CN113956907B - High-sulfur coal sulfur-fixing agent and preparation method thereof - Google Patents
High-sulfur coal sulfur-fixing agent and preparation method thereof Download PDFInfo
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- CN113956907B CN113956907B CN202111140464.9A CN202111140464A CN113956907B CN 113956907 B CN113956907 B CN 113956907B CN 202111140464 A CN202111140464 A CN 202111140464A CN 113956907 B CN113956907 B CN 113956907B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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Abstract
The invention provides a sulfur-fixing agent for high-sulfur coal, which comprises the following raw materials in parts by weight: 20-30 parts of sulfur fixing main agent, 5-15 parts of ionic liquid composite aerogel carrier, 1-5 parts of modified bentonite dispersing agent, 5-10 parts of activated sludge, 1-5 parts of organic alcohol, 1-5 parts of stabilizer and 30-65 parts of water. The calcium salt adopted by the sulfur-fixing agent forms calcium sulfate precipitate after sulfur fixation, the calcium sulfate precipitate coats fuel, the combustion efficiency of the fuel is limited, the active sludge added by the sulfur-fixing agent volatilizes and decomposes at high temperature in the fuel combustion, the porosity of the fuel is promoted to be increased, the structural porosity is improved, the contact area of the fuel and air is enhanced, the combustion efficiency is improved, and in addition, the volatilized gas can destroy the calcium sulfate precipitate, so that the problem of the calcium sulfate precipitate on the fuel coating is further solved.
Description
Technical Field
The invention relates to the technical field of sulfur fixation, in particular to a high-sulfur coal sulfur fixation agent and a preparation method thereof.
Background
Coal, abbreviated as coal, is ancient plant remains buried under the stratum, and carbonized fossil minerals generated by the action of the pressure and temperature conditions of the crust isolated air are mainly used as fuel by human beings; coal is a major industry, or a minor industry, for the modern industry; the industries of energy, metallurgy, chemistry, machinery, light spinning, food and transportation all play an important role, and various industries have consumed a certain amount of coal to some extent, so that coal is known as industrial "true grain". Is one of the main energy sources used in the human world in the eighteenth century. According to the combustion mechanism of coal, metal ions are used as a catalyst, the metal ions react with sulfur dioxide to generate sulfate at high temperature, and the principle that a stabilizer prevents sulfate from decomposing is used for organically preparing the catalyst, the inhibitor and the stabilizer into the high-efficiency sulfur-fixing catalyst.
The sulfur-fixing agent is usually a calcium-based sulfur-fixing agent and fuel which are used together to be used as fuel, but the existing sulfur-fixing agent can perform sulfur fixing effect, but the product CaSO4.2H2O generated in sulfur fixing by the sulfur-fixing agent can perform precipitation, and the combustion efficiency of the fuel is affected instead, so that further improvement treatment is needed for balancing the sulfur fixing and the combustion efficiency of the fuel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-sulfur coal sulfur-fixing agent and a preparation method thereof.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a sulfur-fixing agent for high-sulfur coal, which comprises the following raw materials in parts by weight:
20-30 parts of sulfur fixing main agent, 5-15 parts of ionic liquid composite aerogel carrier, 1-5 parts of modified bentonite dispersing agent, 5-10 parts of activated sludge, 1-5 parts of organic alcohol, 1-5 parts of stabilizer and 30-65 parts of water;
the preparation method of the modified bentonite dispersing agent comprises the following steps:
s1, activating treatment of bentonite: firstly, feeding bentonite into a 3-time weight of auxiliary agent for low-speed stirring treatment, wherein the stirring speed is 100-200r/min, the stirring time is 20-30min, the stirring temperature is 65-75 ℃, and the stirring is finished to obtain active bentonite;
s2, ultrasonic dispersion of bentonite: delivering bentonite into a dispersing agent prepared from sodium dodecyl sulfate and hydrochloric acid according to a weight ratio of 1:2 for ultrasonic dispersion treatment, wherein the weight ratio of the bentonite to the dispersing agent is 1:5, the ultrasonic power is 100-500W, the ultrasonic time is 20-30min, and the ultrasonic treatment is finished;
s3, roasting: delivering bentonite subjected to S2 ultrasonic treatment into a roasting box for roasting treatment, wherein the roasting temperature is 500-1000 ℃, the roasting time is 10-20min, and cooling to 150 ℃ at a speed of 1-5 ℃/min after roasting is finished for standby;
s4, primary grinding treatment: grinding the bentonite subjected to S3 roasting treatment at 1000r/min for 20-30min, and carrying out heat preservation grinding to finish grinding;
s5, water-cooling refrigeration treatment: delivering bentonite subjected to primary grinding treatment in S4 into deionized water at-5 ℃ for high-speed stirring treatment, wherein the stirring rotation speed is 1000-1500r/min, the stirring time is 10-20min, and after stirring, placing the bentonite at-20 ℃ for refrigeration treatment for 5min, taking out, and naturally recovering to room temperature;
s6, secondary grinding treatment: and continuously grinding the bentonite subjected to water cooling and refrigeration treatment at the rotating speed of 500-1000r/min for 10-20min to obtain the modified bentonite dispersing agent.
