CN115466632A - Production method for increasing and homogenizing temperature of material bed by fixed bed high material bed continuous gasification furnace - Google Patents
Production method for increasing and homogenizing temperature of material bed by fixed bed high material bed continuous gasification furnace Download PDFInfo
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- 238000002844 melting Methods 0.000 claims abstract description 164
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- 238000010587 phase diagram Methods 0.000 claims abstract description 33
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 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
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- 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
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- 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 increasing and homogenizing the temperature of a material bed of a fixed bed high material bed continuous gasification furnace, which comprises the steps of analyzing the content of silicon dioxide, aluminum oxide and calcium oxide in raw material ash; adding a dissolution inhibitor to the raw material according to a ternary system phase diagram of silicon dioxide, aluminum oxide and calcium oxide so as to enable the ash melting point of the ash of the raw material to be more than 1600 ℃; raw materials are put into a gasification furnace, and gasification agents are simultaneously introduced from a furnace bottom air inlet part of the gasification furnace and a plurality of rotational flow air inlet parts of the gasification furnace, wherein the rotational flow air inlet parts are arranged at the periphery of the gasification furnace at intervals up and down. The invention can improve the ash melting point of the raw material and improve the adaptability of the raw material to high-temperature gasification; and the uniformity of the axial temperature of the material layer is improved by changing the air inlet mode of the gasification agent.
Description
Technical Field
The invention relates to the technical field of gasification furnaces, in particular to a production method for increasing and homogenizing the temperature of a material bed of a fixed bed high material bed continuous gasification furnace.
Background
At present, an ideal slag gasification furnace of a coal gasification fixed bed is a single-stage gas producer, effective gas components can reach more than 92 percent through a segmented gas making mode of high-temperature slag, liquid slag chilling and solid slag discharging, a gasification agent is distributed by a spray gun (a traditional grate is abandoned), and slag discharging adopts liquid slag height pressure difference intermittent slag discharging; because the gasification agent is distributed unevenly, the material layer resistance is greatly different when the material layer height is changed, the fire layer is gasified unevenly in the radial direction, and a lime cosolvent is required to be added; because the ash component of the raw material has large fluctuation, the temperature of the liquid slag is difficult to be matched with the ash melting point of the ash, the viscosity of the liquid slag is difficult to be stable, the discharge amount of the liquid slag is difficult to control, the operation control difficulty is large, 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 of the slag discharge port supports the continuous combustion of the combustor, so that a large amount of fuel gas is wasted; the water consumption of chilling liquid slag is large, and the treatment capacity of sulfur-containing sewage is large; in addition, the single-stage coal gasifier is only suitable for raw materials with low ash melting points, and the application range of the raw materials is limited.
The gasification temperature of the low-temperature fixed bed pure oxygen continuous gasification furnace cannot exceed the deformation temperature of raw material coal, although the effective gas can reach more than 80 percent, the steam decomposition rate can reach more than 65 percent, and the residual carbon is about 2 percent, the gasification intensity is only 1300m 3 Square meter per hour; the gasification layer has lower temperature, can only operate below the ash melting point of the raw material, and has small load, low steam decomposition rate, large sewage treatment capacity, uneconomical operation, high cost and large environmental protection pressure; solid slag discharge, short material layer, coal gas outlet temperature up to 500 ℃, more entrainment substances, large sewage treatment capacity due to the adoption of a water washing tower for cooling coal gas, serious environmental pollution, unsuitability for coal gasification production and difficult popularization in the coal gasification industry up to now.
The domestic garbage is gasified at low temperature by adopting a fluidized bed, a grate furnace, a circulating fluidized bed or a fixed bed, the produced coal gas is combusted to release heat to produce steam or generate electricity, the biomass is gasified at low temperature by adopting the fluidized bed or the fixed bed, the carbon gas is coproduced, the technical level is low, the produced coal gas is combusted to release heat to produce steam or generate electricity, and a large amount of CO2 is generated and directly discharged to the atmosphere and cannot be recycled.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide a production method for increasing and homogenizing the temperature of a material layer of a fixed bed high material layer continuous gasification furnace, so as to increase the ash melting point of a raw material, improve the adaptability of the raw material to high-temperature gasification and achieve the technical requirement that the effective component of synthesis gas required by a product reaches more than 93 percent; meanwhile, the air inlet mode of the gasifying agent is changed, so that the uniformity of the axial temperature of the material layer is improved, and the gasification strength of a single furnace is improved.
In order to solve the technical problem, the invention provides a production method for increasing and homogenizing the temperature of a material bed of a fixed bed high material bed continuous gasification furnace, which comprises the following steps:
(a) Analyzing oxides in the raw material ash, and performing data analysis accounting on the contents of silicon dioxide, aluminum oxide and calcium oxide;
(b) Adding a dissolution inhibitor to the raw material according to a ternary system phase diagram of silicon dioxide, aluminum oxide and calcium oxide so as to enable the ash melting point of the ash of the raw material to be more than 1600 ℃;
(c) The method comprises the steps of putting raw materials into a gasification furnace, simultaneously introducing gasification agents from a furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, wherein the cyclone air inlet parts are arranged at the periphery of the gasification furnace at intervals up and down, so that the temperature of a material layer in the axial direction and the radial direction is uniform.
According to the invention, firstly, according to the gas components required by the product and the technical requirements of high-temperature gasification determined by the performance of the existing raw materials, the performance of the existing raw materials is improved, and the adaptability of the raw materials to high-temperature gasification is improved.
Secondly, the invention also improves the gas inlet mode of the gasification agent, and improves the traditional mode of only gas inlet from the furnace bottom into the mode of gas inlet from the furnace bottom and gas inlet at the same time around the furnace bottom and the furnace periphery, and by adopting the mode, the flow and the flow rate of the gasification agent entering 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, the over-high gasification intensity of the furnace bottom is relieved,a condition of low operational flexibility; the gasification agent is introduced into the periphery of the gasification furnace in a mode of a rotational flow air inlet part, so that the interior of the gasification furnace is in a multi-fire bed state, the axial temperature of a material bed is favorably homogenized, the effective gas quality is improved, and the CO in a low-temperature area is reduced 2 、CH 4 In addition, the contact time of a gasification agent and raw materials can be prolonged by a rotational flow mode, the reaction is complete and sufficient, the material bed is mild, multiple fire layers are arranged, layered and graded for gasification, the single-point gasification strength is weak, the fire layer temperature is uniform, and the material bed stability is good.
Preferably, when the raw material is coal, the dissolution inhibitor is bauxite raw material, clinker or micro-aluminum powder, and the dissolution inhibitor is added to Al in 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 ash content of the raw material reaches more than 1600 ℃.
Preferably, if Al in the raw ash 2 O 3 /CaO>3, adding the dissolution inhibitor to Al in the raw material ash 2 O 3 +SiO 2 CaO is not less than 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 And + CaO) is more than or equal to 55 percent, so that the ash melting point of the ash of the raw material is more than or equal to 1600 ℃.
