CN114477129A

CN114477129A - Modified water coke and preparation method and application thereof

Info

Publication number: CN114477129A
Application number: CN202111342796.5A
Authority: CN
Inventors: 郑列列; 王浩; 石萍
Original assignee: Shenzhen Hailifang Biological Technology Co ltd
Current assignee: Shenzhen Hailifang Biological Technology Co ltd
Priority date: 2020-11-12
Filing date: 2021-11-12
Publication date: 2022-05-13

Abstract

The invention discloses a modified water coke, a preparation method and application thereof, wherein the modified water coke is a carbon compound with a spongy structure, and the performance of the modified water coke is similar to the function of natural humin. Therefore, can provide the required energy and mineral requirements for soil microorganisms and soil animals; meanwhile, the degradation or inactivation of toxic substances in the soil can be more stably or effectively assisted by forming a mixture of the modified water coke and the soil humus substances; the modified water coke prepared by the invention can buffer the pH value of soil by combining with humus substances, release carbon dioxide and play a role in buffering the concentration of hydrogen ions in the soil. The composition containing the modified water coke, the humic acid and/or the organic carbon medium nutrient can be widely used for soil fertilizers, soil microorganism and soil animal ecological balance promotion, degradation or inactivation promotion of toxic substances in soil, soil pH improvement, plant fertilizers, plant growth promotion, plant irrigation and the like, and can obtain good effects.

Description

Modified water coke and preparation method and application thereof

The present application claims priority rights to a prior application entitled "modified water coke and method of making and using the same" filed on the national intellectual property office of china on 12.11.2020, patent application No. 202011263156.0. The entire contents of said prior application are incorporated by reference into the present application.

Technical Field

The invention belongs to the field of biomass treatment and recycling, and particularly relates to modified water coke and a preparation method and application thereof.

Background

Mineral fertilizers are used when people find that soluble acidic nitrogen phosphorus potassium "fertilizers" have the positive effect of stimulating plant growth, and from the consideration of promoting agricultural production efficiency, N, P, K (nitrogen, phosphorus and potassium) in mineral reserves, namely inorganic "fertilizers" processed and produced from ore raw materials, are used as stimulants for promoting plant growth. However, once the agricultural output of a region depends heavily on the "stimulation" of fertilizers, the cultivated soil in the region deviates from the way of the organic compound circulation in the ecosystem and enters the circulation of soil quality degradation.

Soil microorganisms are the most active part in soil, are driving forces for substance conversion and nutrient circulation in soil, and relate to various processes such as decomposition of organic matters in soil, formation of humus, soil nutrient conversion and circulation and the like. The soil microbial community and the flora structure are influenced by the soil cultivation mode and the fertilization conditions, such as: the requirement of dense population areas on high yield of grains forms a habit of destroying the physicochemical properties of soil, namely continuous cropping of cultivated land and crops; continuous cropping of crops can destroy the diversity of microorganisms in soil and cause flora imbalance, and can cause the reduction of soil activity and the continuous growth obstacle of crops. It goes without saying that the long term use of fertilizers is even more a negative factor that seriously affects the soil microflora, the flora structure. This is a malignant cycle; the continuous crop growth obstacle can form the shortage of grain demand, the grain shortage and the lack of cultivated land drive the large-scale use of crop continuous cropping and fertilizer stimulation methods, and the crop continuous cropping and the fertilizer stimulation in turn push the degradation cycle of soil activity reduction and crop growth obstacle. That is, if the inorganic mineral-derived acidic fertilizer is used for a long period of time in soil lacking sufficient humic substances, many serious social and ecological problems are caused. Therefore, there is a need to develop new technical approaches that can provide "fertilizers", i.e. growth stimulants, to agricultural soils.

It is estimated that: the total energy contained in the wet biomass solid waste and organic liquid waste residues in continental china is about 90MToe (million tons oil equivalent, equivalent to 63 billion barrels of oil), and the proportions of the corresponding wastes are as follows: about 55.5% i.e. about 50MToe (million ton oil equivalent) of agricultural waste residues, about 33.3% i.e. 30MToe (million ton oil equivalent) of forestry waste residues and about 11.1% i.e. 10MToe (million ton oil equivalent) of food residues. In addition to forestry residues, which are high-quality raw materials for various purposes, municipal and agricultural wet wastes, such as sludge, kitchen and kitchen waste, are not developed into renewable resources at present, and become a main urban environmental pollution source. Although, in general, in addition to being used as animal feed, the existing liquid residue treatment methods are mainly as follows: incineration (more than 60 percent), landfill, composting and anaerobic digestion. So that (carbon) -containing energy is currently recovered from these liquid residues (including sewage sludge and digestive juice) only by improving combustion efficiency in addition to the detoxification, weight reduction treatment.

Since the incineration waste heat recovery process is not a way of converting organic matter into high-efficiency energy per se (since more than two thirds of biomass can be consumed in the drying stage before biomass conversion along with the emission of carbon dioxide generated by heat energy dissipation and incineration heating in the process of converting wet biomass into electric energy), even the most popular Watettoenergy power plant at present cannot avoid the harmful emission to the environment, and cannot economically realize independent and feasible commercial logics of wet biomass residue treatment and disposal, so that the disposal and recovery of liquid or wet biomass solid waste become increasingly difficult.

Therefore, how to realize the 'clean' regeneration of wet biomass or organic liquid residue resources without converting the wet biomass or organic liquid residue resources into heat energy for treatment and utilization in the current expensive and inefficient incineration manner, and effectively recombine wet organic wastes in the direction of carbon-containing organic compounds, and efficiently upgrade the low-quality wet biomass and organic liquid residue wastes into high-value resources of various carbon source materials and carbon-based compound products becomes a technical problem to be solved urgently.

Disclosure of Invention

In order to improve the above technical problems, the present invention provides a modified water coke which is a stable carbon compound having a sponge-like structure.

According to an embodiment of the invention, the modified water coke has water retention properties (also called water retention properties).

According to an embodiment of the invention, the modified water coke (at any pH) is insoluble in water.

According to an embodiment of the invention, the modified water coke has acid and base resistance properties, i.e. is neither soluble in base (high pH) nor in acid (low pH).

According to an embodiment of the invention, the modified water coke has a carbon structure and carbon stability properties similar to humins. By analogy with the properties of natural humins in soil, we consider them "artificial humins" obtained from the modification of water coke.

According to an embodiment of the invention, the molecular weight (M) of the modified water coke_W) Not less than 10 ten thousand, such as between 10 ten thousand and 1000 ten thousand, illustratively 10 ten thousand, 20 ten thousand, 50 ten thousand, 80 ten thousand, 100 ten thousand, 200 ten thousand, 300 ten thousand, 400 ten thousand, 500 ten thousand, 600 ten thousand, 800 ten thousand, 1000 ten thousand, or any point value between any two combinations of the aforementioned point values.

According to the embodiment of the invention, the modified water coke takes water coke as a raw material, and the water coke is subjected to nano-structure modification to form a carbon compound with a sponge-like structure, namely the modified water coke.

According to an embodiment of the invention, the water coke is obtained from biomass by hydrothermal reforming (HTR) treatment. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (HTH).

