CN114854453A - Preparation method of biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection - Google Patents

Preparation method of biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection Download PDF

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CN114854453A
CN114854453A CN202210532649.2A CN202210532649A CN114854453A CN 114854453 A CN114854453 A CN 114854453A CN 202210532649 A CN202210532649 A CN 202210532649A CN 114854453 A CN114854453 A CN 114854453A
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biomass
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CN114854453B (en
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张建良
徐润生
刘征建
颉二旺
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/50—Fuel charging devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/80—Other features with arrangements for preheating the blast or the water vapour
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0909—Drying
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a preparation method of biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection. According to the method, the particle size and the moisture content of the biomass are reduced according to the requirement of the blast furnace on solid injection fuel, and the biomass hydrogen-rich micro powder with the remarkably improved heat value is obtained by carrying out hydrodeoxygenation and upgrading in a non-liquid water environment and is directly used for blast furnace injection. The biomass hydrogen-rich micro powder can be further prepared into biomass synthesis gas for blast furnace injection. By the operation, the problem of low volume heating value caused by low biomass volume density can be solved to a certain extent, so that the biomass heating furnace can be better and directly used for blast furnace injection; and the in-situ solid phase upgrading is adopted, so that the process can be simplified, the energy consumption and the preparation time can be reduced, and the moisture content is simply controlled. In addition, the emission of carbon dioxide can be significantly reduced due to the increased hydrogen content.

Description

Preparation method of biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection
Technical Field
The invention relates to the technical field of blast furnace injection fuel, in particular to a preparation method of biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection.
Background
Biomass is a carbon-neutral and environment-friendly renewable energy source and mainly comprises lignin, cellulose and hemicellulose. The biomass is used for the steel working procedure, so that the consumption of fossil fuel and the emission of carbon dioxide can be reduced, and the cleanness and low carbonization of an energy structure can be promoted. In recent years, development and utilization of global biomass energy have been rapidly developed. Meanwhile, due to the characteristics of poor grindability, small volume density, low energy density, high moisture content and the like, the biomass resources have high storage and transportation cost, high industrial processing difficulty, unstable combustion and large combustion rate fluctuation, and the application of the biomass resources in the industry is limited, so the biomass resources are generally required to be converted.
The current approaches to convert biomass into fuels mainly include biogas technology, gasification technology liquefaction technology and pyrolysis. For example, patent CN110218826A discloses a method for blast furnace blowing of biomass hydrothermal charcoal, which comprises the steps of performing hydrothermal carbonization treatment on biomass to obtain biomass hydrothermal charcoal powder, using the biomass hydrothermal charcoal powder for blast furnace blowing to improve comprehensive utilization efficiency of biomass resources and reduce CO in iron-making production 2 And (4) discharging the amount. However, the hydrothermal carbon process takes water as a medium, and requires large energy consumption for water removal in order to reach the moisture content meeting the blast furnace blowing requirement, and the hydrothermal carbonization time is long and the energy consumption is high. Patent CN112280577A discloses a preparation and processing method of biomass coke injected by a blast furnace, which is used for carrying out high-temperature dry distillation on biomass for several hours to obtain the biomass coke for blast furnace injection. Alternatively, the prior art has utilized blast furnace injection gas by pyrolyzing biomass into combustible gas. All have the problems of high energy consumption, long preparation time and the like.
In the prior art, most of the solid fuel injected into the blast furnace is pulverized coal, the calorific value and the specific gravity of the pulverized coal are high, and the comprehensive injection characteristic is excellent. Biomass has low specific gravity and low volumetric heat of combustion, so there has been little research on direct use of 100% biomass alone as a solid fuel for blast furnace injection.
