CN1300286C - Coal combustion and sulfur fixation composite additives - Google Patents
Coal combustion and sulfur fixation composite additives Download PDFInfo
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Abstract
The present invention discloses a composite additive for capturing sulfur in coal, which comprises the following components according to mass percentage: 36% to 74% of CaO and 26% to 64% of BaCO3, and can also contain any one or two of Al2O3, KMnO4 and MnO2, or can simultaneously contain Al2O3, KMnO4 and MnO2. The present invention has the advantages of higher efficiency of capturing sulfur at high temperature, which can reach more than 70% at the temperature of 900 to 1100 DEG C and can reach 40% to 70% when sulfur is captured at the high temperature of 1200 to 1300 DEG C, convenient slag recycle due to the fact that a sulfur capturing substance contains hardening minerals capable of enhancing the hydration activity of the sulfur-captured slag, no mineral of a solvent containing Fe and Si, good high temperature stability of the generated sulfur capturing substance, no slag generated by reduction of coal ash fusion temperature and no secondary pollution.
Description
Technical Field
The invention relates to a solid fuel additive, in particular to a coal-fired composite sulfur-fixing agent.
Background
Coal is the most important energy in China, and a large amount of harmful gas and smoke dust discharged by coal burning cause typical soot type pollution of atmosphere in China. Statistics of the 2003 publication of environmental conditions in China, which was published by the general office for environmental protection of China, shows that the total amount of sulfur dioxide discharged from the exhaust gas of the whole country in 2003 is 2158.7 ten thousand tons, and the pollution of acid rain is very serious. Large amount of SO2Emission of, SO in the atmosphere2The high concentration and the formation of acid rain seriously affect the human health, destroy the ecological system and cause great loss to the industrial and agricultural production. Therefore, for burning coal SO2The control and management of discharge is not slow enough.
At present, SO is controlled abroad2The most effective means of emission is still fluegas desulfurization, but the investment and operation costs are higher. In the process of desulfurization in combustion, a certain amount of sulfur-fixing agent is added into coal, so that sulfur oxides produced in the combustion process of the coal react with the sulfur-fixing agent to generate sulfate or other sulfur-containing compounds which are fixed in coal ash. The method does not need to add extra desulfurization equipment, saves investment, and is suitable for the prior technology, economic conditions and environmental protection requirements in China. The desulfurization technology in coal combustion comprises fluidized bed combustion desulfurization technology, briquette combustion desulfurization technology, in-furnace calcium injection desulfurization technology and the like.
Because the combustion temperature in the fluidized bed furnace is generally 800-900 ℃, the combustion temperature is basically consistent with the optimal sulfur fixing temperature range of the common calcium-based sulfur fixing agent, the calcium-based sulfur fixing efficiency in the fluidized bed furnace can reach 80-90 percent, and the SO can be greatly reduced without increasing equipment and lowering the operation cost2The amount of discharge of (c). However, for a large number of high-temperature industrial kilns or power station boilers such as layered combustion (coal briquette) furnaces, pulverized coal furnaces and the like in China, the medium-calcium-based sulfur fixation is realizedThe technology generally has the problems of low utilization rate of calcium and poor high-temperature sulfur fixation effect. Practice shows that when limestone is used as a sulfur fixing agent, the utilization rate of calcium is generally below 20%, the efficiency of calcium spraying and sulfur fixing in a furnace is only 20-40%, and how to improve the efficiency of calcium-based sulfur fixing during high-temperature combustion in the furnace is a problem generally concerned by people.
SO generated in the process of combustion of coal and energy2Or SO3The substances which are generated by chemical or physical adsorption reaction and form solid residues and remain in the coal ash can be used as the sulfur-fixing agent. The sulfur fixing agent is of various types, such as: limestone, dolomite, calcium oxide, magnesium oxide, sodium carbonate and the like, but the calcium carbonate which is most used, cheap and easily available at present is still calcium carbonate, commonly called calcium-based sulfur fixing agent. According to the analysis of the whole reaction process of calcium-based sulfur fixation, and the research conclusion of various scholars at home and abroad, when calcium carbonate is taken as a sulfur fixing agent, the low sulfur fixation efficiency caused by the combustion of high-temperature coal in a furnace mainly comprises the following three points:
① the separation of sulfur is asynchronous with the sulfur-fixing reaction, the separation of sulfur in coal is in obvious stage under the conditions of temperature programming, layer combustion and briquette combustion, and the sulfur-fixing agent CaCO is3In general, pyrolysis is started at 700 ℃ to 800 ℃ SO that SO is precipitated at low temperature2Cannot be captured in time.
