CN112574789A - High-temperature desulfurizing agent and preparation method and application thereof - Google Patents
High-temperature desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN112574789A CN112574789A CN202011333117.3A CN202011333117A CN112574789A CN 112574789 A CN112574789 A CN 112574789A CN 202011333117 A CN202011333117 A CN 202011333117A CN 112574789 A CN112574789 A CN 112574789A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
Abstract
The invention relates to the technical field of coal gas desulfurization, in particular to a high-temperature desulfurizing agent, and a preparation method and application thereof. The high-temperature desulfurizing agent comprises the following raw materials: water-soluble zirconium salt, water-soluble manganese salt, water-soluble cerium salt, and yttrium-containing compound. According to the high-temperature desulfurizer provided by the invention, four elements of zirconium, manganese, cerium and yttrium are matched with one another, so that the prepared high-temperature desulfurizer is high in desulfurization precision and stable in a high-temperature reducing atmosphere; the mechanical strength is high, and after multiple regeneration, the desulfurization efficiency of the desulfurization agent vulcanization and regeneration cycle is high.
Description
Technical Field
The invention relates to the technical field of coal gas desulfurization, in particular to a high-temperature desulfurizing agent, and a preparation method and application thereof.
Background
At present, clean conversion and efficient utilization technologies of coal resources are important environment-friendly energy utilization technologies, such as new power generation technologies of integrated gasification combined cycle power generation (IGCC), molten carbonate fuel cell (CMFC) and the like, and new coal-based poly-generation technologies of synthetic oil and alcohol ether fuel and the like, and have the advantages of high thermal efficiency, low pollution and the like, so that the clean conversion and efficient utilization technologies of coal resources become a main development direction of clean and efficient utilization of coal.
However, the coal gasification gas still contains H2S、COS、CS2(wherein 90% is H)2S), HCl, HCN, NO, and other harmful gases, among which H2S、COS、CS2These sulfides are highly corrosive, cause corrosion of equipment, piping and gas turbine blades, and also cause catalyst poisoning. In addition, hydrogen production from a typical refinery is used for H in the synthesis gas of sulfur tolerant catalysts2The S content should be less than 10X 10-6H in the gas used as synthesis feed gas2The S content must be less than 0.05X 10-6. Therefore, the desulfurization and purification of the coal gas become an important link in the ammonia synthesis and hydrogen production technology.
The purpose of removing sulfur in gas under high temperature (more than or equal to 800 ℃) is to utilize sensible heat of coal gas, prevent corrosion of sulfide to equipment pipelines and poisoning of various catalysts used in subsequent reactions, improve the efficiency of catalytic reaction and the service life of the catalysts, so that if sulfur in coal gas can be removed to a lower level under high temperature in the coal gasification process, the clean conversion efficiency is improved. Therefore, the high-temperature desulfurization technology of coal gas has become a hot point of research in the field of energy.
The high-temperature gas desulfurizing agent meets the requirements of industrial application, and can withstand repeated cyclic utilization without obvious attenuation of sulfur capacity and reactivity except for requiring higher desulfurization precision and higher sulfur capacity of the desulfurizing agent, which is the key of the high-temperature gas desulfurization technology. But the current symptom restricting the industrialization of the high-temperature gas desulfurizer is low desulfurization precision and less recycling times of the desulfurizer. As disclosed in the prior art, a ZrO2Loaded Mn-based high-temperature desulfurizer which uses zirconium oxide ZrO2As carrier, sodium carbonate Na is used2CO3Zirconium oxychloride octahydrate ZrOCl2·8H2O, Yttrium nitrate hexahydrate Y (NO)3)3·6H2Precipitating O, adding SDS dispersant, and adding manganese nitrate tetrahydrate Mn (NO)3)2·4H2O is prepared by precipitating manganese, filtering, washing, drying and calciningObtaining a finished product of the high-temperature desulfurizer; the desulfurizer can remove hydrogen sulfide in simulated coal gas to below 2ppm, but after the desulfurizer is regenerated for multiple times, the desulfurization and regeneration cycle efficiency of the desulfurizer is low.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the high-temperature gas desulfurizer in the prior art has low efficiency of pulverization and regeneration cycle of the desulfurizer after being regenerated for multiple times, thereby providing the high-temperature desulfurizer as well as the preparation method and the application thereof.