In view of the above, there is a need to design an improved method for preparing biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing biomass hydrogen-rich micro powder and synthesis gas for blast furnace injection. According to the method, the particle size and the moisture content of the biomass are reduced according to the requirement of a blast furnace on solid injection fuel, and the hydrogenation deoxidation and quality improvement are carried out in a non-liquid-phase water environment, so that the biomass hydrogen-rich micro powder with a remarkably improved heat value is obtained, the problem of low volume calorific value caused by low volume density of the biomass can be solved to a certain extent, in-situ solid phase quality improvement is realized, the process can be simplified, the energy consumption and the preparation time are reduced, and the moisture content is controlled simply.
In order to achieve the aim, the invention provides a preparation method of biomass hydrogen-rich micro powder for blast furnace injection, which comprises the following steps: according to the requirement of a blast furnace on solid injection fuel, the particle size and the moisture content of biomass are reduced, hydrodeoxygenation and upgrading are carried out, the biomass hydrogen-rich micro powder is obtained and is directly used for blast furnace injection, and the hydrodeoxygenation and upgrading process is carried out in a non-liquid-phase water environment.
As a further improvement of the invention, the preparation process further comprises reducing the alkali metal content of the biomass.
As a further improvement of the invention, the preparation method also comprises the step of increasing the density of the hydrogen-rich micro powder, namely, biomass and mineral substances are used as raw materials to carry out hydrodeoxygenation quality improvement, and mineral ions in the biomass and the mineral substances are bonded in the hydrodeoxygenation quality improvement process to obtain the high-density biomass hydrogen-rich micro powder which is directly used for blast furnace blowing.
As a further improvement of the invention, all processes of the preparation method are carried out in a non-liquid phase water environment, and the hydrodeoxygenation upgrading is realized by gas phase pressure swing flash evaporation.
As a further refinement of the invention, the gas phase pressure swing flash comprises: sequentially placing the biomass in a plurality of high-temperature high-pressure superheated gas phase reactors, and carrying out pressure reduction and step-by-step flash evaporation to crush the biomass, evaporate water and recombine the structure; the structural reorganization comprises hydrodeoxygenation upgrading and deoxidation carbon extraction.
As a further improvement of the invention, the number of the high-temperature high-pressure superheated gas-phase reactors is more than or equal to 2; the temperature of the first-stage high-temperature high-pressure superheated gas phase reactor is more than 220 ℃, the pressure is more than 2.0MPa, and the retention time is 5-40 min; the temperature of the second-stage high-temperature high-pressure superheated gas phase reactor is 120-160 ℃, the pressure is 1.0-1.4MPa, and the retention time is 5-60 min.
As a further improvement of the invention, the gas phase medium in the high-temperature high-pressure superheated gas phase reactor comprises one or more of superheated steam, carbon dioxide, ammonia gas, methane, shale gas and coke oven gas, blast furnace gas and converter gas.
As a further development of the invention, the gas-phase medium in the high-temperature high-pressure superheated gas-phase reactor contains both superheated steam and ammonia gas.
As a further improvement of the invention, the proportion of the biomass hydrogen-rich micro powder with the granularity of less than 200 meshes is higher than 60 percent, the moisture content is lower than 5 percent, the hydrogen mass content is more than 6 percent, and the oxygen content is lower than 25 percent by weight; the bulk density is 0.4-0.6g/cm 3 。
As a further improvement of the invention, the content of sodium element in the biomass hydrogen-rich micro powder is less than 0.1%, and the content of potassium element in the biomass hydrogen-rich micro powder is less than 0.1%.
A preparation method of biomass synthesis gas for blast furnace injection is characterized in that biomass hydrogen-rich micro powder obtained by any one of the preparation methods is gasified to obtain the biomass synthesis gas for blast furnace injection.
The invention has the beneficial effects that:
1. according to the preparation method of the biomass hydrogen-rich micro powder for blast furnace injection, provided by the invention, the particle size and the moisture content of biomass are reduced according to the requirement of a blast furnace on solid injection fuel, and the hydrogenation deoxidation upgrading is carried out in a non-liquid-phase water environment, so that the biomass hydrogen-rich micro powder with a remarkably improved heat value is obtained, the problem of low volume calorific value caused by low biomass volume density can be solved to a certain extent, the in-situ solid phase upgrading can simplify the process, reduce the energy consumption and the preparation time, and the moisture content is simply controlled. In addition, the emission of carbon dioxide can be significantly reduced due to the increased hydrogen content.
