CN103131519A - Boiler fire coal sulfur fixation composition method - Google Patents

Boiler fire coal sulfur fixation composition method Download PDF

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CN103131519A
CN103131519A CN201310063276XA CN201310063276A CN103131519A CN 103131519 A CN103131519 A CN 103131519A CN 201310063276X A CN201310063276X A CN 201310063276XA CN 201310063276 A CN201310063276 A CN 201310063276A CN 103131519 A CN103131519 A CN 103131519A
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coal
sulfur
combustion
calcium
limestone
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CN201310063276XA
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张亚南
吴迪
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洛阳大泽节能环保科技有限公司
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Abstract

The invention discloses a boiler fire coal sulfur fixation composition method. The composition of boiler fire coal comprises 30-50wt% of limestone, 3-20wt% of calcium hydroxide, 10-20wt% of calcium carbonate, 3-15wt% of sodium carbonate, 10-20wt% of ammonium nitrate and 10-30wt% of a clinker burning aid, the sum of the weight proportions of the above components is 100%, the water content is less than 2%, and the content of calcium oxide in limestone is not lower than 40%. The method has the advantages of easy buying of the above raw materials in the market, saving of above 13% coal, and reduction of the sulfur dioxide discharge amount by above 90%.

Description

一种锅炉用燃煤助燃固硫组配方法 A boiler with a combustion coal desulfurization method of assembling

技术领域 FIELD

[0001] 本发明属助燃固硫技术领域,尤其是一种锅炉用燃煤助燃固硫组配方法。 Genus [0001] combustion desulfurization technique of the present invention, and in particular a boiler fired with solid sulfur group combustion method.

背景技术 Background technique

[0002] 随着国民经济的快速发展,我国煤炭的地下储藏量也趋于迅速减少的势头,优质煤因超量开采和大量出口,其减少的势头尤为严重,而像石头一样的劣质高硫煤留在国内,由于其热值低和污染严重给工业生产和人民生活带来了严重困难,同时给大气环境造成了严重危害。 [0002] With the rapid development of the national economy, China's underground reserves of coal also tends to reduce the momentum of rapid, high-quality coal due to over-exploitation and large exports, reducing its momentum is particularly serious, like a stone the poor quality of high-sulfur coal remain in the country, due to its low calorific value and serious pollution to industrial production and people's life has brought serious difficulties, while causing serious harm to the atmosphere. 从发展和战略眼光来看,环境污染和能源匮乏问题,已对国民的生存与发展构成了严重威胁,到了非解决不可的地步。 From the strategic point of view and development, environment pollution and energy shortage problems have been on the survival and development of the national poses a serious threat to the point must be solved.

[0003] 市场上生产燃煤助燃固硫剂种类甚多,但真正能解决煤炭燃烧过程中的环保、节能、除硫等问题的微乎其微,例如燃煤不充分,粉尘、结焦酸性有害气体排放不彻底,不除硫等等,造成不能有效的提高热效率及含硫气体排入大气。 [0003] production in the market many types of coal-fired combustion desulfurization agent, but really solve the coal combustion process of environmental protection, in addition to sulfur and the like are little, is not sufficient for example coal dust, coke acid is not harmful emissions thoroughly, and the like in addition to sulfur, resulting in not effectively improve the thermal efficiency and sulfur-containing gas into the atmosphere. 煤中硫是最有害的化学成分。 Sulfur in coal is the most harmful chemicals. 煤燃烧时,其中硫生成二氧化硫,腐蚀金属设备,污染环境。 When coal combustion, wherein the sulfur to form sulfur dioxide, corrosion of metal equipment, pollution of the environment.

