CN116622984A

CN116622984A - Method for producing solid composite material

Info

Publication number: CN116622984A
Application number: CN202310653625.7A
Authority: CN
Inventors: 李春柱; 李婷婷
Original assignee: Renergi Pty Ltd
Current assignee: Renergi Pty Ltd
Priority date: 2018-04-16
Filing date: 2019-04-11
Publication date: 2023-08-22
Also published as: WO2019200424A1; JP7365360B2; JP2021521342A; AU2019254838A1; CN111971402A; AU2019254838B2

Abstract

The present disclosure provides methods of producing solid composites. The method includes providing a biological coarse material formed from a heat treatment of a carbonaceous feedstock including biomass. The biomeal is capable of hardening at elevated temperatures. The method further includes mixing the biological coarse material with a solid or paste to form a crude composite material, and heating the crude composite material to produce a hardened solid composite material.

Description

Method for producing solid composite material

Technical Field

The present invention relates to a method of producing a solid composite material, in particular a mineral containing composite material.

Background

Many industrial processes are both energy-intensive and carbon-intensive. Examples of such processes include production of pig iron and steel from iron ore minerals and production of silicon from silica minerals. Fossil fuels, such as coal, are often the primary sources of energy and carbon. For example from high qualityCoked metallurgical coke of bituminous coal is the predominant form of carbon used in the iron and steel industry, especially in the feed of blast furnaces. These industrial sectors are greenhouse gases (in particular CO ₂ ) And actively find alternative and low emission means for supplying the energy and carbon required in the process.

Although many renewable energy sources are available to meet the energy requirements of such industrial processes to reduce their CO ₂ Biomass is the only renewable energy source that can be directly used to meet the carbon requirements of these industrial processes.

Beneficiation is a process commonly used to improve the quality (purity) of raw mineral materials such as iron ore. It generally involves comminution and thus the production of fine mineral matter. The fines must then be made into large granules, for example by granulation or briquetting, so that the fines become large granules, such as feed in the form of pellets and briquettes, which are suitable for the desired process, for example as feed for a blast furnace. Clays, such as bentonite, are commonly used as binders. However, such inorganic binders will tend to introduce undesirable inorganic impurities into the process which can adversely affect the main process and ultimately be discharged from the process as slag to be treated. An organic binder would be desirable, especially if the organic binder could also interact physically and/or chemically with the mineral to be processed to form a composite material and become part of the carbon required in the process. In producing a composite material of high mechanical strength, chemical reaction between the binder and the mineral will be advantageous.

Although carbon may also be an energy source, the "carbon" required by the industry sector mentioned above is generally a reactant, for example as a reducing agent, to reduce iron ore to iron, or silica to silicon. As used herein, "carbon" need not be pure carbon, but rather refers primarily to carbonaceous materials rich in carbon. Metallurgical coke and activated carbon are typical examples of these "carbon" materials. Intimate contact between the carbonaceous material and the mineral to be reacted (reduced) in the composite will have many beneficial effects on process acceleration and process efficiency improvement.

During the production of the carbon material and/or during the subsequent preparation of the carbon material, so that the carbon material requiring a particle size range may be fed into a desired industrial process, such as a blast furnace or an arc furnace, a number of fines may be produced. For example, when metallurgical coke is crushed so that coke of a desired particle size range can be produced and fed to a blast furnace, a number of metallurgical coke fines can be produced. These coke fines cannot be fed directly into the blast furnace and have a lower commercial value than the coke slab. Another example is the production of biochar fines during the production and preparation of biochar as a feed material that can be fed into an electric arc furnace to produce silicon. Also, biochar fines cannot be fed into the arc furnace and have a lower commercial value than biochar blocks. The use of the corresponding fines to produce bulk carbon materials would be an important commercial outcome. In particular, the bulk carbon material produced from fines should meet the quality requirements of the intended use, for example the coke slab should have sufficient mechanical strength for the blast furnace required to produce pig iron and steel, or the biochar slab should have sufficient mechanical strength for the arc furnace required to produce silicon.

The scope of the invention should in no way be limited by the examples cited above. Other examples may be cited in which the fines should be made into large particles, as large particles have a higher commercial value than fines.