② Sulfur-fixing agent CaCO3The CaO generated after calcination is easy to sinter in a high-temperature environment in a furnace, the specific surface area and the porosity are obviously reduced, and a stable and compact combination is formed, so that the reaction activity is greatly reduced.
③CaSO4The decomposition rate increases sharply at temperatures above 1200 ℃. Practice shows that the pyrolysis of calcium sulfate is the most main factor of low sulfur fixation efficiency in a grate-fired furnace (the furnace temperature is up to 1200-1400 ℃) and a pulverized coal furnace (the furnace temperature is up to 1300-1600 ℃).
In view of the above-mentioned sulfur-fixing problem, many researchers add one or more additives to the calcium-based sulfur-fixing agent to improve the efficiency of calcium-based sulfur-fixing.
01114874.8 (application number) discloses a high-efficiency sulfur-fixing agent for fire coal and a preparation method thereof. The sulfur-fixing agent is prepared by adding one or more components of hematite, magnesite, kaolin, clay ore, solid alkaline compound and waste iron powder industrial waste catalyst into limestone ore as a main body, crushing, sieving, stirring and mixing, wherein the content of the auxiliary agent is controlled within the range of 1.5-15 wt%. The invention utilizes the principle of sulfur fixation by catalysis, and porous substances such as industrial waste catalyst and kaolin are added into limestone, thereby improving the specific surface area and the adsorption force of the sulfur-fixing agent and further improving the sulfur-fixing efficiency of the sulfur-fixing agent. However, in the embodiment provided by the invention, although the sulfur fixing efficiency of the sulfur fixing agent can reach 50-70% in the temperature range of 800-1000 ℃, the sulfur fixing efficiency is only 23-25% at 1100 ℃; in addition, mineral components such as magnesite, kaolin and the like contained in the sulfur fixing agent need to absorb a large amount of heat in the reaction process, so that the problems of deterioration of coal combustion performance, difficult ignition and the like can be caused.
01110303.5 discloses a high-temperature combustion-supporting sulfur-fixing agent for coal, which is prepared by using dolomite or magnesite containing Ca and Mg as main base material, adding sodium nitrate, potassium permanganate, blast furnace slag and bauxite, and then adding a blending agent of dilute nitric acid and ammonia water. The composite sulfur-fixing agent provided by the invention containsMultiple metal ions form a Ca-X-S-Si-O heat-resistant system (wherein X represents a variable valence metal element such as Fe and Mn) at high temperature, and the system covers or wraps CaSO at high temperature4The crystal delays and prevents CaSO4The sulfur fixation efficiency is obviously improved. However, the nitrate substance contained in the sulfur-fixing agent is corrosive to furnace equipment, and the emission of nitrogen oxides is increased, thereby causing secondary pollution.
Disclosure of Invention
The invention aims to overcome the defects of the coal-fired sulfur fixing agent in the prior art, and provides the coal-fired sulfur fixing composite additive, which can obviously improve the high-temperature sulfur fixing efficiency of the coal, simultaneously realize combustion supporting and high-efficiency sulfur fixing, improve the utilization value of ash slag and avoid secondary pollution.
