CN107177732A - It is a kind of to prepare high strength bainite agglomerate and gas iron co-production as bonding carrier with biomass - Google Patents
It is a kind of to prepare high strength bainite agglomerate and gas iron co-production as bonding carrier with biomass Download PDFInfo
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- CN107177732A CN107177732A CN201710355348.6A CN201710355348A CN107177732A CN 107177732 A CN107177732 A CN 107177732A CN 201710355348 A CN201710355348 A CN 201710355348A CN 107177732 A CN107177732 A CN 107177732A
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- biomass
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
Abstract
The a kind of of the present invention prepares high strength bainite agglomerate and gas iron co-production with biomass as bonding carrier, belongs to technical field of ferrous metallurgy.The preparation method of iron content agglomerate of the present invention, iron-bearing material, biomass and additive are mixed, iron content agglomerate is prepared by cuber hot pressing, biomass is by being modified processing in modified solution.The specific method of the present invention is to immerse biomass in modified solution to be modified processing, the biomass after modification, iron-bearing material and additive are mixed into pressurization again iron content agglomerate is made, and heated in elevated temperature vessel, biomass generates imflammable gas by gasification, and ferriferous oxide is reduced generation DRI.Biomass in the present invention is used as the reducing agent of ferriferous oxide and the C sources of imflammable gas and H sources, ferriferous oxide serves as source of iron and oxygen source, without adding binding agent and improving the intensity of iron content agglomerate, the degree of metalization of DRI is improved while improving gasification of biomass yield.
Description
Technical field
The present invention relates to ironmaking technology field, prepared more specifically to one kind biomass as bonding carrier high
Intensity iron content agglomerate and gas iron co-production.
Background technology
Biomass energy (biomass energy) is the form of energy that solar energy is stored in chemical energy form in biomass,
I.e. using biomass as the energy of carrier.It directly or indirectly derives from the photosynthesis of green plants, is a kind of renewable energy
Source.Biomass energy has the advantages that renewable, low stain, widely distributed.Biomass energy rationally is utilized, is effectively reduced to ore deposit
The dependence of the thing energy, by mitigating the pollution that energy-consuming is caused to environment.Nowadays the development and utilization of biomass energy into
For the focus of international concern, Biomass Energy Technology has suitable vast potential for future development.Process of the existing biomass in application
In, often biomass is gasified, gasification of biomass be under certain thermodynamic condition, by means of air part (or
Oxygen), the effect of vapor, make biomass high polymer occur pyrolysis, oxidation, reduction reforming reaction, be eventually converted into an oxygen
Change carbon, the process of the fuel gas such as hydrogen and low molecular hydrocarbon.
Steel and iron industry means the industry of the production pig iron, steel, ingot iron and ferroalloy, is all industrialized countries of the world
One of basic industries.At the same time, steel and iron industry is also resource, energy intensive industry, is also typical high material-consumption, high energy
Consumption, high pollutive industries, consume the limited resources such as substantial amounts of iron ore, coal, water, while discharge substantial amounts of again in process of production
Discarded object, serious pollution is caused to environment.Iron and Steel Enterprises in China energy consumption about occupies the 10% of national total energy consumption, waste water,
Solid waste, discharge amount of exhaust gas account for the 14% of national emission of industrial pollutants total amount, 17%, 16% respectively.At present, China's steel
Iron industrial expansion faces the dual restriction of the energy and environment, the energy and environment oneself turn into influence steel and iron industry survival and development
Significant problem.Promote the energy-saving and emission-reduction policy of steel and iron industry, increase energy-saving and emission-reduction dynamics, improve efficiency of energy utilization, development with
" low-carbon economy " based on low energy consumption, low stain, could promote the sustainable development of steel and iron industry.It therefore, it can biology
Matter is applied in steel and iron industry, and the coal and coke of traditional iron-smelting process are replaced using biomass.
Through retrieval, existing related technical staff carries out research in this respect, for example：Qingdao Technological University carries out related
Research, and applied for patent：A kind of direct reduction iron making device and method (number of patent application based on biomass
201110408416.3, the applying date：2011-12-09) and a kind of direct reduction iron making device based on biomass pyrolytic tar and
Method (number of patent application 201310107214.4, applying date 2013-03-29), its use biomass pyrolytic tar substitute coal and
Natural gas carries out direct reduction iron making, so as to reduce dependence of the iron-smelting process to fossil energy, improves direct-reduction iron product
The harm to environment can also be reduced while quality.But this method be often using biomass as fuel substitute, still
Biomass is during reduction ore, the cracking of simultaneous biomass, and cracking easily occurs for biomass not exclusively during this
And substantial amounts of tar is produced, the waste of biomass energy is not only caused, and serious environmental pollution is caused, this problem needs solution badly
Certainly.And existing biomass pellet strength is poor, have impact on further reaction and the reduction process of pelletizing.
