阅读说明：本技术 一种高硫煤用固硫添加剂及其制备方法 (Sulfur-fixing additive for high-sulfur coal 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：本发明提供了一种高硫煤用固硫添加剂及其制备方法。本发明提供的一种高硫煤用固硫添加剂,按重量份计,包括以下组分：6-7份的氧化钙、2-3份的氯化锌和(3-4份的氧化镁)。其是将该固硫添加剂与原煤按重量百分占比为90-94％的原煤和6-10％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℃,得到半焦直接燃烧,实现燃烧过程中的固硫减排。本发明的高硫煤用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 sulfur-fixing additive for high-sulfur coal and a preparation method thereof. The invention provides a sulfur fixation additive for high-sulfur coal, which comprises the following components in parts by weight: 6-7 parts of calcium oxide, 2-3 parts of zinc chloride and (3-4 parts of magnesium oxide). The sulfur-fixing additive is mixed with raw coal 90-94 wt% and sulfur-fixing additive 6-10 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 for direct combustion and to realize sulfur-fixing and emission reduction. The sulfur-fixing additive for high-sulfur coal 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 sulfur fixing additive for the high-sulfur coal is characterized by comprising the following components in parts by weight: 6-7 parts of calcium oxide, 2-3 parts of zinc chloride and 3-4 parts of magnesium oxide.

2. The sulfur fixing additive for high-sulfur coal according to claim 1, comprising the following components in parts by weight: 6.75 parts of calcium oxide, 2.25 parts of zinc chloride and 3.45 parts of magnesium oxide.

3. The sulfur-fixing additive for high-sulfur coal according to claim 1, wherein the amount of the sulfur-fixing additive added to raw coal is 6 to 10% by mass.

4. The sulfur-fixing additive for high-sulfur coal according to claim 3, wherein the amount of the sulfur-fixing additive added to raw coal is 8% by mass.

5. Clean coal containing the sulfur-fixing additive for high-sulfur coal according to any one of claims 1 to 4, characterized in that the clean coal comprises the following components in percentage by weight: 90-94% of raw coal and 6-10% of sulfur-fixing additive.

6. The method for preparing the sulfur fixation additive for the high-sulfur coal according to any one of claims 1 to 4, wherein the sulfur fixation additive is prepared by grinding and mixing calcium oxide, zinc chloride and magnesium oxide, which are components in the sulfur fixation additive.

7. The use of the sulfur-fixing additive for high-sulfur coal as claimed in 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 after semicoke is obtained, the mixture is directly combusted.

Technical Field

The invention belongs to the technical field of sulfur fixing agents, and particularly relates to a sulfur fixing additive for high-sulfur coal 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 toxic and side effects are caused to the environment, the human body and the like, and the pollution is caused to the economy of ChinaA certain loss is generated. In order to solve the problem, 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 with a good sulfur fixing effect to reduce the release of sulfur oxides and to significantly improve the high-temperature sulfur fixing effect of the sulfur fixing agent, and particularly to improve the thermal efficiency of coal combustion for sulfur fixing of high-sulfur coal combustion.

Disclosure of Invention

The invention aims to solve the technical problems and provides a sulfur fixing additive for high-sulfur coal and a preparation method thereof. The calcium-based sulfur fixing agent for high-sulfur coal, provided by the invention, has a good sulfur fixing effect, can be used for remarkably reducing the release of sulfur oxides, remarkably improving the high-temperature sulfur fixing effect of the sulfur fixing agent, improving the heat efficiency of coal combustion, and has a great popularization and application prospect.

One purpose of the invention is to provide a sulfur-fixing additive for high-sulfur coal, which comprises the following components in parts by weight: 6-7 parts of calcium oxide, 2-3 parts of zinc chloride and 3-4 parts of magnesium oxide.

As a preferable scheme, the sulfur fixing additive comprises the following components in parts by weight: 6.75 parts of calcium oxide, 2.25 parts of zinc chloride and 3.45 parts of magnesium oxide.

Further, the addition amount of the sulfur fixing additive in the raw coal is 6-10% by mass percentage.

Preferably, the addition amount of the sulfur fixing additive in the raw coal is 8% by mass.

The invention also aims to provide clean coal containing the sulfur-fixing additive for high-sulfur coal, which comprises the following components in percentage by weight: 90-94% of raw coal and 6-10% of sulfur-fixing additive.