In order to achieve the purpose, the invention adopts the technical scheme that: a kind ofThe sulfur-fixing composite additive for coal contains CaO of calcium oxide and BaCO of barium carbonate3And aluminum oxide Al2O3CaO, by mass percent: 36-73% of BaCO3：26～63％，Al2O3：1～10％。
In order to further realize the purpose of the invention, the invention adopts the following three technical schemes:
a sulfur-fixing composite additive for coal contains CaO calcium oxide and BaCO barium carbonate3And aluminum oxide Al2O3Also contains potassium permanganate KMnO4CaO, by mass percent: 36-72% of BaCO3：26～62％，Al2O3：1～10％，KMnO4：0.5～5％。
A sulfur-fixing composite additive for coal contains CaO calcium oxide and BaCO barium carbonate3And aluminum oxide Al2O3And manganese dioxide MnO2CaO, by mass percent: 36-72% of BaCO3：26～62％，Al2O3：1～10％，MnO2：1～4％。
A sulfur-fixing composite additive for coal contains CaO calcium oxide and BaCO barium carbonate3Aluminum oxide Al2O3And potassium permanganate KMnO4And manganese dioxide MnO2CaO, by mass percent: 36-71% of BaCO3：26～61％，Al2O3：1～10％，KMnO4：0.5～5％，MnO2：1～4％。
The preparation process of the invention can be as follows: respectively crushing calcium oxide, barium carbonate, aluminum oxide, potassium permanganate and manganese dioxide into powder with the granularity of less than 1mm, then proportioning the powder according to the mass percent of the components of the additive, uniformly mixing the powder and the additive, and grinding the mixture until the fineness of the mixture is less than or equal to 8 percent of the screen residue of a 150-mesh sieve. The potassium permanganate in the additive raw material can be crushed, ground and sieved by a 100-mesh sieve, and then the potassium permanganate is prepared into an aqueous solution according to the mass ratio of 1: 5-20, and the aqueous solution is sprayed into coal for use.
The raw materials of the invention have wide sources, and the raw materials for preparing the composite additive can also be quicklime (the main component is CaO) and witherite (the main component is BaCO)3) Bauxite (Al as the main component)2O3) Potassium permanganateand manganese slag (MnO as main component)2) The purity of each raw material is preferably more than 80%, and the preparation method and the process are the same as those described above.
The combustion supporting and high-efficiency sulfur fixing principle of the invention is as follows: the invention combines the theories of catalytic combustion, high-temperature sulfur fixation and solid-phase reaction, introduces barium-based minerals into the sulfur-fixing agent, promotes the sulfur-fixing product to form a high-temperature-resistant sulfur-containing phase, and fundamentally solves the problem of high-temperature decomposition of calcium sulfate. The main reaction mechanism is as follows:
CaO and BaCO in additive3Belongs to alkaline earth metal oxides and carbonates, CaO, BaCO3And BaCO3Barium oxide (BaO) generated after decomposition reacts with sulfur dioxide released in the coal combustion process to generate calcium sulfate (CaSO)4) Barium sulfate (BaSO)4) (see formulas 1-4); meanwhile, BaO can be reacted with generated CaSO at high temperature4Reaction to convert it to BaSO4(see equation 5); in addition, CaO and the sulfur-fixing product CaSO formed4、BaSO4And Al contained in the coal ash2O3Can also react at high temperature to generate a sulfur-containing phase-calcium sulphoaluminate (3 CaO.3Al) which is stable at high temperature2O3·CaSO4) Barium calcium sulphoaluminate (3CaO 3 Al)2O3·BaSO4) (see equations 6-7). The complex sulfur-fixing reaction process makes the sulfur-fixing product no longer only in CaSO4But in the form of a plurality of sulphur-containing phases which are more stable at high temperatures.
Al in the additive2O3Can further promote sulfur fixation products CaSO4、BaSO4To 3 CaO.3 Al2O3·CaSO4And 3 CaO.3 Al2O3·BaSO4(see equations 6-7).
The sulfur-fixing chemical reaction formula of the coal-fired sulfur-fixing composite additive is 1-7:
In addition, CaO, BaCO3The contained calcium and barium ions have catalytic action on the oxidation combustion reaction of the coal. KMnO in additives4、MnO2Capable of releasing O at different temperatures2Promote the combustion of coal, andKMnO4、MnO2the contained potassium ions and manganese ions belong to alkali metal ions and transition metal ions, have remarkable catalytic activation effects on coal combustion and sulfur fixation reaction, can promote sulfur fixation at the same time, eliminate adverse effects on combustion caused by ash content increase after the addition of the additive, reduce the burning point of high-ash coal and improve the burnout rate.
Compared with the prior art, the invention has the following outstanding advantages:
(1) the invention uses CaO and BaCO3As the sulfur-fixing main agent, the sulfur-fixing reaction can be directly carried out and eliminatedTo a large amount of CaCO3、MgCO3The heat of carbonate desorption, the delay of sulfur fixation and the negative influence on combustion caused when the sulfur-fixing main agent is used.