The content of the invention
1. the invention technical problem to be solved
It is an object of the invention to overcome in the prior art, binding agent reduces the deficiency of the quality of DRI, carries
For one kind biomass high strength bainite agglomerate and gas iron co-production are prepared as bonding carrier；
A kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass wherein provided, by using modification
Biomass can improve the intensity of iron content agglomerate, improve the quality of DRI as bonding carrier, modified biomass；Enter
One step, the mating reaction of each component can promote the decomposition of larger molecular organicses, reduce tar content, while improving gas
Change yield；Degree of metalization can further be improved；
What is wherein provided is a kind of with gas iron co-production of the biomass as bonding carrier, and bonding is used as with modified biomass
Biomass in carrier, iron content agglomerate generates imflammable gas by gasification, and ferriferous oxide is reduced generation DRI, can be with
The quality of DRI is improved, tar content can be reduced, while improving gasifyin g yield, is contained by biomass modified improve
The intensity of iron agglomerate；Degree of metalization can further be improved.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
A kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass of the present invention, step is by iron content
Raw material, biomass and additive mixing, iron content agglomerate is prepared by cuber hot pressing, and described biomass is molten by modification
Processing is modified in liquid, described modified solution is alkaline solution.
Preferably, including iron-bearing material, biomass and additive；Described iron-bearing material, biomass and additive is by such as
Lower mass fraction composition：
50-60 parts of biomass；
100-200 parts of iron-bearing material；
5-10 parts of additive.
Preferably, comprise the following steps that：
(1) biomass is immersed in modified solution and soaks 1-2h, dried in an oven after the completion of immersion, complete biomass
It is modified；
(2) biomass, iron-bearing material, additive are mixed, iron content is prepared in 150-400 DEG C of hot pressing by cuber
Agglomerate.
Preferably, the temperature that described modified solution is modified processing to biomass is 80-95 DEG C.
Preferably, described modified solution is NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
The present invention's is a kind of with gas iron co-production of the biomass as bonding carrier, and biomass is immersed in modified solution
It is modified processing, described modified solution is alkaline solution, then by the biomass after modification, iron-bearing material and additive
Iron content agglomerate is made in mixing pressurization, and iron content agglomerate is put into elevated temperature vessel and heated, and biomass is flammable by gasification generation
Gas, ferriferous oxide is reduced generation DRI, and described additive includes sodium carbonate, lateritic nickel ore, dolomite and grass
Wood ash.
Preferably, the temperature that described modified solution is modified processing to biomass is 80-95 DEG C.
Preferably, described modified solution is NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
Preferably, comprise the following steps that：
(1) biomass is immersed in modified solution and soaks 1-2h, dried in an oven after the completion of immersion, complete biomass
It is modified；
(2) biomass, iron-bearing material, additive are mixed, iron content is prepared in 150-400 DEG C of hot pressing by cuber
Agglomerate；
(3) dried iron content agglomerate is put into 800-900 DEG C of elevated temperature vessel, keeps 5-10min, then be warming up to
1150-1250 DEG C, and it is incubated 30-60min.
Preferably, described iron-bearing material, biomass and additive are constituted by following mass fraction：
50-60 parts of biomass；
100-200 parts of iron-bearing material；
5-10 parts of additive.
3. beneficial effect
The technical scheme provided using the present invention, compared with existing known technology, with following remarkable result：
(1) a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass of the invention, biomass contains
Iron agglomerate includes iron-bearing material, biomass and additive, and biomass uses modification biological by being modified processing in modified solution
Matter can improve the intensity of iron content agglomerate, improve the quality of DRI as bonding carrier, modified biomass；Biomass
Complex oxide in iron content agglomerate strengthens its ion deviation effect to pyrolysis products such as tar at high temperature, promotes tar
In electron cloud is destroyed and loss of stability, promoted coke tar cracking to generate small organic molecule, the combustibility being cracked to form
Gas enhances the reduction process to ferriferous oxide to ferriferous oxide, improves the metallization for the DRI that reaction is obtained
Rate；
(2) a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass of the invention, iron content agglomerate
In metal ion high-temperature heating process adsorb on biomass and its surface of catabolite, promoted C-C and C-O bond angles
Skew, elongated, the carbocyclic ring irregular deformation of bond distance etc., and cause bond energy to reduce, tar and other catabolites of biomass are thermally-stabilised
Property reduction, can promote the decomposition of larger molecular organicses, reduce tar content, while improving gasifyin g yield；
(3) it is of the invention a kind of with gas iron co-production of the biomass as bonding carrier, the biomass in iron content agglomerate
Imflammable gas is generated by gasification, ferriferous oxide is reduced generation DRI, can reduce tar content, while improving gas
Change yield, and degree of metalization can be improved, and by adding modified biomass, with modified biomass as bonding carrier,
The intensity of iron content agglomerate can be improved, the quality of DRI is improved；
(4) one kind biomass of the invention is as bonding carrier gas iron co-production, and biomass is used as ferriferous oxide
The C sources and H sources of reducing agent and imflammable gas, ferriferous oxide serve as the standby source of iron of steel and carbon reaction generation CO oxygen
Source, improves the degree of metalization of DRI；On the other hand the catalysis for promoting tar and biomass other catabolites is split
Solution；
(5) one kind biomass of the invention passes through modified biomass and iron content as bonding carrier gas iron co-production
Raw material is hot-forming at high temperature, improve the intensity of iron content agglomerate, it is to avoid iron content agglomerate it is broken, promote iron content agglomerate
Gasification of biomass, improve the efficiency of reaction；Further increasing Iron grade, and prepared it is high-quality directly also
Former iron.
