CN111534355A - Fluxing agent for reducing coal ash melting point - Google Patents
Fluxing agent for reducing coal ash melting point Download PDFInfo
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- CN111534355A CN111534355A CN202010249590.7A CN202010249590A CN111534355A CN 111534355 A CN111534355 A CN 111534355A CN 202010249590 A CN202010249590 A CN 202010249590A CN 111534355 A CN111534355 A CN 111534355A
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- ash
- melting point
- coal
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- coal ash
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
Abstract
The invention discloses a fluxing agent for reducing the melting point of coal ash, which comprises the following components in percentage by weight: 20-90% of organic matters; 0-70% of CaO; 1-40% of MgO; fe2O30～50％；Na20 to 30% of O and K20-30% of O. The fluxing agent effectively increases the liquid phase amount generated by ash fusion, and improves the high-temperature fluidity of ash; the low softening point can promote the formation of a eutectic system; can reduce ash fusion point and simultaneously utilize organic hazardous waste to produce H2CO and the like; organic matters are used as a binder and a hydrophobic agent, so that the addition amount of the additive for reducing the ash melting point can be greatly higher than that of other additives for reducing the ash melting point, and the yield of effective gas is not influenced; the phenomenon that the addition amount is increased like limestone and the melting point of the coal ash is increased is avoided. The fluxing agent solves the problems of high melting point of coal ash of coal (such as Huainan coal) with high ash melting point and difficult gasification, high treatment cost and the like.
Description
Technical Field
The invention relates to the technical field of liquid slag discharge, in particular to a fluxing agent for reducing the melting point of coal ash.
Background
In order to reduce the negative influence of coal on the environment, the development of clean coal technology is an important way for improving the utilization efficiency of coal and reducing environmental pollution. It includes gasification technology, synthetic fuel technology, including alcohol fuels and hydrocarbon fuels, etc. In these techniques, whether ash can be smoothly discharged is a key to smooth operation of the apparatus. Coal gasification devices represented by Shell pulverized coal gasification and Texaco coal water slurry pressurization gas adopt a liquid-state slag discharge technology, and have certain requirements on the melting point of coal ash. The slag tapping requires that the melting temperature of the coal ash is lower than the operating temperature, the operating temperature is generally about 50 ℃ higher than the flowing temperature, and the ash is discharged in a liquid state. The gasification temperature of the coal high-temperature entrained-flow bed gasification furnace is 1300-1600 ℃, and the gasification reaction of pure carbon can be rapidly carried out at 1100 ℃. The reason for the high temperature operation is mainly to melt the ash in the coal to improve the utilization rate of the carbon and to achieve smooth slag discharge. In this sense, the entrained-flow coal gasifier reaction does not control the progress of gasification mainly by coal, but determines key operating parameters of gasification and equipment materials thereof by ash. In addition, in order to increase the gasification temperature of the gasification furnace, it is necessary to increase the amount of oxygen oxidation reaction, that is, the amount of combustion, to supply heat, but this results in an increase in CO2To make available gas (H)2The content of + CO) decreases, and the economy of the plant decreases. The gasification temperature of the gasification furnace is increased, so that the corrosion of the gasification furnace is aggravated, the heat preservation difficulty is increased, and the like. Therefore, coal having a low ash fusion point is selected as coal for a coal gasification apparatus or a coal raw material having a low ash fusion point as proposed in CN 106833786 a in actual industrial production.
The existing research shows that the mineral substances in the coal mainly comprise silicate such as clay mineral and aluminosilicate, the product of the mineral substances in the coal after being burned at a higher temperature is coal ash, and the chemical components of the coal ash mainly comprise SiO2、Al2O3、CaO、MgO、Fe2O3、K2O、Na2O、TiO2、SO3And the like, are influenced by the mineral components of the coal ash, and the relationship between the melting temperature of the coal ash and the chemical composition of the coal ash is not determined. But in generalIn particular, TiO, which is an acidic oxide, is contained in the coal ash2、Al2O3、SiO2Has the function of increasing the melting temperature of the coal ash; CaO, MgO, Fe being alkaline oxides2O3、K2O、Na2O has the function of lowering the melting temperature of the coal ash. Wherein, TiO2The effect of raising ash fusion temperature is always achieved, the increase and decrease of the content of the TiO-based composite material has great influence on the rise and fall of the ash fusion temperature, and the TiO-based composite material has the advantages of2The ash melting temperature is increased by 36-46 ℃ when the mass fraction is increased by 1 percent; al (Al)2O3Has firm crystal structure, melting point of 2050 ℃, plays a role of skeleton in the process of melting the coal ash, and is Al2O3The higher the content, the more the "skeleton" component, the higher the melting point. The general trend of ash fusion temperature of coal is along with Al in ash2O3The content is increased and gradually increased; SiO 22Is an oxide of tetrahedral structure, SiO at high temperature2It is easy to form a glass body with other metal and non-metal oxides.