Preferably, when the raw material is biomass, siO in the ash of the raw material 2 /Al 2 O 3 >3, the dissolution inhibitor is limestone, quicklime and hydrated lime; the dissolution inhibitor is added to the raw material fly ash Al 2 O 3 +SiO 2 The CaO is more than or equal to 80 percent, and the CaO/(Al) 2 O 3 +SiO 2 + CaO) is more than or equal to 50 percent, so that the ash melting point of the ash of the raw material reaches 1600 ℃;
or SiO in the raw ash 2 /Al 2 O 3 >3, the dissolution inhibitor is micro silicon powder, silica, quartz ore or kaolin; the dissolution inhibitor is added to SiO in the raw material fly ash 2 More than or equal to 70 percent, and the ash melting point of the ash content of the raw material reaches more than 1600 ℃.
Preferably, the cyclone air inlet part comprises a plurality of air inlets uniformly distributed around the circumference of the gasifier, and on the cross section of the cyclone air inlet part, an included angle is formed between the center line of the air inlets and a base line, and the base line is defined as: and the connecting point of the central line of the gas inlet and the side wall of the gasification furnace is connected with the connecting line of the center of the gasification furnace on the cross section.
Preferably, the included angle is 30 °.
Preferably, the distance between two adjacent cyclone air inlets in the vertical direction is 1-1.5m.
Preferably, the distance between two adjacent cyclone air inlets in the vertical direction is 1-1.5m. The data research and practice prove that: the center of the thickness of the ash layer on the grate is 200mm, the edge of the ash layer is 500mm, the thickness of the gasification layer above the ash layer is about 1-1.5m, the thickness of the gasification layer is the optimal gasification layer, 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 the gasification layer corresponding to each fire layer is 1-1.5m, so that the gasification effect is improved.
The invention adds different fusing retarding agents to different raw materials according to the characteristics of ash content of the raw materials so as to improve the ash fusion point of the raw materials and supply CO 2 The reduction provides higher reaction temperature and longer reaction time, so that CO can be obtained 2 Can be more completely reacted for recovering CO 2 The gasification agent is used for reducing the CO, so that sufficient conditions are provided, and the effective gas quality is improved.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic structural view of a fixed-bed single-stage gasification furnace according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a fixed bed cyclone gas inlet section according to an embodiment of the present invention;
FIG. 3 is a distribution diagram of different material regions of a ternary phase diagram of silicon, aluminum and calcium oxides according to an embodiment of the present invention;
FIG. 4 is a plot of the three-element phase distribution of Si, al and Ca oxides for different coal feedstocks according to an embodiment of the present invention;
FIG. 5 is a schematic illustration of a three-element phase distribution diagram of oxides of silicon, aluminum and calcium corresponding to a coal feed of Jintai coal 1 in accordance with an exemplary embodiment of the present invention;
FIG. 6 is a three-element phase distribution diagram of oxides of silicon, aluminum and calcium corresponding to different raw materials of domestic garbage according to an embodiment of the present invention;
FIG. 7 is a phase distribution diagram of the ternary system of silicon, aluminum and calcium oxide corresponding to the raw material of the household garbage 3 in the embodiment of the present invention;
FIG. 8 is a three-element phase region distribution diagram of silicon, aluminum and calcium oxide corresponding to different biomass raw materials according to an embodiment of the present invention;
FIG. 9 is a distribution diagram of three-component phase domains of silicon, aluminum and calcium oxide corresponding to wheat straw in accordance with 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-a furnace bottom air inlet part; 2-a cyclone air inlet part; 21-an air inlet; 3-a second upper furnace cyclone air inlet part; 4-a cyclone air inlet part of the second lower-section furnace; 5-a second hearth gas inlet.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The embodiment discloses a production method for increasing and homogenizing the temperature of a material bed by a fixed bed high material bed continuous gasification furnace, which comprises the following steps:
raw material analysis: analyzing the content of all oxides in the raw material ash, and carrying out mass fraction accounting on the acidic oxides and the basic oxides;
mixing: when the ratio of the acid oxide in the ash content of the raw material exceeds 60%, adding 0.02-0.2 weight fraction of acid fluxing agent into one unit weight fraction of the raw material; when the proportion of the basic oxide in the ash of the raw material exceeds 60 percent, 0.02 to 0.2 weight percent of basic fusing inhibitor is added into one unit weight percent of the raw material;
a gasification step: and putting the mixed raw material obtained in the mixing step into a gasification furnace, and simultaneously introducing a gasification agent from a furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, wherein the plurality of cyclone air inlet parts are arranged at the periphery of the gasification furnace at intervals up and down.
In the mixing step, the acidic fluxing agent refers to bauxite raw material, clinker or micro-aluminum powder, and the alkaline fluxing agent refers to limestone, quicklime or hydrated lime.
Referring to fig. 1 and 2, the above-mentioned gasification furnace may be a fixed bed single-stage gasification furnace and a fixed bed composite gasification furnace, the single-stage gasification furnace has a furnace bottom air inlet portion 1 (i.e. a 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, on the cross section where the cyclone air inlet portion 2 is located, an included angle is formed between the center line of the air inlet 21 and a base line, and the base line is defined as: the connecting point of the central line of the gas inlet 21 and the side wall of the gasification furnace is connected with the connecting line of the center of the gasification furnace on the cross section. The data research and practice prove that: the center of the thickness of the ash layer on the grate is 200mm, the edge of the ash layer is 500mm, the thickness of the gasification layer above the ash layer is about 1-1.5m, the thickness of the gasification layer is the optimal gasification layer, 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 the gasification layer corresponding to each fire layer is 1-1.5m, so that the gasification effect is improved. In the present embodiment, the distance between two adjacent swirl inlet portions 2 is preferably 1m.
Further, be equipped with the cooling chamber in the oven of single-stage furnace of this embodiment, can let in the coolant liquid in the cooling chamber to prevent that the condition of raw materials wall built-up from taking place, be favorable to clearing up furnace.
The included angle is preferably 30 degrees, then the gasifying agent enters the furnace and can generate rotational flow, and the radius of an imaginary circle formed by the gasifying agent of the rotational flow is 1/2 of the radius of the furnace body in combination with the resistance action of the material layer.