Therefore, the invention provides the following technical scheme:
a high-temperature desulfurizing agent comprises the following raw materials: water-soluble zirconium salt, water-soluble manganese salt, water-soluble cerium salt, and yttrium-containing compound.
Optionally, the molar ratio of zirconium in the water-soluble zirconium salt to cerium in the water-soluble cerium salt is 1 (2-5.5);
the molar ratio of yttrium in the yttrium-containing compound to manganese in the water-soluble manganese salt is 1 (2.5-6).
Optionally, the molar ratio of zirconium in the water-soluble zirconium salt to yttrium in the yttrium-containing compound is 1 (1-5).
Optionally, the molar ratio of cerium in the water-soluble cerium salt to yttrium in the yttrium-containing compound is 1 (0.4-1.1).
Optionally, the water-soluble zirconium salt is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate;
the water-soluble cerium salt is one or more of cerium chloride, cerium sulfate and cerium nitrate;
the water-soluble manganese salt is one or more of manganese chloride, manganese sulfate and manganese nitrate;
the yttrium-containing compound is one or more of yttrium oxide and yttrium nitrate.
Optionally, the raw material of the high-temperature desulfurizing agent also comprises acid, and the molar ratio of manganese in the water-soluble manganese salt to the acid is 1 (1-5);
preferably, the acid is one or more of hydrochloric acid, nitric acid, phosphoric acid, citric acid, carbonic acid, oxalic acid, formic acid, acetic acid.
Optionally, the raw material of the high-temperature desulfurizing agent further comprises an organic base, wherein the organic base is ammonia water; preferably, the concentration of the ammonia water is 25 wt%;
the invention also provides a preparation method of the high-temperature desulfurizer, which comprises the following steps:
preparing a precursor solution: mixing water-soluble zirconium salt, water-soluble cerium salt and water to obtain a mixed aqueous solution of zirconium and cerium; mixing acid and water-soluble manganese salt, adding the mixed water solution of zirconium and cerium, uniformly stirring, and adjusting the pH value to 5-6 to obtain a precursor solution;
preparing a semi-finished product: drying and grinding the precursor solution to obtain a semi-finished product;
preparing a high-temperature desulfurizing agent: and mixing the semi-finished product with a compound containing yttrium, molding, drying and roasting to obtain the high-temperature desulfurizer.
Optionally, the organic base is used for adjusting the pH of the mixed aqueous solution of the water-soluble zirconium salt, the water-soluble cerium salt, the inorganic acid and the water-soluble manganese salt to be 5-6.
Optionally, the drying in the step of preparing the semi-finished product comprises the following steps:
drying the precursor solution at 80 ℃ for 5-10h under the stirring state, and then drying at 120 ℃ for 5-10 h.
Optionally, the milled particle size is no greater than 500 mesh.
Optionally, in the step of preparing the high-temperature desulfurizer, the drying temperature is 110 ℃, the drying time is 6-10 hours, the roasting temperature is 800 ℃, and the roasting time is 1-5 hours.
The invention also provides an application of the high-temperature desulfurizer or the high-temperature desulfurizer prepared by the preparation method in removing sulfur in coal gasification gas.
The technical scheme of the invention has the following advantages:
1. the inventor has found that the existing ZrO made from ZrO2As a desulfurizing agent for the carrier, since ZrO2The temperature-variable crystal transformation exists, and the phase transformation is accompanied with the volume change, so that the pulverization or the inactivation of the desulfurizer can be caused, and the mechanical property is realizedThe strength is lowered, thereby affecting the regeneration performance of the desulfurizing agent. According to the high-temperature desulfurizer provided by the invention, the water-soluble zirconium salt, the water-soluble manganese salt, the water-soluble cerium salt and the yttrium-containing compound are used as raw materials, on one hand, the element zirconium and the rare earth element cerium can form a stable cerium pickaxe solid solution, and not only can later-stage ZrO be effectively prevented2The transformation of the variable temperature crystal forms leads the desulfurizer to be pulverized or inactivated, provides support for doping Mn, and part of element Ce can be transformed into CeOn (n) under the high-temperature reducing atmosphere<2) Can effectively avoid the problem of ZrO due to ZrO2The desulfurizer is pulverized or inactivated due to the transformation of the temperature-variable crystal form, and the regeneration cycle efficiency is high; on the other hand, by adopting the yttrium-containing compound, the mechanical strength of the desulfurizing agent can be improved by matching the element yttrium with the element cerium.
