CN110746996A - Pulverized coal quality-based comprehensive utilization method - Google Patents
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Abstract
The invention relates to the technical field of coal processing and utilization, and discloses a pulverized coal quality-based comprehensive utilization method, which is used for carrying out low-temperature pyrolysis reaction on dried pulverized coal to prepare upgraded coke powder and high-temperature oil gas; and cooling and separating the high-temperature oil gas to obtain crude gas, fine coke powder with the granularity less than 200 mu m, pyrolysis water and coal tar, and finally carrying out subsequent processing on the crude gas, the fine coke powder, the pyrolysis water and the coal tar to produce products with high added values, so that the graded utilization and clean and efficient conversion of the pulverized coal are realized. The method of the invention classifies and processes the unit products taking pulverized coal pyrolysis as the tap, so that the final products are more refined and the benefit is maximized, the by-products generated in the pyrolysis process are effectively recycled, the comprehensive utilization rate is high, and the environmental protection is also facilitated.
Description
Technical Field
The invention relates to the technical field of coal processing and utilization, in particular to a pulverized coal quality-based comprehensive utilization method.
Background
China is the largest coal producing country and consuming country in the world at present, coal resources occupy a very critical position in the energy policy of China, and the sustainable and rapid development of national economy is effectively supported. According to the prediction of relevant data, the energy consumption demand of China will continue to steadily increase until 2030 years ago, wherein the annual consumption of coal will still be kept at 35 hundred million tons, accounting for more than 50% of the total energy consumption, and the proportion of coal in an energy consumption structure will be more than 40% by 2050 years, so that coal will be the pillar industry of energy of China for a long time in the future. But at the present stage, the method mainly uses coal combustion and adopts a wild utilization mode, thereby greatly wasting precious coal resources, causing serious environmental pollution and bringing about the emission of a large amount of greenhouse gases. Therefore, the method promotes the clean and efficient utilization of coal, reduces the emission of pollutants and carbon dioxide caused by coal consumption, and is a necessary choice for solving the energy and environmental problems in China.
Coal pyrolysis, also known as dry distillation or thermal decomposition of coal, refers to a complex process in which coal is heated under the condition of air isolation, and a series of physical changes and chemical reactions occur at different temperatures, so that volatile substances such as tar and coal gas in the coal are evaporated, thereby increasing the calorific value of the coal and reducing the sulfur content. The coal is pyrolyzed to obtain tar, pyrolysis gas and semicoke, and the tar, the pyrolysis gas and the semicoke are subjected to subsequent processing to produce products with high added values, so that the coal is utilized in a grading manner and is converted cleanly and efficiently. The processing mode of coal pyrolysis realizes graded and graded utilization of coal with low cost, and becomes one of the most effective ways for realizing high-efficiency clean utilization of coal (especially low-rank coal). However, at present, the industrial application of the mature coal pyrolysis technology mainly aims at low-rank lump coal raw materials, and with the development of science and technology, the proportion of pulverized coal is increased, but the utilization rate of the raw materials is low, and the yield of tar is low; fine coke powder and fine coal powder generated in the pulverized coal pyrolysis process are very easy to be natural and are difficult to transport and store; meanwhile, the handling capacity of the device is generally 10 ten thousand tons per year, and the scale is small; and the environmental protection technology matched with the method is dispersed, and cannot be comprehensively treated.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the technology for efficiently and cleanly utilizing the pulverized coal is lacked in the prior art, so that a method for comprehensively utilizing the pulverized coal according to the quality is provided, and meanwhile, a device utilizing the method is also provided.
