CN115466632B - Production method for raising and homogenizing material layer temperature of fixed bed high material layer continuous gasification furnace - Google Patents
Production method for raising and homogenizing material layer temperature of fixed bed high material layer continuous gasification furnace Download PDFInfo
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- CN115466632B CN115466632B CN202210830661.1A CN202210830661A CN115466632B CN 115466632 B CN115466632 B CN 115466632B CN 202210830661 A CN202210830661 A CN 202210830661A CN 115466632 B CN115466632 B CN 115466632B
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- 238000002309 gasification Methods 0.000 title claims abstract description 108
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 353
- 239000000292 calcium oxide Substances 0.000 claims abstract description 185
- 238000002844 melting Methods 0.000 claims abstract description 160
- 230000008018 melting Effects 0.000 claims abstract description 156
- 239000002994 raw material Substances 0.000 claims abstract description 123
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 238000010587 phase diagram Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002956 ash Substances 0.000 claims description 313
- 235000012255 calcium oxide Nutrition 0.000 claims description 190
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 147
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 121
- 239000003245 coal Substances 0.000 claims description 42
- 239000002028 Biomass Substances 0.000 claims description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 12
- 230000004907 flux Effects 0.000 claims description 10
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- 235000019738 Limestone Nutrition 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
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- 239000010453 quartz Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
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- 238000007405 data analysis Methods 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
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- 229910052661 anorthite Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 229910052918 calcium silicate Inorganic materials 0.000 description 8
- 235000012241 calcium silicate Nutrition 0.000 description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 229910052882 wollastonite Inorganic materials 0.000 description 8
- 239000010456 wollastonite Substances 0.000 description 8
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- 239000010883 coal ash Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 238000000197 pyrolysis Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052863 mullite Inorganic materials 0.000 description 6
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 6
- 235000019976 tricalcium silicate Nutrition 0.000 description 6
- 239000000378 calcium silicate Substances 0.000 description 5
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- 235000007164 Oryza sativa Nutrition 0.000 description 4
- QEQZNLVOHQQDDK-UHFFFAOYSA-N [Ca+2].[Si+4].[O-2].[Al+3] Chemical compound [Ca+2].[Si+4].[O-2].[Al+3] QEQZNLVOHQQDDK-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
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- 235000009566 rice Nutrition 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000012296 anti-solvent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
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- 239000010865 sewage Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- -1 calcium-silicon-aluminum Chemical compound 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000007316 Xerochrysum bracteatum Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000006184 cosolvent Substances 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/725—Redox processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/726—Start-up
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
- C10J2300/1628—Ash post-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a production method for improving and homogenizing the temperature of a material layer of a fixed bed high material layer continuous gasifier, which comprises the steps of analyzing the content of silicon dioxide, aluminum oxide and calcium oxide in raw material ash; adding a solvent inhibitor to the raw material according to a ternary phase diagram of silicon dioxide, aluminum oxide and calcium oxide so that the ash melting point of the ash of the raw material is higher than 1600 ℃; the method comprises the steps of putting raw materials into a gasification furnace, simultaneously introducing gasifying agents from a furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, and arranging the cyclone air inlet parts at the upper and lower intervals on the periphery of the gasification furnace. The invention can improve the ash melting point of the raw material and the adaptability of the raw material to high-temperature gasification; the uniformity of the axial temperature of the material layer is improved by changing the air inlet mode of the gasifying agent.
Description
Technical Field
The invention relates to the technical field of gasifiers, in particular to a production method for improving and homogenizing the material layer temperature of a fixed bed high material layer continuous gasifier.
Background
At present, an ideal slag gasifier of a coal gasification fixed bed is a single-stage gas producer, the effective gas component can reach more than 92% through a sectional gas making mode of high-temperature slag, liquid slag chilling and solid slag discharging, a gasifying agent is distributed by adopting a spray gun (a traditional grate is abandoned), and slag discharging adopts liquid slag high-pressure difference intermittent slag discharging; because gasifying agents are unevenly distributed, when the material layer height is changed, the material layer resistance is quite different, the radial gasification of a fire layer is uneven, and lime cosolvent is required to be added; because the fluctuation of the ash content of the raw materials is large, the temperature of the liquid slag is difficult to be matched with the ash melting point of ash, the viscosity of the liquid slag is difficult to be stabilized, the discharge amount of the liquid slag is difficult to control, the operation control difficulty is high, the high-load operation cannot be realized, the operation is unstable, and the furnace penetration and the slag discharge are easy to be unsmooth. The pressure bearing burner of the slag discharging port continuously burns, and a great deal of fuel gas is wasted; the water consumption of the chilling liquid slag is large, and the sulfur-containing sewage treatment capacity is large; in addition, the single-stage coal gasifier is only applicable to raw materials with low ash melting points, and the application range of the raw materials is limited.
Low-temperature fixed bed pure oxygen continuous gasification furnace, gasification temperature can not exceed raw materialThe deformation temperature of the coal can reach more than 80 percent of effective gas, the steam decomposition rate can reach more than 65 percent, the residual carbon is about 2 percent, but the gasification strength is only 1300m 3 The square meter is/h; the gasification layer temperature is lower, the gasification layer can only operate below the ash fusion point of the raw material, the load is small, the steam decomposition rate is low, the sewage treatment capacity is large, the operation is uneconomical, the cost is high, and the environmental protection pressure is large; the slag is discharged from the solid, the material layer is shorter, the temperature of the gas outlet is up to 500 ℃, the carried-out matter is more, the gas is cooled by adopting a water washing tower, the sewage treatment capacity is large, the environmental pollution is serious, the slag is not suitable for coal gasification production, and the slag is difficult to popularize in the coal gasification industry until now.
The domestic garbage adopts fluidized bed, grate furnace, circulating fluidized bed or fixed bed gasification to be low-temperature gasification, and the produced coal gas is produced by burning exothermic heat to produce steam or generate electricity, biomass adopts fluidized bed or fixed bed gasification to be low-temperature gasification, carbon gas CO-production is carried out, the technical level is low, and the produced coal gas is produced by burning exothermic heat to produce steam or generate electricity, so that a large amount of CO2 is directly discharged to the atmosphere and cannot be recycled.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a production method for improving the temperature of a high-bed continuous gasification furnace and a homogenizing material layer of a fixed bed, so as to improve the ash melting point of raw materials, improve the adaptability of the raw materials to high-temperature gasification and achieve the technical requirement that the effective components of synthesis gas required by products reach more than 93%; meanwhile, the air inlet mode of the gasifying agent is changed to improve the uniformity of the axial temperature of the material layer and the single-furnace gasification strength.
In order to solve the technical problems, the invention provides a production method for improving and homogenizing the temperature of a material layer of a fixed bed high material layer continuous gasifier, which comprises the following steps:
(a) Analyzing oxides in raw ash, and carrying out data analysis and accounting on the contents of silicon dioxide, aluminum oxide and calcium oxide;
(b) Adding a solvent inhibitor to the raw material according to a ternary phase diagram of silicon dioxide, aluminum oxide and calcium oxide so that the ash melting point of the ash of the raw material is higher than 1600 ℃;
(c) The raw materials are put into a gasification furnace, gasifying agents are simultaneously introduced from the furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, and the cyclone air inlet parts are arranged at the upper and lower intervals on the periphery of the gasification furnace, so that the temperature of a flame layer in the axial direction and the radial direction of a material layer is uniform.
According to the invention, the performance of the existing raw materials is improved according to the gas components required by the product and the high-temperature gasification technical requirements determined by the performances of the existing raw materials, the adaptability of the raw materials to high-temperature gasification is improved, the influence of ash components of the raw materials and each component on ash meltability is mainly researched, according to the ash components of different raw materials, different fusing inhibitors are adopted to improve the ash melting point of the raw materials, the adaptability of the raw materials to high-temperature gasification can be improved by improving the ash melting point of the raw materials, the effective components of the synthesis gas required by the product are achieved, and the economic benefit and the environmental benefit are improved.