Preferably, the water coke is a dense structure water coke.

According to embodiments of the invention, the biomass includes, but is not limited to, one, two or more of the following: all plants, microorganisms and animals that feed on them, as well as waste products from their metabolism and/or production. For example, the biomass is at least one of grain, straw other than fruit, lignocellulose such as trees, organic fractions in agricultural and forestry waste, food waste, or municipal solid waste (OFMSW), and the like. More preferably, the biomass is a wet biomass with a high water content, such as a wet biomass with a water content above 30 wt%, such as a wet biomass with a water content above 40 wt%, 50 wt%, 60 wt%, 70 wt%, exemplified by at least one of plant straw, chaff, vegetation fallen leaves, garden pruning fallen leaves, landscaping waste, organic fraction of food waste or municipal solid waste, etc.

The invention also provides a preparation method of the modified water coke, which comprises the step of modifying the water coke in a nano structure by taking the water coke as a raw material to form a carbon compound with a spongy structure, namely the modified water coke.

According to an embodiment of the invention, the water coke is obtained from biomass by hydrothermal reforming (HTR) treatment. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) or hydrothermal humification (i.e., a mixing process of HTH and hydrothermal carbonization). Preferably, the biomass has the meaning as described above.

According to embodiments of the present invention, the method of modifying nanostructures may be an oxygen-free pyrolysis method.

According to embodiments of the present invention, the treatment temperature for the water coke HTC forming process is 200-280 deg.C, such as 220-270 deg.C, and exemplary 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C, 267 deg.C, 270 deg.C, 280 deg.C.

The order of operation of the HTC process step or the HTC and HTH mixing process step according to embodiments of the present invention is not particularly limited, as the HTH process step precedes the HTC process step.

According to an embodiment of the present invention, the HTH process is performed at a temperature of not less than 150 ℃ and less than 200 ℃, for example, 160 ℃ and 190 ℃, and exemplary temperatures are 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 191 ℃, and 195 ℃.

According to an embodiment of the invention, the temperature of the anaerobic pyrolysis process is 350-.

According to an embodiment of the invention, the oxygen-free pyrolysis process is carried out under an inert atmosphere. For example, the inert atmosphere may be provided by nitrogen and/or helium, preferably nitrogen. Further, the flow rate of the nitrogen gas is 0.5 to 3L/min, for example, 1 to 2L/min.

According to an embodiment of the invention, the anaerobic pyrolysis process is carried out for a time of 1 to 5h, such as 2 to 4h, exemplarily 1h, 2h, 3h, 4h, 5 h.

According to an embodiment of the present invention, the anaerobic pyrolysis treatment may be carried out in the presence or absence of a catalyst. For example, the catalyst is KOH.

According to an embodiment of the present invention, the method for preparing the modified water coke comprises the steps of: carrying out hydrothermal recombination treatment on the biomass to obtain water coke; and (3) carrying out anaerobic pyrolysis treatment on the water coke to obtain the modified water coke.

The invention also provides application of the modified water coke in the fields of soil, planting industry and the like. For example, as soil fertilizers, to promote the ecological balance of soil microorganisms and soil animals, to promote the degradation or inactivation of toxic substances in soil, to improve soil pH, to fertilizer plants, to promote plant growth, to irrigate plants, and the like.

The invention also provides a fertilizer which contains the modified water coke or a fertilizer prepared by taking the modified water coke as a raw material. Wherein, the fertilizer can be a solid-liquid mixed fertilizer or a solid fertilizer. Preferably, the fertilizer is used as a soil fertilizer and/or a plant fertilizer.

According to an embodiment of the invention, humic acid (humic acid or/and fulvic acid) is also added to the fertilizer. Preferably, the humic acid may be natural humic acid or artificial humic acid (also referred to as "artificial humic acid").

According to an embodiment of the invention, the artificial humic acid contains a high content of aromatic and long-chain aliphatic hydrocarbon structures. For example, the content of the aromatic hydrocarbon is 7.30 to 7.50%, and the content of the long-chain aliphatic hydrocarbon is 7.10 to 7.20%. Illustratively, the content of aromatic hydrocarbons is 7.43%, and the content of long-chain aliphatic hydrocarbons is 7.15%.

According to an embodiment of the present invention, the artificial humic acid may be prepared according to the method disclosed in Fan Yang et al, A hydrophytic process to turn waste biological inter-organic humic fluidic and nucleic acids for soil registration, Science of the Total environmental, 686(2019), 1140-1151.

According to an embodiment of the invention, the fertilizer further comprises an organic carbon medium nutrient.

According to an embodiment of the invention, the source of organic carbon media nutrients comprises: a liquid phase working medium obtained in the preparation process of the hydrothermal working procedures such as HTC and/or HTH; or the liquid phase working medium is further concentrated and circularly treated.

According to an embodiment of the present invention, the liquid-phase working medium contains at least one of inorganic elements such as potassium, phosphorus, nitrogen, and the like. Preferably, the inorganic element may also be present in the form of a salt thereof, such as a potassium salt, a phosphate, a nitrate, and the like. Preferably, the concentration of the inorganic element is adjustable, for example, to suit the application of the modified water coke product, such as having a designed concentration of the inorganic element.

According to an embodiment of the invention, the liquid phase working medium contains organic carbon in different forms.

According to an embodiment of the present invention, the liquid phase working medium contains organic matter. Examples of the organic substance include carboxylic acids and furfural, preferably short-chain carboxylic acids (meaning fatty acids having less than 6 carbon atoms in the carbon chain), Hydroxymethylfurfural (HMF), and exemplified by formic acid, acetic acid, propionic acid, levulinic acid, amino acids, and the like. Preferably, the concentration of the organic substance is adjustable, for example, according to the application of the liquid phase working medium, such as containing the designed concentration of the organic substance.

According to an embodiment of the present invention, the liquid phase working medium may further contain one, two or more of plant amine, lignophenol, furan, fulvic acid, humic acid, and the like. Preferably, the concentration of these substances is adjustable, for example, according to the application of the liquid-phase working medium, such as to contain the designed concentration.

According to an embodiment of the present invention, the liquid phase working medium contains no or little substances harmful to plants (preferably crops), animals, soil, etc. For example, the harmful material includes, but is not limited to, at least one of harmful organic substances, harmful inorganic substances, heavy metal elements, and the like. Wherein, the hardly containing means that the content of harmful substances is below 0.05%, for example below 0.02%, as well as below 0.01% or other design content.

According to an embodiment of the invention, the number of concentration cycles is at least one, two, three or more. Preferably, the concentration of the elements in the liquid phase working medium after the concentration cycle corresponds to the desired nutrient content in the agricultural product.

According to embodiments of the present invention, during the concentration cycle treatment, one, two or more treatment modes may include, but are not limited to, adjusting pH, adjusting hydrothermal carbonization feed, adjusting components of hydrothermal carbonization liquid phase working medium, component output, optionally adding or not adding other reactants, additives (e.g., heavy metal settling agents, etc.), and the like.

