CN105925742B - A kind of Fe/C compound porous structure materials prepared with oolitic hematite and preparation method thereof - Google Patents
A kind of Fe/C compound porous structure materials prepared with oolitic hematite and preparation method thereof Download PDFInfo
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- CN105925742B CN105925742B CN201610326921.6A CN201610326921A CN105925742B CN 105925742 B CN105925742 B CN 105925742B CN 201610326921 A CN201610326921 A CN 201610326921A CN 105925742 B CN105925742 B CN 105925742B
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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
- C21B13/0073—Selection or treatment of the reducing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of Fe/C compound porous structure materials prepared with oolitic hematite and preparation method thereof, it is characterised in that：Fe/C compound porous structure materials be by oolitic hematite powder and biomass powder after mixing, being molded, then under reducing atmosphere through pyrolysis and reduction reaction obtain, main object mutually be biomass carbon and Zero-valent Iron.The Fe/C compound porous structures material of the present invention has high open porosity, high magnetic susceptibility, high adsorption and high biochemical activity, is suitble to apply in micro-polluted water purifies, especially be applied in the processing of eutrophication water simultaneous denitrification.
Description
First, technical field
The present invention relates to oolitic hematites and biomass recycling use, belong to mineral Environmental Engineering Material field.
2nd, background technology
Oolitic hematite resource has extensive distribution in China, 37.2 hundred million tons of proved reserves, prospective reserves more than 100 hundred million
Ton.Ore is mainly made of oolitic hematite, secondly for siderite, magnetic iron ore, limonite, gangue mineral mainly have calcite,
Quartz, collophane, dolomite, calcedony, chamosite etc..Ore ferrous grade is generally 30%-45%, and phosphorus content is usually
0.4-1.1%.The outstanding feature of such ore is that Iron grade is low, phosphorus is high, and mineral grain grain size therein is small, most of mineral particles
Diameter is all inlayed closely between micron even nanoscale, particle, leads to ore dressing processing difficulties, such iron ore does not obtain so far
Rationally utilize.How such mineral resources be there is an urgent need to research and solve the problem of is made good use of.
China produces about 1,000,000,000 tons of various stalks every year, and agriculture and forestry product and the industrial enterprise using biomass as raw material also produce
Residual processing object of the raw number in terms of hundred million tons.With rural economic development and improvement of living standard, lead to stalk in the whole country
It is interior excessive.Every harvest season, crop straw burning causes serious atmosphere pollution, while there is also serious fire hazards
With aviation flight safety problem.Recycling is carried out to agricultural product castoffs such as stalks and has become governmental environmental in all parts of the country
The task of top priority of comprehensive treatment.Biomass energyization, which utilizes, following several approach；Pyrolytic gasification, pyrolysis liquefaction, directly burning,
Molding burning, molding carbonization etc..Pyrolytic gasification currently encounters the problem of tar purifying in pyrolysis gas；Made from pyrolysis liquefaction exists
The problem of liquid fuel calorific value is low, complicated component；Directly there is boiler carbon distribution in burning.Molding burning at present and molding carbon
Change receives significant attention.
3rd, invention content
The present invention is to avoid the problems of above-mentioned prior art, providing a kind of Fe/C prepared with oolitic hematite
Compound porous structure material and preparation method thereof, it is intended to while realize the recycling of oolitic hematite and biomass.
The present invention solves technical problem, adopts the following technical scheme that：
Fe/C compound porous structure materials prepared by present invention oolitic hematite, its main feature is that：The Fe/C is compound more
Pore structure material be by oolitic hematite powder and biomass powder after mixing, being molded, then under reducing atmosphere through 650~
900 DEG C of pyrolysis and reduction reaction obtain；The main object of the Fe/C compound porous structures material is mutually biomass carbon and Zero-valent Iron.
The Fe/C compound porous structures material has open macropore gap, and pore volume ratio is not less than 40%, magnetization
Rate is not less than 50m not less than 1000SI, specific surface area2/g；The Fe/C compound porous structures material has to react with dissolved oxygen
Constantly form the characteristic of iron hydroxide.
The oolitic hematite is appositional pattern iron ore, is mainly made of bloodstone, the grade of iron is in 30-52%.
The biomass is：All kinds of agricultural crop straws, timber processing waste sawdust, wood shavings, garden and greening finishing
The solid residue that deadwood leaf or processing of farm products generate.
