CN1312355A - Sulfur-fixing dust-eliminating combustion-supporting briquet additive - Google Patents
Sulfur-fixing dust-eliminating combustion-supporting briquet additive Download PDFInfo
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- CN1312355A CN1312355A CN 01104436 CN01104436A CN1312355A CN 1312355 A CN1312355 A CN 1312355A CN 01104436 CN01104436 CN 01104436 CN 01104436 A CN01104436 A CN 01104436A CN 1312355 A CN1312355 A CN 1312355A
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Abstract
The combustion-supporting additive is formed from sulfur-fixing agent, binder, expansion loose adsorbing agent, sulfur-fixing catalyst and combustion-supporting oxidizing agent. It is applicable to civil or industrial shaped coal, for example civil honeycomb briquette. Its sulfur-fixing rate can be up to 65-98%, the coal can be saved by 15-20%, and the carbon content contained in the cinder can be reduced by 40-65%.
Description
The invention relates to the technical field of pollution control of coal-fired sulfur dioxide and smoke dust and combustion-supporting energy conservation, in particular to a high-efficiency sulfur-fixing dust-removing combustion-supporting additive for briquettes.
China is the largest coal producing country and consuming country in the world, coal accounts for 75% of energy structures, 85% of coal is directly used for combustion, sulfur dioxide and carbonaceous dust discharged in combustion become main pollutants of atmosphere in China, statistics show that 80% of smoke dust and 90% of sulfur dioxide in atmospheric pollution come from fire coal, acid rain caused by fire coal pollution becomes public nuisance, and 40% of China's territory area is in an acid rain pollution control area. Therefore, the treatment of coal pollution and the reduction of the emission of sulfur dioxide and smoke dust of the coal are the major problems of environmental protection work in China at present. The civil cooking range has a plurality of wide distribution quantities in rural areas and cities in China, carbon smoke is large due to insufficient coal combustion, unified management and centralized treatment are difficult, low-altitude emission of smoke is avoided, diffusion is not easy, the ground concentration of sulfur dioxide and carbon dust is high, and great threat is brought to human health. Therefore, the method solves the problem of pollution of sulfur dioxide and carbon dust of coal of civil stoves, is also a key for controlling urban coal-smoke type atmospheric pollution, and becomes an effective measure which is necessary to be taken in northern areas to improve the atmospheric environmental quality in winter.
At present, the method for adopting the additive in the domestic technology for treating the pollution of the molded coal is one of the methods. The method has the following relevant reports: CN1229129A discloses that natural dolomite is added into common coal, the raw materials of the method are easy to obtain and cheap, but the addition amount is too large, and reaches 40 percent, and the ash content is too high, so that the combustion and the service performance of the coal are influenced; the high-efficiency coal-saving purifying agent disclosed in CN1134973A can improve flame temperature and heat efficiency, save coal and reduce pollution, but the chemical reagents used are too many to be popularized and promoted; CN1169461A discloses a briquette additive and a manufacturing method thereof, the components are relatively complex, only the combustion performance and the bonding use function of the briquette are taken into consideration, and pollutants such as sulfur dioxide and the like are not treated. In addition, CN1177628A and CN1169462A are complex in additive components, are expensive chemical materials in many cases, and have low sulfur fixation rate.
The invention aims to provide a novel briquette additive which integrates bonding, sulfur fixation and combustion supporting, keeps higher sulfur fixation rate under high temperature condition and plays roles of reducing smoke dust and supporting combustion, aiming at the defects of low sulfur fixation rate, large smoke dust amount, incomplete combustion and the like in the prior briquette technology.
The additive of the invention is composed of a sulfur-fixing agent, a binder, an expansion loose adsorbent, a sulfur-fixing catalyst and a combustion-supporting oxidant, and the contents of the sulfur-fixing agent, the binder, the expansion loose adsorbent, the sulfur-fixing catalyst and the combustion-supporting oxidant in raw coal are as follows: the molar ratio of Ca to S of the sulfur-fixing agent is 2-2.5, the binder is 4-17%, preferably 10-15%, the sulfur-fixing catalyst is 0.1-0.6%, the expansion adsorbent is 4-17%, preferably 5-10%, and the combustion-supporting oxidant is 0.1-0.6%, preferably 0.4-0.6%.