Brief description of the drawings
Fig. 1 is a kind of with flow chart of the biomass as the gas iron co-production of bonding carrier of the present invention；
Fig. 2 is the scanning electron microscopic picture of embodiments of the invention iron content agglomerate.
Label declaration in schematic diagram：
S100, step (1)；S200, step (2)；S300, step (3).
Embodiment
Hereafter the detailed description to the exemplary embodiment of the present invention with reference to accompanying drawing, one of accompanying drawing formation description
Point, show enforceable exemplary embodiment of the invention as example in the figure.Although these exemplary embodiment quilts
Fully describe in detail to enable those skilled in the art to implement the present invention, it is to be understood that can realize other embodiment and
Can without departing from the spirit and scope of the present invention to the present invention various changes can be made.Hereafter to embodiments of the invention
More detailed description is not limited to required the scope of the present invention, and just to be illustrated and do not limit pair
The description of the features of the present invention and feature, to propose the best mode for performing the present invention, and is sufficient so that those skilled in the art
The present invention can be implemented.Therefore, the scope of the invention is only defined by the appended claims.
Hereafter detailed description of the present invention and example embodiment can be more fully understood with reference to accompanying drawing, wherein the present invention
Element and feature are identified by reference.
Embodiment 1
Application has been achieved for a series of breakthrough during early-stage Study, and improves gasifyin g yield and direct-reduction
The quality of iron, with significant progressive, and applied patent of invention (a kind of gasification of biomass of 2017101469513- with directly also
Former iron co-production and additive therefor, the applying date is：2016-03-13).Applicant enters one during follow-up continuation is studied
The discovery of step, when producing imflammable gas and DRI using biomass iron content agglomerate, produces obtained iron content agglomerate
Intensity it is poor, easily cause iron content agglomerate crushing, and then influence iron content agglomerate reduction process；In addition, binding agent can also influence
The iron taste of DRI and gas yield, in order to further improve the quality of DRI, applicant carried out more
The further investigation of one step, creative proposes in iron content agglomerate without binding agent, and passes through modified biomass and iron content
Raw material is hot-forming at high temperature, and with modified biomass as bonding carrier, modified biomass can improve the strong of iron content agglomerate
Degree, it is to avoid iron content agglomerate it is broken, improve the quality of DRI, promote the gasification of biomass of iron content agglomerate, carry
The high efficiency of reaction；Iron grade is further increasing, and has prepared high-quality DRI.
With reference to Fig. 1, of the invention is a kind of with gas iron co-production of the biomass as bonding carrier, wherein described gas is
Imflammable gas, iron is DRI, and specific step is as follows：
S100：Biomass is immersed in modified solution and soaks 1-2h by step (1), and the present embodiment is 1.5h, modified solution pair
The temperature that biomass is modified processing is 80-95 DEG C, and the present embodiment is 90 DEG C；Dry, dry in an oven after the completion of immersion
Temperature is 105 DEG C, and granularity need to be crushed to when broken less than 80 mesh, and requires that the ash content of biomass is less than 3%, completes biomass
Modification；
It is worth noting that modified solution therein is alkaline solution, described alkaline solution is NaOH solution, and NaOH is molten
The mass concentration of liquid is 2%.What deserves to be explained is：Wherein the source of biomass includes removing grain fruit in agriculture and forestry production process
The lignocellulosics such as stalk, trees in addition, farming industry leftover bits and pieces, agriculture and forestry organic waste material, industrial bio matter discarded object；When
Can also be so fowl and animal excrement and discarded object during Animal husbandry production etc..