(2) Mixing BaCO3The calcium barium-based composite sulfur fixing agent is introduced to form the calcium barium-based composite sulfur fixing agent, so that the sintering resistance of CaO is improved, barium sulfate, calcium sulphoaluminate and barium calcium sulphoaluminate high-temperature-resistant sulfur fixing phases are formed in the sulfur-fixing ash slag, and the CaSO is fundamentally overcome4High temperature decomposition is easy.
(3) Al contained in the invention2O3Can promote the generation of early-strength mineral calcium sulphoaluminate and barium calcium sulphoaluminate, improve the hydration activity of the solid sulfur ash and facilitate the resource utilization of the ash.
(4) CaO and BaCO contained in the invention3、KMnO4、MnO2The calcium, barium, potassium and manganese ions in the coal have catalytic action on coal combustion, the potassium and manganese ions have catalytic and activating action on sulfur fixation reaction, and the KMnO4、MnO2It is also possible to release O at different temperatures2Combustion supporting and reducing the adverse effect of the addition of the additive on coal combustion.
(5) The invention has better high-temperature sulfur fixation efficiency, and the sulfur fixation efficiency is more than 70 percent within the temperature range of 900-1100 ℃; the sulfur fixing efficiency can reach 40-70% at the high temperature of 1200-1300 ℃.
(6) The invention does not contain nitrate and chlorate substances, and does not cause secondary pollution in the using process; meanwhile, the invention does not contain Fe and Si flux minerals, and the generated sulfur-fixing phase has good high-temperature stability, and can not reduce the melting point of coal ash to cause slag bonding.
Detailed Description
The invention contains calcium oxide CaO and barium carbonate BaCO3. In addition, the calcium oxide CaO and the barium carbonate BaCO are contained3The additive of (A) may further contain aluminum oxide Al2O3Potassium permanganate KMnO4Manganese dioxide MnO2Either or both of them, or both of them contain aluminum oxide Al2O3Potassium permanganate KMnO4And manganese dioxide MnO2. The present invention will be described in further detail with reference to examples.
Example 1
The chemical components of the composite additive are as follows: contains CaO: 36% of BaCO3：64％。
A preparation method of the composite additive comprises the following steps: the raw materials for preparing the composite additive are calcium oxide and barium carbonate, the calcium oxide and the barium carbonate are respectively crushed into powder with the granularity of less than 1mm, 36 parts of the calcium oxide and 64 parts of the barium carbonate are uniformly mixed according to the parts by weight and ground until the fineness of the calcium oxide and the barium carbonate passes through a 150-mesh sieve, the mixture is not more than 8 percent, and the calcium oxide and the barium carbonate can be used after being inspected to be qualified and packaged.
Example 2
The chemical components of the composite additive are as follows: contains CaO: 74% of BaCO3：26％。
A preparation method of the composite additive comprises the following steps: the raw materials for preparing the composite additive are quicklime and witherite. Firstly, respectively crushing quicklime and witherite into powder with the particle size of less than 1mm, and taking 78 parts of quicklime containing 95% CaO and 90% BaCO according to parts by weight3And 29 parts of witherite are uniformly mixed and ground until the fineness of the witherite is less than or equal to 8 percent, and the witherite is qualified after inspection and then packaged for use.
Example 3
The chemical components of the composite additive are as follows: contains CaO: 36% of BaCO3：63％，Al2O3：1％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that 36 parts by weight of calcium oxide, 63 parts by weight of barium carbonate and 1 part by weight of aluminum oxide are used.
Example 4
The chemical components of the composite additive are as follows: contains CaO: 64% of BaCO3：26％，Al2O3：10％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that 64 parts by weight of calcium oxide, 26 parts by weight of barium carbonate and 10 parts by weight of aluminum oxide are used.
Example 5
The chemical components of the composite additive are as follows: contains CaO: 70% of BaCO3：29.5％，KMnO4：0.5％。
A preparation method of the composite additive comprises the following steps: the raw materials for preparing the composite additive are calcium oxide, barium carbonate and potassium permanganate. The calcium oxide and the barium carbonate are respectively crushed into powder with the granularity of less than 1mm, 70 parts of the calcium oxide and 29.5 parts of the barium carbonate are uniformly mixed according to parts by weight and ground until the fineness of the calcium oxide and the barium carbonate passes through a 150-mesh sieve, the balance is less than or equal to 8 percent, and the calcium oxide and the barium carbonate are packaged after being inspected to be qualified and can be used. 0.5 part of potassium permanganate in the raw materials is crushed, ground and sieved by a 100-mesh sieve, then aqueous solution is prepared according to the mass ratio of 1: 15, and the aqueous solution is stirred until the potassium permanganate is completely dissolved and stored in a glass container for later use.