Secondly, the invention improves the air inlet mode of the gasifying agent, and improves the traditional mode of only air inlet from the furnace bottom into the mode of air inlet at the same time between the furnace bottom and the furnace periphery, in this way, the flow rate and the flow velocity of the gasifying agent entering from the furnace bottom can be reduced, the material layer in the furnace is prevented from being blown loose, the oxygen-carbon ratio of the furnace bottom is reduced, and the conditions of overhigh gasification intensity and small operation elasticity of the furnace bottom are relieved; the gasification agent is introduced into the gasification furnace by adopting a cyclone air inlet part at the periphery, so that the gasification furnace is in a multi-flame-layer state, the axial temperature of the homogenization layer is facilitated, the effective gas quality is improved, and the CO in a low-temperature region is reduced 2 、CH 4 In addition, the cyclone mode can prolong the contact time of the gasifying agent and the raw materials, the reaction is complete and sufficient, the material layer is mild, the multi-fire-layer layered and graded gasification is carried out, the single-point gasification strength is weak, the temperature of the fire layer is uniform, and the material layer stability is good.
Preferably, when the raw material is coal, the solvent inhibitor is bauxite raw material, clinker or micro-aluminum powder, and the solvent inhibitor is added into Al in the ash of the raw material 2 O 3 +SiO 2 ≥85％、Al 2 O 3 More than or equal to 40 percent of Al 2 O 3 /SiO 2 More than 0.9, and the ash melting point of the raw ash reaches over 1600 ℃.
PreferablyIn the case of Al in the raw ash 2 O 3 /CaO>3, adding the solvent to Al in the raw ash 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO) is more than or equal to 55 percent, so that the ash melting point of the raw material ash is more than or equal to 1600 ℃.
Preferably, when the feedstock is biomass, siO in the feedstock ash 2 /Al 2 O 3 >3, the solvent resistance is limestone, quicklime and slaked lime; the antisolvent is added to the raw material fly ash Al 2 O 3 +SiO 2 +CaO is more than or equal to 80%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, so that the ash melting point of the raw material ash reaches 1600 ℃;
alternatively, siO in the raw ash 2 /Al 2 O 3 >3, the solvent resistance is silica fume, silica, quartz ore or kaolin; the antisolvent is added to SiO in the raw fly ash 2 More than or equal to 70 percent, so that the ash melting point of the raw ash reaches more than 1600 ℃.
Preferably, the cyclone air inlet part comprises a plurality of air inlets uniformly distributed around the periphery of the gasification furnace, an included angle is formed between the central line of the air inlets and a base line on the cross section where the cyclone air inlet part is positioned, and the base line is defined as: and a connecting line between the connecting point of the center line of the air inlet and the side wall of the gasification furnace and the center of the gasification furnace on the cross section.
Preferably, the included angle is 30 °.
Preferably, the distance between two adjacent cyclone air inlet parts in the vertical direction is 1-1.5m.
Preferably, the distance between two adjacent cyclone air inlet parts in the vertical direction is 1-1.5m. Proved by data research and practice: the thickness center of ash slag layer on the grate is 200mm, the edge is 500mm, the thickness of gasification layer above ash slag layer is about 1-1.5m, therefore, the distance between two adjacent cyclone air inlet parts is designed to be 1-1.5m, a plurality of fire layers can be generated in the gasification furnace, and the thickness of gasification layer corresponding to each fire layer is 1-1.5m, so as to improve gasification effect.
According to the ash characteristics of different raw materials, different fusing inhibitors are added to improve the ash melting point of the raw materials and supply CO 2 Provides a higher reaction temperature and longer reaction time for CO 2 Can be more completely reacted to recycle CO 2 The reduction of the gasifying agent into CO provides sufficient conditions and improves the effective gas quality.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. Like elements or portions are generally identified by like reference numerals throughout the several figures. In the drawings, elements or portions thereof are not necessarily drawn to scale.
FIG. 1 is a schematic view of a fixed bed sheet section gasifier according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a fixed bed cyclone inlet in an embodiment of the invention;
FIG. 3 is a plot of the area of different materials for a ternary phase diagram of silicon, aluminum, and calcium oxides according to an embodiment of the present invention;
FIG. 4 is a graph showing the distribution of ternary phase regions of silicon, aluminum, and calcium oxides corresponding to different raw materials of jin coal in accordance with an embodiment of the present invention;
FIG. 5 is a diagram showing the distribution of ternary system phase areas of silicon, aluminum and calcium oxides corresponding to raw materials of jin coal 1 according to an embodiment of the present invention;
FIG. 6 is a graph showing the distribution of ternary system phase areas of silicon, aluminum and calcium oxides corresponding to different raw materials of the household garbage according to the embodiment of the invention;
FIG. 7 is a diagram showing the distribution of the ternary system phase regions of silicon, aluminum and calcium oxides corresponding to the raw material of the household garbage 3 according to the embodiment of the invention;
FIG. 8 is a plot of the ternary phase regions of silicon, aluminum, and calcium oxides corresponding to different biomass feedstock in accordance with an embodiment of the invention;
FIG. 9 is a plot of the ternary phase region of silicon, aluminum, and calcium oxides corresponding to wheat straw according to an embodiment of the present invention;
fig. 10 is a schematic structural view of a fixed bed composite furnace according to an embodiment of the present invention.
Reference numerals:
1-furnace bottom air inlet part; 2-a swirl air inlet part; 21-an air inlet; 3-a second upper furnace cyclone air inlet part; 4-a second lower furnace cyclone air inlet part; 5-the second furnace bottom air inlet part.
Detailed Description
Embodiments of the technical scheme of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and thus are merely examples, and are not intended to limit the scope of the present invention.
It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
The embodiment discloses a production method for improving and homogenizing the temperature of a material layer of a fixed bed high material layer continuous gasifier, which comprises the following steps:
raw material analysis: analyzing the content of all oxides in the raw ash, and carrying out mass fraction accounting of acidic oxides and alkaline oxides;
mixing: adding 0.02-0.2 weight fraction of acidic fluxing agent to a unit weight fraction of feedstock when the acidic oxide is present in the feedstock ash in excess of 60%; adding 0.02-0.2 weight percent of alkaline fluxing agent to a unit weight fraction of the feedstock when the alkaline oxide is present in the feedstock ash in an amount exceeding 60%;
and (3) gasifying: the mixed raw materials obtained in the mixing step are placed into a gasification furnace, gasifying agents are simultaneously introduced from the bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, and the cyclone air inlet parts are arranged at the upper and lower intervals on the periphery of the gasification furnace.
Wherein, in the mixing step, the acid fusing inhibitor refers to bauxite raw materials, clinker or micro-aluminum powder, and the alkaline fusing inhibitor refers to limestone, quicklime or slaked lime.
Referring to fig. 1 and 2, the above-mentioned gasification furnace may be a fixed bed sheet section gasification furnace and a fixed bed composite gasification furnace, the single section gasification furnace has a furnace bottom air inlet portion 1 (i.e. grate) and a plurality of cyclone air inlet portions 2, wherein the plurality of cyclone air inlet portions 2 are arranged at intervals up and down on the periphery of the gasification furnace, and each cyclone air inlet portion 2 includes a plurality of air inlets 21 uniformly distributed around the periphery of the gasification furnace, the air inlets are made of pipes with diameters of 40-80mm, and on the cross section where the cyclone air inlet portions 2 are located, an included angle is formed between the center line of the air inlets 21 and a base line, and the base line is defined as: the connection point of the center line of the air inlet 21 and the side wall of the gasification furnace is connected with the center of the gasification furnace on the cross section. Proved by data research and practice: the thickness center of ash slag layer on the grate is 200mm, the edge is 500mm, the thickness of gasification layer above ash slag layer is about 1-1.5m, and the thickness of gasification layer is the best, therefore, the distance between two adjacent cyclone air inlet parts 2 is designed to be 1-1.5m, a plurality of fire layers can be generated in the gasification furnace, and the thickness of gasification layer corresponding to each fire layer is 1-1.5m, so as to improve gasification effect. In the present embodiment, the pitch of the adjacent two swirl air inlets 2 is preferably 1m.
