CN111057604A - Method for improving sulfur fixation efficiency in sulfur removal and thermal conversion of coal - Google Patents
Method for improving sulfur fixation efficiency in sulfur removal and thermal conversion of coal Download PDFInfo
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- CN111057604A CN111057604A CN201911254672.4A CN201911254672A CN111057604A CN 111057604 A CN111057604 A CN 111057604A CN 201911254672 A CN201911254672 A CN 201911254672A CN 111057604 A CN111057604 A CN 111057604A
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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
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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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
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
Abstract
A method for improving sulfur removal efficiency in coal and sulfur fixation efficiency in thermal conversion relates to the technical field of clean coal. The specific process comprises the following steps: pyrolyzing coal, soaking in organic acid water solution to release sulfur in coal in gas form; and adding an alkaline component with a desulfurization effect into the acid-treated coal, and reacting the alkaline component with the sulfur-containing acidic gas in the subsequent coal thermal conversion and utilization process to realize a sulfur fixation process. The method has the following advantages: the problem that sulfides in the pyrolysis coal are difficult to remove from the coal can be solved by adopting organic acid washing, the removal efficiency of the sulfur in the coal is greatly improved, and the subsequent coal utilization process is not influenced; most of the sulfur in the coal which is easy to release at low temperature can be removed in the pyrolysis process, the remaining most of the sulfur needs higher temperature to release from the coal, and the alkaline component desulfurization reaction rate is high under the high temperature condition, so that the utilization rate of the desulfurizer and the sulfur fixation efficiency thereof can be greatly improved. In the practical implementation of the method, the existing pyrolysis, coal dressing and coal thermal conversion devices can be used for reference, the process is simple, and the equipment is mature and reliable.
Description
Technical Field
The invention relates to a method for improving sulfur removal efficiency in coal and sulfur fixation efficiency in thermal conversion, and belongs to the technical field of clean coal.
Background
Pollutants generated by coal utilization are the largest pollution source causing ecological environment damage, and become the urgent necessity for global air pollution treatment. Aiming at the problem of removing sulfur oxides generated in the process of utilizing coal, the method mainly adopts a mode of flue gas treatment after utilizing coal, such as a wet method, a semi-dry method or a dry method desulfurization technology, and has the advantages of high desulfurization efficiency, high investment and operation cost, large occupied area and the like. The sulfur oxides in the flue gas mainly come from the sulfur in the coal, the content of the sulfur in the coal is reduced before the coal is utilized, and the sulfur fixation efficiency is improved in the coal thermal conversion process, so that the important way for solving the problems of investment, operation cost and occupied area caused by the flue gas treatment method after the coal is utilized is provided.
Coal dressing is an economically feasible important method for removing sulfur in coal, and can remove inorganic sulfur mainly from pyrite. Before the coal is used, the coal is subjected to pyrolysis treatment, and part of inorganic sulfur and organic sulfur, particularly pyrite in the inorganic sulfur, can be removed (FeS 2). Because most of FeS in the raw coal2FeS is formed during pyrolysis, resulting in a great influence on the pyrolysis desulfurization efficiency. In the process of coal heat utilization, the method for fixing sulfur by adding the alkaline desulfurizing agent into the raw coal has the advantages of easy realization and simple equipment. However, in the actual process, because the release of sulfur in coal has a large temperature range, especially at a low temperature, the reaction rate of sulfur components in flue gas and the desulfurizing agent is low, which easily causes the problem of low sulfur-fixing efficiency of the alkaline desulfurizing agent in coal in the furnace. Therefore, the development of the method for improving the sulfur removal rate in coal and the sulfur fixation efficiency in thermal conversion is of great significance to the technical development of clean coal.
Disclosure of Invention
The invention aims to provide a method for improving the sulfur removal efficiency in coal and the sulfur fixation efficiency in thermal conversion aiming at the problem of low sulfur fixation efficiency in the existing raw coal desulfurization and coal thermal conversion.
The invention is realized by the following technical scheme:
a method for improving sulfur removal efficiency and sulfur fixation efficiency in thermal conversion of coal comprises the following steps:
pyrolyzing coal, and removing part of sulfur elements to obtain pyrolyzed coal;
completely soaking the pyrolysis coal in an organic acid aqueous solution, and releasing sulfur in the coal in a gas form to remove the sulfur in the coal and obtain acid-treated coal;
adding an alkaline component with a desulfurization effect into the acid-treated coal to prepare fuel coal;
the alkaline component reacts with sulfur-containing acidic gas released in the thermal conversion and utilization process of the fuel coal to realize the sulfur fixation process.
In the technical scheme, the coal pyrolysis temperature is 450-1000 ℃.