The sulfur-fixing agent of the invention comprises limestone, dolomite, marble or their tailings, and is mainly characterized by using CaCO3、MgCO3Or their mixture as main chemical component, limestone or dolomite depositThe resources are widely distributed, and the quality is large; the adhesive comprises bentonite, kaolin or higher yellow mud or red mud containing clay minerals, and the bentonite has the following chemical composition: SiO 2256～65％,Al2O310-20 percent of MgO + CaO, 4-7 percent of MgO + CaO, which is calcium-based or sodium-based bentonite taking montmorillonite as a main mineral component, has higher water absorption expansibility and interlayer cation exchange performance, and the mineral products are the dominant mineral resources in China and are distributed in 26 provinces, cities and regions throughout the country; the expanded loose adsorbent comprises vermiculite, expanded perlite or tailings of the vermiculite, wherein the chemical composition of the vermiculite is as follows: SiO 2237～42％,Al2O310～13％,MgO 14～23％,Fe2O3+ FlO 6-10%, it has peculiar characteristic volume expansion and bending performance while glowing, the volume can increase 15-25 times, the vermiculite deposit is large in our country's reserves, distribute extensively, each province has found 100 more places of vermiculite deposit; the sulfur fixing catalyst comprises iron oxide, manganese oxide, halite or fluorite; the oxidant comprises potassium permanganate, potassium perchlorate or potassium chlorate.
The use method of the additive comprises the following steps:
(1) mixing the raw coal powder, the sulfur-fixing agent, the binder and the expanded loose adsorbent;
(2) dissolving a combustion-supporting oxidant and a sulfur-fixing catalyst in water, uniformly mixing, wherein the water amount is 5-10% of the total weight of the raw coal powder and the additive components,
(3) and (3) uniformly stirring the mixture obtained in the step (1) and the step (2), and then pressing and forming.
The sulfur fixation principle of the technology of the invention is as follows:
the sulfur in coal is divided into inorganic sulfur and organic sulfur, wherein the inorganic sulfur comprises elemental sulfur and pyrite sulfur and sulfate sulfur, mainly pyrite sulfur, which are oxidized into sulfur dioxide in the combustion process of coal, as shown in formulas (1), (2) and (3); the chemical process of the sulfur fixation behavior of the calcium-based sulfur fixing agent is embodied by the reactions of the formulas (4), (5) and (6), when the granularity of calcium carbonate is reduced, the contact between sulfur dioxide and the effective surface of calcium oxide particles is facilitated, and the utilization rate of calcium oxide is improved, so that the sulfur fixation rate is improved, actually, sub-chemical reaction processes of oxidizing sulfur dioxide into sulfur trioxide exist in the reactions of the formulas (5) and (6), and when a catalyst exists and oxygen with higher concentration exists, the process can directly determine the sulfur fixation efficiency of the fire coal; (7) the formula reveals the reason that the sulfur fixation rate is low at high temperature, the reaction can be carried out at more than 800 ℃ under the reducing environment, the combustion of coal is generally higher than the temperature, andthe sulfur fixation rate can be improved by adding a catalyst and inhibiting the decomposition of sulfate. Research shows that some catalysts can simultaneously play a certain role in inhibiting the decomposition of sulfate. The addition of some minerals with expansion performance at high temperature can lead to the loose integral structure of the briquette coal, promote the diffusion and circulation of oxygen in the coal, facilitate the contact of sulfur dioxide and calcium oxide which is a decomposition product of calcium carbonate, and improve the proportion of active calcium oxide. Meanwhile, the decomposition rate of the sulfur fixation product calcium sulfate is greatly reduced under the reducing atmosphere, so that the sulfur fixation rate is improved; on the other hand, the expansion generates huge specific surface energy and interlayer airspace between layers, and creates excellent mechanical energy conditions and space places for adsorbing and fixing calcium sulfate; in addition, the higher oxygen concentration promotes the combustion of carbon-containing substances in the coal, and the carbon-containing substances and the combustion-supporting oxidant cooperatively play a good combustion-supporting role, so that the carbon dust dispersion and the carbon monoxide emission concentration are reduced.