According to the requirements of coal gasification technology and production yield, the gasification furnace needs higher gasification strength and larger gas forming amount, the diameter and height of the gasification furnace need to be correspondingly increased and improved, the height-diameter ratio of a single-stage furnace is changed from 2 to 4, the diameter of a hearth is changed from 2.4 to 3.6 to 6 meters, the hearth is increased, a furnace body is heightened, the material bed is also increased from 2 to 10 to 15 meters, and the material bed pressure difference is increased from 2 to 5kpa to 6 to 8kpa. The improvement of the material bed height in the furnace changes the thickness distribution proportion of each layer of the low material bed drying layer, the dry distillation layer, the reduction layer, the oxidation layer and the ash residue layer, and the thickness of each layer is relatively elongated. The effective components of the gas are changed, so the charging mode of the gasification agent of the gasification furnace needs to be correspondingly improved to stabilize the uniform and constant axial and radial temperature of the material layer. The height-diameter ratio of the prior gasification furnace is generally 2, the height of a material layer is controlled not to exceed the diameter of a hearth, most of the material layer is controlled to be in the radius of the hearth, and the material layer is shorter. For example, the material layer height distribution size of the 2800mm pure oxygen gasification furnace is about 200mm ash layer, 100mm oxide layer, 300mm first reduction layer, 600mm second reduction layer, 300mm dry distillation layer and 200mm drying layer, the effective gas quality is high and can reach about 86%. Along with the increase of the material layer, the effective gas quality is relatively reduced to about 84 percent. According to the requirement of the current production, the height-diameter ratio of the 3.6 m pure oxygen continuous gasification furnace reaches about 4, when the full charge layer is controlled, the height of the charge layer can reach 14 m, and as the heights of the ash residue layer and the oxidation layer are not changed, the thicknesses of the reduction layer, the dry distillation layer and the drying layer are changed. The thickness of the dry distillation layer and the dry distillation layer can not change greatly, and is mainly the lengthening of the thickness of the reduction layer, so that 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 a steam reduction layer CO, and the third reduction layer is mainly a steam reduction layer CO 2 Fourth, aThe reduction layer is mainly used for generating CH from the low-temperature material layer 4 The reaction of (1). This will result in CO 2 、CH 4 Increase in the amount of active gas components and decrease in the amount of active gas components. Through theoretical analysis and comparison of a large number of material bed heights and gas components, data research and practice prove that: the center of the thickness of the ash layer on the grate is 200mm, the edge is 500mm, the temperature of the gasification layer above the ash layer at about 1000mm is the optimal gasification layer thickness, and the gas composition is optimal, so under the premise that the hearth is enlarged, the height-diameter ratio is improved, the gasification strength, the steam decomposition rate and the effective gas quality are improved, the material layer height is improved, in order to balance the axial and radial material layer temperatures and reduce the temperature difference, the air inlet mode of the gasification agent is improved in the embodiment, the traditional mode of only introducing air from the hearth is changed into the mode that most of the gasification agent enters from the hearth, the flow and the flow rate are relatively reduced, the small part of the gasification agent enters from the air inlet 21, the supposed circle radius of the rotational flow is 1/2 (uniform air distribution) of the hearth radius, the air distribution is matched with the grate, the uniformity of the axial temperature of the material layer is improved, and the gasification strength is improved. For a 3.6 m gasification furnace, 6 layers of radial cyclone gasification agent distribution devices are required to be arranged around the furnace body. The flow ratio of the furnace bottom gasifying agent to the total gasifying agent around the furnace is 1-5, so that the oxygen-carbon ratio of the furnace bottom is reduced, the conditions of overhigh furnace bottom gasifying strength and low operation elasticity are relieved, the axial temperature of a material layer is homogenized, the effective gas quality is improved, and the CO in a low-temperature region is reduced 2 、CH 4 Is generated.
In practice, as shown in fig. 10, the gasification furnace may be a fixed-bed composite gasification furnace. The fixed bed composite gasification furnace is suitable for gasifying high volatile and high moisture materials 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 or carbon, the material layer is relatively thin, and the height-diameter ratio is generally 1.5-2.5; the upper furnace body is mainly subjected to dry distillation cracking and gasification to eliminate tar and moisture volatilization and gasification due to the influence of moisture and volatile components of the raw materials, the material layer height requirement is high, and the height-diameter ratio is generally 2.5-3.5. The gas inlet part 5 at the second bottom of the furnace is distributed in the vertical axial direction, and the gasification agent has vertical impact force on the material layer, so that the material layer is easy to loosen and turn over and more materials are carried out; the upper furnace body gasifying agent is distributed in a radial horizontal cyclone mode through the second upper section furnace cyclone air inlet part 3 and the second lower section furnace cyclone air inlet part 4, the contact time of the gasifying agent and the raw materials is prolonged through the gasification of the gasifying agent cyclone, the reaction is complete and sufficient, the material bed is mild, multiple fire layers are arranged to be layered and gasified in a grading mode, the single-point gasification strength is weak, and the fire layer temperature is uniform. The lower furnace body fixed bed relatively reduces the flow, the flow speed and the gasification strength of the axial gasification agent, thereby not only reducing the blowing-over phenomenon and the stability of the furnace condition, but also reducing the amount of carried-over substances. The upper furnace body is a drying section, a dry distillation section and a gasification section, in order to prevent volatile components and water from rapidly volatilizing and expanding to cause particle bursting, small flow is needed to control combustion and gasification speed, the contact time of the gasification agent and raw materials is prolonged by the rotational flow of the gasification agent, the gasification speed is slow, the reaction completeness is increased, and the sensible heat and dust carrying-out of the gasification agent are reduced. On the other hand, the main purposes of the upper furnace body are to completely dry the moisture, fully participate in gasification, fully dry distill and volatilize the volatile components and gasify partial carbon, the height-diameter ratio of the upper furnace body is generally controlled to be 2.5-3.5m, and the spacing distance and the distribution condition of the gasification agents of the upper furnace body are consistent with those of the upper furnace body, so that the gasification and volatilization of the moisture are facilitated, and the volatile components are thoroughly decomposed and tar is eliminated. For the composite gasification furnace for producing carbon by pyrolysis, the lower furnace body adopts steam and air which are mixed according to a certain proportion to produce gas and cool, so that the equipment under the furnace is protected, and the production safety under the furnace is ensured. The multi-fire-layer gasification furnace with the upper furnace body and the lower furnace body of the fixed bed is suitable for biomass, garbage, sludge forming and soft coal gasification, eliminates the carry-over 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 the improvement of the treatment method of the ash content of the raw material, 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 achieve the effective components of the synthesis gas required by the product.
The ash content in the raw material is mainly metal oxide, has high melting point metal oxide, also has low melting point oxide, also has acid oxide and also has basic oxide, and they are mixed and melted at a certain temperature to form low-temperature eutectic body, and the ash melting point is in the range of 800-1800 deg.C. Table 1 is the melting point or amorphous softening point of the predominant metal oxide crystals in the ash and the ash melting point of mixtures thereof.
TABLE 1 Ash melting Point of the major component in Ash
From the above list it can be seen that: the ash contains different components and corresponding ash melting points, and the components of a mixture formed at different temperatures are different, and the mixture is formed into a whole by the interaction of crystals and non-crystals; the crystal serves as a framework in ash to play a supporting role, the amorphous serves as a cementing body to play a role in network connection of the framework to play a role in adhesion and reinforcement, and SiO in raw materials is generally used 2 Highest content, second is Al 2 O 3 CaO, therefore, in the raw ash analysis, this example considers only the ash component with the most of the above 3 components, and does not consider other small ash components.