According to the embodiment of the invention, during the concentration cycle treatment, the separation (for example, adsorption separation) of toxic substances and/or elements, ions, groups and/or substance molecules which may form toxic substances contained in the water coke obtained from the hydrothermal carbonization treatment from the medium water or the inhibition of the formation of toxic substances can be further included.

For example, the elements that may form toxic substances include, but are not limited to, S, Cl, at least one of heavy metals, and the like.

For example, the ions that may form toxic substances include, but are not limited to, heavy metal ions and the like.

Preferably, the separation can be achieved by adding a catalyst to the hydrothermal carbonization medium water and/or by means of a change and/or addition of an interference loop of the medium water or the like to separate and/or suppress the formation of toxic substances, such as chlorophenol family compounds.

According to an embodiment of the invention, the fertilizer contains the modified water coke, humic acid and organic carbon medium nutrients.

The invention also provides a preparation method of the fertilizer, which comprises the step of preparing the fertilizer from the raw material containing the modified water coke.

According to an embodiment of the invention, the preparation method of the fertilizer comprises the preparation of raw materials containing the modified water coke, humic acid and organic carbon medium nutrient.

The present invention also provides an organic carbon mediator nutrient having the meaning as hereinbefore described.

The invention also provides a preparation method of the organic carbon medium nutrient, which comprises a liquid phase working medium obtained in the preparation process of the hydrothermal working procedures such as HTC and/or HTH; or further concentrating the liquid phase working medium.

The invention also provides a soil fertilizer which contains the modified water coke or is prepared from raw materials containing the modified water coke. Wherein, the soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

The invention also provides a preparation method of the soil fertilizer, which comprises the step of preparing the soil fertilizer from the raw material containing the modified water coke.

The invention also provides a soil conditioner which contains the modified water coke or is prepared from raw materials containing the modified water coke. Wherein, the soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

The invention also provides a preparation method of the soil conditioner, which comprises the step of preparing the soil conditioner from raw materials containing the modified water coke.

The invention also provides a plant fertilizer which contains the modified water coke or is prepared from the raw material containing the modified water coke. Wherein, the plant fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

The invention also provides a preparation method of the plant fertilizer, which comprises the step of preparing the plant fertilizer from the raw material containing the modified water coke.

The invention also provides a plant growth agent which contains the modified water coke or is prepared by taking the modified water coke as a raw material.

The invention also provides a preparation method of the plant growth agent, which comprises the step of preparing the plant growth agent from the raw material containing the modified water coke.

The invention has the beneficial effects that:

(1) the inventors surprisingly found that the modified water coke prepared by the invention has similar structure and function with the humins, can provide good energy sources beneficial to soil organisms, and provides the required energy and mineral requirements for soil microorganisms and soil animals. Beneficial soil organisms lack photosynthetic devices for harvesting energy from the sun and must therefore survive on or in the soil containing residual carbon material. The energy stored within the carbon bonds may provide energy for various metabolic reactions within these organisms. Beneficial soil organisms (algae, yeasts, bacteria, fungal nematodes, mycorrhiza and small animals) have many beneficial functions that affect soil fertility and plant health. For example, bacteria release organic acids, which aid in the solubilization of bound mineral elements in the soil. Bacteria also release complex polysaccharides (sugar-based compounds) that help create soil debris (aggregates). The soil debris gives the soil the desired structure. Other beneficial soil microorganisms, such as actinomycetes, release antibiotics into the soil. These antibiotics are absorbed by plants to protect against pests. Antibiotics also create the ideal ecological balance of soil organisms on the root surface (rhizosphere) and on the soil near the root (rhizosphere). Fungi also have many beneficial functions in soil. For example, mycorrhiza helps plant roots absorb moisture and trace elements. Other fungi break down crop residues and nutrients to release bound nutrients for other organisms. Many organic compounds released by fungi contribute to the formation of humus and soil debris. Beneficial soil animals form tunnel-like pathways in the soil. These channels allow the soil to breathe and exchange gas with the atmosphere. Soil animals also contribute to humus formation and to the balance of soil microbial concentrations. Healthy fertile soil must contain sufficient carbon-containing compounds to sustain the billions of microscopic lives required by fertile soil and healthy plants in a healthy and active manner.

(2) The modified water coke prepared by the invention can guide the degradation or inactivation of toxic substances in soil, and the formed mixture of the modified water coke and soil humus substances can more stably or effectively assist the degradation of the toxic substances (such as nicotine, aflatoxin, antibiotics, chive and most organic pesticides). Not all of the carbon contained in these toxins is released as CO during microbial degradation₂. Some of these toxic molecules, mainly aromatic ring compounds, are stably integrated in the complex polymers of humic substances. The humus has charged sites on the surface, and can attract inactivated pesticide and other toxic substances. Therefore, humic acid in the modified water coke structure prepared by the invention can efficiently clean places occupied and accumulated by toxic wastes in soil, and many biological repairing activities actively apply humic compounds to chelation of toxic elements and combine other humic substances to accelerate degradation and cleaning of poisons (toxins) (destroy the toxicity of various toxic pesticides). Meanwhile, the modified water coke also assists humic acid to stabilize and inactivate enzymes in soil. The enzymes of the soil (complex proteins) are stabilized by the humic substances in the soil by covalent bonds of the carbon element, making these enzymes less susceptible to microbial degradation. Once stabilized and bound to the humic substance, the enzymatic activity is greatly reduced or ceases to function. However, there areMany covalent bonds are relatively weak when changes in pH occur in the soil and these enzymes are released. When certain components of the humic substance react with soil enzymes, they are more tightly bound. For example, phenolase complexes are often attached to clay, further stabilizing the enzyme. These enzyme stabilization processes help to limit the activity of potential plant pathogens. When a potential plant pathogen releases enzymes to disrupt plant defenses, the pathogen enzymes bind to the humus material, preventing the pathogen from invading the potential host plant.

(3) The modified water coke prepared by the invention can buffer (neutralize) the pH value of soil by combining with humus substances, release carbon dioxide and play a role in buffering the concentration of hydrogen ions (pH) in soil. Experimental evidence suggests that the addition of modified water coke to soil helps to neutralize the pH of the soil. Both acidic and alkaline soils are neutralized. Once the soil is neutralized, many of the trace elements previously incorporated in the soil that could not be used in the plant root system are utilized by the plant root system due to alkaline or acidic conditions. The combined action of the modified coke bound humus also releases carbon dioxide CO from calcium carbonate present in the soil₂. The released carbon dioxide is absorbed by the plant and may also form carbonic acid. Carbonic acid will act on the soil minerals, releasing plant nutrients, providing energy to beneficial organisms in the soil, improving the water holding capacity of the soil, affecting the soil structure, releasing plant nutrients from soft minerals, increasing the availability of trace minerals and generally improving the soil fertility. The soil temperature and the water evaporation rate are stabilized by the coaction of the modified water coke and the humus substances. The method is beneficial to stabilizing the soil temperature and slowing down the water evaporation rate. The insulating properties of humus materials help to maintain a more uniform soil temperature, particularly during periods of rapid climatic change, such as cold or hot waves. Soil moisture is less likely to be released into the atmosphere as water is bound in the humus, reducing temperature fluctuations. The range of direct effects includes changes in plant metabolism. Promote the entry of organic macromolecules such as humic acid and fulvic acid compounds into plant cells, and once these compounds enter the plant cells, the membrane and various cytoplasm components of the plant cells undergo several biochemical changes to promote the improvement of plant metabolism conditions。

(4) The composition containing the modified water coke, humic acid (preferably artificial humic acid) and/or organic carbon medium nutrient can be widely used for soil fertilizers, soil microorganism and soil animal ecological balance promotion, soil toxic substance degradation or inactivation promotion, soil pH improvement, plant fertilizers, plant growth promotion, plant irrigation and the like, and can obtain excellent effects.

