CN114437851B - Method for quality improvement and desulfurization of high-sulfur fertilizer coal - Google Patents
Method for quality improvement and desulfurization of high-sulfur fertilizer coal Download PDFInfo
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- CN114437851B CN114437851B CN202210112120.5A CN202210112120A CN114437851B CN 114437851 B CN114437851 B CN 114437851B CN 202210112120 A CN202210112120 A CN 202210112120A CN 114437851 B CN114437851 B CN 114437851B
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Abstract
The invention provides a method for improving quality and desulfurizing high-sulfur fertilizer coal, which relates to the technical field of coking and comprises the following steps: (a) Mixing high-sulfur fat coal, an organic sulfur remover, titanium dioxide and nickel fluoborate to form first slurry; (b) Heating the first slurry, and separating to obtain a first liquid material and a first solid material; (c) Mixing the first solid material and wash oil to form a second slurry; (d) Heating and pressurizing the second slurry, and separating to obtain a second liquid material and a second solid material; (e) Carrying out flash evaporation on the second liquid material to obtain an organic solvent and a third solid material; and drying the third solid material to obtain the desulfurized coal. The invention can remove 50 percent of organic sulfur and 100 percent of inorganic sulfur on the premise of not damaging the cohesiveness of the high-sulfur fertilizer coal, reduces the utilization rate of precious high-quality coking coal while improving the utilization rate of low-quality coke, and has good economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the technical field of coking, in particular to a method for improving quality and desulfurizing high-sulfur fertilizer coal.
Background
Because of the limited yield of Chinese high quality coking coal, large quantities of fat coal are typically used in Chinese coal blending structures to increase the caking index of the coal blend. However, due to the high sulfur content in the Chinese fat coal, the high blending amount can increase the sulfur content in the coke, thereby affecting the quality of pure iron in blast furnace iron making.
Therefore, on the premise of not influencing the main function of the fat coal, namely improving the caking index, the utilization rate of the inferior fat coal can be greatly improved by effectively removing the sulfur, and the coal blending system of a coking plant is further optimized to reduce the cost of the coking process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a method for effectively removing organic sulfur and inorganic sulfur from high-sulfur fat coal on the premise of not changing the caking index of the fat coal, so as to achieve the purpose of improving the blending amount of the poor-quality fat coal in the coking process to reduce the cost.
The invention also aims to provide a coking process for blending coal, which is to blend the desulfurized coal obtained by the desulfurization method into the blended coal for coking.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for quality improvement and desulfurization of high-sulfur fertilizer coal, which comprises the following steps:
(a) Mixing high-sulfur fat coal, an organic sulfur remover, titanium dioxide and nickel fluoborate to form first slurry;
(b) Heating the first slurry obtained in the step (a) for reaction, and then separating to obtain a first liquid material and a first solid material;
(c) Mixing the first solid material obtained in the step (b) and wash oil to form a second slurry;
(d) Heating and pressurizing the second slurry obtained in the step (c), and then separating to obtain a second liquid material and a second solid material;
(e) And (d) carrying out flash evaporation on the second liquid material obtained in the step (d) to obtain an organic solvent and a third solid material, and further drying the third solid material to obtain the desulfurized coal.
Step (a)
The fat coal is one of bituminous coal, has medium coalification degree, is strong caking coal with medium and medium-high volatile contents, and has the volatile content of about 25-35%. High sulfur coal refers to coal containing over 1% sulfur.
In a preferred embodiment, the high sulfur coal is pulverized to raw coal that can pass through a 60 mesh screen and thus has a particle size of less than 0.1-0.2 mm.
The organic sulfur remover is a reagent for removing organic sulfur in high-sulfur fat coal, and is preferably an aqueous citric acid solution.
In a preferred embodiment, the concentration of the aqueous citric acid solution is 0.2-0.3mol/L, such as 0.2, 0.25, 0.3mol/L.
In a preferred embodiment, the mixing ratio of the high-sulfur fat coal, the organic sulfur remover, the titanium dioxide and the nickel fluoborate is 1-2kg:2-3L:0.01-0.03kg:0.01-0.04kg, preferably 1kg:2L:0.02kg:0.01kg.
Step (b)
In a preferred embodiment, the warming reaction is carried out in a reaction vessel under inert atmosphere at atmospheric pressure at a temperature of 150 to 190 ℃, e.g. 150, 160, 170, 180, 190 ℃ for a period of 2 to 2.5h, e.g. 2h.