The ash melting point of the ash of the raw material is generally controlled by the ratio of 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, various oxides break the regular arrangement of the original crystal, various molecules are mutually and uniformly fused together to form a low-temperature eutectic, a balance point is reached, the ash melting point is about 1200 ℃, and the ash melting point is lower. For the raw material coal, when the acid-base ratio A/B =5, the ash melting point is more than 1350 ℃. Generally, A/B = between 4 and 17, when A is more than 60%, the performance characteristics of the acid oxide (the main components are bauxite, quartz, kaolin and mullite) are highlighted in ash, and the mass fraction of the acid oxide can be increased by adding the acid fusing inhibitor into the raw materials so as to improve the ash melting point; for domestic garbage and biomass, when B is greater than 60%, the performance characteristics of alkaline oxide (mainly limestone, ling magnesium stone and potassium oxide) are highlighted in ash content, and alkaline fusing inhibitor is added into the raw materialThe mass fraction of the basic oxide may be increased to increase the ash melting point.
For increasing the effective gas content of coal, household garbage and biomass used as gasification raw materials, a fluxing agent is required to be added for modifying the raw materials to increase the ash fusion point. The refractory agent with high melting point is added, the ash component of the raw material and the production area, the yield and the economy of the raw material added with the refractory agent are considered, lime ore, bauxite raw material and quartz sand are adopted in a proper ratio, and kaolin clay can be considered in the next time. Therefore, the technology only researches the influence of the variation of the main oxides of silicon, aluminum and calcium in the ash on the variation characteristic of the ash melting point of the ash. The ash content of the silicoaluminophosphate type raw material is compared and studied by utilizing the characteristics of meltability of silicoaluminophosphate oxide and a ternary phase diagram (see fig. 3). The ternary phase diagram is a regular triangle phase diagram taking acidic fluxing oxide, acidic non-fluxing oxide and basic oxide as vertexes, and the acidic fluxing oxide refers to SiO 2 、TiO 2 (ii) a Acidic non-fluxing oxide refers to Al 2 O 3 The basic oxide refers to CaO, mgO, fe 2 O 3 。
The raw material ash is generally SiO due to primary ash and secondary ash 2 High mass fraction of SiO 2 /Al 2 O 3 Between 1.2 and 14, siO 2 CaO is between 3 and 30, in general CaO and Al 2 O 3 Lower due to SiO 2 Easily react with other basic oxides to form low-temperature eutectic, resulting in lower ash melting point. In the ash, although SiO 2 The high content of Al is not determined, but exists in an amorphous state, and only one necessary factor for increasing the ash melting point is needed in the ash, and the ash melting point is determined by the Al 2 O 3 And the mass fraction of CaO. This example is based on SiO in Ash 2 、Al 2 O 3 The content of CaO in ash is controlled, the rise of ash melting point is controlled in a targeted manner, and the research method comprises the following steps: glass phase amorphous SiO with highest content in mass fraction of ash 2 Based on CaO and Al added with a fluxing agent for increasing ash fusion point 2 O 3 The crystal is prepared by finding out the appropriate addition amount of the fusing retardant agent required by different raw materials to reach a certain ash melting point by a research method in two directions. CaO, siO 2 、Al 2 O 3 When the contents of the three 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 reaching a certain value, the acid and the alkali are saturated, the addition amount of the acid and the alkali is increased to enable the flux resisting agent to be free, the performance characteristics of the flux resisting agent are highlighted, the flux resisting agent is converted into flux resisting agent crystals, and the ash melting point is improved along with the increase of the addition amount.
Adding Al to ash 2 O 3 (ash melting point is 2050 ℃) and the fusing inhibitor leads ash oxides to be transformed to high-melting-point substances, so that the ash melting point of ash is improved, and the substance transformation process in ash is as follows: al (Al) 2 O 3 Adding leading SiO 2 CaO, caO to anorthite CaO & Al 2 O 3 ·2SiO 2 (ash melting point 1553 ℃) and continuously adding Al 2 O 3 With the remainder being kaolinite Al 2 O 3 ·2SiO 2 ·2H 2 O (ash melting point 1785 ℃) is converted, and the ash melting point is increased; with Al 2 O 3 The mass fraction is gradually added, the kaolin component is increased, the proportion in ash content is increased, the ash melting point is gradually improved, and further Al is added 2 O 3 The mass fraction of the kaolin reaches the limit conversion to generate mullite 2SiO 2 ·3Al 2 O 3 The ash melting point is further increased to 1900 ℃ which is higher; then continuously adding Al 2 O 3 Al in the remaining ash 2 O 3 Saturation to form free corundum crystals Al 2 O 3 (Ash melting point 2050 ℃ C.).
Adding CaO (ash melting point is 2570 ℃) into the ash to guide ash oxides to be converted to high-melting-point substances by a fusing inhibitor, improving the ash melting point of the ash, and performing a substance conversion process in the ash: caO-added leading SiO 2 、Al 2 O 3 Conversion of CaO. Al into anorthite 2 O 3 ·2SiO 2 (ash melting point 1553 ℃) and adding CaO continuously, and adding the rest ash to the gehlenite 2CaO & Al 2 O 3 ·SiO 2 (ash melting Point)1593 ℃) and transforming; then, caO is continuously added, and the residual ash content is added to the CaO & SiO of wollastonite 2 (ash melting point 1544 ℃) conversion; then CaO is continuously added, and the residual ash is added into calcium orthosilicate 2CaO & SiO 2 (ash melting point 2130 ℃) conversion; caO is continuously added, and the rest ash content is added into tricalcium silicate 3CaO & SiO 2 (ash melting point 2180 ℃ C.) conversion; finally, caO is added, and free crystals are formed when CaO in the ash is saturated (ash melting point 2570 ℃).
Adding Al to ash 2 O 3 In the process of changing the melting property of the CaO resisting flux and the matter components in the ash, the following rules are found by combining a calcium-silicon-aluminum ternary system phase diagram: in the vicinity of SiO 2 、CaO、Al 2 O 3 Three pure substance regions, al 2 O 3 More than 55 percent, caO more than 50 percent or CaO less than 5 percent, siO 2 More than 70 percent, the coal ash component is in the main object phase region of corundum, quartz and lime, the phase diagram of the three-element system with the full liquid phase temperature is generally higher, the ash melting point is more than 1600 ℃, the central part of the phase diagram is the eutectic low-temperature liquid phase region of the mixture, the full liquid phase temperature is generally lower, and the chemical components in the interval 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 are converted from low-temperature extensive combustion to high-temperature clean energy gasification, the effective components of the gas are improved from low content to high content, not only the economic benefit is considered, but also the environmental protection benefit is considered, the component performance of the raw material ash is carefully researched, and then the main component SiO in the ash is studied 2 、CaO、Al 2 O 3 The research results of (1) are summarized by comprehensive combing.