Preferably, the high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
22-28 parts of sulfur fixing main agent, 7-13 parts of ionic liquid composite aerogel carrier, 2-4 parts of modified bentonite dispersing agent, 6-8 parts of activated sludge, 2-4 parts of organic alcohol, 2-3 parts of stabilizer and 32-63 parts of water.
Preferably, the high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
25 parts of sulfur fixing main agent, 10 parts of ionic liquid composite aerogel carrier, 3 parts of modified bentonite dispersing agent, 7.5 parts of activated sludge, 3 parts of organic alcohol, 3 parts of stabilizer and 47.5 parts of water.
Preferably, the sulfur fixing main agent comprises the following raw materials in parts by weight: 5-15 parts of calcium salt, 5-10 parts of magnesium salt and 2-10 parts of nitrate, wherein the calcium salt is calcium acetate, the magnesium salt is magnesium chloride and the nitrate is sodium nitrate.
Preferably, the organic alcohol is ethylene glycol; the stabilizer is alumina.
Preferably, the preparation method of the ionic liquid composite aerogel carrier comprises the following steps: adding the silica aerogel and the ionic liquid into a stirrer according to the weight ratio of 1:3, stirring until the mixture is fully mixed, then adding rare earth lanthanum chloride accounting for 10-20% of the total amount of the ionic liquid, stirring for 10-20min at the rotating speed of 100-200r/min, and obtaining the liquid composite aerogel carrier after the stirring is finished.
Preferably, the preparation method of the activated sludge comprises the following steps: adding the sludge into a sodium hydroxide aqueous solution with the mass fraction of 70-80% which is 2 times that of the sludge, stirring and dispersing at the stirring and dispersing speed of 100-500r/min for 10-20min, filtering, washing, taking out, drying at 60-80 ℃ for 10-20min, and then adopting proton irradiation treatment to finish the treatment to obtain the activated sludge.
Preferably, the irradiation power of the proton irradiation treatment is 100-500W, and the irradiation time is 10-20min.
Preferably, the preparation method of the auxiliary agent in the preparation of the modified bentonite dispersing agent comprises the following steps: mixing sodium molybdate dihydrate and methyl acrylate according to a weight ratio of 1:2, then adding sodium acetylsalicylate accounting for 20-30% of the total mass of the sodium molybdate dihydrate, stirring for 20-30min at a rotating speed of 100-500r/min, and ending stirring to obtain the powder aid.
The preparation method of the high-sulfur coal sulfur-fixing agent comprises the following steps: sequentially adding a sulfur fixing main agent, organic alcohol and water into a stirrer for stirring treatment, wherein the stirring rotation speed is firstly 100-200r/min, stirring for 20-30min, then adding activated sludge, an ionic liquid composite aerogel carrier, a modified bentonite dispersing agent and a stabilizer, increasing the stirring rotation speed to 1000-1500r/min, mechanically stirring for 10-20min, then reducing the stirring speed to 500r/min, and continuing stirring for 20-30min to obtain the sulfur fixing agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The sulfur-fixing agent is compounded by adopting a plurality of catalytic components, sulfur-fixing components and dispersing components through physical and chemical actions, is suitable for cement clinker production lines for burning high-sulfur coal, and is particularly suitable for Yun Guichuan and other areas; brown liquid is convenient to add and flexible to use; the use dosage is low, and is usually 0.2 to 0.7 per mill; reducing the crust of a kiln tail smoke chamber by more than 50 percent; reducing standard coal consumption of clinker not less than 3kg/t; the clinker yield is improved to be more than or equal to 50t/d;
when the total sulfur content in coal is high (more than 2%), sulfur alkali rings and sulfur alkali skins are easily generated at kiln tails and smoke chambers after combustion, the internal pressure of a system, the ventilation of wind and materials are influenced, the yield and the quality of clinker are influenced, the stability and the safety of system operation are also influenced, enterprises can manually clean by adopting a spade or a high-pressure water gun, and generally, the higher the sulfur content is, the longer the cleaning times and the cleaning time are. After the sulfur fixing agent is added, the sulfur fixing component can fix SO2 generated by coal combustion, SO that the formation of the sodium sulfate ring (skin) is reduced, the catalytic component can inhibit the formation of new sodium sulfate ring (skin), promote the rapid and complete combustion of coal, avoid the post combustion of coal, and also reduce the generation of the sodium sulfate ring (skin); the dispersing component can promote the sulfur-fixing agent to permeate into the gaps of the coal, and increase the sulfur-fixing effect of the sulfur-fixing component and the catalysis effect of the catalysis component; when the total sulfur content of the coal is 2% -8%, the doping amount is generally 0.2-0.7%.
