CN1294181A - Clean combustion of coal and application and products of its companion substance - Google Patents

Clean combustion of coal and application and products of its companion substance Download PDF

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Publication number
CN1294181A
CN1294181A CN00103328A CN00103328A CN1294181A CN 1294181 A CN1294181 A CN 1294181A CN 00103328 A CN00103328 A CN 00103328A CN 00103328 A CN00103328 A CN 00103328A CN 1294181 A CN1294181 A CN 1294181A
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coal
combustion
companion
zlt
substance
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CN1152124C (en
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郑春雷
郑东风
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Zheng Dongfeng
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Priority claimed from CN 99121977 external-priority patent/CN1248614A/en
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Priority to CNB00103328XA priority Critical patent/CN1152124C/en
Priority to PCT/CN2000/000079 priority patent/WO2001030944A1/en
Priority to AU36542/00A priority patent/AU3654200A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C04B18/084—Flue dust, i.e. fly ash obtained from mixtures of pulverised coal and additives, added to influence the composition of the resulting flue dust
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A clean combustion method of coal includes adding a powder substance to powder coal, grinding and affinity calcine in furnace to generate water steam and adjustable water-hardening powder coal ash as its companion substance. A method for using said powdered coal ash is also disclosed. Its advantages are low carbon content in said powdered coal ash, less discharge of SO2, NO2, CO and CO2 to decrease environmental pollution, and high added value of powdered coal ash.

Description

Application and product of coal purification combustion and companion
The invention relates to an application method of companion and companion produced by coal purification and combustion, in particular to a method and a product for simultaneously producing steam and adjustable hydraulic fly ash with high added value and recycling the fly ash by adding a certain powder doping substance into the coal dust, mixing and grinding the mixture with the coal to form affinity particles, spraying the affinity particles into a coal dust furnace and a cyclone furnace for affinity calcination.
With the development of energy industry, the emission of fly ash in China reaches more than 3 hundred million tons per year, and in 2000, the emission may reach 1.5 hundred million tons per year. The discharge of the fly ash occupies a large amount of land and also becomes a great obstacle to environmental protection. For a long time, various countries have explored various solutions for the purpose of comprehensive treatment and reuse of fly ash. In recent years, developments have been made in the us, uk, france and norway for the reuse of fly ash, wherein one of the more advanced methods is to use fly ash as a base material for concrete to make fly ash concrete, but the drawbacks of this method are: because the fly ash contains a large amount of residual carbon, the quality and the performance of a cement product are influenced, and meanwhile, the fly ash with high carbon content easily forms a layer of hydrophobic film on the surface of the fly ash, so that the hydration reaction of active substances is hindered, and the fly ash can play a discrete destructive role in the agglomeration and aggregation of the cement product. The reason that the carbon content of the fly ash is high is analyzed, and the main factor is that the coal is not combusted sufficiently. Because the coal is not combusted sufficiently, not only the air pollution is caused, but also the fly ash generated after combustion can not be utilized sufficiently, therefore, the fly ash is utilized sufficiently, the current situation that the fly ash with rapid increment causes great adverse effect on environmental protection is changed, and the carbon content in the fly ash is reduced firstly. With the increasing influence of environmental protection on human living society, the coal is also required to be purified and combusted, so that the aims of desulfurizing, reducing nitrogen oxides and reducing the emission of carbon dioxide and carbon monoxide are fulfilled.
In the prior art of the present invention, methods for producing and utilizing cementitious fly ash have been disclosed, which reveal many of the advantages of high calcium fly ash, but the reality is that both the bituminous and anthracite coals used by us have very low calcium content, e.g. less than 10%, which limits the cementitious (setting) properties of the fly ash produced by the coal after combustion. The prior art does not solve the problem of how to improve the calcium content of the fly ash so as to improve the degree of the gelatinization and reuse the fly ash when using bituminous coal and anthracite. The inventor also noticed that in the prior art, the utilization means of the fly ash has been involved, and the problem of desulfurization of coal in combustion is also involved, but the desulfurization rate of raw coal in the prior art is still very low, and no specific means or method for reutilization of fly ash is disclosed, so that the consequences of the coal on the atmospheric environment due to harmful substances discharged during combustion cannot be completely overcome, and the reutilization of fly ash cannot be realized. Obviously, if an economical and appropriate method is available, the calciumcontent in the fly ash can be increased, the content of unreacted silicon dioxide can be reduced to improve the economic value of the fly ash, and the fly ash can be fully utilized again, so that the method has a great positive effect on environmental protection and even human survival status.
The main purpose of the invention is to reduce the carbon content in the fly ash and ash slag generated after the combustion of the coal powder, thereby enabling the coal powder to be fully reused.
A second object of the present invention is to save energy consumption in power generation or heat supply of a power plant or a thermal power plant.
The third purpose of the invention is to be able to positively utilize the low-quality coal, thereby making full use of the low-quality coal existing in large quantity in China and relieving the resource shortage.
A fourth object of the present invention is to provide a method for applying the coal to clean the companion substance generated after combustion, so that the coal can be used for manufacturing cement and concrete.
The fifth purpose of the invention is to utilize the method of the invention to realize the desulfurization of coal in the combustion process and reduce the discharge amount of nitrogen oxides, carbon monoxide and carbon dioxide, thereby effectively protecting the environment which human beings rely on for survival.
The invention is realized by adopting the following technical means: a method for purifying and burning coal and generating companion substances is characterized by comprising the following steps: a ZLT mixed burning substance composed of active silicon dioxide, calcium lime, carbide slag, silicon ash, iron-rich substance, phosphorus-containing substance, electric furnace phosphorus slag and desulfurizing catalyst is added in coal powder, the ZLT mixed burning substance and coal are mixed, ground and homogenized according to a certain proportion and then are closely adsorbed to form affinity particles, and the affinity particles are sprayed into a coal powder furnace or a cyclone furnace to perform affinity calcination in the state of gas-solid-liquid suspension reaction, so that the mass transfer, heat transfer and momentum transfer of the burning substance are realized at the fastest speed.
