CN109705918A - A kind of composite fluxing agent and its preparation method and application improving coal ash - Google Patents
A kind of composite fluxing agent and its preparation method and application improving coal ash Download PDFInfo
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- CN109705918A CN109705918A CN201711006490.6A CN201711006490A CN109705918A CN 109705918 A CN109705918 A CN 109705918A CN 201711006490 A CN201711006490 A CN 201711006490A CN 109705918 A CN109705918 A CN 109705918A
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Abstract
A kind of composite fluxing agent and its preparation method and application improving coal ash.The composite fluxing agent is combined by CaO and red mud, the chemical component and mass content of composite fluxing agent are as follows: basic anhydride are 56.1%~90.6%, and acidic oxide is 9.4%~43.9%.Composite fluxing agent provided by the present invention not only can effectively improve the melting characteristic of high ash melting point coal ash, make the airflow bed gasification furnace it is suitable for slag tap, and be able to achieve the resource utilization of polluting waste red mud, with good economic efficiency and social benefit.
Description
Technical field
The present invention relates to a kind of composite fluxing agents and its preparation method and application for improving high ash melting point coal ash.
Background technique
The energy resource structure in China has the characteristics that " the few oil of rich coal " how cleanly and efficiently to provide using these coals abundant
Source becomes the emphasis of country and related scientific research personnel concern.As a kind of coal conversion technology of high effect cleaning, Coal Gasification Technology day
Benefit is taken seriously.Wherein, air-flow bed coal-gasification technology have coal adaptability wide, operating pressure and temperature are high, efficiency of carbon con version is high,
The features such as producing intensity and big scale, application prospect with good economic efficiency and wide.Entrained flow bed gasification technology is adopted more
Use slag tap.Therefore, it must be melted in the case where being lower than gasification temperature for the ash content in the feed coal of gasification.However, I
50% or more is high-ash-fusion coal in the coal resources of state, how to reduce the grey melting temperature of these high-ash-fusion coals, keeps it suitable
It is a urgent problem to be solved for entrained flow gasification.There are mainly two types of the methods for reducing coal ash melting temperature, and one is will
High-ash-fusion coal and low-ash-fusion coal mixture, another kind are addition fluxing agents.The former is due to being related to the fortune of coal between different zones
Defeated problem will increase the cost of whole flow process.Although the above problem is not present in the latter, a large amount of addition fluxing agents will increase ash and contain
Amount reduces gasification efficiency.Therefore the fluxing agent for developing high-efficiency and economic, makes it in the case where a small amount of addition, can melt high ash
The melting characteristic of point coal is reduced within the temperature range of suitable entrained flow gasification, is current coal gasification field urgent problem to be solved
One of.
The more fluxing agent of current research includes single or two-spot and the multiple elements design such as sodium base, calcium base, magnesium-based, iron-based
Fluxing agent.These fluxing agents all have different types of coal certain fluxing effect.Sodium based fluxing agent has preferable fluxibility,
But it since alkali metal can generate strong corrosiveness to gasification furnace inner lining material, is not used by commercial plant generally.It is iron-based
Fluxing with magnesium-based fluxing agent works well, but due to higher cost, using being restricted.Calcium based fluxing agent is cheap, and
With preferable fluxing effect, become industrial widely used fluxing agent.Calcium oxide and lime stone are that typical calcium base is fluxing
Agent represents, and is industrially widely used, but its general additive amount is larger, on the one hand will increase oxygen demand and deslagging heat loss,
On the other hand it is possible to that gasification furnace can be caused to block up slag parking, causes economic loss.Therefore the exploitation of economical and efficient fluxing agent needs
Further investigation.
CN1970698A discloses a kind of composite fluxing agent for reducing Huainan coal ash fusion temperature, consisting of (weight %):
CaCO382%~93%；Fe2O32%~16%；Remaining is MgCO3.The fluxing agent is uniformly blended into coal, in gasification
Changeable ash melting characteristic, reduces ash fusion point and ash viscosity, so that lime-ash be made to be smoothly discharged in liquid form.
CN101665737A provides a kind of efficient composite fluxing agent for improving melting characteristic of gasified pulverized coal slag, and the fluxing agent is by two kinds
Or it is two or more be combined containing basic anhydride mineral powder, the melting characteristic of the mining area Wan Bei coal can be effectively improved.
