阅读说明：本技术 一种煤炭固硫添加剂及其制备方法 (Coal sulfur-fixing additive and preparation method thereof ) 是由 刘粉荣 闫安 田立萍 祁鹏飞 于 2021-09-23 设计创作，主要内容包括：本发明提供了一种煤炭固硫添加剂及其制备方法。本发明提供的煤炭固硫添加剂,按重量份计,包括以下组分：5-6份的氧化钙、3-5份的碳酸钠和1-2份的二氧化锰。其是将该固硫添加剂与原煤按重量百分占比为90-95％的原煤和5-10％的固硫添加剂进行混合后,置于惰性气氛中升温热解,升温速率10℃/min,终止温度900℃,得到半焦后直接燃烧,实现燃烧过程中的固硫减排。本发明的煤炭固硫添加剂能够显著减少硫氧化物的释放,并能显著提高固硫剂的高温固硫效果、提高煤燃烧的热效率,具有极大的推广应用前景。(The invention provides a coal sulfur-fixing additive and a preparation method thereof. The coal sulfur-fixing additive provided by the invention comprises the following components in parts by weight: 5-6 parts of calcium oxide, 3-5 parts of sodium carbonate and 1-2 parts of manganese dioxide. The sulfur-fixing additive is mixed with raw coal 90-95 wt% and sulfur-fixing additive 5-10 wt%, and the mixture is heated and pyrolyzed in inert atmosphere at the heating rate of 10 deg.c/min and the stopping temperature of 900 deg.c to obtain semi-coke, which is then burnt directly to realize sulfur-fixing and emission reduction. The coal sulfur-fixing additive can obviously reduce the release of sulfur oxides, can obviously improve the high-temperature sulfur-fixing effect of the sulfur-fixing agent and the heat efficiency of coal combustion, and has great popularization and application prospects.)

1. The coal sulfur-fixing additive is characterized by comprising the following components in parts by weight: 5-6 parts of calcium oxide, 3-5 parts of sodium carbonate and 1-2 parts of manganese dioxide.

2. The coal sulfur fixing additive according to claim 1, which comprises the following components in parts by weight: 5.4 parts of calcium oxide, 3.6 parts of sodium carbonate and 1.2 parts of manganese dioxide.

3. The coal sulfur-fixing additive according to claim 1, wherein the amount of the sulfur-fixing additive added to raw coal is 5-10% by mass.

4. The coal sulfur fixation additive of claim 3, wherein the sulfur fixation additive is added to raw coal in an amount of 9% by mass.

5. Clean coal containing a sulfur fixing additive according to any one of claims 1 to 4, characterized in that the clean coal comprises the following components in percentage by weight: 90-95% of raw coal and 5-10% of sulfur-fixing additive.

6. The method for preparing the coal sulfur-fixing additive according to any one of claims 1 to 4, which is characterized by being prepared by mixing calcium oxide, sodium carbonate and manganese dioxide which are components in the sulfur-fixing additive.

7. The use of the coal sulfur-fixing additive according to any one of claims 1 to 4, wherein the sulfur-fixing additive is mixed with raw coal, and then the mixture is put into an inert atmosphere to be heated and pyrolyzed, wherein the heating rate is 10 ℃/min, the termination temperature is 900 ℃, and semicoke is obtained and then is directly combusted.

Technical Field

The invention belongs to the technical field of coal sulfur-fixing agents, and particularly relates to a coal sulfur-fixing additive and a preparation method thereof.

Background

The continuous development of the world industry leads to the increasing demand for energy. China has abundant coal resources and a long history of coal development. However, coal brings a series of environmental pollution problems in the development and utilization processes, and the environment on which human beings live is seriously damaged. SO is used as environmental pollutant caused by large-scale use of coal₂And NO_xThe pollution is the most serious, the traditional Chinese medicine has toxic and side effects on the environment, the human body and the like, and certain loss is caused to the economy of China. To solve this problemAnd various desulfurization technologies appear in the industry, and the treatment standard of the coal-fired flue gas pollutants is more strict in a new period that the environmental protection requirement is stricter and the energy optimization is perfected. At present, the industrial coal combustion realizes near zero emission.

The energy structure of rich coal, poor oil and less gas enables China to still use coal as a main energy source for a long time in the future. The direct combustion and utilization of coal are important reasons for environmental problems such as haze, acid rain and the like. At present, high-quality coal resources in China are greatly consumed in the last decades of mining, and high-sulfur coal with low coalification degree is abundant in reserves. If the low-rank high-sulfur coal with rich reserves can be cleanly utilized, the problems of environmental pollution and energy shortage at present can be effectively relieved.

The desulfurization technology adopted in industry mainly comprises desulfurization before combustion, in-furnace desulfurization and desulfurization of tail flue gas after combustion. The in-furnace desulfurization technology is characterized in that a sulfur-fixing agent is added in a furnace, so that sulfur dioxide generated in the combustion process of coal directly reacts with the sulfur-fixing agent to be solidified, and the effect of reducing the release of the sulfur dioxide is achieved. However, for a long time, domestic products such as coal saving agents, sulfur fixing agents, combustion improvers and the like are difficult to popularize in a large amount due to high price and single product performance, and some products have sulfur fixing effect, but the increase cost is high, so that enterprises are difficult to accept.