The ZLT doped sintering material comprises the following components in percentage by weight:
1-50 quicklime containing active silicon dioxide 5-98
Carbide slag 0-80
0-10 iron-rich substance and 0-10 phosphorus-containing substance
The ratio of the 0-5 desulfurization catalyst 0-5 'ZLT' adulterant of the electric furnace phosphorus slag to the coal is as follows:
50-95% of 'ZLT' blended combustion material 6-55% of coal powder
The active silica-containing substance described in the above method includes: shale ore, pottery clay, silica fume, clay, and desulfurizing catalyst including vanadium pentoxide (V)2O5) And the like. The fineness of affinity particles after the mixed grinding of the ZLT mixed combustion substance and the coal powder is 0.08mm square-hole sieve, and the sieve residue is 2-30%. The "ZLT" blended burning substance can be mixed with low-heat value inferior coal and then subjected to affinity calcination in pulverized coal furnaces and cyclone furnaces of power plants and thermal power plants.
The process flow of the method for purifying and burning the coal and generating the companion comprises the following steps: selecting materials, proportioning coal and ZLT blended combustion materials, grinding machine, coal powder bin, powder feeder, burner, affinity calcination in coal powder boiler, and mixing with other materials (active coal ash or self-hardening coal ash or belite cement clinker and corresponding furnace slag). According to the process flow, the mixed material of the coal and the ZLT blended combustion object enters a coal mill through a conveyor, wherein the coal mill can be a ball mill, a vertical mill or any other form of powder preparation system, so that the ZLT blended combustion object and the coal powder form an affinity particle state. In the method, the active fly ash microbeads can be enriched and refined by adjusting the formula of the ZLT admixture, reducing the viscosity of the reactant and the fineness of the affinity particles formed by mixing and grinding the ZLT admixture and the coal. In the method, the furnace temperature for performing affinity calcination on the mixture of the ZLT doped combustion product and the coal is between 800-1340 ℃, so that the associated product rich in belite can be generated, and the content of nitrogen oxides in the flue gas is reduced.
The specific method of desulfurization in the above-mentioned method for purifying and burning coal and producing associated material is that on the basis of consolidation desulfurization, before the flue of boiler and dust remover the dust-containing flue gas is sprayed with steam, and then the second step of humidification desulfurization is implemented, and the consolidation desulfurization effect can be up to desulfurization 20-70%, and the further humidification desulfurization can be up to 70-90%.
The companion product produced by the coal purification combustion is characterized in that: the paint comprises the following components in percentage by weight:
belite (dicalcium silicate) C2S 5-75
Tricalcium aluminate (C)3A 1-40
Calcium tetra-aluminate ferrite C4AF 1-40
Ignition loss (carbon content) 0-5
The companion product can also contain the following components in proportion:
aluminum calcium ferrous acid C2(A，F) 1-30
Free lime CaO 0.1-8
Free magnesium oxide MgO 0-10
Containing alkali aluminates such as (K, Na)20．8CaO．3Al2O3(K，Na)C8A30-10
Alkali sulfates or nitrates such as (K, Na)2SO4(K，Na)NO30-10
Calcium sulfate and calcium sulfite CaSO4．CaSO30-50
Ca (NO) calcium nitrate and calcium nitrite3)2Ca(NO2)20-10
Phosphorus and other substances 0-10
Calcium sulphoaluminate 3 CaO.3Al2O3．CaSO40-20
In the companion product produced by coal purification combustion, the proportion of the ZLT blended combustion product is adjusted according to the ash content and the component of the raw coal, so that C in the companion product 'active fly ash' produced after affinity calcination2The content of S reaches 0-20%. According to the ash content and different components of raw coal, the proportion of "ZLT" blended combustion material is regulated to make C in the "self-hardening fly ash" of associated material produced after affinity calcination2The content of S reaches 20-50%. According to the ash content and different components of raw coal, the proportion of "ZLT" blended burning material is regulated, so that C in the associated "belite" cement clinker produced after affinity calcination2The content of S reaches 50-75%.
The companion produced by the coal purification combustion can be used for manufacturing cement or concrete.
In the application, the companion produced by coal purification and combustion is subjected to superfine grinding (1 nanometer-3 micrometers) and then is used for producing high-technology cement or high-efficiency concrete. The companion produced by coal clean combustion can be used as a reinforcing agent of any cementing material, and the addition amount of the companion is 0.5-15%. The high-quality cement can be produced by mixing the companion fly ash generated by coal purification and combustion and the portland cement clinker according to the following mixture ratio:
cement clinker 2-95 companion substance 2-95
0-50 of latent hydraulic material or pozzolanic material
Gypsum 1-7
The fineness of the ground cement powder is required to be 0.08mm square-hole sieve, and the sieve allowance is less than 12%. The proportion of the high-quality expansive cement produced by mixing the companion substance generated after the high-sulfur coal is burnt with the portland cement clinker is as follows:
30-95 companion substances 2-70 of cement clinker
0-50 of latent hydraulic material or pozzolanic material
Gypsum 1-7
The fineness of the ground cement powder is required to be 0.08mm square-hole sieve, and the sieve allowance is less than 12%. The companion substance formed after the coal is purified and burned can replace 5 to 95 percent of cement without grinding, and is mixed with sand stone and water to prepare high-quality concrete. Grinding the companion formed after the coal is purified and combusted, replacing 5-95% of cement, and stirring the ground companion with cement, sand, stone and water to prepare high-quality concrete, wherein the specific surface area of the companion is 3800-6500 square centimeters per kilogram. In the application of the companion produced by the coal purification combustion, the companion itself can be used as a hydraulic cementing material. The high-quality high-grade cement can be prepared by the accompanying substances and 0.1-30% of early strength agent.
Compared with the prior art, the invention has the outstanding advantages that:
firstly, the fusion of the blended combustion substance doped in the coal dust and the coal dust is exothermic, so that the combustion speed of coal is higher, and the thermal efficiency of a boiler is improved;
secondly, the blended combustion substance doped in the coal powder melts the coal and makes the coal in a liquid state or a semi-liquid state, and coal particles quickly generate micropores, so that the oxygen transfer, catalysis and oxidation effects are better.
Thirdly, because the coal can be fully combusted due to the doping of the doping combustion materials, the power generation and heat supply cost of a power plant is greatly reduced, for example, a 220 ton/hour pulverized coal boiler can save 1.9 ten thousand tons of coal each year according to the 10 percent coal saving rate, the coal saving rate can reach 6 to 15 percent, and the cost is reduced by about 304 ten thousand yuan per year.