Drawings

FIG. 1 is a graph showing the effect of modified water coke of the present invention on soil pH at 1d, 3d, 6d, 10d, 17d, 21d, 26 d.

FIG. 2 is a graph showing the effect of modified water coke of the present invention on the organic matter content of soil at 1d, 3d, 6d, 10d, 17d, 21d, 26 d.

FIG. 3 is a graph showing the effect of modified water coke of the present invention on the content of available phosphorus in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d.

FIG. 4 is a graph showing the effect of modified water coke of the present invention on the content of quick-acting nitrogen in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d.

FIG. 5 is a graph showing the effect of modified water coke of the present invention on the content of available potassium in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Example 1

A modified water coke, which is a carbon compound having a sponge-like structure.

The modified water coke has water retention properties (also referred to as water retention properties).

The modified water coke is insoluble in water at any pH.

The modified water coke has acid and base resistance properties, i.e., is insoluble in neither base (high pH) nor acid (low pH).

The modified water coke has a carbon structure and properties similar to humins. Wherein the humins can be natural humins or artificial humins.

Molecular weight (M) of the modified water coke_W) Not less than 10 ten thousand, such as between 10 ten thousand and 1000 ten thousand, illustratively 10 ten thousand, 20 ten thousand, 50 ten thousand, 80 ten thousand, 100 ten thousand, 200 ten thousand, 300 ten thousand, 400 ten thousand, 500 ten thousand, 600 ten thousand, 800 ten thousand, 1000 ten thousand, or any point value between any two combinations of the aforementioned point values.

The modified water coke takes water coke as a raw material, and the water coke is subjected to nano-structure modification to form a carbon compound with a spongy structure, namely the modified water coke.

In one embodiment, the water coke is obtained from biomass by hydrothermal reforming (HTR) treatment. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (HTH). Preferably, the water coke is a dense structure water coke.

The biomass includes, but is not limited to, one, two or more of the following: all plants, microorganisms and animals that feed on them, as well as waste products from their metabolism and/or production. For example, the biomass is at least one of grain, straw other than fruit, lignocellulose such as trees, organic fractions in agricultural and forestry waste, food waste, or municipal solid waste (OFMSW), and the like. More preferably, the biomass is a wet biomass with a high water content, such as a wet biomass with a water content above 30 wt%, such as a wet biomass with a water content above 40 wt%, 50 wt%, 60 wt%, 70 wt%, exemplified by at least one of plant straw, chaff, vegetation fallen leaves, garden pruning fallen leaves, landscaping waste, organic fraction of food waste or municipal solid waste, etc.

In one embodiment, the treatment temperature of the hydrothermal carbonization (HTC) process is 200-280 ℃, such as 220-270 ℃, and exemplary 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 267 ℃, 270 ℃, 280 ℃.

In one embodiment, the HTH process is located before the HTC process.

In one embodiment, the HTH process has a treatment temperature of not less than 150 ℃ and less than 200 ℃, such as 190 ℃ at 160 ℃, and exemplary temperatures of 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 191 ℃, and 195 ℃.

Example 2

The method for producing modified water coke according to example 1 includes modifying the water coke into a nano structure using the water coke as a raw material to form a carbon compound having a sponge-like structure, that is, a modified water coke.

The method of modifying the nanostructures is an oxygen-free pyrolysis method.

The water coke is obtained by treating biomass through hydrothermal recombination (HTR). For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (i.e., HTH). Preferably, the water coke, biomass has the meaning as described in example 1.

In one embodiment, the anaerobic pyrolysis process is carried out at a temperature of 350-.

The anaerobic pyrolysis treatment is carried out under an inert atmosphere. For example, the inert atmosphere may be provided by nitrogen and/or helium, preferably nitrogen. Further, the flow rate of the nitrogen gas is 0.5 to 3L/min, for example, 1 to 2L/min.

The anaerobic pyrolysis treatment time is 1 to 5 hours, such as 2 to 4 hours, and is exemplified by 1 hour, 2 hours, 3 hours, 4 hours, 5 hours.

The oxygen-free pyrolysis treatment may be carried out in the presence or absence of a catalyst. For example, the catalyst is KOH.

In one embodiment, the method of making the modified water coke comprises the steps of: carrying out hydrothermal recombination treatment on the biomass to obtain water coke; and (3) carrying out anaerobic pyrolysis treatment on the water coke to obtain the modified water coke.

The modified water coke is applied to the fields of soil, planting industry and the like. For example, as soil fertilizers, to promote the ecological balance of soil microorganisms and soil animals, to promote the degradation or inactivation of toxic substances in soil, to improve soil pH, to fertilizer plants, to promote plant growth, to irrigate plants, and the like.

Example 3

A fertilizer comprising the modified water coke of example 1 or the modified water coke produced by the production method of example 2, or a fertilizer produced from the modified water coke as a raw material. Wherein, the fertilizer can be a solid-liquid mixed fertilizer or a solid fertilizer. Preferably, the fertilizer is used as a soil fertilizer and/or a plant fertilizer.

In one embodiment, the fertilizer further comprises humic acid. Preferably, the humic acid may be natural humic acid or artificial humic acid (also referred to as "artificial humic acid").

The artificial humic acid contains more aromatic hydrocarbons and long-chain aliphatic hydrocarbon structures. For example, the content of the aromatic hydrocarbon is 7.30 to 7.50%, and the content of the long-chain aliphatic hydrocarbon is 7.10 to 7.20%. Illustratively, the content of aromatic hydrocarbons is 7.43%, and the content of long-chain aliphatic hydrocarbons is 7.15%.

The artificial humic acid can be prepared according to the method disclosed in Fan Yang et al, A thermal process to turn waste biological and human acids for soil registration, Science of the Total environmental, 686(2019),1140 and 1151.

In one embodiment, the fertilizer further comprises an organic carbon medium nutrient.

Sources of the organic carbon media nutrients include: a liquid phase working medium obtained in a preparation process of hydrothermal processes such as HTC and/or HTH described in example 2; or the liquid phase working medium is further concentrated and circularly treated.

The liquid phase working medium contains at least one of inorganic elements such as potassium, phosphorus, nitrogen, and the like. Preferably, the inorganic element may also be present in the form of a salt thereof, such as a potassium salt, a phosphate, a nitrate, and the like. Preferably, the concentration of the inorganic element is adjustable, for example, according to the application of the modified water coke product, such as containing the inorganic element at a designed concentration.

The liquid phase working medium contains organic carbon in different forms.