CN104479793A discloses a kind of composite fluxing agent for reducing gasified pulverized coal slag ash fusion point, and the fluxing agent is by paper mill sludge
Powder sample and agstone sample are mixed with the ratio of 1:1~1:3, can not only reduce coal ash fusion temperature, and realize papermaking
The resource utilization of sludge, while the heat of paper mill sludge can also be utilized.
Foregoing invention can reduce particular coal fusion point of ash, but there are higher costs or fluxing agent to add for its described fluxing agent
Measure the problems such as larger.Such as use Fe2O3、MgCO3Deng, compared to merely use lime stone for higher cost compound with lime stone.
For deformation temperature, softening temperature and flowing temperature are all larger than 1520 DEG C of high-ash-fusion coal, paper mill sludge and stone are used
When the compound fluxing agent of lime stone reduces ash fusion point, the additive amount needed is larger, and oxygen consumption, energy consumption increase and gasification efficiency is caused to reduce
Negative consequence.
Red mud is the waste residue generated during producing aluminium oxide, generally 1 ton of aluminium oxide of every production can generate 0.6~
1.8 tons of red muds.For domestic red mud in addition to being applied to manufacture of cement, brickmaking on a small quantity, most outdoor stockpiling of building a dam not only occupies a large amount of soil
Ground, and maintenance cost is high, increases the production cost of aluminium oxide.In addition, the red mud waste liquid of strong basicity, high salinity can pollute
Water body causes the destruction of ecological environment.From another perspective, more minerals are contained in red mud, are a kind of resources, as can
It is rationally utilized, ecological environment problem is not only can solve, can also generate higher social economic value.
Summary of the invention
The present invention provides a kind of composite fluxing agent for improving high ash melting point coal ash and preparation method thereof and answer
With, not only solved the technical problem of the meltbility difference of high ash melting point coal ash, but also solve polluting waste red mud recycling how
The problem of rationally utilizing.
The composite fluxing agent provided by the invention for improving coal ash, the composite fluxing agent are answered by CaO and red mud
It closes, the chemical component and mass content of composite fluxing agent are as follows: basic anhydride are 56.1%~90.6%, acidic oxide
It is 9.4%~43.9%, it is preferable that basic anhydride are 62.4%~88.9%, and acidic oxide is 11.1%~37.6%, institute
Stating basic anhydride includes CaO, Fe2O3And Na2O, the acidic oxide include Al2O3、SiO2。
It is preferred that including TiO in the acidic oxide2, the mass content in composite fluxing agent is lower than 4%.
It is preferred that mass content of the basic anhydride CaO in composite fluxing agent is 26.2%~83.6%, preferably
36.0%~77.2%.
It is preferred that basic anhydride Fe2O3Mass content in composite fluxing agent is 5.6%~22.4%.
It is preferred that acidic oxide Al2O3Mass content in composite fluxing agent is 4.0%~20.3%.
Red mud of the present invention is the waste residue that aluminum oxide industry generates, and it is red that the red mud is selected from Bayer process red mud, sintering process
One or more of mud and mixed combining method red mud, the main chemical compositions of the red mud are CaO, Fe2O3, Al2O3, SiO2, Na2O。
Composite fluxing agent of the present invention does not require the source of red mud and composition specifically.Red mud is aoxidized in production
The waste residue generated during aluminium, generally 1 ton of aluminium oxide of every production can generate 0.6~1.8 ton of red mud.According to alumina producing
The difference of technique, red mud are generally divided into Bayer process red mud, red mud from sintering process and mixed combining method red mud, and wherein sintering process is also known as alkali stone
Grey sintering process needs to add a large amount of lime and carries out ingredient, therefore wherein CaO content is higher.Utilize home ore (mainly one
Diasporite type) when carrying out high-temperature Bayer process, it is also desirable to it adds a certain amount of lime and is dissolved out, and utilize foreign ore (main
If gibbsite type) when carrying out low temperature Bayer Process digestion, then addition lime stone is not needed, therefore CaO contains in its chemical component
It measures relatively low.Typical red mud from sintering process main component weight ratio: SiO215%~20%, Fe2O312%~15%,
Al2O36%~9%, CaO 35%~45%, Na2O 2%~3%.The ingredient of red mud produced by mixed combining method and sintering process is substantially
Identical, the content of iron oxide and aluminium oxide is lower.
