters- sorbitan, tween 20, amines, amides- imidazoles; anionic types, such as sulfonates- arylalkyl sulfonates and sulfate- sodium dodecyl sulfate; cationic types, such as alkyl- amines or ammoniums- quaternary ammoniums; and amphoteric types, such as betaines- cocamidopropyl betaine.
  • nonionic types such as, ethoxylated alcohols, phenols- lauryl alcohol ethoxylates, Fatty acid esters- sorbitan, tween 20, amines, amides- imidazoles
  • the biochar may also be treated by applying ultrasonics.
  • the biochar may be contacted with a treating liquid that is agitated by ultrasonic waves.
  • a treating liquid that is agitated by ultrasonic waves.
  • contaminants may be dislodged or removed from the biochar due to bulk motion of the fluid in and around the biocarbon, pressure changes, including cavitation in and around contaminants on the surface, as well as pressure changes in or near pore openings (cavitation bubbles) and internal pore cavitation.
  • agitation will cause contaminants of many forms to be released from the internal and external structure of the biochar.
  • the agitation also encourages the exchange of water, gas, and other liquids with the internal biochar structure.
  • Contaminants are transported from the internal structure to the bulk liquid (treating fluid) resulting in biochar with improved physical and chemical properties.
  • the effectiveness of ultrasonic cleaning is tunable as bubble size and number is a function of frequency and power delivered by the transducer to the treating fluid
  • raw wood based biochar between 10 microns to 10 mm with moisture content from 0% to 90% may be mixed with a dilute mixture of acetic acid and water (together the treating liquid) in a processing vessel that also translates the slurry (the biochar/treating liquid mixture).
  • the slurry passes near an ultrasonic transducer to enhance the interaction between the fluid and biochar.
  • the biochar may experience one or multiple washes of dilute acetic acid, water, or other treating fluids.
  • the biochar may also make multiple passes by ultrasonic transducers to enhance physical and chemical properties of the biochar.
  • a large volume of slurry can continuously pass an ultrasonic device and be degassed and wetted to its maximum, at a rapid processing rate.
  • the slurry can also undergo a separation process in which the fluid and solid biochar are separated at 60% effectiveness or greater.
  • the pH of the biochar, or other physical and chemical properties may be adjusted and the mesopore and macropore surfaces of the biochar may be cleaned and enhanced.
  • ultrasonic treatment can be used in combination with bulk mixing with water, solvents, additives (fertilizers, etc.), and other liquid based chemicals to enhance the properties of the biochar.
  • the biochar may be subject to moisture adjustment, further treatment and/or inoculation using any of the methods set forth above.
  • the treatment process may include two steps, which in certain applications, may be combined: (i) washing and (ii) inoculation of the pores with an additive.
  • an additive e.g., water
  • the step of washing the pores and inoculating the pores with an additive may be combined.
  • washing is generally done for one of three purposes: (i) to modify the surface of the pore structure of the biochar (i.e., to allow for increased retention of liquids); (ii) to modify the pH of the biochar; and/or (iii) to remove undesired and potentially harmful compounds or gases.
  • the treatment processes of the invention modify the surfaces of the pore structure to provide enhanced functionality and to control the properties of the biochar to achieve consistent and predicable performance.
  • anywhere from at least 10% of the total pore surface area up to 90% or more of the total pore surface area may be modified.
  • such modification may be substantially and uniformly achieved for an entire batch of treated biochar.
  • the hydrophilicity of the surface of the pores of the biochar is modified, allowing for a greater water retention capacity and available water capacity.
  • gases and other substances are also removed from the pores of the biochar particles, also contributing to the biochar particles’ increased water holding capacity.
  • the ability of the biochar to retain liquids, whether water or additives in solution is increased, which also increases the ability to load the biochar particles with large volumes of inoculant, infiltrates and/or additives.
  • a batch of biochar has a bulk density, which is defined as weight in grams (g) per cm 3 of loosely poured material that has or retains some free space between the particles.
  • the biochar particles in this batch will also have a solid density, which is the weight in grams (g) per cm 3 of just particles, i.e., with the free space between the particles removed.
  • the solid density includes the air space or free space that is contained within the pores, but not the free space between particles.
  • the actual density of the particles is the density of the material in grams (g) per cm 3 of material, which makes up the biochar particles, i.e., the solid material with pore volume removed.
  • the treated biochars can have impregnation capacities that are larger than could be obtained without infiltration, e.g., the treated biochars can readily have 10%, 30%, 40%, 50%, or most preferably, 60%-100% of their total pore volume filled with an infiltrate, e.g., an inoculant.
  • the impregnation capacity is the amount of a liquid that a biochar particle, or batch of particles, can absorb.
  • the ability to make the pores surface hydrophilic, and to infuse liquid deep into the pore structure through the application of positive or negative pressure and/or a surfactant, alone or in combination, provides the ability to obtain these high impregnation capabilities.
  • the treated biochars can have impregnation capacities, i.e., the amount of infiltrate that a particle can hold on a volume held/total volume of a particle basis, that is greater than 0.2 cm 3 /cm 3 to 0.8 cm 3 /cm 3 .
  • the water retention capacity of biochar can be greatly increased over the water retention capacities of various soil types and even raw biochar, thereby holding water and/or nutrients in the plant’s root zone longer and ultimately reducing the amount of applied water (through irrigation, rainfall, or other means) needed by up to 50% or more.
  • biochar with increased liquid retention capacities can be beneficial to many animal related applications.
  • the proven water retention capacity increase of treated biochar over raw biochar is demonstrated below in connection with Figure 6.
  • the increased liquid retention capabilities can also be used in subsequent stages of this process to improve the effectiveness of infiltration by allowing more treatment solution to come in contact with more surface area of the material.
  • Figure 6 is a chart showing the water retention capacities of soils versus raw and treated biochar.
  • the raw and treated biochar are derived from coconut biomass.
  • the soils sampled are loam and sandy clay soil and a common commercial horticultural mix.
  • the charts show the retained water as a function of time.
  • chart A the bottom line represents the retained water in the sandy claim loam soil over time.
  • the middle line represents the retained water in the sandy clay soil with 20% by volume percent of unprocessed raw biochar.
  • the top line represents the retained water in the sandy clay loam soil with 20% by volume percent of treated biochar (adjusted and inoculated biochar).
  • Chart B represents the same using common soilless mixes comprised of sphagnum peat moss, course perlite, dolomitic lime and gypsum rather than sandy clay loam soil.
  • the treated biochar has an increased water retention capacity over raw biochar of approximately 1.5 times the raw biochar.
  • results are shown with treated biochar derived from pine, also showing an approximate 1.5 times increase in water retention capacity over raw biochar.
  • the water retention capacity of treated biochar could be as great as three time that of raw biochar.
  • “Water holding capacity,” which may also be referred to as“Water Retention Capacity,” is the amount of water that can be held both internally within the porous structure and in the interparticle void spaces in a given batch of particles. While a summary of the method of measure is provided above, a more specific method of measuring water holding capacity/water retention capacity is measured by the following procedure: (i) drying a sample of material under temperatures of 105 oC for a period of 24 hours or using another scientifically acceptable technique to reduce the moisture content of the material to less than 2%, less than 1%; and preferably less than .5% (ii) placing a measured amount of dry material in a container; (iii) filling the container having the measured amount of material with water such that the material is completely immersed in the water; (iv) letting the water remain in the container having the measured amount of material for at least ten minutes or treating the material in accordance with the invention by infusing with water when the material is a treated biochar; (v) draining the water from the
  • the water holding/water retention capacity is determined by measuring the difference in weight of the material from step (vi) to step (viii) over the weight of the material from step (viii) (i.e., wet weight-dry weight/dry weight).
  • Figure 7 illustrates the different water retention capacities of raw biochar versus treated biochar measured gravimetrically. As illustrated, water retention capacity of raw biochar can be between 100- 200%, whereas treated biochar can have water retention capacities measured gravimetrically between 200-400%.
  • Water holding capacity can also be measured volumetrically and represented as a percent of the volume of water retained in the biochar after gravitationally draining the excess water/volume of biochar
  • the volume of water retained in the biochar after draining the water can be determined from the difference between the water added to the container and water drained off the container or from the difference in the weight of the wet biochar from the weight of the dry biochar converted to a volumetric measurement.
  • This percentage water holding capacity for treated biochar may be 50-55 percent and above by volume.
  • Treated biochar of the present invention has also demonstrated the ability to retain more water than raw biochar after exposure to the environment for defined periods of time.
  • “remaining water content” can be defined as the total amount of water that remains held by the biochar after exposure to the environment for certain amount of time. Exposure to environment is exposure at ambient temperature and pressures.
  • remaining water content can be measured by (i) creating a sample of biochar that has reached its maximum water holding capacity; (ii) determining the total water content by thermogravimetric analysis (H2O (TGA)), as described above on a sample removed from the output of step (i) above, (iii) exposing the biochar in the remaining sample to the environment for a period of 2 weeks (15 days, 360 hrs.); (iv) determining the remaining water content by thermogravimetric analysis (H 2 O (TGA)); and (v) normalizing the remaining (retained) water in mL to 1 kg or 1 L biochar.
  • H2O thermogravimetric analysis
  • the percentage of water remaining after exposure for this two week period can be calculated by the remaining water content of the biochar after the predetermined period over the water content of the biochar at the commencement of the two week period.
  • treated biochar has shown to retain water at rates over 4x that of raw biochar.
  • the following amount of water can remain in treated biochar after two weeks of exposure to the environment: 100-650 mL/kg; 45-150 mL/L; 12-30 gal/ton; 3-10 gal/yd 3 after 360 hours (15 days) of exposure to the environment.
  • biochar treated through vacuum impregnation can increase the amount of retained water in biochar about 3x compared to other methods even after seven weeks.
  • examples of the present biochars can retain more than 5% of their weight, more than 10% of their weight, and more than 15% of their weight, and even more than 50% of their weight compared to an average soil which may retain 2% or less, or between 100-600 ml/kg by weight of biochar.
  • Tests have also shown that treated biochars that show weight loss of > 1% in the interval between 43-60 oC when analyzed by the Thermal Gravimetric Analysis (TGA) (as described below) demonstrate greater water holding and content capacities over raw biochars. Weight loss of > 5%-15% in the interval between 38-68 oC when analyzed by the Thermal Gravimetric Analysis (TGA) using sequences of time and temperature disclosed in the following paragraphs or others may also be realized. Weight percentage ranges may vary from between > 1% - 15% in temperature ranges between 38-68 oC, or subsets thereof, to distinguish between treated biochar and raw biochar.
  • TGA Thermal Gravimetric Analysis
  • FIG. 9 is a chart 900 showing the weight loss of treated biochars 902 versus raw biochar samples 904 when heated at varying temperatures using the TGA testing described below. As illustrated, the treated biochars 902 continue to exhibit weight loss when heated between 40-60 oC when analyzed by the Thermal Gravimetric Analysis (TGA) (described below), whereas the weight loss in raw biochar 804 between the same temperature ranges levels off. Thus, testing demonstrates the presence of additional moisture content in treated biochars 902 versus raw biochars 904.
  • TGA Thermal Gravimetric Analysis
  • the treated biochars 902 exhibit substantial water loss when heated in inert gas such as nitrogen following treatment. More particularly, when heated for 25 minutes at each of the following temperatures 20, 30, 40, 50 and 60 o C the treated samples lose about 5-% to 15% in the interval 43 - 60 o C and upward of 20-30% in the interval between 38- 68 o C.
  • the samples to determine the water content of the raw biochar were obtained by mixing a measured amount of biochar and water, stirring the biochar and water for 2 minutes, draining off the water, measuring moisture content and then subjecting the sample to TGA.
  • the samples for the treated biochar were obtained by using the same measured amount of biochar as used in the raw biochar sample, and impregnating the biochar under vacuum. Similar results are expected with biochar treated with a treatment process consistent with those described in this disclosure with the same amount of water as used with the raw biochar. The moisture content is then measured and the sample is subjected to TGA described above.
  • BCT Bontchev-Cheyne Test
  • Biochars treated with vacuum infiltration to enhance water holding or retention capacities typically exhibit weight loss of > 5% in the interval between 38-68 oC, > 1% in the interval between 43-60 oC.
  • Biochars with greater water holding or retention capacities can exhibit > 5% weight loss in the interval between 43-60 oC measured using the above described BCT.
  • FIG. 10 illustrates the plant available water in raw biochar, versus treated biochar and treated dried biochar and illustrates that treated biochar can have a plant available water percent of greater than 35% by volume.
  • Plant Available Water is the amount of unbound water in a material available for plants to uptake. This is calculated by subtracting the volumetric water content at the permanent wilting point from the volumetric water content at field capacity, which is the point when no water is available for the plants.
  • Field capacity is generally expressed as the bulk water content retained in at ⁇ 33 J/kg (or ⁇ 0.33 bar) of hydraulic head or suction pressure.
  • Permanent wilting point is generally expressed as the bulk water content retained at -1500J/kg (or -15 bar) of hydraulic head or suction pressure.
  • the above described vacuum infiltration processes, surfactant treatment processes, and/or ultrasonic treatment processes have the ability to take raw biochars having detrimental or deleterious pHs and transform those biochars into a treated biochar having pH that is in an optimal range for most plant and animal growth and soil health.
  • a graph 1100 is provided that shows the pH of various starting raw biochars that were made from different starting materials and pyrolysis process temperatures, including coconut shells 1104, pistachio shells 1101, corn at 500°C 1105, corn at 900°C 1102, bamboo 1103, mesquite 1106, wood and coffee 1108, wood (Australia) 1109, various soft woods 1110, 1111, 1112, 1113, 1114, 1115, 1116, 1117, red fir at 900°C 1107, various grasses at 500°C 1118, 1119, 1120, grass 1121, and grass at 900°C 1123.
  • FIG. 12 is a chart 1200 showing percentage of germination for lettuce plants for particular pHs, and an desired germination range 1201.
  • a control 1204 is compared with an optimal pH range 1202, and a distribution 1203 of growth rates across pHs is shown.
  • the treated biochar takes a few days after treatment for the pH to normalize. Once normalized, tests have proven that pH altered biochar remains at a stable pH, typically lower than the pH of the raw biochar, for up to 12 months or more after treatment.
  • the treatment process of the present invention can remove and/or neutralize inorganic compounds, such as the calcium hydroxide ((CaOH)2), potassium oxide (K2OK2OK20), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), and many others that are formed during pyrolysis, and are fixed to the biochar pore surfaces.
  • inorganics in particular calcium hydroxide, adversely affect the biochar's pH, making the pH in some instances as high as 8.5, 9.5, 10.5 and 11.2.
  • These high pH ranges are deleterious, detrimental to crops, and may kill or adversely affect plant life, sometimes rendering an entire field a loss. They may also be deleterious to animal health.
  • pH-adjusted biochars may useful in connection with the use of MSM, since one method by which MSM solubilize minerals is by lowering the pH.