In a preferred embodiment, after the first slurry is heated and reacted, the materials are kept at 300 ℃ and are subjected to vacuum pressure filtration to separate a first liquid material and a first solid material.
The cracking of sulfur bonds is promoted by heating reaction metal catalysts titanium dioxide and nickel fluoborate, so that a large amount of organic sulfur in high-sulfur fertilizer coal is removed through a citric acid solution (the organic sulfur is dissolved in the citric acid aqueous solution to form a citric acid aqueous solution dissolved with the organic sulfur), and solid-liquid separation is carried out to obtain solid materials (mainly granular substances) after the organic sulfur is removed.
In a preferred embodiment, the first solid material after removal of organic sulfur may be further washed with deionized water and subsequently dried, for example at about 110 ℃ for 8-10h.
Step (c)
The wash oil is absorption oil for washing out benzene or naphthalene compounds from coal gas, is fraction in coal tar or petroleum, and is fraction of industrial coal tar at 230-260 ℃ (namely fraction section of 230-260 ℃ obtained by further rectifying the wash oil).
In a preferred embodiment, the ratio of the first solid material to the wash oil is 1-2kg:20-50L, preferably 1kg:25L.
Step (d)
In a preferred embodiment, the reaction is carried out in a stirred tank at elevated temperature and pressure under inert atmosphere at a pressure of 1-2MPa, e.g. 1, 2MPa, a reaction temperature of 350-380 deg.C, e.g. 360, 370 deg.C and a reaction time of 1-2h, e.g. 1, 1.5h;
in a preferred embodiment, after the second slurry is subjected to heating and pressurizing reaction, the materials are kept at 300 ℃ and subjected to vacuum pressure filtration separation to obtain a second liquid material and a second solid material.
The washing oil is utilized to extract the long-chain aliphatic series, the short-chain aliphatic series and the small component aromatic series with caking property by heating and pressurizing reaction, thereby removing the metal inorganic salt influencing the coke quality.
Step (e)
In a preferred embodiment, the flash pressure is 0.1MPa underpressure.
Preferably, the organic solvent obtained by flash evaporation is recycled; and drying the third solid material to obtain the desulfurized coal.
In one embodiment, a typical method for upgrading and desulfurizing high sulfur coal includes the following steps:
(1) Mixing high-sulfur fat coal, citric acid solution, titanium dioxide and nickel fluoborate, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2 hours; (2) After the material is cooled to room temperature, separating the organic solvent and the insoluble particulate matter; (3) Mixing the granular substances with washing oil, stirring and heating to 350 ℃ under the nitrogen atmosphere, and reacting for 1h; (4) Separating the dissolved organic components from the undissolved particulate matter; (5) And (3) separating the organic solvent and the solid substance from the organic component at 150 ℃ by using a flash tank, recycling the solvent, and obtaining the solid substance which is the coal sample subjected to desulfurization and upgrading.
The invention can remove 50 percent of organic sulfur and 100 percent of inorganic sulfur on the premise of not damaging the cohesiveness of the high-sulfur fertilizer coal, the sulfur content of the coke is an important index for determining the quality of the coke, and the price of the domestic low-sulfur fertilizer coal is always high. The method can improve the blending amount of the inferior high-sulfur fat coal and further reduce the blending amount of the high-quality coking coal, and has good economic benefit and environmental benefit.
The invention provides a coal blending coking process on the other hand, which comprises the following steps:
obtaining desulfurized coal by using the method for quality improvement and desulfurization of the high-sulfur fertilizer coal;
and blending the desulfurized coal into blended coal for coking to obtain coke.
Preferably, the blending proportion of the desulfurized coal is 5 to 10wt%.
The technical scheme of the invention has the following beneficial effects:
the invention can remove 45-50% organic sulfur and 100% inorganic sulfur in high-sulfur fertilizer coal, and the excellent caking index is still maintained after desulfurization. Experiments prove that after the modified fat coal after desulfurization is subjected to coal blending and coking, the thermal strength is slightly increased compared with the high-sulfur fat coal.