Further, the cooling cavity is arranged in the furnace wall of the single-section furnace, and cooling liquid can be introduced into the cooling cavity so as to prevent the raw material wall from being hung, and the furnace chamber can be cleaned conveniently.
The included angle is preferably 30 degrees, so that the gasifying agent enters the furnace and can generate rotational flow, the resistance of the material layer is combined, and the radius of an imaginary circle surrounded by the rotational flow gasifying agent is 1/2 of the radius of the furnace body.
According to the requirements of coal gasification technology and production yield, the gasification furnace needs higher gasification intensity and larger gas generation, the diameter and the height of the gasification furnace need to be correspondingly increased and improved, the continuous fixed bed gasification furnace is developed from the height-to-diameter ratio 2 of a single-stage furnace to the height-to-diameter ratio 4, the diameter of a hearth is developed from 2.4 meters to 3.6 meters to 6 meters, the hearth is enlarged, the furnace body is heightened, the original 2 meters of the material layer are increased to 10-15 meters, and the material layer pressure difference is increased from 2-5kpa to 6-8kpa. The improvement of the height of the material layer in the furnace changes the thickness distribution proportion of each layer of the low material layer drying layer, the dry distillation layer, the reduction layer, the oxidation layer and the ash layer, and the thickness of each layer is relatively prolonged. Resulting in the distribution of the gas active ingredientThe gasification agent feeding mode of the gasification furnace needs to be correspondingly improved to stabilize the uniformity and the constancy of the axial direction and the radial direction of the material layer temperature. In the past, the height-diameter ratio of the gasification furnace is generally 2, the height of the material layer is controlled not to exceed the diameter of the hearth, most of the material layer is controlled to be in the radius of the hearth, and the material layer is shorter. If the height distribution size of the 2800mm pure oxygen gasification furnace burden layer is approximately 200mm of ash slag layer, 100mm of oxidation layer, 300mm of first reduction layer, 600mm of second reduction layer, 300mm of dry distillation layer and 200mm of drying layer, the effective gas quality is higher, and can reach about 86%. With the improvement of the material layer, the effective gas quality is relatively reduced to about 84 percent. According to the current production requirement, the height-diameter ratio of the 3.6 meter pure oxygen continuous gasification furnace reaches about 4, when the material layer is full, the height of the material layer can reach 14 meters, and the thickness of the reduction layer, the dry distillation layer and the drying layer is changed as the heights of the ash slag layer and the oxidation layer are unchanged. The thickness of the dry distillation layer and the dry layer is not greatly changed, mainly the thickness of the reduction layer is prolonged, thus the reduction layer is subdivided into a first reduction layer, a second reduction layer, a third reduction layer and a fourth reduction layer, and the first reduction layer mainly reacts with CO 2 The second reduction layer is mainly steam reduction layer CO, and the third reduction layer is mainly steam reduction layer CO 2 The fourth reduction layer is mainly low Wen Liaoceng to generate CH 4 Is a reaction of (a). This results in CO 2 、CH 4 Is increased and the effective gas component is decreased. Theoretical analysis and a large amount of material layer height and gas composition comparison prove that the material is proved by data research and practice: the thickness center of ash layer on the grate is 200mm, the edge is 500mm, the thickness of gasification layer above ash layer is about 1000mm, the thickness of gasification layer is the best, the gas composition is the best, so under the premise of increasing the hearth, increasing the height-diameter ratio, improving the gasification strength, steam decomposition rate and effective gas quality, the height of the material layer is required to be increased, in order to balance the axial and radial material layer temperature and reduce the temperature difference, the embodiment improves the air inlet mode of the gasifying agent, the traditional air inlet mode only from the hearth is changed into the mode that most of gasifying agent enters from the hearth, the flow rate and the flow velocity are relatively reduced, and a small part enters from the air inlet 21, and the swirl imaginary circle radius is 1/2 of the radius of the hearth (uniform gas distribution) and is matched with the air distribution of the grate to improve the air distributionThe uniformity of the axial temperature of the material layer and the gasification strength are improved. For the gasification furnace with 3.6 meters, 6 layers of radial cyclone gasifying agent distribution devices are arranged around the furnace body. The flow ratio of the gasifying agent at the bottom of the furnace to the total gasifying agent at the periphery is 1-5, thus reducing the oxygen-carbon ratio at the bottom of the furnace, relieving the conditions of overhigh gasifying strength at the bottom of the furnace and small operation elasticity, homogenizing the axial temperature of a material layer, improving the effective gas quality and reducing CO in a low-temperature area 2 、CH 4 Is generated.
In practice, as shown in fig. 10, the gasification furnace may also be a fixed bed composite gasification furnace. The fixed bed composite gasification furnace is suitable for gasification of high-volatile matters, such as bituminous coal, biomass, garbage and the like, the lower furnace body is composed of a single-stage furnace and mainly used for gasifying and purifying raw materials to form clean ash slag or carbon, the height of a material layer is relatively thin, and the height-diameter ratio is generally 1.5-2.5; the upper furnace body is mainly subjected to destructive distillation, cracking and gasification due to the influence of moisture and volatile matters of raw materials, tar and moisture volatilization and gasification are eliminated, the height requirement of a material layer is high, and the height-diameter ratio is generally 2.5-3.5. The second furnace bottom air inlet part 5 is distributed in the vertical axial direction, and gasifying agents have vertical impact force on the material layer, so that the material layer is easy to loosen, blow and turn over and more carry-over is caused; the gasification agent of the upper furnace body is distributed by radial horizontal swirl of the second upper furnace swirl air inlet part 3 and the second lower furnace swirl air inlet part 4, the contact time of the gasification agent and raw materials is prolonged by the swirling gasification of the gasification agent, the reaction is complete and full, the material layer is mild, the multi-fire-layer layered and graded gasification is carried out, the single-point gasification intensity is weak, and the temperature of the fire layer is uniform. The fixed bed of the lower furnace body relatively reduces the flow rate and the flow velocity of the axial gasifying agent and the gasification intensity, thereby not only reducing the blow-over phenomenon and the stability of the furnace condition, but also reducing the quantity of carried-out matters. The upper furnace body is a drying section, a carbonization section and a gasification section, in order to prevent volatile matters and moisture from rapidly volatilizing and expanding and causing particle burst, the combustion and gasification speed is controlled by small flow, the contact time of the gasification agent and raw materials is prolonged by the rotational flow of the gasification agent, the gasification speed is low, the completeness of the reaction is improved, and the sensible heat and dust carry-over of the gasification agent are reduced. On the other hand, the main purpose of the upper furnace body is to completely dry the moisture, fully participate in gasification and fully dry distillation and volatilization of volatile matters, and to partially gasify carbon, the height-diameter ratio of the upper furnace body is generally controlled to be 2.5-3.5m, and the spacing distance and distribution condition of gasifying agents of the upper furnace body are consistent with those of the upper furnace body, so that the gasification and the volatilization of the moisture are more facilitated, the volatile matters are thoroughly decomposed, and tar is eliminated. For the composite gasification furnace for producing carbon by pyrolysis, steam and air are mixed in a certain proportion for gas production cooling, so that equipment below the furnace is protected, and production safety below the furnace is ensured. The fixed bed upper and lower furnace body multi-fire layer gasification furnace is suitable for biomass, garbage and sludge forming and bituminous coal gasification, eliminates the bringing of moisture and tar, and realizes environment-friendly and environment-friendly production.