(2) The adopted calcium salt forms calcium sulfate precipitate after sulfur fixation, the calcium sulfate precipitate coats fuel, the fuel combustion efficiency is limited, the active sludge added by the sulfur-fixing agent volatilizes, decomposes and escapes at high temperature in the fuel combustion, the porosity of the fuel is promoted to be increased, the structural porosity is improved, the contact area of the fuel and air is enhanced, the combustion efficiency is improved, in addition, the volatilized gas can destroy the calcium sulfate precipitate, and the problem of the calcium sulfate precipitate coating the fuel is further solved; after the activated sludge is treated by sodium hydroxide alkali solution and proton irradiation, the activity is enhanced, so that the problem of fuel cladding by calcium sulfate precipitate is further solved.
However, because the organic components in the sludge can prevent the sulfur fixation effect of the calcium salt, the invention solves the problems by matching with the ionic liquid composite aerogel carrier:
the ionic liquid composite aerogel carrier is prepared from silica aerogel, ionic liquid and rare earth lanthanum chloride, and the silica aerogel can promote the mixing of raw materials such as calcium salt and magnesium salt in the sulfur-fixing agent, so that the same principle of polarity is facilitated, the raw materials are subjected to better reaction proportion, and the use efficiency of the sulfur-fixing agent is improved; the added ionic liquid can further improve the ionic performance of the product, so that the polar effect of the sulfur-fixing agent is enhanced, the sulfur-fixing efficiency of the product is improved, and the rare earth lanthanum chloride has rare earth activity efficiency, so that the silica aerogel and the ionic liquid are activated, and the working efficiency of the ionic liquid composite aerogel carrier is further improved.
(3) In the sulfur fixation treatment:
the sulfur dioxide is firstly subjected to enhanced adsorption through the polar property of the ionic liquid composite aerogel carrier in the sulfur fixing agent to combine with the sulfur dioxide, the sulfur dioxide is firstly guided, solidified and adsorbed, and then is diffused into the solution of the sulfur fixing agent through the diffusion agent, so that the sulfur dioxide is better treated by the sulfur fixing main agent such as calcium salt, and the sulfur fixing effect is enhanced;
in addition, the ionic liquid composite aerogel carrier is matched with a sludge raw material in fuel combustion to carry out permeation treatment on sludge, so that organic components in the sludge are prevented from damaging sulfur fixation of calcium salt, the ionic liquid composite aerogel carrier and the sludge are matched and complement each other, the two are indispensable, so that sulfur fixation and fuel heat value efficiency of a product are improved, and in addition, after the activated sludge is modified, the activated sludge can be more easily improved by the ionic liquid composite aerogel carrier, so that the synergistic effect is enhanced.
(4) The modified bentonite dispersing agent is beneficial to the lamellar layer-to-layer spacing structure, is inserted into the raw materials of the product to improve the connection efficiency of the product, conducts and disperses sulfur dioxide solidified by the ionic liquid composite aerogel carrier, and is further subjected to sulfur fixation treatment by sulfur fixation main agents such as calcium salt and the like; sulfur fixation efficiency is improved;
in addition, as the modified bentonite has ion exchange performance, firstly calcium ions and magnesium ions are adsorbed, so that the sulfur fixing main agent is fully applied and treated, and then after the ionic liquid composite aerogel carrier is used for curing sulfur dioxide, the calcium ions and the magnesium ions are continuously released through the ion exchange performance, so that slow release efficiency is formed, the sulfur dioxide is continuously cured, and the sulfur fixing efficiency of the product is improved; in addition, the ionic liquid composite aerogel carrier and the modified bentonite both contain ionic properties, so that the ionic liquid composite aerogel carrier and the modified bentonite can play a role in assisting in fuel combustion, enhance the combustion effect of the fuel, and further balance the effects of sulfur fixation and fuel combustion through reasonable blending of raw materials.