1、SiO 2 Influence on Ash melting temperature
1) SiO in ash 2 Has high ash melting point 1460-1716 deg.C, and is generally 30-70%. It has double property, increased content, more amorphous glass body, early softening of ash, easy reaction of alkali metal oxide to produce compound and crystal with low melting point and SiO 2 Influence on melting temperature also with Al 2 O 3 Is related to the mass content of Al 2 O 3 When the mass fraction is high, siO 2 The increase in mass fraction increases the melting temperature with SiO 2 The increase in the mass fraction increases the temperature difference between the ST (softening temperature) and the FT (flow temperature), and the slag fluidity is good. Displaying a large amount of data: when SiO is present 2 At 40-60%, the ash melting point temperature follows SiO 2 Increase and decrease (e.g., jincheng coal in SiO) 2 : adding SiO when the content is 40-60% 2 Also lowering ash fusion points); siO2 2 When the content exceeds 60%, the ash easily foams when being melted, so that porous residues are formed, and the ash melting point is uncertain. This is mainly due to Al 2 O 3 、CaO、K 2 O、Na 2 O、Fe 2 O 3 The content and kind of (A) are related, siO 2 They are easy to react well and fuse to form a low-temperature eutectic. When SiO is present 2 When the melting temperature of the ash exceeds 70 percent, the melting temperature of the ash is higher, and the ash melting point is more than 1600 ℃;
2) In high-alumina coal ash, al 2 O 3 +SiO 2 When more than 75%, siO 2 /Al 2 O 3 The smaller the ash melting point. SiO2 2 /Al 2 O 3 The larger the ash, the lower the ash melting point. SiO of general coal 2 /Al 2 O 3 1.6-4, 0.7-1.5 of high-alumina coal, and Al as the main material in ash 2 O 3 ·2SiO 2 (metakaolin), 3Al 2 O 3 ·2SiO 2 (mullite) predominates when SiO 2 /Al 2 O 3 In the range of 0.7 to 1.2 (Al) 2 O 3 /SiO 2 In the range of 0.8 to 1.4), al 2 O 3 +SiO 2 When the melting point of ash is more than 90 percent, the melting point of ash is more than 1600 ℃;
3) When SiO 2 /Al 2 O 3 If & lt 3, 35% CaO gives the lowest ash melting point, and the main component in the ash is gehlenite (2 CaO. Al) 2 O 3 ·SiO 2 ) In the region, as the CaO content increases, the ash content is changed to high calcium aluminate and gradually changed to CaO. Al 2 O 3 、12CaO·7Al 2 O 3 、3CaO·Al 2 O 3 The ash melting point is gradually increased, and when CaO is more than 50 percent, the ash melting point is more than 1600 ℃;
4) When SiO is present 2 /Al 2 O 3 > 3 and SiO 2 When the content of the ash is more than 50%, the ash melting point is lowest when the content of CaO is 25%, and the ash component in the ash is mainly anorthite CaO & Al 2 O 3 ·2SiO 2 And (4) a region. As the CaO content increases, the ash content gradually changes to calcium silicate, caO & SiO 2 (wollastonite), 2 CaO.2SiO 2 (wollastonite), 2 CaO. SiO 2 (calcium metasilicate), 3 CaO. SiO 2 (tricalcium silicate), the ash melting point increases in turn. When CaO is more than 50 percent, the ash melting point is more than 1600 ℃.
2、Al 2 O 3 Influence on Ash melting temperature
1) Al in coal ash 2 O 3 Content ratio of (A) to (B) SiO 2 Has a low ash melting point of 2050 ℃, generally between 10 and 50 percent, exists in ash as crystals, and contains 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 The mass starts from 15% with Al 2 O 3 The mass fraction of (A) is increased to form linear regular increase;
2) When Al is present 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 present 2 O 3 When the mass fraction exceeds 40%, the ash melting temperature FT exceeds 1500 ℃ regardless of changes in other components. When Al is present 2 O 3 When the melting point of ash is more than 55 percent, the melting point of ash exceeds 1600 ℃;
3) Ash content in CaO & Al 2 O 3 ·2SiO 2 (anorthite) or 2 CaO. Al 2 O 3 ·SiO 2 (gehlenite) region, increased Al 2 O 3 The content and ash content are transferred to the direction of high calcium aluminate and gradually turned to 12 CaO.7 Al 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 When the melting point of ash is more than 55 percent, the melting point of ash is more than 1600 ℃.
3. Effect of CaO on Ash melting temperature
1) The variation of CaO in the coal ash is large, the CaO exists in the ash as crystals, and the CaO is easy to be mixed with SiO 2 、Al 2 O 3 The melting point of CaO is very high, which reaches 2570 ℃, when the CaO content in the ash reaches a certain amount (more than 30%), caO in the ash is saturated into free crystals, which can improve the ash melting point, and the improvement of the CaO mass fraction can obviously improve the ash melting point of the ash, and when the CaO content in the 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 is present 2 /Al 2 O 3 When the content of CaO is less than 3, the ash melting point is lowest when the content of CaO is 35%, and the ash content is in gehlenite 2 CaO. Al 2 O 3 ·SiO 2 In the region, as the CaO content increases, the ash content shifts to high calcium aluminate, gradually shifting to CaO. Al 2 O 3 、12CaO·7Al 2 O 3 、3CaO·Al 2 O 3 Transformation, gradual increase of ash melting point, in Al 2 O 3 When CaO is more than 52 percent and CaO is more than 50 percent, the ash melting points are all more than 1600 ℃;
3) When Al is present 2 O 3 CaO < 3, siO 2 The ash melting point is lowest at 47 percent, and the ash content is anorthite CaO & Al 2 O 3 ·2SiO 2 Region following SiO 2 The content is increased, and the ash content of mullite is transferred in a region, so that the conversion is gradually changed to 3Al 2 O 3 ·2SiO 2 。
4) The CaO content is between 30 and 35 percent when SiO is 2 /Al 2 O 3 When less than 3, al 2 O 3 、CaO、SiO 2 The molecules are mutually and uniformly fused to form a low-temperature eutectic body, and the ash content is (gehlenite) 2 CaO. Al 2 O 3 ·SiO 2 In the region range, an equilibrium point is reached, and the ash melting point is lower. From Al 2 O 3 -CaO-SiO 2 The ternary phase diagram also shows that the areas with high ash melting points are both mixtures or single-phase substances with higher mass fraction contents of two phases;
5)SiO 2 /Al 2 O 3 > 3, and SiO 2 Has high content in ashAt 50%, caO has a lowest ash melting point (anorthite) CaO. Al at 25% 2 O 3 ·2SiO 2 In the region, as the CaO content increases, the ash component is transferred to the direction of calcium silicate and gradually transferred to CaO. SiO 2 (wollastonite), 2CaO 2SiO 2 (wollastonite), 2 CaO. SiO 2 (calcium metasilicate), 3 CaO. SiO 2 (tricalcium silicate), ash melting point successively higher, siO 2 When CaO is more than 75 percent and CaO is more than 50 percent, the ash melting points are all more than 1600 ℃;
6) In general ash, the ash melting point is gradually reduced by adding a certain mass fraction of CaO, and when the mass fraction is in a certain range, such as 25% (35%), the ash melting point is the lowest, but when the mass fraction exceeds 25% (35%), the ash melting point is sharply increased along with the increase of the mass fraction of CaO, namely, the ash is distributed in a V shape.