Example 6
The chemical components of the composite additive are as follows: contains CaO: 38% of BaCO3：57％，KMnO4：5％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that 38 parts by weight of calcium oxide, 57 parts by weight of barium carbonate and 5 parts by weight of potassium permanganate are used.
Example 7
The chemical components of the composite additive are as follows: contains CaO: 70% of BaCO3：29％，MnO2：1％。
A preparation method of the composite additive comprises the following steps: the same procedures used in example 1 were repeated except that 70 parts by weight of calcium oxide, 29 parts by weight of barium carbonate, and 1 part by weight of manganese dioxide were used.
Example 8
The chemical components of the composite additive are as follows: contains CaO: 36% of BaCO3：60％，MnO2：4％。
A preparation method of the composite additive comprises the following steps: the same procedures used in example 1 were repeated except for using 36 parts by weight of calcium oxide, 60 parts by weight of barium carbonate and 4 parts by weight of manganese dioxide.
Example 9
The chemical components of the composite additive are as follows: contains CaO: 40% of BaCO3：55％，Al2O3：3％，KMnO4：2％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that the process is carried out in parts by weight, wherein the parts by weight are 40 parts of calcium oxide, 55 parts of barium carbonate, 3 parts of aluminum oxide and 2 parts of potassium permanganate.
Example 10
The chemical components of the composite additive are as follows: contains CaO: 62% of BaCO3：27％，Al2O3：8％，MnO2：3％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that 62 parts by weight of calcium oxide, 27 parts by weight of barium carbonate, 8 parts by weight of aluminum oxide and 3 parts by weight of manganese dioxide are used.
Example 11
The chemical components of the composite additive are as follows: contains CaO: 45% of BaCO3：53％，KMnO4：1％，MnO2：1％。
A preparation method of the composite additive comprises the following steps: the process is the same as example 1 except that the components are 45 parts by weight of calcium oxide, 53 parts by weight of barium carbonate, 1 part by weight of potassium permanganate and 1 part by weight of manganese dioxide.
Example 12
The chemical components of the composite additive are as follows: contains CaO: 55% of BaCO3：36％；Al2O3：5％，KMnO4：2％，MnO2：2％。
A preparation method of the composite additive comprises the following steps: the process is as in example 1 except that 55 parts by weight of calcium oxide, 36 parts by weight of barium carbonate, 5 parts by weight of aluminum oxide, 2 parts by weight of potassium permanganate and 2 parts by weight of manganese dioxide are used.
Before the composite additive is used, the sulfur content and ash composition of the fire coal are firstly tested, and the coal quality characteristics are analyzed. The proportion of the composite additive to the coal is determined according to the proportion of the total mole number (expressed by M) of calcium and barium contained in the additive and the coal ash to the mole number (expressed by S) of sulfur contained in the coal, and the change range of the proportion (M/S) is 1.5-3. The chemical components of the sulfur-fixing composite additive and the amount of the additive mixed into the coal can be adjusted according to different coal types, coal quality characteristics and different furnace types so as to achieve the best effect.
Examples of the effects of the present invention 1
Sulfur content (S) of Guizhou coalad) Is 1.34 percent, 100 grams of coal is taken and ground intopowder, and the residual quantity of the powder passing through a 150-mesh sieve is less than or equal to 8 percent. The chemical components of the composite additive are as follows: contains CaO: 38% of BaCO3：60％，Al2O3: 2 percent. According to the chemical composition and coal quality analysis data of the composite additive, the total mole number (M) of calcium and barium and the mole number of sulfur (S) can be calculated according to a conversion formula of mass and mole unit, and then according to the proportion of M/S ═ 2, coal powder and the additive are uniformly mixed and pressed into cake-shaped briquette samples. The sample is placed in a high-temperature resistance furnace to be calcined at constant temperature and then is tested and analyzed, the sulfur fixation efficiency is calculated according to a formula 8, and the test result is as follows: at 1000 ℃, the sulfur fixation efficiency is 87%; at 1200 ℃, the sulfur fixation efficiency is 65%; the sulfur fixation efficiency was 52% at 1300 ℃.