On the other hand, the coal briquette technology is an important technology for clean and efficient utilization of coal, the use of civil clean fuel and coal briquettes is encouraged, and the reduction of the scattered burning of civil bituminous coal is an important measure for controlling air pollution. However, the sulfur fixing agent used in the briquette products in the current market generally has the problems of poor high-temperature sulfur fixing effect and reduced combustion performance of the briquette, thereby causing certain resource waste.

The method for improving the desulfurization effect mainly comprises two ways: firstly, the utilization rate of the sulfur fixing agent is improved; secondly, the combustion technology is improved. Therefore, under the condition of certain combustion conditions, the method is an effective way for enhancing the high-temperature sulfur fixation effect of the sulfur fixation agent and improving the heat efficiency of the molded coal.

In addition, the northern part of China is cold in winter, the vast rural areas are limited by various conditions such as economy, geography and the like, centralized heat supply is difficult to realize, and the environment pollution is great because the scattered coal is mainly combusted by each household to pass the winter. If the high-sulfur coal and the sulfur-fixing agent are firstly subjected to centralized co-pyrolysis to obtain the semicoke with good combustion sulfur-fixing performance, and then the semicokes are used for individual heating, the problem of environmental pollution can be effectively solved, and the national energy strategy of coal quality utilization and distribution as required is realized. And the small amount of sulfur-containing gases released during pyrolysis can be combined with flue gas sulfur fixation to further reduce sulfur-containing gas emissions.

In the coal sulfur fixing agent, the calcium-based sulfur fixing agent is cheap and easy to obtain, so that the calcium-based sulfur fixing agent is a sulfur fixing agent which is researched more at present, but the single calcium-based sulfur fixing agent has the problems of low calcium utilization rate and the like. Therefore, it is an urgent technical problem in the art to provide a calcium-based sulfur fixing agent having a good sulfur fixing effect to reduce the release of sulfur oxides, to significantly improve the high-temperature sulfur fixing effect of the sulfur fixing agent, and to improve the thermal efficiency of coal combustion.

Disclosure of Invention

The invention aims to solve the technical problems, and provides a coal sulfur-fixing additive and a preparation method thereof. The calcium-based sulfur fixing agent provided by the invention has a good sulfur fixing effect, can obviously reduce the release of sulfur oxides, can obviously improve the high-temperature sulfur fixing effect of the sulfur fixing agent, can improve the thermal efficiency of coal combustion, and has great popularization and application prospects.

One purpose of the invention is to provide a coal sulfur-fixing additive, which comprises the following components in parts by weight: 5-6 parts of calcium oxide, 3-5 parts of sodium carbonate and 1-2 parts of manganese dioxide.

As a preferable scheme, the sulfur fixing additive comprises the following components in parts by weight: 5.4 parts of calcium oxide, 3.6 parts of sodium carbonate and 1.2 parts of manganese dioxide.

Further, the addition amount of the sulfur fixing additive in the raw coal is 5-10% by mass percent.

Preferably, the sulfur fixing additive is added into raw coal in an amount of 9% by mass.

The invention also aims to provide clean coal containing the sulfur fixing additive, and the clean coal comprises the following components in percentage by weight: 90-95% of raw coal and 5-10% of sulfur-fixing additive.

The invention also aims to provide a preparation method of the coal sulfur-fixing additive, which is prepared by mixing calcium oxide, sodium carbonate and manganese dioxide which are components in the sulfur-fixing additive.

The fourth purpose of the invention is to provide the application of the coal sulfur-fixing additive, which is to mix the sulfur-fixing additive with raw coal, put the mixture in an inert atmosphere to heat and pyrolyze, wherein the heating rate is 10 ℃/min, the termination temperature is 900 ℃, semicoke is obtained and then directly burned, and the sulfur-fixing emission reduction in the combustion process is realized.

The invention has the following beneficial effects:

the sulfur-fixing additive disclosed by the invention is simple in preparation method and low in cost, sulfur-containing gas can be collected in a centralized manner at one time in the pyrolysis process, the added calcium oxide, sodium carbonate and manganese dioxide can play a good synergistic effect under the optimal proportion, and the sulfur-fixing emission reduction in the combustion process is realized.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is described in detail below with reference to the following embodiments, and it should be noted that the following embodiments are only for explaining and illustrating the present invention and are not intended to limit the present invention. The invention is not limited to the embodiments described above, but rather, may be modified within the scope of the invention.

Example 1

The components are fully mixed to form the sulfur fixing additive, wherein the weight part of calcium oxide in the sulfur fixing additive is 5.4 parts, the weight part of sodium carbonate is 3.6 parts, and the weight part of manganese dioxide is 1.2 parts. And (3) combining the sulfur-fixing additive and raw coal into a combustion sample (9 wt% of additive and 91 wt% of raw coal), putting the obtained sample in an inert atmosphere, heating for pyrolysis, wherein the heating rate is 10 ℃/min, the final temperature is 900 ℃, and the obtained semicoke is directly combusted.