The biomeal may be produced from heat treatment of biomass at elevated temperatures and used as a binder or as a component in a binder. A typical type of biological coarse material is bio-oil from the pyrolysis of biomass (which also produces solid by-products called biochar). Upon heating, the bio-oil may devolatilize and harden. Bio-oils contain abundant reactive structures and functional groups that can react with minerals to create very strong bonds between the minerals and components derived from the bio-crude. Hydrothermal liquefaction of biomass can also produce reactive biomeal. The biocrude may also act as a binder for other materials, such as metallurgical coke fines and/or biochar fines.

The organic binder can decompose at high temperatures, releasing flammable volatiles. The use of carbon as a reducing agent may also produce gases such as CO with a useful heating value. Recovery of these volatile and gaseous energy values will be important to the overall process energy efficiency.

The carbon in the organic binder may also become part of the carbon required in the process of upgrading the minerals, for example as a reducing agent in a blast furnace or similar process, to reduce iron ore to iron.

Thus, there is a need to develop organic binders from biomass and/or to subject carbon in intimate contact with the ore (or other materials to be combined) in the composite material to a high temperature process, for example for reducing iron ore to iron.

Disclosure of Invention

According to a first aspect of the present invention there is provided a method of producing a solid composite material, the method comprising:

providing a biomeal formed from heat treatment of a carbonaceous feed comprising biomass, the biomeal being capable of hardening at an elevated temperature;

mixing the biological coarse material with a solid or paste to form a crude composite material; and

the crude composite is heated to produce a hardened solid composite.

Embodiments of the present invention have significant advantages. In particular, the resulting solid composite material may have a relatively high density and strength. In addition, the resulting solid composite may have a relatively low sulfur content and the biomeal may not introduce undesirable impurities into the composite. Furthermore, the biomeal may contain useful substances that may act as fluxing agents, for example, in a subsequent steelmaking process.

As used herein, the term "biomass" refers to any material derived from a living or recently living organism. Although biomass is the preferred feed for producing the organic binder due to its potential carbon neutrality and other characteristics of biomass, other carbonaceous feeds may be used as the feed, including various carbonaceous renewable feeds and non-renewable feeds, including but not limited to coal, solid waste, or mixtures thereof. The solid waste may include, but is not limited to, agricultural waste, forestry waste, and domestic/municipal solid waste or residues from the processing of carbonaceous feedstocks. Indeed, in a broad sense, many solid wastes are considered biomass. Alternatively, biomass is at least a significant component of many solid wastes.

As used herein, the term "heat treatment" is intended to include within its scope any process at elevated temperature, with or without the presence of additional substances. For example, pyrolysis of biomass in an inert, oxidizing or reducing atmosphere is a heat treatment process. Hydrothermal treatment of biomass in subcritical, critical or supercritical water is another heat treatment process.

As used herein, the term "biological coarse material" is intended to include any liquid or paste product from the heat treatment of biomass or other carbonaceous feedstock. Bio-oils from the pyrolysis of biomass are typical bio-coarse materials.

As used herein, the term "biochar" (or "char") is intended to include heat treated solid products from biomass or other carbonaceous feedstock.

As used herein, the term "composite" is intended to include within its scope any material composed of two or more constituent materials having different characteristics. "raw composite" refers to a mixture of precursors that make up the final solid composite. The raw composite material may be in the shape of pellets and agglomerates or any other regular or irregular shape and of any size.

The process of the present invention can be carried out at a wide range of relative proportions between the biomeal and the solids to produce solid composites having widely varying compositions and characteristics.

In an embodiment, the solids comprise minerals, such as iron ore or silica. For example, the solids may be magnetite iron ore.

In another embodiment, the solid comprises a solid carbon material. For example, the solid may be metallurgical coke, biochar or char.

In one embodiment, the solids may have a wide range of particle sizes. For example, magnetite iron ore fines, alone or with magnetite pieces, may be mixed with bio-oil to produce a crude composite. The solids may contain impurities including, but not limited to, water.

In further embodiments, the solids may be in the form of a slurry containing water or other chemicals.

In an embodiment, the solid comprises a mixed solid. For example, the solids may be mixtures of magnetite and hematite iron ores with other impurities. Alternatively, the solids may be a mixture of ore and biochar or a mixture of ore and metallurgical coke.