Examples of the effects of the present invention 2
High ash and low-grade coal in Guangxi province, sulfur content (S)ad) 4.95 percent, pre-grinding the coal to fineness and passing through a 60-mesh sieve. The chemical components of the composite additive are as follows: contains CaO: 55% of BaCO3：37％，Al2O3：4％，KMnO4：2％，MnO2: 2 percent. According to the chemical composition and coal quality analysis data of the composite additive and a conversion formula of mass and mole unit, the total mole number (M) of calcium and barium and the mole number of sulfur (S) can be calculated, then according to the proportion that M/S is 1.5, the coal powder and the additive are uniformly mixed, and the mixture is ground until the screen residue with the fineness of passing through a 150-mesh screen is less than or equal to 8 percent. Burning the prepared sample in a high-temperature settling furnace for 3-5 seconds, and calculating the sulfur fixation efficiency according to the formula (9), wherein the test result is as follows: the sulfur fixing efficiency is 51.5 percent at 1200 ℃; the sulfur fixation efficiency was 42.5% at 1300 ℃.
(formula 9)
Claims (4)
1. A fire coal sulfur fixation composite additive is characterized in that: containing CaO of calcium oxide and BaCO of barium carbonate3And aluminum oxide Al2O3CaO, by mass percent: 36-73% of BaCO3：26～63％，Al2O3：1～10％。
2. The fire coal sulfur-fixing composite additive according to claim 1, characterized in that: also contains potassium permanganate KMnO4CaO, by mass percent: 36-72% of BaCO3：26～62％，Al2O3：1～10％，KMnO4：0.5～5％。
3. The fire coal sulfur-fixing composite additive according to claim 1, characterized in that: and manganese dioxide MnO2CaO, by mass percent: 36-72% of BaCO3：26～62％，Al2O3：1～10％，MnO2：1～4％。
4. The fire coal sulfur-fixing composite additive according to claim 2, characterized in that: and manganese dioxide MnO2CaO, by mass percent: 36-71% of BaCO3：26～61％，Al2O3：1～10％，KMnO4：0.5～5％，MnO2：1～4％。
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| CN105439417A (en) * | 2015-11-18 | 2016-03-30 | 陕西科技大学 | Red mud sulfur-fixing method |
| CN105567272B (en) * | 2016-02-24 | 2018-09-14 | 太原理工大学 | The calcium base barium manganese aluminium compound additive and preparation method of raising domestic coke high-temperature fixed sulfur effect and application |
| CN105733634B (en) * | 2016-02-24 | 2019-04-05 | 太原理工大学 | The calcium base potassium magnesium silicon compound additive and preparation method of raising domestic coke high-temperature fixed sulfur effect and application |
| CN106433854A (en) * | 2016-10-24 | 2017-02-22 | 马鞍山科宇环境工程有限公司 | Coal desulfurization and decoking process |
| CN106823772A (en) * | 2017-04-12 | 2017-06-13 | 湖南云平环保科技有限公司 | Desulfuration in furnace synergist and desulfurizing agent |
| CN108485751B (en) * | 2018-04-03 | 2020-12-18 | 马鞍山科宇环境工程有限公司 | Desulfurization and denitrification combustion improver for pulverized coal injected into blast furnace and preparation method and use method thereof |
| CN108465367A (en) * | 2018-05-11 | 2018-08-31 | 熊燕飞 | A kind of desulfurization denitration method |
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| CN111454010A (en) * | 2020-04-07 | 2020-07-28 | 中海油天津化工研究设计院有限公司 | Calcium sulfate pyrolysis inhibitor and preparation method thereof |
| CN112742204B (en) * | 2020-12-30 | 2022-07-19 | 铜陵铜冠环保科技有限公司 | Flue gas sulfur-fixing agent used in sodium sulfide synthesis process and preparation process thereof |
| CN113717768A (en) * | 2021-09-23 | 2021-11-30 | 内蒙古大学 | Coal sulfur-fixing additive and preparation method thereof |
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| CN1228466A (en) * | 1998-11-20 | 1999-09-15 | 烟台市能源监测中心 | Raw coal treating agent |
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| CN1228466A (en) * | 1998-11-20 | 1999-09-15 | 烟台市能源监测中心 | Raw coal treating agent |
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