[0004] 市场上的燃煤助燃固硫剂成分为锰矿石,碳酸钙和化学外加剂。 [0004] Sulfur coal combustion agent component on the market for manganese ore, calcium carbonate, and chemical admixtures. 锰矿石与化学外加剂共同作用,可以降低煤粉的燃点,提高煤粉灰分的熔点,并在高温下调节燃烧气氛,达到促进劣质煤的集中燃烧的目的;碳酸钙和化学外加剂共同作用,遇煤燃烧后产生的二氧化硫起反应,将硫物质沉淀在煤渣中,从而减少了排入大气的二氧化硫;但是所采用的化学外加剂在自然界比较难于获取,而且在锅炉用中对燃煤固硫的效果要求很高,因此,需要一种更理想的助燃固硫组配方法,能够进一步降低煤粉的燃点,提高煤粉的利用效率,更加节约用煤,进一步将煤燃烧时产生的二氧化硫中的硫元素沉淀在煤渣中,减少有害气体的排放。 Manganese ore and chemical admixtures interaction, can be reduced ignition of pulverized coal, coal ash increase the melting point, and adjusting the atmosphere at a high temperature combustion, to achieve the purpose of promoting combustion of low quality coal concentration; interaction calcium carbonate and chemical admixtures, in case of coal the sulfur dioxide produced by combustion reacts, the slag sulfur precipitated in the material, thereby reducing the sulfur dioxide into the atmosphere; however, used more difficult to obtain the chemical admixture in nature, and in the coal-fired boiler sulfur the high performance requirements, therefore, a need for a better method of assembling sulfur combustion, ignition of pulverized coal can be further reduced, improving the utilization efficiency of pulverized coal, coal more economical, will produce further combustion of coal sulfur dioxide the precipitated elemental sulfur in the slag, the reduction of harmful emissions.

[0005] 鉴于上述原因,现有的燃煤助燃固硫配方需要改进。 [0005] For these reasons, the conventional coal combustion Sulfur formulation needs to be improved.

发明内容 SUMMARY

[0006] 本发明的目的是为了克服现有技术中的不足,提供一种锅炉用燃煤助燃固硫组配方法,原料在市场上容易购买,能够达到节煤13%以上,降低二氧化硫排放量90%以上的效果。 [0006] The object of the present invention is to overcome the deficiencies of the prior art, there is provided a desulfurization method of assembling a boiler with coal combustion, raw materials easily available in the market, more than 13% can be achieved economizer, reducing sulfur dioxide emissions more than 90% of the effect.

[0007] 本发明为了实现上述目的,采用如下技术方案:一种锅炉用燃煤助燃固硫组配方法,组配重量百分比为:石灰石30-50 %,氢氧化钙3-20 %,碳酸钙10-20 %,碳酸钠3_15 %,硝酸铵10-20%,熟料助烧剂10-30%,以上的各组份按重量配比之和为100%。 [0007] To achieve the above object of the present invention, the following technical solution: A boiler fired with solid sulfur group with combustion methods, the group with weight percent: 30-50% limestone, calcium hydroxide, 3-20% calcium carbonate 10-20%, 3_15% sodium carbonate, ammonium nitrate 10-20%, 10-30% clinker sintering aid, the above ratio of the components is 100% by weight.

[0008] 石灰石30-40 %,氢氧化钙10-20%,碳酸钙10_20 %,碳酸钠3_10 %,硝酸铵10-15%,熟料助烧剂10-20%,以上的各组份按重量配比之和为100%。 [0008] The limestone 30-40%, 10-20% calcium hydroxide, calcium carbonate 10_20% sodium carbonate 3_10%, 10-15% ammonium nitrate, 10-20% clinker sintering aid, each of the above components by and the weight ratio of 100%.

[0009] 石灰石中氧化钙的含量不低于40%。 [0009] The limestone content of calcium oxide is not less than 40%.

[0010] 助燃固硫物质为含钴、镉、镧系稀土天然矿物其中的一种或组合。 [0010] Sulfur oxidizing substance containing one or a combination of cobalt, cadmium, the lanthanide rare natural mineral therein.