In further embodiments, the crude composite material may include a fluxing agent, such as lime, to facilitate subsequent processing of the composite material.

In still further embodiments, the crude composite may include additional chemicals, including catalysts, to accelerate the hardening of the composite.

The step of heating the crude composite material may be performed by heating the crude composite material to a temperature between 100 ℃ and 600 ℃, preferably between 150 ℃ and 450 ℃ and still more preferably between 200 ℃ and 350 ℃. The heating may be carried out in an inert atmosphere or a reducing atmosphere or an oxidizing atmosphere.

In another embodiment, the step of heating the crude composite material may be performed by heating the crude composite material to a temperature above 600 ℃ under an inert or reducing or oxidizing atmosphere.

In an embodiment, the step of heating the crude composite material is performed in a stepwise manner. For example, the temperature may be gradually increased at different heating rates and held at selected temperature levels for different times.

The method may include the further step of carbonizing the composite material at an elevated temperature, preferably above 600 ℃, more preferably above 800 ℃ and still more preferably above 1000 ℃, particularly but not limited to carbonizing the biomeal-derived carbonaceous component of the composite material.

The method may include the further step of burning the composite material by reaction with an oxidant, such as air, to at least partially melt or recrystallize the solids in the composite material to achieve better mechanical strength.

According to a second aspect of the present invention there is provided a method of producing a solid composite material, the method comprising:

providing biochar formed from heat treating a carbonaceous feed comprising biomass;

mixing the biomeal and biochar with a solid or paste to form a crude composite; and

the crude composite is heated to produce a hardened solid composite.

The inclusion of biochar in the crude composite may advantageously increase the carbon content of the composite. Biochar and biomeal may be produced from heat treatment of the same or different carbonaceous feeds.

According to a third aspect of the present invention there is provided a method of producing a solid composite material, the method comprising:

mixing the biological coarse material with a solid or paste to form a crude composite material;

heating the crude composite to produce a hardened solid composite; and

volatiles released by heating the crude composite are recovered.

According to a fourth aspect of the present invention there is provided a method of producing a solid composite material, the method comprising:

mixing the biomeal and biochar with a solid or paste to form a crude composite;

heating the crude composite to produce a hardened solid composite; and

volatiles released by heating the crude composite are recovered.

Biochar and biomeal may be produced from heat treatment of the same or different carbonaceous feeds.

In an embodiment of the third or fourth aspect of the invention, the step of recovering volatiles comprises feeding volatiles into a combustion device to provide thermal energy to heat the crude composite.

In a further embodiment of the third or fourth aspect of the invention, the step of recovering the volatiles comprises cooling the volatiles to form a liquid and non-condensable gas mixture. The liquid or non-condensable gas mixture may be used alone or together as a fuel to supply the thermal energy needed to heat the raw composite or for other purposes.

In a specific embodiment of the third or fourth aspect of the invention, the recovered volatiles are used as fuel for power generation. Any suitable method of generating electricity, such as using an internal combustion engine or gas turbine, known now or in the future, may be used for this purpose.

Drawings

Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings:

FIG. 1 is a flow chart of a method of producing a solid composite material according to an embodiment of the invention;

Detailed Description

Embodiments of the present invention relate to methods of producing solid composites. To produce a solid composite material, a biomeal formed by heat treatment of biomass or other carbonaceous feed or mixtures thereof is provided, wherein the biomeal is capable of hardening when heated. Without being bound to any particular theory, the hardening process involves complex chemical reactions involving reactive species and functional groups in the biomeal and solids forming part of the crude composite material, in addition to evaporation of water and light species from the biomeal. The description of the embodiments herein focuses on bio-oils from pyrolysis of biomass, but the bio-coarse material in the present invention is not limited to bio-oils alone. Various biomass pyrolysis techniques now known or later invented may be used to produce bio-oil. For example, the milling pyrolysis technique (PCT/AU 2011/000741) is very effective in producing bio-oils for producing composites using the methods of the present invention. Pyrolysis processes also typically produce solid byproduct biochar and gaseous byproducts including non-condensable gases. Biochar can also be used as a feed for producing solid composites in the present invention.