S200：Step (2) mixes iron-bearing material, biomass and additive, by cuber in 150-400 DEG C of hot pressing
Standby to obtain iron content agglomerate, the pressure of iron content agglomerate is 10-20MPa, and the present embodiment is 15MPa, then by agglomerate as 105 ± 5
Under conditions of DEG C, 3h is to being completely dried for insulation；Described iron-bearing material, biomass, additive are constituted by following mass fraction：It is raw
Material 50-60g, preferably 52g；Iron-bearing material 100-200g, preferably 150g；Additive 5-10g, preferably 8g.Wherein described contains
Iron material includes blast furnace ash, sinter return fine and iron ore concentrate, and the mass percent of each component is：Blast furnace ash：5%th, sinter return fine：
10%th, iron ore concentrate：85%.
Sinter return fine is：Returned mine for the particulate in sintering process, blast furnace gas ash composition is：Blast furnace dust is blast furnace
The raw material dust that coal gas is carried out, contains biological cycle, K2O weight/mass percentage composition is：1.0~2.0%；Na2O quality hundred
Point content is：5.0%~9.0%.Wherein above-mentioned S100：Step (1) and S200：Step (2) is a kind of use of the present invention
The method that biomass prepares high strength bainite agglomerate as bonding carrier.
S300：Dried iron content agglomerate is put into 800-900 DEG C of closed elevated temperature vessel by step (3), and closed
Under the conditions of heated, keep 5-10min, be warming up to 1150-1250 DEG C with 2-3 DEG C/min programming rate, and be incubated 30-
60min.Biomass generates H by gasification2、CO、CH4Deng imflammable gas, ferriferous oxide is reduced generation DRI；
Wherein, additive is made up of sodium carbonate, lateritic nickel ore, dolomite and plant ash, and the mass percent of each component is：
Sodium carbonate：20%, lateritic nickel ore：45%, dolomite：30%, plant ash：5%.Be worth further illustrating is：Lateritic nickel ore,
Dolomite and the mesh percent of pass of vegetation ash particle 200 are more than 90%.Described lateritic nickel ore chemical composition mass percent is：Ni：
1.8%, TFe：24%, SiO2：35%, CaO：1.3%, MgO：16%, Al2O3：3.5%, Cr：0.5%, remaining is impurity.
Dolomitized Ingredient percent is：TFe：0.28%, SiO2：0.66%, Al2O3：0.31%, CaO：
52.12%, MgO：31.03%.Degree of metalization, gas yield and the tar yield for being prepared into DRI are as shown in table 1；No
Gasification of biomass yield is only substantially increased, and improves the degree of metalization of DRI.And detect the iron content of embodiment 1
The compression strength of agglomerate is 4130N, substantially increases the compression strength of iron content agglomerate, it is to avoid the iron content group during reaction
Block is crushed, and promotes the mass transfer of gas, and then improves reduction efficiency, improves degree of metalization, and improve DRI
Grade.
Comparative example 1
The substance be the same as Example 1 of this comparative example, its difference is：Do not add additive, detection reaction wherein
The degree of metalization of DRI, gasification of biomass yield, tar yield afterwards.Experimental result record is as shown in table 1.
Comparative example 2
The substance be the same as Example 1 of this comparative example, its difference is：Sinter return fine is not included in iron-bearing material,
Only it is made up of in iron-bearing material iron ore concentrate and blast furnace ash, the degree of metalization of DRI, gasification of biomass after detection reaction
Yield, tar yield.Experimental result record is as shown in table 1.
Comparative example 3
The substance be the same as Example 1 of this comparative example, its difference is：Lateritic nickel ore is not included in iron-bearing material,
Only it is made up of in iron-bearing material iron ore concentrate and sinter return fine, the degree of metalization of DRI, biogas after detection reaction
Change yield, tar yield.Experimental result record is as shown in table 1.
Comparative example 4
The substance be the same as Example 1 of this comparative example, its difference is：Dried iron content agglomerate is put into reaction
900 DEG C are gradually heating to by room temperature in device, then 1150-1250 DEG C is warming up to 2-5 DEG C/min programming rate, and is incubated 30-
60min, the programming rate of the present embodiment is 3 DEG C/min, and warming temperature is 1200 DEG C, and soaking time is 40min.After detection reaction
The degree of metalization of DRI, gasification of biomass yield, tar yield.Experimental result record is as shown in table 1.
Comparative example 5
The substance be the same as Example 1 of this comparative example, its difference is：Also include binding agent 4g；It is worth explanation
It is that described binding agent is bentonite.The degree of metalization of DRI after detection reaction, gasification of biomass yield, tar production
Rate.Experimental result record is as shown in table 1.In addition, also detecting the compression strength of agglomerate in addition, compression strength is obtained for 420N.