On the basis of improving the air inlet mode, the embodiment further discloses an improvement of a treatment method of the raw material ash so as to improve the ash melting point of the raw material, further improve the adaptability of the raw material to high-temperature gasification and reach the effective components of the synthesis gas required by the product.
The ash in the raw material is mainly metal oxide, and has high-melting point metal oxide, low-melting point oxide, acidic oxide and basic oxide, and the ash is mixed and then melted at a certain temperature to form low-temperature eutectic, and the ash melting point is in the range of 800-1800 ℃. Table 1 is the melting point or amorphous softening point of the primary metal oxide crystals in the ash, and the ash melting point of their mixtures.
TABLE 1 Ash melting Point of the Main component of ash
From the above list it can be seen that: the ash has different components and corresponding ash melting points, and the components of the mixture formed at different temperatures are different and are formed into a whole by the interaction of crystals and amorphous substances; the crystal is used as a framework in ash to play a supporting role, the amorphous is used as a cementing body to play a role in adhering and reinforcing a network connection framework, and SiO in the raw materials is generally used 2 The highest content is next to Al 2 O 3 CaO, therefore, in the raw ash analysis, this example only considers the ash components with the highest ratio of the above 3 components, and does not consider other small amounts of ash components.
The ash melting point of the raw material ash is generally controlled by the ratio of the acid-base compounds, and in general, (Al 2 O 3 +SiO 2 +TiO 2 +SO 3 )/(Fe 2 O 3 +CaO+MgO+K 2 O+Na 2 O) =a/b=1, the regular arrangement of the original crystals is broken by various oxides, various molecules are mutually and uniformly fused together to form a low-temperature eutectic, an equilibrium point is reached, the ash melting point is about 1200 ℃, and the ash melting point is lower. For raw coal, when the acid-base ratio a/b=5, the ash melting point is greater than 1350 ℃. Generally, a/b=between 4 and 17, when a > 60%, the ash has outstanding performance characteristics of acidic oxides (bauxite, quartz, kaolin and mullite are main components), and the mass fraction of the acidic oxides can be increased by adding an acidic solvent to the raw materials so as to increase the ash melting point; for domestic garbage and biomass, when B is more than 60%, the performance characteristics of alkaline oxides (mainly limestone, magnesium stone and potassium oxide) in ash are highlighted, and alkaline fusing inhibitor is added into the raw materials, so that the mass fraction of the alkaline oxides can be increased, and the ash melting point can be improved.
To increase the effective gas content of coal, household garbage, and biomass as gasification raw materials, it is necessary to add a solvent to modify the raw materials to increase ash fusion point. The addition of the high melting point of the flux is generally carried out by adopting lime ore, bauxite raw materials and quartz sand, and kaolin clay can be considered next time in consideration of ash components of raw materials, the production place, yield and economy of the raw materials added with the flux. The technology only researches the influence of the variation of the main silicon, aluminum and calcium three element oxides in the ash on the variation characteristics of the ash melting point. Herein referred to as a sialyl-calcium type raw material, the ash content of the sialyl-calcium type raw material was studied in comparison with the characteristic of the meltability of sialyl oxide and its ternary phase diagram (see fig. 3). The ternary phase diagram is a regular triangle phase diagram with acidic fluxing oxide and acidic non-fluxing oxide, and basic oxide as peaks, and the acidic fluxing oxide refers to SiO 2 、TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Acidic non-fluxing oxides refer to Al 2 O 3 Basic oxide finger CaO, mgO, fe 2 O 3 。
In raw ash, siO is generally produced due to primary ash and secondary ash 2 Higher mass fraction, general SiO 2 /Al 2 O 3 Between 1.2 and 14, siO 2 CaO is between 3 and 30, and is generally CaO and Al 2 O 3 Lower due to SiO 2 Is easy to react with other alkaline oxides to form low-temperature eutectic, resulting in lower ash melting point. In ash, although SiO 2 The content is higher, but usually exists in an amorphous state, the ash melting point is not determined, but is only a necessary factor for improving the ash melting point in the ash, and the ash melting point is dependent on Al 2 O 3 Mass fraction of CaO. This example is based on SiO in ash 2 、Al 2 O 3 The content of CaO in ash is characterized by controlling the ash melting point rise in a targeted way, and the research method is as follows: glass phase amorphous SiO with highest mass fraction in ash 2 Based on adding CaO and Al to raise ash melting point 2 O 3 The research method of the crystal in two directions finds out the proper addition amount of the fusing agent required by different raw materials to reach a certain ash melting point, and the proper addition amount of the fusing agent is targeted for blending. CaO, siO 2 、Al 2 O 3 When the contents of the three components are balanced, the low-temperature mixed eutectic anorthite CaO-Al is generated 2 O 3 ·2SiO 2 The ash melting point is lower than 1553 ℃. With CaO or Al 2 O 3 After a certain value is reached, the acid and alkali are saturated, the adding amount is increased to enable the solvent-resistant material to be free, the performance characteristics of the solvent-resistant material are highlighted, the solvent-resistant material is transformed into a solvent-resistant crystal, and the ash melting point is increased along with the increasing of the adding amount.
Addition of Al to ash 2 O 3 (ash melting point at 2050 ℃) the melting inhibitor leads the conversion of ash oxide to high-melting point substances, improves the ash melting point of ash and the conversion process of substances in ash: al (Al) 2 O 3 Addition of lead SiO 2 CaO-to-anorthite CaO-Al 2 O 3 ·2SiO 2 (ash melting point 1553 ℃) conversion, continuingAddition of Al 2 O 3 The residual ash is converted to kaolinite Al 2 O 3 ·2SiO 2 ·2H 2 O (ash melting point 1785 ℃) conversion, ash melting point increases; with Al 2 O 3 The kaolin is added gradually, the components of the kaolin are increased, the proportion of the kaolin in ash is increased, the melting point of the ash is increased gradually, and the Al is further increased 2 O 3 The mass fraction of the kaolin reaches the limit and is converted into mullite 2SiO 2 ·3Al 2 O 3 The ash melting point is further increased to a higher 1900 ℃; then continue to add Al 2 O 3 Al in the remaining ash 2 O 3 Saturated to form free corundum crystals Al 2 O 3 (ash melting point 2050 ℃ C.).
The CaO (ash melting point is 2570 ℃) is added into the ash to lead the conversion of ash oxide into high-melting point substances, so that the ash melting point is improved, and the conversion process of substances in the ash is as follows: caO-added lead SiO 2 、Al 2 O 3 Conversion of CaO.Al to anorthite 2 O 3 ·2SiO 2 (ash melting point 1553 ℃ C.) CaO is continuously added, and the remained ash is added to gehlenite 2CaO.Al 2 O 3 ·SiO 2 (ash melting point 1593 ℃) conversion; further adding CaO, and adding residual ash to wollastonite CaO/SiO 2 (ash melting point 1544 ℃) conversion; then CaO is continuously added, and the residual ash is divided into calcium metasilicate 2 CaO.SiO 2 (ash melting point 2130 ℃) conversion; continuously adding CaO, and adding residual ash into tricalcium silicate 3 CaO.SiO 2 (ash melting point 2180 ℃ C.) conversion; finally, caO is added, and free crystals (ash melting point 2570 ℃) are formed when CaO in ash is saturated.
