CN111850216A - Method for co-producing synthesis gas by reducing vanadium-titanium magnetite through biomass - Google Patents
Method for co-producing synthesis gas by reducing vanadium-titanium magnetite through biomass Download PDFInfo
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- CN111850216A CN111850216A CN201910344892.XA CN201910344892A CN111850216A CN 111850216 A CN111850216 A CN 111850216A CN 201910344892 A CN201910344892 A CN 201910344892A CN 111850216 A CN111850216 A CN 111850216A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- 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
Abstract
The invention provides a method for reducing vanadium-titanium magnetite coproduction synthesis gas by using biomass to replace coal as a reducing agent, which utilizes the characteristics of good biomass activity, less impurities, low emission and the like to achieve the purpose of low-temperature, rapid and efficient reduction of iron-containing raw materials. Meanwhile, the resource conversion of the biomass components is realized by utilizing the catalytic performance of cracking of lattice oxygen in the iron oxide and macromolecular components such as iron mineral tar and the like. The method has important significance for realizing the high-efficiency comprehensive utilization of the iron-containing raw material, can relieve the tension situation of energy supply in China, obviously reduces the emission of various pollutants and brings huge energy and environmental benefits.
Description
Technical Field
The invention relates to a separation and extraction method of vanadium titano-magnetite, in particular to a method for reducing vanadium titano-magnetite coproduction synthesis gas by using biomass, and belongs to the technical field of separation of mineral substances.
Background
From the world, the current treatment methods for iron-containing raw materials are as follows: (1) the blast furnace ironmaking process comprises a plurality of links such as sintering/pelletizing, coking, a blast furnace and the like, wherein auxiliary processes such as coking, sintering and the like have high energy consumption (about 60-70% of the energy consumption of steel production) and serious pollution, and are main objects of environmental management, and the national aims of strengthening research and development and test of a non-blast furnace smelting new process cleaning technology and the like in 'adjustment and joyful planning of the steel industry' are taken as key tasks for promoting energy conservation and emission reduction of the steel industry; (2) a non-blast furnace process, wherein the coal-based direct reduction process has strict requirements on conditions, low efficiency, unstable product quality and unsatisfactory reduction effect; the gas-based direct reduction process needs to use natural gas resources as raw materials, and the popularization and application of the process in the world are greatly limited.
In the last 50 s, China began to research and develop direct reduction technology. Because of the shortage of natural gas resources, the method is mainly based on the experimental research of the coal-based rotary kiln process, but the development is very slow due to the reasons of high operating cost, high production control and maintenance requirements, difficulty in expanding the production scale and the like. And most products have unstable quality, the use value of DRI is seriously reduced, and the DRI has adverse effect on the development of the steel industry and equipment manufacturing industry in China.
The vanadium titano-magnetite is a composite ore formed by symbiosis of multiple metal elements such as iron, vanadium, titanium and the like, and has high comprehensive utilization value. At present, the vanadium titano-magnetite resource in China has been proved to have the reserve of more than 300 hundred million tons, and the effective development and utilization of the resource are greatly limited due to the complex mineral phase and stable structure and higher solid reduction difficulty.
Since the 80 s of the last century, China has carried out a great deal of research on the direct reduction technology of the coal base of the rotary hearth furnace, but the industrial production is not realized. In recent years, the rotary hearth furnace process has attracted attention with the demands for the treatment of iron-containing dust and sludge, the comprehensive utilization of complex ores, and the expansion of productivity. A plurality of rotary hearth furnaces are put into production for the comprehensive utilization of composite ores (Tetrachuan python, Panzhihua and sunshine), the utilization of iron-containing dust (horse steel and sand steel) and the production of pre-reduction furnace charges (Shanxi winged city, Lai steel and Tianjin Chengcong). The main equipment is similar to an annular heating furnace, the structure is complex, and the operating cost is high; the production control requirement is high, and the production stability (product quality and equipment operation) does not reach the expected level. The rotary hearth furnace uses carbon-containing pellets or carbon-containing briquettes as raw materials, and due to the infiltration of coal ash, the product has low iron grade and high S content, is difficult to meet the requirements of electric furnace steelmaking production, and is still in the development and development stage.