In the above technical scheme, the organic acid includes any one or a mixture of oxalic acid, acetic acid, citric acid, malic acid and tartaric acid.
In the technical scheme, the molar ratio of the organic acid in the organic acid aqueous solution to sulfur in the pyrolysis coal is 1:1-10: 1.
In the technical scheme, the pyrolysis coal is soaked in the organic acid aqueous solution for 5-300 min.
In the technical scheme, the alkaline component is one or a mixture of more of calcium-based desulfurizer, magnesium-based desulfurizer and sodium-based desulfurizer.
The invention has the following advantages and beneficial effects: 1) the removal efficiency of sulfur in coal is high: the problem that the sulfide in the pyrolysis coal is difficult to remove from the coal can be solved by adopting an organic acid washing method, and the removal efficiency of the sulfur in the coal is greatly improved; 2) the subsequent coal combustion or gasification utilization process is slightly influenced: inorganic acid can also be used for dissolving sulfides in the pyrolysis coal, but residual inorganic acid elements have influence on the subsequent coal utilization process, for example, when hydrochloric acid is used, chlorine elements can be brought into the desulfurized coal, which easily causes corrosion of a subsequent coal thermal conversion utilization device (a boiler or a gasification furnace) and generation of harmful components such as dioxin; 3) the sulfur fixation efficiency is high in the coal heat conversion and utilization process: most of the sulfur in the coal which is easy to release at low temperature can be removed in the pyrolysis process, the remaining most of the sulfur needs higher temperature for releasing from the coal, and the desulfurization reaction rate of alkaline components is high under the high-temperature condition, so that the utilization rate of the desulfurizer and the sulfur fixation efficiency thereof can be greatly improved; 4) the preparation method is simple: in the actual operation of the method, a method similar to wet coal preparation is introduced in the existing pyrolysis clean coal preparation process, namely organic acid is added into a wet coal preparation aqueous solution, and then an alkaline desulfurizer is added, so that the aims of efficiently removing sulfur in coal and greatly improving the sulfur fixation efficiency in coal thermal conversion can be fulfilled, and the method is simple in system and mature and reliable in equipment.
Detailed Description
The following will further describe the specific implementation and operation of the present invention with reference to the following examples.
Firstly, pyrolyzing coal to remove partial sulfur elements to obtain pyrolyzed coal. The pyrolysis temperature is selected to be 450-1000 ℃. The temperature is lower than 450 ℃, the release rate and the release amount of sulfur in the coal are low; above 1000 ℃, the loss of combustible components in the coal is large. For different coal types, the pyrolysis temperature and the pyrolysis rate are selected, and the influence rule of the sulfur release in the coal needs to be considered for optimization.
And completely soaking the pyrolysis coal in an organic acid aqueous solution, releasing sulfur in the coal in a gas form, realizing the removal of the sulfur in the coal, and obtaining the acid-treated coal. The organic acid includes: one or more of oxalic acid, acetic acid, citric acid, malic acid and tartaric acid. The concentration of the organic acid in the solution is 0.05-0.5 mol/L. The molar ratio of the organic acid in the organic acid aqueous solution to sulfur in the pyrolysis coal is 1:1-10: 1. And soaking the pyrolytic coal in an organic acid aqueous solution for 5-300 min. The soaking time is mainly influenced by the particle size of the pyrolysis coal, and when the particle size is larger, the time for organic acid to diffuse in the pyrolysis coal particles is long, so that the longer soaking time is needed; when the particle size of the pyrolysis coal is smaller, the time required for diffusion is shorter, and the time required for soaking is shorter. The pyrolysis coal is soaked in the organic acid aqueous solution, and the soaking time can be shortened by adopting the enhanced mass transfer processes of microwave, ultrasonic and the like.
And adding an alkaline component with a desulfurization effect into the acid-treated coal to prepare the fuel coal. The alkaline component is one or a mixture of more of calcium-based desulfurizer, magnesium-based desulfurizer and sodium-based desulfurizer. During the process of adding the alkaline component into the acid-treated coal, the sulfur in the coal can be further removed by methods such as microwave, ultrasonic, electrolysis and the like.
The alkaline component reacts with sulfur-containing acidic gas released in the thermal conversion and utilization process of the fuel coal to realize the sulfur fixation process. The fuel coal provided by the invention can be used as a combustion or gasification raw material of briquette, lump coal and pulverized coal.