2. According to the invention, through gas phase pressure swing flash evaporation treatment, the crushing of biomass raw materials can be realized while the quality improvement of hydrodeoxygenation is realized, the evaporation of water in cells is facilitated, the particle size is reduced, and the water content is reduced. Moreover, the water release process in the biomass cell also has a better effect on the hydrogenation reduction of cellulose in the cell wall.
Drawings
FIG. 1 is a flow chart of preparation of biomass hydrogen-rich micropowder for blast furnace injection.
FIG. 2 is a flow diagram of the preparation of biomass syngas for blast furnace injection.
FIG. 3 is another flow diagram of the production of biomass syngas for blast furnace injection.
Figure 4 is a process scheme for biomass syngas for blast furnace injection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The hydrogen-rich micro powder provided by the invention is based on the requirement and requirement of the blast furnace injection fuel, and the initial carbon-containing raw materials with the parameters of heat value, bulk density, granularity, moisture, alkali metal and the like which do not accord with the blast furnace injection are converted into the fuel which accords with the blast furnace injection through operations (mainly realized through gas-phase blasting) such as hydrodeoxygenation upgrading, carbon-adding deoxidation and the like. The carbonaceous material may be selected from biomass material, waste plastics, rubber, coal and the like.
Referring to fig. 1, the method for preparing biomass hydrogen-rich micropowder for blast furnace injection provided by the invention comprises the following steps: the biomass raw material is subjected to hydrodeoxygenation and quality improvement to obtain biomass hydrogen-rich micro powder, so that the biomass hydrogen-rich micro powder is suitable for being directly used for blast furnace injection. Biomass feedstock is generally composed of several plant cells bound together, the cell walls of which are composed mainly of lignin, cellulose and hemicellulose, wherein lignin also acts as a binder between cells, which cells usually contain large amounts of moisture and small amounts of inorganic salts. The biomass raw material is subjected to hydrodeoxygenation and quality improvement, so that the hydrogen content of lignin, cellulose or hemicellulose is increased, the relative carbon content is reduced, and the carbon dioxide emission is remarkably reduced when the biomass raw material is used for blast furnace injection; moreover, the improvement of the hydrogen content can obviously improve the combustibility and the calorific value, and can make up for the problem of low volume calorific value caused by low volume density of biomass to a certain extent.
Specifically, in the preparation process, the particle size and the moisture content of the biomass are reduced mainly according to the requirements of a blast furnace on solid injection fuel, such as the particle size, the moisture content, the alkali metal content, the volume density and the like, and the hydrogen-enriched biomass micro powder is obtained and directly used for blast furnace injection, wherein the hydrogen-enriched biomass micro powder is obtained by carrying out hydrodeoxygenation upgrading in a non-liquid-phase water environment (preferably, all processes of the preparation method are carried out in the non-liquid-phase water environment), and by doing so, the water content of the fuel product caused by the water environment can be prevented from being high, so that the problem of energy consumption increase due to extra high-strength drying treatment is also needed.
The order and times of the three processes of reducing the particle size and the moisture content and the hydrodeoxygenation upgrading are not required, for example, the biomass can be initially crushed to be less than 5cm (preferably less than 2cm, more preferably less than 1 cm), then the moisture content is controlled to be less than 25%, and then the hydrodeoxygenation upgrading is carried out, so that the hydrogen-rich biomass micro powder is obtained, and the particle size and the moisture content can be further regulated, so that the proportion of the particle size below 200 meshes is higher than 60%, the volatile matter is 30-60%, and the moisture content is lower than 5%, preferably lower than 2%, more preferably lower than 1.5%. The biomass hydrogen-rich micro powder has the hydrogen mass content of more than 6 percent and the oxygen content of less than 30 percent by weight, more preferably less than 20 percent by weight, and more preferably 12 to 18 percent; the bulk density is 0.4-0.6g/cm 3 The calorific value is more than or equal to 24 MJ/kg. The obtained high-density biomass hydrogen-rich micro powder with the parameter index can be directly used for blast furnace injection in percentage, other solid fuels do not need to be compounded, the energy consumption is obviously reduced, the preparation time is shortened, the release amount of carbon dioxide is reduced, and the high-value utilization of biomass wastes is realized.
