CN110054225A - A kind of preparation method of oxygen carrier - Google Patents
A kind of preparation method of oxygen carrier Download PDFInfo
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- CN110054225A CN110054225A CN201910385351.1A CN201910385351A CN110054225A CN 110054225 A CN110054225 A CN 110054225A CN 201910385351 A CN201910385351 A CN 201910385351A CN 110054225 A CN110054225 A CN 110054225A
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- oxygen carrier
- preparation
- pelletizing
- red mud
- steel slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0045—Mixed oxides or hydroxides containing aluminium
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of preparation methods of oxygen carrier, comprising: after steel slag and red mud is successively dry and broken respectively, be uniformly mixed and obtain mixture；It will be dried after the mixture pelletizing, obtain dry bulb group；It is cooling after dry bulb group is roasted under preset temperature, obtain oxygen carrier.The preparation method of oxygen carrier provided by the invention, after steel slag and red mud are distinguished successively drying and are crushed, after forming mixture, using pelletizing and roasting technique, oxygen carrier is obtained, due to broken rear pelletizing, so that contacting between material abundant, be conducive to accelerate calcination rate, due in steel slag in the CaO and red mud of part part Al2O3And Fe2O3It reacts to form low-melting compound, plays consolidation after the cooling period, greatly improve the intensity of pelletizing after roasting；Meanwhile raw material used is metallurgical solid waste, preparation cost is effectively reduced and realizes the recycling of solid waste.
Description
Technical field
The present invention relates to chemical chain gasification technologies and metallurgical solid wastes recycling to utilize technical field, in particular to one
The preparation method of kind oxygen carrier.
Background technique
Chemical chain gasification reaction basic principle be by traditional fuel and the directly catalytic gasification of air by
Be decomposed into 2 gas-solid reactions in the effect of oxygen carrier: air reaction and fuel gasification reaction are taken the oxygen in air by oxygen carrier
It takes in fuel gasification reaction, the fuel gasification oxygen that reaction needs is provided, realize that fuel can also gasify without contacting with air.By
In oxygen carrier need air reaction and fuel gasification reaction between constantly recycle, it requires oxygen carrier oxygen carrying capacity and
The higher the better for mechanical strength, and natural oxygen carrier mechanical strength is low, the oxygen carrier manually prepared, and oxygen carrying capacity and machinery are strong
It spends relatively high, but prepares costly, lead to chemical chain gasification high process cost.
Steel slag is one of main waste of steel and iron industry, in addition to containing a certain amount of Fe, also contains a large amount of Ca, next contains
There are the oxides such as Mg, Si, Al；Red mud is the main waste of alumina producing enterprise, contains a certain amount of Fe, Si, Al, Na etc.
Element, both valuable Metallurgical resources, if using improper, not only waste of resource, but also pollute.Therefore, such as
What realizes that the resource utilization of steel slag and red mud etc. is extremely urgent.
Summary of the invention
In consideration of it, the invention proposes a kind of preparation methods of oxygen carrier, it is intended to solve in existing oxygen carrier preparation process
Preparation cost and oxygen carrier mechanical strength are difficult to the problem of taking into account.
The invention proposes a kind of preparation methods of oxygen carrier, comprising the following steps: step 1, steel slag and red mud are distinguished
After successively drying and being broken, it is uniformly mixed and obtains mixture；Step 2, it will be dried after the mixture pelletizing, obtain dry bulb
Group；Step 3, cooling after dry bulb group being roasted under preset temperature, obtain oxygen carrier.
Further, in the preparation method of above-mentioned oxygen carrier, before the step 2, warp is added in Xiang Suoshu mixture
Dry and break process carbonaceous material is crossed, and is uniformly mixed.
Further, in the preparation method of above-mentioned oxygen carrier, the carbonaceous material is one of coal dust, coke and semicoke
Or it is a variety of.
Further, in the preparation method of above-mentioned oxygen carrier, the mass ratio of the steel slag, red mud and carbonaceous material is 100:
(70 ~ 100): (5 ~ 15).
Further, in the preparation method of above-mentioned oxygen carrier, the steel slag, red mud and carbonaceous material are crushed to granularity
Less than or equal to 0.074mm.