The invention also aims to provide a preparation method of the sulfur fixing additive for the high-sulfur coal, which is prepared by grinding and mixing calcium oxide, zinc chloride and magnesium oxide which are components in the sulfur fixing additive.

The fourth purpose of the invention is to provide the application of the sulfur-fixing additive for high-sulfur coal, 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 to directly burn, and the sulfur-fixing emission reduction in the burning 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 is collected in a centralized manner in a pyrolysis process, calcium oxide, zinc chloride and magnesium oxide in an optimal proportioning range are added to play a synergistic effect, and sulfur-fixing emission reduction in a 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 ground and fully mixed to form the sulfur fixing additive, wherein the weight part of calcium oxide in the sulfur fixing additive is 6.75 parts, the weight part of zinc chloride is 2.25 parts, and the weight part of magnesium oxide is 3.45 parts. The sulfur-fixing additive and raw coal are combined into a combustion sample (8 percent of additive and 92 percent of raw coal in percentage by weight). And 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 sulfur-fixing additive is prepared by grinding the components and fully mixing the components, wherein the weight part of calcium oxide in the sulfur-fixing additive is 6 parts, the weight part of zinc chloride is 2 parts, and the weight part of magnesium oxide is 3 parts. 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 ground and fully mixed to form the sulfur fixing additive, wherein the weight part of calcium oxide in the sulfur fixing additive is 7 parts, the weight part of zinc chloride is 3 parts, and the weight part of magnesium oxide is 4 parts. The sulfur-fixing additive and raw coal are combined into a combustion sample (the weight percentage of the additive is 6 percent and the raw coal is 94 percent), the obtained sample is placed in an inert atmosphere to be heated and pyrolyzed, 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 of 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%, volatile matter was 15.86%, calorific value was 20.26MJ/kg) in a weight percentage ratio of 8% of the sulfur-fixing additive and 92% 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 fixation rate of the mixed coal sample was 97.42% and the combustion sulfur fixation rate was 85.9% (the sulfur fixation rate was measured by the DB37/T4021-2020 modified clean coal, which is the same below).

Application example 2

The sulfur-fixing additive in 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 in a shaker, and the resulting char was directly burned at a temperature of 900 ℃ at a rate of 10 ℃/min under an inert atmosphere. The pyrolysis sulfur fixation rate of the mixed coal sample is 82.92%, and the combustion sulfur fixation rate is 74.59%.

Application example 3

The sulfur-fixing additive in example 3 was mixed with ordinary coal (total sulfur content in ordinary coal was 1.41%, ash content was 16.25%, volatile matter was 34.42%, calorific value was 31.17MJ/kg) in a weight percentage of 6% of the sulfur-fixing additive and 94% of ordinary coal, and then placed in a shaker, and the resulting semicoke was directly burned at a temperature of 900 ℃ at a rate of 10 ℃/min and a final temperature of 10 ℃ under an inert atmosphere for pyrolysis. The pyrolysis sulfur fixation rate of the mixed coal sample was determined to be 88.87%, and the combustion sulfur fixation rate was determined to be 79.94%.

Comparative example 1

Mixing a sulfur-fixing additive consisting of 6.75 parts by weight of calcium oxide and 2.25 parts by weight of zinc chloride with the Ordos high-sulfur coal (12 percent of the sulfur-fixing additive and 82 percent of the Ordos high-sulfur coal are mixed according to weight percentage), putting the mixture into a shaking table, and heating and pyrolyzing the mixture 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 measured to be 69.89%, and the combustion sulfur fixation rate is measured to be 66.75%.

Comparative example 2

Mixing 8.2 parts of calcium oxide and 4.5 parts of magnesium oxide which form a sulfur fixing additive with the Yangquan coal (16 percent of the sulfur fixing additive and 84 percent of the Yangquan coal are mixed according to the weight percentage), putting the mixture into 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 70.16%, and the combustion sulfur fixation rate is 68.81%.

Comparative example 3

Mixing a sulfur fixing additive consisting of 7.4 parts by weight of calcium oxide, 1.6 parts by weight of zinc chloride and 2.8 parts by weight of magnesium oxide with the common coal (8 percent of the sulfur fixing additive and 92 percent 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 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 is 75.58%, and the combustion sulfur fixation rate is 70.79%.