Biological oils are mostly liquids, but those skilled in the art will recognize that biological oils may contain colloids and even solids (including biochar). In addition to water, biological oils may contain many organic compounds that contain various chemical functional groups, especially oxygen-containing functional groups. The bio-oil may also contain dissolved inorganic substances and inorganic solids such as sodium, potassium, magnesium and calcium salts. They may have beneficial effects for subsequent processes using the composite as feed. For example, in the iron and steel industry they can act as fluxes in blast furnaces. In some pyrolysis processes, the bio-oil is produced in the form of a paste or slurry. In some pyrolysis processes, a slurry of bio-oil and bio-char is produced directly.

The bio-oil is mixed with the solids to produce a crude composite. In an embodiment, the bio-oil is mixed with magnetite iron ore to produce a crude composite material comprising bio-oil and magnetite. In another embodiment, bio-oil and bio-char are mixed with magnetite ore to produce a crude composite material. In a further embodiment, various additional chemicals are also added to the mixture to produce a crude composite material having different properties.

In a further embodiment, the bio-oil is mixed with a carbon material to produce a crude composite material. The carbon material may be metallurgical coke or biochar or any solid from the heat treatment of carbonaceous feedstock. Additional chemicals, including catalysts, may also be components of the crude composite.

The mixing process can be performed in various ways and crude composite materials can be produced in various shapes. The bio-oil and solids may be extruded into a crude composite material having a desired shape. In an embodiment, the granulation tray is used to mix and roll bio-oil and iron ore, which may also include bio-char or any other constituent chemicals as described above, into a briquette. In a further embodiment, a granulating drum is used.

The relative proportions of bio-oil, iron ore, and other ingredients in the composite, including bio-char and additional chemicals, can be varied over a wide range to accommodate the needs of subsequent processes in which the composite is used.

The crude composite is then heated to produce a final solid composite product. The heating may be performed in various ways, in an inert atmosphere, a reducing atmosphere, or an oxidizing atmosphere, to harden the composite material.

During heating, many physical processes and chemical reactions can occur. Moisture, for example, in bio-oil or iron ore, will evaporate. Some of the light components in the bio-oil will also evaporate. Depending on the temperature, the reactive functional groups in the bio-oil will also undergo various reactions, especially cracking reactions and polymerization reactions, to produce additional lighter components and heavier components. The heavy components are particularly important for binding together solid (e.g. ore) particles.

Without being bound to any particular theory, the components in the bio-oil may also react with solids (e.g., iron ore, biochar or other carbon materials) to form some new chemical bonds between the bio-oil components and the iron ore. This type of chemical bond will be much stronger than the physical interaction/force, greatly contributing to the mechanical strength of the composite product.

Heating of the raw composite material may be performed in various ways. In an embodiment, the crude composite material is heated in an oxidizing atmosphere to combust at least some of the bio-oil components. Combustion will heat the raw composite to an elevated temperature, causing some degree of melting/sintering of the iron ore, wherein recrystallization or other physical-chemical processes may occur, to produce a composite with high mechanical strength. At the same time as combustion, some of the iron ore may also be at least partially reduced. The combustion process may be performed on the raw composite material or on the final composite material product.

In the steel industry, composites derived from bio-oil and iron ore and/or composites derived from bio-oil and metallurgical coke may be used as part of the feed to a blast furnace. Composite materials derived from bio-oil and solid biochar (or other types of char) may be fed to an arc furnace to produce silicon.

Volatiles released by heating the crude composite may contain many flammable components. If the heating is performed at a relatively low temperature (e.g., less than about 600℃.), some of these volatile components may condense to produce a liquid fuel and a non-condensable gaseous fuel.

Iron ore can be an excellent catalyst for the reformation of the released volatiles into light gases. Thus, in a specific embodiment, the composite material produced in the present invention is used in conjunction with a power generation process wherein volatiles and gases released from the heating of the crude composite material are used to generate power using a power generation device. Examples of such power generation devices include, but are not limited to, internal combustion engines, gas turbines, and fuel cells.

Referring now to FIG. 1, a flow chart illustrating a method 100 is shown, in accordance with a specific embodiment of the present invention.