In order to preferably improve high ash melting point coal ash, the preferably described red mud of the present invention is Bayer process red mud,
Main chemical compositions and mass content are as follows: SiO218%~25%, Fe2O328%~35%, Al2O318%~25%, CaO
2%~6%, Na2O 8%~12%.
The present invention provides the preparation method of any of the above-described composite fluxing agent, including, CaO and red mud are mixed according to a certain percentage
It closes, grinds and be uniformly mixed.
The present invention provides the application method of any of the above-described composite fluxing agent, including, according to mass content, by 2%~6%
The composite fluxing agent is added in high-ash-fusion coal, after mixing, in the airflow bed gasification furnace of coal gasification slag tap
Gasify.
Composite fluxing agent provided by the present invention can not only turn waste into wealth solid waste red mud, and fluxing effect is excellent
Good, the flowing temperature of high ash melting point coal ash can be reduced to 1400 DEG C hereinafter, guaranteeing liquid by only 2%~6% additive amount
The operation temperature of the coal gasification airflow bed gasification furnace of deslagging is within the appropriate range.Simultaneously as the additive amount of CaO is less,
It avoids industrial because of a large amount of addition CaO or CaCO3Slag parking problem is blocked up caused by equal fluxing agents, is the steady of airflow bed gasification furnace
Fixed operation provides powerful guarantee.
Composite fluxing agent provided by the present invention not only can effectively improve the melting characteristic of high ash melting point coal ash, be applicable in it
In the airflow bed gasification furnace of slag tap, and it is able to achieve the resource utilization of polluting waste red mud, there is good economic effect
Benefit and social benefit.
Specific embodiment
It is next by the following examples that the present invention is furture elucidated, it is understood that, described herein as is not to this hair
Bright limitation, only illustrates.
CaO used in embodiment is the analytical reagents of Beijing Chemical Plant's production.
Red mud used is the waste residue that aluminum oxide industry generates in embodiment, and red mud used in embodiment 1-5 is Bayer process
Red mud, main chemical compositions and its mass content are as follows: Fe2O328.3%, Al2O324.5%, SiO218.2%, Na2O
10.2%, CaO 5.6%, TiO24.6%.
Embodiment 1
CaO and Bayer process red mud are uniformly mixed with the ratio of 2:1 in mass ratio, composite fluxing agent is made, then with coal
The 2~6% of base mass content are added in high-ash-fusion coal, grind and are uniformly mixed.The matter of composite fluxing agent neutral and alkali oxide
Measure content (CaO, Fe2O3And Na2O mass content) is 82.5%, and surplus is acidic oxide.The matter of CaO in composite fluxing agent
Amount content is 68.9%, Fe2O3Mass content be 9.3%, Al2O3Mass content be 8.4%, TiO2Mass content be
1.5%.
Embodiment 2
CaO and Bayer process red mud are uniformly mixed with the ratio of 1:1 in mass ratio, composite fluxing agent is made, then with coal
The 2~6% of base mass content are added in high-ash-fusion coal, grind and are uniformly mixed.The matter of composite fluxing agent neutral and alkali oxide
Measure content (CaO, Fe2O3And Na2O mass content) is 73.4%, and surplus is acidic oxide.The matter of CaO in composite fluxing agent
Amount content is 52.8%, Fe2O3Mass content be 14.1%, Al2O3Mass content be 12.7%, TiO2Mass content be
2.3%.
Embodiment 3
CaO and Bayer process red mud are uniformly mixed with the ratio of 1:2 in mass ratio, composite fluxing agent is made, then with coal
The 2~6% of base mass content are added in high-ash-fusion coal, grind and are uniformly mixed.The matter of composite fluxing agent neutral and alkali oxide
Measure content (CaO, Fe2O3And Na2O mass content) is 64.4%, and surplus is acidic oxide.The matter of CaO in composite fluxing agent
Amount content is 36.8%, Fe2O3Mass content be 19.0%, Al2O3Mass content be 17.1%, TiO2Mass content be
3.1%.