The principle of the invention is as follows:
after the raw coal or the sorted coal is pyrolyzed at the temperature of 450-1000 ℃, most of sulfur in the coal is decomposed and released. The important component of sulfur element in coal is inorganic sulfur, and a typical component is pyrite FeS2. Because most of FeS in the raw coal2FeS is formed during the pyrolysis process, so that the desulfurization efficiency of the pyrolysis process is greatly affected. FeS is a compound that is poorly soluble in water and readily soluble in acidic solutions. FeS can be dissolved by using an acid solution, and H is released2S, the aim of removing sulfur in the coal is achieved. Released H2S can be removed by a conventional method. The inorganic acid can also be used for dissolving FeS in the pyrolysis coal, but the influence of residual inorganic acid elements on the subsequent coal thermal conversion utilization process exists. For example, when hydrochloric acid is used, chlorine is introduced into desulfurized coal, which causes corrosion of a heat utilization device (boiler or gasification furnace) and generation of harmful components such as dioxin. And the organic acid is adopted, so that elements harmful to the subsequent combustion of the coal or a gasification device do not exist in the organic acid on the premise of fully removing sulfur in the coal, and harmful pollutants are not generated. The addition of alkaline components with desulfurization effect to the acid-treated coal can be used in the thermal conversion process of briquette, lump coal and powdered coal, such as combustion and gasification. As most of the sulfur in coal which is easy to release at low temperature can be removed in the coal pyrolysis process, the release of most of the residual sulfur from the coal requires higher temperature, and the desulfurization reaction rate of alkaline components is high under the high-temperature condition, the utilization rate of a desulfurizer and the sulfur fixation efficiency thereof can be greatly improved.
The present invention will be further described with reference to specific examples.
Example (b):
coal with the average grain size of 50 microns and the sulfur content of 1 percent is used as a raw material and is pyrolyzed at the temperature of 800 ℃, and the total sulfur is removed by about 40 percent. Preparing 0.2mol/L citric acid aqueous solution, completely soaking the pyrolysis coal in the aqueous solution, wherein the molar ratio of citric acid to sulfur in the pyrolysis coal is 4:1, the soaking time is 20min, and measuring the content of sulfur in the coal after dehydration, wherein the total sulfur in the raw coal is removed by about 30% in the process. Adding Ca (OH) having an average particle size of less than 15 microns to acid-treated coal2The pellet, Ca/S1.75, is used to prepare honeycomb briquette, which is burnt and utilized on the conventional civil honeycomb briquette stove, the sulfur fixing efficiency of the process is about 80 percent, which is equivalent to 24 percent of total sulfur removal of raw coal. The sulfur removal rate of the raw coal in the whole process is 94%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for improving sulfur removal efficiency and sulfur fixation efficiency in thermal conversion of coal is characterized by comprising the following steps:
pyrolyzing coal, and removing part of sulfur elements to obtain pyrolyzed coal;
completely soaking the pyrolysis coal in an organic acid aqueous solution, and releasing sulfur in the coal in a gas form to remove the sulfur in the coal and obtain acid-treated coal;
adding an alkaline component with a desulfurization effect into the acid-treated coal to prepare fuel coal;
the alkaline component reacts with sulfur-containing acidic gas released in the thermal conversion and utilization process of the fuel coal to realize the sulfur fixation process.
2. The method for improving sulfur fixation efficiency in sulfur removal and thermal conversion in coal according to claim 1, wherein the method comprises the following steps: the coal pyrolysis temperature is 450-1000 ℃.
3. The method for improving sulfur fixation efficiency in sulfur removal and thermal conversion in coal according to claim 1, wherein the method comprises the following steps: the organic acid comprises any one or a mixture of oxalic acid, acetic acid, citric acid, malic acid and tartaric acid.
4. The method for improving sulfur fixation efficiency in sulfur removal and thermal conversion in coal according to claim 1, wherein the method comprises the following steps: the molar ratio of the organic acid in the organic acid aqueous solution to sulfur in the pyrolysis coal is 1:1-10: 1.
5. The method for improving sulfur fixation efficiency in sulfur removal and thermal conversion in coal according to claim 1, wherein the method comprises the following steps: and soaking the pyrolytic coal in an organic acid aqueous solution for 5-300 min.
6. The method for improving sulfur fixation efficiency in sulfur removal and thermal conversion in coal according to claim 1, wherein the method comprises the following steps: the alkaline component is one or a mixture of more of calcium-based desulfurizer, magnesium-based desulfurizer and sodium-based desulfurizer.
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Cited By (2)
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| CN112940821A (en) * | 2021-02-22 | 2021-06-11 | 中国矿业大学 | Method for improving nitrogen fixation efficiency in coal pyrolysis by using coal ash |
| CN113621392A (en) * | 2021-07-29 | 2021-11-09 | 中国矿业大学 | Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier |
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| CN113621392A (en) * | 2021-07-29 | 2021-11-09 | 中国矿业大学 | Method for improving sulfur fixation rate in coal pyrolysis by using ash heat carrier |
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