Addition of Al to ash 2 O 3 In the process of changing the substance components in ash and ash meltability, the following rules are found by combining with a calcium-silicon-aluminum ternary system phase diagram: in the vicinity of SiO 2 、CaO、Al 2 O 3 Three pure material regions, al 2 O 3 More than 55%, caO more than 50% or CaO less than 5%, siO 2 More than 70 percent of the coal ash component is in the main phase region of corundum, quartz and lime, the full liquid phase temperature ternary system phase diagram of the coal ash component is generally higher, the ash melting point exceeds 1600 ℃, and the center part of the phase diagramThe method is divided into a mixture eutectic low-temperature liquid phase region, the total liquid phase temperature is generally lower, and the chemical components in the region are as follows: al (Al) 2 O 3 ：10—30％；CaO：20-50％， SiO 2 ：40—70％。
In order to improve the application range of the raw materials, the raw materials can be gasified and converted from low-temperature extensive combustion to Gao Wenjie, the effective components of the gas are improved from low content to high content, the economic benefit is considered, the environmental protection benefit is considered, the component performance of the raw material ash is carefully researched, and the main component SiO in the ash is as follows 2 、CaO、Al 2 O 3 Comprehensive combing summary is carried out on the research results.
1、SiO 2 Influence on ash fusion temperature
1) SiO in ash 2 The ash melting point is 1460-1716 ℃ and generally accounts for 30-70 percent. It has the advantages of double property, increased content, more amorphous glass body, early softening of ash slag, easy reaction of alkaline metal oxide to form low-melting-point compound and crystal, and SiO 2 The effect on melting temperature is also with Al 2 O 3 Related to the mass content of Al 2 O 3 When the mass fraction is high, siO 2 The mass fraction increases to increase the melting temperature, with SiO 2 The mass fraction is improved, the temperature difference between ST (softening temperature) and FT (flowing temperature) is increased, and the fluidity of slag is good. A large amount of data display: when SiO 2 At 40-60%, ash melting point temperature is along with SiO 2 Increasing and decreasing (e.g. jin city coal on SiO) 2 : at 40-60%, siO is added 2 Also lowering ash melting point); siO (SiO) 2 When the content exceeds 60%, the slag tends to foam when melted, and porous residues are formed, and the ash melting point is amorphous. This is mainly with Al 2 O 3 、CaO、K 2 O、Na 2 O、Fe 2 O 3 Is related to the content and the type of SiO 2 They are easy to react and fuse well to form low-temperature eutectic. When SiO 2 When the melting temperature of ash is over 70%, the ash melting temperature is higher, and the ash melting point is higher than 1600 ℃;
2) In the high alumina coal ash, al 2 O 3 +SiO 2 At > 75%, siO 2 /Al 2 O 3 The smaller the ash melting point, the higher. SiO (SiO) 2 /Al 2 O 3 The larger the ash melting point, the lower. General coal SiO 2 /Al 2 O 3 1.6-4, high alumina coal 0.7-1.5, and ash mainly containing Al 2 O 3 ·2SiO 2 (metakaolin), 3Al 2 O 3 ·2SiO 2 (mullite) as the main ingredient, siO 2 /Al 2 O 3 In the range of 0.7 to 1.2 (Al 2 O 3 /SiO 2 0.8-1.4), al 2 O 3 +SiO 2 When the melting point of ash is more than 90%, the ash melting point is more than 1600 ℃;
3) When SiO 2 /Al 2 O 3 When less than 3, caO has the lowest melting point at 35%, and the main substance in the ash is gehlenite (2CaO.Al 2 O 3 ·SiO 2 ) In the region, as the CaO content increases, the ash turns to high calcium aluminate and gradually turns to CaO.Al 2 O 3 、12CaO·7Al 2 O 3 、3CaO·Al 2 O 3 The melting point of the ash is gradually increased, and when CaO is more than 50%, the melting point of the ash is more than 1600 ℃;
4) When SiO 2 /Al 2 O 3 > 3 and SiO 2 When the content of the ash is more than 50%, the melting point of the ash is lowest when the CaO is 25%, and the ash content in the ash is mainly anorthite CaO-Al 2 O 3 ·2SiO 2 An area. As the CaO content increases, the ash content gradually shifts to calcium silicate, caO.SiO 2 (wollastonite), 2CaO.2SiO 2 (tobermorite), 2CaO.SiOSiO 2 (calcium metasilicate), 3 CaO. SiO 2 (tricalcium silicate), the ash melting point increases in sequence. When CaO is more than 50%, the ash melting point is more than 1600 ℃.
2、Al 2 O 3 Influence on ash fusion temperature
1) Al in coal ash 2 O 3 Content ratio of SiO 2 Is present in the ash in crystals at a temperature of 2050deg.C, typically between 10-50%, al 2 O 3 The content is increased, the melting temperature of ash can be obviously improved, and Al in the ash 2 O 3 Quality ofStarting from 15%, with Al 2 O 3 The mass fraction of the (a) is increased to form linear regular increase;
2) When Al is 2 O 3 When the mass fraction is increased to 25%, the temperature difference between ST and FT is reduced as the mass fraction is increased. When Al is 2 O 3 When the mass fraction exceeds 40%, the ash melting temperature FT exceeds 1500 ℃ regardless of the change of other components. When Al is 2 O 3 At > 55%, ash melting point exceeds 1600 ℃;
3) Ash content of CaO/Al 2 O 3 ·2SiO 2 (anorthite) or 2 CaO.Al 2 O 3 ·SiO 2 (gehlenite) region, increase Al 2 O 3 The ash content is transferred to the direction of high calcium aluminate and gradually transferred to 12CaO.7Al 2 O 3 (1455℃)、CaO·Al 2 O 3 (1605℃)、CaO·2Al 2 O 3 (1750℃)、CaO·6Al 2 O 3 (1900 ℃ C.) the ash melting point is gradually increased. Al (Al) 2 O 3 At > 55%, the ash melting point is greater than 1600 ℃.
3. Effect of CaO on ash fusion temperature
1) The CaO in the coal ash varies greatly and exists in the ash as crystals, and the CaO is easy to react with the SiO 2 、Al 2 O 3 The melting point of CaO is very high, but reaches 2570 ℃, when the content of CaO in ash reaches a certain amount (more than 30%), caO in ash is saturated to form free crystals, but the ash melting point can be improved, and the ash melting point of ash can be obviously improved by improving the mass fraction of CaO, for example, when the content of CaO in ash reaches more than 40%, the ash capacity point can reach more than 1400 ℃. After limestone is added, when CaO is more than 50%, the ash melting point exceeds 1600 ℃;
2) When SiO 2 /Al 2 O 3 When the content of CaO is less than 3, the melting point of the ash is lowest at 35 percent, and the ash is 2 CaO.Al of gehlte 2 O 3 ·SiO 2 In the region, as the CaO content increases, ash components are transferred to high calcium aluminate and gradually turn to CaO.Al 2 O 3 、12CaO·7Al 2 O 3 、3CaO·Al 2 O 3 Conversion, ash melting point is gradually changedStep up, at Al 2 O 3 +CaO > 52%, and when CaO > 50%, ash melting point is greater than 1600 ℃;
3) When Al is 2 O 3 When CaO is less than 3, siO 2 The ash has the lowest melting point at 47 percent and the ash is formed by anorthite CaO.Al 2 O 3 ·2SiO 2 Area following SiO 2 The content is increased, the mullite region of ash component is transferred, and the temperature is gradually changed to 3Al 2 O 3 ·2SiO 2 。
4) Meeting CaO of 30-35%, when SiO 2 /Al 2 O 3 When less than 3, al 2 O 3 、CaO、SiO 2 The molecules are mutually and evenly fused together to form a low-temperature eutectic, and the ash content is (gehlenite) 2CaO.Al 2 O 3 ·SiO 2 The area range reaches an equilibrium point, and the ash melting point is lower. From Al 2 O 3 -CaO-SiO 2 The ternary phase diagram can also show that the areas with high ash melting points are all mixtures or single-phase substances with high mass fraction of two phases;
5)SiO 2 /Al 2 O 3 > 3, and SiO 2 When the content of the ash is more than 50%, the lowest ash component with the ash melting point of CaO at 25% is CaO.Al (anorthite) 2 O 3 ·2SiO 2 The area range is gradually changed to CaO.SiO as the ash content is changed to the direction of calcium silicate with the increase of CaO content 2 (wollastonite), 2CaO.2SiO 2 (tobermorite), 2CaO.SiOSiO 2 (calcium metasilicate), 3 CaO. SiO 2 (tricalcium silicate), the ash melting point is increased in turn, siO 2 +CaO > 75%, and CaO > 50%, the ash melting point is greater than 1600 ℃;
6) In the general ash, caO with a certain mass fraction is added, the ash melting point is gradually reduced, and when the mass fraction is in a certain range, such as 25 percent (35 percent), the ash melting point is lowest, but when the mass fraction is increased to more than 25 percent (35 percent) along with the increase of the mass fraction of CaO, the ash melting point is sharply increased, namely, the ash melting point is distributed in a V shape.