(5) In the concrete modification, the modified bentonite is firstly subjected to activation treatment by adopting raw materials such as sodium molybdate dihydrate and methyl acrylate in a powder aid, so that the ultrasonic dispersion effect of the bentonite in a dispersing agent is improved, the dispersion capacity of the bentonite is improved, in the roasting treatment, the bentonite sheets are expanded, the interlayer spacing structure of the bentonite is further improved, the sulfur dioxide solidified by the ionic liquid composite aerogel carrier is conducted and dispersed, the roasted bentonite is refined by one-time grinding treatment, then the water-cooling refrigeration treatment is carried out, and the flexibility among the bentonite sheets is further improved by shrinking the refined bentonite in the water-cooling refrigeration treatment, so that the dispersion capacity and interlayer spacing effect of the bentonite are further improved; finally, the bentonite is further refined through secondary grinding treatment, so that the dispersing capability of the bentonite in the raw materials of the product is improved, the connection efficiency of the product is improved by combining the penetration of the bentonite sheets into the raw materials of the product, and the sulfur dioxide solidified by the ionic liquid composite aerogel carrier is conducted and dispersed, so that the sulfur fixing effect of the product is improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1.
The high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
20 parts of sulfur fixing main agent, 5 parts of ionic liquid composite aerogel carrier, 1 part of modified bentonite dispersing agent, 5 parts of activated sludge, 1 part of organic alcohol, 1 part of stabilizer and 30 parts of water;
the preparation method of the modified bentonite dispersing agent comprises the following steps:
s1, activating treatment of bentonite: firstly, feeding bentonite into a 3-time weight of auxiliary agent for low-speed stirring treatment, wherein the stirring speed is 100r/min, the stirring time is 20min, the stirring temperature is 65 ℃, and the stirring is finished to obtain active bentonite;
s2, ultrasonic dispersion of bentonite: delivering bentonite into a dispersing agent prepared from sodium dodecyl sulfate and hydrochloric acid according to a weight ratio of 1:2 for ultrasonic dispersion treatment, wherein the weight ratio of the bentonite to the dispersing agent is 1:5, the ultrasonic power is 100W, the ultrasonic time is 20min, and the ultrasonic treatment is finished;
s3, roasting: delivering the bentonite subjected to S2 ultrasonic treatment into a roasting box for roasting treatment, wherein the roasting temperature is 500 ℃, the roasting time is 10min, and cooling to 150 ℃ at a speed of 1 ℃/min after roasting is finished for later use;
s4, primary grinding treatment: grinding the bentonite subjected to S3 roasting treatment at 1000r/min for 20min, and carrying out heat preservation grinding to finish grinding;
s5, water-cooling refrigeration treatment: delivering bentonite subjected to primary grinding treatment in S4 into deionized water at-5 ℃ for high-speed stirring treatment, wherein the stirring rotation speed is 1000r/min, the stirring time is 10min, after stirring, the bentonite is subjected to cold storage treatment at-20 ℃ for 5min, and then taking out the bentonite and naturally recovering to room temperature;
s6, secondary grinding treatment: and continuously grinding the bentonite subjected to water cooling and refrigeration treatment at the rotating speed of 500r/min for 10min to obtain the modified bentonite dispersing agent.
The sulfur fixing main agent of the embodiment comprises the following raw materials in parts by weight: 5 parts of calcium salt, 5 parts of magnesium salt and 2 parts of nitrate, wherein the calcium salt is calcium acetate, the magnesium salt is magnesium chloride and the nitrate is sodium nitrate.
The organic alcohol of this embodiment is ethylene glycol; the stabilizer is alumina.
The preparation method of the ionic liquid composite aerogel carrier in the embodiment comprises the following steps: adding the silica aerogel and the ionic liquid into a stirrer according to the weight ratio of 1:3, stirring until the mixture is fully mixed, then adding rare earth lanthanum chloride accounting for 10% of the total amount of the ionic liquid, stirring for 10min at the rotating speed of 100r/min, and obtaining the liquid composite aerogel carrier after stirring.
The preparation method of the activated sludge in the embodiment comprises the following steps: adding the sludge into a sodium hydroxide aqueous solution with the mass fraction of 70% which is 2 times that of the sludge for stirring and dispersing treatment, wherein the stirring and dispersing speed is 100r/min, the stirring time is 10min, filtering, washing out, drying at 60 ℃ for 10min, and then adopting proton irradiation treatment to finish the treatment to obtain the activated sludge.
