阅读说明：本技术 利用溶胀反应协助超临界流体萃取传质作用对煤脱除有机硫试验方法 (Test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction ) 是由 金智新 彭垠 高飞 赵刚强 桂夏辉 张世明 宋璇 于 2019-11-21 设计创作，主要内容包括：本发明公开了一种利用溶胀反应协助超临界流体萃取传质作用对煤脱除有机硫试验方法,涉及煤炭燃前脱硫领域。本发明以溶胀反应协助超临界流体萃取传质为核心工艺,首先进行煤的溶胀预处理,煤与极性较强的溶剂混合,在外力作用下离心搅拌,可使大分子与小分子间的作用力减弱,煤中的共价键断裂,将预处理后的煤样放入萃取釜中,进行超临界流体的萃取传质反应,其分离过程主要是利用超临界流体的溶解能力与密度的关系,即利用压力和温度对超临界流体溶解能力的影响进行的。本发明煤样经预处理后再进行萃取实验,可大幅度提高萃取过程的转化率和轻油组分的回收率；而且工艺简单,成本较低,能够实现对煤中复杂有机硫组分大幅度脱除,平均脱硫率为20%。(The invention discloses a test method for removing organic sulfur from coal by using a swelling reaction to assist supercritical fluid extraction mass transfer effect, and relates to the field of desulfurization before combustion of coal. The invention takes swelling reaction to assist mass transfer of supercritical fluid extraction as a core process, firstly, swelling pretreatment is carried out on coal, the coal is mixed with a solvent with stronger polarity, centrifugal stirring is carried out under the action of external force, the acting force between macromolecules and micromolecules can be weakened, covalent bonds in the coal are broken, the pretreated coal sample is put into an extraction kettle to carry out mass transfer reaction of the supercritical fluid, and the separation process is mainly carried out by utilizing the relation between the dissolving capacity and the density of the supercritical fluid, namely, the influence of pressure and temperature on the dissolving capacity of the supercritical fluid. According to the invention, the coal sample is pretreated and then subjected to an extraction experiment, so that the conversion rate in the extraction process and the recovery rate of light oil components can be greatly improved; and the process is simple, the cost is low, the complex organic sulfur components in the coal can be greatly removed, and the average desulfurization rate is 20%.)

1. A test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction is characterized in that: the method comprises the following steps:

(1) coal sample pretreatment: crushing a coal sample to a certain particle size, selecting the coal sample with the particle size of 1-3mm or 3-6 mm, placing the dried coal sample in a centrifugal tube, centrifuging the centrifugal tube at 3500-4500 rpm for 20-30 min at room temperature, adding the coal sample into a polar organic solvent according to a solid-liquid ratio of 1:50, adding the solvent while stirring to fully contact the coal and the organic solvent, standing vertically for 1h, and centrifuging at 3500-4500 rpm again and continuously stirring for 20-30 min;

(2) filling a sample into a tank: filling the filtered coal sample obtained in the step (1) into a material bag; two wrenches are matched to loosen screws at the upper opening of the extraction kettle, material bags are put in the extraction kettle, a gasket is arranged on the inner wall of the kettle body close to the screw buckles, an annular sealing ring on the kettle cover is sleeved tightly, and the kettle cover is screwed tightly to be tightly combined with the kettle body without leakage;

(3) removing air and impurities in the kettle body: opening the inlet valve and the outlet valve of the extraction kettle to be connected with a supercritical fluid storage container, circulating the whole closed-loop system by using the supercritical fluid, carrying an ethanol cleaning pipeline by an auxiliary pump, and closing the outlet valve of the extraction kettle;

(4) checking the tightness of the pipeline, observing whether leakage exists, and if leakage exists, reinforcing by using a tool after pressure relief; simultaneously starting a temperature adjusting system;

(5) desulfurization experiment:

① regulating temperature and pressure, wherein in supercritical fluid extraction, the temperature and pressure parameters in the extraction kettle are regulated to reach the critical point of the supercritical fluid, and a static or dynamic extraction mode is selected according to specific requirements, and the reaction time of extraction and the addition amount of entrainer are controlled;

② separating the fluid from the solute by removing organic sulfur from the coal by permeation and dissolution of supercritical fluid and by pressure reduction to separate the fluid from the organic solute;