As one embodiment, hydrodeoxygenation upgrading is accomplished by vapor pressure swing flash. The gas phase medium in the high-temperature high-pressure superheated gas phase reactor comprises superheated steam, carbon dioxide, ammonia gas, methane, shale gas, coke oven gas, blast furnace gas, converter gas and other industrial waste gases, and can also contain hydrogen, CO and CO 2 And the like, gas phase medium and containing hydrogen elements. Active hydrogen, such as hydrogen ions or hydrogen radicals, is dissociated by using hydrogen elements under the conditions of high temperature and high pressure gas phase, and then the biomass is catalyzed to be self-disassembled, degraded and converted, so that the hydrogenation, the deoxidation and the quality improvement are realized. In the process, other catalysts capable of catalyzing hydrogenation can be added to promote the reaction. The gas phase pressure swing flash treatment can realize the hydrogenation, deoxidation and quality improvement, and can also realize the crushing of biomass raw materials, thereby being beneficial to the evaporation of water in cells, reducing the granularity and the water content. Moreover, the water release process in the biomass cell also has a better effect on the hydrogenation reduction of cellulose in the cell wall.
In particular, the gas phase medium in the first stage high temperature high pressure superheated gas phase reactor comprises superheated steam and ammonia gas. Oxygen in the biomass is mainly removed in the form of small molecular carboxylic acid, and separation and removal of acidic substances can be promoted by adding a proper amount of ammonia gas, so that the deoxidation effect is improved. The volume ratio of the superheated steam to the ammonia gas is (90%: 10%) - (50%: 50%).
Specifically, the vapor pressure swing flash comprises: sequentially placing biomass raw materials in a plurality of high-temperature high-pressure superheated gas phase reactors, and carrying out pressure reduction and step-by-step flash evaporation to crush the biomass, evaporate water and recombine the structure; the structural reorganization comprises hydrodeoxygenation upgrading and deoxidation carbon extraction. The number of the high-temperature high-pressure overheated gas phase reactors is more than or equal to 2; and the temperature of the first-stage high-temperature high-pressure superheated gas-phase reactor is more than 220 ℃, and the pressure is more than 2.0 MPa.
For example, the temperature of the first-stage high-temperature high-pressure superheated gas phase reactor is 240-280 ℃, the pressure is 2.4-2.8MPa, and the retention time is 0.5-3 min; the temperature of the second-stage high-temperature high-pressure superheated gas-phase reactor is 140-160 ℃, the pressure is 1.2-1.4MPa, the retention time is 5-15min, and the like.
For another example, the temperature of the first-stage high-temperature high-pressure superheated gas-phase reactor is 240-280 ℃, the pressure is 2.4-2.8MPa, the residence time is 5-40min, preferably 15-40 min; the temperature of the second-stage high-temperature high-pressure superheated gas phase reactor is 120-160 ℃, preferably 140-160 ℃, the pressure is 1.0-1.4MPa, and the retention time is 5-60 min.
In some embodiments, the method further comprises reducing the alkali metal content of the biomass, and the ash content and the harmful elements in the ash component can be ensured to meet the requirements by screening the initial biomass or proportioning according to the components. Or promoting the release of alkali metal ions in cells in the process of gas phase pressure swing flash evaporation and then separating. The content of sodium element in the biomass hydrogen-rich micro powder is less than 0.1 percent, and the content of potassium element in the biomass hydrogen-rich micro powder is less than 0.1 percent.