  • the pH of the biochar can be reduced to the range of about pH 5 to about pH 8, and more preferably from about pH 6.4 to about 7.2, and still more preferably around 6.5 to 6.8, recognizing that other ranges and pHs are contemplated and may prove useful, under specific environmental or agricultural situations or for animal health.
  • the present treated biochars, particles, batches and both have most, essentially all, and more preferably all, of their pore surfaces modified by the removal, neutralization and both, of the calcium hydroxide that is present in the starting biochar material.
  • biochars have pHs in the range of about 5 to about 8, about 6.5 to about 7.5, about 6.4 to about 7, and about 6.8.
  • biochar Prior to and before testing, biochar is passed through a 2mm sieve before pH is measured. All measurements are taken according to Rajkovich et. al, Corn growth and nitrogen nutrition after additions of biochars with varying properties to a temperate soil, Biol. Fertil. Soils (2011), from which the International Biochar Initiative (IBI) method is based.
  • IBI International Biochar Initiative
  • TMCC US Composting Council
  • the test method for the TMCC comprises mixing biochar with distilled water in 1 : 5 [mass : volume] ratio, e.g., 50 grams of biochar is added to 250 ml of pH 7.0 ⁇ 0.02 water and is stirred for 10 minutes; the pH is then the measured pH of the slurry.
  • the treatment processes are capable of modifying the pore surfaces to remove or neutralize deleterious materials that are otherwise difficult, if not for all practical purpose, impossible to mitigate.
  • deleterious materials For example, heavy metals, transition metals, sodium and phytotoxic organics, polycyclic aromatic hydrocarbons, volatile organic compounds (VOCs), and perhaps other phytotoxins.
  • the resulting treated biochar has essentially all, and more preferably all, of their pore surfaces modified by the removal, neutralization and both, of one or more deleterious, harmful, potentially harmful material that is present in the starting biochar material.
  • washing can reduce the total percentage of residual organic compounds (ROC), including both the percentage of heavy ROCs and percentage of VOCs.
  • ROC residual organic compounds
  • percentage heavy ROC content can be reduced to 0-20% wt.%
  • VOC content can be reduced to less than 5% wt.%.
  • “Residual organic compounds” are defined as compounds that burn off during thermogravimetric analysis, as defined above, between 150 degrees C and 950 degrees C.
  • Residual organic compounds include, but are not limited to, phenols, polyaromatic hydrocarbons, monoaromatic hydrocarbons, acids, alcohols, esters, ethers, ketones, sugars, alkanes and alkenes.
  • phenols polyaromatic hydrocarbons
  • monoaromatic hydrocarbons acids, alcohols, esters, ethers, ketones, sugars, alkanes and alkenes.
  • VOCs light organic compounds
  • a gas chromatograph / mass spectrometer may be used if needed for higher degrees of precision. It should be noted that the treatment or“washing” process does not have to use water as a base solvent. Other known solvents or other liquids can be used and targeted toward the removal of or reaction with specific compounds resident in the biochar to be treated.
  • the percent water, total organic compounds, total light organic compounds (volatiles or VOC) and total heavy organic compounds, as referenced in this application as contained in a biochar particle or particles in a sample may all be measured by thermogravimetric analysis.
  • Thermogravimetric analysis is performed by a Hitachi STA 7200 analyzer or similar piece of equipment under nitrogen flow at the rate of 110 mL/min.
  • the biochar samples are heated for predetermined periods of time, e.g., 20 minutes, at a variety of temperatures between 100 and 950 oC.
  • the sample weights are measured at the end of each dwell step and at the beginning and at the end of the experiment.
  • Thermogravimetric analysis of a given sample indicating percentage water in a sample is determined by % mass loss measured between standard temperature and 150 degrees C.
  • Thermogravimetric analysis of a given sample indicating percentage of residual organic compounds is measured by percentage mass loss sustained between 150 degrees C and 950 degrees C.
  • Thermogravimetric analysis of a given sample indicating percentage of light organic compounds (volatiles) is measured by percentage mass loss sustained between 150 degrees C and 550 degrees C.
  • Thermogravimetric analysis of a given sample indicating percentage of heavy organic compounds is measured by percentage mass loss sustained between 550 degrees C and 950 degrees C.
  • Figure 13 is an example of a Thermogravimetric Analysis (TGA) plot outlining the above explanation and the measure of water, light organics and heavy organics.
  • Dioxins may also be removed through the treatment processes of the present invention. Dioxins are released from combustion processes and thus are often found in raw biochar. Since some dioxins may be carcinogenic even at low levels of exposure over extended periods of time, the FDA views dioxins as a contaminant and has no tolerances or administrative levels in place for dioxins in animal feed. Dioxins in animal feed can cause health problems in the animals themselves. Additionally the dioxins may accumulate in the fat of food-producing animals and thus consumption of animal derived foods (e.g. meat, eggs, milk) could be a major route of human exposure to dioxins. Thus, if biochar is used in animal applications, where the animals ingest the biochar, the ability to remove dioxins from the raw biochar prior to use is of particular significance.
  • animal derived foods e.g. meat, eggs, milk
  • the biochar may, in accordance with one implementation of invention, be washed with water by applying a pressure differential or a vacuum on the biochar, ranging from approximately 5-30” Hg for a period of less than 10 minutes.
  • Results have proven to remove dioxins from raw biochar by applying the treatment process of the present invention.
  • samples of both raw biochar and treated biochar, derived from coconut and treated within the parameters set forth above were sent out for testing. The results revealed that the dioxins in the raw biochar were removed through treatment as the dioxins detected in the raw biochar sample were not detected in the treated biochar sample.
  • a treated biochar sample has greater than 50% by volume of its porosity in macropores (pores greater than 300 nanometers). Further, results indicate that greater than 75% of pores in treated biochar are below 50,000 nanometers. Also, results indicate that greater than 50% by volume of treated biochar porosity are pores in the range of 500 nanometers and 100,000 nanometers. Bacterial sizes are typically 500 nanometers to several thousand nanometers. Bacteria and other microbes have been observed to fit and colonize in the pores of treated biochar, thus supporting the pore size test results.
  • Macropore volume is determined by mercury porosimetry, which measures the meso and/or macro porosity by applying pressure to a sample immersed in mercury at a pressure calibrated for the minimum pore diameter to be measured (for macroporosity this is 300 nanometers). This method can be used to measure pores in the range of 3 nm to 360,000 nm. Total volume of pores per volumetric unit of substance is measured using gas expansion method.
  • FIG 14 is a chart 1400 showing the impact of treatment on pores sizes of biochar derived from coconut.
  • the majority of the coconut based biochar pores are less than 10 microns. Many are less than 1 micron.
  • Vacuum processing of the biochar results in small reduction of 10 to 50 micron pores, with increase of smaller pores on vacuum processing.
  • the mercury porosimetry results of the raw biochar are represented by 1402 (first column in the group of three).
  • the vacuum treated biochar is represented by 1404 (second column in the group of three) and the surfactant treated biochar is 1406 (third column in the group of three).
  • FIG 15 is a chart 1500 showing the impact of treatment on pores sizes of biochar derived from pine.
  • the majority of the pine based biochar pores are 1 to 50 microns, which is a good range for micro-biologicals.
  • Vacuum processing results in significant reduction of the 10 to 50 micron pores, with an increase of smallest and largest pores.
  • the mercury porosimetry results of the raw biochar are represented by 1502 (first column in the group of three).
  • the vacuum treated biochar is represented by 1504 (second column in the group of three) and the surfactant treated biochar is 3006 (third column in the group of three).
  • the electrical conductivity (EC) of a solid material-water mixture indicates the amount of salts present in the solid material. Salts are essential for plant growth.
  • the EC measurement detects the amount of cations or anions in solution; the greater the amount of ions, the greater the EC.
  • the ions generally associated with salinity are Ca 2+ , Mg 2+ , K + , Na + , H + , NO3-, SO4 2- , Cl-, HCO3-, OH- . Electrical conductivity testing of biochar was done following the method outlined in the USDA’s Soil Quality Test Kit Guide and using a conventional EC meter.
  • the biochar sample is mixed with DI water in a 1:1 biochar to water ratio on a volume basis. After thorough mixing, the EC (dS/m) is measured while the biochar particles are still suspended in solution. Treatment, as outlined in this disclosure can be used to adjust the ions in the char. Testing of treated biochar shows its EC is generally greater than 0.2 dS/m and sometimes greater than 0.5 dS/m.
  • CEC cation exchange capacity
  • Indirect methods for CEC calculation involves the estimation of extracted Ca 2 + , Mg2 + , K + , and Na + in a standard soil test using Mehlich 3 and accounting for the exchangeable acidity (sum of H + , Al3 + , Mn2 + , and Fe2 + ) if the pH is below 6.0 (see Mehlich, A.1984, Mehlich- 3 soil test extractant: a modification of Mehlich-2 extractant, Commun. Soil Sci. Plant Anal. 15(12): 1409-1416).
  • treated biochars When treated using the above methods, including but not limited by washing under a vacuum, treated biochars generally have a CEC greater than 5 millieq/l and some even have a CEC greater than 25 (millieq/l). To some extent, treatment can be used to adjust the CEC of a char. [0164] 7. Anion Exchange Capacity
  • anion exchange capacity may be calculated directly or indirectly- saturated paste extraction of exchangeable anions, Cl-, NO 3 -, SO 4 2- , and PO4 3- to calculate anion sum or the use of potassium bromide to saturate anions sites at different pHs and repeated washings with calcium chloride and final measurement of bromide (see Rhoades, J.D. 1982, Soluble salts, p. 167-179.
  • AEC anion exchange capacity
  • treated biochars When treated using the above methods, including but not limited by washing under a vacuum, treated biochars generally have an AEC greater than 5 millieq/l and some even have an AEC greater than 20 (millieq/l). To some extent, treatment can be used to adjust the CEC of a char.
  • the ability to control the hydrophilicity of the pores provides the ability to load the biochar particles with larger volumes of inoculant. The more hydrophilic the more the biochars can accept inoculant or infiltrate. Tests show that biochar treated in accordance with the above processes, using either vacuum or surfactant treatment processes increase the hydrophilicity of raw biochar. Two tests may be used to test the hydrophobicity/hydrophilicity of biochar: (i) the Molarity of Ethanol Drop (“MED”) Test; and (ii) the Infiltrometer Test.
  • MED Molarity of Ethanol Drop
  • the MED test was originally developed by Doerr in 1998 and later modified by other researchers for various materials.
  • the MED test is a timed penetration test that is noted to work well with biochar soil mixtures. For 100% biochar, penetration time of different mixtures of ethanol/water are noted to work better. Ethanol/Water mixtures verses surface tension dynes were correlated to determine whether treated biochar has increased hydrophilicity over raw biochar. Seven mixtures of ethanol and deionized water were used with a sorption time of 3 seconds on the biochar.
  • the biochar (“material/substrate”) is placed in convenient open container prepared for testing. Typically, materials to be tested are dried 110o C overnight and cooled to room temperature. The test starts with a deionized water solution having no ethanol. Multiple drips of the solution are then laid onto the substrate surface from low height. If drops soak in less than 3 seconds, test records substrate as“0”. If drops take longer than 3 seconds or don’t soak in, go to test solution 1. Then, using test solution 1, multiple drops from dropper are laid onto the surface from low height. If drops soak into the substrate in less than 3 seconds, test records material as“1”. If drops take longer than 3 seconds, or don’t soak in, go to test solution 2.
  • test solution 2 multiple drops from dropper laid onto the surface from low height. If drops soak into the substrate in less than 3 seconds, test records material as“2”. If drops take longer than 3 seconds, or don’t soak in, go to test solution 3. Then, using test solution 3, multiple drops from dropper laid onto the surface from low height. If drops soak into the substrate in less than 3 seconds, test records material as“3”. If drops take longer than 3 seconds, or don’t soak in, go to solution 4.
  • Example test results using the MED test method is illustrated below.
  • the data is then processed to determine the results.
  • the data is processed by the input of the volume levels and time to the corresponding volume column.
  • the following equation is used to calculate the hydrophobicity index of R
  • Figure 16 illustrates one example of the results of a hydrophobicity test performed on raw biochar, vacuum treated biochar and surfactant treated biochar. As illustrated, both the vacuum treated and surfactant treated biochar are more hydrophilic than the raw biochar based upon the lower Index rating. In accordance with the test data in Figure 16, the hydrophobicity of raw biochar was reduced 23% by vacuum processing and 46% by surfactant addition.
  • the biochar can also be infused with soil enhancing agents.
  • infusing liquid into the pore structure through the application of positive or negative pressure and/or a surfactant, alone or in combination, provides the ability to impregnate the macropores of the biochar with soil enhancing solutions and solids.
  • the soil enhancing agent may include, but not be limited to, any of the following: water, water solutions of salts, inorganic and organic liquids of different polarities, liquid organic compounds or combinations of organic compounds and solvents, mineral and organic oils, slurries and suspensions, supercritical liquids, fertilizers, plant growth promoting rhizobacteria, free-living and nodule-forming nitrogen fixing bacteria, organic decomposers, nitrifying bacteria, phosphate solubilizing bacteria, biocontrol agents, bioremediation agents, saprotrophic fungi, ectomycorrhizae and endomycorrhizae, among others.
  • the pore surface properties of the biochar can be enhanced.
  • Such treatment processes may also permit subsequent processing, may modify the pore surface to provide predetermined properties to the biochar, and/or provide combinations and variations of these effects.
  • it may be desirable or otherwise advantageous to coat substantially all, or all of the biochar macropore and mesopore surfaces with a surface modifying agent or treatment to provide a predetermined feature to the biochar, e.g., surface charge and charge density, surface species and distribution, targeted nutrient addition, magnetic modifications, root growth facilitator, and water absorptivity and water retention properties.
  • additives infused within the pores of the biochar provide a time release effect or steady flow of some beneficial substances to the root zones of the plants and also can improve and provide a more beneficial environment for microbes which may reside or take up residence within the pores of the biochar.
  • additive infused biochars placed in the soil prior to or after planting can dramatically reduce the need for high frequency application of additives, minimize losses caused by leaching and runoff and/or reduce or eliminate the need for controlled release fertilizers.
  • additives infused within the pores of biochar can be exceptionally beneficial in animal feed applications by providing an effective delivery mechanism for beneficial nutrients, pharmaceuticals, enzymes, microbes, or other substances.
  • a sensory enhancer such as a smell or flavor (e.g. salt), could be infused to increase the animal’s desire to ingest said biochar.
  • “infusion” of a liquid or liquid solution into the pores of the biochar means the introduction of the liquid or liquid solution into the pores of the biochar by a means other than solely contacting the liquid or solution with the biochar, e.g., submersion.
  • the infusion process includes a mechanical, chemical or physical process that facilitates or assist with the penetration of liquid or solution into the pores of the biochar, which process may include, but not be limited to, positive and negative pressure changes, such as vacuum infusion, surfactant infusion, or infusion by movement of the liquid and/or biochar (e.g., centrifugal force and/or ultrasonic waves) or other method that facilitates, assists, forces or accelerates the liquid or solution into the pores of the biochar.