Fourthly, the low-calorific-value inferior coal can be effectively utilized without influencing normal power generation and normal work of the boiler, and the low-calorific-value inferior coal is combusted or blended by adopting the method of the invention without any modification of the boiler. In China, huge social benefits and economic benefits generated by effective utilization of the low-quality coal are obvious. While the heat value of coal is required to be over 5000 calories/kg in a common pulverized coal furnace, if the heat value of the coal is low, the pulverized coal is easy to catch fire in the boiler, so that the power plant can not normally generate electricity and supply heat. However, the data table material shows that about 20% of the coal reserves in China are inferior coals below 4000 calories/kg, and if the coals cannot be fully utilized, the wastes of energy and data are inevitably caused. China is one of the countries with relative shortage of energy, so the countries have encouraged to use the low-quality coal.
Fifthly, due to the application of the method, the carbon content in the fly ash is reduced, the free calcium oxide of harmful substances in the high-calcium fly ash is eliminated, and the original waste fly ash and ash are completely changed into product raw materials with high added values, so that the burning companion is completely utilized, thereby playing a great positive role in environmental protection and creating considerable economic benefit.
Sixth, because the invention can effectively reduce the furnace temperature, especially in the high oxygen area of the boiler, and the excess air coefficient is reduced due to the burnout efficiency of the coal, the formation of nitrogen oxides is indirectly destroyed, and the emission of the nitrogen oxides is effectively reduced.
Seventh, due to the application of the present invention, the combustion of coal is more sufficient, and the emission of carbon monoxide is also reduced.
Eighth, the application of the invention fully improves the utilization rate of coal, so that thecarbon dioxide discharged in power generation or heat supply is reduced.
Ninth, due to the application of the invention, the temperature distribution in the boiler is more uniform, the boiler can be controlled better, and the boiler abrasion is reduced.
Tenth, because the invention is applied, the maximum desulfurization (the desulfurization rate can reach more than 90 percent) can be realized, thus effectively protecting the environment;
eleventh, due to the application of the present invention, high performance cement materials can be produced, and the blended high calcium material can be adjusted to various calcium contents by adjusting the mixture ratio thereof, thereby satisfying different requirements (e.g., pozzolana-low calcium; pozzolana-medium calcium, cement-high calcium).
The invention will be further illustrated with reference to a number of specific examples.
Example 1 is a specific composition example and implementation effect of a "ZLT" admixture
In this example, the raw materials for the "ZLT" blended burnt material formulation include the following:
shale: sio2Quicklime with a content of 66%: CaO content is 92%
Silica fume: sio2Carbide slag with the content of 88 percent: p2O5The content is 10 to 15 percent;
iron ore powder: fe2O369% content of electric furnace phosphorus slag
Raw coal: calorific value 6230 kcal/kg ash 21%
The shale is high-quality active shale of shale ore, and the shale ore is formed by depositing basalt after weathering decomposition, and contains SiO2The amount may be 66%;
the raw coal is Shanxi high-quality anthracite, the calorific value is 6230 kcal/kg, the ash content is 21 percent, and the water content is 1 percent. The specific ingredients of the "ZLT" blend are shown in the following table:
raw materials Shale Quick lime Silica fume Carbide slag Iron ore powder Electric furnace phosphorus slag
Percentage of 23 69.5 2 2 2 1.5
The mixture ratio of the ZLT blended combustionmaterial to the raw coal is as follows: "ZLT blended combustion product 25%, raw coal 75%
The process flow is as follows:
after the selected ingredients enter a factory, the ingredients are conveyed to a storage and ingredient warehouse of each raw material through conveying equipment, an electronic ingredient scale is arranged below the ingredient warehouse, and the raw materials are accurately proportioned through the electronic ingredient scale according to the following mixing ratio.
The mixture of coal and "ZLT" blended combustion material is fed into coal mill by conveyer, said coal mill can be ball mill, vertical mill or other powder-making system, and the "ZLT" blended combustion material component and coal fine powder are in fully mixed adsorption state. The ground coal powder is sent into a coal powder bin of a coal powder boiler of a power plant #3-220 t/h.
When the pulverized coal sprayed by the sprayer is combusted in the hearth, the temperature of the hearth is between 1000 ℃ and 1500 ℃. The ZLT mixed combustion material and raw coal generate a series of physical and chemical changes to form various minerals in the combustion process of a power plant boiler.
800-900℃
(calcium ferrite)
(Monocalcium aluminate)
Above 900 ℃, CaCO in the material releases CO very quickly and the solid phase reaction accelerates due to the temperature rise, wherein:
900-1000℃
(dicalcium ferrite)
(pentacalcium aluminate)
800-1300℃
(dicalcium silicate)
1000-1300℃
(tetracalcium aluminoferrite)
1300-1450℃ C3A and C4AF melts into the liquid phase and undergoes the following reaction:
the carbon content of the fly ash collected from the dust removal of a pulverized coal boiler and an electric appliance is controlled to be below 3 percent through detection.
In the implementation of the embodiment, the boiler normally supplies heat and generates electricity, and the operation is not influenced; the brightness of the flame in the hearth is obviously enhanced, the combustion is promoted and stabilized, and the burn-out rate is improved; the fly ash is obviously changed into ash, the specific gravity is improved by 30 percent, and the content of residual carbon is reduced to 1.5 percent from the original 8 percent; the boiler coal saving amount reaches 8.5%; the boiler bottom slag is increased by 20%; increasing the amount of the boiler fly ash; the temperature of the flue gas at the outlet of the boiler hearth is reduced by 120 ℃; realizes the coal purification combustion and produces all available companion substances.
Example 2 is the specific application of the method of the present invention to achieve the purposes of desulfurization and nitrogen reduction.
In this example, the raw materials for the "ZLT" blended burnt material formulation include the following:
shale: sio2Quicklime with the content of 69 percent: CaO content is 89%
Silica fume: sio2Carbide slag with content of 85%
Iron ore powder: fe2O356% content of electric furnace phosphorus slag
Raw coal: the calorific value is 5850 kcal/kg ash content is 16%
The specific ingredients of the "ZLT" blended combustion material are as follows:
raw materials Shale Quick lime Silica fume Carbide slag Iron ore powder Electric furnace phosphorus slag
Percentage of 19 69 2 5 3 2
The proportion of the ZLT blended combustion material to the raw coal is as follows: "ZLT" blending combustion material 28%, raw coal 72%
The ZLT mixed combustion material and raw coal generate a series of physical and chemical changes to form various minerals in the combustion process of a power plant boiler.