The coal ash is a mixture of a plurality of minerals, wherein the types of the minerals are different according to different geological conditions of coal, and the minerals are quartz, clay minerals, carbonate minerals, sulfide minerals and sulfate minerals. The mineral form of the element also has an important influence on the melting property of the coal ash, the obvious difference of the melting temperature of the coal ash with similar chemical components depends on the contents of quartz, kaolin and feldspar, the melting temperature of the coal ash is gradually increased along with the increase of the content of the kaolin, and the melting temperature of the coal ash with the same content of the kaolin is reduced along with the increase of the content of the feldspar. During the heating process, the mineral substances in the coal ash are changed, and complex reactions exist among the mineral substances at high temperature, so that the mineral substances are finally changed into various silicate minerals and composite oxides. Meanwhile, low-temperature eutectic phenomenon also occurs among all the minerals, and the behavior of the minerals in the heating process determines the melting characteristic of the coal ash. The researchers at home and abroad have studied the heating behavior of the coal ash mineral and the change rule of the mineral form after adding the fluxing agent, and utilize CaO-2Fe2O3-2SiO2And FeO-2Al2O3-2SiO2Ternary system phase diagram vs. CaO and Fe2O3The fluxing mechanism is explained. After the CaO reagent is added into the coal ash, anorthite, gehlenite, calcium aluminate and wollastonite are easily formed with other mineral substances at high temperature, and the mineral substances are eutectic at low temperature together, so that the melting point of the coal ash is reduced, and after the CaO is added to a large amount, the periclase (melting point 2570 ℃) is generated, and the melting point of the coal ash is increased rapidly. Adding Fe into coal ash2O3The reagent is converted into FeO under the weak reducing atmosphere and high temperature, the FeO is easy to form fayalite, hercynite and hercynite with other mineral substances, and from the phase diagram of a ternary system, the mineral substances can generate low-temperature eutectic action, so that the melting point of the coal ash is reduced and converged to about 1200 ℃. Therefore, the key to developing new fluxing agents is not in the amount of material added to the fluxing agent, but in the ability of the added material to form more eutectic with the mineral in the coal.
Research shows that CaO and Fe are added into coal ash2O3And MgO, which can greatly reduce the melting temperature of the coal ash in a weak reducing atmosphere. The order of the effects is CaO > MgO > Fe2O3＞Na2O；K2O exhibits intermediate behavior. The oxide capable of raising flowing temperature of coal ash is TiO according to the sequence of action from large to small2＞Al2O3＞SiO2. Among the fluxes used at present, iron-based or magnesium-based fluxes are superior to calcium-based fluxes, but the cost is high, and a mixture of pyrite and magnesium ore is not applicable in some cases, especially in a process for producing synthesis gas, which increases the load and difficulty of a gas purification apparatus.
CN 105199811A proposes adding limestone, calcite or mica as fluxing agent, and decomposing limestone into CaO and CO at high temperature by adding fluxing agent2Energy consumption, increased oxygen consumption, reduced gasification efficiency, and low effective gas content. In addition, the limestone is taken as the fluxing agent and is only suitable for the coal with the flowing temperature of the coal cinder less than 1550 ℃, and for the coal with the deformation temperature, the softening temperature and the flowing temperature of the coal cinder more than 1500 ℃, the limestone is simply added as the fluxing agentToo large an amount to be practical. Typical coal with high ash fusion point and difficult gasification, such as Huainan coal, has coal cinder deformation temperature, softening temperature and flowing temperature higher than 1500 ℃. Therefore, limestone is used as the coal ash fluxing agent, and the addition amount is large, so that the limestone is not suitable for the ultra-high coal ash melting point.