The biomass is a general term of organic combustible materials generated by photosynthesis, has the characteristics of low sulfur and nitrogen, has good reaction activity, is a very good reducing agent in the field of metallurgy, and generates CO2Participate in carbon circulation of the atmosphere, replace fossil energy such as coke powder, anthracite and the like, relieve the tension of energy supply in China and obviously reduce various pollutants (CO)x、SOx、NOx) And (4) discharging. Meanwhile, biomass carbon, biological oil, hydrocarbon-containing gas phase and other three products generated by thermal decomposition of biomass can be efficiently converted into resources under the participation of iron oxide (lattice oxygen), and part of iron-containing minerals show good catalytic performance in cracking of macromolecular components such as tar. Compared with the expensive oxygen-enriched biomass conversion, the method has obvious economic and technical advantages.
In the prior art, coal is used as a reducing agent in the direct reduction process of iron-containing ores, so that the problems of high reaction temperature, long reaction time, poor product quality and the like are difficult to overcome. At present, the research for iron ore biomass reduction at home and abroad mainly uses biomass charcoal (one of biomass pyrolysis products) as a reducing agent. Compared with blocky coal coke with a compact structure, the biomass carbon has the characteristics of porosity and high specific surface area, and the characteristics of combustibility, reactivity and the like of the biomass carbon are obviously better than those of coal. The reduction process using biomass charcoal as a reducing agent has lower reaction temperature, higher reaction rate and higher reduction degree and lower impurity content of the product. The biomass carbon has higher research value and application prospect in the aspects of low-grade ore magnetizing roasting, high-phosphorus iron ore dephosphorization, high-metal-content dust treatment, direct reduction of carbon-containing pellets and the like. However, the conversion utilization in reduction of the other two products of biomass pyrolysis (bio-oil, gas phase) has not attracted attention.
Disclosure of Invention
Aiming at the defects of high reaction temperature, long time, high energy consumption, low efficiency and poor product quality of the coal-based direct reduction process in the prior art. The invention adopts biomass to replace coal as a reducing agent, and achieves the aim of reducing the iron-containing raw material at low temperature, quickly and efficiently by utilizing the characteristics of good activity, less impurities, low emission and the like. Meanwhile, the resource conversion of the biomass components is realized by utilizing the catalytic performance of cracking of lattice oxygen in the iron oxide and macromolecular components such as iron mineral tar and the like. The method has important significance for realizing the high-efficiency comprehensive utilization of the iron-containing raw material, can relieve the tension situation of energy supply in China, obviously reduces the emission of various pollutants and brings huge energy and environmental benefits. The method for coupling the efficient reduction of the iron-containing raw material and the biomass conversion fully exerts the characteristics of green biomass and good activity, and integrates the lattice oxygen and the iron mineral in the iron material into the same reaction system by utilizing the catalytic performance of the lattice oxygen and the iron mineral in the iron material, thereby synchronously strengthening the direct reduction of the iron-containing raw material and the gasification conversion of biomass resources.
According to the technical scheme provided by the invention, the method for co-producing the synthesis gas by reducing the vanadium titano-magnetite by using the biomass is provided.
A method for co-producing synthesis gas by reducing vanadium titano-magnetite with biomass comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; the biomass is pre-reduced by tar and volatile components obtained by catalytic cracking to obtain a pre-reduced iron-containing raw material.
Preferably, the method further comprises: and (3) carrying out hot-press molding on the pre-reduced iron-containing raw material to obtain the high-activity iron-making furnace burden.
Preferably, the method further comprises: and (4) carrying out deep reduction process on the pre-reduced iron-containing raw material obtained in the step (2) or the high-activity iron-making furnace charge obtained in the step (3) to obtain a deep-reduced iron-containing raw material.
Preferably, the method further comprises: and (5) grinding, selecting and separating the deep reduced iron-containing raw material obtained in the step (4) to obtain an iron-rich raw material and a vanadium-rich titanium material.
Preferably, the method further comprises: and (6) sequentially carrying out condensation, drying and decarburization processes on the synthesis gas obtained in the step (2) to obtain high-quality synthesis gas.
Preferably, step (1) further comprises: firstly, vanadium titano-magnetite is pretreated, and then the pretreated vanadium titano-magnetite is mixed with biomass.
Preferably, the pretreatment is grinding.
Preferably, coal is also added to the mixture of step (1).
Preferably, additives and/or binders are also added to the mix.
Preferably, in the step (3), the pre-reduced iron-containing raw material and the biomass charcoal obtained in the step (2) are mixed, and are subjected to a hot press molding process and then a deep reduction process in the step (4) to obtain a deep reduced iron-containing raw material.
Preferably, in the step (4), the pre-reduced iron-containing raw material obtained in the step (2) and the biomass charcoal obtained in the step (2) are mixed and subjected to a deep reduction process to obtain a deep-reduced iron-containing raw material.