Further, the relationship between the alumina content and the ash melting point (softening point ST) is shown in Table 2.
TABLE 2 relationship of alumina, calcia content and ash melting point (softening point ST)
| Al 2 O 3 Content% | Ash melting Point (ST)/. Deg.C | CaO content% | Ash melting Point (ST)/. |
| 20 | 1250 | 10 | 1500 |
| 30 | 1350 | 15 | 1400 |
| 35 | 1400 | 20 | 1350 |
| 40 | 1500 | 35 | 1300 (minimum) |
| ≥55 | ≥1600 | 40 | 1500 |
| ≥50 | ≥1600 |
Based on the above analysis, the following analysis was conducted one by one for the case where the raw materials were coal, domestic garbage and biomass.
(1) The raw material is coal
The melting point ranges of oxides and ash in the ash of different raw materials are shown in table 3;
TABLE 3 melting point ranges of oxides and ash in ash of coal of different raw materials
The composition of the different raw coals was analyzed and the results are shown in table 4:
TABLE 4 analytical composition of different feedstock coals
| Species of | Moisture content | Ash content | Volatile component | |
| Huainan | ||||
| 1 | 1.45 | 33.99 | 22.22 | 42.96 |
| |
1.42 | 9.09 | 29.49 | 60.87 |
| Two-crossing 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 |
| Jin city | 2.59 | 15.92 | 5.21 | 76.28 |
| Jin city | 3.26 | 20.73 | 9.32 | 66.56 |
| Jin city | 0.86 | 12.15 | 8.35 | 78.65 |
| Jin city | 3.59 | 13.54 | 7.86 | 78.21 |
| Jin city | 2.9 | 15.88 | 9.79 | 73.76 |
| Yangquan coal | 2-3 | 14-16 | 7-8 | 75-84 |
| Coal of Chinese county | 6.9 | 15.27 | 17.78 | 59.99 |
The analysis of the ash content of the different feed coals is shown in table 5:
TABLE 5 analysis of ash content of different feedstocks and three-phase analysis
The ternary phase analysis is shown in FIG. 4, and it 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 of Jincheng coal 1 2 O 3 And SiO 2 Draw lines on the ternary phase diagram shown in FIG. 3 to obtain corresponding intersections, see black in FIG. 4And (4) line intersection.
2,Al for Jincheng coal 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 of Jincheng coal 2 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see yellow line intersections 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 of Jincheng coal 3 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersections of blue lines in fig. 4.
In the ash content of each of the jin town coal 3, the jin town coal 2 and the jin town coal 1, caO and Al are contained 2 O 3 、SiO 2 The content of (b) 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 CaO > 5, and it was found from the graph analysis in FIG. 4 that the ash melting points of Jincheng coal 3, jincheng coal 2 and Jincheng coal 1 are in the mullite region, and Al is increased in this case 2 O 3 The ash content, ash melting point, will gradually increase. In CaO. Al 2 O 3 ·SiO 2 In ternary phase diagram, al is added to ash 2 O 3 Substance, stand out Al 2 O 3 In an amount to divert the ash component to Al 2 O 3 ·2SiO 2 (metakaolin), 3Al 2 O 3 ·2SiO 2 (mullite), corundum, al 2 O 3 /SiO 2 In the range of 0.8-1.4 (SiO) 2 /Al 2 O 3 In the range of 0.7 to 1.2), al 2 O 3 +SiO 2 When the melting point is more than 90 percent, the ash melting points are all more than 1600 ℃.
In summary, the content of the mass fraction of three oxides (CaO, AL2O3, siO 2) in the ash of the existing coal raw material satisfies the following three points:
1、SiO 2 +CaO+AL 2 O 3 more than 80 percent; 2.S/A is in the range of 0.7-1.7; 3.S/C > 5.
Increasing the amount of refractory by example study to increase ash melting point;
according to the ash component analysis and ash melting point condition of the existing raw materials, the ash melting point is improved by accounting the addition amount of the fusing inhibitor according to a silicon-calcium-aluminum ternary system phase diagram, the raw material Jincheng 1 with the lowest ash melting point is selected to be added according to 5 percent and 8 percent of the weight of the raw materials, and CaO and AL are calculated 2 O 3 、SiO 2 And the contents of the elements are marked in a silicon-calcium-aluminum oxide ternary system phase diagram, and a Jincheng 1, jincheng 1+5 percent and Jincheng 1+8 percent ash melting point temperature region is determined; wherein, the ash content of the raw material coal after adding the dissolution inhibitor is shown in table 6:
TABLE 6
The ternary system phase diagram analysis is shown in FIG. 5;
the added alumina melting inhibitor accounts for 5 percent and 8 percent of the weight of the raw materials and is marked as CaO-AL 2 O 3 -SiO 2 In ternary phase diagram (FIG. 5), in which 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 phase diagram of Ca, si and Al, the dissolution inhibitor is added to the Jin coal 1 to make Al in the ash of the raw material 2 O 3 /CaO>3, al in the ash of the raw material 2 O 3 +SiO 2 CaO is more than or equal to 85 percent, and Al 2 O 3 /(Al 2 O 3 +SiO 2 And CaO) is not less than 55 percent, and the ash melting point of the ash content of the raw material is not less than 1600 ℃. Specifically, the difference between the melting point of the ash of Jin coal 1 and the melting point of the ash of Jin coal 1+5% is 150 ℃, and the difference between the melting point of the ash of Jin coal 1+5% and the melting point of the ash of Jin coal 1+8% is 50 ℃. Since only the ash melting point of the three main mixtures of calcium, silicon and aluminum is studied, and other minor oxides in ash have influence on the ash melting point of ash, the ash melting point shown in the calcium, silicon and aluminum ternary phase diagram is higher, but the result of practical production application is not influenced.
Pure alumina is adopted in calculation, and bauxite raw ore (containing 70-98% of alumina) is adopted in industrial production; because of different raw materials, the difference of the calcium-silicon-aluminum oxide components is increased, and the different raw materials are added according to the situation and the ash melting point requirement, and generally do not exceed 10 percent of the weight of the raw materials. In order to enlarge the application range of raw material and control the actual addition quantity of resisting flux to be 2-20% of weight of raw material
In summary, when the raw material is coal, the dissolution inhibitor is bauxite raw material, clinker or micro-aluminum powder, and the dissolution inhibitor is added to Al in the ash content 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, the ash melting point of the raw material ash can reach more than or equal to 1600 ℃.
If Al in the raw ash 2 O 3 /CaO>3, adding a dissolution inhibitor to Al in the raw material ash 2 O 3 +SiO 2 CaO is not less than 85%, and Al 2 O 3 /(Al 2 O 3 +SiO 2 And CaO) is more than or equal to 55 percent, so that the ash melting point of the ash of the raw material is more than or equal to 1600 ℃.