The combustion-supporting principle of the technology of the invention is as follows:
the additive has combustion supporting effect under the synergistic action of the combustion supporting oxidant and the expanding and loosening adsorbent, potassium permanganate or potassium chlorate decomposes to generate oxygen at 200 or 300 ℃ respectively to generate an oxygen-enriched environment inside the molded coal, and the oxidizing reaction is promoted to be carried out when the potassium permanganate or potassium chlorate is contacted with combustible gas evaporated or decomposed and escaped at low temperature of coal phase, so that the ignition point is reduced, the ignition is facilitated, the flame temperature is increased, under the high-temperature condition, the expanding and loosening agent is heated to expand the internal structure of the molded coal to loosen, a channel is provided for external oxygen to smoothly enter, the slagging phenomenon caused by incomplete combustion at high temperature inside the molded coal is effectively prevented, the thermal efficiency of the coal is fully utilized, the coal is saved, and meanwhile, smoke dust caused by incomplete combustion is reduced.
The bonding forming principle of the technology of the invention is as follows:
the inorganic clay is used as the binder, so that the harmful and toxic elements generated by the fire coal can be adsorbed, the fire coal pollution is reduced, and the energy is saved. The clay mineral such as bentonite and the like adopted by the invention has good water absorption capacity, after absorbing water, the volume expands greatly, so that a clay structure layer is slightly changed, the plasticity, the adhesiveness and the cohesiveness become strong, the clay mineral is mixed and bonded with raw coal particles and other additives, the granulation performance is obviously optimized, and the plasticity and the associativity of a mixture are greatly improved, thereby improving the wet and dry strength of the molded coal.
The invention has the main advantages that: according to the analysis of the sulfur fixation, combustion and bonding forming principles, the additive is added into the molded coal, particularly the additive contains an expanded loose adsorbent and a bonding agent, so that the sulfur fixation rate is improved, different formulas are adopted at different combustion temperatures, the sulfur fixation rate is 65-98 percent, the sulfur fixation rate is improved by about 4 times compared with that of raw coal, and the sulfur fixation rate is 3 times higher than that of commercial Beijing civil honeycomb briquette under the same combustion working condition; the molded coal has good caking property, is directly mixed with raw coal and is formed under the pressure of 30MPa, the compressive strength index (1.0-1.4 MPa) of the molded coal is greater than that (0.7-1.1 MPa) of honeycomb coal sold in the Beijing area on the market, and the molded coal has higher strength after being combusted; the raw materials used by the invention are mainly natural ores with abundant reserves, so the raw materials are easy to obtain and low in cost; the additive added into coal has the advantages of low ignition point, strong firepower, less smoke and dust, high combustion efficiency, long combustion time, high coal utilization rate, coal saving of 15-20%, reduction of carbon content of coal slag by 40-65% and small environmental pollution. The additive of the present invention is suitable for bituminous coal and anthracite.
The features of the present invention are further illustrated by the following specific examples.
The raw coals of examples 1 to 3 below were high-sulfur bituminous coals of fatcheng, Shandong, and the raw coals of examples 4 to 6 were the same anthracite coals of Shanxi. Limestone powder is produced by Tangshan Huali calcium carbonate Co., Ltd, bentonite is an ultra-large bentonite ore bed in Wei groove of Xuanhua county of Hebei province, the two raw materials are crushed into 200 meshes and screened, and vermiculite tailings are prepared from ore dressing wastes, namely tailings, of vermiculite production factory of the third geological team of Xinjiang geological mineral institute, and are screened by 60 meshes.
