CN107119166A - A kind of biomass iron content agglomerate mini-mill steelmaking and the method for producing stainless steel - Google Patents
A kind of biomass iron content agglomerate mini-mill steelmaking and the method for producing stainless steel Download PDFInfo
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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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/005—Manufacture of stainless steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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Abstract
A kind of biomass iron content agglomerate mini-mill steelmaking of the present invention and the method for producing stainless steel, belong to technical field of ferrous metallurgy.The method for making steel step one of the present invention：DRI is produced, iron content agglomerate is put into elevated temperature vessel and heated, ferriferous oxide is reduced generation DRI；Step 2：Electro-smelting, DRI hot charging is sent into electric furnace, and adds slag former into electric furnace, is tapped after oxygen blast melting；The method of the stainless steel of the present invention is that above-mentioned molten steel is added into decarburization in AOD furnace to heat up, then adds into stove the raw metal containing chromium and carry out alloying, then molten steel is transported in VOD stoves carries out deep decarburization, obtains stainless steel.The present invention realizes the mini-mill steelmaking of biomass iron content agglomerate, improves efficiency of energy utilization by obtaining qualified molten steel by iron content agglomerate reduction generation DRI, then by melting in DRI hot charging feeding electric furnace；Production stainless steel can further be smelted.
Description
Technical field
The present invention relates to technical field of ferrous metallurgy, refined more specifically to a kind of biomass iron content agglomerate short route
Steel and the method for producing stainless steel.
Background technology
Direct-reduction is ferriferous oxide in non-fusible, not slag making, the technique that metallic iron is reduced in the solid state.Direct-reduction
Product is referred to as DRI (Direct Reduction Iron, be abbreviated as DRI), and direct-reduction is to have realized on a large scale
Industrialized processing technique, having realized the direct-reduction process of industrialized production has 10 kinds of number.World DRI (DRI/ in 2008
HBI the t of yield) about 68,450,000, about the 7.23% of the t of WORLD PIG IRON PRODUCTION 9.30 hundred million.DRI is because product is pure, matter
Amount is stable, metallurgy characteristic is excellent, is that world steel market is most well sold and in short supply as production high-quality steel, the indispensable raw material of clean steel
One of commodity, direct-reduction is an indispensable part of world steel production.
The steel accumulation of China is not enough, and the need for steel scrap yield is far from steel production is met, steel scrap shortage is shadow
Ring the key factor of China's electric steel development；The main energy sources of China Steel production simultaneously are coke, worldwide coking coal resource
Shortage, the serious interference of rapid rise of price and the sustainable development that threaten China's steel industry.Development of Direct-Reduced Iron is directly refined
Steel is conducive to improving the energy resource structure of steel production in China, breaks away from yoke of the coking coal resource to development, is to reduce steel production pair
The dysgenic important channel of environment.The energy-saving and emission-reduction policy of steel and iron industry is promoted, energy-saving and emission-reduction dynamics is increased, improves the energy
Utilization ratio, " low-carbon economy " developed based on low energy consumption, low stain, could promote the sustainable development of steel and iron industry.
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.It therefore, it can biomass being applied in steel and iron industry, utilize
Biomass replaces the coal and coke of traditional iron-smelting process.Exigence is developed a kind of using biomass progress iron content agglomerate smelting
The mini-mill steelmaking method of refining, so as to be the harmful effect for reducing steel production to environment, improves efficiency of energy utilization, and realize
Sustainable development.