Further, in the preparation method of above-mentioned oxygen carrier, the mass percent of CaO is 30 ~ 40% in the steel slag.
Further, in the preparation method of above-mentioned oxygen carrier, Fe in the red mud2O3Mass percent be 40 ~ 60%, institute
State Na in red mud2The mass percent of O is more than or equal to 7 %.
Further, in the preparation method of above-mentioned oxygen carrier, the mass percent of C is more than or equal in the carbonaceous material
70%, the mass percent of ash content is less than or equal to 15%.
Further, in the preparation method of above-mentioned oxygen carrier, in the step 2, the pelletizing partial size that obtains through pelletizing is 1 ~
5mm。
Further, in the preparation method of above-mentioned oxygen carrier, in the step 3, the temperature of roasting is 1250 ~ 1350 DEG C.
Compared with prior art, the beneficial effects of the present invention are the preparation method of oxygen carrier provided by the invention passes through
After steel slag and red mud are distinguished successively drying and be crushed, after forming mixture, using pelletizing and roasting technique, oxygen carrier is obtained
Body, so that contacting sufficiently between material, is conducive to accelerate calcination rate, due to part in steel slag due to broken rear pelletizing
CaO and red mud in part Al2O3And Fe2O3It reacts to form low-melting compound, plays consolidation after the cooling period, make
The intensity of pelletizing greatly improves after roasting；Meanwhile raw material used is metallurgical solid waste, preparation cost is effectively reduced and reality
The recycling of solid waste is showed.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
The present invention also provides a kind of preparation methods of oxygen carrier, comprising the following steps:
Step 1, it after steel slag and red mud is successively dry and broken respectively, is uniformly mixed and obtains mixture.
Specifically, the mass ratio of steel slag and red mud can be 100:(70 ~ 100), preferably 100:(70 ~ 80).It is practical
In, it also needs to carry out levigate operation after steel slag and red mud is broken, i.e. progress second-time breakage processing, enables steel slag and red mud
More uniform mixing, wherein ball mill, airflow milling or micronizer can be selected to carry out broken and levigate operation.This reality
It applies in example, steel slag and red mud is crushed to granularity less than or equal to 0.074mm, in order to carry out subsequent pelletizing work after mixing
Skill.It is since red mud viscosity is larger, its independent pelletizing is difficult, and intensity is not high, after steel slag, it is easier to pelletizing and preparation
The intensity of oxygen carrier can obtain larger raising.
Since moisture may be contained in steel slag and red mud, it is unfavorable for subsequent levigate and pellet forming process, then needs in advance
The two is dried, dry temperature can be 90-110 DEG C, preferably 105 DEG C.
Preferably, the carbonaceous material by dry and break process can also be added in mixture prepared by the step,
And it is uniformly mixed.Since moisture may be contained in carbonaceous material, it is also desirable to be dried, dry temperature can be 90-
110 DEG C, preferably 105 DEG C.Likewise, be also required to carry out levigate operation after carrying out grinding operation to carbonaceous material, it will be carbon containing
Material is levigate to granularity less than or equal to 0.074mm, in order to adequately be mixed with the mixture of steel slag and red mud composition, respectively
It is come into full contact between material, is conducive to form uniform hole in subsequent roasting process.
Further, the mass ratio of steel slag, red mud and carbonaceous material can be 100:(70 ~ 100): (5 ~ 15), preferably
100:(70 ~ 80): (10-15).
The mass percent of CaO is 30 ~ 40% in the steel slag selected in the present embodiment, such as can be 32.5%, 40% etc.；
Fe in red mud2O3Mass percent be 40 ~ 60%, such as can be 40%, 45.8%, 49.1%, 57.3%, 60% etc..By subsequent
Roasting technique, in steel slag in the CaO and red mud of part part Al2O3And Fe2O3It reacts and to form low-melting compound and exist
Consolidation is played after cooling, greatly improves the intensity of pelletizing after roasting.
Na in red mud2The mass percent of O is more than or equal to 7 %, such as 7.3%, 8.7%, 7.6% etc., Na element tool therein
There is catalysis coal gasification effect, if Na2If the mass percent of O is too small, then it is difficult to give full play to the catalytic action of Na element.