According to the high-temperature desulfurizer provided by the invention, four elements of zirconium, manganese, cerium and yttrium are matched with one another, so that the prepared high-temperature desulfurizer has high desulfurization precision (less than 0.5ppm) and is stable in a high-temperature reducing atmosphere; the mechanical strength is high, and after multiple regeneration, the desulfurization efficiency of the desulfurization agent vulcanization and regeneration cycle is high.
2. The high-temperature desulfurizing agent provided by the invention is prepared by limiting the molar ratio of zirconium in the water-soluble zirconium salt to cerium in the water-soluble cerium salt to be 1 (2-5.5); the stability of the cerium-zirconium solid solution can be improved; the mechanical strength of the high-temperature desulfurizing agent can be improved by limiting the molar ratio of yttrium in the yttrium-containing compound to manganese in the water-soluble manganese salt to be 1 (2.5-6); the molar ratio of zirconium in the water-soluble zirconium salt to cerium in the water-soluble cerium salt and the molar ratio of yttrium in the yttrium-containing compound to manganese in the water-soluble manganese salt are simultaneously limited, so that the desulfurization precision of the high-temperature desulfurizing agent can be further improved, and the desulfurization efficiency of the desulfurizing agent in vulcanization and regeneration cycles after multiple regeneration is improved.
3. The high-temperature desulfurizer provided by the invention can further improve the regeneration performance and desulfurization precision of the high-temperature desulfurizer by further limiting the molar ratio of cerium in the water-soluble cerium salt to yttrium in the yttrium-containing compound to be 1 (0.4-1.1).
4. The high-temperature desulfurizer provided by the invention is characterized in that the acid is added, and the molar ratio of the acid to manganese in the water-soluble manganese salt is further limited to (1-5): 1; can increase the acid position of manganese salt and further improve the desulfurization effect of the high-temperature desulfurizer.
5. According to the high-temperature desulfurizer provided by the invention, zirconium is used as a high-temperature resistant material, and can form a eutectic with cerium, so that the desulfurization effect is improved at high temperature; zirconium and cerium form a eutectic which can be effectively combined with manganese, so that the desulfurization effect of a sample is improved, and yttrium and zirconium are matched with each other to improve the strength of the desulfurizer. The high-temperature desulfurizer provided by the invention has the advantages that the raw materials are mutually matched, and the desulfurization effect and the regeneration performance at high temperature can be obviously improved.
6. According to the preparation method of the high-temperature desulfurizer, the desulfurization precision of the high-temperature desulfurizer prepared by the preparation method of the high-temperature desulfurizer is high (less than 0.5ppm), and the high-temperature desulfurizer is stable in a high-temperature reducing atmosphere; the mechanical strength is high, and after multiple regeneration, the desulfurization efficiency of the desulfurization agent vulcanization and regeneration cycle is high.