800-900℃
(calcium ferrite)
(Monocalcium aluminate)
CaCO in the material at over 900 DEG C3CO is discharged quickly2And due to the temperature increase, the solid phase reaction is accelerated, wherein:
900-1000℃
(dicalcium ferrite)
(pentacalcium aluminate)
800-1300℃
(dicalcium silicate)
1000-1300℃
(tetracalcium aluminoferrite)
1300-1450℃ C3A and C4AFMelted into the liquid phase and subjected to the following reaction:
c formed during the combustion of the ZLT blended combustion material and raw coal4AF is fast in solid solution, is beneficial to desulfurization and fast burning, and the key of the solid desulfurization lies in fast cooling to enable SO3The volatilization rate of (2) is reduced.
The essence of consolidated desulfurization is that the maximum possible reduction of SO3Is volatilized and the part of SO volatilized3Further collide with the fine particles to reform Ca2SO3、Ca2SO4And humidifying SO3And is further absorbed.
In the present embodiment, the principle of achieving efficient desulfurization is as follows:
there are three forms of sulfur in coal:
the first organic sulfur is organic hydrocarbon, such as H2S。
The second kind is called sulfide, and Fe impurity is mainly existed2And (S) in the step (A).
The third is sulfate, and is present in various sulfates, such as CaSO4、MgSO4、Fe2(SO4)3、Na2SO4、K2SO4And the like.
Sulfur in organic sulfur and iron sulfide can be combusted to generate SO2SO called combustible sulfur, a small portion of sulfur in sulfate is decomposed at high temperature to form SO3In addition, the rest is left in the ash. The key points of desulfurization are oxygen enrichment, high calcium, addition and reaction of a catalyst. The use of a superheater makes the flash cooling possible, and the key to the desulfurization of the clean coal combustion is the flash cooling. Due to the particles of the combustible material in this embodimentSmall size, can fully exchange heat with air, and has the rapid heat exchange of a water wall and a superheater, SO that the material is easily burnt through rapidly, is also easily and rapidly cooled, is also easily combined with oxygen, cannot generate local reducing atmosphere, and does not generate SO in raw coal2At the moment that the release is not carried out, the materials are firstly fixed and melted on the other materialsIn the mineral, the eutectic point is reduced, the function of the mineralizer is fully exerted, and SO is reduced in the rapid cooling process2And SO3Is released. This example differs from conventional desulphurisation in that a relatively stable mineral is formed and is solid-melted in the silicate mineral.
During combustion, sulfur is in the high-CaO phase, the following reactions occur:
(400-450℃)
(600℃)
(above 600 ℃ C.)
(600-800℃)
(400-800℃)
(above 800 ℃ C.)
In the range of 800 ℃ and 1000 ℃, CaO of the catalyst strongly absorbs SO3And has a higher reaction rate and a part of SO3Solid-melted in silicate minerals. CaAlSO4It is formed at 950 deg.C, kept stable at 1350 deg.C and begins to decompose at 1400 deg.C.
The humidifying and desulfurizing mechanism is as follows:
the consolidation desulfurization data using the method of this example is shown in the following table:
test conditions Raw coal of No. 5 furnace Raw coal and desulfurizer for No. 5 furnace
Flue gas amount Nm3／h 92570 92570
SO2Concentration mg/Nm3 8334.9 2667.2
SO2Discharge amount kg/h 771.56 246.9
Desulfurization efficiency after adding the "ZLT" blended combustion material:(771.56-246.9)/771.56 × 100% = 68.1% on the basis of the consolidation desulfurization, spraying humidifying steam in front of a boiler tail flue and an electric dust remover, and performing a second step of humidifying desulfurization, wherein the table is as follows:
test conditions Raw coal of # B furnace Raw coal and desulfurizer for # B furnace
Flue gas amount Nm3／h 92570 92570
SO2Concentration mg/Nm3 8334.9 1105.7
SO2Discharge amount kg/h 771.56 102.4
Adding a ZLT doped combustion substance and spraying humidifying steam, and then desulfurizing efficiency: (771.56-102.4)/771.56 × 100% = 86.7%
In this example, it can be seen that when the ZLT co-combustion material is added to the raw coal, SO in the flue gas2The desulfurization efficiency was 68.1%, and the desulfurization efficiency was 86.7% when the ZLT co-fired material was added to the raw coal and humidified steam was injected.
In this embodiment, the nitrogen reduction mechanism is:
there are two main sources of nitrogen oxide production in coal,
the first is that the coal contains organic nitrogen and generates Nitrogen Oxide (NO) during combustionx) (ii) a Secondly, the high-temperature flame makes nitrogen in the air react with oxygen to generate nitrogen-oxygen compound (NO)x). The essence of nitrogen reduction is that the maximum possible NO reductionxIs volatilized and the part of NO volatilizedxFurther colliding with the fine particles, reforming nitrogen oxides, and humidifying NOxAnd is further absorbed. The combustion heat transfer efficiency of the ZLT mixed combustion material and the raw coal in the furnace is high, the heat transfer efficiency of the furnace wall is improved, the temperature of fire points in the furnace is reduced, the temperature of each point in the furnace is more uniform, and the temperature of each point in the furnace can be reduced by 100 ℃ and 150 ℃ as seen from a hearth outlet flue gas temperature measuring meter, so that NO can be reducedxThe amount of production of (c). At the moment that organic nitrogen in the coal is not released, the organic nitrogen is firstly and fixedly fused in other minerals, the eutectic point is reduced, the function of a mineralizer is fully exerted, and NO are reduced in theprocess of rapid cooling2Or NOxIs released. The nitrogen reduction method in this embodiment is different from the conventional nitrogen reduction method in that a relatively stable mineral is formed and is solid-melted in a silicate mineral, and the reaction formula is as follows:
the mechanism of further humidifying and reducing nitrogen is as follows:
the effect of the embodiment is detected, and the content of nitrogen oxide in the discharged flue gas is NO in the following table2Is expressed by the content of (A).