In other embodiments, the method further comprises increasing the density of the hydrogen-rich micropowder, for example, by complexing the biomass hydrogen-rich micropowder with a heavy metal element to increase its specific gravity. For example, the biomass raw material and iron ore powder or desulfurized ash are subjected to gas phase pressure swing flash evaporation together, so that a product obtained by disassembling the biomass can be complexed with heavy metal ions in the iron ore powder or desulfurized ash, and the modified biomass hydrogen-rich micro powder is obtained. The heavy metal ions can also play a role in promoting combustion in the combustion process.
With biomass as a processing object, three bottleneck problems faced by blast furnace injection industrial application are mainly as follows:
(1) the granularity is coarse, the proportion of the granularity-200 meshes produced according to the prior patent technology is only 18 percent, and the problem of the granularity needs to be solved.
The biomass crushing device in the previous procedure crushes the biomass to 1-2 mm. Set up multistage pore sieve in the breaker, adjust the pore sieve figure according to the living beings attribute, for example good broken living beings reduce small particle size pore sieve, not good broken living beings increase small particle size pore sieve. The grain size of the raw materials entering the furnace is flexibly adjusted, so that the grain size requirement of-200 meshes after subsequent flash explosion can be met, and the crushing efficiency can be improved as much as possible.
(2) The moisture content is high, the material produced according to the prior patent technology receives 22 percent of tested moisture, is too high and cannot be directly sprayed, the moisture content needs to be reduced as much as possible, and the product is mainly a porous material which can easily absorb the environmental moisture. And the moisture plays the following roles in the pressure swing flash evaporation process: as field transfer media for acidic species and hydrolysis intermediates, etc.; the heat transfer medium, and therefore the moisture content regulation of the process, has a significant impact on the product structure.
At present, the moisture content of the biomass after treatment is about 10%, and a drying device needs to be added, for example, a microwave drying device is added at the back, so that the moisture is removed on one hand, and biomass radicals are activated on the other hand, and the combustion reaction activity of the biomass is improved. After drying, the mixture is directly loaded into a tank car or a damp-proof bag to avoid absorbing environmental water.
(3) The existing biomass has higher oxygen content, low hydrogen content and low effective heat value of blast furnace injection
Referring to fig. 1 and 2, according to the existing estimation, the hydrogen-rich micro powder of the prior art has low effective calorific value and low theoretical substitution ratio, and the oxygen content in the product needs to be continuously reduced and the hydrogen content in the product needs to be increased by adopting the technology. Such as raising the flash evaporation temperature, prolonging the time, and adopting other industrial hydrogen-rich gas for hydrogenation.
Taking steam pressure swing flash evaporation as an example, the influence factors of the biomass steam explosion process are mainly classified into the following four types: material parameters, operating parameters, equipment parameters, and product parameters. The material parameters mainly comprise the chemical composition, the physical structure, the moisture state and the particle size (related to the charging coefficient) of the biomass material, determine the selected steam explosion process and the operating conditions, and are closely related to the energy consumption and the steam explosion effect in the steam explosion process and the performance of subsequent products. The invention takes the blast furnace injection fuel as the guide, and regulates and controls each influence factor to obtain the high-performance hydrogen-rich micro powder.
It is believed that during steam explosion, hemicellulose is partially converted from hydrolysis to monosaccharides and oligomers (acids), while lignin is degraded to sugars and phenolic oligomers. At high temperature, the hydrolysis of the glycosidic bond of hemicellulose and the beta-ester bond of lignin is accelerated by the formation of acetic acid from the acetyl group hydrolyzed from the hemicellulose chain. Therefore, the greater the treatment strength within a certain range, the greater the degree of hydrolysis of hemicellulose and degradation of lignin, and the more significant the effect of decomposition of components. The water content of the material has great influence on the blasting effect, the liquid proportion is large, and the blasting effect is poor; it is not necessary that the higher the pressure is, the better the blasting is.