Through retrieval, existing related technical staff carries out research in this respect, for example：A kind of Electromagnetic Heating carbonaceous pelletizing connects
Continuous direct steelmaking method (application number：201510465009.4 the applying date：2015-07-29), the Electromagnetic Heating of the program is carbon containing
The continuous direct steelmaking method of pelletizing, its step is：Formation, the prereduction of carbonaceous pelletizing in molten bath are bathed in the preheating of carbonaceous pelletizing, steel
With molten point of reaction of slag iron, by using the technical scheme in the present invention, can smelter iron, steel-making be integrated, pass through and control to add
Carbonaceous pelletizing in C/O mol ratios, realize the control to [C] content in molten steel, be not required to be blown just can directly by containing
Carbon pellets produce qualified high-quality molten steel, and capacity usage ratio is high, and production efficiency is high, realizes continuous steelmaking, and capital construction cost
Significantly saved with equipment investment.But still it is difficult to the mini-mill steelmaking of biomass iron content agglomerate.In addition, such as invention wound
That makes is entitled：A kind of direct steel making process for iron ore (application number：200810139695.6 the applying date：2008-09-04), should
Method first adds iron ore or prereduction miberal powder in slag iron bath, and iron ore or prereduction miberal powder are dissolved into slag, with carbon directly also
Stoste state ferriferous oxide, by the oxidisability bathed to slag iron molten bath slag area and the oxygen blast of molten iron area, control slag and iron, obtains carbon and contains
Molten steel of the amount less than 1.3%.Consume low this solution provides productivity ratio, ton steel carbon, but be still difficult to biomass iron content group
The mini-mill steelmaking of block.
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, the short stream of biomass iron content agglomerate is not yet realized in the prior art
There is provided a kind of biomass iron content agglomerate mini-mill steelmaking and the method for producing stainless steel for the problem of journey is made steel；
A kind of biomass iron content agglomerate mini-mill steelmaking method wherein provided, is made by the way that biomass iron content agglomerate is reduced
DRI is obtained, then melting in electric furnace is sent into DRI hot charging and obtains qualified molten steel, biomass iron content group is realized
The mini-mill steelmaking of block；Further, imflammable gas can be produced during production DRI, and reduces tar and contained
Amount, while improving gasifyin g yield；
The method that a kind of biomass iron content agglomerate short route for wherein providing produces stainless steel, by by biomass iron content group
DRI is made in block reduction, then melting obtains qualified molten steel, and AOD, VOD refining obtain stainless steel, biomass iron content agglomerate
Short route smelting stainless steel；Further, imflammable gas can be produced during production DRI, and reduces Jiao
Oil content, while improving gasifyin g yield.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention,
Step one：Produce DRI
Biomass, iron-bearing material and additive are mixed into pressurization iron content agglomerate is made, iron content agglomerate is put into elevated temperature vessel
Middle to be heated, ferriferous oxide is reduced generation DRI, and described additive includes sodium carbonate, lateritic nickel ore, white clouds
Stone and plant ash；
Step 2：Electro-smelting
DRI hot charging is sent into electric furnace, and slag former is added into electric furnace, is tapped after oxygen blast melting.
Preferably, is modified processing in described biomass immersion modified solution, then by the biomass after modification,
Iron content agglomerate is made in iron-bearing material and additive mixing pressurization, and the temperature that modified solution is modified processing to biomass is 80-
95℃。
Preferably, described modified solution is alkaline solution.
Preferably, described modified solution is NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
Preferably, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker.
Preferably, step one：Production DRI is comprised 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.
Preferably, the sodium carbonate, lateritic nickel ore, dolomite and the mesh percent of pass of vegetation ash particle 200 are more than 90%.
The method that a kind of biomass iron content agglomerate short route of the present invention produces stainless steel, using above-mentioned mini-mill steelmaking
Method, which is smelted, obtains molten steel, and molten steel is added into decarburization in AOD furnace is warming up to 1650-1680 DEG C, then adds into stove the gold containing chromium
Belong to raw material and carry out alloying；The molten steel after alloying is transported in VOD stoves again and carries out deep decarburization, stainless steel is obtained.
Preferably, AOD furnace, which smelts to be transported in VOD stoves through processing of skimming after completion, carries out deep decarburization, endpoint carbon content
0.02-0.04%.