  • positive and negative pressure changes such as vacuum infusion, surfactant infusion, or infusion by movement of the liquid and/or biochar (e.g., centrifugal force and/or ultrasonic waves) or other method that facilitates, assists, forces or accelerates the liquid or solution into the pores of the biochar.
  • FIG. 17 is a flow diagram 1700 of one example of a method for infusing biochar with an additive.
  • the biochar may first be washed or treated at step 1702, the wash may adjust the pH of the biochar, as described in more detail above, or may be used to remove elemental ash and other harmful organics that may be unsuitable for the desired infused fertilizer or animal feed.
  • the moisture content of the biochar may then be adjusted by drying the biochar at step 1704, also as described in further detail above, prior to infusion of the additive or inoculant at step 1706.
  • the infusion process may be performed with or without any washing, prior pH adjustment or moisture content adjustment.
  • the infusion process may be performed with the wash and/or the moisture adjustment step. All the processes may be completed alone or in the conjunction with one or more of the others.
  • the pores of the biochar may be filled by 25%, up to 100%, with an additive solution, as compared to 1-20% when the biochar is only submerged in the solution or washed with the solution for a period of less than twelve hours. Higher percentages may be achieved by washing and/or drying the pores of the biochar prior to infusion.
  • FIG. 18 is a chart illustrating the results of the experiment.
  • the lower graph 1802 of the chart which shows the results of soaking over time, shows a Wt.% of water of approximately 52%.
  • the upper graph 1804 of the chart which shows the results of vacuum impregnation over time, shows a Wt.% of water of approximately 72%.
  • Figures 19a and 19b show two charts that further illustrate that the total water and/or any other liquid content in processed biochar can be significantly increased using vacuum impregnation instead of soaking.
  • Figure 196a compares the mL of total water or other liquid by retained by 1 mL of treated pine biochar.
  • the graph 1902 shows that approximately .17 mL of water or other liquid are retained through soaking, while the graph 1904 shows that approximately .42 mL of water or other liquid are retained as a result of vacuum impregnation.
  • Figure 19b shows that the retained water of pine biochar subjected to soaking consists entirely of surface and interstitial water 1906, while the retained water of pine biochar subjected to vacuum impregnation consists not only of surface and interstitial water 1908a, but also water impregnated in the pores of the biochar 1908b.
  • the percentage of water retained in the pores of pine derived biochar was measured to determine the difference in retained water in the pores of the biochar (i) soaked in water, and (ii) mixed with water subjected to a partial vacuum.
  • 250 mL of raw biochar was mixed with 500 mL water in a beaker.
  • aliquots of the suspended solid were taken, drained on a paper towel and analyzed for moisture content.
  • 250 mL of raw biochar was mixed with 500 mL water in a vacuum flask. The flask was connected to a vacuum pump and negative pressure of 15” has been applied, aliquots of the treated solid were taken, drained on a paper towel and analyzed for moisture content.
  • the total retained water amounts were measured for each sample.
  • the moisture content of biochar remains virtually constant for the entire duration of the experiment, 52 wt.% (i.e. 1 g of “soaked biochar” contains 0.52 g water and 0.48 g“dry biochar”).
  • the volume of the 0.48 g“dry biochar” is 3.00 mL (i.e.3 mL dry biochar can“soak” and retain 0.52 mL water, or 1 mL dry biochar can retain 0.17 mL water (sorbed on the surface and into the pores)).
  • the moisture content of the biochar remains virtually constant for the entire duration of the experiment, 72 wt.%, (i.e. 1 g of vacuum impregnated biochar contains 0.72 g water and 0.28 g“dry biochar”).
  • the volume of the 0.28 g“dry biochar” is 1.75 mL (i.e.1.75 mL dry biochar under vacuum can“absorb” and retain 0.72 mL water, or 1 mL dry biochar can retain 0.41 mL water (sorbed on the surface and into the pores)).
  • the particles could be modeled and then tested to determine if soaking and/or treating the biochar could infuse enough water to make the density of the biochar greater than that of water.
  • the dry biochar would float and, if enough water infused into the pores, the soaked or treated biochar would sink. Knowing the density of water and the density of the biochar, calculations were done to determine the percentage of pores that needed to be filled with water to make the biochar sink. In this specific experiment, these calculations determined that more than 24% of the pore volume would need to be filled with water for the biochar to sink.
  • the two processed biochars, soaked and vacuum treated were then immersed in water after 1 hour of said processing. The results of the experiment showed that the vast majority of the soaked biochar floated and remained floating after 3 weeks, while the vast majority of the vacuum treated biochar sank and remained at the bottom of the water column after 3 weeks.
  • the biochar particles can be idealized to estimate how much more water is in the pores from the vacuum treatment versus soaking. Since the external surface of the materials are the same, it was assumed that the samples retain about the same amount of water on the surface. Then the most conservative assumption was made using the boundary condition for particles to be just neutral, i.e. water into pores equal 24%, the water distribution is estimated as follows:
  • the pores may be substantially filled or completely filled with additives to provide enhanced performance features to the biochar, such as increased plant growth, improved rumen quality, nutrient delivery, water retention, nutrient retention, disadvantageous species control, e.g., weeds, disease causing bacteria, insects, volunteer crops, etc.
  • additives include, but are not limited to, soil or animal health enhancing solutions and solids.
  • the additive may be a soil enhancing agent that include, but is not be limited to, any of the following: water, water solutions of salts, inorganic and organic liquids of different polarities, liquid organic compounds or combinations of organic compounds and solvents, mineral and organic oils, slurries and suspensions, supercritical liquids, fertilizers, PGPB (including plant growth promoting rhizobacteria, free-living and nodule-forming nitrogen fixing bacteria, organic decomposers, nitrifying bacteria, and phosphate solubilizing bacteria), biocontrol agents, bioremediation agents, saprotrophic fungi, ectomycorrhizae and endomycorrhizae, among others.
  • PGPB including plant growth promoting rhizobacteria, free-living and nodule-forming nitrogen fixing bacteria, organic decomposers, nitrifying bacteria, and phosphate solubilizing bacteria
  • Fertilizers that may be infused into the biochar include, but are not limited to, the following sources of nitrogen, phosphorous, and potassium: urea, ammonium nitrate, calcium nitrate, ammonium sulfate, monoammonium phosphate, ammonium polyphosphate, potassium sulfate, or potassium chloride.
  • bio pesticides such as: bio pesticides; herbicides; insecticides; nematicides; plant hormones; plant pheromones; organic or inorganic fungicides; algicides; antifouling agents; antimicrobials; attractants; biocides, disinfectants and sanitizers; miticides; microbial pesticides; molluscicides; bacteriacides; fumigants; ovicides; repellents; rodenticides, defoliants, desiccants; insect growth regulators; plant growth regulators; beneficial microbes; and, microbial nutrients or secondary signal activators, that may also be added to the biochar in a similar manner as a fertilizer.
  • beneficial macro- and micro- nutrients such as, calcium, magnesium, sulfur, boron, zinc, iron, manganese, molybdenum, copper and chloride may also be infused into the biochar in the form of a water solution or other solvent
  • Examples of compounds, in addition to fertilizer, that may be infused into the pores of the biochar to promote plant health include, but are not limited to: phytohormones, such as, abscisic acid (ABA), auxins, cytokinins, gibberellins, brassinosteroides, salicylic acid, jasmonates, planet peptide hormones, polyamines, karrikins, strigolactones; 2,1,3- Benzothiadiazole (BTH), an inducer of systemic acquired resistance that confers broad spectrum disease resistance (including soil borne pathogens); signaling agents similar to BTH in mechanism or structure that protects against a broad range or specific plant pathogens; EPSPS inhibitors; synthetic auxins; photosystem I inhibitors photosystem II inhibitors; and HPPD inhibitors.
  • phytohormones such as, abscisic acid (ABA), auxins, cytokinins, gibberellins, brassinosteroides, salicylic acid, jasmonates, planet peptide
  • a 1000 ppm NO 3 - N fertilizer solution is infused into the pores of the biochar.
  • the method to infuse biochar with the fertilizer solution may be accomplished generally by placing the biochar in a vacuum infiltration tank or other sealable rotating vessel, chamber or tank.
  • a vacuum may be applied to the biochar and then the solution may be introduced into the tank.
  • the solution and biochar may both be introduced into the tank and, once introduced, a vacuum is applied.
  • the amount of solution to introduce into the tank necessary to fill the pore of the biochar can be determined. When infused in this manner, significantly more nutrients can be held in a given quantity of biochar versus direct contact of the biochar with the nutrients alone.
  • the biochar and additive solution may be added to a tank along with 0.01 - 20% of surfactant, but more preferably 1-5% of surfactant by volume of fertilizer solution.
  • the surfactant or detergent aids in the penetration of the wash solution into the pores of the biochar.
  • the same or similar equipment used in the vacuum infiltration process can be used in the surfactant treatment process.
  • the vacuum infiltration tank or any other rotating vessel, chamber or tank can be used. Again, while it is not necessary to apply a vacuum, a vacuum may be applied or the pressure in the vessel may be changed.
  • the surfactant can be added with or without heat or cooling either of the infiltrate, the biochar, the vessel itself, or any combination of the three.
  • the utility of infusing the biochar with fertilizer is that the pores in biochar create a protective“medium” for carrying the nutrients to the soil that provides a more constant supply of available nutrients to the soil and plants and continues to act beneficially, potentially sorbing more nutrients or nutrients in solution even after introduction to the soil.
  • By infusing the nutrients in the pores of the biochar immediate oversaturation of the soil with the nutrients is prevented and a time released effect is provided.
  • This effect is illustrated in connection with Figures 21 and 22 below.
  • biochars having pores infused with additives, using the infusion methods described above have been shown to increase nutrient retention, increase crop yields and provide a steadier flow of fertilizer to the root zones of the plants.
  • Figure 21 is a chart showing improved mass yield in lettuce with fertilizer infused biochar using vacuum impregnation.
  • Figure 21 compares the mass yield results of lettuce grown in different environments.
  • One set of data measurements represents lettuce grown in soil over a certain set time period with certain, predetermined amounts of fertilizer infused into the biochar.
  • a second set of data represents lettuce grown in soil over a certain set period of time with the same amount of unimpregnated biochar added at the beginning of the trial and certain predetermined amounts of NPK solution added to the soil over time. Growth comparisons were made between the same amount of fertilizer solution infused into the biochar as added directly to the soil, using the same watering schedule.
  • test results demonstrated a 15% yield increase in growth when infusing approximately 750 mg/pot of NPK into the biochar than when applying it directly to the soil.
  • same mass yield of lettuce is achieved at 400 mg NPK/pot with infused biochar than at 750 mg/pot when adding the fertilizer solution directly to the soil.
  • FIG 22 is a chart illustrating the concentration of nitrate (N) found in distilled water after washing differentially treated biochar.
  • N nitrate
  • two biochar samples 500 ml each
  • 1000 ppm NO3- N fertilizer solution were washed with distilled water.
  • the resulting wash was then tested for the presence of nitrate (N), measured in ppm.
  • the biochar was submerged in and mixed with the nutrient solution.
  • the biochar was mixed or washed with a nutrient solution augmented with 1% surfactant by volume (i.e., 1 ml of surfactant per 100 ml of fertilizer solution) in a tumbler.
  • the biochar was not dried completely before infusion with the NO 3 - N fertilizer solution, but used as received with a moisture content of approximately 10-15%.
  • the biochar was mixed with solution and/or surfactant (in the case of a second sample) with a bench scale tumbler, rotating the drum for four (4) minutes without vacuum.
  • the results demonstrate that the biochar treated with the 1% surfactant increases the efficiency of infiltrating nitrate fertilizer into biochar and then demonstrates the release of the nutrient over time. To yield the above data, the test was repeated six times for each treatment sample, with 10 washes for each sample per repeat test.
  • the additive may include, but not be limited to, water, water solutions of salts, inorganic and organic liquids of different polarities, liquid organic compounds or combinations of organic compounds and solvents, vitamins, supplements and/or medications, nutrients, minerals, oils, amino acids, fatty acids, supercritical liquids, growth promotants, proteins and enzymes, phytogenics, carbohydrates, antimicrobial additives and sensory additives (e.g. flavor enhancers salt or sweeteners or smell enhancers), among others, to provide nutrition, promote the overall health of the animal, and increase the animal’s desire to ingest said biochar. Vitamins, supplements, minerals, nutritional and/or medications may be used to prevent, treat or cure animal illnesses and diseases and/or control the nutritional value of the animals overall diet.
  • vitamins, supplements and/or medications may be used to prevent, treat or cure animal illnesses and diseases and/or control the nutritional value of the animals overall diet.
  • dietary supplementation with certain nutrients can regulate gene expression and key metabolic pathways to improve fertility, pregnancy outcome, immune function, neonatal survival and growth, feed efficiency, and meat quality.
  • nutrients e.g., arginine, glutamine, zinc, and conjugated linoleic acid
  • Such additives in the biochar can help provide the proper balance of protein, energy, vitamins and nutritionally important minerals in animal diets.
  • the additive may include, for example, coccidiostats and/or histomonostats, which are both shown to control the health of the poultry.
  • the present invention can be used to help correct deficiencies in basal diets (e.g., corn- and soybean meal-based diets for swine; milk replacers for calves and lambs; and available forage for ruminants).
  • additive infused biochar is a case when the beneficial inoculant contains microbes (fungi and/or PGPB) or microbial spores. These beneficial microbes interact with and enhance the performance of the plants’ root systems when the so processed biochar is mixed with the soil in the root zone.
  • microbes fungi and/or PGPB
  • microbial spores fungi and/or PGPB
  • P GP B include, for example, plant growth promoting rhizobacteria, free-living and nodule-forming nitrogen fixing bacteria, organic decomposers, nitrifying bacteria, MSM, biocontrol agents, bioremediation agents, archea, actinomycetes, thermophilic bacteria, purple sulfur bacteria, cyanobacteria, and combinations and variations of these.
  • Beneficial fungi include, for example, saprotrophic fungi, ectomycorrhizae, endomycorrhizae, ericoid mycorrhizae, and combinations and variations of these.
  • treated biochar can have a microbial community in its pores (macro-, meso-, and combinations and variations of these), on its pore surfaces, embedded in it, located on its surface, and combinations and variations of these.
  • the microbial community can have several different types, e.g., species, of biologics, such as different types of bacteria or fungi, or it may have only a single type.
  • a primary purpose in agricultural applications, among many purposes, in selecting the microbial population is looking toward a population that will initiate a healthy soil, e.g., one that is beneficial for, enhances or otherwise advance the desired growth of plants under particular environmental conditions. .
  • a primary purpose, among many purposes, in selecting the microbial population in animal related applications is looking toward a population that will promote animal health either directly or through interactions with other microbes in the animals digestive tract.