The following tables show the index parameters before and after anthracite, bituminous, and biomass treatment.
Figure BDA0003642939970000081
As can be seen from the table, the biomass was high in volatiles and moisture, fixed carbon and lower in calorific value. Anthracite coal: H/C is 0.043; bituminous coal: H/C is 0.047; biomass: H/C is 0.12. Therefore, it is necessary to perform deoxidation, hydrogenation and carbon extraction on biomass so that the biomass can be directly used for blast furnace injection.
Referring to fig. 2-4, the invention further provides a method for preparing biomass synthesis gas for blast furnace injection, wherein the biomass hydrogen-rich micro powder obtained by any one of the above preparation methods is gasified to obtain biomass synthesis gas for blast furnace injection.
In the existing technology for treating biomass and organic solid waste, biomass gasification is suitable for treating various wastes, and has high application potential in waste treatment. The biomass gasification refers to that after the biomass raw material is pressed and molded or is simply crushed and processed, the high polymer of the biomass is subjected to pyrolysis, oxidation, reduction and reforming reactions under certain thermodynamic conditions in a gasification furnace, the tar associated with the pyrolysis is further subjected to thermal cracking or catalytic cracking to form small molecular hydrocarbons, and the small molecular hydrocarbons are subjected to gas purification treatment to finally obtain the H-containing biomass 2 And CO-based syngas process. The gasification agent is reasonably utilized, the proper gasification condition is regulated and controlled, the gas production process of the biomass gas is optimized, the gas production rate and the gas production quality are further improved, and the biomass gas gasification process is favorable for replacing fossil energy such as natural gas, coal and petroleum.
Furthermore, the biomass and the metal mineral powder can be prepared into biomass hydrogen-rich micro powder together and then gasified to prepare the synthesis gas, so that the element content of the hydrogen-rich micro powder can be further regulated, and the composite metal can play a role in catalysis in the gasification process, thereby improving the gasification efficiency. The mass ratio of the biomass to the metal mineral powder is (1-20):1, preferably (5-15):1, more preferably (8-12): 1; the particle size of the biomass and the mineral substance are both below 2cm, and the moisture content is controlled below 25%. The particle size of the metal mineral powder is 2mm or less, more preferably 0.5mm or less, more preferably 0.2mm or less; so as to promote the penetration of the mineral substances into the biomass and further improve the bonding degree of mineral ions in the biomass and the mineral substances. The mineral comprises one or more of iron ore powder, desulfurized ash and metallurgical waste residue. The mineral ions are mainly calcium ions, iron ions and the like, and can be bonded with residual oxygen-containing groups in the biomass, such as hydroxyl, carboxyl, alkoxy and the like. Because the molar mass of the mineral ions is far larger than that of hydrogen, the mineral ions can correspondingly improve the volume density of the hydrogen-rich micro powder after replacing H atoms in the oxygen-containing active groups.
Example 1
A preparation method of biomass hydrogen-rich micro powder for blast furnace injection comprises the following steps:
s1, crushing a biomass raw material to obtain particles with the particle size of 1-2 cm;
s2, feeding the particles into a first-stage high-temperature high-pressure superheated steam reactor, wherein the temperature is 320 ℃, the pressure is 3.2MPa, and the retention time is 5 min; then the mixture is instantaneously decompressed and placed into a second-stage high-temperature high-pressure superheated steam reactor, the temperature is 130 ℃, the pressure is 1.2MPa, and the retention time is 20 min.
On the basis of the process, the biomass hydrogen-rich micro powder obtained by finely regulating and controlling the process can reach the following conditions: the bulk density was 0.41kg/m 3 The C, H, O element content of the biomass hydrogen-rich micro powder is 65.2 percent, 9.8 percent and 18.2 percent respectively, and the calorific value is about 24.03 MJ/kg.