CN1970698A reports the use of CaCO3、Fe2O3、MgCO3The flux with three components achieves certain results, but compared with the pure limestone flux, the Fe2O3Powder and MgCO3The cost of the method is high, the sulfur content in the raw materials is required to be less, and the existing solid wastes, such as iron slag and carbonate minerals with high sulfur content, can not be fully utilized, and the solid wastes such as desulfurized gypsum of a power plant and the like can not be used.
CN101580751A discloses a fluxing agent for reducing the melting point of coal ash, which comprises 30-60 parts of SiO by weight2And other CaO and Fe in different amounts2O3MgO, or further adding Al2O3、Na2O、K2And O and the like, and the components are ground, melted and crushed to be used as a fluxing agent for reducing the melting point of the coal ash. But with the addition of alkaline compounds, CaO, Na2O、K2Substances such as O and the like are dissolved in water, so that the pH value of the coal water slurry is increased, and the viscosity of the coal water slurry is greatly increased and the application is impossible.
To solve the problem of viscosity increase, CN105400570A proposes to use SiO2And CaO, Fe2O3MgO and the like are mixed and melted, and then are made into powder to be added into the coal water slurry. However, the processes of mixing, melting and powdering are complex and energy consumption is high. And influence on the Ash melting Point, SiO2、Al2O3And CaO, Fe2O3MgO belongs to different categories and is a pair of spears, and the addition of MgO after mixing will affect the fluxing effect.
CN108410505A proposes a method for preparing water gas by utilizing organic hazardous waste, and the organic hazardous waste is used for preparing water gas together with water-coal-slurry. However, the blended coal water slurry is needed, the ash melting point of the coal used in the process is not improved, and the coal with low ash melting point is still needed.
The invention provides a fluxing agent for reducing the melting point of coal ash, aiming at solving the problems of high melting point of the coal ash of coal which is difficult to gasify, such as Huainan coal, high melting point of the coal ash, high treatment cost and the like.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a fluxing agent for reducing the melting point of coal ash.
The technical scheme of the invention is as follows:
a fluxing agent for reducing the melting point of coal ash comprises the following components in percentage by weight: 20-90% of organic matters; 0-70% of CaO; 1-40% of MgO; fe2O30～50％；Na20 to 30% of O and K2O 0～30％。
Preferably, the kinematic viscosity of the organic matter is more than 1mm at 40 DEG C2And heating the organic matter which can be melted into liquid.
Preferably, the kinematic viscosity of the organic matter is more than 1mm at 40 DEG C2And heating the hazardous organic waste which can be melted into a liquid.
Preferably, the organic hazardous waste is hazardous waste with a heat value of more than 20000kJ/kg, such as residue generated by washing oil regeneration in a gas purification process; rectifying the primary phenol to produce a rectification residue of resorcinol; waste mineral oil and oil sludge produced in the centralized dismantling process of internal combustion engines, automobiles, ships and the like; unqualified asphalt; thick oil, etc. (organic hazardous waste is very large, these are examples only).
Preferably, the preparation method of the fluxing agent for reducing the melting point of the coal ash comprises the following steps: respectively grinding the inorganic oxide raw materials, sieving the inorganic oxide raw materials by a 60-mesh sieve, and uniformly mixing; then mixing with organic matter, grinding and sieving with a 20-mesh sieve to obtain the powder fluxing agent.
Preferably, the addition amount of the fluxing agent in use accounts for 0.5-200% of the content of the raw material coal ash.
The invention has the advantages that:
1. the invention effectively increases the liquid phase amount generated by ash fusion and improves the high-temperature fluidity of ash;
2. the invention has lower softening point, can quickly generate liquid phase so as to accelerate mass transfer effect and promote the formation of a eutectic system;
3. the invention can reduce ash melting point and simultaneously utilize organic hazardous waste (organic waste/organic leftover) to produce H2CO and the like;
4. the invention can reduce ash fusion point, safely dispose organic hazardous waste and produce H2CO and the like, saves raw material coal and the like;
5. according to the invention, organic matters are used as a binder and a hydrophobic agent, so that the addition amount of the additive for reducing the ash melting point can be greatly higher than that of other additives for reducing the ash melting point, and the yield of effective gas is not influenced;
6. the glass phase fluxing agent does not have the phenomena that the addition amount is increased like limestone, and the melting point of coal ash is increased.