Further, the relationship between alumina, calcium oxide content and ash melting point (softening point ST) is shown in table 2.
TABLE 2 relation between alumina and calcium oxide content and ash melting point (softening point ST)
| Al 2 O 3 Content% | Ash melting point (ST)/DEGC | CaO content% | Ash melting point (ST)/DEGC |
| 20 | 1250 | 10 | 1500 |
| 30 | 1350 | 15 | 1400 |
| 35 | 1400 | 20 | 1350 |
| 40 | 1500 | 35 | 1300 (lowest) |
| ≥55 | ≥1600 | 40 | 1500 |
| ≥50 | ≥1600 |
Based on the above analysis, the following analyses were performed one by one for the cases where the raw materials were coal, household garbage, and biomass, respectively.
(1) The raw material is coal
The ranges of the melting point of the oxides and the ash in the ash of different raw materials are shown in table 3;
TABLE 3 melting point ranges of oxides and ashes in different raw coal ashes
The ingredients of the different raw materials were analyzed, and the analysis results are shown in table 4:
TABLE 4 analytical Components of different raw materials coal
| Species of type | Moisture content | Ash content | Volatile component | Fixed carbon |
| Huainan 1 | 1.45 | 33.99 | 22.22 | 42.96 |
| Huainan 2 | 1.42 | 9.09 | 29.49 | 60.87 |
| Two-transition coal | 0.54 | 10.4 | 13.2 | 75.38 |
| Gao Yangmei | 0.46 | 8.42 | 16.5 | 74.19 |
| Zhu Jixi | 1.62 | 12.48 | 30.46 | 55.44 |
| Jincheng (a promotion of a city) | 2.59 | 15.92 | 5.21 | 76.28 |
| Jincheng (a promotion of a city) | 3.26 | 20.73 | 9.32 | 66.56 |
| Jincheng (a promotion of a city) | 0.86 | 12.15 | 8.35 | 78.65 |
| Jincheng (a promotion of a city) | 3.59 | 13.54 | 7.86 | 78.21 |
| Jincheng (a promotion of a city) | 2.9 | 15.88 | 9.79 | 73.76 |
| Yangquan coal | 2-3 | 14-16 | 7-8 | 75-84 |
| Uygur county coal | 6.9 | 15.27 | 17.78 | 59.99 |
Analysis of ash fractions of different raw materials is shown in table 5:
TABLE 5 analysis Components of different raw coal ashes and three-phase analysis
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Ternary phase analysis is shown in FIG. 4, and as can be seen from Table 5 and FIG. 4,
for Jincheng coal 3, al 2 O 3 +SiO 2 +CaO＝90.68％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝8.7％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝44.6％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =46.7%. CaO and Al according to jin city coal 1 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see black line intersection points in fig. 4.
For Jincheng coal 2, al 2 O 3 +SiO 2 +CaO＝90.41％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝2.3％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝42.2％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =55.5%. CaO and Al according to jin city coal 2 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the yellow line intersection points in fig. 4.
For Jincheng coal 1, al 2 O 3 +SiO 2 +CaO＝80.06％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝5.2％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝36.6％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =58.2%. CaO and Al according to jin city coal 3 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersection points of blue lines in fig. 4.
CaO and Al in ash of the jin city coal 3, the jin city coal 2 and the jin city coal 1 2 O 3 、SiO 2 The content of (2) satisfies the following relationship: al (Al) 2 O 3 +SiO 2 +CaO＞80％，SiO 2 /Al 2 O 3 In the interval of 1.0-1.7, siO 2 As can be seen from the line drawing analysis in FIG. 4, the ash melting points of the jin coal 3, the jin coal 2 and the jin coal 1 are all in the mullite area, and at this time, al is added 2 O 3 The ash melting point gradually increases. In CaO. Al 2 O 3 ·SiO 2 In ternary phase diagram, AL is added into ash 2 O 3 Substances, highlighting Al 2 O 3 Is used to divert ash component to Al 2 O 3 ·2SiO 2 (metakaolin), 3Al 2 O 3 ·2SiO 2 (mullite), corundum, as Al 2 O 3 /SiO 2 In the range of 0.8 to 1.4 (SiO 2 /Al 2 O 3 0.7-1.2), al 2 O 3 +SiO 2 At > 90%, the ash melting point is greater than 1600 ℃.
To sum up, the contents of the mass fractions of three oxides (CaO, AL2O3 and SiO 2) in the ash of the existing coal raw material meet the following three points:
1、SiO 2 +CaO+AL 2 O 3 > 80%; 2. S/A is in the interval of 0.7-1.7; 3.S/C > 5.
The following increases in the amount of melt-blocking agent to raise the ash melting point by way of example studies;
according to the ash component analysis and ash melting point conditions of the existing raw materials, the ash melting point is improved by accounting the addition amount of the blocking agent according to the ternary system phase diagram of the silicon, calcium and aluminum, 5 percent and 8 percent of the raw materials of Jincheng 1 with the lowest ash melting point are selected to be added according to the weight of the raw materials, and CaO and AL are calculated 2 O 3 、SiO 2 The content of the ash is marked in a ternary system phase diagram of the silicon-calcium-aluminum oxide to determine the ash melting point temperature region of 1+5% in jin city and 1+8% in jin city; wherein, the ash content of the raw material coal after adding the antisolvent is shown in table 6:
TABLE 6
Ternary phase diagram analysis is shown in fig. 5;
the melting resistance of the added alumina is 5 percent and 8 percent of the weight of the raw material, and is marked at CaO-AL 2 O 3 -SiO 2 In the ternary phase diagram (FIG. 5), caO+AL 2 O 3 +SiO 2 ＝100,CaO＝5.19；AL 2 O 3 ＝36.6； SiO 2 = 58.23 (blue line intersection); caO+AL 2 O 3 +SiO 2 ＝100,CaO＝3.7；AL 2 O 3 ＝55.16 SiO 2 = 41.78 (yellow line intersection); caO+AL 2 O 3 +SiO2＝100,CaO＝3.12；AL 2 O 3 ＝61.96 SiO 2 = 34.96 (red line intersection);
as can be seen from the ternary system phase diagram of calcium, silicon and aluminum, by adding the solvent resistance agent in jin coal 1, al in raw material ash is caused 2 O 3 /CaO>3 Al in the raw ash 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO) is more than or equal to 55 percent, and the ash melting point of the raw ash is more than or equal to 1600 ℃. Specifically, the melting point of jin coal 1 ash is 150 ℃ different from that of jin coal 1+5% ash, and the melting point of jin coal 1+5% and that of jin coal 1+8% ash are 50 ℃. Since only the ash melting point of the three main mixtures of calcium, silicon and aluminum is studied, other secondary oxides in the ash can have an effect on the ash melting point of the ash, so that the ash melting point displayed in the calcium, silicon and aluminum three-system phase diagram is higher, but the actual production and application results are not affected.