  • These types of beneficial microbes are essential to a functional gastrointestinal tract and immune system in many types of animals, serving many functional roles, including degradation of ingesta, pathogen exclusion, production of short- chain fatty acids, compound detoxification, vitamin supplementation, and immunodevelopment.
  • beneficial bacteria include Lactobacillus acidophilus LA1 (which decreases adhesion of diarrheagenic Escherichia coli to Caco-2 cells by 85% and prevents invasion of the same cells by E.
  • biochar may be impregnated with probiotic bacteria to treat diseases in farm- raised fish.
  • Infectious diseases pose one of the most significant threats to successful aquaculture.
  • the maintenance of large numbers of fish crowded together in a small area provides an environment conducive for the development and spread of infectious diseases.
  • fish are stressed and more susceptible to disease.
  • the water environment, and limited water flow facilitates the spread of pathogens within crowded populations.
  • One alternative disease control relies on the use of probiotic bacteria as microbial control agents.
  • Another implementation of the invention therefore involves the impregnation of biochar for consumption by aquatic animals as a treatment or preventative for disease.
  • biochar may be infused with bacteria which prove helpful in methane reduction.
  • bacteria which are able to metabolize methane as a source of carbon and energy.
  • Bacteria which metabolize methane are useful in two regards– they can reduce the environmental methane emissions from the rumen and they (the bacteria) also serve as nutrition for the animal itself, leading to increased weight gain. Infusing biocarbon with microbes such as these can lead to methane reduction in cattle applications that exceeds the methane reduction of solely untreated biochar itself.
  • Treatment can also impact the hydrophobicity of raw biochar (reduce it) which makes the biochar not only more suitable to house microbes, but also more able to associate with and interact with water and water soluble nutrients in the soil.
  • Additive infused biochar may be mixed with the animals regular feeds or may be included within a salt or mineral block and made available for animals to self-feed or self-administer the additives.
  • Methods for integrating a microbial community with a biochar particle may include, but are not be limited to the following: while under vacuum, pulling the microbial solution through a treated biochar bed that is resting on a membrane filter; spraying a microbial solution on top of a treated biochar bed; lyophilizing a microbial solution and then blending said freeze dried solution with the treated biochar; again infusing, as defined previously, the treated biochar with a microbial solution; adding treated biochar to a growth medium, inoculating with the microbe, and incubating to allow the microbe to grow in said biochar containing medium; infusing, as defined previously, the biochar with a food source and then introducing the substrate infused biochar to a microbe and incubating to allow the microbes to grow; blending commercially available strains in dry form with treated biochar; adding the treated biochar to a microbial solution and then centrifuging at a high speed, potentially with a density gradient in order to promote the
  • the treated biochar may need to be sterilized prior to these methods for integrating a microbial community.
  • the sterilization can be done with standard methods including but not limited to thermal, radiation, or chemical.
  • the sterilization method does not need to eliminate all microbial life. It can be a mild sterilization to reduce total populations or a method to target reduction or elimination of specific microbes.
  • the biochar can be handled via sterile or sanitary methods from pyrolysis through treatments including microbial community integration to limit contamination particularly of competing microbe communities or pathogenic microbes. All or parts of the above manners and methods may be combined to create greater efficacy.
  • those skilled in the art will recognize that there may be additional manners or methods of infusing biochars with microbials, including those created by the combination of one or more of the manners and methods listed above, without departing from the scope of the present invention.
  • PLFA Phospholipid-derived fatty acids
  • Biological cell membranes are composed of a phospholipid bilayer with fatty acid side chains that are unique to certain families of organisms.
  • PLFA analysis extracts the fatty acid side chains of phospholipid bilayers and measures the quantity of these biomarkers using GC-MS.
  • An estimate of the microbial community population can thus be determined through PLFA analysis.
  • the microbial activity may also be inferred through PLFA analysis by monitoring the transformation of specific fatty acids. N ext generation sequencing of the conserved ribosomal RNA regions of the bacteria and fungi may allow for more direct and accurate measurements than PLFA.
  • Treated biochars can have a mixture of bacteria and fungi, or other microbes.
  • a preferred functional biochar can have a preferred range for bacterial population of from about 50-5000000 micrograms/g biochar; and for fungi, from about 5 to 500000 micrograms/g biochar.
  • the impregnated populations of examples of the present treated biochars are stable over substantially longer periods of time, e.g., at least an 8 week period and in some cases 1 year or more as measured by PLFA.
  • the impregnation of the biochar with a microbial population provides for extended life of the microbes by at least 5x, 10x, or more over simple contact or immersion.
  • Figure 23 shows the total fungi/bacteria ratio for two biochars derived from different biochar starting materials, e.g., feedstocks. Each biochar was loaded with different levels of moisture, and the total fungi/bacteria ratio was monitored during the first week. Biochar A 2301 showed a constant total fungi/bacteria ratio of 0.08 across moisture levels ranging from 15% to 40%, while Biochar B 2302 showed a constant total fungi/bacteria ratio of 0.50 for moisture levels ranging from 30% to 40%.
  • a fungi/bacteria ratio between 0.05 and 0.60 is an effective prescription for a stable biochar composition.
  • This composition allows a commercially viable product, which has sufficient shelf life that it can be delivered to storage houses waiting for the proper planting window.
  • the stable shelf life of an example of a biochar product having a microbial population is the period of time over which the product can be stored in a warehouse, e.g., dry environment, temperature between 40°F- 90°F, with a less than 50% decrease in microbial population.
  • Biochar having an open pore structure, e.g., more interconnected pores, promotes more bacteria formation; while closed pores, e.g., relatively non-connected nature of the pores, tends to promote fungi formation.
  • Biochars with differing microbial communities may be beneficial for specific applications in commercial agriculture. Thus, custom or tailored loading of the microbial population may be a desired implementation of the present invention.
  • Biochar A 2401 shows that it has a greater population of, e.g., is inhabited by, more gram negative, gram positive and actinomycetes than Biochar B 2402.
  • Biochar A would be more applicable for use with certain agricultural crops in which P GP B species in the actinomycetes, gram (-) pseudomonas, and bacillus groups are used for nutrient utilization and uptake.
  • Many vegetable and short cycle row crops such as tomatoes, lettuce, and celery form mutualistic relationships with bacteria that lead to the formation of biofilms on root hairs that function not only in nutrient uptake but also in plant pathogen resistance.
  • Biochar A The presence of biofilms in Biochar A would consequently promote bacterial colonization of plant root hairs as they encounter the biochar in the soil.
  • biochars with greater fungal development may be better suited for perennial crops such as grapes, almonds, blueberries, and strawberries in which symbiotic relationships with arbuscular mycorrhizal fungi (AMF) are favored over PGPRs.
  • AMF arbuscular mycorrhizal fungi
  • the presence of high concentrations of AMF spores in biochars can therefore rapidly promote fungal colonization of plant root hairs leading to extensive mycelial development. Increased plant root associations with mycelial filaments would consequently increase nutrient and water uptake.
  • bacteria communicate via the distribution of signaling molecules which trigger a variety of behaviors like swarming (rapid surface colonization), nodulation (nitrogen fixation), and virulence.
  • Biochars can bind signaling molecules and in particular it is believed can bind a major signaling molecule to their surface. This binding ability can be dependent upon many factors including on the pyrolysis temperature. This dependency on pyrolysis temperature and other factors can be overcome, mitigated, by the use of examples of the present vacuum infiltration techniques. For example, a signaling molecule that is involved in quorum sensing- multicellular-like cross-talk found in prokaryotes can be bound to the surface of biochars.
  • Concentration of biochars required to bind the signaling molecule decreased as the surface area of biochars increased.
  • These signaling molecules may be added to the surface of a biochar and may be used to manipulate the behavior of the bacteria.
  • An example of such a use would be to bind the molecules which inhibit cell-to-cell communication and could be useful in hindering plant pathogens; using techniques in the present invention signaling molecules may be added to the surface of a biochar to engineer specific responses from various naturally occurring bacteria.
  • treated biochar may bind organic toxins as they pass through an animal’s digestive system, for example, when cattle are suffering from botulism or diarrhea.
  • biochars of the present inventions are the ability to provide an environment where bacteria communities can flourish. Bacterial communities can shift their morphology to increase nutritional access and decrease predation. One such modification is that the bacteria may attach to surfaces, such as those found in biochar, in a densely compacted community. In this compacted form they may form an extracellular polymeric substance (EPS) matrix called a biofilm. These communities can contain a few hundred different species which find shelter under the protective EPS coating from predatory protozoa, pathogens, contaminants, and other environmental stressors. Thus, examples of biochars produced in accordance with the vacuum infiltration methods may be used as carriers for established biofilms; and thus biochars with such films many used in agricultural settings.
  • EPS extracellular polymeric substance
  • additive infused biochar may be produced for use for consumption by humans.
  • Biochar may be infused in the same manner as described above with nutrients (such as carbohydrates, minerals, proteins, lipids), vitamins, drugs and/or other supplements (such as enzymes or hormones, to name a few), or a combination of any of the foregoing, for consumption by humans .
  • nutrients such as carbohydrates, minerals, proteins, lipids
  • vitamins, drugs and/or other supplements such as enzymes or hormones, to name a few
  • Coloring, flavor agents and/or coating may also be infused into the pores of the biochar or applied to the surface. The foregoing may be included to enhance the performance of the substance in the digestive tract or to ease or facilitate the ingestion of the biochar.
  • PGPB includes, for example, plant growth promoting rhizobacteria, free-living and nodule-forming nitrogen fixing bacteria, organic decomposers, nitrifying bacteria, phosphate solubilizing bacteria, biocontrol agents, bioremediation agents, archea, actinomycetes, thermophilic bacteria, purple sulfur bacteria, cyanobacteria, and combinations and variations of these.
  • PGPB may promote plant growth either by direct stimulation such as iron chelation, phosphate solubilization, nitrogen fixation and phytohormone production or by indirect stimulation, such as suppression of plant pathogens and induction of resistance in host plants against pathogens.
  • beneficial bacteria produce enzymes (including chitinases, cellulases, -1,3 glucanases, proteases, and lipases) that can lyse a portion of the cell walls of many pathogenic fungi.
  • enzymes including chitinases, cellulases, -1,3 glucanases, proteases, and lipases
  • PGPB that synthesize one or more of these enzymes have been found to have biocontrol activity against a range of pathogenic fungi including Botrytis cinerea, Sclerotium rolfsii, Fusarium oxysporum, Phytophthora spp., Rhizoctonia solani, Pythium ultimum.
  • the method developed for determining this CO2 production as an indicator of bacterial growth consists of the following.
  • the substrate e.g., biochar or peat
  • a bacterial stock solution is then created.
  • Tryptic Soy Broth was solidified with agar at 1.5% w/v in petri plates to isolate the gram negative non- pathogenic organism Escherichia coli ATCC 51813 (15h growth at 37°C).
  • an isolated colony is captured with an inoculating loop and suspend in 10 ml sterile buffer (phosphate buffer saline or equivalent) to create the bacterial stock solution. Lactose containing assays are then used.
  • test tubes that contain 13 ml of either Lauryl Tryptose Broth (LTB) or Brilliant Green Broth (BGB) that also contain a Durham tube were used.
  • a negative control is generated by adding 10 ⁇ L of sterile buffer to triplicate sets of LTB and BGB tubes.
  • a positive control is generated by adding 10 ⁇ L of bacterial stock solution to triplicate sets of LTB and BGB tubes.
  • a negative substrate is generated by adding 1.25 ml ( ⁇ 1% v/v) of sterile substrate to triplicate sets of LTB and BGB tubes.
  • a positive substrate is generated by adding 1.25 ml ( ⁇ 1% v/v) of sterile substrate and 10 ⁇ L of bacterial stock solution to triplicate sets of LTB and BGB tubes.
  • FIG. 24 is an example of carbon dioxide production captured as a continuous gas bubble in BGB (left two tubes) and LTB (right two tubes) growth medium. The percent carbon dioxide production is then calculated by dividing the recorded bubble length by the total Durham tube length and multiplying by 100.
  • Actinovate products are biofungicides that protect against many common foliar and soil-borne diseases found in outdoor crops, greenhouses and nurseries.
  • the formulations are water-soluble.
  • Figure 27 illustrates the effects upon the growth of Streptomyces lidicus using conventional peat versus biochars.
  • an Actinovate powder was blended with peat, placed in an inoculated media and incubated at 25°C.
  • the photograph shows the distribution and density of white colonies after 3 days.
  • an Actinovate powder was blended with the treated biochar, placed in an inoculated media and incubated at 25°C.
  • the photograph also shows the distribution and density of white colonies after 3 days, the distribution and density of which are significantly greater than those achieved with peat.
  • Figure 28 further illustrates the improved growth of the Actinovate bacterium using biochar versus peat.
  • the left photograph shows only limited and restricted growth away from the peat carrier.
  • the right photograph shows abundant growth of the bacterium spread much farther out from the biochar carrier.
  • Mycorrhizal fungi including but not limited to Endomycorrhizae and Ectomycorrhizae, are known to be an important component of soil life. The mutualistic association between the fungi and the plant can be particularly helpful in improving plant survivability in nutrient-poor soils, plant resistance to diseases, e.g. microbial soil-borne pathogens, and plant resistance to contaminated soils, e.g. soils with high metal concentrations. Since mycorrhizal root systems significantly increase the absorbing area of plant roots, introducing mycorrhizal fungi may also reduce water and fertilizer requirements for plants.
  • inoculated biochar may be used to coat the seeds by, for example, using a starch binder on the seeds and then subjecting the seeds to inoculated biochar fines or powder.
  • Another method is by placing the mycorrhizae inoculum in the soil near the seeding or established plant but is more costly and has delayed response as the plants initial roots form without a mycorrhizal system. This is because the dormant mychorrhize are only activated when they come close enough to living roots which exude a signaling chemical. In addition, if the phosphorus levels are high in the soil, e.g. greater than 70 ppm, the dormant mycorrhizae will not be activated until the phosphorus levels are reduced. Thus applying inoculant with or near fertilizers with readily available phosphorus can impede the desired mycorrhizal fungi growth.
  • a third option is to dip plant roots into an inoculant solution prior to replanting, but this is costly as it is both labor and time intensive and only applicable for transplanting.
  • An ideal carrier for the mycorrhizae would have moisture, air, a neutral pH, a surface for the fungi to attach, and a space for the roots and fungi to meet.
  • a previously infused biochar created by the method disclosed above would be a better carrier than raw biochar alone.
  • the infused biochar could be physically mixed with a solid mycorrhizal fungi inoculant or sprayed with a liquid mycorrhizal inoculant prior to or during application at seeding or to established plants.
  • the infused biochar and mycorrhizal fungi inoculant could be combined to form starter cubes, similar to Organo-Cubes, rockwool, oasis cubes, and peat pots.