[0011] 熟料助烧剂组配重量百分比为:氧化钴55-70%,氧化镉20-40%,镧系稀土二氧化镧5-10%,以上的各组份按重量配比之和为100%。 [0011] group with clinker sintering aids weight percent: 55-70% cobalt oxide, cadmium oxide, 20-40%, lanthanide 5-10% lanthanum oxide, the above ratio of the components, by mass, and 100%. [0012] 催化燃烧的特点是降低反应所需的活化能,使反应能在较低的温度下进行。 [0012] Catalytic combustion is characterized by reduced activation energy required for the reaction, the reaction can be performed at lower temperatures. 煤粉在着火阶段,主要表现为挥发分的释放和燃烧。 Pulverized coal ignition stage, mainly for the release of volatiles and combustion. 随着大部分挥发分释放完毕,周围的氧气逐渐扩散到煤粉裂解后的焦炭表面并渗透到孔隙结构中,在一定的温度作用下,氧气和焦碳表面碳和氢作用形成二氧化碳和水为主的产物并往外扩散。 With most of the volatile evolution is complete, ambient oxygen is gradually diffused into the surface of the coal char cracking and penetrate into the porous structure, at a certain temperature effect, and the surface of the carbon oxygen and hydrogen to form carbon dioxide and water acting as coke and diffusion out of the main product. 在这个阶段,促进氧气与焦碳的充分接触能提高煤粉的燃尽。 At this stage, the promotion of full contact with oxygen and can improve coke burn pulverized coal. 特别是在煤粉燃烧的后期阶段,由于有机碳的消耗,煤粉体积逐渐收缩,煤粉中的灰分逐渐覆盖在外层,阻碍了氧气往煤焦内部的进一步扩散,不可避免的造成难燃尽。 Especially in the later stages of coal combustion, the organic carbon consumption, gradual contraction of the volume of the pulverized coal, the coal ash gradually cover the outer layer, to hinder further diffusion of oxygen inside the coal, inevitably result in difficult burnout .

[0013] 上述组分中,硝酸铵与熟料助烧剂在高温下发生一系列的物理化学变化,硝酸铵与熟料助烧剂形成二氧化铵,金属离子(如铵、钴、镧)等等。 [0013] In the above components, the ammonium nitrate clinker sintering aids at high temperature range of physical and chemical changes, ammonium nitrate and ammonium clinker sintering aid forming dioxide, metal ions (e.g., ammonium, cobalt, lanthanum) and many more. 氧化钙可以起到增氧作用,改变煤燃烧时局部缺氧的状况,且热量集中,有助于煤的进一步燃烧,继而提高煤的燃烧率,减小煤粒外排,降低空气污染和能源浪费;而金属离子与煤碳中含有的腐植酸盐将进行盐基交换而生成着火点较低的腐值酸盐,当煤粉表面的这些气态分子量的碳氢化合物质量分数达到一定值时,与氧气化合反应放热远远大于散热,使反应迅速加快,形成着火,改变了煤碳的着火性能。 Calcium oxide can play a role in oxygen, changing the local hypoxia during coal combustion, and heat concentration, contributes to further combustion of the coal, in turn, increase the rate of combustion of coal, the coal particles is reduced efflux, reducing air pollution and energy waste; humate and coal with a metal ion contained in the base exchange will generate a low ignition point value salt corrosion, when such gaseous hydrocarbon mass fraction of molecular weight of coal powder reaches a certain value, and oxygen compound is far greater than the exothermic reaction heat, the reactor is rapidly accelerated, forming fire, changing the ignition quality of the coal. 同时,某些金属盐分解的断裂分解,使气态挥发分较快释放出来,增加了易燃的挥发分含量,从而加快了煤的着火速度。 Also, some decomposition of metal fracture decomposition, the gaseous volatiles released faster, increasing the content of volatile flammable, thus accelerating the speed of ignition of coal.

[0014] 在燃烧过程中,氧气不断从金属向碳原子传递,加快了氧气的扩散速度,有利于加速碳的燃烧,增加煤的燃烬率,但金属离子也会与煤中的氧基官能团结合,同时在燃烧中也会与煤中矿物质作用,因此在使用锅炉用燃煤助燃固硫组配方法时应注意含量对催化效果的影响,并不是掺量越多越好。 [0014] In the combustion process, oxygen is continuously transferred from the metal to the carbon atom, to accelerate the diffusion rate of oxygen, it is conducive to accelerate the combustion of carbon, increasing the rate of burnout of coal, but also the metal ions in the group the functional groups of coal binding, but also, so attention in coal combustion in a boiler should be the role of the mineral group with solid sulfur coal combustion method contents on the catalytic effect is not better dosage.