Test conditions Raw coal of # B furnace Raw coal of # B furnace + desulfurizing agent
Flue gas amount Nm3／h 92570 92570
NO2Concentration mg/Nm3 707.2 518.9
Adding a ZLT doped combustion substance and spraying humidifying steam, and then solidifying, humidifying and nitrogen reducing efficiency: (707.2-518.9)/707.2 × 100% = 26.8%
In this example, it can be seen that the nitrogen reduction efficiency is 26.8% when adding the "ZLT" blend to the raw coal and injecting the moisturized steam.
Example 3 is a specific example of the use of activated fly ash and activated bottom ash produced by the process of the present invention for producing high quality cement
In this embodiment, the raw materials for the "ZLT" blended combustible material include the following:
shale: sio2Quicklime with a content of 66%: CaO content is 92%
Silica fume: sio2Carbide slag with content of 88%
Iron ore powder: fe2O369% content of electric furnace phosphorus slag
Raw coal: the specific ingredients of the 21% "ZLT" adulterate with the calorific value of 6230 kcal/kg ash are shown in the following table: TABLE 1
Raw materials Shale Quick lime Silica fume Carbide slag Iron ore powder Electric furnace phosphorus slag
Percentage of 19 69 2 5 3 2
The mixture ratio of the ZLT blended combustion material to the raw coal is as follows: 20% of "ZLT" blended combustion product and 80% of raw coal of companion product obtained in the exampleThe concrete conditions are as follows: obtaining active fly ash and active bottom slag under the condition that the boiler normally operates for heat supply and power generation, wherein the content of fCaO in the active fly ash is 1-4 percent, the residual carbon content is 0.5-3 percent,the fCaO content in the active furnace bottom slag is 0.1-2%, and the residual carbon content is 0.1-1%.
The clinker is selected from cement clinker normally produced by a certain suspension kiln cement plant, and the performance of the clinker is shown in the following table: TABLE 2
Compressive strength (Mpa) Breaking strength (Mpa)
Reference numerals 3d 7d 28d 3d 7d 28d
625 34 46 64 6.3 7.5 9.0
The ratio of the active flyash to the selected clinker is shown in the following table: TABLE 3
Material(s) Active fly ash Clinker Gypsum plaster
Percentage of 60 38 2
The proportions of the active fly ash and active bottom slag obtained in this example to the selected clinker are shown in the following table: TABLE 4
Material(s) Active fly ash Bottom slag Clinker Gypsum plaster
Percentage of 45 15 38 2
The physical properties of the cement prepared according to the formulation shown in table 3 in this example were determined as follows:
compressive strength (Mpa) Breaking strength (Mpa)
Reference numerals 3d 7d 28d 3d 7d 28d
525 24.2 36.9 55.3 4.6 5.6 7.5
525 23.8 33.8 57.5 4.7 5.8 7.9
The cement produced by mixing and grinding the active fly ash and the clinker has the grade reaching the national standard No. 525 cement standard and qualified stability. The physical properties of the milled cement of the compound of Table 4 of this example were determined as follows:
compressive strength (Mpa) Breaking strength (Mpa)
Reference numerals 3d 7d 28d 3d 7d 28d
525 23.2 35.3 58.4 4.8 6.3 8.5
525 23.6 39.7 61.5 5.2 6.8 8.9
The grade of the cement produced by mixing and grinding the active furnace bottom slag, the active fly ash and the cement clinker reaches the national standard No. 525Standard cement number, and qualified stability.
It can be seen from this example that the cement produced by mixing and grinding the active fly ash produced by the method of the present invention and the conventional cement clinker in a ratio has a qualified product stability and excellent performance indexes. The cement produced by mixing and grinding the active furnace bottom slag, the active fly ash and the traditional cement clinker in proportion has qualified product stability and excellent performance indexes.
Example 4 is an example of the production of self-hardening reactive fly ash cement by the process of the present invention.
In this embodiment, the raw materials for the "ZLT" blended combustible material include the following:
shale: sio2Quicklime with the content of 68 percent: CaO content 93%
Silica fume: sio2Carbide slag with content of 90%
Iron ore powder: fe2O369% content of electric furnace phosphorus slag
Raw coal: thespecific ingredients of the 5970 kcal/kg ash content 23% elemental sulfur (S) 0.6% "ZLT" blended burning material are shown in the table 1: TABLE 1
Raw materials Shale Quick lime Silica fume Carbide slag Iron ore powder Phosphogypsum
Percentage of 15 74 2 5 2.5 1.5
The ratio of the ZLT blended combustion material to raw coal is as follows: 30% of "ZLT" blended combustion materials and 70% of raw coal. The performance parameters of the associated self-hardening fly ash clinker and the associated slag clinker obtained in the example are shown in the following table 2: TABLE 2
Name (name) FCaO Loss on ignition
Self-hardening flyash clinker 3.5％ 1.2％
Self-hardening bottom slag clinker 0.2％ 0.7％
The self-hardening active flyash cement consists of C2S is the main component, and the early strength is low, so that 1.5 percent of alum serving as an early strength excitant is added into the self-hardening fly ash cement.
The properties of the self-hardening fly ash cement produced in this example are shown in Table 3:
test for Test (experiment) Weaving machine Number (C) Mixing ratio Specific surface Product cm2/g Coagulation test Strength test
Pulverized coal Ash of Furnace with a heat exchanger Bottom Slag Stone (stone) Ointment Ming dynasty Alum (alum) First stage Coagulation of water Final (a Chinese character of 'gan') Coagulation of water Anti-folding Resist pressure
3d 7d 28 d 3d 7d 28d
B-1 97 0 3 0 5600 0:55 2:00 2.7 3.1 6.2 18. 4 22.0 42.3
B-2 95.5 0 3 1.5 6400 0:45 1:50 4.5 5.8 7.1 25. 3 37.2 58.7
B-3 65.5 30 3 1.5 6100 0:47 2:04 4.8 5.6 8.2 24 35.6 56.4
In this example, it can be seen that the self-hardening fly ash clinker and the bottom slag clinker produced by the present invention can produce high grade cement with high quality after adding a certain amount of early strength excitant.
Example 5 is an example of the method of the present invention for saving coal in a power plant boiler.