Pure alumina is adopted in calculation, bauxite raw ore (containing 70-98% of alumina) is adopted in industrial production; because of the increased difference of the components of the calcium-silicon-aluminum oxide of different raw materials, the different raw materials are added according to the conditions and the ash melting point requirement, and the weight of the raw materials is generally not more than 10 percent. In order to expand the application range of the raw materials and control the actual addition amount of the fusing inhibitor in practical production to 2-20% of the weight of the raw materials
In combination, when the raw material is coal, the solvent is bauxite raw material, clinker or micro-aluminum powder, and the solvent is addedTo Al in the raw ash 2 O 3 +SiO 2 ≥85％、Al 2 O 3 More than or equal to 40 percent of Al 2 O 3 /SiO 2 More than 0.9, can lead the ash melting point of the raw ash to be more than or equal to 1600 ℃.
If Al in the raw ash 2 O 3 /CaO>3, adding a solvent inhibitor to Al in the raw ash 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO) is more than or equal to 55 percent, and the ash melting point of the raw ash is more than or equal to 1600 ℃.
(2) The raw material is household garbage
When the raw material is household garbage, siO in ash of the raw material 2 /Al 2 O 3 >3, the solvent is limestone, quicklime or slaked lime; addition of a dissolution inhibitor to the raw ash of Al 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, and the ash melting point of the raw material ash is more than or equal to 1600 ℃.
The different garbage components are analyzed, and the analysis results are shown in table 7:
TABLE 7
| Species of type | Moisture content | Ash content | Volatile component | Fixed carbon |
| Household garbage 1 | 43.8 | 21.9 | 26.2 | 8.1 |
| Household garbage 2 | 18 | 14.8 | 52.9 | 14.3 |
| RDF1 | 27.29 | 31.53 | 48 | 20.48 |
| RDF2 | 26.37 | 26.40 | 48.66 | 24.94 |
| RDF3 | 27.96 | 27.79 | 49.08 | 23.13 |
Three kinds of household garbage are described in detail below. Table 8 shows the ash content analysis tables and ternary phase diagram analysis of three kinds of household garbage.
Table 8 ash content analysis table of household refuse
For household garbage 1, al 2 O 3 +SiO 2 +CaO＝79.7％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝30.7％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝19.5％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =49.8%. CaO and Al according to household garbage 1 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the yellow line intersection points in fig. 6.
For domestic garbage 2, al 2 O 3 +SiO 2 +CaO＝76.0％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝40.5％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝13.8％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =45.7%. CaO and Al according to household garbage 2 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see black line intersection points in fig. 6.
For household garbage 3, al 2 O 3 +SiO 2 +CaO＝76.52％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝24.5％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝15.1％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =60.4%. CaO and Al according to household garbage 3 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersection points of blue lines in fig. 6.
By analyzing the ash components of the household garbage, the following conclusion is obtained:
1.SiO 2 +CaO+AL 2 O 3 more than 75 percent, the content of calcium oxide is generally not less than 20 percent, the content of silicon oxide with alumina not more than 10 percent is obviously reduced compared with raw material coal,
2.S/A < 3, the melting point of the ash is lowest when CaO is 35%, the melting point of the ash is increased along with the increase of the CaO content,
3.S/A > 3 and SiO 2 High content in ashAt 50%, the melting point of CaO is lowest at 25%, and as the CaO content increases, the melting point of the ash increases.
SiO2 < 60%, increase SiO 2 The content of the silica, clay and quartz ore is not suitable for increasing the ash melting point.
5. The quick lime has low price and the bauxite has higher price.
The content of CaO in the garbage ash is higher, so that the problem of lower melting point of the garbage ash is solved, and the amount of CaO is highlighted to form anorthite, wollastonite ash melting point 1540 ℃, wollastonite 1590 ℃, calcium silicate 2130 ℃, tricalcium silicate and lime; lime ore is adopted in the production to increase the amount of calcium oxide.
Of the ash contents of the household garbage 1, the household garbage 2 and the household garbage 3, siO of the household garbage 1 2 /Al 2 O 3 <3, the screening requirements of the raw materials in the embodiment are not met, but SiO of the household garbage 2 and the household garbage 3 are not met 2 /Al 2 O 3 >3, belonging to the range of raw materials which can be processed in the embodiment; further, in the case of the refuse 3 having the lowest content of refuse calcium oxide, since limestone is relatively inexpensive, the addition amount of the solvent is 10% by weight of the raw material, and the ash content after the addition of the solvent is shown in table 9:
TABLE 9
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The ternary system phase diagram of the garbage 3 is shown in FIG. 7, and calcium oxide is added to the raw material to satisfy Al in the ash of the raw material 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, and the ash melting point of the raw material ash is more than or equal to 1600 ℃. Specifically, the ash melting point of the waste 3 differs from the ash melting point temperature of the waste 3+10% by 800 ℃. Since only three main components of calcium, silicon and aluminum are studiedThe ash melting point of the mixture is affected by other secondary oxides in the ash, so that the ash melting point shown in the calcium-silicon-aluminum three-system phase diagram is higher, but the actual production and application results are not affected.
Pure calcium oxide is adopted in calculation, and slaked lime is adopted in industrial production; because of the increased difference of the components of the calcium-silicon-aluminum oxide of different raw materials, the different raw materials are added according to the conditions and the ash melting point requirement, and the weight of the raw materials is generally not more than 10 percent. In order to expand the application range of the raw materials and control the actual addition amount of the fusing agent in the actual production application to be 2-20% of the weight of the raw materials.
(3) Raw materials are biomass
For biomass, siO in the ash of the raw material 2 /Al 2 O 3 >3, the solvent is limestone, quicklime and slaked lime; adding a solvent resistant agent into raw material fly ash to obtain Al 2 O 3 +SiO 2 +CaO is more than or equal to 80%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, so that the ash melting point of the raw material ash can reach 1600 ℃;
alternatively, siO in the raw ash 2 /Al 2 O 3 >3, the solvent is silica fume, silica, quartz ore or kaolin; adding a solvent resistant agent into the raw material fly ash to form SiO 2 More than or equal to 70 percent, the ash melting point of the raw ash can reach 1500-1700 ℃. The contents of the components in the ash of different biomass and ash melting points are shown in Table 10:
table 10
The content of the different biomass components is shown in table 11:
TABLE 11
| Species of type | Moisture content | Ash content | Volatile component | Fixed carbon |
| Ranges of the components | 2-11 | 3-13 | 61-74. | 12-20 |
Several different biomass were subjected to the following composition analysis, the analysis being shown in table 12:
table 12
Then, the ash components and ternary phase diagrams of the following different biomass materials were analyzed; the analysis results are shown in table 14 and fig. 8:
TABLE 14
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For biomass 1 (sunflower shell), al 2 O 3 +SiO 2 +CaO＝48％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝33％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝6％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =61%. CaO, al according to Biomass 1 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see black line intersection points in fig. 6.
For biomass 2 (straw), al 2 O 3 +SiO 2 +CaO＝80.72％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝3.7％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝1.3％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =92.5%. CaO, al based on biomass 2 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersection points of blue lines in fig. 6.