In the invention, in the mixture in the step (1), the vanadium titano-magnetite and the biomass are added in an amount such that the mass ratio of Fe/C in the mixture is 1:0.1-0.9, preferably 1:0.15-0.8, and more preferably 1: 0.2-0.4.
In the present invention, the weight of the added coal is 5-50%, preferably 8-40%, more preferably 10-20% of the weight of the vanadium titano-magnetite in the mixture.
In the present invention, in the pre-reduction treatment step in step (2), the temperature of the heating treatment is 700-.
In the present invention, in the pre-reduction treatment step in step (2), the time for the heat treatment is 0.1 to 8 hours, preferably 0.3 to 6 hours, and more preferably 0.5 to 3 hours.
In the present invention, the pressure of the hot press molding step in step (3) is 0.1 to 1MPa, preferably 0.4 to 0.8 MPa; the pressure time of the hot press molding process is 1-10min, preferably 2-8 min.
In the present invention, the deep reduction step in step (4) is a heating treatment, and the heating temperature is 900-.
In the present invention, the deep reduction step in step (4) is a heat treatment, and the time of the heat treatment is 0.1 to 6 hours, preferably 0.2 to 4 hours, and more preferably 0.5 to 2 hours.
Preferably, the deep reduction step is performed by microwave heating.
In the invention, the biomass is one or more of rice straw, wheat straw, corn straw, bagasse, sorghum straw, sawdust, waste ore wood, firewood, couch grass, cassava vine and pine wood.
In the invention, the additive is one or more of sodium carbonate, sodium sulfate, sodium chloride, sodium borate, calcium chloride, calcium fluoride and ferric chloride.
Preferably, the additive is added in an amount of 0-10%, preferably 0.1-8%, more preferably 0.2-5% by weight of the vanadium titano-magnetite in the mix.
In the invention, the binder is one or more of bentonite, composite bentonite, calcium oxide, water glass and pellitol.
Preferably, the amount of binder added is 0-5%, preferably 0.1-4%, more preferably 0.2-3% by weight of the vanadium titano-magnetite in the mix.
The main phase components of the vanadium titano-magnetite are magnetite and ilmenite which are closely symbiotic, the separation is difficult by adopting a conventional beneficiation mode, and vanadium is mainly enriched in the magnetite in a homogeneous homography mode.
The invention adopts biomass as a reducing agent for reducing vanadium titano-magnetite. Pre-reducing the iron-containing raw material by using gas and oil phase of biomass cracking, and directionally converting the gas and the oil phase by using lattice oxygen in the iron-containing raw material to obtain three products, namely a pre-reduced iron material, synthesis gas and biomass charcoal; then, mixing the biomass charcoal, the pre-reduced iron material and the additive according to a certain proportion, carrying out pretreatment, and forming the pretreated material; the formed material is reduced and roasted to obtain two products of iron-rich raw material and synthetic gas.
According to the invention, gas and oil generated by biomass pyrolysis are adopted to pre-reduce the iron-containing raw material, and meanwhile, the gas and oil are directionally converted by lattice oxygen in the iron-containing raw material, so that two process flows are coupled in one link, and the purposes of simplifying the flow and improving the efficiency are achieved; the biochar which is good in activity, less in impurity and low in emission is used as a reducing agent, so that the low-temperature and rapid metallization reduction of the iron-containing material is realized, and meanwhile, the biochar is converted into a synthesis gas component. The invention integrates two relatively independent technological processes of direct reduction of iron-containing materials and gasification and transformation of biomass into one system to complete, gives full play to respective advantages, effectively promotes respective transformation processes, and realizes good effects of 1+1> 2.
Biomass has a relatively low carbon content and a high elemental oxygen content compared to coke, and a low content of S, P, which is a cleaner fuel. The biomass has higher volatile content and oxygen content and stronger activation than coal, so the biomass is more suitable for the gasification of fuel than the coal.
The gasification process of biomass is accompanied by a pyrolysis process, wherein the pyrolysis is the first step of the gasification process. At present, biomass gasification is mainly applied to preparation of synthesis gas, and generally a catalyst is needed to eliminate or inhibit tar generated by the biomass gasification. The catalyst also has a large influence on the gasification process of biomass. The catalyst has a great influence on the generation of tar and the composition of fuel gas. The catalyst not only strengthens the biomass gasification reaction, but also promotes the cracking of tar, thereby being beneficial to improving the volume ratio of small molecule gas in the product gas, and further improving the heat value and the yield of the product gas.