  • the infused biochar could be further improved upon by initially or further infusing the biochar with micronutrients for mycorrhizal fungi, for example but not limited to humic acid, molasses, or sugar.
  • the growth nutrient infused biochar would further expedite the colonization of the mycorrhizal fungi when physically combined with the inoculant and applied to seeds or plants.
  • Another improvement to the infused biochar would be to initially infusing or further infusing the biochar with the signaling molecules of mycorrhizal fungi.
  • the signaling molecule infused biochar would further expedite the colonization of the mycorrhizal fungi when physically combined with the inoculant and applied to seeds or plants, as it would bring the mycorrhizae out of dormancy quicker and thus establish the mycorrhizal root system quicker.
  • Another method for establishing and improving mycorrhizal fungi colonies would be by growing mycorrhizae into the infused biochar and then applying the mycorrhizal fungi inoculated biochar to seeds or plants. Similar to a sand culture (see“Buying and Applying Mycorrhizal Fungi,” by Lester, Donald, published by Maximum Yield USA, Sept. 2009, pg. 128 citing Ojala and Jarrell 1980 (http://jhbiotech.com/docs/Mycorrhizae-Article.pdf), which article is incorporated herein by reference), a bed of infused biochar is treated with a recycled inoculated nutrient solution by passing it through the bed multiple times.
  • the most important macro nutrients for healthy plant growth are nitrogen, phosphorus and potassium. Also needed are secondary macronutrients such as calcium, sulfur and magnesium, and trace minerals such as boron, chlorine, manganese, iron, zinc, copper, molybdenum and nickel. Among the macronutrients needed for animals are nitrogen, potassium, calcium, magnesium, phosphorus, sodium and chlorine; and micronutrients include copper, zinc, selenium and iodine.
  • Phosphorus is the second most important nutrient after nitrogen for healthy plant growth. While phosphorus is relatively abundant in most soils, its availability for plant uptake is restricted because of poor solubility and its fixation in soil. Poor availability or deficiency of phosphorus markedly reduces plant size and growth. Phosphorus accounts for about 0.2 - 0.8% of the plant dry weight.
  • phosphorus is usually added to soil as chemical fertilizer; however synthesis of chemical phosphorus fertilizer is a highly energy intensive process, and has long term impacts on the environment in terms of eutrophication, soil fertility depletion, and carbon footprint. Moreover, plants can use only a small amount of this phosphorus since 75–90% of added phosphorus is precipitated by metal–cation complexes, and rapidly becomes fixed in soils. Such environmental concerns have led to the search for sustainable ways of making phosphorus available to plants. Mineral solubilizing microorganisms (“MSMs”) are being increasingly viewed as the most eco-friendly means to accomplish this goal.
  • MSMs Mineral solubilizing microorganisms
  • Potassium is a very important plant nutrient. Without adequate availability of potassium, plants will have poorly developed roots, grow slowly, produce small seeds and have lower yields, as well as increased susceptibility to diseases and pests. As with phosphorus, potassium is generally supplied as fertilizer, as large areas of the agricultural land of the world are deficient in potassium, and subject to the same environmental concerns expressed above. As with phosphorus, MSM is expected to play an ever-increasing role in making potassium available to plants in an eco-friendly manner.
  • MSM are able to release potassium from insoluble minerals.
  • MSM can provide beneficial effects on plant growth through suppressing pathogens and improving soil nutrients and structure.
  • certain bacteria can weather silicate minerals to release potassium, silicon and aluminum, and secrete bio-active materials to enhance plant growth.
  • MSM that solubilize phosphorus or potassium include, but are not limited to, the following bacterial generas and species, Bacillus (for example Bacillus mucilaginosus, Bacillus edaphicus, Bacillus circulans, Bacillus megaterium, Bacillus polymyxa, Paenibacillus spp., Acidothiobacillus, Bacilus subtilis, lysinibacillus sphaericus, lysinibacillus fusiformis), ferrooxidans, Pseudomonas (for example Pseudomonas striata, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas putida), Rhizobium, Cephalosporium, Klebsiella variicola, Arthrobacter sp, Pantoea agglomerans, Microbacterium laevaniformans, Micrococcus
  • Mineral intake of animals may also need to be supplemented.
  • grasses may not provide sufficient macro or micronutrients for grazing animals, resulting in mineral imbalances that can result in illnesses such as grass tetany, a magnesium deficiency that can occur in ruminants, as well as sheep, especially lactating ewes with twins, that can result in animal death.
  • Enhanced availability of nitrogen and potassium for forage, such as that produced by MSM-infused biochar can minimize the risk of grass tetany.
  • Restoring available soil phosphorus using MSM-infused biochar to concentrations adequate for good plant growth can also elevate magnesium and calcium concentrations in grass leaves.
  • An ideal carrier for the MSM would have moisture, air, a neutral pH, and a surface for the MSM to attach.
  • a previously infused biochar created by the method disclosed above would be a better carrier than raw biochar alone.
  • the infused biochar could be physically mixed with a liquid MSM inoculant prior to or during application at seeding or to established plants. Additionally, the infused biochar and MSM inoculant could be combined to form starter cubes, similar to Organo-Cubes, rockwool, oasis cubes, and peat pots.
  • the infused biochar could be further improved upon by initially or further infusing the biochar with micronutrients or growth media for MSM.
  • the growth nutrient infused biochar would further expedite the colonization of the MSM when physically combined with the inoculant and applied to seeds or plants.
  • Another method for establishing and improving MSM colonies would be by growing MSM into the infused biochar and then applying the MSM inoculated biochar to seeds or plants. Similar to a sand culture (see above reference), a bed of infused biochar is treated with a recycled inoculated nutrient solution by passing it through the bed multiple times.
  • MSM, minerals, and/or growth media could be infused with the method disclosed previously, using vacuum, surfactant, or ultrasound. All of the infusion methods listed could be used independently, in conjunction, in any order and even repeated as needed. These MSM-infused biochars can then be used to solubilize useful minerals for plants and animals in several different implementations.
  • the biochar to be infused with MSM already has the desired minerals in it.
  • the biochar itself may have some minerals infused in it from the original biomass (e.g. organic phosphorus in the biomass) and the pyrolysis process (e.g. from the inorganic phosphates and pyrophosphates in the biomass) or minerals that were added to the biomass prior to pyrolysis or added into the biochar after the pyrolysis process itself or it could have acquired additional minerals as a result of being used for example in a water purification process, such as that taught by U.S. Patent application 2015/0144564 (Moller et al.), which is herein incorporated by reference in its entirety.
  • Mineral levels of the biochar may include for example, at least 10 ppm or higher of phosphorous, nitrogen/nitrates, and/or potassium.
  • the minerals can be 50 ppm or greater or may be significantly greater when, for example, high levels of fertilizing minerals are desired.
  • This application discloses embodiments of a system for treating water contaminated with, among other things, phosphates, nitrates and other minerals, using, in part, carbon capture, such as that provided by biochar.
  • Modified biochar particulates form part of the reject stream resulting from the disclosed purification process. These modified particulates can, if large enough, then be infused with MSM (or if not, the particles can be pelletized and infused as part of the pellet creation process).
  • the MSM-infused biochar can then either be used as a soil enhancement in agricultural applications, or fed to animals. Research has indicated that the MSM will reproduce faster and more efficiently in the biochar environment, as disclosed above, and act to solubilize the minerals present.
  • biochar can be infused with MSM, and this MSM- infused biochar can be used as a soil amendment or fed to animals to act upon insoluble minerals either in the root zone of plants or in the ruminant or digestive system of animals.
  • biochar can be infused with potassium, phosphorous, or other minerals which MSM act upon, and then either mixed with, deployed with, or subsequently infused with MSM.
  • This biochar infused with nutrients and either infused or deployed with MSM can then be used as a soil amendment, fed to animals, or used to yield many of the benefits already stated in this application.
  • biochar can be used to filter soluble nutrients from wastewater, stormwater, runoff, or other water in general. Then, the biochar laden with potentially useful, but usually immobile nutrients can be mixed with, deployed with, or infused with MSM to mobilize these nutrients. As the treated biochar is added to the soil, the MSM will mobilize the nutrients, allowing for true recycling of the nutrients retained in the biochar.
  • MSM infused biochar may be of beneficial use both for plant and animal health and growth, including humans, for whom minerals are an important nutrient and who can also benefit from the greater availability of those minerals provided by MSM.
  • MSM-infused biochars may be useful without departing from the scope of the invention.
  • Biotechnology specifically the use of biological organisms, usually microorganisms, to address chemical, industrial, medical, or agricultural problems is a growing field with new applications being discovered daily.
  • Much research has focused on identifying, developing, producing and deploying microbes for various uses.
  • Most current technology for microbial carriers in agriculture is based on technologies or products that are highly variable and, in many cases, lead to highly unpredictable performance of microbes in the field.
  • many commercial microbes in agricultural settings are delivered on peat, clay, or other carriers derived from natural sources, accompanied by limited engineering or process control.
  • Biochar have a proclivity to interact positively with many microbes relevant to plant health, animal health, and human public health applications.
  • biochar in conjunction with microbes or materials with microbes, e.g. compost.
  • biochars especially in raw form, often suffer from many characteristics which make their interaction with microbial organisms extremely unpredictable. Key among these undesirable characteristics is a high degree of variability. Because of this and other factors, biochar has been, to date, unused in large scale commercial biotechnology applications. There are several methods by which this variability can be ameliorated. At a high level, the methods to overcome these challenges fall into two categories: (i) making the biochar a more favorable habitat for the microbes– either by modifying its properties, adding materials beneficial to microbes, or removing materials deleterious to microbes, or (ii) inoculating, applying, or immobilizing the microbes on the biochar in ways that mitigate the underlying variability in the material. Both of these high-level methods can be used independently or in conjunction and have been shown to have a significant impact on the suitability of biochar in many biotechnology applications.
  • Biochar Before delving into the varying treatment methods that will turn the biochar into a microbial carrier or co-deploying with microbes, it is important to be able to view biochar as a habitat for microbes.
  • Biochar, especially treated biochar has many physical properties that make it interesting as a microbial habitat. The most obvious of these is its porosity (most biochars have a surface area of over 100 m2/g and total porosity of 0.10 cm3/cm3 or above).
  • many biochars have significant water holding and nutrient retention characteristics which may be beneficial to microbes. Previous disclosure has outlined how these characteristics can be further improved with treatment, e.g., US Patent Application Serial No.15/156,256, filed on May 16, 2016, and titled Enhanced Biochar.
  • the properties of the biochar can be made to match the properties expected by particular microbes, or groups of microbes, empirical data has shown that a much greater impact can be delivered in many applications– whether the targeted biochar is used as a carrier, substrate, co-deployed product, or merely is introduced into the same environment at a separate time. It stands to reason, as many real-world environments are composed of very complex microbial ecosystems, that giving certain microbes in these ecosystems a more favorable habitat, can ultimately help those microbes to become more successfully established, and potentially shift the entire ecosystem based on their improved ability to compete for resources. Clearly this is a very desirable characteristic when the successful deployment and establishment of a targeted microbe into a new environment is a desired outcome.
  • a habitat which may be important to certain microbes, but some of the most important are: pH, hydrophobicity or hydrophilicity, ability to hold moisture, ability to retain and exchange certain types of nutrients, ion exchange capacity (cationic and anionic), physical protection from predatory or competitive microbes or protozoa (usable and inhabitable porosity), presence or absence of nutrients, micronutrients, or sources of metabolic carbon, ability to host other symbiotic microbes or plant systems (such as plant root tissue), or others which may be important to various types or species of microbes.
  • Ability to either enhance or suppress the availability of certain enzymes can also be an extremely important factor in building a viable habitat.
  • This invention focuses on methods and systems that can be used to consistently produce biochar which has these targeted characteristics, methods that can be used to effectively create a particular formulation of biochar targeted to match a particular microbe or group of microbes, and techniques for deploying the desired microbes along with this targeted biochar, through inoculation, co-deployment, integrated growth / fermentation, or other methods.
  • CEC cationic exchange capacity
  • lowering the CEC of the material will in many cases reduce its ability to exchange sodium cations, while raising the CEC will typically enhance the ability of the material to exchange sodium cations, with exceptions occurring if other cations are present in quantities that cause them to preferentially exchange instead of the sodium cations present.
  • differing biomass feedstock contains differing levels of sodium– selecting an appropriate feedstock prior to pyrolysis will result in a raw or untreated biochar with reasonably controlled levels of sodium. For example, pine wood, when pyrolyzed, results in a raw char with lower levels of sodium, while coconut shells result in char with higher levels of sodium after pyrolysis.
  • One very important quality of a microbial habitat is the availability of shelter from environmental or biological hazards.
  • environmental hazards are high temperature, UV radiation, or low moisture
  • an example of a biological hazard is the existing of predatory multicellular microbes such as protozoa, including both flagellates and ciliates.
  • the material must consist of pores or openings of a size which can be inhabited by the microbe in question (ii) but prevent the hazard from entering (e.g.
  • the pore size distribution of a biochar can be adjusted by the selection of the biomass feedstock to be pyrolyzed and the conditions of the pyrolysis process itself. For example, pine wood has a relatively narrow pore size distribution, with most pores falling in the range from 10-70 ⁇ m.
  • coconut shells have a much wider size distribution, with many pores below 1 ⁇ m, and also a high percentage of porosity above 100 ⁇ m. It is theorized that materials with pores of a single size or where most pores are of similar size can potentially be good carriers or habitats for certain, targeted microbes, while materials consisting of broader ranges of pore sizes may be better habitats for communities, consortia or groups of microbes, where each microbe may prefer a slightly different pore size.
  • the pore size of a material may also be controlled during the pyrolysis process by increasing temperature or performing“activation” or other steps common in activated carbon production to react or remove carbon, leaving larger pores, or exposing availability of pores that were once inaccessible from the exterior surface of the material. Adjusting the particle size of the material may also change the pore size distribution in at least two ways: (i) exposing pores that were not available or accessible previously, or (ii) destroying larger pores by fracturing, splitting, or dividing them. In many cases, raw biochar may contain a proper pore size distribution, but for one reason or another, the pores are not usable by the microbes in question. In other cases, the pore size distribution provided by the natural feedstock may be undesirable.
  • Both properties may also be impacted through treatment of the raw biochar itself.
  • Larger pores can be created using strong acids or other caustic substances either by simple washing or through forced or rapid infusion into the pores.
  • a material with fewer usable pores may be created by intentionally“clogging” or filling the larger pores with either solids, gums, or liquids designed to stay resident in the pores themselves. This treatment may be done in a controlled way to only partially fill the pores. For example, one could infuse a limited amount of heated liquid, such as a resin, that will become solid at normal atmospheric temperatures. If the volume of liquid used is less than the available pore volume of the material being infused, some of the porosity of the material will be left untreated and available for use.