For biomass 3 (wheat straw), al 2 O 3 +SiO 2 +CaO＝55.2％，CaO/(Al 2 O 3 +SiO 2 +CaO)＝6.7％, Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO)＝6.3％,SiO 2 /(Al 2 O 3 +SiO 2 +cao) =87.0%. CaO, al based on biomass 3 2 O 3 And SiO 2 The corresponding intersection points are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the yellow line intersection points in fig. 6.
As can be seen from table 14 and fig. 8:
1, rice straw and rice straw, the ash content of leaves is high, and the rest of the straw and trees are not high;
2, silicon oxide, calcium oxide and potassium oxide are high in content, and the difference of different biomass components is large;
3, the silicon oxide content is not more than 70 percent (rice husk is removed), and a silicon oxide flux is not generally adopted; siO (SiO) 2 Less than 60 percent, increase SiO 2 The content of the silica, clay and quartz ore is not suitable for the silica, clay and quartz ore, and the ash melting point is not increased.
4. The alumina content is too small, and the cost of adopting alumina as a flux is too high
5.S/A > 3 and SiO 2 The ash content is more than 50%, the melting point of the ash is lowest when the CaO content is 25%, and the melting point of the ash is increased along with the increase of the CaO content.
6.CaO、K 2 O-homopolar interactions do not affect each other, related data show K 2 The ash melting point is lowest at 13.9% O, with K 2 The ash melting point increases with increasing O content.
In addition, the biomass straw, wheat straw and sunflower shell all meet the requirement of SiO 2 /Al 2 O 3 >3, the ash content of the biomass is low, and in order to improve the ash melting point, the cost is comprehensively considered, and the treatment method comprises the following steps: the CaO is highlighted to form anorthite, wollastonite, calcium silicate, tricalcium silicate and lime; the related data display: the wheat straw and rice straw adopts AL 2 O 3 、AL 2 O 3 .2SiO 2 CaO as a flux, at the same amount, ash melting point temperature AL 2 O 3 ＞AL 2 O 3 .2SiO 2 CaO, but not so much. Lime ore is adopted in the production to increase the amount of calcium oxide, so that the amount of CaO is highlighted, and anorthite, wollastonite ash melting point 1540 ℃, wollastonite 1590 ℃, calcium silicate 2130 ℃ and tricalcium silicate and lime are formed;
then, the above biomass wheat straw was used as an example, and the addition amount of the flux was calculated to be 10% by weight of the raw material because limestone was relatively inexpensive, and the ash content after the addition of the solvent was shown in table 15:
TABLE 15
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The ternary system phase diagram of the biomass is shown in FIG. 9, and calcium oxide is added into the raw material to enable the raw material ash to meet the requirement of Al in the raw material fly ash 2 O 3 +SiO 2 +CaO is more than or equal to 80%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, and the ash melting point of the raw ash can reach more than or equal to 1600 ℃. Specifically, the melting point of wheat straw ash differs from the temperature of 600 ℃ from the melting point of wheat straw +10% ash. Since only the ash melting point of the three main mixtures of calcium, silicon and aluminum is studied, other secondary oxides in the ash can have an effect on the ash melting point of the ash, so that the ash melting point displayed in the calcium, silicon and aluminum three-system phase diagram is higher, but the actual production and application results are not affected.
Pure calcium oxide is adopted in calculation, and slaked lime is adopted in industrial production; because of the increased difference of the components of the calcium-silicon-aluminum oxide of different raw materials, the different raw materials are added according to the conditions and the ash melting point requirement, and the weight of the raw materials is generally not more than 10 percent. In order to expand the application range of the raw materials and control the actual addition amount of the fusing agent in the actual production application to be 2-20% of the weight of the raw materials.
In the embodiment, the fusing inhibitor is added into the raw material to improve the ash fusion point of the raw material, and meanwhile, the air inlet mode of the gasifying agent is improved, the uniformity of the axial temperature of the material layer is improved, and CO is fed 2 Provides a higher reaction temperature and longer reaction time for CO 2 Can be more completely reacted to recycle CO 2 The reduction of the gasifying agent into CO provides sufficient conditions and improves the effective gas quality. Whereas in Wen Liaoceng at 1600℃C, CO 2 Almost all of the conversion into CO 2 Has the double effects of environmental protection and economic benefit. Through intensive research and experiments, CO is adopted 2 Furnace returning technology process, utilizing compressor to make CO 2 Is sent into the gasification furnace through an air pipeline to replace a part of steam. Experiments show that CO 2 After returning to the furnace, the production operation is stable. CO 2 Furnace return test data can realize CO 2 Greatly converts into the effective component CO, not only reduces the CO 2 Is used for the discharge amount of the fuel,but also reduces the usage amount of steam and realizes energy conservation and environmental protection.
In the description of the present invention, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, systems, and techniques have not been shown in detail in order not to obscure an understanding of this description.
In the description of the present specification, a description of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., means that a particular feature, system, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, systems, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (8)
1. The production method for increasing and homogenizing the temperature of the material layer by the fixed bed high material layer continuous gasifier is characterized by comprising the following steps:
(a) Analyzing oxides in raw ash, and carrying out data analysis and accounting on the contents of silicon dioxide, aluminum oxide and calcium oxide;
(b) According to the ternary phase diagram of silicon dioxide, aluminum oxide and calcium oxide, adding a blocking agent into the raw material so as to enable the ash melting point of the ash of the raw material to be higher than 1600 ℃;
(c) The method comprises the steps of putting raw materials into a gasification furnace, simultaneously introducing gasifying agents from a furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, and arranging the cyclone air inlet parts at the upper and lower intervals on the periphery of the gasification furnace.
2. The production method according to claim 1, wherein when the raw material is coal, the flux is bauxite raw material, clinker or micro-aluminum powder, and the flux is added to Al in the raw material ash 2 O 3 +SiO 2 ≥85％、Al 2 O 3 More than or equal to 40 percent of Al 2 O 3 /SiO 2 More than 0.9, and the ash melting point of the raw ash reaches over 1600 ℃.
3. The method of claim 2, wherein if Al in the raw ash 2 O 3 /CaO>3, adding the solvent to Al in the raw ash 2 O 3 +SiO 2 +CaO is more than or equal to 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 +CaO) is more than or equal to 55 percent, so that the ash melting point of the raw material ash is more than or equal to 1600 ℃.
4. The method of claim 1, wherein when the feedstock is biomass, the feedstock ash is SiO 2 /Al 2 O 3 >3, the fusing inhibitor is limestone, quicklime and slaked lime; the solvent is added to the raw material fly ash Al 2 O 3 +SiO 2 +CaO is more than or equal to 80%, and CaO/(Al) 2 O 3 +SiO 2 +CaO) is more than or equal to 50 percent, so that the ash melting point of the raw ash reaches more than 1600 ℃;
alternatively, siO in the raw ash 2 /Al 2 O 3 >3, the resistorThe flux is silica fume, silica, quartz ore or kaolin; the said flux is added to SiO in the said raw fly ash 2 More than or equal to 70 percent, so that the ash melting point of the raw ash reaches more than 1600 ℃.
5. The method of claim 1, wherein the swirl inlet portion comprises a plurality of inlets uniformly distributed around the periphery of the gasifier, and wherein an included angle is formed between a centerline of the inlet and a baseline of the inlets in a cross section of the swirl inlet portion, the baseline being defined as: and a connecting line between the connecting point of the center line of the air inlet and the side wall of the gasification furnace and the center of the gasification furnace on the cross section.
6. The method of claim 5, wherein the included angle is 30 °.
7. The production method according to claim 5, wherein the pitch of two adjacent swirl air inlets in the vertical direction is 1-1.5m.
8. The method of claim 1, wherein CO is recovered 2 As a reducing agent.
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