7. According to the preparation method of the high-temperature desulfurizer, parameters in the drying step, grinding particle size and roasting parameters are limited, and the steps are matched with each other, so that the desulfurization effect and the regeneration performance of the prepared desulfurizer at high temperature can be obviously improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 72g of cerium nitrate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 150g of manganese nitrate and 80g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured into the reactor, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, so that a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 81g of yttrium nitrate hexahydrate, extruding and molding by using a phi 4 strip, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 2
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium sulfate solid and 55g of cerium chloride solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 20g of manganese chloride and 80g of analytically pure hydrochloric acid (36 wt% concentrated hydrochloric acid) were mixed, the mixed aqueous solution of zirconium and cerium was poured in, and after stirring uniformly, the solution pH was adjusted to 6 with 25 wt% ammonia water to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 10h to be gelatinous by using a constant-temperature water bath at 70 ℃ under the stirring state of 50 r/min, then drying the gelatinous precursor solution for 8h in a drying box at 110 ℃, and grinding and sieving the gelatinous precursor solution by using a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 29.7g of yttrium oxide, extruding and molding by using phi 4 strip, drying at 100 ℃ for 6h, and roasting at 750 ℃ at a heating rate of 5 ℃/min for 1h to obtain the high-temperature desulfurizer.
Example 3
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 150g of cerium sulfate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; 100g of manganese sulfate and 80g of formic acid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, after uniform stirring, the pH value of the solution is adjusted to 5.5 by 25 wt% of ammonia water, and a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 44g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 4
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 50g of cerium nitrate solid into 100g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 50g of manganese sulfate and 80g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, so that a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 24g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 5
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 213g of cerium nitrate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 200g of manganese chloride and 432g of oxalic acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, after uniform stirring, the pH value of the solution is adjusted to 5 by 25 wt% of ammonia water, and a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 8 hours in a constant-temperature water bath at 75 ℃ under the stirring state of 50 revolutions per minute to form a gel, then drying the gel in a drying oven at 115 ℃ for 10 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 151g of yttrium nitrate hexahydrate, extruding and molding by using phi 4 strips, drying at 105 ℃ for 10h, and roasting at 780 ℃ at the heating rate of 5 ℃/min for 5h to obtain the high-temperature desulfurizer.
Example 6
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 88g of cerium nitrate solid into 270g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; 130g of manganese nitrate and 146g of concentrated nitric acid (the mass fraction is 68 wt%) are mixed, the mixed aqueous solution of zirconium and cerium is poured into the mixture, and after the mixture is uniformly stirred, 25 wt% ammonia water is used for adjusting the pH value of the solution to 5, so that a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 56g of yttrium nitrate hexahydrate, extruding and molding by using phi 4 strip, drying at 110 ℃ for 8h, and roasting at 800 ℃ at the heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 7
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 85g of cerium nitrate solid into 260g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 150g of manganese sulfate and 161g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, so as to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 59g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at the heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 8
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 131g of cerium nitrate solid into 260g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 150g of manganese sulfate and 645g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, thus obtaining a precursor solution. Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 126g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 9
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 260g of cerium nitrate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; and mixing 530g of manganese chloride and 2079g of oxalic acid solid, pouring the mixed aqueous solution of zirconium and cerium, uniformly stirring, and adjusting the pH value of the solution to 5 by using 25 wt% of ammonia water to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 247g of yttrium nitrate hexahydrate, extruding and molding by using a phi 4 strip, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 10
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 98.5g of cerium nitrate solid into 100g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 50g of manganese sulfate and 80g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, so that a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 24g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 11
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 131g of cerium nitrate solid into 260g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; 170g of manganese sulfate and 645g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, after uniform stirring, the pH value of the solution is adjusted to 5 by 25 wt% of ammonia water, and a precursor solution is obtained. Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 81g of yttrium oxide, extruding and molding by using a phi 4 strip, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 12
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 260g of cerium nitrate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; mixing 377.5g of manganese chloride and 810g of oxalic acid solid, pouring the mixed aqueous solution of zirconium and cerium, uniformly stirring, and adjusting the pH value of the solution to 5 by using 25 wt% of ammonia water to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 247g of yttrium nitrate hexahydrate, extruding and molding by using a phi 4 strip, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 13
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium nitrate solid and 72g of cerium nitrate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; after 150g of manganese nitrate and 564g of anhydrous citric acid solid are mixed, the mixed aqueous solution of zirconium and cerium is poured into the reactor, and after uniform stirring, the pH value of the solution is adjusted to 5 by using 25 wt% of ammonia water, so as to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 81g of hexahydrated yttrium nitrate, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Example 14
The embodiment provides a high-temperature desulfurizing agent, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium sulfate solid and 55g of cerium chloride solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; and (3) mixing 20g of manganese chloride with the mixed aqueous solution of zirconium and cerium, uniformly stirring, and adjusting the pH value of the solution to 6 by using 25 wt% of ammonia water to obtain a precursor solution.