  • usable pore volume may be increased through the act of simply removing contaminants (physical or chemical) from the pores. Rapid infusion and extraction of liquids may be used to accomplish this. As discussed previously, appropriate solvents may be infused or extracted to remove chemical contaminants. Additionally, gasses or liquids may be driven into or out of the pores to force the removal of many solid obstructions, such as smaller particles of ash or simply smaller particles of raw biochar which may have become lodged in the pore in question. Regardless of the mechanism used, it has been shown that the available, uncontaminated, usable pore volume and pore size has a major role in determining the efficacy of biochars in microbial roles.
  • Figures 29 and 30 are images that show how different sized bacteria will fit in different biochar pore size structures.
  • Figure 29 is rod-shaped gram-positive bacteria, Bacillus thuringiensis israelensis, in a treated pine biochar, with pore openings of ⁇ 10-20 ⁇ m and bacteria of ⁇ 2-5 ⁇ m.
  • Figure 30 is rod-shaped gram-negative bacteria, Serratia liquefaciens, in a treated coconut shell biochar, with pore openings of ⁇ 2-10 ⁇ m and bacteria of ⁇ 1-2 ⁇ m.
  • FIG. 31 illustrates release rate data verse total pore volume data for both coconut shell and pine based treated biochars inoculated with a releasable bacteria. As illustrated in Figure 31, the data was plotted in a graph, and clearly shows that as pore volume increases so does the release rate.
  • microbial carriers Two important properties of microbial carriers are: (i) their ability to release microbes from their surfaces and (ii) their ability to immobilize or stabilize microbes on their surfaces. Depending on the final application or use of the carrier, one or both of these properties may be desired. For example, for carriers designed to quickly release a microbe into a targeted domain such as a lake, river, or other waterway, the release characteristics of the material are paramount. For other applications, such as applications of certain symbiotic microbes in agriculture, rapid release may be undesirable, rather it may be important to sustain the microbes within the porosity of the material until plant tissue, such as root biomass, is nearby to provide nutrition for the microbes in question.
  • the surface and pore geometry of the material used as a carrier can be critical to determine this behavior. For example, material with generally smooth, uniform surfaces will typically release many microbes much more effectively, while material with more rugged, varied, tortuous pore surfaces and geometry will typically retain and immobilize microbes more effectively.
  • the biomass used in the production of the final material is one of the most important factors in surface geometry. However, even this quality can be altered through treatment. Specifically, smooth surfaces may be etched by implementing the treatment and infusion processes previously disclosed with strong acids, rendering them rougher. Conversely, rough surfaces may be treated with either organic or inorganic compounds to coat and remove contour. Mechanical means may also be used to affect changes in particle geometry. Many forms of charred material have relatively low crush strength and are relatively brittle.
  • the method used to grind, or size particles can have a large impact on the geometry of the final particles.
  • particles milled using a ball mill or other type of grinding technology will typically have a smoother exterior geometry after the milling is complete and may lose a good amount of their porosity through the simple mechanical crushing of pores.
  • particles sized using ultrasonic vibrations or even simple physical vibrations to shatter, rather than crush larger particles into smaller ones will typically retain their geometry, or sometimes result in smaller particles with more rugged geometries than the particles at the beginning. It should be apparent to one skilled in the art that there are various mechanical mechanisms available to effect these changes, but the resulting particles can be tailored to meet a particular microbial release or immobilization outcome.
  • interparticle void space is also an important factor and can be optimized for a particular microbe or set of microbes by providing a range of particle sizes and geometries.
  • porous carbonaceous materials can exchange nutrients: (i) sorption or retention of the nutrients on the interior and exterior surfaces of the material, and (ii) retention of the nutrients either in suspension or solution in liquid or gasses residing in the pore volume of the material. Both mechanisms are very useful, but also very different in function. Surface sorption or retention is driven by two main properties, among others: (i) ion exchange capacity of the material and. (ii) reactivity or electrical charge of compounds present on or coating the surfaces of the material.
  • Retention of nutrients in solution or suspension are impacted by other, different characteristics of the material, such as hydrophilicity, oil sorption capacity, usable pore volume and pore size distribution, and interior pore geometry and tortuosity.
  • the surface retention of nutrients can be targeted by selecting the feedstock biomass (some materials render a char after pyrolysis with vastly differing ionic exchange capacities (CEC and AEC) than others). It can also be impacted by adjusting pyrolysis conditions. Higher pyrolysis temperatures tend to reduce CEC and nutrient adsorption capability. See Gai, Xiapu et al.“Effects of Feedstock and Pyrolysis Temperature on Biochar Adsorption of Ammonium and Nitrate.” Ed. Jonathan A. Coles.
  • the surface retention of nutrients can be impacted by treating the surfaces of the material with substances targeted towards adjusting the ionic exchange characteristics. For example, using the previously disclosed treatment methods to infuse H2O2 into the pores of the carbonaceous material and then evaporating the liquid can increase the cationic exchange properties of the material.
  • Another way to exchange nutrients more efficiently is to use the pore volume rather than, or in addition to, the pore surfaces— namely keeping the nutrients in solution or liquid or gaseous form and placing them in the volume of the pores rather than attempting to sorb them on the surfaces of the material.
  • This can be an incredibly useful technique not only for plant life and soil health, but also for microbes.
  • the food sources can vary from simple to complex such as glucose, molasses, yeast extract, kelp meal, or bacteria media (e.g. MacConkey, Tryptic Soy, Luria-Bertani).
  • nutrient exchange is the ability to treat the pore volume, pore surfaces, exterior surfaces, or any combination of these with not only custom broths or growth media, but also other forms of carbon known to be beneficial to microbes and plant life.
  • Some examples of this are carbohydrates (simple and complex), humic substances, plant macro and micronutrients such as nitrogen (in many forms, such as ammonium and nitrates), phosphorous, potassium, iron, magnesium, calcium, and sulfur and trace elements such as manganese, cobalt, zinc, copper, molybdenum.
  • These nutrients may either be infused in liquid or gaseous form, or even as a suspended solid in liquid. The liquid may be left in the pores, or may be removed.
  • Another approach for some toxic compounds is, rather than removing the compounds in question, to react them in place with other compounds to neutralize the toxicant.
  • This approach can be used either with washing, or forced / assisted infusion, and in these cases a removal step is less necessary– although it still can be used to prepare the material for another, subsequent phase of treatment.
  • a variation on this approach is to infuse, treat, or wash the material with a selectively toxic compound, such as a targeted antibiotic or pharmaceutical targeted towards interrupting the lifecycle of a specific set of microorganisms or organisms, thereby giving other microbes, either through infusion or merely contact in situ the opportunity to establish.
  • a selectively toxic compound such as a targeted antibiotic or pharmaceutical targeted towards interrupting the lifecycle of a specific set of microorganisms or organisms, thereby giving other microbes, either through infusion or merely contact in situ the opportunity to establish.
  • a selectively toxic compound such as a targeted antibiotic or pharmaceutical targeted towards interrupting the lifecycle of a specific set of microorganisms or organisms, thereby giving other microbes, either through infusion or merely contact in situ the opportunity to establish.
  • antifungals such as cycloheximide
  • the methods may be used alone, or in combination with one another. Specifically, a toxic compound such as ethanol, may be infused, removed, and then steps may be
  • the physical surface and pore structure of the material is critically important to its suitability as a microbial habitat. There are many factors that contribute to the surface structure of the material. The most notable of these factors is the biomass used to produce the carbonaceous material– the cellular structure of the biomass dictates the basic shape of many of the pores. For example, pyrolyzed coconut shells typically have less surface area, and a more diverse distribution of pore sizes than pyrolyzed pine wood, which, when pyrolyzed at the same temperature, has greater surface area, but a more uniform (less diverse) pore size distribution. Tortuosity, or the amount of curvature in a given path through a selected pore volume is also an extremely important characteristic of engineered porous carbonaceous materials.
  • Figure 32 shows the total fungi/bacteria ratio for two biochars derived from different biochar starting materials, e.g., feedstocks. Each biochar was loaded with different levels of moisture, and the total fungi/bacteria ratio was monitored during the first week.
  • Biochar A 3201 showed a constant total fungi/bacteria ratio of 0.08 across moisture levels rang5000ng from 15% to 40%, while Biochar B 2602 showed a constant total fungi/bacteria ratio of 0.50 for moisture levels ranging from 30% to 40%. It is theorized that, a fungi/bacteria ratio between 0.05 and 0.60 is an effective prescription for a stable biochar composition. This composition allows a commercially viable product, which has sufficient shelf life that it can be delivered to storage houses waiting for the proper planting window.
  • Biochar having an open pore structure, e.g., more interconnected pores, promotes more bacteria formation; while closed pores, e.g., relatively non-connected nature of the pores, tends to promote fungi formation.
  • Biochars with differing microbial communities may be beneficial for specific applications in commercial agriculture. Thus, custom or tailored loading of the microbial population may be a desired implementation of the present invention.
  • Biochar A 3301 shows that it has a greater population of, i.e., is inhabited by, more gram negative, gram positive and actinomycetes than Biochar B 3302.
  • Biochar A would be more applicable for use with certain agricultural crops in which Plant Growth Promoting Bacteria (PGPB) species in the actinomycetes, gram (-) pseudomonas, and bacillus groups are used for nutrient utilization and uptake.
  • PGPB Plant Growth Promoting Bacteria
  • Post treatment focused on a forced infusion of a strong acid, or other reactive substance into the pore space of the carbonaceous material can also be used to modify the pore size and pore volume of material by removing or breaking down the carbon matrix which forms the structure of the biochar, or other porous carbonaceous material.
  • Acid etching or infusion can also be used to make smoother surfaces rougher. Rough surfaces can be very useful in the attachment and immobilization of microbes. Smooth surfaces can be useful for the easy release of carried microbes. Coating the surface area with materials such as starches is a technique to make rough surfaces smoother.
  • Ultrasound, with or without a transmission media gel, liquid, oil, or other
  • Flash gasification either at atmospheric pressure, or under negative or positive pressure, of liquid infused into the pores by the methods previously disclosed can also be used to crack, disrupt, or fracture solid material separating adjacent pores.
  • the pore structure can also be modified by the coating, forced infusion, and/or addition of materials which will bond to the carbon and consume pore volume, smooth surfaces, add tortuosity, change the exterior surfaces, or all of these.
  • materials may be added to coat surfaces or fill pore volume either through forced infusion, simple contact, or other means.
  • a super saturated solution of a substance that will crystalize such as sucrose, sodium chloride, or other common or uncommon substances known to form crystals.
  • the crystals or substances used to create them do not need to be water soluble, and in fact in many cases it is desirable if they are not.
  • the crystals may also be composed of nutrients or substances which may be beneficial to microbial or plant life. Examples of this are sucrose and monoammonium phosphate, both known for their ability to easily crystalize and be beneficial for microbial and plant life respectively.
  • sucrose and monoammonium phosphate both known for their ability to easily crystalize and be beneficial for microbial and plant life respectively.
  • a hybrid material is formed which can have many properties that are exceptionally useful for the delivery and establishment of microbial systems. Crystallization is also way to add tortuosity to a carbonaceous material and typically is much more effective in this aspect than coating with solids alone.
  • Biofilms can be an important factor in the survival of a microbe in extreme or challenging conditions.
  • Bacterial communities can shift their morphology to increase nutritional access and decrease predation.
  • One such modification is that the bacteria may attach to surfaces, such as those found in biochar, in a densely compacted community. In this compacted form, they may form an extracellular polymeric substance (EPS) matrix called a biofilm.
  • EPS extracellular polymeric substance
  • biofilms are undesirable as they typically allow pathogenic microbes to survive exposure to antiseptics, antibiotics, predatory microbes such as protozoa, or other agents which may eliminate them or negatively impact their prospects for survival. But in agricultural settings, encouraging target biofilm establishment could lead to improved microbe survival and thus improved agricultural or crop benefits.
  • treatment of raw biochar can be used to adjust the surface pH to a level suitable for biofilm formation.
  • adjusting the humidity by selectively leaving a measured or controlled amount of water resident in the pore volume of the material can also provide benefit.
  • the techniques outlines for modifying the physical surface properties of the material either by smoothing or roughening can be key factors also.
  • the surface charge of a porous carbonaceous material can be crucially important in the association and establishment of targeted microbes with or on the material. For example, most bacteria have a net negative surface charge and in certain conditions a specific bacterium may favor attachment to positively charged surfaces. In some biological applications, this attachment may be preferred, in others, attachment may not be preferred. However, modifying the surface charge of the material is clearly a way to impact the suitability for attachment of certain microbes. There are many ways in which the surface charge of a carbonaceous material may be changed or modified. One way to accomplish this is by treating the surface area of the material with a solution containing a metal, such as Mn, Zn, Fe, or Ca.
  • a metal such as Mn, Zn, Fe, or Ca.
  • the surface charge of the material can be modified by encouraging loading of O2- or other anions, or conversely, N + , NH2 + , or other cations. This modification of surface charge can have a profound impact on the ability of certain microorganism to be immobilized on the interior and exterior surfaces of the material.
  • Another application of surface charge can be found by temporarily charging the carbonaceous material during inoculation with microbes.
  • Carbon is used as a cathode or anode in many industrial applications. Because of its unique electrical properties, carbon, or more specifically porous carbonaceous materials, may be given a temporary surface charge by the application of a difference in electrical potential.
  • One application of this mechanism is to create a temporarily positively charged surface to encourage microbial attachment. Then, while the charge is maintained, allowing the microbes to attach themselves to and colonize the carrier. Once the colonization is complete, the charge can be released and the carrier, laden with microbes can either be deployed as is, or can undergo further treatment to stabilize the microbes such as lyophilization, or freeze drying.
  • enzyme activity is every bit as important as the availability of energy or nutrition. Enzymes can be critical in the ability of microbes to metabolize nutrition, which in turn can be a key element of reproduction, survival, and effective deployment. There are six main types of enzymes: hydrolases, isomerases, ligases, lyases, oxidoreductases, and transferases. These enzymes can be important in microbial applications. Through treatment or even simple contact, enzymes, like nutrients and energy sources, can be deposited on the surfaces or within the pore volume of porous carbonaceous materials, either as solids, or in solution/suspension, ensuring the enzymes are not degraded through the process.
  • the carbonaceous material can be used to deliver enzymes alone into an environment where both a habitat and enzymes are needed to promote or encourage the growth of certain indigenous microbes.
  • Another important aspect of enzyme activity is that some bacteria make extra-cellular enzymes which could be bound by the biochar or either reduce or even stop biochemical reactions.
  • the carbonaceous material can be used to inhibit or make certain enzymes ineffective. For example, if the biochar is being used as a carrier for food or certain chemicals that are vulnerable to breakdown by enzymatic degradation and these specific enzymes would be bound by the biochar, then using the carbonaceous material as the carrier would provide for greater shelf-life and viability of the product versus traditional carriers.
  • infusion with antiseptics or antibiotics are a way to accomplish this.