Carbonaceous material is one of coal dust, coke and semicoke or a variety of, preferably coal dust, can reduce the system of oxygen carrier
Standby cost.
Carbonaceous material after addition drying is levigate, the C in roasting process in coal dust, which can be burned off, leaves a small amount of ash, shape
At hole, while there is gaseous products evolution, the pelletizing (oxygen carrier) after making roasting is in porous state, voidage with higher,
Be conducive to rapid oxygen carrier or oxygen release in chemical chain gasification.
Since C content is too low in carbonaceous material, ash content is excessively high, and the oxygen carrier voidage of formation is lower, it is difficult to give full play to
The oxygen carrying capacity of oxygen carrier, therefore, the mass percent of C is more than or equal to 70% in carbonaceous material, and the mass percent of ash content is less than
Mass percent equal to C in 15%, such as coal dust can be 72.3%, 78.7% etc., and the mass percent of ash content can be
14.2%, 11.3% etc..
Step 2, it will be dried after the mixture pelletizing, obtain dry bulb group.
Specifically, liquid feeding body, liquid therefore can would generally be needed after pelletizing for water into mixture when due to pelletizing
It dries, dry temperature can be 120 ~ 150 DEG C, preferably 120 DEG C.It in practice, can be by the mixture of steel slag and red mud
Or drum type brake, disc type, oscillatory type or stirring-type pelletizer is added in the mixture of steel slag, red mud and carbonaceous material together with water
Pelletizing is inside made.
Since partial size is excessive, the oxygen carrier of acquisition fluidizes difficult in the reaction of subsequent fuel gasification；Undersized then carries
Oxysome is easily blown out reactor after fluidisation, it is difficult to play the oxygen carrying capacity of oxygen carrier, therefore, in step 2, obtain through pelletizing
Pelletizing partial size can be 1 ~ 5mm, preferably 1 ~ 3mm.
Step 3, cooling after dry bulb group being roasted under preset temperature, obtain oxygen carrier.
Since maturing temperature is too low, calcining time is too short, and pelletizing consolidation is insufficient, and the carbonaceous material burning in pelletizing is endless
Entirely, and then cause oxygen carrier intensity and voidage lower；And maturing temperature is excessively high, calcining time is too long, and pelletizing can melt, and carries
It can be sintered between oxysome particle, it is difficult to separate.It is preferred, therefore, that the temperature of roasting is 1250 ~ 1350 DEG C, preferably
1300℃；Calcining time can be 60 ~ 120min.
It can be concluded that, in the present invention, after steel slag and red mud is successively dry and broken respectively, mixing is formed by above
After material, using pelletizing and roasting technique, oxygen carrier is obtained, due to broken rear pelletizing, so that contacting sufficiently, favorably between material
In accelerate calcination rate, due in steel slag in the CaO and red mud of part part Al2O3And Fe2O3Reacting, it is low to be formed
Melting point compounds play consolidation after the cooling period, greatly improve the intensity of pelletizing after roasting；Meanwhile raw material used is smelting
Golden solid waste, preparation cost are effectively reduced and realize the recycling of solid waste；Further, it is added in mixture carbon containing
Material, the C in carbonaceous material can be burnt during roasting leaves a small amount of ash, to form hole, and has gaseous state production
Object evolution, the oxygen carrier voidage with higher after making roasting, is conducive to rapid oxygen carrier or oxygen release in chemical chain gasification.
The advantage of the preparation method of the oxygen carrier provided for the present invention will be described in detail embodiment, underneath with specific implementation
The present invention will be described for example.
Embodiment 1
By 100 parts of steel slags (CaO:32.5%), 100 parts of red mud (Fe2O3: 45.8%, Na2O:7.3%), 5 parts of coals (C:72.3%, ash contents
14.2%) dry at 105 DEG C, then by its it is levigate to 0.074mm or less and mix acquisition mixture, by mixture pelletizing, pelletizing
Granularity is 1mm, and drying obtains dry bulb group at 120 DEG C by made pelletizing, and dry bulb group is roasted at 1250 DEG C in roaster
120min is burnt, it is cooling to obtain oxygen carrier.