③ energy-saving pressure-reducing heat exchange, wherein in the separation stage in the separation kettle, the supercritical fluid is completely changed into gas by energy-saving pressure reduction and temperature regulation in the heat exchanger, and the removed organic sulfur is separated into liquid phase and precipitated at the bottom of the separator, and the gas is discharged through a pipeline or recycled through a cooling system;

(6) collecting samples: after the extraction process is finished, opening a dynamic and static valve and a back pressure valve, collecting a product, and when dynamic extraction is adopted, discharging gas in the extraction kettle at a certain discharge rate; when the static extraction is adopted, a gas steel cylinder valve is closed, a gas high-pressure pump is closed, a high-pressure pump refrigerating machine is closed, gas in the kettle is slowly emptied, an extraction kettle heater is closed, and a dynamic and static method valve and a back pressure valve are closed; after no pressure exists in the extraction kettle, opening the extraction cover, taking out the charging basket and taking out the coal sample; collecting extract liquor at a separation kettle while taking materials, and subsequently performing liquid chromatography mass spectrometry analysis;

(7) and (3) product post-treatment: and (3) washing the extracted product with deionized water for three to five times, carrying out suction filtration for three to five times with hot water to realize solid-liquid separation, and drying and then testing the sample.

2. The test method for removing organic sulfur from coal by mass transfer by supercritical fluid extraction assisted by swelling reaction as claimed in claim 1, wherein: in the step (1), the polar organic solvent is acetone, pentanone, tetrahydrofuran or pyridine.

3. The test method for removing organic sulfur from coal by mass transfer by supercritical fluid extraction assisted by swelling reaction as claimed in claim 1, wherein: the temperature adjusting system in the step (4) comprises a circulating water tank, an electric heating pipe, a circulating pump and a cooling water source.

4. The test method for removing organic sulfur from coal by mass transfer by supercritical fluid extraction assisted by swelling reaction as claimed in claim 1, wherein: and (4) checking the sealing performance, dipping soap water by a brush and uniformly coating the soap water on each connector of the pipeline, and observing the sealing performance of the pipeline.

5. The test method for removing organic sulfur from coal by mass transfer by supercritical fluid extraction assisted by swelling reaction as claimed in claim 1, wherein: supercritical fluid adopts CO₂。

6. The test method for removing organic sulfur from coal by mass transfer by supercritical fluid extraction assisted by swelling reaction as claimed in claim 5, wherein: in the step (5), the temperature and pressure range is adjusted, the gas is heated and pressurized to be above the critical point, the temperature is within 35-40 ℃, and the pressure is within 7-10 Mpa.

Technical Field

The invention relates to the field of desulfurization before combustion of coal, in particular to a test method for removing organic sulfur from coal by using a swelling reaction to assist supercritical fluid extraction mass transfer effect, which is suitable for greatly removing organic sulfur from coal.

Background

China has abundant coal resources and is the biggest world coal producing and consuming country, but sulfur-containing substances in coal release high-concentration SO to the atmosphere in the combustion process₂Harmful gases have adverse effects on human health and growth of animals and plants, and emissions after combustion cause a series of environmental problems such as air pollution, acid rain, climate change and the like, so how to desulfurize coal before combustion needs to be solved urgently.

The inorganic sulfur in the coal can be effectively removed by a physical method, and the process of gravity separation and deashing is accompanied with the removal of the inorganic sulfur. But the organic sulfur component is complex, and the sulfur has thioether and thiol aliphatic structure sulfur, thiophene, sulfone and sulfoxide conjugated structure sulfur, the existing desulfurization method such as physical washing technology is widely and economically applied, but only inorganic sulfur can be removed; biological and chemical methods can remove inorganic sulfur, but can only remove partial aliphatic organic sulfur, the removal effect on sulfur with macromolecular conjugated structure is not obvious, the production cost is high, and the method has a large difference from industrial application; the gasification and liquefaction of coal are further researched and perfected, and the technology is not enough to be formed. However, as the coal density increases, the content of organic sulfur such as thioether and mercaptan fatty structures decreases, and the content of organic sulfur such as thiophene and (sulfoxide) increases, so that the difficulty in removing organic sulfur further increases. The prior method adopted in the field of pre-combustion desulfurization has the following problems: (1) the organic sulfur in the coal cannot be removed greatly; (2) the process is complex, the cost is high, and large-scale industrialization cannot be realized; (3) some methods adopt the desulfurization auxiliary agent to change the coal quality characteristics of the coal in the coal treatment process, or remove the used medicament again after removing the sulfur component, and the process is complex. Therefore, how to effectively remove the organic sulfur with complex components in the coal is an important problem to be solved urgently.