  • Boiling, or more preferably, forced infusion of steam is also a technique that can be used to remove resident microbial life. Heating to a temperature above 100 degrees C, and preferably between 100 and 150 degrees C is also effective for removing some microbial life. Heating may be required for ideally 30 minutes or more, depending on volume, method, and extent (temperature, radiation). Autoclaving can also be used 30 minutes, 121 degrees C, 20 psig.
  • gamma irradiation can be used, with dosages adjusted for the level of sterility needed in ranges of 5 to 10 kGy or even 50 to 100 kGy or even higher dosage levels.
  • dosages adjusted for the level of sterility needed in ranges of 5 to 10 kGy or even 50 to 100 kGy or even higher dosage levels.
  • the extent of treatment required will depend on the volume of material and the required level of sterilization. In general, sterilization, using heat, should be done for at least 30 minutes, but should be adjusted as needed.
  • This method focuses on deploying the microbes at the same time as the biochar. This can be done either by deploying the biochar into the environment first, followed by microbes or by reversing the order, or even deploying the two components simultaneously. An example of this would be the deployment of a commercial brady rhizobium inoculant simultaneously with the introduction of a treated biochar into the soil media.
  • the system here is the combination use of a biochar and microbes in the environment, and more preferably a char treated to have suitable properties for a target microbe or group of microbes which it is used with in a targeted application for a specified purpose, for example a symbiotic crop of said microbe(s).
  • Figure 34 is a chart comparing shoot biomass when the biochar added to a soilless mix containing soybean seeds is treated with microbial product containing bradyrhizobium japonicum. and when it is untreated. As illustrated in Figure 34, shoot biomass increased with the biochar was treated.
  • Figure 35 shows the comparison of root biomass in a microbial inoculated environment versus one without inoculation. As illustrated in Figure 35, when inoculated, root biomass decreased with the inoculant alone yet increased with the use of all the treated biochars with or without inoculant.
  • Figure 36 is a chart comparing the nitrogen levels when the biochar is inoculated with the rhizobial inoculant verses when it is not inoculated. Statistical significance in the chart in Figure 36 is marked with a star. In all cases, nitrogen levels increase with inoculation.
  • Another example of co-deployment benefit could be using a biochar that has strong absorption properties in combination with fertilizer (or infused with fertilizer) and microbes in an agricultural setting.
  • the biochar properties that help retain and then slowly release nutrients and ions will also help the targeted microbe population to establish and grow without being impacted by the high levels of fertilizer salts or nutrients which can often impede and sometimes kill the microbes being deployed.
  • the biochar in question can be treated, produced, or controlled to assist with this deployment, making this case slightly different than merely inoculating a microbe on untreated biochar.
  • microbes suspended in liquid are deposited on the biochar and mixed together until both materials are well integrated and then the material is deployed as a granular solid. It has been shown that materials that have been treated to be more hydrophilic typically accept this inoculation more readily than hydrophobic materials– demonstrating yet another way in which the treatment of biochar can enhance performance.
  • the biochar is delivered in suspension in the liquid also carrying the microbes.
  • This biochar/liquid/microbe slurry is then deployed as a liquid.
  • sizing the biochar particles in such a way that their surface properties and porosity is maintained is a key element of effectiveness. Additionally, ensuring that the pores are treated to allow easy association of both liquid and microbes with the surfaces of the biochar is important.
  • An example of a basic inoculation method of biochar for a bacteria in lab scale is as follows:
  • the material and the microbes may be deployed immediately, stored for future use, or stabilized using technology such as lyophilization.
  • assisted inoculation involves providing mechanical, chemical, or biological assistance to move the targeted microbe either into the pore volume of the carrier or onto interior surfaces of the material that normally may not be accessible.
  • the most straightforward method of assisted inoculation requires infiltrating the pore volume of the material with water prior to contact with the targeted microbes. This water infusion can be done using the treatment methods described previously in this disclosure. It has been shown that, with certain microbes, making this change alone will have a positive impact on the ability of microbes to associate with and infiltrate the material.
  • Changes can also be made in the media to reduce surface tension and increase flowability through the addition of a surfactant to the water, either into the liquid used to carry the microbes, or into the pores of the material itself, through simple contact, or preferably forced infusion.
  • microbes themselves may be assisted into the pores using the treatment techniques previously outlined. Care needs to be taken to match the microbe to the technique used, but many microbes are capable of surviving vacuum infiltration if performed at relatively gentle, lower pressure differentials (+/- 10% of standard temperature and pressure). Some microbes, and many spores however are capable of surviving vacuum infiltration even at relatively large pressure differentials (+/- 50, 75, or even 90 or 95% or more variation from standard temperature and pressure).
  • a liquid mixture is constructed containing both liquid to be infused and the microbe or microbes in question. The liquid is then used as the“infiltrant” outlined in previous disclosure related to placing liquid into the pore volume of the material.
  • the final material, infiltrated with microbes, may then be heated to incubate the microbes, cooled to slow development of the microbes or stabilize the microbes, or have other techniques applied such as lyophilization.
  • the material may then be delivered in solid granular form, powdered, further sized downward by grinding or milling, upward by agglomerating, aggregating, or bonding, or suspended in a liquid carrier.
  • a clear advantage to this assisted infusion approach is that the material can be processed or handled after inoculation with more microbial stability because the targeted microbes are inhabiting the interior pore volume of the material and are less prone to degradation due to contact with exterior surfaces, or other direct physical or environmental contact.
  • This method may be applied repeatedly, with one or more microbes, and one to many moisture removal steps. It may also be combined with the other inoculation methods disclosed here either in whole or in part.
  • Figures 38a, 38b and 38c show scanning electron microscopy (SEM) images of raw biochar compared to ones that have been processed by being infused under vacuum with bio- extract containing different microbial species.
  • Figure 38a is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of raw biochar.
  • Figure 38b is a SEM (10KV x 3.00K 10.0 ⁇ m) of pore morphology of raw biochar of Figure 38a after it has been infused with microbial species.
  • Figure 38c is a SEM (10KV x 3.00K 10.0 ⁇ m) of a pore morphology of another example of raw biochar of Figure 38a after it has been infused with microbial species.
  • the images confirm the ability to incorporate different microbes into the pores of biochar by treatment. In turn, these beneficial microbes can interact with and enhance the performance of the environment they are deployed into, for example the plants’ root systems when the inoculated biochar is mixed with the soil in the root zone.
  • the impregnated populations of examples of the present treated biochars are stable over substantially longer periods of time, e.g., at least an 8 week period and in some cases 1 year or more as measured by PLFA(Phospholipid-derived fatty acids) analysis.
  • PLFA analysis extracts the fatty acid side chains of phospholipid bilayers and measures the quantity of these biomarkers using GC- MS. An estimate of the microbial community population can thus be determined through PLFA analysis.
  • the microbial activity may also be inferred through PLFA analysis by monitoring the transformation of specific fatty acids.
  • the impregnation of the biochar with a microbial population provides for extended life of the microbes by at least 5x, 10x, or more over simple contact or immersion.
  • some microbes may be better suited to surfactant infiltration versus vacuum infiltration and vice versa and this may impact the shelf life, penetration, viability, or other characteristics of the microbes.
  • the stable shelf life of an example of a biochar product having a microbial population is the period of time over which the product can be stored in a warehouse, e.g., dry environment, temperature between 40°F- 90°F, with a less than 50% decrease in microbial population.
  • An example of this method involves preparing the biochar material for the microbes, sometimes through thorough cleansing, other times through addition of either enzymes or energy sources needed by the microbe in question, preferably using the treatment techniques described previously in this disclosure.
  • the microbes are placed onto the material, or infused into the material and then incubated for a period of time.
  • the microbes themselves will inhabit the material and form close affiliations with available surfaces and pore volume.
  • the material can be deployed with the microbes actively attached and affiliated. With many microbes, especially fungi, this is a preferred method of deployment and shows many advantages over co-deployment, or basic inoculation because of the tight integration of biological life with the material itself.
  • An example of an integrated growth inoculation method of biochar for a fungus in lab scale is as follows : 1) Make petri dishes containing corn meal agar (17 g/L), glucose (10 g/L), and yeast extract (1 g/L)
  • biochars, and specifically treated biochars can also be extremely effective substrates for solid state fermentation— particularly when growth media or energy sources are added to the pore volume of the material. So, once incubation is ongoing, the material can either be removed, with the integrated microbes, and deployed, or it can be stabilized for long term storage, or it can be left in situ and used as a fermentation or growth substrate to develop or grow more microbes– especially those that require a solid to propagate and develop.
  • growth media, energy sources, enzymes, or other beneficial / necessary components for microbial growth may be infused into the pore volume or coated onto the surfaces of the material in question.
  • This method can be combined with any of the other inoculation techniques disclosed here. It has been shown that with certain microbes and certain types of material, inoculation with growth media or enzymes can significant impact the effectiveness of the biochar material as a carrier.
  • microbes which, because of symbiotic associations with host organisms, such as plants, prefer to develop in the vicinity of the organism, such as the active root or other plant tissue.
  • An effective method for deploying these organisms can be to develop and deploy the plant/microbe/habitat (biochar) system together as a unit.
  • An example of this is germinating seed or transplanting a seedling or developing juvenile plant in the presence of treated or untreated biochar, and the targeted microbes.
  • Biochar that has been treated to encourage hydrophilicity and neutral pH typically allows for easier affiliation of plant root tissue with the material.
  • Another option is to develop and then remove the biochar from the“incubation” system either by stripping the biochar material from the symbiotic organism, such as the root mass, or by sieving or sifting the media used to grow the plant. At this point, the microbes can either be deployed directly or stabilized for storage.
  • a microbial community e.g., population
  • This integration of a microbial community with a biochar particle, and biochar batches provides the ability to have controlled addition, use and release of the microbes in the community.
  • this integration c a n further enhance, promote and facilitate the growth of roots, e.g., micro- roots, in the biochar pores, e.g., pore morphology, pore volume.
  • Other methods for integrating a microbial community with a biochar particle may include, but are not be limited to the following: while under vacuum, pulling the microbial solution through a treated biochar bed that is resting on a membrane filter; spraying a microbial solution on top of a treated biochar bed; lyophilizing a microbial solution and then blending said freeze dried solution with the treated biochar; again infusing, as defined previously, the treated biochar with a microbial solution; adding treated biochar to a growth medium, inoculating with the microbe, and incubating to allow the microbe to grow in said biochar containing medium; infusing, as defined previously, the biochar with a food source and then introducing the substrate infused biochar to a microbe and incubating to allow the microbes to grow; blending commercially available strains in dry form with treated biochar; adding the treated biochar to a microbial solution and then centrifuging at a high speed, potentially with a density gradient in order to promote the
  • the treated biochar may need to be sterilized prior to these methods for integrating a microbial community. All or parts of the above manners and methods may be combined to create greater efficacy. In addition, those skilled in the art will recognize that there may be additional manners or methods of infusing biochars with microbials, including those created by the combination of one or more of the manners and methods listed above, without departing from the scope of the present invention. Further, when using any of the above methods for integrating the microbes with the biochar, including but not limited to infusing the microbes in the biochar, it is recognized that such microbes or other MSM or minerals can continue to be deployed in the soil once the biochar is in situ.
  • treated biochar can have a microbial community in its pores (macro-, meso-, and combinations and variations of these), on its pore surfaces, embedded in it, located on its surface, and combinations and variations of these.
  • the microbial community can have several different types, e.g., species, of biologics, such as different types of bacteria or fungi, or it may have only a single type.
  • a preferred functional biochar can have a preferred range for bacterial population of from about 50-5000000 micrograms/g biochar; and for fungi, from about 5 to 500000 micrograms/g biochar.
  • a primary purpose in agricultural settings, among many purposes, in selecting the microbial population is looking toward a population that will initiate a healthy soil, e.g., one that is beneficial for, enhances or otherwise advance the desired growth of plants under particular environmental conditions.
  • Two types of microbial infused biochars will be discussed further for agricultural settings: bacteria and fungi.
  • the microbes may also be used in other applications, including but not limited to animal health, either directly or through interactions with other microbes in the animals’ digestive tract and public health applications, such as microbial larvicides (e.g. Bacillus thuringiensis var. israelensis (Bti)) and Bacillus sphaericus used to fight Malaria).
  • Methanotrophic bacteria are proteobacteria with diverse respiration capabilities, enzyme types, and carbon assimilation pathways.
  • Methylosinus trichosporium OB3b is one of the few methanotrophs that can be manipulated by environmental conditioning to exclusively produce methanol from methane.
  • M. trichosporium OB3b is one of the most well studied aerobic C 1 degraders and can be grown in either batch or continuous systems. As mentioned earlier, the large pore volume and surface area of biochar is suitable for bacterial colonization and should subsequently increase substrate access to enzyme activation sites.
  • biochar as a support material for the aerobic bioconversion of methane to methanol provides a pore distribution suitable for both adsorptions of methane and impregnation with bacteria. By providing biological and adsorptive functionality the biochar can intensify the bacteria in the biochar and increases the conversion rate.
  • bacteria communicate via the distribution of signaling molecules which trigger a variety of behaviors like swarming (rapid surface colonization), nodulation (nitrogen fixation), and virulence.
  • Biochars can bind signaling molecules and in particular it is believed can bind a major signaling molecule to their surface. This binding ability can be dependent upon many factors including on the pyrolysis temperature. This dependency on pyrolysis temperature and other factors can be overcome, mitigated, by the use of examples of the present vacuum infiltration techniques. For example, a signaling molecule that is involved in quorum sensing- multicellular-like cross-talk found in prokaryotes can be bound to the surface of biochars.
  • Concentration of biochars required to bind the signaling molecule decreased as the surface area of biochars increased.
  • These signaling molecules may be added to the surface of a biochar and may be used to manipulate the behavior of the bacteria.
  • An example of such a use would be to bind the molecules which inhibit cell-to-cell communication and could be useful in hindering plant pathogens; using techniques in the present invention signaling molecules may be added to the surface of a biochar to engineer specific responses from various naturally occurring bacteria.
  • the treatment processes described above are particularly well suited for large scale production of biochar.
  • the processes and biochars of the present invention provide a unique capability to select starting materials and pyrolysis techniques solely on the basis of obtaining a particular structure, e.g., pore size, density, pore volume, amount of open pores, interconnectivity, tortuosity, etc.
  • these starting materials and processes can be selected without regard to adverse, harmful, phytotoxic side effects that may come from the materials and processes.
  • the infiltration steps have the capability of mitigating, removing or otherwise address those adverse side effects.
  • a truly custom biochar can be made, with any adverse side effects of the material selection and pyrolysis process being mitigated in later processing steps.
  • the processes are capable of treating a large, potentially variable, batch of biochar to provide the same, generally uniform, predetermined customized characteristics for which treatment was designed to achieve, e.g., pH adjustment.
  • Treatment can result in treated biochar batches in which 50% to 70% to 80% to 99% of the biochar particles in the batch have same modified or customized characteristic, e.g., deleterious pore surface materials mitigated, pore surface modified to provide beneficial surface, pore volume containing beneficial additives.