The experimental data of table 1
Above-mentioned conclusion is contrasted, it can be deduced that to draw a conclusion：
(1) discovery is contrasted by comparative example 1 and embodiment 1, under the same conditions, when not adding additive, gasification production
Rate is relatively low, and tar yield is higher, and substantial amounts of metal ion is contained in additive；
(2) discovery is contrasted by comparative example 2 and embodiment 1, under the same conditions, when without sinter return fine, tar
Conversion ratio and gasification efficiency decrease, its reason is probably the complex oxide containing part in sinter return fine, the complexity
Oxide may produce oxide or the complexity such as iron-nickel-magnesium with the metallic element of additive under the high temperature conditions heating
Oxide, and these oxides react on metal ion, strengthen its ion to pyrolysis products such as tar at high temperature
Deviation effect, promotes the electron cloud in tar destroyed and loss of stability, C-C keys, c h bond is easily broken, so that
Coke tar cracking has been promoted to generate small organic molecule, the H being cracked to form2、CH4Ferriferous oxide is enhanced pair Deng imflammable gas
The reduction process of ferriferous oxide, improves the degree of metalization for the DRI that reaction is obtained.
(3) discovery is contrasted by comparative example 3 and embodiment 1, under the same conditions, when without blast furnace ash, biomass
Gasification efficiency reduction, its reason is still unintelligible, but be probably due to containing substantial amounts of Na, K, Pb, Zn in blast furnace ash, these
Metal ion on the one hand enhance the attraction to larger molecular organicses electronics, skew, on the other hand may under the high temperature conditions with
Ferriferous oxide or nickel iron compound are combined, and improve ferriferous oxide, the catalytic activity of nickel iron compound, so as to improve catalysis effect
Really；Above-mentioned element not only promotes the decomposition of larger molecular organicses, at the same improve improve ferriferous oxide, nickel iron compound it is anti-
Should be active, and the reduction of ferriferous oxide is promoted, so as to improve degree of metalization.
(4) comparative example 4 is contrasted with embodiment 1 and found, under the conditions of identical raw material proportioning, when slow heating, tar
Yield increase, wherein be probably that relatively large number of tar is produced during slowly being heated up due to early stage, and tar is in generation
During just volatilize and go out in container, and the oxide such as iron-nickel-magnesium or complex oxide are not yet effective during low temperature
Formed, another aspect metal ion be difficult in chilling process the larger molecular organicses that are effectively facilitated in tar occur cracking,
Reform, so that the yield of incrementss tar.
(5) comparative example 5 is contrasted with embodiment 1 it can be found that under the same conditions, if being incorporated binding agent, leading to
Cross and processing is modified to biomass, to biomass and iron content powder mixing briquetting, applicant has surprisingly found that and improved on the contrary
The compression strength of iron content agglomerate, by multiple seminar, finally thinks that mechanism therein is probably：Biomass is not modified
When, the cellulose components in biomass have certain toughness, easy resilience after compacting, result in inside the pelletizing after compacting
Intergranular causes the intensity decreases of iron content agglomerate away from increase.And by being modified to biomass, the iron content agglomerate prepared,
There is more preferable intensity on the contrary in the case of without binding agent, by Fig. 2 it can be found that adding the carbonaceous pelletizing after biomass
Inside occurs in that substantial amounts of sheet region, and this is due to that biomass produces crosslinking in carbonaceous pelletizing content and melted, and makes coal dust
Grain and iron ore powder particles closely link together, so as to improve the intensity of carbonaceous pelletizing, improve the intensity of iron content agglomerate,
Avoid iron content agglomerate from being crushed during reaction, promote the gas transfer in iron content agglomerate, so as to promote iron content agglomerate
In ferriferous oxide with reduction solid/liquid/gas reactions, promote the progress of reaction, at the same time ferriferous oxide promotes the decomposition of biomass,
So as to improve the gasifyin g yield of biomass, and degree of metalization is improved simultaneously.And after being modified due to biomass, it is biological
Matter is sufficiently mixed with the NaOH in alkaline solution, and NaOH is immersed to the inside of biomass, while being modified, and Na elements are not
It is evitable to remain in inside biomass, and Na contacts more abundant with biomass, biomass and its decomposition under the high temperature conditions
The electronics of product carbon atom and oxygen atom is influenceed in various degree by Na, promoted C-C and C-O bond angles skew, bond distance it is elongated,
Carbocyclic ring irregular deformation etc., and cause bond energy to reduce, tar and biomass other catabolite heat endurances reduction, so as to enter one
Improve gasifyin g yield to step；At the same time, the reducibility gas of generation is fully combined with the ferriferous oxide in iron-bearing material, is entered
And degree of metalization is improved, the basis of DRI is provided for the steel-making of follow-up short route, Jiao is at the same time reduced
The yield of oil.