In a first step 102, a biomeal material formed by heat treatment of biomass and capable of hardening is provided. In this embodiment, the bio-coarse is bio-oil obtained from pyrolysis of biomass.

In step 104, biochar is provided. While bio-oil and bio-char are typically produced simultaneously from pyrolysis of the same biomass, bio-oil and bio-char may also be produced from different biomasses and using different heat treatment processes.

Specific examples of pyrolysis processes are described in more detail in PCT international patent application No. PCT/AU 2011/000741.

In a next step 106, the bio-oil and biochar are mixed together with the solids to form a crude composite. In this particular embodiment, the solids are magnetite iron ore, especially magnetite iron ore fines after beneficiation. Instead of biochar and iron ore, the solids may also be biochar fines produced during the production and preparation of biochar for use in the silicon production process. In a further embodiment, silica may be added to form a crude composite so that the silica in the final composite product is in intimate contact with carbon to facilitate its reduction to form silicon in an electric arc furnace. The mixing may be performed at room temperature. In this particular example, mixing is performed to form the desired shape. The raw composite material may be formed by extrusion.

The crude composite is then heated in step 108 to a temperature at which the bio-oil hardens through complex physical and chemical processes. The bond between the C-containing components (including reaction products from bio-oil) and magnetite includes physical and chemical bonds.

In step 110, volatiles released by reactions involving bio-oils are recovered to extract their energy value. They can also be used as chemical feeds for other chemical processes.

In the claims which follow and in the description of the invention preceding it, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Claims

1. A method of producing a solid composite material, the method comprising:

heating the crude composite material to undergo physical and chemical processes to produce a hardened solid composite material,

wherein the raw composite material is formed by extrusion and is spherical and agglomerate-shaped or any other regular or irregular shape;

wherein the solid or paste comprises iron ore, and

wherein the hardened solid composite forms part of a blast furnace or arc furnace feed.

2. The method of claim 1, wherein the solid or paste further comprises a carbon material.

3. The method of claim 1, wherein the solids further comprise metallurgical coke fines.

4. The method of claim 1, wherein the step of heating the crude composite material is performed to at least partially melt or sinter and/or carbonize the composite material.

5. The method of claim 1, wherein the step of heating the crude composite is performed by heating the crude composite to combust organic components in the crude composite.

6. The method of any one of the preceding claims 1 to 5, further comprising the steps of providing biochar formed from heat treatment of a carbonaceous feedstock comprising biomass and mixing the biochar with the biomeal and the solids to form a crude composite material.

7. The method of any one of the preceding claims 1 to 5, further comprising the step of providing a catalyst to increase the rate of hardening of the crude composite.

8. The method of claim 6, further comprising the step of providing a catalyst to increase the rate of hardening of the crude composite material.

9. The method of any one of the preceding claims 1 to 5, wherein the biomeal is formed by pyrolysis or hydrothermal treatment or liquefaction of a carbonaceous feed comprising biomass.

10. The method of claim 6, wherein the biological coarse material is formed by pyrolysis or hydrothermal treatment or liquefaction of a carbonaceous feed comprising biomass.

11. The method of claim 7, wherein the biological coarse material is formed by pyrolysis or hydrothermal treatment or liquefaction of a carbonaceous feed comprising biomass.

12. The method of claim 8, wherein the biological coarse material is formed by pyrolysis or hydrothermal treatment or liquefaction of a carbonaceous feed comprising biomass.

13. The method of claim 9, further comprising the step of recovering volatiles and other gases released by the heating of the crude composite.

14. The method of claim 13, wherein the recovered volatiles and other gases are combusted to provide energy to heat the crude composite.

15. The method of claim 10, further comprising the step of recovering volatiles and other gases released by the heating of the crude composite.

16. The method of claim 15, wherein the recovered volatiles and other gases are combusted to provide energy to heat the crude composite.

17. The method of claim 11, further comprising the step of recovering volatiles and other gases released by the heating of the crude composite.

18. The method of claim 17, wherein the recovered volatiles and other gases are combusted to provide energy to heat the crude composite.

19. The method of claim 12, further comprising the step of recovering volatiles and other gases released by the heating of the crude composite.

20. The method of claim 19, wherein the recovered volatiles and other gases are combusted to provide energy for heating the crude composite.