Disclosure of Invention

The invention provides a test method for removing organic sulfur from coal by using a swelling reaction to assist mass transfer effect of supercritical fluid extraction in order to solve the problem of removing organic sulfur from complex components in coal.

The invention is realized by the following technical scheme: a test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction comprises the following steps:

(1) coal sample pretreatment: crushing a coal sample to a certain particle size, selecting the coal sample with the particle size of 1-3mm or 3-6 mm, placing the dried coal sample in a centrifugal tube, centrifuging the centrifugal tube at 3500-4500 rpm for 20-30 min at room temperature, adding the coal sample into a polar organic solvent according to a solid-liquid ratio of 1:50, adding the solvent while stirring to fully contact the coal and the organic solvent, standing vertically for 1h, and centrifuging at 3500-4500 rpm again and continuously stirring for 20-30 min. In the step, the conversion rate of the extraction process can be obviously improved after the coal is swelled, the swelling degree of the coal is larger in a polar solvent on the whole, and the polar solvent is smaller in a non-polar solvent, so that the hydrogen bonds among macromolecules of the coal are easily destroyed by the polar solvent, and the swelling effect is enhanced; and selecting a coal sample with the granularity of 1-3mm or 3-6 mm, namely crushing the extract into fine particles, and enabling the extract to be in maximum contact with fluid under the same extraction conditions.

(2) Filling a sample into a tank: filling the coal sample obtained in the step (1) into a material bag; because the granularity of coal is fine, need pack into the material bag, put into reation kettle after the bundling, prevent by the fluid blowin pipeline, produce the jam phenomenon. Two wrenches are used for matching, screws at the upper opening of the extraction kettle are loosened, material bags are put in, a gasket is arranged on the inner wall of the kettle body close to the screw buckles, an annular sealing ring on the kettle cover is sleeved tightly, the kettle cover is screwed tightly, and the kettle body is tightly combined with the kettle body without leakage.

(3) Removing air and impurities in the kettle body: opening the inlet valve and the outlet valve of the extraction kettle to be connected with a supercritical fluid storage container, circulating the whole closed-loop system by using the supercritical fluid, carrying an ethanol cleaning pipeline by an auxiliary pump, and closing the outlet valve of the extraction kettle;

(4) checking the tightness of the pipeline, observing whether leakage exists, and if leakage exists, reinforcing by using a tool after pressure relief; simultaneously starting a temperature adjusting system;

(5) desulfurization experiment:

① temperature and pressure regulation, wherein in supercritical fluid extraction, the critical point of supercritical fluid is reached by regulating the temperature and pressure parameters in the extraction kettle, and a static or dynamic extraction mode is selected according to specific requirements, and simultaneously the reaction time of extraction and the addition amount of entrainer are controlled, static extraction is carried out under the conditions of constant temperature and constant pressure, dynamic extraction is carried out under the environment of variable temperature and variable pressure, the entrainer is polar and nonpolar, if the supercritical fluid is nonpolar, nonpolar organic sulfur can be carried out in the desulfurization process, so the entrainer can carry polar organic sulfur, if the supercritical fluid is polar, polar organic sulfur can be carried out in the desulfurization process, so the entrainer can carry nonpolar organic sulfur, and the specific reaction time and the addition amount of the entrainer are quantified according to actual conditions.