According to the invention, through experiments, in the gasification process of taking vanadium titano-magnetite as an oxygen carrier, biomass can be well or partially converted, and part of iron-containing minerals and macromolecular components such as tar show good catalytic performance through cracking. In addition, the nickel-based modification of the oxygen carrier mineral can effectively increase the reaction activity of the oxygen carrier mineral and promote the gasification and conversion of the biomass energy. According to the invention, vanadium titano-magnetite is used as an oxygen carrier to gasify the biomass, so that the comprehensive utilization of biomass and iron ore resources is realized to efficiently convert the biomass and iron ore resources into usable synthesis gas; the lattice oxygen in the vanadium titano-magnetite replaces pure oxygen to be used as a gasifying agent.
The vanadium titano-magnetite is beneficial to gasification and pyrolysis of biomass, and has two main reasons. Firstly, the iron ore is a catalyst, can promote the pyrolysis of biomass, improve the pyrolysis speed and generate more gas phases within a certain time; in addition, iron ore acts as an oxidant, providing oxygen atoms, oxidizing a certain amount of the macromolecular carbon skeleton and fixed carbon (carbon residue) to CO and CO2. Vanadium titano-magnetite as gasifying agent for biomass gasification can promote the conversion of carbon element in biomass to gas phase product. The main reasons are as follows: firstly, vanadium titano-magnetite is used as a catalyst, so that the cracking of a solid-phase carbon skeleton in biomass is promoted, and high-molecular organic matters such as cellulose are converted into a micromolecular gas-phase product and a macromolecular liquid-phase product; second, vanadium titano-magnetite is used as an oxidizing agent for oxidizing carbon residue in a solid phase after biomass gasification to produce CO and CO2Further reducing the conversion rate of solid phase product carbon.
The addition of vanadium titano-magnetite as oxygen carrier promotes the conversion of solid and liquid phase products to gas phase products, improves the effective gasification rate of C, and slightly reduces the effective gasification rate of H. The addition of the oxygen carrier can accelerate the cracking of each group in the biomass. At the same time, the reduction of the biomass promotes the conversion of magnetite and ilmenite in the oxygen carrier to metallic iron.
In addition, the vanadium titano-magnetite and the biomass are mixed for use, tar generated by cracking the vanadium titano-magnetite catalytic biomass is continuously decomposed, and the generation amount of tar in the gas production process of the biomass is reduced or even eliminated, so that the generation of pollutants (tar) is reduced. In the prior art, the synthesis gas is produced by using biomass, and tar serving as a byproduct is a pollutant and needs to be continuously treated by adopting subsequent procedures. The vanadium titano-magnetite and the biomass are simultaneously mixed and mutually utilized, and due to the addition of the vanadium titano-magnetite, the production of tar is reduced, and the yield of the synthesis gas is improved. The vanadium titano-magnetite and the biomass produce synergistic effect and the effect is obvious.
Vanadium titano-magnetite belongs to a mineral which is difficult to reduce, and higher temperature is often needed for reducing iron oxide, but vanadium can enter metallic iron at too high temperature. Previous studies have shown that the reduction temperature should be kept as low as possible below 1300 c in order to allow the vanadium to enter the slag phase with the titanium. Compared with the method for reducing iron ore by using the coal powder (coke powder), the method for reducing the vanadium titano-magnetite by using the biomass has the advantages that the reaction activation energy is lower, the reaction temperature can be reduced by 100-150 ℃, the reaction time is greatly shortened, and the obtained product has the characteristics of low S, P, C and the like.
Anthracite is used as a reducing agent, the metallization rate of a reduced product is extremely low under a low-temperature condition, the metallization rate of the product is only 16.05% at 950 ℃, the metallization rate of the product is gradually increased along with the increase of the temperature, and the metallization rate of the product is increased to 83.22% at 1200 ℃. Therefore, when anthracite is used as a reducing agent, the vanadium titano-magnetite is difficult to reduce under the low-temperature condition, and the reduction of the vanadium titano-magnetite can be greatly promoted by raising the temperature. In addition, when the carbon-iron ratio is increased from 0.6 to 1.4 when the vanadium titano-magnetite is reduced by using anthracite as a reducing agent, the metallization rate of the product is increased from 74.98 percent to 86.96 percent,
biomass is used as a reducing agent, the metallization rate of a reduced product is increased in an S shape along with the increase of the reduction temperature within the range of 950-1200 ℃, and the metallization rate of the product is 54.89-76.80% at the temperature of 950-1050 ℃. When the temperature rises to 1100 ℃, the metallization rate reaches 83.17 percent, which is equivalent to the metallization rate of the product under the condition of 1200 ℃ by using anthracite as a reducing agent. The temperature rises to 1150 ℃, and the metallization rate of the product rises to 86.96%; when the temperature reaches 1200 ℃, the metallization rate is 88.25 percent. When the biomass is used as a reducing agent to reduce the vanadium titano-magnetite, when the carbon-iron ratio is 0.2, the metallization rate of the roasted product is 72.89%, and when the carbon-iron ratio is increased to 0.4, the metallization rate is increased to 88.65%.