Certainly, in order to realize recycling application of the biomass in steel industry, the sustainable development of steel and iron industry is realized,
Existing related technical staff, has carried out the technical research of related fields.For example, innovation and creation is entitled：Joint Production is given birth to
The method and apparatus of iron and high-quality synthesis gas, number of patent application：201180048198.5, patent application day is：2011-08-
03.The patent application utilizes the oxidation of biomass reduction iron by the way that by iron ore and gas co-production, although this method realizes
Thing prepares DRI, while production imflammable gas, but be due to the larger molecular organicses such as tar in gasification
It cannot effectively crack, reform so that tar clearance is relatively low, and gasification result is poor, this problem is also that limitation biomass is effective
The key issue of resource application.
The inventor of this patent have finally chosen appropriate component as biomass with containing by exploration unremitting for a long time
The gas iron co-production of iron material reaction, substantially increases the gasification efficiency and tar clearance of biomass, with prominent
Substantive distinguishing features and significant progress, those skilled in the art unlikely select so to add without performing creative labour
Plus agent, and it is applied to the co-production that iron-bearing material prepares imflammable gas and DRI.Above-mentioned reaction mechanism is still not
It is completely clear, and the inventor of this patent is annoying always.In order to find out the reaction theory of the reaction, applicant has carried out repeatedly
Seminar is discussed, and thinks wherein to be probably following reason：
During 900 DEG C of insulations of early stage, form to form micropore on iron content agglomerate, increase the specific surface area of agglomerate,
And be that the oxides such as follow-up iron-nickel-magnesium or complex oxide provide larger reaction interface with promotion coke tar cracking, increase simultaneously
The big response area of biomass cracking gas reducing iron oxides, on the one hand promotes the reduction step by step and life of ferriferous oxide
Gasification substance, cracking process produce a large amount of H2, CO, hydrocarbon, with higher reproducibility, the reducibility gas is promoted
Ferriferous oxide low-temperature reduction, and additive promotes the generation of low melting point solid solution phase so that and biomass only need to be in relatively low temperature
Iron ore can just be reduced under degree, when reducing agent and the C source of imflammable gas and H of the biomass as ferriferous oxide
Source.Ferriferous oxide serves as the standby source of iron of steel and carbon reaction generation CO oxygen source.DRI is produced with standard biologic matter
Method it is different, the inner loop of the oxygen from iron content agglomerate of this method, rather than from by oxygen, so as to improve directly also
The degree of metalization of former iron；On the other hand the catalytic pyrolysis of other catabolites of tar and biomass is promoted.
In addition, blast furnace ash and additive contain substantial amounts of alkaline metal ionses, process of the metal ion in high-temperature heating
Absorption is on biomass and its surface of catabolite, biomass and its catabolite carbon atom and oxygen atom under the high temperature conditions
Electronics is influenced to different extents, has promoted the skew of C-C and C-O bond angles, elongated, the carbocyclic ring irregular deformation of bond distance etc., and make
Into bond energy reduction, tar and biomass other catabolite heat endurances reduction.But, during without additive, metal ion
It is difficult to absorption on the surface of biomass cellulose so that biomass de- poly- reaction be leading, and generation is a series of containing carbocyclic
Hydrocarbon so that tar yield is higher.
Also, during the continuous rise biomass heating reducing iron oxides of temperature, a series of active iron of production-
The complex oxides such as nickel-magnesium, including：Calcium iron compound, calcium and magnesium compound, fayalite, iron-doped nickel oxide etc., high temperature bar
These material surfaces have higher reactivity and polar activation position under part, on the one hand promote the movement of metal ion, plus
Strong ion deviation effect of the metal ion to pyrolysis products such as tar at high temperature；In addition, the fused ring compound in tar contains
There is the pi-electron system of negatively charged, pi-electron cloud is destroyed and loss of stability, C-C keys, c h bond is easily broken, from
And cracking activation energy is reduced, the oxide such as iron-nickel-magnesium or complex oxide further promote the larger molecular organicses such as tar to send out
Raw catalytic degradation so that open loop cleavage reaction occurs for the larger molecular organicses in tar, easily degrades, and generate a series of
Low-molecular-weight hydrocarbon, improves the gasification transformation efficiency of biomass, and reduces the yield of tar.Wherein, particularly nickel
Ferriferous oxide reduces hydrocarbon and CH4Content, H in fuel gas2Dramatically increased with CO contents, certain ferriferous oxide
During organic matter is catalytically decomposed, itself is also constantly participating in course of reaction, and constantly reduces and obtain directly also
Former iron, so as to improve the degree of metalization of DRI.