The invention creatively removes 50 percent of organic sulfur and 100 percent of inorganic sulfur without changing the caking index of the fat coal, and the excellent caking index of the fat coal is analyzed from a mechanism angle because the fat coal contains a large amount of long-chain aliphatic series which can be melted at high temperature. Because sulfur is usually present in the fat chain (bond energy 200 KJ/mol) in the coking coal. This makes the strong acid coal washing desulfurization means can influence the coking ability of the coking coal. According to the invention, a metal catalyst titanium dioxide and nickel fluoborate capable of promoting the breaking of sulfur bonds are added into the citric acid solution used as the organic sulfur remover, so that the sulfur bonds can be broken under a low-temperature condition (low-temperature reaction below 400 ℃ for coal pyrolysis), and a large amount of organic sulfur in high-sulfur fertilizer coal is removed through the citric acid solution. However, the content of metal salt in the coking process can reduce the thermal strength of the coke, so the method utilizes the similar compatibility principle, utilizes the industrial light washing oil containing a large amount of naphthalene organic matters to further improve the quality of the fat coal after the organic sulfur is removed, and extracts the long-chain aliphatic group with caking property and the small-component aromatic group to further remove the metal inorganic salt which influences the quality of the coke. The invention greatly improves the application of the low-quality high-sulfur coal, and the coal treated by the process has an effect of improving the thermal strength of coke compared with the raw coal.
The present invention has been described in detail hereinabove, but the above embodiments are merely illustrative in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following examples.
Unless expressly stated otherwise, a numerical range throughout this specification includes any sub-range therein and any numerical value incremented by the smallest sub-unit within a given value. Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the operating examples provided at the end of the detailed description, all numbers expressing quantities or conditions of parameters (e.g., quantities or conditions) used in the specification (including the appended claims) are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so stated is allowed to be somewhat imprecise (with some approach to exactness in that value; about or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include variations of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows the sulfur content of the desulfurized coal of examples 1-3 and the undesulfurized raw coal of examples 1-3.
FIG. 2 is a graph showing the caking index (G value) between the desulfurized coal of examples 1 to 3 and the undesulfurized raw coal of examples 1 to 3.
FIG. 3 is a CSR of coke obtained by blending the desulfurized coal and undesulfurized raw coal of examples 1 to 3 in the same amount.
FIG. 4 is a graph showing the sulfur content of the desulfurized coals of examples 1-3 and comparative examples 1-9.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention.
The starting materials, reagents, methods and the like used in the examples are those conventional in the art unless otherwise specified.
The quality parameters of the high sulfur coal used in the examples are shown in table 1.
Table 1 example industrial analysis parameters using fat coal
In the embodiment of the method, the rectification and rectification wash oil produced by coking is light wash oil (purchased from Hebei Schchen Taixu Yang coal chemical Co., ltd.) which is heated and distilled under normal pressure, and the fraction evaporated from the solution in boiling at 230-260 ℃ is collected.
Example 1
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 3.95%), 0.1kg of titanium dioxide, 0.05kg of nickel fluoborate and 10L of citric acid aqueous solution (0.2 mol/L) into slurry, stirring and heating to 150 ℃ under the nitrogen atmosphere, and reacting for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.2kg of desulfurized coal was obtained.
Example 2
Mixing 5kg of Huaihe ore high-sulfur fertilizer coal (sulfur content: 1.6%), 0.1kg of titanium dioxide, 0.05kg of nickel fluoborate and 10L of citric acid aqueous solution (0.2 mol/L) into slurry, stirring and heating to 150 ℃ under the nitrogen atmosphere, and reacting for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg solid material with 25L of distillation and rectification wash oil (230-260 deg.C fraction) produced by coking, pressurizing under 2Mpa, stirring, heating to 350 deg.C, and reacting for 1 hr; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.25kg of desulfurized coal was obtained.
Example 3
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 2.2%), 0.1kg of titanium dioxide, 0.05kg of nickel fluoborate and 10L of citric acid aqueous solution (0.2 mol/L) into slurry, stirring and heating to 150 ℃ under the nitrogen atmosphere, and reacting for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.1kg of desulfurized coal was obtained.