In order to solve the technical problem, the invention provides a pulverized coal quality-based comprehensive utilization method, which comprises the following steps:
(1) heating pulverized coal with the particle size of less than or equal to 30mm to 110-200 ℃, and removing dust to obtain fine pulverized coal with the particle size of less than 200 mu m, dried pulverized coal with the particle size of 0.2-30 mm and dried water;
(2) heating the dried pulverized coal obtained in the step (1) to 600-650 ℃ under the anaerobic or oxygen-limited condition for carrying out pyrolysis reaction to obtain upgraded coke powder and high-temperature oil gas;
(3) cooling and separating the high-temperature oil gas to obtain crude gas, fine coke powder with the granularity less than 200 mu m, pyrolysis water and coal tar;
(4) performing primary compression, temperature swing adsorption, secondary compression, primary purification, drying and secondary compression on the crude gas in the step (3)Purifying and carrying out cryogenic separation to obtain LPG, LNG and C2 products, hydrogen-rich gas and CO-rich gas; PSA pressure swing adsorption of the hydrogen-rich gas and/or CO shift of the CO-rich gas to produce H2；
Performing asphaltene extraction and delayed coking treatment on the coal tar obtained in the step (3) to obtain a needle coke product and a crude oil product; extracting crude phenol from the crude oil to obtain a phenol product and/or hydrogenating the crude oil to obtain a fuel oil product;
burning at least one of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) or a mixture of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) and raw coal to prepare superheated steam; and/or performing gasification reaction on at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) or a mixture of at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) and raw coal with steam and oxygen to prepare synthetic coal gas, and then desulfurizing the synthetic coal gas to obtain fuel gas; and/or preparing H from the synthetic coal gas by CO conversion and PSA adsorption2。
Further, the medium used for heating in the step (1) is flue gas with the temperature of 450-580 ℃.
Furthermore, the medium is flue gas with the temperature of 500-550 ℃.
Further, the temperature of the dried pulverized coal is 110-200 ℃.
Furthermore, the temperature of the dried pulverized coal is 120-150 ℃.
Further, the water content of the dried pulverized coal is less than 0.5 wt%.
Furthermore, the heating in the step (1) adopts an internal heating type rotary drying furnace with a dust removing function.
Further, an external heating type rotary reaction furnace is adopted in the pyrolysis reaction in the step (2).
Further, the step (2) also comprises the step of cooling the upgraded coke powder from 550-650 ℃ to 80-250 ℃, and then spraying water to humidify the dried water in the step (1) to obtain a passivated upgraded coke powder product with the water content of 8-10 wt% and the temperature of 80-100 ℃.
Furthermore, the temperature of the upgraded coke powder is 600-620 ℃.
Further, the cooling adopts a dividing wall type heat exchanger or a rotary cooler.
Further, the water content of the passivated and upgraded coke powder product is 10 wt%.
Further, the step (3) of dedusting the high-temperature oil gas is also included before cooling and separating.
Furthermore, the dust removal adopts at least one of a cyclone oil-gas separator, a filter type dust remover and a gravity settling chamber.
Further, the cooling separation in the step (3) is to send the high-temperature oil gas after dust removal into an oil gas cooling washing tower for spray washing, so that the temperature of the oil gas is reduced from 550-600 ℃ to 70-115 ℃; at least one part of the tower plate in the oil-gas cooling washing tower is arranged in a herringbone structure.
Further, the medium for spraying and washing is at least one of coal tar and pyrolysis water; the spraying density is 10-30 m3/m2H, the air velocity of the empty tower is 0.5-2 m/s.
Further, the temperature of the coal tar obtained through cooling and separation is 125-150 ℃.
And (3) further comprising the step of carrying out sewage treatment on the pyrolysis water obtained in the step (3) to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water is used for supplementing water to the industrial circulating cooling water.
Further, the primary purification in the step (4) comprises organic sulfur hydrolysis, demercuration and deacidification steps.
Further, the cryogenic separation adopts circulating coolant refrigeration and four-stage rectifying tower separation.
Further, before the delayed coking treatment in the step (4), the coal tar in the step (3) is separated, so that the content of mechanical impurities is less than 1 wt%; and returning the separated tar residue to the pyrolysis reaction equipment for pyrolysis to prepare coal tar and upgraded coke powder.
Further, the temperature of the gasification reaction in the step (4) is 1200-1600 ℃, and the step of grinding the raw coal to the particle size of less than 200 μm is also included before the gasification reaction.
Further, the gasification reaction in the step (4) is specifically to burn at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) or a mixture of at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) and raw coal to prepare superheated steam; and/or feeding at least one of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) or a mixture of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) and raw coal, steam and oxygen into a dry powder gasification furnace, and carrying out high-temperature gasification reaction at 1200-1600 ℃ to prepare synthetic coal gas, wherein CO and H in the synthetic coal gas2The total volume content is more than or equal to 90 percent.