In addition, the biomass is directly mixed with the vanadium titano-magnetite, and the heating treatment is carried out, so that the volatile components generated in the heating treatment process of the biomass are fully utilized, the activity and the reducibility of the volatile components are utilized, the reducibility of the biomass to the vanadium titano-magnetite is greatly improved, and the metallization rate of the vanadium titano-magnetite reduction product is improved.
Preferably, the pre-reduced iron-containing raw material is subjected to a hot-press forming process, and the pre-reduced material (containing part of residual carbon) can form a relatively compact internal carbon-mixed briquette through the hot-press process, so that on one hand, the reducing agent (biomass carbon and/or additionally added coal powder) is wrapped by the iron mineral to form an internal carbon-mixed structure, the contact area between the reducing agent (biomass carbon and/or additionally added coal powder) and the iron mineral is increased, the conditions that the direct reduction reaction of the iron mineral and carbon particles occurs and the Boolean reaction of the carbon particles occurs are improved, and the subsequent deep reduction process is facilitated to be strengthened; on the other hand, the pores of the pre-reduced material are reduced as the material is compacted, the mass transfer effect in the deep reduction process is improved, the migration transmission distance of the new metal phase can be obviously shortened, the aggregation and growth effect of iron crystal grains is enhanced, and favorable mineralogical conditions can be created for the efficient separation of the subsequent iron and vanadium and titanium.
Preferably, the vanadium titano-magnetite is pretreated by the method, and the pretreatment is preferably ground. After the vanadium titano-magnetite is subjected to ore grinding pretreatment, compared with an unreduced sample, a reduction product has obvious shrinkage and smaller volume than before reduction. Compared with a reduction sample which is not subjected to ore grinding pretreatment, the shrinkage is more obvious, and the structure of the reduction sample is more compact along with the extension of ore grinding time. The metallization rate of the product can be effectively improved through ore grinding pretreatment. The iron crystal grains of the reduction product which is not subjected to ore grinding pretreatment are fine and form a net structure, and more slag phases are mixed in the middle and are not separated from the iron phase. After the ore grinding pretreatment, iron crystal grains grow obviously and form a relatively complete metallic iron phase, and the middle of the iron phase basically has no slag phase mixed with the iron phase. The pretreatment greatly reduces the specific surface and pore volume of the reduction product, the agglomerate is more compact, the space between mineral particles is reduced, and the interconnection and growth of iron grains are facilitated.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. according to the invention, the biochar which is good in activity, less in impurity and low in emission is used as a reducing agent, so that the low-temperature and rapid metallization reduction of the iron-containing material is realized, and meanwhile, the biochar is converted into a synthesis gas component;
2. According to the invention, the biomass is adopted to reduce the vanadium titano-magnetite, and the vanadium titano-magnetite is beneficial to gasification and pyrolysis of the biomass;
3. according to the invention, vanadium titano-magnetite is used as an oxygen carrier to gasify the biomass, so that the comprehensive utilization of biomass and iron ore resources is realized to efficiently convert the biomass and iron ore resources into usable synthesis gas; the lattice oxygen in the vanadium titano-magnetite replaces pure oxygen to be used as a gasifying agent.
Drawings
FIG. 1 is a process flow chart of the co-production of synthesis gas by pre-reducing vanadium titano-magnetite with biomass according to the present invention;
FIG. 2 is a process flow diagram of the present invention for co-producing synthesis gas by reducing vanadium titano-magnetite with biomass and subjecting iron-containing raw material to deep reduction;
FIG. 3 is a flow chart of the process for co-producing synthesis gas by reducing vanadium titano-magnetite with biomass, separating iron-rich raw material and purifying synthesis gas according to the present invention;
FIG. 4 is a full-flow process diagram of the co-production of synthesis gas by using biomass to reduce vanadium titano-magnetite according to the present invention;
FIG. 5 is a FTIR spectrum of biomass feedstock;
FIG. 6 is a schematic diagram showing the effect of volatile components in the reduction process;
FIG. 7 is a graph showing the effect of volatiles on the microstructure of the vanadium titano-magnetite reduction product.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
Example 1
As shown in fig. 1, a method for coproducing synthesis gas by using biomass to reduce vanadium titano-magnetite comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; the biomass is pre-reduced by tar and volatile components obtained by catalytic cracking to obtain a pre-reduced iron-containing raw material.