Embodiment 2
The substance be the same as Example 1 of the present embodiment, difference is：Described additive is by sodium carbonate, laterite nickel
Ore deposit, dolomite, plant ash and chromium slag composition；The mass percent of each component is：Sodium carbonate：15%th, lateritic nickel ore：30%th, it is white
Marble：30%th, plant ash：15%, chromium slag：10%.Described chromium dreg chemistry Ingredient percent is as follows：SiO2：28%,
Al2O3：8%, CaO：30%, MgO：15%, Fe2O3：10%, Cr2O6：0.8% and Na2Cr2O7：1%, remaining is impurity.Detection
The degree of metalization of DRI after reaction, gasification of biomass yield, tar yield.Experimental result record is as shown in table 1.One side
Face chromium slag is effectively reduced under the high reductive condition of gasification of biomass to chromium slag, generates the chromated oxide of reserve price, chromium oxygen
Compound is combined with the ferriferous oxide in agglomerate, calcium and magnesium compound, promotes the high efficiency cracking of the larger molecular organicses in tar,
So as to generate small molecule imflammable gas, ferriferous oxide is constantly reduced and obtained certainly during organic matter is catalytically decomposed
DRI.
It is worth noting that modified solution therein is alkaline solution, described alkaline solution is KOH solution, KOH solution
Mass concentration be 3%.
Embodiment 3
The substance be the same as Example 1 of the present embodiment, difference is：Iron ore concentrate is by breathing out Yang Di, Tu Balang powder plus taking
Big fine powder, the mixed powder in Kazakhstan and Jin Buba powder composition, as shown in table 2, the mass percent of various miberal powders is the composition of ore deposit：Breathe out Yang Di：
10%th, Tu Balang powder：20%th, Canadian fine powder：40%th, mixed powder is breathed out：15%th, Jin Buba powder：15%.After detection reaction directly also
The degree of metalization of former iron, gasification of biomass yield, tar yield, experimental result record is as shown in table 1.
The miberal powder composition (wt/%) of table 2
The degree of metalization of DRI is further improved, and by discussing repeatedly, inventor thinks：This process be probably
During 900 DEG C of insulations, the crystallization water in Iron Ore Powder is thermally decomposed, and produces more space in iron content agglomerate, so that
The gas-solid reaction interface of ferriferous oxide reduction is increased, these spaces increase ferriferous oxide and its complex compound in tar
Larger molecular organicses catalytic action, and the crystallization water by thermal decomposition produce H2O diffuses in the reactor, and the vapor is in iron
Under oxide catalyst, cracking/reformation of macromolecular is promoted, so as to improve the transformation efficiency of tar, iron is aoxidized during this
Thing constantly reduces during organic matter is catalytically decomposed and obtains DRI.
It is worth noting that modified solution therein is alkaline solution, described alkaline solution is NaOH and Ca (OH)2's
Mixed solution, the mass concentration of mixed solution is 4%, NaOH and Ca (OH)2Mass ratio be 4:1.
Embodiment 4
The substance be the same as Example 1 of the present embodiment, difference is：Additive is by sodium carbonate, potassium chloride, laterite nickel
Ore deposit, dolomite, plant ash are constituted, and the mass percent of each component is：Sodium carbonate：15%th, potassium chloride：20%th, lateritic nickel ore：
25%th, dolomite：30%th, plant ash：10%.The degree of metalization of DRI, gasification of biomass yield, Jiao after detection reaction
Oily yield.Experimental result record is as shown in table 1.Alkali metal ion is mainly alkali metal and promotes the larger molecular organicses such as tar
Further cracking, it is suppressed that small molecule is reunited under hot environment, improves the transformation efficiency of tar, and additive promotes iron oxidation
Thing is combined with larger molecular organicses, and ferriferous oxide is constantly reduced and obtained directly also during organic matter is catalytically decomposed
Former iron.
It is worth noting that modified solution therein is alkaline solution, described alkaline solution is NaOH solution, and NaOH is molten
The mass concentration of liquid is 1%.