Embodiment 4
CaO and Bayer process red mud are uniformly mixed with the ratio of 1:3 in mass ratio, composite fluxing agent is made, then with coal
The 2~6% of base mass content are added in high-ash-fusion coal, grind and are uniformly mixed.The matter of composite fluxing agent neutral and alkali oxide
Measure content (CaO, Fe2O3And Na2O mass content) is 60.1%, and surplus is acidic oxide.The matter of CaO in composite fluxing agent
Amount content is 29.3%, Fe2O3Mass content be 21.2%, Al2O3Mass content be 19.1%, TiO2Mass content be
3.4%.
Embodiment 5
CaO and Bayer process red mud are uniformly mixed with the ratio of 4:1 in mass ratio, composite fluxing agent is made, then with coal
The 2~6% of base mass content are added in high-ash-fusion coal, grind and are uniformly mixed.The matter of composite fluxing agent neutral and alkali oxide
Measure content (CaO, Fe2O3And Na2O mass content) is 89.4%, and surplus is acidic oxide.The matter of CaO in composite fluxing agent
Amount content is 81.1%, Fe2O3Mass content be 5.7%, Al2O3Mass content be 5.1%, TiO2Mass content be
0.9%.
The present invention can requirement according to the grey chemical component and gasification furnace of different types of coal to coal ash melting temperature, appropriate adjustment
The compound proportion and additive amount of fluxing agent.
Comparative example 1
To analyze pure CaO as fluxing agent, the CaO that mass fraction is 4% is added separately to HN coal, Q56 coal and Q60 coal
In (components of coal ash and melting temperature are shown in Tables 1 and 2), grind and be uniformly mixed.4%CaO fluxing agent is to coal ash melting temperature
Influence is shown in Table 3.
Embodiment 6
The composite fluxing agent that embodiment 2 is prepared is added in HN coal, Q56 coal and Q60 coal by the 4% of matrix of coal amount, is ground
Study carefully influence of the composite fluxing agent to high ash melting point coal ash melting temperature, concrete outcome is shown in Table 4.
Embodiment 7
It selects red mud from sintering process compound with CaO, studies its influence to high ash melting point coal ash melting temperature.Sintering process used
The chemical component and its mass content of red mud are as follows: Fe2O314.6%, Al2O38.2%, SiO219.6%, Na2O 2.9%,
CaO 40.7%, TiO23.2%.
CaO and above-mentioned red mud from sintering process are uniformly mixed with the ratio of 1:1 in mass ratio, composite fluxing agent is made, it is compound
Mass content (CaO, Fe of fluxing agent neutral and alkali oxide2O3And Na2O mass content) is 79.1%, and surplus is acidic oxidation
Object.The mass content of CaO is 70.3%, Fe in composite fluxing agent2O3Mass content be 7.3%, Al2O3Mass content be
4.1%, TiO2Mass content be 1.6%.High-ash-fusion coal is added by the 4% of matrix of coal amount content in the composite fluxing agent
In, it grinds and is uniformly mixed.Influence of the composite fluxing agent to high ash melting point coal ash melting temperature the results are shown in Table 5.
Each composition quality score/% in 1 high ash melting point coal ash of table
2 high ash melting point coal ash melting temperature of table
(wherein DT is deformation temperature, and ST is softening temperature, and HT is hemispherical fusion temperature, and FT is flowing temperature)
Table 3CaO fluxing agent (additive amount: 4%) to the influence of coal ash melting temperature
4 composite fluxing agent of table (is prepared, additive amount: 4%) to coal ash melting temperature by embodiment 2
It influences
5 composite fluxing agent of table (is prepared, additive amount: 4%) to the influence of coal ash melting temperature by embodiment 7
As can be seen from the above-described embodiment, composite fluxing agent of the present invention has good fluxing work to high-ash-fusion coal
With, preferably composite fluxing agent in 2%~6% few additive can by the flowing temperature of high ash melting point coal ash reduce by 100~
180 DEG C, its flowing temperature is made to be reduced to 1400 DEG C hereinafter, meeting the requirement of air flow bed slag tap.The fluxing agent is used for
High ash melting point coal ash melting temperature is reduced, not only can produce the fluxing effect better than CaO fluxing agent, and can avoid because being individually added into
Slag parking problem is blocked up caused by a large amount of CaO fluxing agents, is conducive to the stable operation of gasification furnace.It compound is helped in addition, of the present invention
Flux is effectively utilized industrial waste red mud, and fluxing excellent effect, therefore, the utilization of the composite fluxing agent can not only reduce gas
Chemical conversion originally, and can realize the resource utilization of red mud, generate good economic benefit and social benefit.