In this embodiment, according to the selection and formulation of the "ZLT" blended combustible and the method of mixing, grinding and burning in example 3, the ratio of the "ZLT" blended combustible to the raw coal is: 23% of "ZLT" blended combustion materials and 77% of raw coal.
In the embodiment, when the ZLT mixed burning substance and raw coal are burnt in the boiler, the coal ash component absorbs heat when decomposed, the ZLT mixed burning substance reacts with the coal ash component to release heat, so that the burning is complete, the carbon residue is reduced, the burning speed is accelerated, the temperature of flue gas contacting with a water-cooled wall is increased, the heat absorption efficiency of the water-cooled wall is improved, the ZLT mixed burning substance also improves the flame blackness of the coal-fired boiler, the radiation heat transfer efficiency is improved, the heat efficiency of the boiler is greatly improved, and the coal saving of the boiler of a power plant can reach 6-15% by using the method. The following table is a coal consumption experiment comparison table of doped burning and non-doped burning 'ZLT' doped burning materials; a75 ton/hour boiler coal saving statistical data table of power plant (the coal is western mountain soft coal of Shanxi province)
Time of day 3 month 4 month Month 5 6 month 7 month 8 month Average
Actual coal consumption (ton) after blending combustion of' ZLT 5240 4718 5889 5248 5054 5334 5253
Coal consumption required by equal load non-blended combustion of' ZLT Volume (ton) 5829 5173 6464 5930 5704 6007 5851
Coal saving (percentage) for same load 10.1 8.8 8.9 10.9 11.4 11.2 10.2
B power plant 220 ton/hour boiler coal-saving statistical data table(the coal type is soft coal)
Time of day 11 month 12 month 1 month 2 month 3 month 4 month Average
Actual coal consumption (ton) after blending combustion of' ZLT 17745 18627 19168 20438 19915 19916 19168
Coal consumption after equal load non-blended burning of' ZLT Volume (ton) 20034 21104 21564 22788 22285 21410 21545
Coal saving (percentage) for same load 11.4 11.7 11.1 10.3 10.6 19.7 11.0
C220 ton/hour boiler coal saving statistical data table of power plant (the coal is soft coal)
Time of day Month 5 6 month 7 month 9 month 10 month 12 month Average
Actual coal consumption (ton) after blending combustion of' ZLT 13646 14838 13698 13116 14725 14497 14087
Coal consumption after equal load non-blended burning of' ZLT Volume (ton) 15595 16323 15891 14905 16714 16072 15918
Coal saving (percentage) for same load 12.5 9.1 13.8 12.0 11.9 9.8 11.5
It can be seen from this example that, after the "ZLT" blended combustion materials are blended, the "ZLT" blended combustion materials are not added under the same load, and the coal saving rate of the boiler is as follows: the coal saving rate of a 75 ton/hour boiler of the A power plant is averagely 10.2; the coal saving rate of a 220 ton/hour boiler of a B power plant is averagely 11.0; the coal saving rate of the 220 ton/hour boiler of the C power plant is 11.5 on average. The coal saving rate of the boiler is proved to be obvious after the 'ZLT' blended combustion materials are blended and combusted.
Example 6 is an example of the carbon reduction of power plant fly ash achieved by the method of the present invention.
In this example, the selection and control method of "ZLT" doped burned material of example 4 was followed. The specific ingredients of the "ZLT" blended burnt material are shown in Table 1: TABLE 1
Raw materials Shale Quick lime Silica fume Carbide slag Iron ore powder Phosphogypsum
Percentage of 12 77 2 5 2.5 1.5
The proportion of the ZLT blended combustion material to the raw coal is as follows: 19% of "ZLT" blend and 81% of raw coal in the practice of this example, the "ZLT" blend absorbs heat when the ash components decompose when it is combusted with the raw coal in the boiler, and the "ZLT" blend reacts with it to release heat, thus allowing complete combustion and reducing carbon residue.
The following table is a comparison table of the loss-on-ignition experiment of the doped-burning and non-doped-burning 'ZLT' doped-burning pulverized coal ash;
the variety of the A power plant and coal is soft coal
Group of 1 2 3 4 5 6 Average
Loss on ignition of undoped burning "ZLT" dust (in weight percent) Than) 6.6 7.4 6.8 5.2 4.8 8.0 6.47
Loss of ignition (weight percentage) of blended ignition "ZLT" ash 0.4 2.2 1.2 1.2 1.6 1.0 1.27
The variety of the A power plant and coal is soft coal
Group of 1 2 3 4 5 6 Average
Loss on ignition of undoped burning "ZLT" dust (in weight percent) Than) 9.3 10.4 7.7 17.4 8.6 11.2 10.73
Loss of ignition (weight percentage) of blended ignition "ZLT" ash 3.0 1.4 1.4 1.3 2.1 1.1 1.72
B, the power plant and the coal are anthracite
Group of 1 2 3 4 5 6 Average
Loss on ignition of undoped burning "ZLT" dust (in weight percent) Than) 39.9 17.6 21.0 29.6 24.9 15.8 6.47
Loss of ignition (weight percentage) of blended ignition "ZLT" ash 2.5 0.9 2.1 3.4 3.0 2.8 2.28
As can be seen from the comparison, the carbon reduction condition of the doped combustion "ZLT" doped pulverized coal ash is obvious, and the average residual carbon content of the pulverized coal ash in the first test of the power plant A is reduced from 6.47% to 1.27%; the average residual carbon content of the fly ash in the second test of the power plant A is reduced from 10.73 percent to 1.72 percent; the average carbon residue content of the fly ash of the B power plant is reduced from 6.74 percent to 2.28 percent, and the carbon residue content of the fly ash is greatly reduced.
Example 7 is an example of the production of expanded cement using the companion "activated fly ash" and "activated bottom ash" produced by the method of the present invention in combination with conventional cement clinker.
In this example, the raw materials for the "ZLT" blended burnt material formulation include the following:
shale: sio2Quicklime with the content of 68 percent: CaO content 93%
Silica fume: sio2Carbide slag with content of 90%
Iron ore powder: fe2O369% content of electric furnace phosphorus slag
Raw coal: the specific ingredients of 5970 kcal/kg ash 23% elemental sulfur (S) 0.6% "ZLT" blended burning material are shown in Table 1:TABLE 1
Raw materials Shale Stone Ash of Silica fume Calcium carbide Slag Iron ore Powder Phosphogypsum Containing V2O5Waste material Slag
Percentage of 15 74 2 5 2 1.5 0.5
"ZLT" blended calciners andthe raw coal comprises the following components in percentage by weight: 28% of "ZLT" blended combustion materials and 72% of raw coal.