3. beneficial effect
The technical scheme provided using the present invention, compared with existing known technology, with following remarkable result：
(1) a kind of biomass iron content agglomerate mini-mill steelmaking method of the invention, is held by the way that iron content agglomerate is put into high temperature
Heated in device, ferriferous oxide is reduced generation DRI, then melting in electric furnace is sent into DRI hot charging and obtained
To qualified molten steel, realize the mini-mill steelmaking of biomass iron content agglomerate, using biomass replace traditional iron-smelting process coal and
Coke, improves efficiency of energy utilization, and realize sustainable development；And produce DRI during gasification of biomass
Production obtains imflammable gas, and reduces tar content, while improving gasifyin g yield；
(2) a kind of biomass iron content agglomerate mini-mill steelmaking method of the invention, biomass iron content agglomerate can be improved directly
The degree of metalization of reduced iron is connect, wherein biomass is used as the reducing agent of ferriferous oxide and the C sources of imflammable gas and H sources, iron
Oxide serves as the standby source of iron of steel and carbon reaction generation CO oxygen source, improves the degree of metalization of DRI；It is another
Aspect promotes the catalytic pyrolysis of tar and biomass decomposition product；
(3) a kind of biomass iron content agglomerate mini-mill steelmaking method of the invention, passes through modified biomass and iron-bearing material
It is hot-forming at high temperature, improve the intensity of iron content agglomerate, it is to avoid iron content agglomerate it is broken, promote the life of iron content agglomerate
Gasification substance, improves the efficiency of reaction；Iron grade is further increasing, and has prepared high-quality direct-reduction
Iron, the mini-mill steelmaking for biomass iron content agglomerate provides necessary requirement, is laid a good foundation to smelt qualified molten steel；
(4) method that a kind of biomass iron content agglomerate short route of the invention produces stainless steel, by by biomass iron content
DRI is made in agglomerate reduction, then melting obtains qualified molten steel, and AOD, VOD refining obtain stainless steel, biomass iron content group
The short route smelting stainless steel of block, the stainless steel of production has low-carbon, low P advantage, improves the quality of stainless steel；Smelt not
Metal ion during rust steel in iron content agglomerate is adsorbed in biomass and its table of catabolite in the process of high-temperature heating
Face, has promoted the skew of C-C and C-O bond angles, elongated, the carbocyclic ring irregular deformation of bond distance etc., and causes bond energy to reduce, tar and biology
Matter other catabolite heat endurances reduction, can promote the decomposition of larger molecular organicses, reduce tar content, improve simultaneously
Gasifyin g yield.
Brief description of the drawings
Fig. 1 produces the flow chart of DRI for the step one of the present invention；
Fig. 2 is a kind of flow chart of biomass iron content agglomerate mini-mill steelmaking method of the present invention.
Label declaration in schematic diagram：
S100, step one：Produce DRI；S110, step (1)；S120, step (2)；S130, step (3)；
S200：Step 2：Electro-smelting.
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
Step uses the process for making of biomass iron content agglomerate short route, and prepares the molten steel of high-quality, substantially reduces smelting iron and steel
Technical process there is provided the efficiency of smelting.
Applicant carried out further furtheing investigate, creative proposes in iron content agglomerate without binding agent,
And it is by modified biomass hot-forming at high temperature with iron-bearing material, improve the intensity of iron content agglomerate, it is to avoid iron content group
Crushing for block, promotes the gasification of biomass of iron content agglomerate, improves the efficiency of reaction；Iron grade is further increasing, and
High-quality DRI has been prepared, and the raw material of high-quality is provided for mini-mill steelmaking, to produce the molten steel of high-quality
Lay the foundation.
With reference to Fig. 2, a kind of biomass iron content agglomerate mini-mill steelmaking method, step is as follows：
S100：Step one, DRI is produced,
Biomass, iron-bearing material and additive are mixed into pressurization iron content agglomerate is made, iron content agglomerate is put into elevated temperature vessel
Middle to be heated, ferriferous oxide is reduced generation DRI, and described additive includes sodium carbonate, lateritic nickel ore, white clouds
Stone and plant ash；As shown in figure 1, comprising the following steps that：
S110：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..
S120：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 and constituted by following mass fraction：
Biomass 50-60g, preferably 52g；Iron-bearing material 100-200g, preferably 150g；Additive 5-10g, preferably 8g.It is wherein described
Iron-bearing 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%.