Furthermore, the solid raw material after grinding has a particle size of less than 95 μm of more than 95 wt%.
Further, acidic water generated in at least one of the processes of coal tar hydrogenation, delayed coking, crude gas purification, synthesis gas desulfurization and gasification reaction is subjected to acidic water stripping to prepare acidic gas, liquid ammonia and purified water; and/or the step of preparing the sulfur by performing a Claus sulfur recovery process on the acid gas generated in at least one of the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
The technical scheme of the invention has the following advantages:
1. the pulverized coal quality-based comprehensive utilization method provided by the invention is used for carrying out low-temperature pyrolysis reaction on dried pulverized coal to prepare upgraded coke powder and high-temperature oil gas; and cooling and separating the high-temperature oil gas to obtain crude gas, fine coke powder with the granularity less than 200 mu m, pyrolysis water and coal tar, and finally carrying out subsequent processing on the crude gas, the fine coke powder, the pyrolysis water and the coal tar to produce products with high added values, so that the graded utilization and clean and efficient conversion of the pulverized coal are realized. The method of the invention classifies and processes the unit products taking pulverized coal pyrolysis as the tap, so that the final products are more refined and the benefit is maximized, the by-products generated in the pyrolysis process are effectively recycled, the comprehensive utilization rate is high, and the environmental protection is also facilitated.
2. According to the pulverized coal quality-based comprehensive utilization method provided by the invention, the crude gas is subjected to temperature swing adsorption after being compressed for one time, so that a large amount of impurities in the gas, including benzene, naphthalene, coal tar and ammonia, can be removed, and an oil washing tower and a deamination tower do not need to be additionally arranged, so that the process is favorably shortened, the working efficiency is improved, and the production cost is reduced.
3. According to the pulverized coal quality-based comprehensive utilization method provided by the invention, the pulverized coal is heated to 110-200 ℃ in a high-temperature flue gas direct heating mode or a combination mode of direct heating and indirect heating, and is dried, and dust is removed at the same time, so that the pulverized coal with the particle size of less than 200 mu m in the coal is removed, the content of the pulverized coal with the particle size of less than 200 mu m in the coal tar is reduced, and the yield of the coal tar product is improved.
4. The invention provides a pulverized coal quality-based comprehensive utilization method, which comprises the steps of carrying out gasification reaction on at least one of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) or a mixture of at least one of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) and raw coal with water vapor and oxygen to prepare coal gas, wherein CO and H in the obtained coal gas2The total volume content is more than or equal to 90 percent, and the content of effective gas is high; the raw materials do not need to be dried, so that the cost is saved, and the problem of recycling the coal powder and the coke powder is solved.
5. According to the pulverized coal quality-based comprehensive utilization method provided by the invention, the drying water generated in the pulverized coal drying process is used for spraying water to humidify the high-temperature upgraded coke powder, so that the temperature and the reaction activity of the upgraded coke powder are reduced, the discharging equipment can be protected, the water content of the upgraded coke powder is increased, and the requirements of long-term storage, long-distance transportation and use of the upgraded coke powder are met. Meanwhile, the drying water generated in the process of drying the pulverized coal is adopted, and the industrial reuse water utilization of water treatment is also realized.
6. According to the pulverized coal quality-based comprehensive utilization method provided by the invention, at least one part of the tower plate in the oil-gas cooling washing tower is arranged in a herringbone structure, and the structure not only effectively avoids the problem that oil sludge in high-temperature oil gas and coal tar blocks the tower plate due to dust entering the washing tower, but also is beneficial to improving the cooling and washing effects on the high-temperature oil gas.
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 is a schematic view of the structure of an oil-gas-cooled scrubber in example 1 of the present invention;
1-high temperature oil gas; 2-tower plate; 3-oil gas cooling washing tower.