Preparing a semi-finished product:
and heating and drying the precursor solution for 10h to be gelatinous by using a constant-temperature water bath at 70 ℃ under the stirring state of 50 r/min, then drying the gelatinous precursor solution for 8h in a drying box at 110 ℃, and grinding and sieving the gelatinous precursor solution by using a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
mixing the semi-finished product with 29.7g of yttrium oxide, extruding and molding by using phi 4 strip, drying at 100 ℃ for 6h, and roasting at 750 ℃ at a heating rate of 5 ℃/min for 1h to obtain the high-temperature desulfurizer.
Comparative example 1
The comparative example provides a high-temperature desulfurizer, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 150g of cerium sulfate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; 100g of manganese sulfate and 80g of formic acid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, after uniform stirring, the pH value of the solution is adjusted to 4 by 25 wt% of ammonia water, and a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 44g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Comparative example 2
The comparative example provides a high-temperature desulfurizer, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid and 150g of cerium sulfate solid into 300g of distilled water, and stirring and dissolving to obtain a mixed aqueous solution of zirconium and cerium; 100g of manganese sulfate and 80g of formic acid are mixed, the mixed aqueous solution of zirconium and cerium is poured in, after uniform stirring, the pH value of the solution is adjusted to 7 by 25 wt% of ammonia water, and a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 44g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Comparative example 3
The comparative example provides a high-temperature desulfurizer, and the preparation method comprises the following steps:
preparing a precursor solution:
adding 30g of zirconium chloride solid into 300g of distilled water, and stirring and dissolving to obtain a zirconium aqueous solution; 100g of manganese sulfate and 80g of formic acid are mixed, the aqueous solution of zirconium is poured in, after uniform stirring, the pH value of the solution is adjusted to 5.5 by 25 wt% of ammonia water, and a precursor solution is obtained.
Preparing a semi-finished product:
and heating and drying the precursor solution for 5 hours in a constant-temperature water bath at 80 ℃ to form a gel under the stirring state of 50 r/min, then drying the gel in a drying oven at 120 ℃ for 5 hours, and grinding and sieving the gel with a 500-mesh sieve to obtain a semi-finished product.
Preparing a high-temperature desulfurizing agent:
and mixing the semi-finished product with 44g of yttrium oxide, extruding and molding by using phi 4 strips, drying at 110 ℃ for 8h, and roasting at 800 ℃ at a heating rate of 5 ℃/min for 2h to obtain the high-temperature desulfurizer.
Experimental example 1
The desulfurization performance of the high-temperature desulfurization agents prepared in the above examples and comparative examples was tested under the following test conditions:
simulating raw material gas: h2S50 ppm, thiophene 10ppm, dimethyl disulfide 10ppm
The operating conditions are as follows: space velocity of 8000h-1Temperature of operationThe temperature is 800 ℃, and the pressure is normal;
loading of high-temperature desulfurizer: 16mL, outlet sulfur content above 1ppm was considered breakthrough;
a detection instrument: the sulfur content analysis adopts a TS-3000 type ultraviolet fluorescence sulfur detector of national institute of analysis instruments, Inc. in Thizhou. The corresponding test results are shown in table 1 below:
TABLE 1 desulfurization accuracy of desulfurizing agent
Note: the desulfurization precision refers to the total sulfur (H) at the outlet2S, thiophene, and dimethyl disulfide).
As can be seen from the data in the table above, the high-temperature desulfurizing agent provided by the invention has high desulfurization precision through the mutual matching of the four elements of zirconium, manganese, cerium and yttrium.