(2) The raw material is domestic garbage
When the raw material is domestic garbage, siO in ash of the raw material 2 /Al 2 O 3 >3, the dissolution inhibitor is limestone, quicklime or hydrated lime; addition of antisolvent to Al in raw ash 2 O 3 +SiO 2 The CaO is more than or equal to 85 percent, and the CaO/(Al) 2 O 3 +SiO 2 + CaO) is greater than or equal to 50%, thenThe ash melting point of the ash content of the raw material can be more than or equal to 1600 ℃.
The analysis results of different domestic waste components are shown in Table 7:
TABLE 7
| Species of | Moisture content | Ash content | Volatile component | Fixed |
| Household garbage | ||||
| 1 | 43.8 | 21.9 | 26.2 | 8.1 |
| |
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 |
The following will explain three kinds of domestic waste in detail. Table 8 shows the ash content analysis table and ternary phase diagram analysis of three kinds of domestic garbage.
TABLE 8 analysis table of ash content of domestic garbage
For domestic waste 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 from the domestic garbage 1 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see yellow line intersections in fig. 6.
For domestic waste 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 from the domestic garbage 2 2 O 3 And SiO 2 In the ratio of (A) to (B) in FIG. 3The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown, see the intersections of the black lines in fig. 6.
3,Al for domestic garbage 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 from the domestic garbage 3 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersections of blue lines in fig. 6.
Through the analysis of the ash content 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 alumina which is not more than 10 percent and silicon oxide is obviously reduced compared with the raw material coal,
2.S/A < 3, where the ash melting point is lowest at 35% CaO, increases with increasing CaO content,
3.S/A > 3, and SiO 2 The ash content is more than 50%, the ash melting point is lowest when the CaO content is 25%, and the ash melting point is increased along with the increase of the CaO content.
4.SiO2 < 60%, siO is added 2 Content, ash melting point can not be increased, and silica, clay and quartz ore are not applicable to increasing ash melting point.
5. The quicklime is low in price, and the bauxite is high in price.
The content of CaO in the garbage ash is high, and in order to solve the problem of low ash melting point of the garbage ash, the amount of CaO is highlighted, and anorthite, gehlenite and wollastonite ash melting points are formed, namely, 1540 ℃ of anorthite, 1590 ℃ of calcium metasilicate, 2130 ℃ of calcium metasilicate, tricalcium silicate and lime; lime ore is adopted in the production to increase the amount of calcium oxide.
In the ash content of the domestic garbage 1, the domestic garbage 2 and the domestic garbage 3, siO in the domestic garbage 1 2 /Al 2 O 3 <3, the domestic waste does not meet the screening requirement of the embodiment on the raw materialsSiO of refuse 2 and domestic refuse 3 2 /Al 2 O 3 >3, belonging to the range of raw materials which can be processed in the embodiment; further, the refuse 3 having the lowest calcium oxide content was disposed by way of example, and since limestone was relatively inexpensive, the amount of the dissolution inhibitor added was calculated as 10% by weight of the raw material, and the ash content after addition of the dissolution inhibitor is shown in table 9:
TABLE 9
The ternary phase diagram of the refuse 3 is shown in FIG. 7, and calcium oxide is added to the raw material to satisfy Al content in the ash of the raw material 2 O 3 +SiO 2 CaO is more than or equal to 85 percent, and CaO/(Al) 2 O 3 +SiO 2 And + CaO) is more than or equal to 50 percent, the ash melting point of the ash content of the raw material can be more than or equal to 1600 ℃. Specifically, the temperature difference between the melting point of garbage 3 ash and the melting point of garbage 3+10% ash is 800 ℃. Since only the ash melting point of the three main mixtures of calcium, silicon and aluminum is studied, and other minor oxides in ash have influence on the ash melting point of ash, the ash melting point shown in the calcium, silicon and aluminum ternary phase diagram is higher, but the result of practical production application is not influenced.
Pure calcium oxide is adopted in calculation, and slaked lime is adopted in industrial production; because of different raw materials, the difference of the calcium-silicon-aluminum oxide components is increased, and the different raw materials are added according to the situation and the ash melting point requirement, and generally do not exceed 10 percent of the weight of the raw materials. In order to enlarge the application range of raw material and control the actual addition quantity of the fusing-retarding agent for production and practical application at 2-20% of weight of raw material.
(3) The raw material is biomass
When the raw material is biomass, siO in the ash of the raw material 2 /Al 2 O 3 >3, the dissolution inhibitor is limestone, quicklime and hydrated lime; addition of antisolvent to raw fly ash Al 2 O 3 +SiO 2 +CaO≥80% and CaO/(Al) 2 O 3 +SiO 2 And CaO) is more than or equal to 50 percent, so that the ash melting point of the ash of the raw material can reach 1600 ℃;
or SiO in the raw ash 2 /Al 2 O 3 >3, the dissolution inhibitor is silica powder, silica, quartz ore or kaolin; adding dissolution inhibitor to SiO in raw material fly ash 2 More than or equal to 70 percent, the ash melting point of the ash content of the raw material can reach 1500-1700 ℃. The component contents and ash melting points of the ash contents of different biomasses are shown in table 10:
TABLE 10
The content of the different biomass components is shown in table 11:
TABLE 11
| Species of | Moisture content | Ash content | Volatile component(s) | Fixed carbon |
| Ranges of each component | 2-11 | 3-13 | 61-74. | 12-20 |
The following compositional analyses were performed on several different biomasses, the analyses being shown in table 12:
TABLE 12
Then, analyzing ash components and ternary system phase diagrams of the following different biomasses; the results of the analysis are shown in table 14 and fig. 8:
TABLE 14
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 intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersections of the black lines 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 according to Biomass 2 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see the intersections 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 according to Biomass 3 2 O 3 And SiO 2 The corresponding intersections are obtained by drawing lines on the ternary phase diagram shown in fig. 3, see yellow line intersections in fig. 6.
As can be seen from table 14 and fig. 8:
1, rice straws and rice stalks have high ash content in leaves, and other straws and trees are not high;
2, the contents of silicon oxide, calcium oxide and potassium oxide are high, and the composition difference of different biomasses is large;
3, the content of silicon oxide is not more than 70 percent (rice husk is removed), and a silicon oxide dissolution inhibitor is not generally adopted; siO2 2 Less than 60 percent, increase SiO 2 Content, ash melting point can not be increased, and silica, clay and quartz ore are not applicable.
4. The content of alumina is too low, and the cost is too high by adopting the alumina as the dissolution inhibitor
5.S/A > 3, and SiO 2 The ash content is more than 50%, the ash melting point is lowest when the CaO content is 25%, and the ash melting point is increased along with the increase of the CaO content.
6.CaO、K 2 O is not affected by the homogeneity, and related data display K 2 Ash melting point is lowest at 13.9% O, with K 2 The higher the O content, the higher the ash melting point.