[0015] 燃烧中产生的二氧化铵,氧化钠等金属氧化物本身热容小,且能催化煤炭中长链脂肪族烷烃键的断裂,变成相对较小的分子,增加分子的运动,降低煤的热容,提高了煤的热传递。 [0015] dioxide, ammonium, sodium oxide and other metal oxides produced during combustion itself small heat capacity, capable of long-chain aliphatic hydrocarbons catalyzed bond coal fracture into relatively smaller molecules, increased molecular motion, reduced coal heat capacity, improve heat transfer coal. 电子转移学说从电子催化理论入手,认为金属离子嵌入碳晶格的内部使碳的微观结构发生变化并作为电子给予体,通过电子转移加速部分反应步骤,此外,催化剂中的金属离子在加热过程中能够被活化,从而其自身的电子发生转移成为电子给予体,金属离子将形成空穴,而碳表面的电子构型也将发生变化,这种电荷的迁移将加速某些反应,从而提高了整个反应的速度,使燃烧得更充分。 Electron transfer from the electron theory start catalytic theory, that inside of the metal ions into the carbon lattice structure of the carbon that the microstructure is changed and as the electron donor, electron transfer through the accelerating portion of the reaction step, in addition, the metal ion catalyst is heated during the can be activated, so that occurrence of electron transfer itself becomes an electron donor, a metal ion will form a hole, and the electronic configuration of the carbon surface will also change, migration of such charge will accelerate certain reactions, thereby improving the overall the reaction rate of the combustion more fully. 同时,熟料助烧剂中的一种无机盐受热达到一定温度时发生微爆,使周围的可燃物膨松,增加供氧面积,使燃煤能够得到更加充分的燃烧,燃煤热效率得到了显著提高。 Meanwhile, the occurrence of an inorganic salt is heated in the clinker sintering agent reaches a certain temperature microburst, combustibles around bulky, increase oxygen supply area, so that coal can be more complete combustion, thermal efficiency of coal-fired Significantly increased.

[0016] 煤在燃烧时产生高温,硫与氧反应生成二氧化硫,石灰石中的氧化钙与二氧化硫反应生成亚硫酸钙,亚硫酸钙再和氧气反应生成硫酸钙,通过这个过程大多数的硫就被固定下来了,不会以二氧化硫的形式释放到大气中形成酸雨。 [0016] Coal is at a high temperature combustion, sulfur reacts with oxygen to sulfur dioxide, calcium oxide and sulfur dioxide in the reaction of limestone to form calcium sulfite, calcium sulfite and then react with oxygen to produce calcium sulfate, most of the sulfur by this process was fixed, and not released into the atmosphere as acid rain, sulfur dioxide is formed.

[0017] 本发明的有益效果是:原料在市场上容易购买,能够达到节煤13%以上,降低二氧化硫排放量90%以上的效果。 Advantageous Effects [0017] The present invention is: the raw material easily available in the market, more than 13% can be achieved economizer, reducing sulfur dioxide emissions more than 90% effect.

[0018] 加入氧化镉可提高生料的活性和稳定性,适量的氧化镉加入后能显著提高熟料质量,但是掺加过量则使得熟料游离氧化钙增加,熟料质量下降。 [0018] The addition of cadmium oxide can improve the activity and stability of the raw material, after the addition of an appropriate amount of cadmium oxide can significantly improve the quality of the clinker, but adding an excess of free calcium oxide is increased so that the clinker, clinker quality decrease.

[0019] 镧在高温下对加快反应速度起到明显的作用,镧系稀土元素是以镧为代表的一族元素,具有相似的外层电子结构,对熟料的煅烧均具有促进作用,镧系稀土元素在熟料烧成固相反应阶段可通过形成中间产物促进固相反应,在烧成阶段对硅酸盐矿物形成起催化作用,能使碳酸盐分解温度、固相反应温度、阿特利形成温度等下降10-35度,达到同样烧成程度的时间缩短5-10秒,当在体系中添加镧系稀土元素时,可夺取反应分子形成反应活化体,然后再转变为产物分子,从而大大加快了矿物的形成速率,与此相应,矿物形成速[率的加快又促使氧化钙粒子扩散迁移速度的加快,使新分解而产生的氧化钙能快速地与酸性氧化物反应形成中间产物,并导致正在分解的碳酸盐颗粒的产物层迅速变薄,进而又加快碳酸盐分解反应的速度,加快二氧化硫与氧化钙的 [0019] La acts to accelerate the reaction rate at high temperatures of significant effects, lanthanide rare earth elements are lanthanum family elements represented have similar outer electron configuration, it has a clinker calcined promoted, lanthanoid clinker earth elements in the solid phase reaction stage solid-phase reaction promoted by the formation of an intermediate product in the firing stage is formed from a silicate mineral catalysis can carbonate decomposition temperature, the solid phase reaction temperature, Art facilitate the formation of temperature drop of 10-35, the firing time to reach the same degree shortening 5-10 seconds, when the lanthanum series rare earth element in the system, the abstraction reactions of activated molecules to form a reaction, and then converted to product molecules, thus greatly accelerating the rate of formation of the mineral, with this, mineral formation accelerating speed [rate of calcium oxide particles, while promoting the migration to accelerate diffusion rate, so that the new generated by decomposition reaction of calcium oxide can quickly form an intermediate product with an acidic oxide and cause decomposition product layer being rapidly thinned carbonate particles, which in turn speed the decomposition reaction of carbonate, calcium oxide and sulfur dioxide accelerate 应生成亚硫酸钙的速度,同时催化亚硫酸钙在生成时迅速与氧气发生反应生成硫酸钙,并促使硫酸钙固化成块。 Speed ​​should be generated calcium sulfite, and calcium sulfite catalyzed rapid calcium sulfate reacts with oxygen generating, and causes calcium sulfate solidified into block.