The ZLT blended combustion materials and raw coal are mixed according to the proportion and then enter a boiler powder making system for grinding, and ground coal powder is sent into a coal powder bin of a coal powder boiler of a power plant #3-220 t/h and is sprayed into a hearth of the boiler for combustion through a powder feeder.
In the embodiment, the active fly ash and the active bottom slag are obtained under the condition that the boiler normally operates for heat supply and power generation, wherein the fCaO content in the active fly ash is 1-4%, the residual carbon content is 0.5-3%, the fCaO content in the active bottom slag is 0.1-2%, and the residual carbon content is 0.1-1%. The performance of the traditional cement clinker is shown in the following table 2: TABLE 2
Compressive strength (Mpa) Breaking strength (Mpa)
Clinker Reference numerals 3d 7d 28d 3d 7d 28d
A 625 33.8 47.5 65.1 6.4 7.8 9.1
B 625 32.4 46.5 68.1 6.7 7.9 8.8
Cooking the materials of Table 2 aboveThe physical properties of the materials milled into the expansive cement according to the mixture ratio of Table 3 are shown in tables 3 and 4:TABLE 3
Water (W) Mud Weaving machine Number (C) Mixing ratio Water (W) Mud All-grass of Longtube Fang Cooking Material Height of Sulfur Improvement of Property of (2) Powder Coal (coal) Ash of Proportion table Area of m2/kg High sulfur Modification of Pulverized coal Ash of SO2 Content (wt.) Coagulation time Stabilization of Property of (2) (boiling) Boiling) 1:3 hard sand mortar Strength Mpa
Cooking Material Height of Sulfur Improvement of Property of (2) Powder Coal (coal) Ash of Stone (stone) Ointment
Flexural strength Mpa Compressive strength Mpa
Initial setting n:min Final coagulation n:min
3d 7d 28d 3d 7d 28d
D01 65 30 5 A A1 426 13.2 1:48 3:15 Qualified 5.0 6.5 7.9 27.2 42.4 60.8
D02 61 35 4 B B1 429 12.8 1:24 3:24 Qualified 4.8 6.2 7.8 26.4 40.6 58.6
Note: the technical requirements are as follows: the specific surface area is more than 400m 2/kg, the initial setting is more than 20min, and the final setting is less than 10 h. TABLE 4
Water (W) Mud Weaving machine Number (C) Linear expansion of the clear paste
Maintenance in water Moisture maintenance
1d 3d 7d 14d 21d 28d 390d 1d 3d 7d 14d 21d 28d
D02 0.525 0.530 0.534 0.548 0.550 0.572 0.590 0.056 0.046 0.049 0.050 0.044 0.046
D02 0.625 0.634 0.642 0.654 0.662 0.674 0.681 0.045 0.048 0.039 0.038 0.045 0.042
Note: the linear expansion 1d of the curing paste is more than 0.3 percent, the linear expansion 3d is basically stable, the water-wet expansionrate generally fluctuates between 0.3 and 1.0 percent, and the long-term stability is good.
As can be seen from the above table, the active fly ash and active furnace bottom slag produced by the invention can produce the expansive cement with the grade reaching the national standard No. 525 cement standard with the traditional cement clinker according to a certain proportion.
Example 8 is an example of the method of the present invention for enriching and refining fly ash microbeads from a power plant.
In this example, the "ZLT" blended combustible and the coal are proportioned and controlled according to the material selection and proportioning of the "ZLT" blended combustible in example 1.
In this example, the fineness of the "ZLT" blend and coal mixed grinding is 0.08mm square hole sieve, and the screen residue is 4.5%.
Table 1 shows the technical performance indexes of the fly ash before and after the blending combustion of the ZLT blending combustion substance;
TABLE 1
Sequence of steps Number (C) Name (name) Plant A B plant
Before blending and burning After mixed burning Before blending and burning After mixed burning
1 Fineness (0.08mm square mesh screen) (%) 11 4.6 12 4.4
2 Water demand ratio (%) 98 89 100 90
3 Ignition loss (%) 3.84 1.06 22.61 2.00
4 Water content (%) 1.00 0.86 1.00 0.89
5 Coal saving amount (%) 9.96 8.68
Table 2 shows the indexes of the special grade fly ash products after carbon reduction, bead enrichment and refinement
TABLE 2
Serial number Name (name) Super index
1 Fineness (0.08mm square mesh screen residue) (%) ≤5
2 Water demand ratio (%) ≤90
3 Ignition loss (%) ≤3
4 Water content (%) ≤1
As can be seen from the above examples, the activated fly ash produced by the power plant A and the power plant B after the method of the invention is used for blending and burning the 'ZLT' blending and burning substance in the boiler reaches the national special grade fly ash standard.

Claims (23)

1. A method for purifying and burning coal and generating companion substances is characterized by comprising the following steps: the coal powder is added with a ZLT doped burning substance which is composed of active silicon dioxide containing substance, quicklime, carbide slag, silica fume, iron-rich substance, phosphorus-containing substance, electric furnace phosphorus slag and desulfurization catalyst according to the weight ratio, the ZLT doped burning substance and coal are mixed, ground and homogenized according to a certain proportion and then are tightly adsorbed to form affinity particles, and the affinity particles are sprayed into a coal powder furnace or a cyclone furnace to carry out affinity calcination in the state of gas-solid-liquid suspension reaction, so that the mass transfer, heat transfer and momentum transfer of the burning substance are fastest.
The ZLT doped sintering material comprises the following components in percentage by weight:
1-50 quicklime containing active silicon dioxide 5-98
Carbide slag 0-80
0-10 iron-rich substance and 0-10 phosphorus-containing substance
0-5 desulfurization catalyst for electric furnace phosphorus slag 0-5
The proportion of the ZLT blended combustion materials to the coal is as follows:
50-95% of 'ZLT' blended combustion material 6-55% of coal powder
2. The method for purifying and burning coal and generating companion substance according to claim 1, wherein the method comprises the following steps: the active silica-containing material includes: shale ore, pottery clay, silica fume, clay, and desulfurizing catalyst including vanadium pentoxide (V)2O5) And the like.