Example 2
As shown in fig. 2, a method for coproducing synthesis gas by using biomass to reduce vanadium titano-magnetite comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; carrying out pre-reduction on vanadium titano-magnetite by tar and volatile components obtained by catalytic cracking of biomass to obtain a pre-reduced iron-containing raw material;
(3) carrying out hot press molding on the pre-reduced iron-containing raw material to obtain a high-activity iron-making furnace burden;
(4) and (4) carrying out a deep reduction process on the high-activity iron-making furnace charge obtained in the step (3) to obtain a deep-reduced iron-containing raw material.
Example 3
A method for co-producing synthesis gas by reducing vanadium titano-magnetite with biomass comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; carrying out pre-reduction on vanadium titano-magnetite by tar and volatile components obtained by catalytic cracking of biomass to obtain a pre-reduced iron-containing raw material;
(4) and (3) carrying out a deep reduction process on the pre-reduced iron-containing raw material obtained in the step (2) to obtain a deep-reduced iron-containing raw material.
Example 4
As shown in fig. 3, a method for coproducing synthesis gas by using biomass to reduce vanadium titano-magnetite comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; carrying out pre-reduction on vanadium titano-magnetite by tar and volatile components obtained by catalytic cracking of biomass to obtain a pre-reduced iron-containing raw material;
(3) mixing the pre-reduced iron-containing raw material with the biomass charcoal obtained in the step (2), and performing a hot-press molding process to obtain a high-activity iron-making furnace burden;
(4) Carrying out a deep reduction process on the high-activity iron-making furnace charge obtained in the step (3) to obtain a deep-reduced iron-containing raw material; the deep reduction process adopts microwave heating treatment;
(5) and (4) grinding, selecting and separating the deep reduced iron-containing raw material obtained in the step (4) to obtain an iron-rich raw material and a vanadium-rich titanium material.
Example 5
Example 3 is repeated except that the method further comprises: and (6) sequentially carrying out condensation, drying and decarburization processes on the synthesis gas obtained in the step (2) to obtain high-quality synthesis gas.
Example 6
As shown in fig. 4, the embodiment 4 is repeated, except that the step (1) further includes: firstly, pretreating vanadium titano-magnetite, and then mixing the pretreated vanadium titano-magnetite with biomass, wherein the pretreatment is grinding; coal, sodium carbonate and bentonite are also added into the mixture in the step (1).
Experiments were carried out using the method of example 6, using vanadium titano-magnetite from Panzhihua Sichuan and pine wood as the biomass.
The chemical composition of vanadium titano-magnetite is shown in the following table. Wherein: the iron content is 55.62%, and the content of TiO is higher212.46% of V2O50.64% in content and secondly higher Al content2O3MgO and SiO2The P, S content is lower.
The experimental results are as follows:
The present invention additionally carried out the above experiments using rice straw, wheat straw, corn straw, bagasse, sorghum straw, sawdust, waste ore, firewood, thatch, and cassava vine as biomass, with similar results to those described above.
Example 7
Example 6 was repeated except that sodium chloride was used instead of sodium carbonate.
Example 8
Example 6 was repeated except that calcium fluoride was used instead of sodium carbonate.
Example 9
Example 6 was repeated except that calcium oxide was used instead of bentonite.
Example 10
Example 6 was repeated except that perylenes was used instead of bentonite.