② separating the fluid from the solute by removing organic sulfur from the coal by permeation and dissolution of supercritical fluid and by pressure reduction to separate the fluid from the organic solute;

③ energy-saving pressure-reducing heat exchange, wherein in the separation stage in the separation kettle, the supercritical fluid is completely changed into gas by energy-saving pressure reduction and temperature regulation in the heat exchanger, and the removed organic sulfur is separated into liquid phase and precipitated at the bottom of the separator, and the gas is discharged through a pipeline or recycled through a cooling system;

(6) collecting samples: after the extraction process is finished, opening a dynamic and static valve and a back pressure valve, collecting a product, and when dynamic extraction is adopted, discharging gas in the extraction kettle at a certain discharge rate; when the static extraction is adopted, a gas steel cylinder valve is closed, a gas high-pressure pump is closed, a high-pressure pump refrigerating machine is closed, gas in the kettle is slowly emptied, an extraction kettle heater is closed, and a dynamic and static method valve and a back pressure valve are closed; after no pressure exists in the extraction kettle, opening the extraction cover, taking out the charging basket and taking out the coal sample; collecting extract liquor at a separation kettle while taking materials, and subsequently performing liquid chromatography mass spectrometry analysis;

(7) and (3) product post-treatment: and (3) washing the extracted coal sample with deionized water for three to five times, performing suction filtration for three to five times with hot water to realize solid-liquid separation, and drying and then testing the sample.

The invention takes swelling reaction to assist mass transfer of supercritical fluid extraction as a core process, firstly, swelling pretreatment is carried out on coal, the coal is mixed with a solvent with stronger polarity, centrifugal stirring is carried out under the action of external force, the action can weaken the acting force between macromolecules and micromolecules, covalent bonds in the coal are broken, the fluidity is enhanced, the volume of the coal can be expanded, the coal is looser after the structure treatment, and the conversion rate and the recovery rate of light oil components in the extraction process can be greatly improved by carrying out extraction experiments after the pretreatment. The pretreated coal sample is put into an extraction kettle to carry out the extraction mass transfer reaction of the supercritical fluid, and the separation process is mainly carried out by utilizing the relation between the dissolving capacity and the density of the supercritical fluid, namely, the influence of pressure and temperature on the dissolving capacity of the supercritical fluid. When gas is in supercritical state, it has density close to that of liquid, viscosity higher than that of gas but obviously lower than that of liquid, its diffusion coefficient is 10-100 times that of liquid, and at the same time it has relatively high mass transfer and heat transfer coefficient, and gives consideration to the characteristics of liquid phase and gas phase, so that it has special selective dissolving capacity for organic matter. Along with the change of the temperature and the pressure of the fluid, the solubility and the mass transfer flux of the fluid to various organic matters are greatly influenced, so that the sulfur-containing organic matters can be selectively extracted according to the difference of the solubilities. Therefore, the supercritical fluid has stronger dissolving capacity and permeability to materials, can permeate into closed or semi-closed gaps in the coal, extracts and separates organic sulfur components in the coal, and realizes the removal of the organic sulfur in the coal. Along with the change of the temperature and the pressure of the fluid, the solubility and the mass transfer flux of the fluid to various organic matters are greatly influenced, so that the sulfur-containing organic matters can be selectively extracted according to the difference of the solubilities, and the combustion property of the solid is not damaged.

Compared with the prior art, the invention has the following beneficial effects: the test method (1) for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction can greatly remove complex organic sulfur components in coal, and has an average desulfurization rate of 20%; (2) the process is simple, the control of temperature and pressure is easy to realize, the cost is low, the supercritical fluid can be recycled, and the large-scale industrialization can be realized; (3) the fluid in the method has no pollution and residue on the product, and does not need subsequent treatment; (4) the method can remove the organic sulfur component in the coal without destroying the solid combustion property, and can produce the liquid chemical product as a byproduct, (5) the invention utilizes the swelling reaction pretreatment combined with the special performance of the supercritical fluid to extract and extract the organic sulfur in the coal, and can completely extract components such as mercaptan, thioether and the like under the critical condition.

Drawings

FIG. 1 is a process flow diagram of the present invention.

FIG. 2 is a block diagram of the apparatus of the present invention.

Detailed Description

The present invention is further illustrated by the following specific examples.