[0020] 燃煤助燃固硫配方内含有大量的活性金属氧化物,除了和二氧化硫发生化学反应之外,还起到助燃和催化燃烧的作用,改变了原来燃烧不充分的状况。 [0020] Sulfur the coal combustion formulation contains a lot of active metal oxide, and sulfur dioxide in addition to a chemical reaction, but also play the role of combustion and catalytic combustion, combustion is not sufficient to change the original condition. 燃煤助燃固硫配方内还有相当数量的单质金属高能燃料,燃烧时和强氧化剂发生置换反应释放出大量的热能,使燃烧温度提高50-100度以上,把劣质煤中原来不能燃烧的成份,如煤矸石也能充分燃烧,使燃烧后炉渣含量下降5-10%。 Sulfur coal combustion the formulation of a substantial number of high-energy elemental metal fuel, combustion, and strong oxidizing agents replacement reaction releases large amounts of heat, the combustion temperature is increased by 50-100 degrees, the low-quality coal can burn ingredients originally , such as the combustion can be sufficiently gangue, the slag content after combustion decreased 5-10%. 加入固硫配方后,使炉膛内的燃烧温度提高50-100,把那些微细煤粉面及悬浮颗粒物充分燃烧转化成热能。 After the addition of solid sulfur formulation, the combustion temperature in the furnace to improve 50-100, that the suspended particles and the fine coal powder combustion surface into thermal energy.

[0021] 因此,提高煤的燃烧热效率,同时又大大地降低了烟尘污染,使烟尘格曼黑度达到国家要求和控制的标准。 [0021] Thus, to improve the thermal efficiency of coal combustion, while greatly reducing the smoke pollution, a black smoke reaches Gehman national requirements and control standards. 解决了环境污染问题,不会给天空排放黑烟和灰尘,减少了对大气质量的破坏,大大降低烟气中二氧化硫排量,提高燃烧温度,使燃料燃烧充分,消除黑烟,净化空气,减少对环境的污染。 Solve the problem of environmental pollution is not discharged to the sky black smoke and dust, reducing the damage to the air quality, greatly reduced emissions of sulfur dioxide in flue gas, to improve the combustion temperature, the combustion of the fuel sufficiently to eliminate smoke, purify the air, reducing pollution of the environment.

[0022] 燃煤助燃固硫配方中各组分对煅烧设备无损害,通过节煤固硫可有效减少硫气体排放,因此,具有重大经济、社会、环保效益,可广泛用于锅炉用生产中。 [0022] coal combustion sulfur-free formulation of each component of the burning equipment damage, by saving coal sulfur can effectively reduce sulfur emissions, therefore, is of great economic, social and environmental benefits can be widely used in the production of boiler .

具体实施方式 Detailed ways

[0023] 下面结合实施例对本发明作进一步说明: [0023] below with reference to embodiments of the present invention is further described:

[0024] 实施例1 [0024] Example 1

[0025] 组配重量百分比为:石灰石30-50%,氢氧化钙3-20%,碳酸钙10_20%,碳酸钠3-15%,硝酸铵10-20%,熟料助烧剂10-30%,以上的各组份按重量配比之和为100% ;石灰石中氧化钙的含量不低于40%。 [0025] group with weight percent: 30-50% limestone, calcium hydroxide, 3-20%, 10_20% calcium carbonate, sodium carbonate, 3-15%, 10-20% ammonium nitrate, 10-30 clinker sintering aid % or more, the ratio of the components is 100% by weight and; limestone calcium oxide content not less than 40%.