Detailed Description
Example 1
CaO powder, MgO powder and Fe according to mass percentage2O3Powder, Na2O powder, K2Mixing O powder, grinding to 60 mesh, and mixing with hazardous organic waste (the hazardous organic waste is residue generated by washing oil regeneration during gas purification, the residue is heavy component with boiling point of above 280 deg.C under normal pressure, and kinematic viscosity of above 8mm at 40 deg.C2And/s, the heat value is 34000kJ/kg), grinding until the powder is sieved by a 20-mesh sieve to obtain the powder fluxing agent.
The fluxing agent comprises the following effective components in percentage by mass:
examples 1 to 1
The residue generated by the regeneration of the washing oil in the coal gas purification process is 40 percent, CaO is 20 percent, MgO is 10 percent and Fe2O326% of Na2O is 2% and K2O is 2 percent.
Examples 1 to 2
The residue generated by the regeneration of the washing oil in the coal gas purification process is 60 percent, CaO is 10 percent, MgO is 5 percent and Fe2O321% of Na2O is 2% and K2O is 2 percent.
Examples 1 to 3
The residue generated by the regeneration of the washing oil in the coal gas purification process is 20 percent, CaO is 25 percent, MgO is 15 percent and Fe2O330% of Na2O is 5% and K2The content of O is 5 percent.
Example 2
CaO powder, MgO powder and Na are mixed according to mass percentage2O powder, K2Mixing O powder, grinding respectively to fineness of 60 mesh, and mixing with organic hazardous waste (the organic hazardous waste is rectification residue of resorcinol produced by primary phenol rectification, and has kinematic viscosity of more than 2mm at 40 deg.C2And/s, the heat value is 38000kJ/kg), grinding until the powder is sieved by a 20-mesh sieve to obtain the powder fluxing agent.
The fluxing agent comprises the following effective components in percentage by mass:
example 2-1
The amount of rectification residue is 85 percent, CaO is 12 percent, MgO is 1 percent, and Na2O is 1% and K2O is 1%.
Examples 2 to 2
90 percent of rectification residue, 7 percent of CaO, 1 percent of MgO and Na2O is 1% and K2O is 1%.
Examples 2 to 3
The amount of rectification residue is 70%, CaO is 15%, MgO is 5%, and Na2O is 5% and K2The content of O is 5 percent.
Example 3
Mixing MgO powder and Fe according to mass percentage2O3Powder, Na2O powder, K2Mixing O powder, grinding to 60 mesh, and mixing with organic hazardous waste (such as waste mineral oil and oil sludge generated during centralized disassembly of internal combustion engine, automobile, ship, etc., and having kinematic viscosity of more than 15mm at 40 deg.C2And/s, the heat value is 28000kJ/kg), grinding until the powder is sieved by a 20-mesh sieve to obtain the powder fluxing agent.
The fluxing agent comprises the following effective components in percentage by mass:
example 3-1
Waste mineral oil and25% of sludge, 10% of MgO and Fe2O368% of Na2O is 2% and K2O is 2 percent.
Examples 3 to 2
40% of waste mineral oil and sludge, 14% of MgO and Fe2O340% of Na2O is 3% and K2O is 3 percent.
Examples 3 to 3
20% of waste mineral oil and oil sludge, 18% of MgO and Fe2O360% of Na2O is 1% and K2O is 1%.
Example 4
CaO powder, MgO powder and Fe according to mass percentage2O3Powder, Na2O powder, K2And fully mixing and grinding the O powder to the fineness of 60-mesh sieve respectively, mixing with organic hazardous waste (the organic hazardous waste is unqualified asphalt and has the heat value of 36000kJ/kg), and grinding to 20-mesh sieve to obtain the powder fluxing agent.
The fluxing agent comprises the following effective components in percentage by mass:
example 4-1
The unqualified asphalt content is 40%, CaO is 18%, MgO is 18%, and Fe2O320% of Na2O is 2% and K2O is 2 percent.