Example 2

The components are fully mixed to form the sulfur fixing additive, wherein the weight part of calcium oxide in the sulfur fixing additive is 5 parts, the weight part of sodium carbonate is 3 parts, and the weight part of manganese dioxide is 1 part. The sulfur-fixing additive and raw coal are combined into a combustion sample (10 percent of additive and 90 percent of raw coal in percentage by weight), the obtained sample is placed in an inert atmosphere for heating pyrolysis, the heating rate is 10 ℃/min, the final temperature is 900 ℃, and the obtained semicoke is directly combusted.

Example 3

The components are fully mixed to form the sulfur fixing additive, wherein the weight part of calcium oxide in the sulfur fixing additive is 6 parts, the weight part of sodium carbonate is 5 parts, and the weight part of manganese dioxide is 2 parts. The sulfur-fixing additive and raw coal are combined into a combustion sample (5 percent of additive and 95 percent of raw coal in percentage by weight), the obtained sample is placed in an inert atmosphere for heating pyrolysis, the heating rate is 10 ℃/min, the final temperature is 900 ℃, and the obtained semicoke is directly combusted.

Application example 1

The sulfur-fixing additive in example 1 was mixed with Ordos high-sulfur coal (the total sulfur content in Ordos high-sulfur coal was 3.02%, ash content was 31.85%, volatiles content was 15.86%, and calorific value was 20.26MJ/kg) in a weight percentage of 9% of the sulfur-fixing additive and 91% of Ordos high-sulfur coal, and the mixture was put in a shaker, and the resulting semicoke was directly burned at a temperature of 10 ℃/min and 900 ℃ at the final temperature in an inert atmosphere. The pyrolysis sulfur-fixing rate of the mixed coal sample was 88.65% and the combustion sulfur-fixing rate was 87.05% (the sulfur-fixing rate was determined by DB 37/T4021-.

Application example 2

The sulfur-fixing additive of example 2 was mixed with Yangquan coal (containing 2.11% of total sulfur, 18.96% of ash, 5.87% of volatile matter, and 25.54MJ/kg of calorific value) in an amount of 10% by weight of the sulfur-fixing additive and 90% of the Yangquan coal, and the mixture was put into a shaker and pyrolyzed by heating in an inert atmosphere at a heating rate of 10 ℃/min and a final temperature of 900 ℃. Directly burning the obtained semicoke. The pyrolysis sulfur fixation rate of the mixed coal sample is 85.22%, and the combustion sulfur fixation rate is 77.01%.

Application example 3

The sulfur-fixing additive in example 3 was mixed with ordinary coal (ordinary coal contains 1.41% of total sulfur, 16.25% of ash, 34.42% of volatile matter, and 31.17MJ/kg of calorific value) in a weight ratio of 5% of the sulfur-fixing additive and 95% of ordinary coal, and then placed in a shaker, and the mixture was pyrolyzed by heating in an inert atmosphere at a heating rate of 10 ℃/min and a final temperature of 900 ℃. Directly burning the obtained semicoke. The pyrolysis sulfur fixation rate of the mixed coal sample was determined to be 86.78%, and the combustion sulfur fixation rate was determined to be 80.14%.

Comparative example 1

Mixing a sulfur-fixing additive consisting of 5.4 parts by weight of calcium oxide and 3.6 parts by weight of sodium carbonate with the Ordos high-sulfur coal (15% of the sulfur-fixing additive and 85% of the Ordos high-sulfur coal are mixed according to the weight percentage), putting the mixture in a shaking table, heating and pyrolyzing the mixture in an inert atmosphere at a heating rate of 10 ℃/min and a final temperature of 900 ℃, and directly burning the obtained semicoke. The pyrolysis sulfur fixation rate of the mixed coal sample was 67.32%, and the combustion sulfur fixation rate was 65.21%.

Comparative example 2

Mixing a sulfur fixing additive consisting of 6.8 parts by weight of calcium oxide and 2.1 parts by weight of sodium carbonate with the Yangquan coal (12% of the sulfur fixing additive and 92% of the Yangquan coal are mixed according to the weight percentage), putting the mixture in a shaking table, heating and pyrolyzing the mixture in an inert atmosphere at the heating rate of 10 ℃/min and the final temperature of 900 ℃, and directly burning the obtained semicoke. The pyrolysis sulfur fixation rate of the mixed coal sample is 65.54 percent, and the combustion sulfur fixation rate is 63.38 percent.

Comparative example 3

Mixing a sulfur fixing additive consisting of 6.5 parts by weight of calcium oxide, 2.5 parts by weight of sodium carbonate and 0.8 part by weight of manganese dioxide with the common coal (10% of the sulfur fixing additive and 90% of the common coal are mixed according to the weight percentage), putting the mixture in a shaking table, heating and pyrolyzing the mixture in an inert atmosphere at the heating rate of 10 ℃/min and the final temperature of 900 ℃, and directly burning the obtained semicoke. The pyrolysis sulfur fixation rate of the mixed coal sample is 70.96%, and the combustion sulfur fixation rate is 67.83%.