Application example 1
The desulfurized coal obtained in example 1 was blended with the blended coal shown in Table 2, and the ratio of the desulfurized coal to the blended coal for coking was 10% by weight and the ratio of the other blended coal for coking was 90% by weight. The prepared blended coal is crushed and mixed evenly and then is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
TABLE 2 blending coal
Application example 2
The desulfurized coal obtained in example 2 was blended with the blended coal shown in Table 2, and the ratio of the desulfurized coal to the blended coal for coking was 10% by weight and the ratio of the other blended coal for coking was 90% by weight. The prepared blended coal is crushed and mixed evenly and then is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
Application example 3
The desulfurized coal obtained in example 3 was blended with the blended coal shown in Table 2, and the ratio of the desulfurized coal to the blended coal for coking was 10% by weight and the ratio of the other blended coal for coking was 90% by weight. The prepared blended coal is crushed and mixed evenly and then is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
Application comparative example 1
The east Pang Gao sulfur-containing raw coal used in example 1 was blended with the blended coal shown in table 2, and the high-sulfur coal ratio was 10wt%, and the other coking blended coal ratio was 90 wt%. The prepared blended coal is crushed and mixed evenly and then is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
Comparative application example 2
The Huai mine high-sulfur fertilizer coal raw coal used in example 2 was blended with the blended coal shown in Table 2, wherein the high-sulfur coal proportion was 10wt%, and the other coking blended coal proportion was 90 wt%. The prepared blended coal is crushed and mixed evenly and then is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
Comparative application example 3
The east Pang Gao sulfur-containing raw coal used in example 3 was blended with the blended coal shown in table 2, and the high-sulfur coal ratio was 10wt%, and the other coking blended coal ratio was 90 wt%. Blended coal after blendingAfter being crushed and mixed evenly, the mixture is filled into a 40kg experiment coke oven, and the bulk density is controlled to be 1.04kg/m 3 The coking time is 22h, and the coke is cooled by adopting a wet quenching method.
Comparative example 1
5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 3.95%) and 10L of citric acid aqueous solution (0.2 mol/L) are mixed into slurry, stirred and heated to 150 ℃ under the nitrogen atmosphere, and reacted for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating the liquid material and the residue at 150 ℃ by using a heat-preservation filter; the solvent was recovered using a flash tank and 4.26kg of desulfurized coal was obtained.
Comparative example 2
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 3.95%) with 0.05kg of nickel nitrate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating the liquid material and the residue at 150 ℃ by using a heat-preservation filter; the solvent was recovered using a flash tank and 4.23kg of desulfurized coal was obtained.
Comparative example 3
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 3.95%) with 0.1kg of titanium sulfate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.22kg of desulfurized coal was obtained.
Comparative example 4
Mixing 5kg of Huaihe ore high-sulfur fertilizer coal (sulfur content: 1.6%) and 10L of citric acid aqueous solution (0.2 mol/L) into slurry, stirring and heating to 150 ℃ under the atmosphere of nitrogen, and reacting for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg solid material with 25L of distillation and rectification wash oil (230-260 deg.C fraction) produced by coking, pressurizing under 2Mpa, stirring, heating to 350 deg.C, and reacting for 1 hr; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.3kg of desulfurized coal was obtained.
Comparative example 5
Mixing 5kg of Huai mine high-sulfur fertilizer coal (sulfur content: 1.6%) with 0.05kg of nickel nitrate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating the slurry to 150 ℃ under the atmosphere of nitrogen, and reacting for 2 hours; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating the liquid material and the residue at 150 ℃ by using a heat-preservation filter; the solvent was recovered using a flash tank and 4.28kg of desulfurized coal was obtained.
Comparative example 6
Mixing 5kg of Huai mine high-sulfur fertilizer coal (sulfur content: 1.6%) with 0.1kg of titanium sulfate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating to 150 ℃ in nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating the liquid material and the residue at 150 ℃ by using a heat-preservation filter; the solvent was recovered using a flash tank and 4.26kg of desulfurized coal was obtained.
Comparative example 7
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 2.2%) and 10L of citric acid aqueous solution (0.2 mol/L) into slurry, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg solid material with 25L of distillation and rectification wash oil (230-260 deg.C fraction) produced by coking, pressurizing under 2Mpa, stirring, heating to 350 deg.C, and reacting for 1 hr; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.2kg of desulfurized coal was obtained.
Comparative example 8
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 2.2%) with 0.05kg of nickel nitrate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.17kg of desulfurized coal was obtained.
Comparative example 9
Mixing 5kg of east Pang Gao sulfur fertilizer coal (sulfur content: 2.2%) with 0.1kg of titanium sulfate and 10L of citric acid aqueous solution (0.2 mol/L) to form slurry, stirring and heating to 150 ℃ under nitrogen atmosphere, and reacting for 2h; after the materials are cooled to room temperature, separating the solvent, cleaning the solid materials by using deionized water, and then putting the solid materials into a drying box to dry for 8 hours at 110 ℃; mixing 1kg of solid material with 25L of distillation and rectification washing oil (230-260 ℃ fraction section) produced by coking, pressurizing at 2Mpa under nitrogen atmosphere, stirring and heating to 350 ℃ for reaction for 1h; separating liquid material and residue at 150 deg.C with heat-insulating filter; the solvent was recovered using a flash tank and 4.15kg of desulfurized coal was obtained.