The irradiation power of the proton irradiation treatment of the embodiment is 100-500W, and the irradiation time is 10-20min.
The preparation method of the auxiliary agent in the preparation of the modified bentonite dispersing agent comprises the following steps: mixing sodium molybdate dihydrate and methyl acrylate according to a weight ratio of 1:2, then adding sodium acetylsalicylate accounting for 20% of the total mass of the sodium molybdate dihydrate, stirring for 20min at a rotating speed of 100r/min, and obtaining the powder aid after stirring.
The preparation method of the high-sulfur coal sulfur fixing agent comprises the following steps: sequentially adding a sulfur fixing main agent, organic alcohol and water into a stirrer for stirring treatment, wherein the stirring rotation speed is firstly stirring for 20min at a rotation speed of 100r/min, then adding activated sludge, an ionic liquid composite aerogel carrier, a modified bentonite dispersing agent and a stabilizer, increasing the stirring rotation speed to 1000r/min, mechanically stirring for 10min, then reducing the rotation speed to 500r/min, and continuing stirring for 20min to obtain the sulfur fixing agent.
Example 2.
The high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
30 parts of sulfur fixing main agent, 15 parts of ionic liquid composite aerogel carrier, 5 parts of modified bentonite dispersing agent, 10 parts of activated sludge, 5 parts of organic alcohol, 5 parts of stabilizer and 65 parts of water;
the preparation method of the modified bentonite dispersing agent comprises the following steps:
s1, activating treatment of bentonite: firstly, feeding bentonite into a 3-time weight of auxiliary agent for low-speed stirring treatment, wherein the stirring speed is 200r/min, the stirring time is 30min, the stirring temperature is 75 ℃, and the stirring is finished to obtain active bentonite;
s2, ultrasonic dispersion of bentonite: delivering bentonite into a dispersing agent prepared from sodium dodecyl sulfate and hydrochloric acid according to a weight ratio of 1:2 for ultrasonic dispersion treatment, wherein the weight ratio of the bentonite to the dispersing agent is 1:5, the ultrasonic power is 500W, the ultrasonic time is 30min, and the ultrasonic treatment is finished;
s3, roasting: delivering the bentonite subjected to S2 ultrasonic treatment into a roasting box for roasting treatment, wherein the roasting temperature is 1000 ℃, the roasting time is 20min, and cooling to 150 ℃ at a speed of 5 ℃/min after the roasting is finished for later use;
s4, primary grinding treatment: grinding the bentonite subjected to S3 roasting treatment at 1000r/min for 30min, and carrying out heat preservation grinding to finish grinding;
s5, water-cooling refrigeration treatment: delivering bentonite subjected to primary grinding treatment in S4 into deionized water at-5 ℃ for high-speed stirring treatment, wherein the stirring speed is 1500r/min, the stirring time is 20min, after stirring, the bentonite is subjected to cold storage treatment at-20 ℃ for 5min, and then taking out the bentonite and naturally recovering the bentonite to room temperature;
s6, secondary grinding treatment: and continuously grinding the bentonite subjected to water cooling and refrigeration treatment at the rotating speed of 1000r/min for 20min to obtain the modified bentonite dispersing agent.
The sulfur fixing main agent of the embodiment comprises the following raw materials in parts by weight: 15 parts of calcium salt, 10 parts of magnesium salt and 10 parts of nitrate, wherein the calcium salt is calcium acetate, the magnesium salt is magnesium chloride and the nitrate is sodium nitrate.
The organic alcohol of this embodiment is ethylene glycol; the stabilizer is alumina.
The preparation method of the ionic liquid composite aerogel carrier in the embodiment comprises the following steps: adding the silica aerogel and the ionic liquid into a stirrer according to the weight ratio of 1:3, stirring until the mixture is fully mixed, then adding the rare earth lanthanum chloride accounting for 20% of the total amount of the ionic liquid, stirring for 20min at the rotating speed of 200r/min, and obtaining the liquid composite aerogel carrier after stirring.
The preparation method of the activated sludge in the embodiment comprises the following steps: adding the sludge into a sodium hydroxide aqueous solution with the mass fraction of 80% which is 2 times that of the sludge for stirring and dispersing treatment, wherein the stirring and dispersing speed is 500r/min, the stirring time is 20min, filtering, washing out, drying at 80 ℃ for 20min, and then adopting proton irradiation treatment to finish the treatment to obtain the activated sludge.
The irradiation power of the proton irradiation treatment in this example was 500W and the irradiation time was 20min.