Embodiment 2
By 100 parts of steel slags (CaO:32.5%), 80 parts of red mud (Fe2O3: 49.1%, Na2O:8.7%), 10 parts of coal dusts (C:78.7%, ashes
Point 11.3%) dry at 105 DEG C, then its levigate to 0.074mm or less and is mixed into acquisition mixture.By mixture pelletizing, ball
Granule degree is 3mm, and drying obtains dry bulb group at 120 DEG C by made pelletizing, by dry bulb group in roaster at 1300 DEG C
90min is roasted, it is cooling to obtain oxygen carrier.
Embodiment 3
By 100 parts of steel slags (CaO:32.5%), 70 parts of red mud (Fe2O3: 57.3%, Na2O:7.6%), 15 parts of coal dusts (C:72.3%, ashes
Point 14.2%) dry at 105 DEG C, then by its it is levigate to 0.074mm or less and mix acquisition mixture, by mixture pelletizing, ball
Granule degree is 5mm, and drying obtains dry bulb group at 120 DEG C by made pelletizing, by dry bulb group in roaster at 1350 DEG C
60min is roasted, it is cooling to obtain oxygen carrier.
Embodiment 4
By 100 parts of steel slags (CaO:40%), 80 parts of red mud (Fe2O3: 40%, Na2O:7%), 15 parts of coke (C:70%, ash content 15%) exist
It is dry at 90 DEG C, then by its it is levigate to 0.074mm or less and mix acquisition mixture, by mixture pelletizing, pellet size is
5mm, and by made pelletizing, drying obtains dry bulb group at 120 DEG C, and dry bulb group is roasted at 1350 DEG C in roaster
60min, it is cooling to obtain oxygen carrier.
Embodiment 5
By 100 parts of steel slags (CaO:30%), 70 parts of red mud (Fe2O3: 60%, Na2O:8.7%), 10 parts of semicokes (C:78.7%, ash contents
11.3%) dry at 110 DEG C, then its levigate to 0.074mm or less and is mixed into acquisition mixture.By mixture pelletizing, pelletizing
Granularity is 3mm, and drying obtains dry bulb group at 120 DEG C by made pelletizing, and dry bulb group is roasted at 1300 DEG C in roaster
90min is burnt, it is cooling to obtain oxygen carrier.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method of oxygen carrier, which comprises the following steps:
Step 1, it after steel slag and red mud is successively dry and broken respectively, is uniformly mixed and obtains mixture；
Step 2, it will be dried after the mixture pelletizing, obtain dry bulb group；
Step 3, cooling after dry bulb group being roasted under preset temperature, obtain oxygen carrier.
2. the preparation method of oxygen carrier according to claim 1, which is characterized in that before the step 2, mixed to described
The carbonaceous material being added in material by dry and break process is closed, and is uniformly mixed.
3. the preparation method of oxygen carrier according to claim 2, which is characterized in that the carbonaceous material is coal dust, coke
With one of semicoke or a variety of.
4. the preparation method of oxygen carrier according to claim 2 or 3, which is characterized in that the steel slag, red mud and carbon containing object
The mass ratio of material is 100:(70 ~ 100): (5 ~ 15).
5. the preparation method of oxygen carrier according to claim 2 or 3, which is characterized in that by the steel slag, red mud and carbon containing
Material is crushed to granularity less than or equal to 0.074mm.
6. the preparation method of oxygen carrier according to any one of claim 1 to 3, which is characterized in that CaO in the steel slag
Mass percent be 30 ~ 40%.
7. the preparation method of oxygen carrier according to any one of claim 1 to 3, which is characterized in that in the red mud
Fe2O3Mass percent be 40 ~ 60%, Na in the red mud2The mass percent of O is more than or equal to 7 %.
8. the preparation method of oxygen carrier according to claim 2 or 3, which is characterized in that the quality of C in the carbonaceous material
Percentage is more than or equal to 70%, and the mass percent of ash content is less than or equal to 15%.
9. the preparation method of oxygen carrier according to claim 1 or 2, which is characterized in that in the step 2, obtained through pelletizing
The pelletizing partial size arrived is 1 ~ 5mm.
10. the preparation method of oxygen carrier according to claim 1 or 2, which is characterized in that in the step 3, the temperature of roasting
Degree is 1250 ~ 1350 DEG C.
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| CN110054225B (en) | 2022-02-22 |
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