Example 2
A preparation method of biomass hydrogen-rich micro powder for blast furnace injection comprises the following steps:
s1, crushing a biomass raw material to obtain particles with the particle size of 1-2 cm;
s2, feeding the particles into a first-stage high-temperature high-pressure superheated steam reactor, wherein the temperature is 250 ℃, the pressure is 2.5MPa, and the retention time is 20 min; then the mixture is instantaneously decompressed and placed into a second-stage high-temperature high-pressure superheated steam reactor, the temperature is 150 ℃, the pressure is 1.3MPa, and the retention time is 20 min.
On the basis of the process, the biomass hydrogen-rich micro powder obtained by finely regulating and controlling the process can reach the following conditions: the bulk density is 0.40kg/m 3 The element content of C, H, O in the biomass hydrogen-rich micro powder is 65.45%, 8.11% and 20.87%, and the heat productivity is about 23.32 MJ/kg.
Example 3
A preparation method of biomass hydrogen-rich micro powder for blast furnace injection comprises the following steps:
s1, crushing a biomass raw material to obtain particles with the particle size of 1-2 cm;
s2, feeding the particles into a first-stage high-temperature high-pressure reactor (comprising superheated steam and ammonia gas with the volume ratio of 80-20%), wherein the temperature is 320 ℃, the pressure is 3.2MPa, and the retention time is 15 min; then the mixture is instantaneously decompressed and placed into a second-stage high-temperature high-pressure superheated steam reactor, the temperature is 130 ℃, the pressure is 1.2MPa, and the retention time is 20 min.
On the basis of the process, the biomass hydrogen-rich micro powder obtained by finely regulating and controlling the process can reach the following conditions: the bulk density is 0.42kg/m 3 The C, H, O element content of the biomass hydrogen-rich micro powder is 66.1 percent, 10.5 percent and 12.3 percent respectively, and the calorific value is about 25.14 MJ/kg.
Example 4
A preparation method of biomass hydrogen-rich micro powder for blast furnace injection comprises the following steps:
s1, crushing a biomass raw material to obtain particles with the particle size of 1-2 cm;
s2, feeding the particles into a first-stage high-temperature high-pressure superheated steam reactor, wherein the temperature is 250 ℃, the pressure is 2.5MPa, and the retention time is 10 min; then the mixture is instantaneously decompressed and placed into a second-stage high-temperature high-pressure superheated steam reactor, the temperature is 150 ℃, the pressure is 1.3MPa, and the retention time is 10 min.
On the basis of the process, the biomass hydrogen-rich micro powder obtained by finely regulating and controlling the process can reach the following conditions: the bulk density is 0.40kg/m 3 The C, H, O element content of the biomass hydrogen-rich micro powder is 59.28%, 6.99% and 26.14%, and the calorific value is about 21.93 MJ/kg.
Therefore, the processing parameters such as processing temperature, atmosphere, time, pressure and the like all have important influence on the structural composition of the product. The invention aims at being suitable for blast furnace injection, and precisely regulates and controls the pressure swing flash evaporation process parameters, so as to prepare the hydrogen-rich micro powder, which can be directly used for blast furnace injection by 100 percent, obviously reduce the emission of titanium dioxide and save energy consumption.
In conclusion, according to the preparation method of the biomass hydrogen-rich micro powder and the synthesis gas for blast furnace injection, provided by the invention, the particle size and the moisture content of biomass are reduced according to the requirement of a blast furnace on solid injection fuel, and the hydrogenation deoxidation and quality improvement are carried out in a non-liquid-phase water environment, so that the biomass hydrogen-rich micro powder with a remarkably improved heat value is obtained, the problem of low volume heating value caused by low biomass volume density can be solved to a certain extent, and the in-situ solid phase quality improvement can simplify the process, reduce the energy consumption and the preparation time, and is simple in moisture content control. In addition, the emission of carbon dioxide can be significantly reduced due to the increased hydrogen content. The synthesis gas obtained by gasifying the prepared hydrogen-rich micro powder is the same as the blast furnace injection, the oxygen and moisture content in the biomass can be firstly highly controlled, and preliminary macromolecule self-disassembly is realized, so that the problem that tar is easily produced in the biomass gasification in the prior art is solved, the gasification process can be accelerated, and the gasification energy consumption is reduced.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.