  • the ability to product large quantities of biochar having a high level of consistency, predictability and uniformity provides numerous advantages in both large and small agricultural applications, among other things.
  • the ability to provide large quantities of biochar having predetermined and generally uniform properties will find applications in large scale agriculture applications.
  • treated biochar batches from about 100lbs up to 50,000+lbs and between may have treated biochar particles with predetermined, uniform properties.
  • the treated biochar batches are made up of individual biochar particles, when referring to uniformity of such batches it is understood that these batches are made up of tens and hundreds of thousands of particles. Uniformity is thus based upon a sampling and testing method that statistically establishes a level of certainty that the particles in the batch have the desired uniformity.
  • a treated batch of biochar when referring to a treated batch of biochar as being“completely uniform” or having“ complete uniformity” it means that at least about 99% (e.g., two nines) of all particles in the batch, measured on a volume basis, a weight basis, or on both a volume and a weight basis, have at least one or more property or feature that is the same.
  • substantially uniform or having“substantial uniformity” it means that at least about 95% of all particles in the batch, again measured on a volume or weight basis, have at least one or more property or feature that is the same.
  • a treated batch of biochar is referred to as“essentially uniform” or having“essential uniformity” it means that at least about 80% of all particles in the batch, measured on a volume or weight basis, have at least one or more property or feature that is the same.
  • the batches can have less than 25%, 20% to 80%, and 80% or more particles in the batch that have at least one or more property or feature that is the same. Further, the batches can have less than 25%, 20% to 80%, and 80% or more particles in the batch that have at one, two, three, four, or all properties or features that are the same.
  • treated biochar of the present inventions can be used throughout the world, in numerous soil types, agricultural applications, horticultural, large and small scale farming, organic farming, and in a variety of soil management applications and systems, and combinations and variations of these.
  • this particular solution provides the capability to custom- manufacture biochar for a particular climate, environment, geographical area, soil type, or application by more precisely controlling key characteristics.
  • Examples of these applications include for example, use in acidic and highly weathered tropical field soils, use in temperate soils of higher fertility, use in large commercial applications, use for the production of large scale crops such as, soybean, corn, sugarcane and rice, in forestry applications, for golf courses (e.g., greens, fairways), for general purpose turf grasses, wine grapes, table grapes, raisin grapes, fruit and nut trees, ground fruits (e.g., strawberries, blueberries, blackberries), row crops (e.g., tomatoes, celery, lettuce, leafy greens), root crops (e.g., tubers, potatoes, beets, carrots), mushrooms, and combinations and variations of these.
  • golf courses e.g., greens, fairways
  • general purpose turf grasses e.g., wine grapes, table grapes, raisin grapes, fruit and nut trees
  • ground fruits e.g., strawberries, blueberries, blackberries
  • row crops e.g., tomatoes, celery, lettuce
  • Treated biochars and agriculture practices and methods provide for improved soil structure, increased water retention capability, increased water holding ability of the soil over time, reduced runoff or leaching, increased holding ability for nutrients, increase holding of nutrients over time, and combinations and variations of these, and other features that relate to the increased holding and retention features and soil aggregation of the present biochars and processes. It further being understood that in addition to nutrients, other material additives, (e.g., herbicide, pesticide), can be utilized and benefit from the increased holding and retention capacities of the present biochars and methods.
  • material additives e.g., herbicide, pesticide
  • Treated biochar may also be used in other applications, for example, such mixing with manure in holding ponds to potentially reduce gaseous nitrogen losses, soil remedial (for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components), ground water remediation, other bioremediations, storm water runoff remediation, mine remediation, mercury remediation, water filtration, and as a cattle or poultry feed additive.
  • soil remedial for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components
  • ground water remediation other bioremediations
  • storm water runoff remediation mine remediation
  • mercury remediation mercury remediation
  • water filtration water filtration
  • cattle or poultry feed additive as a cattle or poultry feed additive.
  • the present invention could be used to clean and/or infiltrate the pores of biochar with a variety of substances, for a number of purposes, including but not limited to, infiltrating the pores of biochar with nutrients, vitamins, drugs and/or other supplements, or a combination of any of the foregoing, for consumption by either humans and/or animals.
  • the treated biochar may also be applied to animal pens, bedding, and/or other areas where animal waste is present to reduce odor and emission of unpleasant or undesirable vapors. Furthermore it may be applied to compost piles to reduce odor, emissions, and temperature to enable the use of the food waste and animal feed in composting.
  • Biochar can also be applied to areas where fertilizer or pesticide runoff is occurring to slow or inhibit leaching and runoff.
  • the biochar may also be treated with additives which make it easier to dispense or apply, such as non-toxic oils, anti-clumping/binding additives, surface drying agents, or other materials.
  • Biochar may also be used in other applications, for example, such mixing with manure in holding ponds to among other things potentially reduce gaseous nitrogen losses, soil remedial (for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components), ground water remediation, other bioremediations, storm water runoff remediation, mine remediation, mercury remediation, and as a cattle or poultry feed additive.
  • soil remedial for example absorption and capture of pesticide, contaminates, heavy metals, or other undesirable, disadvantageous soil components
  • ground water remediation other bioremediations
  • storm water runoff remediation mine remediation
  • mercury remediation mercury remediation
  • biochar In general, in the agricultural application of biochar to soil, the biochar should be located near the soil's surface in the root zone, or in or adjacent to the rhizosphere, where the bulk of nutrient cycling and uptake by plants takes place.
  • benefits may be obtained from the application of biochar in layers above, below, in and combinations and variation of these, the root zone, for example during landscaping for carbon sequestration, or if using biochar for moisture management.
  • Layering of biochar at various depths above, below, in and combinations and variation of these, the root zone, the surface, and combinations and variations of these, may also be employed.
  • the biochar layers may have different predetermined properties for each layer, based upon, for example, the depth of the layer, soil type, geography, crop, climate and other factors.
  • the present invention can be used on any type of soil application, including, but not limited to, the following: crops, turf grasses, potted plants, flowering plants, annuals, perennials, evergreens and seedlings.
  • treated biochar may be incorporated into or around the root zone of a plant.
  • the above applications will generally be effective incorporating the biochar around the root zone from the top surface of the soil and up to a depth of 24” below the top surface of the soil, depending on the plant type and species, or alternatively, within a 24” radius surrounding the roots regardless of root depth or proximity from the top surface of the soil.
  • the incorporation of the biochar within the top 2- 6” inches of the soil surface may also be effective. Greater depths are more beneficial for plants having larger root zones, such as trees.
  • the treated biochar can be applied in amounts (e.g., rates of addition as measured by weight of treated biochar per area of field) of from about 0.0005 ton of treated biochar per acre to about 150 tons of treated biochar per acre, from about 2.5 tons of treated biochar per acre to about 100 tons of treated biochar per acre, and from about 5 tons of treated biochar per acre to about 70 tons of treated biochar per acre, although larger and smaller amounts may be used.
  • a dditional rates of from about 1/2 tons of treated biochar to about 10 tons of treated biochar may be used. For example, 1 ton of treated biochar was added per acre to a soil for a lettuce crop where the soil had a pH of about 7.
  • biochar can be preferably added using existing farm equipment and incorporated into existing farming operations.
  • treated biochar can be applied and incorporated together with lime, since lime is often applied as a fine solid, which must be well incorporated into soil.
  • the examples of the present inventions may give rise to new equipment and utilizations based upon the features, performance and capabilities of the present inventions.
  • treated biochar may be applied to fields, by way of example through the use of manure or compost spreaders, lime spreaders, plowing method (e.g., from hand hoes, animal draft plows, disc harrows, chisels, rotary hoes, etc.), large scale tillage equipment, including rotary tillers, mulch finishers, draw offset discs, and disc harrows (such as for example JOHN DEERE DH51, DH52F, PC10, RT22, and RC22).
  • plowing method e.g., from hand hoes, animal draft plows, disc harrows, chisels, rotary hoes, etc.
  • large scale tillage equipment including rotary tillers, mulch finishers, draw offset discs, and disc harrows (such as for example JOHN DEERE DH51, DH52F, PC10, RT22, and RC22).
  • Treated biochar may also be applied by modified large scale nutrient applicators (such as, for example, JOHN DEERE 2410C, 2510H, 25105 Strip-Till Medium Residue Applicator), large scale draw dry spreaders (such as JOHN DEERE DN345), large scale no-till planters, large scale dry fertilizer sub- surface applicators, and liquid slurry surface or subsurface applicators. Similar, and various other types of large farming, and earth moving and manipulation equipment may be used to apply the treated biochar to the field, such as for example, drop spreaders or drills.
  • modified large scale nutrient applicators such as, for example, JOHN DEERE 2410C, 2510H, 25105 Strip-Till Medium Residue Applicator
  • large scale draw dry spreaders such as JOHN DEERE DN345
  • large scale no-till planters such as JOHN DEERE DN345
  • large scale dry fertilizer sub- surface applicators such as for example,
  • treated biochar may be applied using banding techniques, which is an operation involving applying the biochar in a narrow band, using equipment that cuts the soil open, without disturbing the entire soil surface. Using this technique the biochar can be placed inside the soil while minimizing soil disturbance, making it possible to apply biochar after crop establishment, among other applications.
  • treated biochar may be mixed with other soil amendments, or other materials, such as for example manure, sand, topsoil, compost, turf grass substrate, peat, peat moss, or lime before soil application, which are already scheduled or part of the existing operations, and in this manner by combining these steps (e.g., biochar application with existing application step) can improve efficiency by reducing the number of field operations required.
  • treated biochar can also be mixed with liquid, (e.g., liquid manures) and applied as a slurry.
  • liquid e.g., liquid manures
  • Finer biochar particles may be preferably used with this type of slurry application using existing application equipment, and dust problems associated with these finer particles may be mitigated, managed or eliminated.
  • treated biochar can be top dressed on perennial pastures or other perennial vegetation, such as spaces between fruit trees in orchards. Treated biochar may also be applied with individual plants while transplanting or mixed with topsoil and other amendments while preparing raised beds. In forestry or similar operations where replanting of seedlings takes place, treated biochar can be applied by broadcasting (e.g., surface application) or incorporation over the entire planting area, it can be added in the planting holes, and combinations and variations of these. Before or after tree establishment, biochar could also be applied by traditional and subsurface banding or top-dressed over perennial vegetation in orchards, but care should be taken to minimize root damage and soil compaction.
  • broadcasting e.g., surface application
  • biochar could also be applied by traditional and subsurface banding or top-dressed over perennial vegetation in orchards, but care should be taken to minimize root damage and soil compaction.
  • treated biochar can be applied in trenches radiating out from the base of established trees (“radial trenching”) or in holes dug at some distance from the base of the tree (“vertical mulching”); biochar could also potentially be applied to soil using“air excavation tools”.
  • These tools use pressurized air to deliver material, e.g., compost, under the soil surface and reduce compaction. Some of these tools are referred to as Air Spades or Air Knifes.
  • the soil around tree roots can be excavated and treated biochar applied before covering with soil.
  • particle size distribution of treated biochar materials may vary widely depending on the feedstock and the pyrolysis technique used to produce the biochar, uniformity if required or preferred, can be achieved by various milling and grinding techniques that may be employed during processing or during the distribution and application to soil. When smaller particles are utilized, and in particular for surface applications, care should be taken to apply the treated biochar in ways that minimize loss due to wind or water erosion.
  • the treated biochar of the present invention may be used in various agriculture activities, and the fields of edaphology and pedology, as well as other activities and in other fields. Additionally, the treated biochar may be used, for example, with: farming systems and technologies, operations or activities that may be developed in the future; and with such existing systems, operations or activities which may be modified, in-part, based on the teachings of this specification. Further, the various treated biochar and treatment processes set forth in this specification may be used with each other in different and various combinations.

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Abstract

Un charbon de biomasse traité comprend une particule carbonée poreuse qui a été traitée et mélangée à un milieu contenant un micro-organisme de solubilisation de minéraux, la particule carbonée poreuse ayant conservé, après le mélange, le micro-organisme de solubilisation de minéraux.
PCT/US2017/035759 2016-06-02 2017-06-02 Charbons de biomasse infusés par des micro-organismes de solubilisation de minéraux WO2017210609A1 (fr)

Applications Claiming Priority (12)

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US201662344865P 2016-06-02 2016-06-02
US62/344,865 2016-06-02
US201662357668P 2016-07-01 2016-07-01
US62/357,668 2016-07-01
US201662432253P 2016-12-09 2016-12-09
US62/432,253 2016-12-09
US15/393,176 US10118870B2 (en) 2011-06-06 2016-12-28 Additive infused biochar
US15/393,214 2016-12-28
US15/393,176 2016-12-28
US15/393,214 US10173937B2 (en) 2011-06-06 2016-12-28 Biochar as a microbial carrier
US15/419,976 US9980912B2 (en) 2014-10-01 2017-01-30 Biochars for use with animals
US15/419,976 2017-01-30

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CN113046344A (zh) * 2021-03-19 2021-06-29 西南石油大学 一种纤维状苦荞壳生物炭及土壤修复固定化菌剂制备方法
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CZ309512B6 (cs) * 2021-12-22 2023-03-15 FERTICHAR s.r.o. Způsob výroby půdního kondicionéru a půdní kondicionér vyrobený tímto způsobem

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3417691A1 (fr) * 2017-06-21 2018-12-26 Polyor SARL Fertilisation azotobactérienne sans inoculation des résidus de cultures
FR3067904A1 (fr) * 2017-06-21 2018-12-28 Sarl Polyor Fertilisation azotobacterienne sans inoculation des residus de cultures
CN113046344A (zh) * 2021-03-19 2021-06-29 西南石油大学 一种纤维状苦荞壳生物炭及土壤修复固定化菌剂制备方法
CN113046344B (zh) * 2021-03-19 2022-03-29 重庆地质矿产研究院 一种纤维状苦荞壳生物炭及土壤修复固定化菌剂制备方法
CN114132913A (zh) * 2021-10-03 2022-03-04 北京工业大学 一种负载蛤蜊壳热解提高城镇污泥中磷生物利用度及固化重金属的方法与应用
CN113952926A (zh) * 2021-10-08 2022-01-21 农业农村部环境保护科研监测所 一种联合生物/化学手段制备的负载水铁矿纳米颗粒生物炭同步去除砷和有机污染物的方法
CN113952926B (zh) * 2021-10-08 2024-01-23 农业农村部环境保护科研监测所 一种联合生物/化学手段制备的负载水铁矿纳米颗粒生物炭同步去除砷和有机污染物的方法
CZ309512B6 (cs) * 2021-12-22 2023-03-15 FERTICHAR s.r.o. Způsob výroby půdního kondicionéru a půdní kondicionér vyrobený tímto způsobem
CN115650625A (zh) * 2022-12-20 2023-01-31 生物炭建材有限公司 一种基于改性生物炭负载微生物的混凝土修复剂制备方法

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