A test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction is shown in figures 1 and 2 and comprises the following steps:

(1) coal sample pretreatment: crushing a coal sample to a certain particle size, selecting the coal sample with the particle size of 1-3mm or 3-6 mm, placing the dried coal sample in a centrifugal tube, centrifuging the centrifugal tube at 3500-4500 rpm for 20-30 min at room temperature, adding the coal sample into a polar organic solvent according to a solid-liquid ratio of 1:50, adding the solvent while stirring to fully contact the coal and the organic solvent, standing vertically for 1h, and centrifuging at 3500-4500 rpm again and continuously stirring for 20-30 min;

(2) filling a sample into a tank: filling the filtered coal sample obtained in the step (1) into a material bag; two wrenches are matched to loosen screws at the upper opening of the extraction kettle, material bags are put in the extraction kettle, a gasket is arranged on the inner wall of the kettle body close to the screw buckles, an annular sealing ring on the kettle cover is sleeved tightly, and the kettle cover is screwed tightly to be tightly combined with the kettle body without leakage;

(3) removing air and impurities in the kettle body: opening the inlet valve and the outlet valve of the extraction kettle to be connected with a supercritical fluid storage container, circulating the whole closed-loop system by using the supercritical fluid, carrying an ethanol cleaning pipeline by an auxiliary pump, and closing the outlet valve of the extraction kettle;

(4) checking the tightness of the pipeline, observing whether leakage exists, and if leakage exists, reinforcing by using a tool after pressure relief; simultaneously starting a temperature adjusting system;

(5) desulfurization experiment:

① regulating temperature and pressure, wherein in supercritical fluid extraction, the temperature and pressure parameters in the extraction kettle are regulated to reach the critical point of the supercritical fluid, and a static or dynamic extraction mode is selected according to specific requirements, and the reaction time of extraction and the addition amount of entrainer are controlled;

② separating the fluid from the solute by removing organic sulfur from the coal by permeation and dissolution of supercritical fluid and by pressure reduction to separate the fluid from the organic solute;

③ energy-saving pressure-reducing heat exchange, wherein in the separation stage in the separation kettle, the supercritical fluid is completely changed into gas by energy-saving pressure reduction and temperature regulation in the heat exchanger, and the removed organic sulfur is separated into liquid phase and precipitated at the bottom of the separator, and the gas is discharged through a pipeline or recycled through a cooling system;

(6) collecting samples: after the extraction process is finished, opening a dynamic and static valve and a back pressure valve, collecting a product, and when dynamic extraction is adopted, discharging gas in the extraction kettle at a certain discharge rate; when the static extraction is adopted, a gas steel cylinder valve is closed, a gas high-pressure pump is closed, a high-pressure pump refrigerating machine is closed, gas in the kettle is slowly emptied, an extraction kettle heater is closed, and a dynamic and static method valve and a back pressure valve are closed; opening the extraction cover after no pressure exists in the extraction kettle, taking out the charging basket, and taking out the coal sample; collecting extract liquor at a separation kettle while taking materials, and subsequently performing liquid chromatography mass spectrometry analysis;

(7) and (3) product post-treatment: and (3) washing the extracted product with deionized water for three to five times, carrying out suction filtration for three to five times with hot water to realize solid-liquid separation, and drying and then testing the sample.

In this embodiment, in the step (1), acetone, pentanone, tetrahydrofuran, or pyridine is used as the polar organic solvent; the temperature adjusting system in the step (4) comprises a circulating water tank, an electric heating pipe, a circulating pump and a cooling water source; checking the tightness in the step (4), dipping soapy water by a brush and uniformly coating the soapy water on each connector of the pipeline, and observing the tightness of the pipeline; in this embodiment, CO is used as the supercritical fluid₂(ii) a In the step (5), the temperature and pressure range is adjusted, the gas is heated and pressurized to be above the critical point, the temperature is within 35-40 ℃, and the pressure is within 7-10 Mpa.

In this example, CO is used as the supercritical fluid₂The extraction adopts static extraction, and the specific steps are as follows:

(1) coal sample pretreatment: crushing raw coal to 1-3mm, dispersing a coal sample into a centrifugal tube of a high-speed centrifuge, starting the centrifuge, setting the centrifugation time to be 20-30 min, setting the centrifugation speed to be 3500-4500 rpm, then adding a strong-polarity organic solvent, measuring various parameters of interaction between the coal and the organic solvent according to a reverse gas chromatography technology, preferentially selecting the organic solvent which is remarkably swelled with the coal, such as acetone, pentanone, tetrahydrofuran, pyridine and the like, stirring while adding the solvent to fully contact the coal and the organic solvent, vertically standing for 24h, starting the centrifuge to perform centrifugal rotation with the same set parameters, and finishing pretreatment.