3. The method for clean-up combustion of coal and production of companion substance as claimed in claim 1, wherein: the fineness of affinity particles after the mixed grinding of the ZLT mixed burning substance and the coal powder is 0.08mm square-hole sieve, and the sieve residue is 2-30%.
4. The method for clean-up combustion of coal and production of companion substance as claimed in claim 1, wherein: the "ZLT" blended burning substance can be mixed with low-heat value inferior coal and then subjected to affinity calcination in pulverized coal furnaces and cyclone furnaces of power plants and thermal power plants.
5. The method for clean-up combustion of coal and production of companion substance as claimed in claim 1, wherein: the process flow is as follows: selecting materials, proportioning coal and ZLT blended combustion materials, grinding machine, coal powder bin, powder feeder, burner, affinity calcination in coal powder boiler, and mixing with other materials (active coal ash or self-hardening coal ash or belite cement clinker and corresponding furnace slag).
6. The method for coal clean-up combustion and companion production as claimed in claim 1 and claim 5, wherein: the mixture of coal and "ZLT" blended combustion material is fed into a coal mill by a conveyor, and the coal mill can be a ball mill, a vertical mill or any other form of pulverizing system, so that the "ZLT" blended combustion material and coal powder form an affinity particle state.
7. The method for coal clean-up combustion and companion generation as claimed in claims 1 and 5, wherein: the active fly ash micro-beads can be enriched and refined by adjusting the formula of the 'ZLT' blending combustion substance, reducing the viscosity of the reactant and the fineness of 'affinity particles' formed by mixing and grinding the 'ZLT' blending combustion substance and coal.
8. The method for coal clean-up combustion and companion production as claimed in claim 1 and claim 5, wherein: the furnace temperature of the affinity calcination can generate the associated product rich in belite at 800-1340 ℃, and simultaneously reduce the content of nitrogen oxide and CO in the flue gas.
9. The method for clean-up combustion of coal and production of companion substance as claimed in claim 1, wherein: the method for purifying, burning and desulfurizing coal is characterized by that on the basis of consolidation desulfurization, before the flue of boiler and dust-removing device a steam is sprayed into the dust-containing flue gas, and the second step of humidification desulfurization is implemented, and the consolidation desulfurization effect can be up to desulfurization 20-70%, and the further humidification desulfurization can be up to 70-90%.
10. An associated product produced by coal clean-up combustion, comprising: it comprisesComprises the following components in proportion: belite (dicalcium silicate) C2S 5-75
Tricalcium aluminate (C)3A 1-40
Calcium tetra-aluminate ferrite C4AF 1-40
Ignition loss (carbon content) 0-5
11. The companion product produced by the clean combustion of coal as recited in claim 10, further comprising: it can also contain the following components in proportion: aluminum calcium ferrous acid C2(A, F) 1-30 parts of free lime CaO 0.1-8
Free magnesium oxide MgO 0-10
Containing alkali aluminates such as (K, Na)20．8CaO．3Al2O3(K，Na)C8A30-10
Alkali sulfates or nitrates such as (K, Na)2SO4(K，Na)NO30-10
Calcium sulfate and calcium sulfite CaSO4．CaSO30-50
Ca (NO) calcium nitrate and calcium nitrite3)2Ca(NO2)20-10
Phosphorus and other substances 0-10
Calcium sulphoaluminate 3 CaO.3Al2O3．CaSO40-20
12. The companion product produced by the clean combustion of coal as claimed in claim 10 wherein: according to the different ash content and components of raw coal, the proportion of "ZLT" blended combustion material is regulated, so that C in the companion substance "active fly ash" produced after affinity calcination is ensured2The content of S reaches 0-20%.
13. The companion product produced by the clean combustion of coal as claimed in claim 10 wherein: according to the ash content and different components of raw coal, the proportion of "ZLT" blended combustion material is regulated to make C in the "self-hardening fly ash" of associated material produced after affinity calcination2The content of S reaches 20-50%.
14. The companion product produced by the clean combustion of coal as claimed in claim 10 wherein: according to the ash content and different components of raw coal, the proportion of "ZLT" blended burning material is regulated, so that C in the associated "belite" cement clinker produced after affinity calcination2The content of S reaches 50-75%.
15. The companion produced by clean combustion of coal as claimed in claim 10 used in the manufacture of cement or concrete.
16. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the companion substance generated by coal purification and combustion is subjected to superfine grinding (1 nanometer-3 micrometers) and then is used for producing high-technology cement or high-efficiency concrete.
17. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the companion produced by coal clean combustion can be used as a reinforcing agent of any cementing material, and the addition amount of the companion is 0.5-15%.
18. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the high-quality cement can be produced by mixing the companion fly ash generated by coal purification and combustion and the portland cement clinker according to the following mixture ratio:
cement clinker 2-95 companion substance 2-95
0-50 of latent hydraulic material or pozzolanic material
Gypsum 1-7
The fineness of the ground cement powder is required to be 0.08mm square-hole sieve, and the sieve allowance is less than 12%.
19. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the proportion of the high-quality expansive cement produced by mixing the companion substance generated after the high-sulfur coal is burnt with the portland cement clinker is as follows:
30-95 companion substances 2-70 of cement clinker
0-50 of latent hydraulic material or pozzolanic material
Gypsum 1-7
The fineness of the ground cement powder is required to be 0.08mm square-hole sieve, and the sieve allowance is less than 12%.
20. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the companion substance formed after the coal is purified and burned can replace 5 to 95 percent of cement without grinding, and is mixed with sand stone and water to prepare high-quality concrete.
21. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: grinding the companion formed after the coal is purified and combusted, replacing 5-95% of cement, and stirring the ground companion with cement, sand, stone and water to prepare high-quality concrete, wherein the specific surface area of the companion is 3800-6500 square centimeters per kilogram.
22. "self-hardening fly ash" and its use, produced according to claim 14 and claim 15, characterized in that: the companion itself can be used as a hydraulic binder.
23. Use of the companion produced by clean-up combustion of coal as claimed in claim 15 wherein: the high-quality high-grade cement can be prepared by the accompanying substances and 0.1-30% of early strength agent.
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