S130：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, improves the compression strength of iron content agglomerate, it is to avoid the iron content agglomerate powder during reaction
It is broken, the mass transfer of gas is promoted, and then reduction efficiency is improved, degree of metalization is improved, and improve the product of DRI
Position.
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 year binding agent, due to biomass carbonaceous pelletizing content produce crosslinking and
Fusing, makes pulverized coal particle and iron ore powder particles closely link together, so as to improve the intensity of carbonaceous pelletizing, improves and contain
The intensity of iron agglomerate, it is to avoid iron content agglomerate is crushed during reaction, promotes the gas transfer in iron content agglomerate, so as to promote
The ferriferous oxide entered in iron content agglomerate and reduction solid/liquid/gas reactions, promote the progress of reaction, at the same time ferriferous oxide is promoted
The decomposition of biomass, so as to improve the gasifyin g yield of biomass, and improves degree of metalization simultaneously.And because biomass is entered
Row is modified, and biomass is sufficiently mixed with the NaOH in alkaline solution, and NaOH is immersed to the inside of biomass, what is be modified
Meanwhile, Na elements are inevitably remained in inside biomass, and Na contacts more abundant with biomass, gives birth under the high temperature conditions
The electronics of material and its catabolite carbon atom and oxygen atom is influenceed in various degree by Na, has promoted C-C and C-O bond angles inclined
Shifting, elongated, the carbocyclic ring irregular deformation of bond distance etc., and cause bond energy to reduce, tar and biomass other catabolite heat endurances
Reduction, so as to further increasing gasifyin g yield；At the same time, the iron oxidation in the reducibility gas and iron-bearing material of generation
Thing is fully combined, and then improves degree of metalization, the basis of DRI is provided for the steel-making of follow-up short route, with this
The yield of tar is reduced simultaneously.
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
Iron material is reacted, coproduction imflammable gas and DRI, and the gasification efficiency and tar for substantially increasing biomass are removed
Rate, with prominent substantive distinguishing features and significant progress, those skilled in the art more can not without performing creative labour
Additive so can be selected, and is applied to the co-production that iron-bearing material prepares imflammable gas and DRI.It is above-mentioned
Reaction mechanism it is not completely clear, and annoying the inventor of this patent always.In order to find out the reaction theory of the reaction, Shen
Ask someone to have carried out multiple seminar and discuss, and think 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.
S200：Step 2：Electro-smelting
DRI hot charging is sent into electric furnace, and slag former is added into electric furnace, oxygen blast melting is carried out using oxygen rifle,
Tapped after oxygen blast melting, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker；The present embodiment
FeO contents are 15%, dual alkalinity R=1.5.And controlling tapping temperature to be 1520 DEG C -1620 DEG C, the present embodiment is 1580
DEG C, P content<0.02%.The slag former includes lime and iron scale, and wherein mass percent is lime 90%, iron oxide
Skin 10%.The composition of smelting molten steel is [C]：0.09%, [S]：0.05%, [P]：0.15%.
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention, by the way that iron content agglomerate is put into elevated temperature vessel
Heated, ferriferous oxide is reduced generation DRI, then melting in electric furnace is sent into DRI hot charging and closed
Lattice molten steel, realizes the mini-mill steelmaking of biomass iron content agglomerate, has broken what smelting molten steel in the prior art must be blown
Technology is cognitive, the step of biomass iron content agglomerate one is directly produced liquid molten steel, has simplified traditional iron of iron-bearing mineral one
The technique of water or the molten steel of DRI one, production efficiency is high, and obtained molten steel composition complies fully with requirement, utilizes biomass
Instead of the coal and coke of traditional iron-smelting process, efficiency of energy utilization is improved, and realize sustainable development；In production direct-reduction
Gasification of biomass production obtains imflammable gas during iron, and reduces tar content, while raising gasifyin g yield, flammable
Gas can be used for toasting, preheating metallurgical equipment or raw material, improve the utilization rate of the energy.