The preparation method of the auxiliary agent in the preparation of the modified bentonite dispersing agent comprises the following steps: mixing sodium molybdate dihydrate and methyl acrylate according to a weight ratio of 1:2, then adding sodium acetylsalicylate accounting for 30% of the total weight of the sodium molybdate dihydrate, stirring for 30min at a rotating speed of 500r/min, and obtaining the powder aid after stirring.
The preparation method of the high-sulfur coal sulfur fixing agent comprises the following steps: sequentially adding a sulfur fixing main agent, organic alcohol and water into a stirrer for stirring treatment, wherein the stirring rotation speed is firstly at a rotation speed of 200r/min for 30min, then adding activated sludge, an ionic liquid composite aerogel carrier, a modified bentonite dispersing agent and a stabilizer, increasing the stirring rotation speed to 1500r/min, mechanically stirring for 20min, then reducing the rotation speed to 500r/min, and continuing stirring for 30min to obtain the sulfur fixing agent.
Example 3.
The high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
25 parts of sulfur fixing main agent, 10 parts of ionic liquid composite aerogel carrier, 3 parts of modified bentonite dispersing agent, 7.5 parts of activated sludge, 3 parts of organic alcohol, 3 parts of stabilizer and 47.5 parts of water;
the preparation method of the modified bentonite dispersing agent comprises the following steps:
s1, activating treatment of bentonite: firstly, feeding bentonite into a 3-time weight of auxiliary agent for low-speed stirring treatment, wherein the stirring speed is 150r/min, the stirring time is 25min, the stirring temperature is 70 ℃, and the stirring is finished to obtain active bentonite;
s2, ultrasonic dispersion of bentonite: delivering bentonite into a dispersing agent prepared from sodium dodecyl sulfate and hydrochloric acid according to a weight ratio of 1:2 for ultrasonic dispersion treatment, wherein the weight ratio of the bentonite to the dispersing agent is 1:5, the ultrasonic power is 300W, the ultrasonic time is 25min, and the ultrasonic treatment is finished;
s3, roasting: delivering the bentonite subjected to S2 ultrasonic treatment into a roasting box for roasting treatment, wherein the roasting temperature is 750 ℃, the roasting time is 15min, and cooling to 150 ℃ at a speed of 3 ℃/min after roasting is finished for later use;
s4, primary grinding treatment: grinding the bentonite subjected to S3 roasting treatment at 1000r/min for 20-30min, and carrying out heat preservation grinding to finish grinding;
s5, water-cooling refrigeration treatment: delivering bentonite subjected to primary grinding treatment in S4 into deionized water at-5 ℃ for high-speed stirring treatment, wherein the stirring rotation speed is 1250r/min, the stirring time is 15min, after stirring, placing the bentonite at-20 ℃ for refrigeration treatment for 5min, taking out, and naturally recovering to room temperature;
s6, secondary grinding treatment: and continuously grinding the bentonite subjected to water cooling and refrigeration treatment at the rotating speed of 750r/min for 15min to obtain the modified bentonite dispersing agent.
The sulfur fixing main agent of the embodiment comprises the following raw materials in parts by weight: 10 parts of calcium salt, 7.5 parts of magnesium salt and 6 parts of nitrate, wherein the calcium salt is calcium acetate, the magnesium salt is magnesium chloride and the nitrate is sodium nitrate.
The organic alcohol of this embodiment is ethylene glycol; the stabilizer is alumina.
The preparation method of the ionic liquid composite aerogel carrier in the embodiment comprises the following steps: adding the silica aerogel and the ionic liquid into a stirrer according to the weight ratio of 1:3, stirring until the mixture is fully mixed, then adding rare earth lanthanum chloride accounting for 15% of the total amount of the ionic liquid, stirring for 15min at a rotating speed of 150r/min, and obtaining the liquid composite aerogel carrier after stirring.
The preparation method of the activated sludge in the embodiment comprises the following steps: adding the sludge into a sodium hydroxide aqueous solution with the mass fraction of 75% which is 2 times that of the sludge for stirring and dispersing treatment, wherein the stirring and dispersing speed is 300r/min, the stirring time is 15min, filtering, washing with water, taking out, drying at 70 ℃ for 15min, and then adopting proton irradiation treatment to finish the treatment to obtain the activated sludge.
The irradiation power of the proton irradiation treatment in this example was 300W and the irradiation time was 15min.
The preparation method of the auxiliary agent in the preparation of the modified bentonite dispersing agent comprises the following steps: mixing sodium molybdate dihydrate and methyl acrylate according to a weight ratio of 1:2, then adding sodium acetylsalicylate accounting for 25% of the total mass of the sodium molybdate dihydrate, stirring for 25min at a rotating speed of 300r/min, and obtaining the powder aid after stirring.