The preparation method of above-mentioned Fe/C compound porous structures material is：By oolitic hematite powder and biomass powder according to
Mass ratio 1:2~15 mixing granulations, then under reducing atmosphere through 650~900 DEG C of pyrolysis and 15~60min of reduction roasting, then
The cooled to room temperature under oxygen-free atmosphere obtains the compound porous knots of Fe/C using biomass carbon and Zero-valent Iron as main object phase
Structure material.Specifically carry out as follows：
(1) by oolitic hematite ore reduction, screening, the oolitic hematite powder that grain size is not more than 0.15mm is obtained；It will
Biomass is broken into the biomass powder that grain size is not more than 1mm；
(2) by oolitic hematite powder and biomass powder according to mass ratio 1:2~15 are uniformly mixed, and obtain mixture；
(3) the rod-shpaed particle object for being diameter 4-12mm the mixture extrusion molding with biomass forming machine；
(4) by the rod-shpaed particle object under reducing atmosphere in 650~900 DEG C of pyrolysis and 15~60min of reduction roasting, then
The cooled to room temperature under oxygen-free atmosphere obtains the compound porous knots of Fe/C using biomass carbon and Zero-valent Iron as main object phase
Structure material.
Above-mentioned reducing atmosphere is hydrogen atmosphere.
It can be added in the mixture of step (2) and account for the used oil type organic that mixture gross mass is not more than 3%, so
It carries out step (3) again afterwards, to improve the mixed effect of oolitic hematite powder and biomass powder, and reduces rubbing for extrusion molding
Wipe power.
Beneficial effects of the present invention are embodied in the following aspects：
1st, oolitic hematite powder and biomass powder mixing simultaneously extrusion molding, biomass have in the embryo material of extrusion molding
There is cementation, make molding embryo material that there is higher granule strength, without adding binding agent；650~900 DEG C under reducing atmosphere
During pyrolysis and reduction reaction, as clay mineral of impurity composition etc. and the potassium sodium in biomass in oolitic hematite ore
Chemical reaction has the function of enhancing sintering, improves granule strength.
2nd, on the one hand the pyrolytic gasification of biomass under reducing atmosphere can improve the porosity and specific surface area of material,
Obtain the material of porous structure, another aspect pyrolysis reduction gas H2, CO, volatile organic matter react with bloodstone and be changed into zero
Valency iron.Biomass is both the pore-foaming agent of material and the reducing agent of iron or the presoma for forming charcoal.
3rd, oolitic hematite is selected, low-grade iron ore resource had not only been utilized, but also the mineral of oolitic hematite resource are utilized
Learn characteristic.It has been investigated that the bloodstone in oolitic hematite ore belongs to nano-sheet crystal, compared to non-nano crystal,
With higher reduction reaction activity, reduzate Zero-valent Iron also has relatively low crystallinity and higher reactivity.
4th, the chemical oxygen in ferriferous oxide not only has the function of to enhance biomass pyrogenation gasification, also with catalysis biomass
The effect of coke tar cracking during pyrolytic gasification, can eliminate the tar in pyrolysis gas.
5th, the mixture of oolitic hematite powder and biomass powder passes through pyrolytic reaction under extrusion molding, reducing atmosphere,
The charcoal that not only bloodstone restores the Zero-valent Iron to be formed with biology carbonization is formed is closely compound, but also material has specific grain
Diameter, the macropore gap of opening, and pore volume are big, magnetism is strong, specific surface area is high, adsorptivity and chemical reactivity are good, are suitble to
Application in micro-polluted water purification is especially applied in the processing of eutrophication water simultaneous denitrification.
4th, it illustrates
Fig. 1 is the x-ray diffractogram of powder spectrum of the Fe/C compound porous structure materials prepared by embodiment 1, and display is wherein
Main object is mutually fe；
Fig. 2 and Fig. 3 is the SEM image of the Fe/C compound porous structure materials prepared by embodiment 1, and wherein Fig. 2 can be seen
Biomass carbonizes the pore property to be formed, and Fig. 3 can be seen that oolitic hematite is reduced to the shape characteristic of Nanoscale Iron.
5th, specific embodiment
Embodiment 1
The present embodiment prepares Fe/C compound porous structure materials as follows：
(1) 51.4% oolitic hematite ore sample of Iron grade is selected, crushed, cross 0.15mm sieves, it is red to obtain roe shape
Iron ore powder；Rape stalk is crushed, crosses 1mm sieves, obtains fibrous straw powder；
(2) according to mass ratio 1:2 weigh oolitic hematite powder and fibrous straw powder；It is in fibrous straw powder spray little water first
Existing humidity shape, then adds in oolitic hematite powder and mix is uniform, and drying obtains mixture；
(3) above-mentioned mixture is added in screw extrusion molding machine hopper, extrusion molding is the rod-shpaed particle of diameter 6mm
Object；
(4) molding rod-shpaed particle is roasted into 25min under hydrogen atmosphere in tube furnace in 850 DEG C, then in no oxygen
Cooled to room temperature under atmosphere obtains the Fe/C compound porous structure materials using biomass carbon and Zero-valent Iron as main object phase.