The liquid phase working medium contains organic matter. Examples of the organic substance include carboxylic acids and furfural, preferably short-chain carboxylic acids (meaning fatty acids having less than 6 carbon atoms in the carbon chain), Hydroxymethylfurfural (HMF), and exemplified by formic acid, acetic acid, propionic acid, levulinic acid, amino acids, and the like. Preferably, the concentration of the organic substance is adjustable, for example, according to the application of the liquid phase working medium, such as containing the designed concentration of the organic substance.

In one embodiment, the liquid phase working medium may further contain one, two or more of plant amine, lignophenol, furan, fulvic acid, humic acid, and the like. Preferably, the concentration of these substances is adjustable, for example, according to the application of the liquid-phase working medium, such as to contain the designed concentration.

In one embodiment, the liquid working medium contains no or little substances harmful to plants (preferably crops), animals, soil, etc. For example, the harmful material includes, but is not limited to, at least one of harmful organic substances, harmful inorganic substances, heavy metal elements, and the like. Wherein, the hardly containing means that the content of harmful substances is below 0.05%, for example below 0.02%, as well as below 0.01% or other design content.

Wherein the number of concentrating cycles is at least one, two, three or more. Preferably, the concentration of the elements in the liquid phase working medium after the concentration cycle corresponds to the desired nutrient content in the agricultural product.

In one embodiment, during the concentration cycle treatment, one, two or more treatments may include, but are not limited to, adjusting pH, adjusting hydrothermal carbonization feed, adjusting the composition of the hydrothermal carbonization liquid phase working medium, component output, optionally with or without the addition of other reactants, additives (e.g., heavy metal settling agents, etc.), and the like.

In one embodiment, the concentration cycle treatment process may further include separating toxic substances and/or elements, ions, radicals and/or substance molecules which may form toxic substances contained in the water coke obtained from the hydrothermal carbonization treatment from the medium water (e.g., adsorption separation), or inhibiting the formation of toxic substances.

In one embodiment, the fertilizer contains the modified water coke, humic acid, and organic carbon media nutrients.

The preparation method of the fertilizer comprises the step of preparing the fertilizer from raw materials containing the modified water coke prepared in the example 1 and/or the modified water coke prepared in the preparation method in the example 2.

In one embodiment, the method of producing the fertilizer comprises producing a feedstock comprising the modified water coke of example 1 and/or the modified water coke of example 2, humic acid, and organic carbon media nutrient.

Example 4

An organic carbon mediator nutrient having the meaning as described in example 3.

The preparation method of the organic carbon medium nutrient comprises the steps of preparing a liquid-phase working medium in the hydrothermal working procedure preparation processes of HTC, HTH and the like in the embodiment 2; or further concentrating the liquid phase working medium.

Example 5

A soil fertilizer comprising the modified water coke of example 1 and/or the modified water coke obtained by the production method of example 2 or produced from a raw material comprising the modified water coke. Wherein, the soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

The preparation method of the soil fertilizer comprises the step of preparing the soil fertilizer from raw materials containing the modified water coke prepared in the embodiment 1 and/or the modified water coke prepared in the embodiment 2.

Example 6

A soil conditioner comprising the modified water coke of example 1 and/or the modified water coke prepared by the method of example 2 or prepared from a raw material comprising the modified water coke. Wherein, the soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

The preparation method of the soil conditioner comprises the step of preparing the modified water coke prepared by the preparation method of example 1 and/or example 2 from raw materials.

Example 7

A plant fertilizer, which contains the modified water coke described in the embodiment 1 and/or the modified water coke prepared by the preparation method described in the embodiment 2 or is prepared by raw materials containing the modified water coke. Wherein, the plant fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

The preparation method of the plant fertilizer comprises the step of preparing the plant fertilizer from raw materials containing the modified water coke prepared in the embodiment 1 and/or the modified water coke prepared in the preparation method in the embodiment 2.

Example 8

A plant growth agent, which contains the modified water coke described in the embodiment 1 and/or the modified water coke prepared by the preparation method described in the embodiment 2 or is prepared by using the modified water coke as a raw material.

The preparation method of the plant growth agent comprises the step of preparing the plant growth agent from raw materials containing the modified water coke prepared in the embodiment 1 and/or the modified water coke prepared in the preparation method in the embodiment 2.

Example 9: preparation of samples

Raw materials: dry sludge of municipal sludge is selected as a raw material, wherein the municipal sludge is derived from excess sludge of a sewage treatment plant, the water content of the excess sludge is 90.4 percent, and the excess sludge is dried at 105 ℃ to constant weight to obtain the dry sludge. 5g of the above raw material was treated by the following method:

(1) pyrolysis: and (3) carrying out anaerobic pyrolysis treatment for 1h at 700 ℃ under the vacuum condition of an atmosphere furnace to obtain a sample 1.

(2) Hydrothermal carbonization: 145mL of water was added to 5g of dry sludge, and then hydrothermally carbonized at 200 ℃ under the own pressure (no applied pressure) for 1h to obtain sample 2.

(3) Hydrothermal carbonization pyrolysis: adding 145mL of water into 5g of dry sludge, performing hydrothermal carbonization for 1h at 200 ℃ under self pressure (no external pressure), performing solid-liquid separation, drying the solid to constant weight at 105 ℃, and performing anaerobic pyrolysis treatment for 1h at 700 ℃ under the vacuum condition of an atmosphere furnace to obtain a modified water coke sample 3 which is a carbon material with a spongy structure.

(4) Hydrothermal carbonization pyrolysis activation: carrying out hydrothermal carbonization for 1h at 200 ℃ under self pressure (no external pressure), carrying out solid-liquid separation, drying the solid at 105 ℃ to constant weight, carrying out anaerobic pyrolysis treatment for 1h at 700 ℃ under the vacuum condition of an atmosphere furnace, using a potassium hydroxide solution with the concentration of 3mol/L as an activating agent, soaking for 8h according to the solid-liquid ratio of 1:45, washing with ultrapure water until the pH value of a cleaning solution is neutral, and drying at 150 ℃ to constant weight to obtain a modified water coke sample 4.

(5) Process (4) was repeated except that an aqueous nitric acid solution having a concentration of 6mol/L was used as an activator, to obtain a modified water coke sample 5.

(6) Process (4) was repeated except that a sodium hydroxide solution having a concentration of 3mol/L was used as an activator to obtain modified water coke sample 6.

Test example 1: determination of specific surface area

The samples 1 to 4 of example 9 were ground, respectively, and then passed through a 200-mesh sieve, and the specific surface area thereof was measured using a physical adsorption apparatus, and the results are shown in table 1 below.

TABLE 1

The results in table 1 show that the specific surface area of the sample can be remarkably increased compared with the sample treated by the anaerobic pyrolysis method, wherein the modified water coke is obtained by performing hydrothermal carbonization treatment and anaerobic pyrolysis treatment on the biomass raw material; and after the active modification treatment, the specific surface area of the modified water coke can be further increased (about two times of the specific surface area). Therefore, the specific surface area of the modified water coke can be obviously improved by adopting a mode of combining hydrothermal carbonization and an anaerobic pyrolysis method through the synergistic effect of the hydrothermal carbonization and the anaerobic pyrolysis method.