Comparative example 1
By adopting the process of example 6, anthracite and rice straw are respectively selected as reducing agents to perform reduction separation on the vanadium titano-magnetite to extract iron-rich raw materials, and the results are as follows:
anthracite is used as a reducing agent, the metallization rate of a reduction product is extremely low under a low-temperature condition, and the metallization rate of the product is only 16.05 percent at 950 ℃; the metallization of the product gradually increases with increasing temperature, and at a reduction temperature of 1200 ℃, the metallization of the product increases to 83.22%. Therefore, when anthracite is used as a reducing agent, the vanadium titano-magnetite is difficult to reduce under the low-temperature condition, and the reduction of the vanadium titano-magnetite can be greatly promoted by raising the temperature. In addition, when the carbon-iron ratio is increased from 0.6 to 1.4 when the vanadium titano-magnetite is reduced by using anthracite as a reducing agent, the metallization rate of the product is increased from 74.98 percent to 86.96 percent,
Rice straw is used as a reducing agent, and the metallization rate of the product is 54.89-76.80% at the temperature of 950-1050 ℃. When the temperature rises to 1100 ℃, the metallization rate reaches 83.17 percent, which is equivalent to the metallization rate of the product under the condition of 1200 ℃ by using anthracite as a reducing agent. The temperature rises to 1150 ℃, and the metallization rate of the product rises to 86.96%; when the temperature reaches 1200 ℃, the metallization rate is 88.25 percent. When the biomass is used as a reducing agent to reduce the vanadium titano-magnetite, when the carbon-iron ratio is 0.2, the metallization rate of the roasted product is 72.89%, and when the carbon-iron ratio is increased to 0.4, the metallization rate is increased to 88.65%.
In addition, according to the technical scheme of the invention, gas and oil generated by biomass pyrolysis are utilized to pre-reduce the iron-containing raw material, and meanwhile, lattice oxygen in the iron-containing raw material directionally converts the gas and oil in the biomass to obtain the synthesis gas. Detecting to obtain the synthesis gas containing CO and H2The total content of (A) is more than 70%.
Comparative example 2
The procedure of example 6 was followed using pine-wood carbon to reduce vanadium titano-magnetite at 1150 ℃ under the same fixed carbon ratio (C: Fe ═ 0.4), and a comprehensive comparison was made with the pine-wood reduction process under the same conditions.
As shown in fig. 6, the metallization rate of the pine wood as-reduced is much greater than that of the pine wood as-reduced carbon in the whole reduction process. When the metal content of the product reduced by the pine wood carbon is reduced for 10min, the metal content of the product reduced by the pine wood carbon is 60.11%, and the metal content of the product reduced by the pine wood carbon is only 23.82%; and after the mixture is roasted for 40min, the metallization rates of the two materials tend to be stable, the metallization rate of the product reduced by the pine wood is 87.13%, and the metallization rate of the product reduced by the pine wood carbon is 68.10%, which is different from 19.03%. In the whole reduction process, the same fixed carbon is added into both the pine wood and the pine wood carbon, and the only difference of the two reducing agents is the content of volatile components, the pine wood contains a large amount of volatile components, and the pine wood carbon only contains a small amount of volatile components. It can thus be derived: in the process of reducing vanadium titano-magnetite from pine wood, the existence of volatile components greatly improves the reduction effect and can improve the metallization rate of a roasted sample by nearly 20 percent.
As can be seen from FIG. 7, in the reduction time of 15min, the product micro-morphology reduced by using the pine wood carbon basically keeps the particle morphology of the raw ore, and only a small amount of metallic iron is generated at the edge of the mineral particles; in the product reduced by pine wood, the raw ore particles are basically decomposed to generate dense and hemp metallic iron particles. When the reduction is carried out for 30min, in the product reduced by pine wood carbon, metal iron grains begin to appear in the interior of mineral particles, but are sparse and exist in a granular form basically; in the product reduced by the pine wood, the generated metallic iron is denser than that generated in the reduction for 15min, and iron crystal grains are hooked with each other to form a grid shape. When the reduction is carried out for 45min, metal iron crystal grains in the product reduced by the pine wood carbon are obviously increased, and adjacent iron crystal grains are adhered to each other; and iron crystal grains which are a product of pine wood reduction are migrated and aggregated together to grow up, so that a strip shape is formed. In fig. 7, reference numeral 1 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood carbon for 15min, reference numeral 2 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood carbon for 30min, reference numeral 3 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood carbon for 45min, reference numeral 4 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood for 15min, reference numeral 5 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood for 30min, and reference numeral 6 denotes a microstructure diagram of reducing vanadium titano-magnetite by pine wood for 45 min.
From the above analysis, it can be known that, in the process of solid-phase reduction of vanadium titano-magnetite from biomass, the volatile matter has an obvious promotion effect on the reduction of iron ore.
Claims (10)
1. A method for co-producing synthesis gas by reducing vanadium titano-magnetite with biomass comprises the following steps:
(1) mixing vanadium titano-magnetite with biomass to obtain a mixture;
(2) heating the mixture, and catalytically cracking the biomass by using vanadium titano-magnetite to obtain synthesis gas, tar, biomass carbon and volatile components; the biomass is pre-reduced by tar and volatile components obtained by catalytic cracking to obtain a pre-reduced iron-containing raw material.