Embodiment 2
The substance be the same as Example 1 of the present embodiment, difference is：
The additive of the step one is made up of sodium carbonate, lateritic nickel ore, dolomite, plant ash and chromium slag；Each component
Mass percent is：Sodium carbonate：15%th, lateritic nickel ore：30%th, dolomite：30%th, plant ash：15%, chromium slag：10%.It is described
Chromium dreg chemistry Ingredient percent it is as follows：SiO2：28%, Al2O3：8%, CaO：30%, MgO：15%, Fe2O3：10%,
Cr2O6：0.8% and Na2Cr2O7：1%, remaining is impurity.The degree of metalization of DRI, gasification of biomass after detection reaction
Yield, tar yield.Experimental result record is as shown in table 1.It is worth noting that modified solution therein is alkaline solution, it is described
Alkaline solution be KOH solution, the mass concentration of KOH solution is 3%.High reproducibility bar of the one side chromium slag in gasification of biomass
Under part, chromium slag is effectively reduced, the chromated oxide of reserve price, chromated oxide and the ferriferous oxide in agglomerate, calcium-magnesium ratio is generated
Compound is combined, and promotes the high efficiency cracking of the larger molecular organicses in tar, so that small molecule imflammable gas is generated, iron oxygen
Compound constantly reduces during organic matter is catalytically decomposed and obtains DRI,
The step 2：Electro-smelting：DRI hot charging is sent into electric furnace, and adds into electric furnace slag former,
Tapped after oxygen blast melting, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker；The present embodiment
FeO contents are 18%, dual alkalinity R=2.6.And control tapping temperature be 1520 DEG C -1620 DEG C, the present embodiment be 1600 ±
10 DEG C, P content<0.02%, described slag former is lime；Certainly slag former herein can also be used, in the prior art often
The slag former of rule is replaced.
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention, by the way that iron content agglomerate is put into elevated temperature vessel
Heated, ferriferous oxide is reduced generation DRI, then melting in electric furnace is sent into DRI hot charging and closed
Lattice molten steel, realizes the mini-mill steelmaking of biomass iron content agglomerate；The present invention's improves the quality of DRI, and after being
Continuous molten steel is laid a good foundation；Chromated oxide is reduced and is deposited in DRI simultaneously, adds the chromium in steel
Content, is that subsequent smelting stainless steel provides the foundation, and reduces the addition of the raw metal in alloying process, so as to drop
Low smelting cost.
Embodiment 3
The substance be the same as Example 1 of the present embodiment, difference is：
The iron ore concentrate of the step one is constituted by breathing out Yang Di, Tu Balang powder, Canadian fine powder, the mixed powder in Kazakhstan and Jin Buba powder,
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, Canada's essence
Powder：40%th, mixed powder is breathed out：15%th, Jin Buba powder：15%.The degree of metalization of DRI after detection reaction, gasification of biomass production
Rate, tar yield, experimental result record are as shown in table 1.
The miberal powder composition (wt/%) of table 2
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.
The step 2：Electro-smelting：DRI hot charging is sent into electric furnace, and adds into electric furnace slag former,
Tapped after oxygen blast melting, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker；The present embodiment
FeO contents are 12%, dual alkalinity R=2.1.And control tapping temperature be 1520 DEG C -1620 DEG C, the present embodiment be 1620 ±
10 DEG C, P content<0.02%, described slag former is lime；Certainly slag former herein can also be used, in the prior art often
The slag former of rule is replaced.
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention, by the way that iron content agglomerate is put into elevated temperature vessel
Heated, ferriferous oxide is reduced generation DRI, wherein inventor thinks：This process is probably in 900 DEG C of insulations
During, the crystallization water in Iron Ore Powder is thermally decomposed, and produces more space in iron content agglomerate, so as to increase iron oxygen
The gas-solid reaction interface of compound reduction, these spaces increase ferriferous oxide and its complex compound to be had to the macromolecular in tar
The catalytic action of machine thing, and the H that the crystallization water is produced by thermal decomposition2O is diffused in the reactor, and the vapor is catalyzed in ferriferous oxide
Under, cracking/reformation of macromolecular is promoted, so as to improve the transformation efficiency of tar, ferriferous oxide is in catalysis point during this
During solving organic matter, constantly reduce and obtain DRI.Melting in electric furnace is sent into DRI hot charging again
Qualified molten steel is obtained, the mini-mill steelmaking of biomass iron content agglomerate is realized, having broken smelting molten steel in the prior art must be carried out
The technology of blowing is cognitive, the step of biomass iron content agglomerate one is directly produced liquid molten steel, has simplified and traditional has contained iron ore
The technique of the molten iron of thing one or the molten steel of DRI one, production efficiency is high, and obtained molten steel composition complies fully with requirement.