Test example
1. The desulfurized coals of examples 1 to 3 were subjected to sulfur content measurement and caking index G value measurement.
The sulfur content of the raw coal is detected according to the national standard GB/T214-2007, and the caking index is detected according to the national standard GB/T5447-2014. The results are shown in FIGS. 1-2.
As shown in figures 1-2, the high-sulfur fertilizer coal treated by the process has remarkable desulfurization effect and still has excellent caking property after desulfurization treatment.
2. CSR measurement is carried out on the cokes obtained in the application examples 1-3 and the application comparative examples 1-3, and the hot-state quality CSR of the coke is detected according to the national standard GB/T4000-2017. The results are shown in FIG. 3.
As shown in fig. 3, compared with Gao Liufei coal blending coking, the upgraded fat coal can further improve the thermal strength of the coke. Therefore, the method for processing the high-sulfur fertilizer coal greatly improves the application of the inferior coal and reduces the coking coal blending cost.
3. The desulfurized coals of comparative examples 1 to 9 described above were subjected to sulfur content measurement.
The sulfur content of the raw coal is detected according to the national standard GB/T214-2007, and the result is shown in figure 4. As can be seen from fig. 4, the best desulfurization effect is achieved by using titanium dioxide and nickel fluoborate as catalysts. Therefore, the organic sulfur removal yield can be improved by the method.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same. While the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: modifications may be made to the embodiments described above, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the invention as defined by the claims; but such modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (7)
1. A method for quality improvement and desulfurization of high-sulfur fertilizer coal is characterized by comprising the following steps:
(a) Mixing high-sulfur fat coal, an organic sulfur remover, titanium dioxide and nickel fluoborate to form first slurry;
the mixing proportion of the high-sulfur fat coal, the organic sulfur remover, the titanium dioxide and the nickel fluoborate is 1-2kg:2-3L:0.01-0.03kg:0.01-0.04kg;
the organic sulfur remover is selected from citric acid aqueous solution, and the concentration of the citric acid aqueous solution is 0.2-0.3mol/L;
(b) Heating the first slurry to react, separating to obtain a first liquid material and a first solid material, and carrying out heating reaction under an inert atmosphere at normal pressure and 150-190 ℃ for 2-2.5h;
(c) Mixing the first solid material and wash oil to form a second slurry;
(d) Heating and pressurizing the second slurry, and then separating to obtain a second liquid material and a second solid material;
(e) Carrying out flash evaporation on the second liquid material to obtain an organic solvent and a third solid material; and drying the third solid material to obtain the desulfurized coal.
2. The method according to claim 1, wherein in the step (c), the wash oil is a fraction of industrial coal tar at 230-260 ℃.
3. The method of claim 1, wherein in step (c), the ratio of the first solid material to the wash oil is 1-2kg:20-50L.
4. The method of claim 1, wherein the heating and pressurizing reaction in step (d) is carried out under an inert atmosphere at a pressure of 1 to 2Mpa, a reaction temperature of 350 to 380 ℃ and a reaction time of 1 to 2 hours.
5. The process of claim 1, wherein in step (e), the organic solvent obtained by flashing is recovered for reuse.
6. A coal blending coking process is characterized by comprising the following steps:
obtaining desulphurised coal using the method of any one of claims 1 to 5;
and (3) blending the desulfurized coal into blended coal for coking to obtain coke.
7. The process of claim 6, wherein the blending ratio of the desulfurized coal is 5 to 10wt%.
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| CN103194250A (en) * | 2013-04-28 | 2013-07-10 | 安徽工业大学 | High-sulfur fertilizer coal modification method and application thereof in coking coal blending |
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| GB2599374A (en) * | 2020-09-25 | 2022-04-06 | Abundia Biomass To Liquids Ltd | Converting biomass to LPG |
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| US4233034A (en) * | 1979-05-03 | 1980-11-11 | Union Oil Company Of California | Desulfurization of coal |
| WO1994029411A1 (en) * | 1992-12-31 | 1994-12-22 | Sunggyu Lee | Processes for desulfurizing coal |
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