Example 1
120 parts of raw coal, 30 parts of limestone powder, 20 parts of bentonite, 0.5 part of iron oxide powder, 0.5 part of potassium permanganate and 5 parts of vermiculite tailings, 10 parts of water is added, the mixture is uniformly stirred and then put into a die, and a cylindrical briquette sample with the diameter of 25mm and the height of about 22mm is prepared under the pressure of 30 MPa.
Example 2
120 parts of raw coal, 30 parts of limestone powder, 20 parts of bentonite, 0.5 part of iron oxide powder, 0.5 part of potassium permanganate, 10 parts of vermiculite tailings and 10 parts of water are added, and the mixture is uniformly stirred and then formed according to the method of example 1.
Example 3
120 parts of raw coal, 30 parts of limestone powder, 20 parts of bentonite, 0.5 part of iron oxide powder, 0.5 part of potassium permanganate, 20 parts of vermiculite tailings and 10 parts of water are added, and the mixture is uniformly stirred and then formed according to the method of example 1.
Example 4
120 parts of raw coal, 1.6 parts of limestone powder, 5 parts of bentonite, 0.2 part of ferric oxide, 0.3 part of potassium permanganate and 5 parts of vermiculite tailings, and 10 parts of water is added, and the mixture is uniformly stirred and then formed according to the method of example 1.
Example 5
120 parts of raw coal, 1.6 parts of limestone powder, 5 parts of bentonite, 0.2 part of ferric oxide, 0.3 part of potassium permanganate and 5 parts of vermiculite tailings, and 10 parts of water is added, and the mixture is uniformly stirred and then formed according to the method of example 1.
Example 6
120 parts of raw coal, 1.6 parts of limestone powder, 5 parts of bentonite, 0.2 part of ferric oxide, 0.3 part of potassium permanganate and 5 parts of vermiculite tailings, and 10 parts of wateris added, and the mixture is uniformly stirred and then formed according to the method of example 1.
Example 7
This example was conducted to test the properties of the molded coal samples of examples 1 to 6.
Combustion experiments: the samples of examples 1 to 6 and the briquette samples prepared by the same method as in example 1 were put into a box-type electric furnace for a combustion experiment, air was kept circulating during combustion to completely burn out the briquette samples, the briquette samples were taken out for analysis, and the briquette samples were combusted at 650 ℃, 750 ℃, 850 ℃, 950 ℃ and 1050 ℃, and after combustion, the remaining coal slag remained as it was, had a good shape, no significant cracks, no slag, and light weight, except for the collapse of the raw coal samples.
Sulfur fixation efficiency test for samples of examples 1 to 6: the method of GB212-77 is adopted to measure the sulfur fixation rate of the coal ash under the ash making condition, and the calculation formula isWherein, the analysis of sulfur is determined by a combustion method in a coal carbon test center in the northern part of the mine. The test results are shown in FIG. 1 and Table 1. TABLE 1
| Sample number | Combustion temperature (. degree.C.) | Coal sample (g) | Total sulfur content (g) of coal | Total sulfur content of slag (g) | Sulfur fixation Rate (%) |
| Commercial honeycomb briquette | 850 | 15.7640 | 0.33 | 0.32 | 23.0878 |
| Example 4 | 850 | 13.5115 | 0.38 | 1.68 | 77.4727 |
| Example 5 | 850 | 13.9908 | 0.38 | 1.52 | 89.8370 |
| Example 6 | 850 | 13.6331 | 0.38 | 1.76 | 91.3550 |
Claims (4)
1. The sulfur-fixing, dust-removing and combustion-supporting additive for the moulded coal is characterized by comprising the following components in percentage by weight:
2-2.5 percent of sulfur-fixing agent Ca/S, 4-17 percent of binder, 0.1-0.6 percent of sulfur-fixing catalyst, 4-17 percent of expansion loosening adsorbent and 0.1-0.6 percent of combustion-supporting oxidant. The percentages are all based on the weight of raw coal, and the sulfur-fixing dosage is calculated by the molar ratio of Ca atoms in the sulfur-fixing agent to S atoms in the coal.