Fig. 1 is the X ray diffracting spectrum of the Fe/C compound porous structure material powders prepared by the present embodiment, shows product
In main object be mutually fe, show in primary sample that ferriferous oxide by biomass reduction is fe.After tested, it is single in product
Matter iron content is 68%, and the content of charcoal is 9%.
Fig. 2, Fig. 3 can be seen that biomass for Fe/C compound porous structures material SEM image, Fig. 2 prepared by the present embodiment
The pore property formed is carbonized, Fig. 3 can be seen that oolitic hematite is reduced to the shape characteristic of fe.After tested, product
Pore volume ratio is 56%, magnetic susceptibility 12269SI, specific surface area 64.6m2/g。
Embodiment 2
The present embodiment prepares Fe/C compound porous structure materials as follows：
(1) 45.7% oolitic hematite ore sample of Iron grade is selected, crushed, cross 0.15mm sieves, it is red to obtain roe shape
Iron ore powder；Rape stalk is crushed, crosses 1mm sieves, obtains fibrous straw powder；
(2) according to mass ratio 1:5 weigh oolitic hematite powder and fibrous straw powder；It is in fibrous straw powder spray little water first
Then now humidity shape adds in oolitic hematite powder and mix is uniform, dries, obtains mixture；
(3) above-mentioned mixture is added in screw extrusion molding machine hopper, extrusion molding is the rod-shpaed particle of diameter 6mm
Object；
(4) molding rod-shpaed particle object is roasted into 30min under hydrogen atmosphere in tube furnace in 750 DEG C, then in anaerobic
Cooled to room temperature under atmosphere obtains the Fe/C compound porous structure materials using biomass carbon and Zero-valent Iron as main object phase
Material.
Through characterization, ferriferous oxide is fe by biomass reduction in the present embodiment primary sample.Simple substance in products therefrom
Iron content is 34%, and the content of charcoal is 26%.And product pore volume ratio is 67%, magnetic susceptibility 7269SI, specific surface
Product is 67.7m2/g。
Claims (5)
1. a kind of Fe/C compound porous structure materials prepared with oolitic hematite, it is characterized in that：The compound porous knots of Fe/C
Structure material is by oolitic hematite powder and biomass powder after mixing, being molded, then under reducing atmosphere through 650~900 DEG C
Pyrolysis and reduction reaction obtain；The main object of the Fe/C compound porous structures material is mutually biomass carbon and Zero-valent Iron；
The Fe/C compound porous structures material has open macropore gap, and pore volume ratio is not less than 40%, and magnetic susceptibility is not
It is not less than 50m less than 1000SI, specific surface area2/g；The Fe/C compound porous structures material, which has, reacts continuous with dissolved oxygen
Form the characteristic of iron hydroxide.
2. Fe/C compound porous structures material according to claim 1, it is characterized in that：The biomass is：Crops straw
Stalk, timber processing waste sawdust, wood shavings, the solid that the deadwood leaf or processing of farm products of garden and greening finishing generate are residual
Slag.
3. a kind of preparation method of the Fe/C compound porous structure materials described in claims 1 or 2, it is characterised in that：By roe shape
Bloodstone powder and biomass powder are according to mass ratio 1:2~15 mixing granulations, then under reducing atmosphere through 650~900 DEG C
Pyrolysis and 15~60min of reduction roasting, then the cooled to room temperature under oxygen-free atmosphere, that is, obtain with biomass carbon and Zero-valent Iron
Fe/C compound porous structure materials for main object phase；
The reducing atmosphere is hydrogen atmosphere.
4. preparation method according to claim 3, it is characterised in that be specifically to carry out as follows：
(1) by oolitic hematite ore reduction, screening, the oolitic hematite powder that grain size is not more than 0.15mm is obtained；It will be biological
Matter is broken into the biomass powder that grain size is not more than 1mm；
(2) by oolitic hematite powder and biomass powder according to mass ratio 1:2~15 are uniformly mixed, and obtain mixture；
(3) the rod-shpaed particle object for being diameter 4-12mm the mixture extrusion molding with biomass forming machine；
(4) by the rod-shpaed particle object under reducing atmosphere in 650~900 DEG C of pyrolysis and 15~60min of reduction roasting, then in nothing
Cooled to room temperature under oxygen atmosphere obtains the Fe/C compound porous structure materials using biomass carbon and Zero-valent Iron as main object phase
Material.
5. preparation method according to claim 4, it is characterised in that：It is added in the mixture of step (2) and accounts for mixture
Gross mass is not more than 3% used oil type organic, step (3) is then carried out again, to improve oolitic hematite powder and biology
The mixed effect of matter powder, and reduce the frictional force of extrusion molding.
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