Example 4 to 2
The unqualified asphalt content is 25%, CaO is 28%, MgO is 19%, and Fe2O38% of Na2The content of O is 20 percent.
Examples 4 to 3
The unqualified asphalt content is 50%, CaO is 12%, MgO is 18%, and Fe2O3Is 18% of Na2O is 1% and K2O is 1%.
Example 5
CaO powder, MgO powder and Fe according to mass percentage2O3Powder, Na2O powder, K2Mixing O powder, grinding to 60 mesh, and mixing with hazardous organic waste (thick oil, kinematic viscosity at 40 deg.C greater than 5 mm)2And/s, the calorific value is 37000kJ/kg), grinding until the mixture is sieved by a 20-mesh sieve, and obtaining the powder fluxing agent.
The fluxing agent comprises the following effective components in percentage by mass:
example 5-1
The fluxing agent comprises the following effective components in percentage by mass: 60% of heavy oil, 15% of CaO, 3% of MgO and Fe2O3Is 18% of Na2O is 1% and K2O is 1%.
Examples 5 and 2
The fluxing agent comprises the following effective components in percentage by mass: 85% of heavy oil, 5% of CaO, 2% of MgO and Fe2O33% of Na2The content of O is 5 percent.
Examples 5 to 3
The fluxing agent comprises the following effective components in percentage by mass: 35% of heavy oil, 15% of CaO, 12% of MgO and Fe2O3Is 8%, K2The content of O is 30%.
The test result of the fluxing agent applied to Huainan coal for reducing the ash melting point shows that the coal ash melting point of the Huainan coal can be reduced to 1550 ℃ to 1300 ℃ below by adding the fluxing agent. The effect on melting temperature when the final ash composition was the composition shown in table 1, using the co-solvents of examples 1-1, 2-1 and 3-1, respectively, added to the ash of Huainan coal in the appropriate proportions, is shown in table 1.
Table 1: after the cosolvent is added, the influence on the melting temperature is caused under the condition of different coal ash compositions;
from the above data it can be seen that:
the fluxing agent can be added in a large amount, is uniformly mixed into high-ash fusion point coal in the using process, and produces H from organic matters in the gasification process2CO and other gases and inorganic matters can change the viscosity-temperature characteristics of ash slag and reduce the ash melting point and the ash viscosity, so that the ash slag can be smoothly discharged in a liquid form, and the problem that high-ash-melting-point coal cannot be used in the liquid state is solvedThe technical problem of the slag discharging furnace is solved, and organic hazardous waste can be safely disposed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The fluxing agent for reducing the melting point of the coal ash is characterized by comprising the following components in percentage by weight: 20-90% of organic matters; 0-70% of CaO; 1-40% of MgO; fe2O30～50％；Na20 to 30% of O and K2O 0～30％。
2. The fluxing agent for reducing the melting point of coal ash according to claim 1, wherein the kinematic viscosity of the organic matter is greater than 1mm at 40 ℃2And heating the organic matter which is melted into liquid.
3. The fluxing agent for reducing the melting point of coal ash according to claim 1, wherein the kinematic viscosity of the organic matter is greater than 1mm at 40 ℃2And heating the hazardous organic waste which can be melted into liquid.
4. A fluxing agent for reducing the melting point of coal ash as claimed in claim 2 or claim 3, wherein the calorific value of the organic matter or hazardous organic waste is above 20000 kJ/kg.
5. A fluxing agent for reducing the melting point of coal ash as claimed in any one of claims 2 to 4, wherein the preparation method comprises the following steps: respectively grinding the inorganic oxide raw materials, sieving the inorganic oxide raw materials by a 60-mesh sieve, and uniformly mixing; then mixing with organic matter, grinding and sieving with a 20-mesh sieve to obtain the powder fluxing agent.
6. A flux for reducing the melting point of coal ash according to any one of claims 2 to 5, wherein the amount of the flux added in use is 0.5 to 200% of the content of the raw coal ash.
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| CN112191666A (en) * | 2020-10-22 | 2021-01-08 | 山西明峰科技有限公司 | Method for recycling industrial waste |
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