Experimental example 2
The high-temperature desulfurizing agents prepared in the above examples and comparative examples adsorb sulfides (organic sulfur and hydrogen sulfide) until the adsorption saturation is reached and the outlet is more than 0.5ppm, the high-temperature desulfurizing agent after the adsorption saturation is calcined at 800 ℃ for regeneration, and the desulfurization effect of the regenerated high-temperature desulfurizing agent is measured. The test results are shown in table 2 below.
The desulfurization effect of the regenerated high-temperature desulfurizer is equal to the desulfurization precision of the regenerated high-temperature desulfurizer/the desulfurization precision of the newly prepared high-temperature desulfurizer is multiplied by 100 percent;
TABLE 2 desulfurization Effect of the regenerated desulfurization agent
The data in the above table show that, the high-temperature desulfurizer provided by the invention has high desulfurization efficiency of desulfurization and regeneration cycles after the high-temperature desulfurizer is regenerated for multiple times through the mutual matching of the four elements of zirconium, manganese, cerium and yttrium, which indicates that the regeneration effect is good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The high-temperature desulfurizing agent is characterized by comprising the following raw materials: water-soluble zirconium salt, water-soluble manganese salt, water-soluble cerium salt, and yttrium-containing compound.
2. The high-temperature desulfurization agent according to claim 1, wherein the molar ratio of zirconium in the water-soluble zirconium salt to cerium in the water-soluble cerium salt is 1: 2-5.5;
the molar ratio of yttrium in the yttrium-containing compound to manganese in the water-soluble manganese salt is 1: 2.5-6.
3. The high-temperature desulfurizing agent according to claim 1 or 2, wherein the molar ratio of cerium in the water-soluble cerium salt to yttrium in the yttrium-containing compound is 1: 0.4-1.1.
4. The high-temperature desulfurizing agent according to any one of claims 1 to 3, wherein the water-soluble zirconium salt is one or more of zirconium chloride, zirconium sulfate and zirconium nitrate;
the water-soluble cerium salt is one or more of cerium chloride, cerium sulfate and cerium nitrate;
the water-soluble manganese salt is one or more of manganese chloride, manganese sulfate and manganese nitrate;
the yttrium-containing compound is one or more of yttrium oxide and yttrium nitrate.
5. The high-temperature desulfurizing agent according to any one of claims 1 to 4, wherein the raw material of the high-temperature desulfurizing agent further comprises an acid, and the molar ratio of manganese to the acid in the water-soluble manganese salt is 1: 1-5;
preferably, the acid is one or more of hydrochloric acid, nitric acid, phosphoric acid, citric acid, carbonic acid, oxalic acid, formic acid, acetic acid.
6. The preparation method of the high-temperature desulfurizing agent is characterized by comprising the following steps of:
preparing a precursor solution: mixing water-soluble zirconium salt, water-soluble cerium salt and water to obtain a mixed aqueous solution of zirconium and cerium; mixing acid and water-soluble manganese salt, then adding the mixed aqueous solution of zirconium and cerium, uniformly stirring, and adjusting the pH value to 5-6 to obtain a precursor solution;
preparing a semi-finished product: drying and grinding the precursor solution to obtain a semi-finished product;
preparing a high-temperature desulfurizing agent: and mixing the semi-finished product with a compound containing yttrium, molding, drying and roasting to obtain the high-temperature desulfurizer.
7. The method for preparing a high-temperature desulfurizing agent according to claim 6, wherein the drying in the step of preparing the semi-finished product comprises the steps of:
drying the precursor solution at 70-80 ℃ for 5-10h under the stirring state, and then drying at 110-120 ℃ for 5-10 h.
8. The method according to claim 6 or 7, wherein the ground particle size is not greater than 500 mesh.
9. The method for preparing a high-temperature desulfurizing agent according to any one of claims 6 to 8, wherein the drying temperature in the step of preparing the high-temperature desulfurizing agent is 110 ℃ for 6 to 10 hours, the roasting temperature is 800 ℃ for 750 ℃ and the roasting time is 1 to 5 hours.
10. Use of the high-temperature desulfurization agent according to any one of claims 1 to 5 or the high-temperature desulfurization agent produced by the method according to any one of claims 6 to 9 for removing sulfur from a coal gasification gas.
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