Test example 2: determination of iodine adsorption value

The iodine adsorption values of modified water coke samples 4, 5 and 6 were measured in accordance with "measurement of iodine adsorption value in test method for Wood-based activated carbon (GB/T12496.8-1999)" and the results are shown in Table 2 below.

TABLE 2

Sample (I)	Sample No. 4	Sample No. 5	Sample No. 6
				Iodine value (mg/g)	426	564	548

Test example 3: determination of available phosphorus and potassium content

According to the method for measuring the content of available phosphorus in the compound fertilizer, the content of available phosphorus in a dry sludge raw material and a modified water coke sample 3 is measured; and the potassium content of the modified water coke sample 3 was determined according to the aqua regia extraction-inductively coupled plasma mass spectrometry. The results are shown in table 3 below.

TABLE 3

Sample (I)	Raw material of dry sludge	Modified water coke
			Effective phosphorus content (in P)₂O₅Meter)	29.775g/kg	134.675g/kg
Potassium content	-	77.918g/kg

Note: "-" means not determined.

From the above table results, it can be seen that: after the dry sludge is modified by hydrothermal carbonization and anaerobic pyrolysis treatment, the content of available phosphorus is remarkably improved.

Test example 3: adsorption Capacity test

The samples 5 and 6 prepared in example 9 and a coconut shell activated carbon sample (sample Y, the iodine value of which is 997mg/g) are respectively mixed with a hydrothermal treatment liquid (liquid before adsorption), wherein the dosage of the samples is 10% of the mass of the hydrothermal treatment liquid, and after shaking at normal temperature overnight, the COD and ammonia nitrogen contents in the solution are detected. Wherein: the COD content is determined according to a dichromate method; the ammonia nitrogen content was measured by the nano-assay spectrophotometry, and the results are shown in table 4 below.

TABLE 4

	COD(g/L)	Ammonia nitrogen (mg/L)
			Pre-adsorption liquid	13.05	452.4
Post-adsorption liquid (sample 5)	5.34	111.6
			Post-adsorption liquid (sample 6)	5.15	152.4
Post-adsorption liquid (sample Y)	5.31	263.2

From the above table results, it can be seen that: compared with the commercially available coconut shell activated carbon, the modified water coke prepared by the method has the same COD adsorption capacity as the commercially available coconut shell activated carbon, but the ammonia nitrogen adsorption capacity is obviously higher than that of the coconut shell activated carbon.

Test example 4: test for sustained Release

(1) Samples 5 and 6 in test example 3, which had absorbed the hydrothermal treatment solution, were dried at 105 ℃ to constant weight, and ultrapure water was added thereto, wherein the mass ratio of the dried sample to water was 1: 10. After shaking and soaking overnight at normal temperature (counting as the 1 st time of soaking), the COD and ammonia nitrogen content in the aqueous solution are detected.

(2) And (3) separating the solid in the mixture obtained in the step (1), drying again under the same drying condition, adding water with the same mass as that in the step (1), repeating the steps for 3 times (respectively counting as soaking for the 2 nd time, the 3 rd time and the 4 th time), and respectively measuring the contents of COD and ammonia nitrogen in the solution, wherein the contents are summarized in the following table.

TABLE 5

From the above table results, it can be seen that: the modified water coke prepared by the invention has a slow release effect.

Test example 5: improving soil nutrition

Air-dried soil passing through a 2mm sieve was taken and mixed into the modified water coke sample 5 adsorbed in test example 3 in an amount of 1% of the total soil amount, and after uniformly mixing, the mixture was placed in 20 identical plastic containers respectively and cultured, the soil loading in each container was 200g, and air-dried soil not mixed with modified water coke was similarly placed in another 20 plastic containers and cultured as a control. During the experiment, the soil moisture in the pot is controlled to be about 28 percent (equivalent to 75 percent of field moisture capacity) by a weighing method.

In the initial stage of soil culture, samples of soil were taken at 1d, 3d, 6d, 10d, 17d, 21d and 26d, and physicochemical analysis was performed for a total of 26 d. After the soil sample is air-dried, part of the soil sample is screened by 20-mesh and 100-mesh soil screens by a quartering method and then is used for measuring soil quality indexes.

Wherein, the physical and chemical properties of the soil are measured by the method of Baysantin.

The content of organic matters is measured by a potassium dichromate volumetric method-an external heating method; the pH value adopts a pH meter method (the water-soil ratio is 5: 1); the content of the quick-acting nitrogen is measured by an alkaline hydrolysis diffusion method; the content of the quick-acting phosphorus is measured by 0.5mol/L sodium bicarbonate leaching-molybdenum-antimony anti-colorimetric method; the content of the quick-acting potassium is determined by adopting 1mol/L ammonium acetate extraction-ICP-OES method.

FIG. 1 is a graph showing the effect of modified water coke of the present invention on soil pH at 1d, 3d, 6d, 10d, 17d, 21d, 26 d. FIG. 2 is a graph showing the effect of modified water coke of the present invention on the organic matter content of soil at 1d, 3d, 6d, 10d, 17d, 21d, 26 d. FIG. 3 is a graph showing the effect of modified water coke of the present invention on the content of available phosphorus in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d. FIG. 4 is a graph showing the effect of modified water coke of the present invention on the content of quick-acting nitrogen in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d. FIG. 5 is a graph showing the effect of modified water coke of the present invention on the content of available potassium in soil at 1d, 3d, 6d, 10d, 17d, 21d, and 26 d. As can be seen from the figure: the soil added with the modified water coke has more stable pH value, obviously improves the contents of soil organic matters, quick-acting nitrogen and quick-acting potassium, and especially has obvious effect of improving the content of the quick-acting potassium in the soil (after 20 days of incubation, the content of the quick-acting potassium in the soil added with the modified water coke is nearly doubled compared with the content of the quick-acting potassium in the soil without the modified water coke). Therefore, the modified water coke can obviously improve the content of effective nutrient substances in the soil, thereby improving the nutrient structure of the soil and providing a better growth environment for plants so as to promote the growth of the plants.

Test example 6: determination of nutrient content and heavy metal concentration in hydrothermal treatment liquid

60g of residual sludge (with the water content of 90.4 percent and fresh sludge) of a sewage treatment plant is added with 90mL of water for the first time, the retention time is 1h at 200 ℃, the stirring speed is 300rpm, and the mixture is recorded as 0-time circulation hydrothermal treatment liquid; filtering after the completion, adding 60g of fresh sludge into 90mL of filtrate, standing for 1h at 200 ℃, and recording as 1-time circulation hydrothermal treatment solution, wherein the stirring speed is 300 rpm; and filtering after the completion, adding 60g of fresh sludge into 90mL of filtrate, and keeping the mixture at 200 ℃ for 1h at the stirring speed of 300rpm, wherein the result is recorded as the circulation 2-time hydrothermal treatment solution.

After 2 cycles in ICP-MS, the final filtrate was filtered to obtain the heavy metal content (mg/L). The test results are shown in table 6.

And respectively taking 5mL of hydrothermal treatment solution in each circulation process to measure the contents of COD, ammonia nitrogen, total nitrogen and total phosphorus in the hydrothermal treatment solution.