Claims (10)

1. A preparation method of biomass hydrogen-rich micro powder for blast furnace injection is characterized by comprising the following steps: according to the requirement of a blast furnace on solid injection fuel, the particle size and the moisture content of biomass are reduced, hydrodeoxygenation and upgrading are carried out, the biomass hydrogen-rich micro powder is obtained and is directly used for blast furnace injection, and the hydrodeoxygenation and upgrading process is carried out in a non-liquid-phase water environment.
2. The method for producing a biomass hydrogen-rich micropowder for blast furnace injection according to claim 1, characterized by further comprising reducing the alkali metal content of the biomass; the content of sodium element in the biomass hydrogen-rich micro powder is less than 0.1%, and the content of potassium element in the biomass hydrogen-rich micro powder is less than 0.1%.
3. The method for preparing the biomass hydrogen-rich micro powder for blast furnace blowing according to claim 1, further comprising increasing the density of the hydrogen-rich micro powder, namely performing hydrodeoxygenation upgrading by using biomass and minerals as raw materials, wherein mineral ions in the biomass and the minerals are bonded in the hydrodeoxygenation upgrading process to obtain the high-density biomass hydrogen-rich micro powder for blast furnace blowing directly.
4. The method for preparing the biomass hydrogen-rich micro powder for blast furnace injection according to any one of claims 1 to 3, characterized in that all processes of the preparation method are carried out in a non-liquid phase water environment, and the hydrodeoxygenation upgrading is realized by gas phase pressure swing flash evaporation.
5. The method for preparing biomass hydrogen-rich micropowder for blast furnace injection according to claim 4, wherein the gas phase pressure swing flash distillation comprises: sequentially placing the biomass in a plurality of high-temperature high-pressure superheated gas phase reactors, and carrying out pressure reduction and step-by-step flash evaporation to crush the biomass, evaporate water and recombine the structure; the structural recombination comprises hydrodeoxygenation upgrading and deoxidation carbon extraction.
6. The method for preparing the biomass hydrogen-rich micro powder for blast furnace injection according to claim 5, wherein the number of the high-temperature high-pressure superheated gas phase reactors is not less than 2; the temperature of the first-stage high-temperature high-pressure superheated gas phase reactor is more than 220 ℃, the pressure is more than 2.0MPa, and the retention time is 5-40 min; the temperature of the second-stage high-temperature high-pressure superheated gas phase reactor is 120-160 ℃, the pressure is 1.0-1.4MPa, and the retention time is 5-60 min.
7. The method for preparing the biomass hydrogen-rich micropowder for blast furnace injection according to claim 6, wherein the gas phase medium in the high-temperature high-pressure superheated gas phase reactor comprises one or more of superheated steam, carbon dioxide, ammonia gas, methane, shale gas and coke oven gas, blast furnace gas and converter gas.
8. The method for preparing biomass hydrogen-rich micropowder for blast furnace injection according to claim 7, wherein the gas phase medium in the high-temperature high-pressure superheated gas phase reactor contains superheated steam and ammonia gas at the same time.
9. The method for preparing the biomass hydrogen-rich micro powder for blast furnace blowing according to claim 1, wherein the proportion of the biomass hydrogen-rich micro powder with the particle size below 200 meshes is higher than 60%, the moisture content is lower than 5%, the hydrogen mass content is higher than 6%, and the oxygen content is lower than 25 wt%; the bulk density is 0.4-0.6g/cm 3 。
10. A method for preparing biomass synthesis gas for blast furnace injection, which is characterized in that biomass hydrogen-rich micro powder obtained by the preparation method of any one of claims 1 to 9 is gasified to obtain biomass synthesis gas for blast furnace injection.
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