2. Additive according to claim 1, characterized in that its composition and its content are:
2-2.5 percent ofsulfur-fixing agent Ca/S, 10-15 percent of binder, 0.1-0.6 percent of sulfur-fixing catalyst, 5-10 percent of expansion loosening adsorbent and 0.4-0.6 percent of combustion-supporting oxidant. The percentages are all based on the weight of raw coal, and the sulfur-fixing agent is calculated by the molar ratio of Ca atoms in the sulfur-fixing agent to S atoms in the coal.
3. The additive of claim 1 wherein the sulfur-fixing agent comprises limestone, dolomite, marble or their tailings, the binder comprises bentonite or kaolin, the expanded porous adsorbent comprises vermiculite or expanded perlite and their tailings, the sulfur-fixing catalyst comprises iron oxide, manganese oxide, halite, or fluorite powder, and the combustion-supporting oxidant comprises potassium permanganate, potassium perchlorate, or potassium chlorate.
4. A method of using the additive of claim 1, 2 or 3, comprising the steps of:
(1) mixing the raw coal powder, the sulfur-fixing agent, the binder and the expanded loose absorbent,
(2) dissolving a combustion-supporting oxidant and a sulfur-fixing catalyst in water, uniformly mixing, wherein the water amount is 5-10% of the total weight of the raw coal powder and the additive components,
(3) and (3) uniformly stirring the mixture obtained in the step (1) and the step (2), and then pressing and forming.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011044365A CN1137251C (en) | 2001-02-27 | 2001-02-27 | Sulfur-fixing dust-eliminating combustion-supporting briquet additive |
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| CNB011044365A CN1137251C (en) | 2001-02-27 | 2001-02-27 | Sulfur-fixing dust-eliminating combustion-supporting briquet additive |
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| CN1137251C CN1137251C (en) | 2004-02-04 |
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|---|---|---|---|---|
| CN101077986B (en) * | 2006-05-25 | 2010-11-03 | 林鼎华 | Multifunctional and highly effective synthesis ammonia gas preparation molded coal cementing agent |
| CN102161926A (en) * | 2011-03-08 | 2011-08-24 | 南通同盛生物能源科技有限公司 | Biomass carbon-based briquetted coal for replacing fossil fuel and production process thereof |
| CN103937577A (en) * | 2014-03-17 | 2014-07-23 | 中国地质大学（北京） | Modified Bayer red mud-mineral material collaborative fuel coal sulphur-fixing agent |
| CN104449926A (en) * | 2014-12-26 | 2015-03-25 | 重庆大学 | Tobacco straw coal-biomass briquette and preparation method thereof |
| CN104479784A (en) * | 2014-12-01 | 2015-04-01 | 葫芦岛市南票区腾兴生物质燃料厂 | Environment-friendly type carbon-adding biomass fuel and processing method thereof |
| CN104804796A (en) * | 2015-03-25 | 2015-07-29 | 天津神侬环保科技有限公司 | Special environment-friendly slag and ash removal agent for biomass boiler |
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| CN105567365A (en) * | 2014-10-09 | 2016-05-11 | 无锡荣博能源环保科技有限公司 | Modified coal and manufacturing method thereof |
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| CN106753681A (en) * | 2016-12-13 | 2017-05-31 | 广州吉前化工有限公司 | A kind of coal-saving agent |
| CN107345168A (en) * | 2017-08-18 | 2017-11-14 | 新疆维吾尔自治区煤炭科学研究所 | For slowing down the additive and preparation and application of the quasi- high-alkali coal coking property in east |