Embodiment 5
Additive is made up of sodium carbonate, lateritic nickel ore, dolomite, plant ash, chromium slag and v-ti magnetite slag, each component
Mass percent is：Sodium carbonate：15%th, lateritic nickel ore：30%th, dolomite：20%th, plant ash：10%th, chromium slag：10%th, vanadium titanium
Magnet slag：15%.The degree of metalization of DRI (DRI), gasification of biomass yield, tar yield after detection reaction.It is real
Test result record as shown in table 1.Ferrovanadium, the oxide of iron nickel are generated during heating, in metal ion promotes tar
Electronic migration occurs for larger molecular organicses, reduces on the basis of degrading activity, ferrovanadium, the oxide of iron nickel promote biomass
In coke tar cracking, ferrovanadium, iron nickel oxide be catalytically decomposed organic matter during, constantly reduce and obtain directly also
Former iron, improves degree of metalization.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that can not take off
Various modifications and variations are carried out in the case of from the scope of the present invention being defined by the following claims.Detailed description and drawings
Should be to be considered only as it is illustrative and not restrictive, if there is any such modifications and variations, then they all will
Fall into the scope of the present invention described here.In addition, background technology is intended to illustrate the Development Status and meaning of this technology,
It is not intended to limit the application field of the present invention or the application and the present invention.
Although more specifically, have been described herein the present invention exemplary embodiment, the invention is not limited in
These embodiments, but including those skilled in the art according to above detailed description it can be appreciated that it is modified, omit,
Any and whole embodiments of (such as between each embodiment) combination, adaptive change and/or replacement.In claim
Restriction can widely be explained according to the language used in claim, and be not limited in foregoing detailed description or in reality
The example described during this application is applied, these examples are considered as nonexcludability.For example, in the present invention, term is " preferably
Ground " not exclusively, preferably, here it means that " but be not restricted to that ".It is in office where method or process claims
In any step for enumerating can perform and be not limited to the order proposed in claim in any order.Therefore, it is of the invention
Scope only should be determined by appended claims and its legal equivalents, rather than by descriptions and examples given above Lai
It is determined that.
Claims (10)
1. a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass, it is characterised in that：Step is to contain
Iron material, biomass and additive mixing, prepare iron content agglomerate, described biomass passes through modification by cuber hot pressing
Processing is modified in solution, described modified solution is alkaline solution.
2. a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass according to claim 1, its
It is characterised by：Including iron-bearing material, biomass and additive；Described iron-bearing material, biomass and additive presses following quality
Number is constituted：
50-60 parts of biomass；
100-200 parts of iron-bearing material；
5-10 parts of additive.
3. a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass according to claim 1, its
It is characterised by：Comprise the following steps that：
(1) biomass is immersed in modified solution and soaks 1-2h, dried in an oven after the completion of immersion, complete changing for biomass
Property；
(2) biomass, iron-bearing material, additive are mixed, iron content group is prepared in 150-400 DEG C of hot pressing by cuber
Block.
4. according to claim any one of 1-3 it is a kind of with biomass as bonding carrier prepare high strength bainite agglomerate
Method, it is characterised in that：The temperature that described modified solution is modified processing to biomass is 80-95 DEG C.
5. a kind of method for preparing high strength bainite agglomerate as bonding carrier with biomass according to claim 4, its
It is characterised by：Described modified solution is NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
6. it is a kind of with gas iron co-production of the biomass as bonding carrier, it is characterised in that：Biomass is immersed into modified solution
In be modified processing, described modified solution is alkaline solution, then by the biomass after modification, iron-bearing material and addition
Iron content agglomerate is made in agent mixing pressurization, and iron content agglomerate is put into elevated temperature vessel and heated, and biomass is flammable by gasification generation
Property gas, ferriferous oxide is reduced generation DRI, described additive include sodium carbonate, lateritic nickel ore, dolomite and
Plant ash.
7. it is according to claim 6 a kind of with iron co-production of the biomass as bonding carrier gas, it is characterised in that：Institute
The temperature that the modified solution stated is modified processing to biomass is 80-95 DEG C.
8. one kind biomass according to claim 6 is used as bonding carrier gas iron co-production, it is characterised in that：It is described
Modified solution be NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
9. one kind biomass according to claim any one of 6-8 is used as bonding carrier gas iron co-production, its feature
It is：Comprise the following steps that：
(1) biomass is immersed in modified solution and soaks 1-2h, dried in an oven after the completion of immersion, complete changing for biomass
Property；
(2) biomass, iron-bearing material, additive are mixed, iron content group is prepared in 150-400 DEG C of hot pressing by cuber
Block；
(3) dried iron content agglomerate is put into 800-900 DEG C of elevated temperature vessel, keeps 5-10min, then be warming up to 1150-
1250 DEG C, and it is incubated 30-60min.
10. it is according to claim 9 a kind of with gas iron co-production of the biomass as bonding carrier, it is characterised in that：
Described iron-bearing material, biomass and additive is constituted by following mass fraction：
50-60 parts of biomass；
100-200 parts of iron-bearing material；
5-10 parts of additive.
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