Embodiment 4
The substance be the same as Example 1 of the present embodiment, difference is：
The additive of the step one is made up of sodium carbonate, potassium chloride, lateritic nickel ore, dolomite, plant ash, each component
Mass percent is：Sodium carbonate：15%th, potassium chloride：20%th, lateritic nickel ore：25%th, dolomite：30%th, plant ash：10%.Inspection
Survey the degree of metalization of DRI after reaction, gasification of biomass yield, tar yield.Experimental result record is as shown in table 1.Value
Obtain it is to be noted that modified solution therein is alkaline solution, described alkaline solution is NaOH solution, and the quality of NaOH solution is dense
Spend for 1%.Alkali metal ion is mainly the further cracking that alkali metal promotes the larger molecular organicses such as tar, it is suppressed that high temperature
Small molecule is reunited under environment, improves the transformation efficiency of tar, additive promotes ferriferous oxide and combined with larger molecular organicses,
Ferriferous oxide constantly reduces during organic matter is catalytically decomposed and obtains DRI.
The step 2：Electro-smelting：DRI hot charging is sent into electric furnace, and adds into electric furnace slag former,
Tapped after oxygen blast melting, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker；The present embodiment
FeO contents are 12%, dual alkalinity R=2.1.And control tapping temperature be 1520 DEG C -1620 DEG C, the present embodiment be 1520 ±
10 DEG C, P content<0.02%, described slag former is lime, fluorite and manganeisen, and mass percent is：Lime：90%, firefly
Stone：2%, ferromanganese：8%；Certainly slag former herein can also be used, and conventional slag former is replaced in the prior art.Smelting
Make steel the basic be the same as Example 1 of composition of water.
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention, by the way that iron content agglomerate is put into elevated temperature vessel
Heated, ferriferous oxide is reduced generation DRI, then melting in electric furnace is sent into DRI hot charging and closed
Lattice molten steel, realizes the mini-mill steelmaking of biomass iron content agglomerate, the step of biomass iron content agglomerate one is directly produced liquid
State molten steel, the technique for having simplified the traditional molten iron of iron-bearing mineral one or the molten steel of DRI one, production efficiency is high, and obtain
Molten steel composition complies fully with requirement.
Embodiment 5
The substance be the same as Example 1 of the present embodiment, difference is：
The additive of the step one is by sodium carbonate, lateritic nickel ore, dolomite, plant ash, chromium slag and v-ti magnetite slag
Constitute, the mass percent of each component is：Sodium carbonate：15%th, lateritic nickel ore：30%th, dolomite：20%th, plant ash：10%th,
Chromium slag：10%th, v-ti magnetite slag：15%.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.Ferrovanadium, the oxide of iron nickel are generated during heating, is promoted in metal ion
Electronic migration occurs for the larger molecular organicses in tar, reduces on the basis of degrading activity, ferrovanadium, the oxide of iron nickel promote
Coke tar cracking in biomass, ferrovanadium, the oxide of iron nickel are reduced simultaneously during organic matter is catalytically decomposed, constantly
To DRI, degree of metalization is improved, for the content for the beneficial element for improving molten steel.
The step 2：Electro-smelting：DRI hot charging is sent into electric furnace, and adds into electric furnace slag former,
Tapped after oxygen blast melting, FeO contents are 12~20%, dual alkalinity R=2~3 in electro-smelting heat of oxidation clinker；The present embodiment
FeO contents are 18%, dual alkalinity R=3.0.And control tapping temperature be 1520 DEG C -1620 DEG C, the present embodiment be 1580 ±
10 DEG C, P content<0.02%, described slag former is lime, and slag former herein can also be used certainly, in the prior art often
The slag former of rule is replaced.The basic be the same as Example 1 of composition of smelting molten steel.