The preparation method of the high-sulfur coal sulfur fixing agent comprises the following steps: sequentially adding a sulfur fixing main agent, organic alcohol and water into a stirrer for stirring treatment, wherein the stirring rotation speed is 150r/min for 25min, then adding activated sludge, an ionic liquid composite aerogel carrier, a modified bentonite dispersing agent and a stabilizer, increasing the stirring rotation speed to 1250r/min, mechanically stirring for 15min, then reducing the rotation speed to 500r/min, and continuing stirring for 25min to obtain the sulfur fixing agent.
Comparative example 1.
The only difference from example 3 is that no activated sludge was added.
Comparative example 2.
The only difference from example 3 was that no ionic liquid composite aerogel carrier was added.
Comparative example 3.
The only difference from example 3 is that no modified bentonite dispersing agent was added.
Control group:
the proportioning experiment was performed using the raw materials of example 2 in CN110194982a literature.
Experimental example 1:
sulfur fixation performance test is carried out according to the method of GB/T31098-2014, and the test result is as follows:
| group of | Sulfur fixation efficiency (%) |
| Example 1 | 93 |
| Example 2 | 92 |
| Example 3 | 94 |
| Comparative example 1 | 95 |
| Comparative example 2 | 83 |
| Comparative example 3 | 85 |
| Control group | 50 |
As can be seen from examples 1-3, comparative examples 1-3 and the control group, the sulfur fixation efficiency of the invention can reach 94%, the sulfur fixation effect of the invention can be improved without adding activated sludge, and the sulfur fixation efficiency is effectively reduced without adding the ionic liquid composite aerogel carrier and the modified bentonite dispersing agent.
Experimental example 2:
preparing 20 parts of peanut shells, 10 parts of soybean straws, 3 parts of zinc oxide and 3 parts of sulfur-fixing agent into fuel for performance test, and testing according to GB 5816-1985 (biomass fuel calorific value test method);
from examples 1-3 and comparative examples 1-3, it can be seen that the addition of activated sludge can effectively increase the heat value of the product, and the addition of activated sludge can reduce the sulfur fixation efficiency, but the functional efficiency of the two can be coordinated through the cooperation of the ionic liquid composite aerogel carrier, and in addition, the sulfur fixation efficiency of the product can be further enhanced through the addition of the modified bentonite dispersing agent.
Comparative example 4:
the preparation of the modified bentonite dispersing agent does not adopt auxiliary agent treatment.
Comparative example 5:
the preparation of the modified bentonite dispersing agent does not adopt one-time grinding treatment.
Comparative example 6:
the water-cooling refrigeration treatment is not adopted in the preparation of the modified bentonite dispersing agent.
The product properties of example 3 and comparative examples 4-6 were tested as follows:
| group of | Sulfur fixation efficiency (%) |
| Example 3 | 94 |
| Comparative example 4 | 89 |
| Comparative example 5 | 87 |
| Comparative example 6 | 88 |
From comparative examples 4-6, it can be seen that the lack of one grinding treatment, water-cooling refrigeration treatment and powder assisting treatment in the preparation of the modified bentonite dispersing agent can reduce the sulfur fixation efficiency, and the one grinding treatment has the greatest influence on the sulfur fixation efficiency, and probably because the one grinding treatment can refine the bentonite subjected to roasting treatment, the water-cooling refrigeration treatment has an intermediate transition effect, so that the lamellar diffusion effect is improved, and the sulfur fixation efficiency is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (5)
1. The high sulfur coal sulfur fixing agent is characterized by comprising the following raw materials in parts by weight:
20-30 parts of sulfur fixing main agent, 5-15 parts of ionic liquid composite aerogel carrier, 1-5 parts of modified bentonite dispersing agent, 5-10 parts of activated sludge, 1-5 parts of organic alcohol, 1-5 parts of stabilizer and 30-65 parts of water;
the preparation method of the modified bentonite dispersing agent comprises the following steps:
s1, activating treatment of bentonite: firstly, feeding bentonite into a 3-time weight of auxiliary agent for low-speed stirring treatment, wherein the stirring speed is 100-200r/min, the stirring time is 20-30min, the stirring temperature is 65-75 ℃, and the stirring is finished to obtain active bentonite;