(2) Filling a sample into a tank: filling the coal sample obtained in the step (1) into a material bag; putting the weighed sample into a charging barrel, and putting the sample into the charging barrel, wherein the raw material is not too full (according to the product process), and is generally 2-3 cm away from an upper filter screen; putting a white plastic O-shaped sealing ring; placing a sintered steel perforated plate; putting and screwing a stainless steel pressing ring with threads; the charging barrel is placed into a charging barrel cavity of a 1L extraction kettle in the host machine by a special handle.

(3) Removing air and impurities in the kettle body: examination of CO₂The outlet pressure of the steel cylinder is ensured to be 5-6 MPa; connecting the gas in the steel cylinder to the gas inlet of the extraction kettle, unscrewing the gas valve on the steel cylinder, ventilating, and observing a gas pressure gauge beside. With CO₂Purging the whole pipeline system for a plurality of minutes after the gas flows out, and closing an outlet valve of the extraction kettle after purging is finished;

(4) checking the pipeline tightness and starting a temperature regulating system: dipping soap water with a brush and uniformly coating the soap water on each connector of the pipeline, observing the sealing property of the pipeline, and if leakage occurs, reinforcing the pipeline with a tool after pressure relief; the water in each circulating water tank in the device is heated by the electric heating tube and is conveyed by the circulating pump to be used for heating and keeping constant temperature of the extraction kettle and the separation kettle. And checking whether the cooling water source is smooth (relative to the water cooling unit), and the cooling box is filled with a 30% glycol aqueous solution.

(5) Desulfurization experiment:

① temperature and pressure regulation, wherein in the supercritical fluid extraction, the temperature and pressure parameters in the extraction kettle are regulated to reach the critical point of the supercritical fluid, a static or dynamic extraction mode is selected according to specific requirements, and the reaction time of extraction and the addition of entrainer are controlled simultaneously;

② separating the fluid from the solute by removing organic sulfur from the coal by permeation and dissolution of supercritical fluid and by pressure reduction to separate the fluid from the organic solute;

③ energy-saving pressure-reducing heat exchange, wherein in the separation stage in the separation kettle, the supercritical fluid is completely changed into gas by energy-saving pressure reduction and temperature regulation in the heat exchanger, and the removed organic sulfur is separated into liquid phase and precipitated at the bottom of the separator, and the gas is discharged through a pipeline or recycled through a cooling system;

(6) collecting samples: after the experiment is finished, the STOP button in the digital operator is pressed, the running of the refrigerator pump is stopped, the plunger pump (high-pressure pump) is stopped, the heating switches of the circulating heating water tanks are closed, and the heating and the circulation of the circulating water tanks are stopped. Slowly discharging the gas in the reaction kettle; meanwhile, the gas circuit connection is removed, and cooling is carried out; after no pressure exists in the extraction kettle, taking out the reaction kettle, taking out the sealing element, taking out the coal sample for post-treatment, collecting the extract liquor at the separation kettle while sampling, and subsequently performing liquid chromatography mass spectrometry analysis;

(7) and (3) product post-treatment: in the coal sample post-treatment process, firstly, washing the coal sample with deionized water to remove extracted organic matters possibly existing on the surfaces of coal particles, repeatedly washing for three to five times, and then, carrying out suction filtration on the washed coal sample with hot deionized water through a suction filtration machine to realize solid-liquid separation. And drying the treated sample to prepare a sample, and performing subsequent detection.

According to the comparison of the reacted data and the original data, the sulfur in the coal is obviously reduced, and according to the detection result of the morphological sulfur, the organic sulfur is also greatly reduced, and the desulfurization effect is obvious. From the industrial analysis results, the caking property, the calorific value and the like are basically unchanged, which shows that the method does not influence the original coal quality while effectively separating the organic sulfur. From the results of element analysis, the sulfur content is reduced, and the contents of other elements are not changed, which shows that the whole process link does not bring new impurity component influence on the coal. The composition of the extract is analyzed, and the components of the organic liquid are mostly mercaptan and thioether substances and part of complex thiophene organic sulfur components, so that different operating conditions can be set for different types of organic sulfur, and different components can be extracted step by step.

The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.