[0026] 实施例2 [0026] Example 2

[0027] 石灰石30-40 %,氢氧化钙10-20%,碳酸钙10_20 %,碳酸钠3_10 %,硝酸铵10-15%,熟料助烧剂10-20%,以上的各组份按重量配比之和为100% ;石灰石中氧化钙的含量不低于40%。 [0027] limestone 30-40%, 10-20% calcium hydroxide, calcium carbonate 10_20% sodium carbonate 3_10%, 10-15% ammonium nitrate, 10-20% clinker sintering aid, each of the above components by and the weight ratio of 100%; the content of calcium oxide in the limestone of not less than 40%.

[0028] 实施例3 [0028] Example 3

[0029] 助燃固硫物质为含钴、镉、镧系稀土天然矿物其中的一种或组合。 [0029] Sulfur oxidizing substance containing one or a combination of cobalt, cadmium, the lanthanide rare natural mineral therein.

[0030] 实施例4 [0030] Example 4

[0031] 熟料助烧剂组配重量百分比为:氧化钴55-70%,氧化镉20-40%,镧系稀土二氧化镧5-10%,以上的各组份按重量配比之和为100%。 [0031] group with clinker sintering aids weight percent: 55-70% cobalt oxide, cadmium oxide, 20-40%, lanthanide 5-10% lanthanum oxide, the above ratio of the components, by mass, and 100%.

Claims (5)

1.一种锅炉用燃煤助燃固硫组配方法,其待征在于:组配重量百分比为:石灰石30-50 %,氢氧化钙3-20 %,碳酸钙10-20 %,碳酸钠3_15 %,硝酸铵10-20 %,熟料助烧剂10-30%,以上的各组份按重量配比之和为100%。 A method of assembling a boiler with solid sulfur coal combustion, which is to be characterized in that: the group with weight percent: 30-50% limestone, calcium hydroxide, 3-20%, 10-20% calcium carbonate, sodium carbonate 3_15 %, 10-20% ammonium nitrate, 10-30% clinker sintering aid, the above ratio of the components is 100% by weight.
2.根据权利要求1所述的一种锅炉用燃煤助燃固硫组配方法,其待征在于:石灰石30-40%,氢氧化钙10-20%,碳酸钙10-20%,碳酸钠3_10%,硝酸铵10-15 %,熟料助烧剂10-20%,以上的各组份按重量配比之和为100%。 2. A boiler according to claim 1 Sulfur group with coal combustion method, which is to be characterized in that: 30-40% limestone, calcium hydroxide, 10-20%, 10-20% calcium carbonate, sodium carbonate 3_10%, 10-15% ammonium nitrate, 10-20% clinker sintering aid, the above ratio of the components is 100% by weight.
3.根据权利要求1所述的一种锅炉用燃煤助燃固硫组配方法,其待征在于:石灰石中氧化钙的含量不低于40%。 3. A boiler according to claim 1 Sulfur group with coal combustion method, which is to be characterized in that: limestone content of calcium oxide is not less than 40%.
4.根据权利要求1所述的一种锅炉用燃煤助燃固硫组配方法,其待征在于:助燃固硫物质为含钴、镉、镧系稀土天然矿物其中的一种或组合。 4. A boiler according to claim 1 Sulfur group with coal combustion method, which is to be characterized in that: Sulfur oxidizing substances containing cobalt, cadmium, the lanthanide rare earth minerals natural one or a combination of them.
5.根据权利要求1所述的一种锅炉用燃煤助燃固硫组配方法,其待征在于:熟料助烧剂组配重量百分比为:氧化钴55-70%,氧化镉20-40%,镧系稀土二氧化镧5-10%,以上的各组份按重量配比之和为100%。 5. A boiler according to claim 1 Sulfur group with coal combustion method, which is to be characterized in that: the clinker sintering aids group with weight percent: 55-70% cobalt oxide, cadmium oxide 20-40 %, lanthanide 5-10% lanthanum oxide, the above ratio of each component and the sum is 100% by weight.
CN201310063276XA 2013-02-07 2013-02-07 Boiler fire coal sulfur fixation composition method CN103131519A (en)

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