In addition, the biomass rice straw, the wheat straw and the sunflower shell all meet SiO 2 /Al 2 O 3 >3, the biomass has a low ash content, and is comprehensively considered to be high in ash melting pointThe processing method comprises the following steps: projecting the amount of CaO to form anorthite, gehlenite, wollastonite, calcium metasilicate, tricalcium silicate and lime; and displaying related data: the wheat straw and the rice straw adopt AL 2 O 3 、AL 2 O 3 .2SiO 2 CaO as a fluxing agent, and the ash melting point temperature AL of the same amount 2 O 3 ＞AL 2 O 3 .2SiO 2 CaO, but the temperature difference is not large. The lime ore is adopted in the production to increase the amount of calcium oxide, the amount of CaO is proper, and the formed anorthite, gehlenite and wollastonite ash melting point is 1540 ℃, the wollastonite is 1590 ℃, the calcium silicate is 2130 ℃, the tricalcium silicate and the lime;
then, the biomass wheat straw was prepared as an example, and since limestone was inexpensive, the amount of the dissolution inhibitor added was calculated as 10% by weight of the raw material, and the ash components after addition of the dissolution inhibitor are shown in table 15:
watch 15
The ternary phase diagram of the biomass is shown in FIG. 9, and calcium oxide is added into the raw material to satisfy Al in the fly ash of the raw material ash 2 O 3 +SiO 2 The CaO is more than or equal to 80 percent, and the CaO/(Al) 2 O 3 +SiO 2 And CaO) is more than or equal to 50 percent, so that the ash melting point of the ash content of the raw material can reach more than or equal to 1600 ℃. Specifically, the melting point of the wheat straw ash is 600 ℃ different from the melting point of the wheat straw plus 10% ash. Since only the ash melting point of the three main mixtures of calcium, silicon and aluminum is studied, and other minor oxides in ash have influence on the ash melting point of ash, the ash melting point shown in the three-series phase diagram of calcium, silicon and aluminum is higher, but the influence is not influencedIn response to the results of the actual production application.
Pure calcium oxide is adopted in the calculation, and slaked lime is adopted in the industrial production; because of different raw materials, the difference of the calcium-silicon-aluminum oxide components is increased, and the different raw materials are added according to the situation and the ash melting point requirement, and generally do not exceed 10 percent of the weight of the raw materials. In order to enlarge the application range of raw material and control the actual addition quantity of the fusing-retarding agent for production and practical application at 2-20% of weight of raw material.
In the embodiment, the fusing inhibitor is added into the raw materials to improve the ash melting point of the raw materials, and simultaneously, the air inlet mode of the gasifying agent is improved, so that the uniformity of the axial temperature of the material layer is improved, and CO is supplied 2 The reduction provides higher reaction temperature and longer reaction time, so that CO can be obtained 2 Can be more completely reacted for recovering CO 2 The gasification agent is used for reducing the CO, so that sufficient conditions are provided, and the effective gas quality is improved. And in the high-temperature material layer at 1600 deg.C, CO 2 Almost total conversion to CO, CO 2 The recycling of the waste water has double effects of environmental protection and economic benefit. Through deep research and experiment, CO is adopted 2 Returning to furnace technique, using compressor to compress CO 2 Is sent into the gasification furnace through an air pipeline to replace a part of steam. Tests show that CO 2 After the furnace is returned, the production operation is stable. CO2 2 The furnace returning test data can realize CO 2 Greatly converted into effective component CO, thereby not only reducing CO 2 The discharge amount of the steam is reduced, and the energy conservation and environmental protection are realized.
In the description of the present invention, numerous specific details are set forth. It is understood, however, 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 specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like 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, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, systems, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.
Claims (8)
1. A production method for increasing and homogenizing the temperature of a material bed by a fixed bed high material bed continuous gasification furnace is characterized by comprising the following steps:
(a) Analyzing oxides in the raw material ash, and performing data analysis accounting on the contents of silicon dioxide, aluminum oxide and calcium oxide;
(b) Adding a dissolution inhibitor to the raw material according to a ternary system phase diagram of silicon dioxide, aluminum oxide and calcium oxide so as to enable the ash melting point of the ash of the raw material to be more than 1600 ℃;
(c) The method comprises the steps of putting raw materials into a gasification furnace, and simultaneously introducing a gasification agent from a furnace bottom air inlet part of the gasification furnace and a plurality of cyclone air inlet parts of the gasification furnace, wherein the cyclone air inlet parts are arranged at the periphery of the gasification furnace at intervals up and down.
2. The production method according to claim 1, wherein when the raw material is coal, the dissolution inhibitor is bauxite raw material, clinker or fine aluminum powder, and the dissolution inhibitor is added to the raw materialAl in feed 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 material ash reaches more than 1600 ℃.
3. The production method according to claim 2, wherein if Al in the raw ash is contained in the raw ash 2 O 3 /CaO>3, adding the dissolution inhibitor to Al in the raw material ash 2 O 3 +SiO 2 CaO is more than or equal to 85 percent, and Al 2 O 3 /(Al 2 O 3 +SiO 2 And + CaO) is more than or equal to 55 percent, so that the ash melting point of the ash of the raw material is more than or equal to 1600 ℃.
4. The production method according to claim 1, wherein when the raw material is biomass, siO in the raw ash 2 /Al 2 O 3 >3, the dissolution inhibitor is limestone, quicklime and hydrated lime; the dissolution inhibitor is added to the raw material fly ash Al 2 O 3 +SiO 2 The CaO is more than or equal to 80 percent, and the CaO/(Al) 2 O 3 +SiO 2 + CaO) is more than or equal to 50 percent, so that the ash melting point of the ash of the raw material reaches more than 1600 ℃;
or SiO in the raw material ash 2 /Al 2 O 3 >3, the dissolution inhibitor is silica powder, silica, quartz ore or kaolin; the dissolution inhibitor is added to SiO in the raw material fly ash 2 Not less than 70 percent, and the ash melting point of the ash content of the raw material reaches more than 1600 ℃.
5. The production method according to claim 1, wherein the cyclone air inlet portion comprises a plurality of air inlets uniformly distributed around the circumference of the gasifier, and on a cross section of the cyclone air inlet portion, a center line of the air inlets and a base line have an included angle therebetween, and the base line is defined as: and the connecting point of the central line of the gas inlet and the side wall of the gasification furnace is connected with the connecting line of the center of the gasification furnace on the cross section.
6. The method of production in accordance with claim 5 wherein the included angle is 30 °.
7. The production method according to claim 5, wherein the interval between two adjacent cyclone air inlets in the vertical direction is 1-1.5m.
8. The production process according to claim 1, wherein CO is recovered 2 As a reducing agent.
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| CN113969192A (en) * | 2021-10-08 | 2022-01-25 | 陈松涛 | Centrifugal suspension fixed bed composite gasification furnace, production system and production method |
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| WO2024080212A1 (en) * | 2022-10-11 | 2024-04-18 | 三菱重工業株式会社 | Method for operating biomass gasifier, and biomass gasifier |
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