| CN107740113A (en) * | 2017-11-10 | 2018-02-27 | 威海翔泽新材料科技有限公司 | Boiler fire side corrosion inhibitor |
| CN108479327A (en) * | 2018-03-22 | 2018-09-04 | 北京阳光欣禾科技有限公司 | A kind of desulphurization denitration composite material and its production technology |
| CN110194979A (en) * | 2019-07-03 | 2019-09-03 | 贵州师范大学 | A kind of honeycomb brick moulded coal and preparation method thereof |
| CN111440647A (en) * | 2020-04-22 | 2020-07-24 | 兖矿集团有限公司 | Composite clean fuel, preparation method and application thereof |
| CN118460261A (en) * | 2024-06-25 | 2024-08-09 | 神木市翔宇能源化工有限公司 | NGE novel environment-friendly solid fuel |
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- 2001-02-27 CN CNB011044365A patent/CN1137251C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101077986B (en) * | 2006-05-25 | 2010-11-03 | 林鼎华 | Multifunctional and highly effective synthesis ammonia gas preparation molded coal cementing agent |
| CN102161926A (en) * | 2011-03-08 | 2011-08-24 | 南通同盛生物能源科技有限公司 | Biomass carbon-based briquetted coal for replacing fossil fuel and production process thereof |
| CN102161926B (en) * | 2011-03-08 | 2013-07-10 | 南通同盛生物能源科技有限公司 | Production process of biomass carbon-based briquetted coal for replacing fossil fuel |
| CN103937577A (en) * | 2014-03-17 | 2014-07-23 | 中国地质大学（北京） | Modified Bayer red mud-mineral material collaborative fuel coal sulphur-fixing agent |
| CN105567375A (en) * | 2014-10-09 | 2016-05-11 | 无锡荣博能源环保科技有限公司 | Composite additive |
| CN105567375B (en) * | 2014-10-09 | 2019-02-26 | 无锡荣博能源环保科技有限公司 | Compound additive |
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| CN104479784A (en) * | 2014-12-01 | 2015-04-01 | 葫芦岛市南票区腾兴生物质燃料厂 | Environment-friendly type carbon-adding biomass fuel and processing method thereof |
| CN104449926A (en) * | 2014-12-26 | 2015-03-25 | 重庆大学 | Tobacco straw coal-biomass briquette and preparation method thereof |
| CN104804796B (en) * | 2015-03-25 | 2017-12-15 | 天津神侬环保科技有限公司 | A kind of biomass boiler special environment protection scarfing cinder deashing agent |
| CN104804796A (en) * | 2015-03-25 | 2015-07-29 | 天津神侬环保科技有限公司 | Special environment-friendly slag and ash removal agent for biomass boiler |
| CN104910989A (en) * | 2015-05-12 | 2015-09-16 | 天津神侬环保科技有限公司 | Powder cleaning fuel |
| CN105001934A (en) * | 2015-07-17 | 2015-10-28 | 孝昌县鑫波农业发展有限公司 | Preparation method for biomass fuel |
| CN105969448A (en) * | 2016-03-22 | 2016-09-28 | 安徽徽明建设集团有限公司 | High-strength biomass briquette and manufacturing method thereof |
| CN106753681A (en) * | 2016-12-13 | 2017-05-31 | 广州吉前化工有限公司 | A kind of coal-saving agent |
| CN107345168A (en) * | 2017-08-18 | 2017-11-14 | 新疆维吾尔自治区煤炭科学研究所 | For slowing down the additive and preparation and application of the quasi- high-alkali coal coking property in east |
| CN107740113A (en) * | 2017-11-10 | 2018-02-27 | 威海翔泽新材料科技有限公司 | Boiler fire side corrosion inhibitor |
| CN108479327A (en) * | 2018-03-22 | 2018-09-04 | 北京阳光欣禾科技有限公司 | A kind of desulphurization denitration composite material and its production technology |
| CN108479327B (en) * | 2018-03-22 | 2020-12-11 | 北京阳光欣禾科技有限公司 | Desulfurization and denitrification composite material and production process thereof |
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| CN111440647A (en) * | 2020-04-22 | 2020-07-24 | 兖矿集团有限公司 | Composite clean fuel, preparation method and application thereof |
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