A kind of biomass iron content agglomerate mini-mill steelmaking method of the present invention, by the way that iron content agglomerate is put into elevated temperature vessel
Heated, ferriferous oxide is reduced generation DRI, then melting in electric furnace is sent into DRI hot charging and closed
Lattice molten steel, realizes the mini-mill steelmaking of biomass iron content agglomerate, the step of biomass iron content agglomerate one is directly produced liquid
State molten steel, the technique for having simplified the traditional molten iron of iron-bearing mineral one or the molten steel of DRI one.
Embodiment 6
The method of the kind biomass iron content agglomerate short route production stainless steel of the present embodiment, substance be the same as Example 1, no
It is with part：Step 2 is smelted to decarburization in obtained molten steel addition AOD furnace and is warming up to 1650-1680 DEG C, the present embodiment is
1660 ± 10 DEG C, then add into stove the raw metal containing chromium and carry out alloying, the raw metal containing chromium includes ferrochrome, chromium
The combination of iron ore or both, and ferrosilicon and lime are added as exothermic mixture, utilize the chemistry of oxidation releases of the Si in molten bath
Hot heated molten bath, so as to smelt the stainless steel containing chromium using heating, adding lime raising basicity of slag can anti-non-return sulphur.Again will
Molten steel after alloying, which is transported in VOD stoves, carries out deep decarburization, and argon bottom-blowing stirring when reaching component requirements, terminates VOD vacuum
Refining, endpoint carbon content 0.02-0.04%, the present embodiment endpoint carbon content 0.02%.
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 biomass iron content agglomerate mini-mill steelmaking method, it is characterised in that：
Step one：Produce DRI
Biomass, iron-bearing material and additive are mixed into pressurization iron content agglomerate is made, iron content agglomerate is put into elevated temperature vessel
Row heating, ferriferous oxide is reduced generation DRI, described additive include sodium carbonate, lateritic nickel ore, dolomite and
Plant ash；
Step 2：Electro-smelting
DRI hot charging is sent into electric furnace, and slag former is added into electric furnace, is tapped after oxygen blast melting.
2. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 1, it is characterised in that：Described life
Processing is modified in material immersion modified solution, then the mixing of the biomass after modification, iron-bearing material and additive is added
Iron content agglomerate is suppressed to obtain, the temperature that modified solution is modified processing to biomass is 80-95 DEG C.
3. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 2, it is characterised in that：Described changes
Property solution be alkaline solution.
4. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 3, it is characterised in that：Described changes
Property solution be NaOH, Ca (OH)2, one or more kinds of combinations in KOH.
5. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 4, it is characterised in that：Electro-smelting
FeO contents are 12~20%, dual alkalinity R=2~3 in heat of oxidation clinker.
6. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim any one of 1-5, it is characterised in that：
Step one：Production DRI is comprised 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.
7. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 6, it is characterised in that：Described contains
Iron 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.
8. a kind of biomass iron content agglomerate mini-mill steelmaking method according to claim 6, it is characterised in that：The carbonic acid
Sodium, lateritic nickel ore, dolomite and the mesh percent of pass of vegetation ash particle 200 are more than 90%.
9. a kind of method that biomass iron content agglomerate short route produces stainless steel, it is characterised in that：Using described in claim 1-8
Mini-mill steelmaking method smelt and obtain molten steel, molten steel is added into decarburization in AOD furnace is warming up to 1650-1680 DEG C, then into stove
Add the raw metal containing chromium and carry out alloying；The molten steel after alloying is transported in VOD stoves again and carries out deep decarburization, is obtained not
Become rusty steel.
10. the method that a kind of biomass iron content agglomerate short route according to claim 9 produces stainless steel, its feature exists
In：AOD furnace, which smelts to be transported in VOD stoves through processing of skimming after completion, carries out deep decarburization, endpoint carbon content 0.02-0.04%.
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