s2, ultrasonic dispersion of bentonite: delivering bentonite into a dispersing agent prepared from sodium dodecyl sulfate and hydrochloric acid according to a weight ratio of 1:2 for ultrasonic dispersion treatment, wherein the weight ratio of the bentonite to the dispersing agent is 1:5, the ultrasonic power is 100-500W, the ultrasonic time is 20-30min, and the ultrasonic treatment is finished;
s3, roasting: delivering bentonite subjected to S2 ultrasonic treatment into a roasting box for roasting treatment, wherein the roasting temperature is 500-1000 ℃, the roasting time is 10-20min, and cooling to 150 ℃ at a speed of 1-5 ℃/min after roasting is finished for standby;
s4, primary grinding treatment: grinding the bentonite subjected to S3 roasting treatment at 1000r/min for 20-30min, and carrying out heat preservation grinding to finish grinding;
s5, water-cooling refrigeration treatment: delivering bentonite subjected to primary grinding treatment in S4 into deionized water at-5 ℃ for high-speed stirring treatment, wherein the stirring rotation speed is 1000-1500r/min, the stirring time is 10-20min, and after stirring, placing the bentonite at-20 ℃ for refrigeration treatment for 5min, taking out, and naturally recovering to room temperature;
s6, secondary grinding treatment: continuously grinding the bentonite subjected to water cooling and refrigeration treatment at the rotating speed of 500-1000r/min for 10-20min to obtain a modified bentonite dispersing agent;
the sulfur fixing main agent comprises the following raw materials in parts by weight: 5-15 parts of calcium salt, 5-10 parts of magnesium salt and 2-10 parts of nitrate, wherein the calcium salt is calcium acetate, the magnesium salt is magnesium chloride and the nitrate is sodium nitrate;
the organic alcohol is ethylene glycol; the stabilizer is alumina;
the preparation method of the ionic liquid composite aerogel carrier comprises the following steps: adding the silica aerogel and the ionic liquid into a stirrer according to a weight ratio of 1:3, stirring until the mixture is fully mixed, then adding rare earth lanthanum chloride accounting for 10-20% of the total amount of the ionic liquid, stirring for 10-20min at a rotating speed of 100-200r/min, and obtaining a liquid composite aerogel carrier after the stirring is finished;
adding sludge into a sodium hydroxide aqueous solution with the mass fraction of 70-80% which is 2 times that of the sludge, stirring and dispersing at the stirring and dispersing speed of 100-500r/min for 10-20min, filtering, washing, taking out, drying at 60-80 ℃ for 10-20min, and then adopting proton irradiation treatment to finish the treatment to obtain activated sludge;
the preparation method of the auxiliary agent in the preparation of the modified bentonite dispersing agent comprises the following steps: mixing sodium molybdate dihydrate and methyl acrylate according to a weight ratio of 1:2, then adding sodium acetylsalicylate accounting for 20-30% of the total mass of the sodium molybdate dihydrate, stirring for 20-30min at a rotating speed of 100-500r/min, and ending stirring to obtain the powder aid.
2. The high sulfur coal sulfur fixing agent as claimed in claim 1, wherein the high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
22-28 parts of sulfur fixing main agent, 7-13 parts of ionic liquid composite aerogel carrier, 2-4 parts of modified bentonite dispersing agent, 6-8 parts of activated sludge, 2-4 parts of organic alcohol, 2-3 parts of stabilizer and 32-63 parts of water.
3. The high sulfur coal sulfur fixing agent as claimed in claim 1, wherein the high sulfur coal sulfur fixing agent comprises the following raw materials in parts by weight:
25 parts of sulfur fixing main agent, 10 parts of ionic liquid composite aerogel carrier, 3 parts of modified bentonite dispersing agent, 7.5 parts of activated sludge, 3 parts of organic alcohol, 3 parts of stabilizer and 47.5 parts of water.
4. The sulfur-fixing agent for high sulfur coal as claimed in claim 1, wherein the irradiation power of the proton irradiation treatment is 100-500W and the irradiation time is 10-20min.
5. A method for preparing the sulfur-fixing agent for high sulfur coal as claimed in any one of claims 1 to 4, comprising the steps of: sequentially adding the sulfur fixing main agent, the organic alcohol and the water into a stirrer for stirring treatment, wherein the stirring rotation speed is firstly 100-200r/min, stirring for 20-30min, then adding the activated sludge, the ionic liquid composite aerogel carrier, the modified bentonite dispersing agent and the stabilizer, increasing the stirring rotation speed to 1000-1500r/min, mechanically stirring for 10-20min, then reducing the stirring speed to 500r/min, and continuing stirring for 20-30min to obtain the sulfur fixing agent.
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