Wherein: the COD content is determined according to a dichromate method; the method for testing the total nitrogen content is an alkaline potassium persulfate digestion ultraviolet spectrophotometry; the method for testing the total phosphorus content is a neutral potassium persulfate digestion spectrophotometry; the ammonia nitrogen content is measured by a nano-reagent spectrophotometry. The test results are shown in table 7.

TABLE 6

TABLE 7

Sample (I)	COD(mg/L)	Ammonia nitrogen (mg/L)	Total phosphorus (mg/L)	Total nitrogen (mg/L)
					Fresh sludge centrifugated filtrate	123.4	44.88	33.41	66.12
0-time circulation hydrothermal treatment liquid	14295	555.6	65.9	1446
					Circulating the hydrothermal treatment solution for 1 time	22575	736.8	118.1	1929
Circulating the hydrothermal treatment liquid for 2 times	25960	823.2	148.7	2248.5

As shown in table 7, the recycling of the hydrothermal treatment solution is beneficial to enriching the nutrient components in the hydrothermal treatment solution, so as to increase the concentration of the nutrient substances and further reduce the consumption of water.

Test example 7: content determination of humic acid in hydrothermal treatment liquid and water coke obtained after hydrothermal carbonization of sludge

Adding 100mL of water into 50g of fresh sludge, carrying out hydrothermal carbonization reaction in a sealed hydrothermal carbonization reaction kettle at the stirring speed of 300rpm, heating to 200 ℃, and preserving heat for 1 h. After the reaction is finished, the reaction material is cooled to room temperature, and then solid-liquid separation is carried out. Adding hydrochloric acid into the separated hydrothermal treatment liquid, adjusting the pH value to 2, standing for 30min, centrifuging, removing supernatant, dissolving precipitate with 1mol/L ammonia water, and determining the volume to 100ml, and then measuring the content of humic acid (namely the content of humic acid in the hydrothermal treatment liquid) by a volumetric method;

and drying the rest precipitate (water coke) at 105 ℃ to constant weight, weighing about 0.2g of sample, adding 100mL of 0.03mol/L sodium pyrophosphate solution, carrying out water bath at 80 ℃ for 1.5h, carrying out suction filtration, discarding filter residue, adding hydrochloric acid into the filtrate, adjusting the pH value to 2, standing for 30min, centrifuging, removing supernatant, dissolving the precipitate with 1mol/L ammonia water, fixing the volume to 100mL, and measuring the content of humic acid (namely the content of humic acid in the water coke) by a volumetric method.

Wherein: the method for measuring the content of humic acid by a volumetric method comprises the following steps:

10.0mL of the two solutions to be detected are sequentially and accurately sucked into a 250mL conical flask, 5.0mL of 0.8mol/L potassium dichromate solution is respectively added, 20mL of concentrated sulfuric acid is slowly added, and the two solutions are heated and oxidized for 30min in a boiling water bath. And taking the oxidized solution down from the boiling water bath, cooling to room temperature, adding 70mL of water and 5-6 drops of phenanthroline-ferrous mixed indicator, titrating by using ferrous sulfate standard titration solution (0.2mol/L), and finally changing the solution from orange to bright green and changing the solution to dark red as an end point. The volume (V) consumed by the ferrous sulfate standard titration solution was recorded. Blank experiments were performed according to the above procedure except that no sample was added. V when the absolute difference of the titration numbers of the two blank experiments is not more than 0.05mL₀The values are the two arithmetic averages.

The content omega of the water-soluble humic acid is expressed by mass fraction (%) and is calculated according to the following formula:

in the formula:

c, the concentration of the ferrous sulfate standard titration solution used in the titration sample and blank experiment is in unit of mol per liter (mol/L);

V₀-in a blank experiment, the concentration of the ferrous sulfate standard titration solution is consumed in units of moles per liter (mol/L);

v is the concentration of ferrous sulfate standard titration liquid in mol per liter (mol/L) when a sample is measured;

0.003-a value of carbon content equivalent to 1.00 ferrous sulfate standard titrant;

1.724-coefficient of organic carbon converted to organic matter;

1.43-product of oxidation correction factor 1.3 and humic acid precipitation factor 1.1;

m-the mass of the sample in (g).

The arithmetic mean of the replicates was taken as the assay (results retain three significant digits). The results of measuring the humic acid content in the hydrothermal treatment liquid and the water coke obtained by hydrothermal carbonization of the sludge are shown in table 8.

TABLE 8

Sample (I)	Content of humic acid
		Hydrothermal treatment liquid	100.55mg/L
Water coke	29.12mg/g

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A modified water coke, characterized in that the modified water coke is a carbon compound having a sponge-like structure.

Preferably, the modified water coke has water retention properties (also referred to as water retention properties).

Preferably, the modified water coke (at any pH) is insoluble in water.

Preferably, the modified water coke has acid and base resistance properties, i.e., is insoluble in neither base (high pH) nor acid (low pH).

Preferably, the modified water coke has a carbon structure and properties similar to humins. Wherein the humins can be natural humins or artificial humins.

Preferably, the molecular weight (M) of the modified water coke_W) Not less than 10 ten thousand, such as between 10 ten thousand and 1000 ten thousand, illustratively 10 ten thousand, 20 ten thousand, 50 ten thousand, 80 ten thousand, 100 ten thousand, 200 ten thousand, 300 ten thousand, 400 ten thousand, 500 ten thousand, 600 ten thousand, 800 ten thousand, 1000 ten thousand, or any point value between any two combinations of the aforementioned point values.

2. The modified water coke of claim 1, wherein the modified water coke is produced by using a water coke as a raw material and modifying the water coke to have a nano structure to form a carbon compound having a sponge-like structure, i.e., a modified water coke.

Preferably, the water coke is obtained from biomass by hydrothermal reforming (HTR) treatment. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (i.e., HTH). Preferably, the water coke is a dense structure water coke.

Preferably, the biomass includes, but is not limited to, one, two or more of the following: all plants, microorganisms and animals that feed on them, as well as waste products from their metabolism and/or production. For example, the biomass is at least one of grain, straw other than fruit, lignocellulose such as trees, organic fractions in agricultural and forestry waste, food waste, or municipal solid waste (OFMSW), and the like. More preferably, the biomass is a wet biomass with a high water content, such as a wet biomass with a water content above 30 wt%, such as a wet biomass with a water content above 40 wt%, 50 wt%, 60 wt%, 70 wt%, exemplified by at least one of plant straw, chaff, vegetation fallen leaves, garden pruning fallen leaves, landscaping waste, organic fraction of food waste or municipal solid waste, etc.

3. The method for preparing modified water coke according to claim 1 or 2, wherein the method comprises using water coke as a raw material, and performing nanostructure modification on the water coke to form a carbon compound having a sponge-like structure, i.e., modified water coke.

Preferably, the method of modifying the nanostructures may be an oxygen-free pyrolysis method.

Preferably, the water coke is obtained from biomass by hydrothermal reforming (HTR) treatment. For example, the hydrothermal recombination includes hydrothermal carbonization (HTC) and/or hydrothermal humification (HTH). Preferably, the biomass has the meaning as defined in claim 2.