Claims (10)
1. a kind of composite fluxing agent for improving coal ash, which is characterized in that the composite fluxing agent is answered by CaO and red mud
It closes, the chemical component and mass content of composite fluxing agent are as follows: basic anhydride are 56.1%~90.6%, acidic oxide
It is 9.4%~43.9%, the basic anhydride include CaO, Fe2O3And Na2O, the acidic oxide include Al2O3、SiO2。
2. composite fluxing agent according to claim 1, which is characterized in that the chemical component and mass content of composite fluxing agent
Are as follows: basic anhydride are 62.4%~88.9%, and acidic oxide is 11.1%~37.6%.
3. composite fluxing agent according to claim 1 or 2, which is characterized in that include TiO in the acidic oxide2,
Mass content in composite fluxing agent is lower than 4%.
4. composite fluxing agent according to claim 1 or 2, which is characterized in that basic anhydride CaO is in composite fluxing agent
Mass content be 26.2%~83.6%, preferably 36.0%~77.2%.
5. composite fluxing agent according to claim 1 or 2, which is characterized in that basic anhydride Fe2O3In composite fluxing agent
In mass content be 5.6%~22.4%.
6. composite fluxing agent according to claim 1 or 2, which is characterized in that acidic oxide Al2O3In composite fluxing agent
In mass content be 4.0%~20.3%.
7. composite fluxing agent according to claim 1, which is characterized in that the red mud is the useless of aluminum oxide industry generation
Slag, the red mud are selected from one or more of Bayer process red mud, red mud from sintering process and mixed combining method red mud, the red mud it is main
Chemical component is CaO, Fe2O3, Al2O3, SiO2, Na2O。
8. composite fluxing agent according to claim 7, which is characterized in that the red mud is Bayer process red mud, is mainly changed
It studies point and mass content are as follows: SiO218%~25%, Fe2O328%~35%, Al2O318%~25%, CaO 2%~
6%, Na2O 8%~12%.
9. the preparation method of -8 any composite fluxing agents according to claim 1, which is characterized in that by CaO and red mud according to
Certain proportion mixing, grinds and is uniformly mixed.
10. the application method of -8 any composite fluxing agents according to claim 1, which is characterized in that, will according to mass content
2%~6% composite fluxing agent is added in high-ash-fusion coal, after mixing, in the air-flow of coal gasification slag tap
Gasify in bed gasification furnace.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115261097A (en) * | 2022-09-06 | 2022-11-01 | 山西潞安煤基清洁能源有限责任公司 | Preparation method of raw material coal fluxing agent of liquid slag-discharging gasification furnace |
| CN115446097A (en) * | 2022-08-31 | 2022-12-09 | 北京工商大学 | Silicon-aluminum base alkali metal curing agent, preparation method thereof and method for inhibiting alkali metal volatilization in synergistic temperature range |
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| JP3442817B2 (en) * | 1993-05-28 | 2003-09-02 | 三菱重工業株式会社 | Method for producing zeolite composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115446097A (en) * | 2022-08-31 | 2022-12-09 | 北京工商大学 | Silicon-aluminum base alkali metal curing agent, preparation method thereof and method for inhibiting alkali metal volatilization in synergistic temperature range |
| CN115261097A (en) * | 2022-09-06 | 2022-11-01 | 山西潞安煤基清洁能源有限责任公司 | Preparation method of raw material coal fluxing agent of liquid slag-discharging gasification furnace |
| CN115261097B (en) * | 2022-09-06 | 2024-01-19 | 山西潞安煤基清洁能源有限责任公司 | Preparation method of raw material coal fluxing agent of liquid slag-discharging gasifier |
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