2. The method of claim 1, wherein: the method further comprises the following steps: step (3) performing hot-press molding on the pre-reduced iron-containing raw material to obtain a high-activity iron-making furnace burden; and/or
(4) And (3) carrying out a deep reduction process on the pre-reduced iron-containing raw material obtained in the step (2) or the high-activity iron-making furnace charge obtained in the step (3) to obtain a deep-reduced iron-containing raw material.
3. The method of claim 2, wherein: the method further comprises the following steps: step (5) grinding, selecting and separating the deep-reduced iron-containing raw material obtained in the step (4) to obtain an iron-rich raw material and a vanadium-rich titanium material; and/or
(6) And (3) sequentially carrying out condensation, drying and decarburization processes on the synthesis gas obtained in the step (2) to obtain high-quality synthesis gas.
4. The method according to any one of claims 1-3, wherein: the step (1) also comprises the following steps: firstly, pretreating vanadium titano-magnetite, and then mixing the pretreated vanadium titano-magnetite with biomass; preferably, the pretreatment is grinding; and/or
Coal is also added into the mixture in the step (1); preferably, additives and/or binders are also added to the mix.
5. The method according to any one of claims 2-4, wherein: in the step (3), mixing the pre-reduced iron-containing raw material with the biomass charcoal obtained in the step (2), performing a hot-press molding process, and performing a deep reduction process in the step (4) to obtain a deep-reduced iron-containing raw material; and/or
And (4) mixing the pre-reduced iron-containing raw material obtained in the step (2) with the biomass charcoal obtained in the step (2), and carrying out a deep reduction process to obtain a deep-reduced iron-containing raw material.
6. The method according to any one of claims 4-5, wherein: in the mixture obtained in the step (1), the adding amount of the vanadium titano-magnetite and the biomass enables the mass ratio of Fe/C in the mixture to be 1:0.1-0.9, preferably 1:0.15-0.8, and more preferably 1: 0.2-0.4; and/or
The weight of the added coal is 5-50%, preferably 8-40%, and more preferably 10-20% of the weight of the vanadium titano-magnetite in the mixture.
7. The method according to any one of claims 1-6, wherein: in the pre-reduction treatment step in the step (2), the temperature of the heating treatment is 700-1200 ℃, preferably 750-1150 ℃, and more preferably 800-1100 ℃; the time for the heat treatment is 0.1 to 8 hours, preferably 0.3 to 6 hours, and more preferably 0.5 to 3 hours.
8. The method according to any one of claims 2-7, wherein: the pressure of the hot-press molding process in the step (3) is 0.1MPa-1MPa, preferably 0.4-0.8 MPa; the pressure time of the hot press molding process is 1-10min, preferably 2-8 min.
The deep reduction procedure in the step (4) is heating treatment, and the heating temperature is 900-; the time of the heat treatment is 0.1 to 6 hours, preferably 0.2 to 4 hours, and more preferably 0.5 to 2 hours; preferably, the deep reduction step is performed by microwave heating.
9. The method according to any one of claims 1-8, wherein:
the biomass is one or more of rice straw, wheat straw, corn straw, bagasse, sorghum straw, sawdust, waste ore wood, firewood, couch grass, cassava vine and pine wood.
10. The method according to any one of claims 4-9, wherein: the additive is one or more of sodium carbonate, sodium sulfate, sodium chloride, sodium borate, calcium chloride, calcium fluoride and ferric chloride; preferably, the addition amount of the additive is 0-10%, preferably 0.1-8%, more preferably 0.2-5% of the weight of the vanadium titano-magnetite in the mixture; and/or
The binder is one or more of bentonite, composite bentonite, calcium oxide, water glass and pellitol; preferably, the amount of binder added is 0-5%, preferably 0.1-4%, more preferably 0.2-3% by weight of the vanadium titano-magnetite in the mix.
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| CN115970649A (en) * | 2023-03-20 | 2023-04-18 | 四川省冶勘设计集团生态环境工程有限公司 | Citrus biochar and preparation method and application thereof |
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| CN113355118B (en) * | 2021-06-04 | 2022-06-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Production method of iron coke for titanium slag smelting and iron coke |
| CN115970649A (en) * | 2023-03-20 | 2023-04-18 | 四川省冶勘设计集团生态环境工程有限公司 | Citrus biochar and preparation method and application thereof |
| CN115970649B (en) * | 2023-03-20 | 2023-05-12 | 四川省冶勘设计集团生态环境工程有限公司 | Citrus biochar as well as preparation method and application thereof |
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