Preferably, the HTC process has a treatment temperature of 200-.

Preferably, the HTH process step precedes the HTC process step.

Preferably, the HTH process has a treatment temperature of not less than 150 ℃ and less than 200 ℃, such as 160 ℃ and 190 ℃, and exemplary temperatures of 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 191 ℃, 195 ℃.

Preferably, the temperature of the anaerobic pyrolysis treatment is 350-700 ℃, such as 400-650 ℃, and exemplary 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃.

Preferably, the oxygen-free pyrolysis treatment is carried out under an inert atmosphere. For example, the inert atmosphere may be provided by nitrogen and/or helium, preferably nitrogen. Further, the flow rate of the nitrogen gas is 0.5 to 3L/min, for example, 1 to 2L/min.

Preferably, the anaerobic pyrolysis process is carried out for a time of 1 to 5h, such as 2 to 4h, exemplary 1h, 2h, 3h, 4h, 5 h.

Preferably, the oxygen-free pyrolysis treatment may be carried out in the presence or absence of a catalyst. For example, the catalyst is KOH.

Preferably, the preparation method of the modified water coke comprises the following steps: carrying out hydrothermal recombination treatment on biomass to obtain water coke; and (3) carrying out anaerobic pyrolysis treatment on the water coke to obtain the modified water coke.

4. Use of the modified water coke according to claim 1 or 2 and/or the modified water coke obtained by the method according to claim 3 in the fields of soil, planting industry and the like. For example, as soil fertilizers, to promote the ecological balance of soil microorganisms and soil animals, to promote the degradation or inactivation of toxic substances in soil, to improve soil pH, to fertilizer plants, to promote plant growth, to irrigate plants, and the like.

5. A fertilizer comprising the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3 or a fertilizer produced from the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3. Wherein, the fertilizer can be a solid-liquid mixed fertilizer or a solid fertilizer. Preferably, the fertilizer is used as a soil fertilizer and/or a plant fertilizer.

Preferably, the fertilizer also contains humic acid. Preferably, the humic acid may be natural humic acid or artificial humic acid (also referred to as "artificial humic acid").

Preferably, the artificial humic acid contains more aromatic hydrocarbons and long-chain aliphatic hydrocarbon structures. For example, the content of the aromatic hydrocarbon is 7.30 to 7.50%, and the content of the long-chain aliphatic hydrocarbon is 7.10 to 7.20%. Illustratively, the aromatic hydrocarbon content is 7.43% and the long-chain aliphatic hydrocarbon content is 7.15%.

Preferably, the fertilizer also contains organic carbon medium nutrient.

Preferably, the source of organic carbon media nutrients comprises: a liquid phase working medium obtained during the preparation of the hydrothermal process such as HTC and/or HTH according to claim 3; or the liquid phase working medium is further concentrated and circularly treated.

Preferably, the liquid-phase working medium contains an inorganic element, such as at least one of potassium, phosphorus, nitrogen, and the like. Preferably, the inorganic element may also be present in the form of a salt thereof, such as a potassium salt, a phosphate, a nitrate, and the like. Preferably, the concentration of the inorganic element is adjustable, for example, to suit the application of the modified water coke product, such as having a designed concentration of the inorganic element.

Preferably, the liquid phase working medium contains organic carbon in different forms.

Preferably, the liquid phase working medium contains organic matter. Examples of the organic substance include carboxylic acids and furfural, preferably short-chain carboxylic acids (meaning fatty acids having less than 6 carbon atoms in the carbon chain), Hydroxymethylfurfural (HMF), and exemplified by formic acid, acetic acid, propionic acid, levulinic acid, amino acids, and the like. Preferably, the concentration of the organic substance is adjustable, for example, according to the application of the liquid phase working medium, such as containing the designed concentration of the organic substance.

Preferably, the liquid phase working medium may further contain one, two or more of plant amine, lignin phenol, furan, fulvic acid, humic acid, and the like.

Preferably, the liquid-phase working medium contains no or little substances harmful to plants (preferably crops), animals, soil, etc. For example, the harmful material includes, but is not limited to, at least one of harmful organic substances, harmful inorganic substances, heavy metal elements, and the like. Wherein, the hardly containing means that the content of harmful substances is below 0.05%, for example below 0.02%, as well as below 0.01% or other design content.

Preferably, the number of concentrating cycles is at least one, two, three or more. Preferably, the concentration of the elements in the liquid phase working medium after the concentration cycle corresponds to the desired nutrient content in the agricultural product.

Preferably, during the concentration cycle treatment, one, two or more treatment modes can be selected from, but not limited to, adjusting the pH, adjusting the hydrothermal carbonization feed, adjusting the components of the hydrothermal carbonization liquid phase working medium, adjusting the output quantity of the components, optionally adding or not adding other reactants, additives (such as heavy metal settling agents and the like), and the like.

Preferably, during the concentration cycle, the separation (e.g. adsorption separation) of toxic substances and/or elements, ions, radicals and/or substance molecules which may form toxic substances contained in the water coke obtained from the hydrothermal carbonization treatment from the medium water or the suppression of the formation of toxic substances may also be included.

Preferably, the fertilizer contains the modified water coke, humic acid and organic carbon medium nutrient.

Preferably, the preparation method of the fertilizer comprises the step of preparing the fertilizer from a raw material containing the modified water coke of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3.

Preferably, the preparation method of the fertilizer comprises the preparation of raw materials containing the modified water coke of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3, humic acid and organic carbon medium nutrient.

6. An organic carbon mediator nutrient having the meaning of claim 5.

Preferably, the preparation method of the organic carbon medium nutrient comprises the step of preparing the liquid-phase working medium obtained in the hydrothermal process such as HTC and/or HTH according to claim 3; or further concentrating the liquid phase working medium.

7. A soil fertilizer characterized in that it comprises the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3 or is produced from a raw material comprising the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3. Wherein, the soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

Preferably, the method for preparing the soil fertilizer comprises the step of preparing the soil fertilizer from a raw material containing the modified water coke of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3.

8. A soil conditioner characterized in that it comprises the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3 or is produced from a raw material comprising the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3. Wherein, the soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

Preferably, the preparation method of the soil conditioner comprises the step of preparing the soil conditioner from raw materials containing the modified water coke prepared by the preparation method of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3.

9. A plant fertilizer, characterized in that the plant fertilizer comprises the modified water coke according to claim 1 or 2 and/or the modified water coke obtained by the production method according to claim 3 or is produced from a raw material comprising the modified water coke according to claim 1 or 2 and/or the modified water coke obtained by the production method according to claim 3. Wherein, the plant fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

Preferably, the method for preparing the plant fertilizer comprises the step of preparing the plant fertilizer from a raw material containing the modified water coke of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3.

10. A plant growth agent comprising the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3, or produced from a raw material comprising the modified water coke according to claim 1 or 2 and/or the modified water coke produced by the production method according to claim 3.

Preferably, the method for preparing the plant growth agent comprises the step of preparing the plant growth agent from a raw material containing the modified water coke of claim 1 or 2 and/or the modified water coke prepared by the preparation method of claim 3.