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
Feeding raw material pulverized coal with the particle size of less than or equal to 30mm into an internal heating type rotary drying furnace with a dust removal function, introducing 550 ℃ high-temperature flue gas into the furnace, and heating until the pulverized coal reaches 150 ℃ to obtain fine pulverized coal with the particle size of less than 200 mu m, dried pulverized coal with the particle size of 0.2-30 mm and drying water, wherein the water content of the dried pulverized coal is 0.3 wt%; sending the dry pulverized coal into an external heating type rotary reaction furnace for carrying out pyrolysis reaction at 620 ℃ and in an oxygen-free environment to generate high-temperature oil gas at 600 ℃ and high-temperature upgraded coke powder at 600 ℃, removing dust from the high-temperature oil gas through a cyclone oil-gas separator, then feeding the high-temperature oil gas into an oil-gas cooling washing tower, and carrying out spray washing on the high-temperature oil gas by using coal tar and pyrolysis water, wherein the spray density is 30m3/(m2H), the gas velocity of the empty tower is 2m/s, and crude gas at the top of the tower, pyrolysis water and coal tar at the bottom of the tower are obtained. As shown in fig. 1, in this embodiment, the tray inside the oil-gas cooling washing tower is in the shape of a Chinese character 'ren', and of course, according to the needs of actual conditions, the tray can be in the shape of a Chinese character 'ren' combined with other structures, so that the problem that the tray is blocked by oil sludge formed by entering the washing tower due to dust in high-temperature oil gas and coal tar is effectively avoided, and the cooling washing effect on the high-temperature oil gas is improved.
Crude gas is separated by an oil-gas cooling tower, and the crude gas contains the following components in volume: 14% of hydrogen, 16% of carbon monoxide, 42% of methane, and C2-C515%, and has high effective component content and heat value of more than 7000Kcal/Nm3. The method comprises the steps of compressing and boosting the pressure of crude gas to 0.5MPa for the first time, then removing benzene, naphthalene, ammonia, HCN and coal tar in the gas by Temperature Swing Adsorption (TSA), boosting the pressure of the gas to 3.2MPa for the second time, sending the gas into a hydrolysis tower for organic sulfur hydrolysis, adsorbing mercury by sulfur-carrying activated carbon in a demercuration tower, desulfurizing by a wet method for deacidification, and regenerating a solvent to remove H in the solvent2S and CO2And (4) regenerating. The purified coal gas is sent to temperature swing adsorption for drying and dehydration, other impurities in the dried coal gas are adsorbed and removed by using a molecular sieve so as to meet the requirement of LNG cryogenic liquefaction separation, and finally LPG, LNG, C2 products, hydrogen-rich gas and CO-rich gas are obtained by using circulating coolant refrigeration and a four-stage rectifying tower for separation. PSA pressure swing adsorption is carried out on the hydrogen-rich gas to obtain high-purity H2CO conversion of the CO-rich gas to produce H2。
The coal tar obtained by cooling and separating high-temperature oil gas is 150 ℃ and the water content is less than 0.2 wt%, the coal tar is sent to a horizontal screw centrifuge for centrifugal separation, so that the mechanical impurity content is less than 1 wt%, and the separated coal tar is sent to a delayed coking device for asphaltene extraction and delayed coking treatment to obtain needle coke and crude oil products; sending part of the high-phenol-content crude oil product to a crude phenol extraction device to extract crude phenol, and refining the crude phenol in a fine phenol device to obtain phenol products such as phenol, o-cresol, m-cresol and p-cresol; and (4) sending the rest crude oil products to a coal tar hydrogenation device for carrying out hydrofining and hydrocracking reactions to obtain naphtha and diesel oil. The oil residue ratio of the centrifugally separated tar residue is 1:1, and the tar residue is conveyed to a rotary reactor through a residual oil conveying device for pyrolysis to obtain high-temperature oil gas and upgraded coke powder.
The temperature of high-temperature upgraded coke powder generated by pyrolysis in the pyrolysis reactor is 600 ℃, the high-temperature upgraded coke powder is cooled to be below 250 ℃ by dividing wall type heat exchange, and then dried water generated by drying pulverized coal is used for humidifying and passivating to obtain a passivated upgraded coke powder product with the temperature of 100 ℃ and the water content of 8 wt%. The dry gas obtained by evaporation of the drying furnace is dedusted, cooled and washed to obtain coal powder fine coal powder with the granularity less than 200 mu m and dry water, the dry water contains trace suspended coal powder and has low impurity content, and the dry gas is used for cooling, humidifying and recycling upgraded coke powder, thereby not only cooling the upgraded coke powder, being beneficial to storage and transportation without soot, but also reducing the treatment capacity of waste water and effectively recycling the waste water.
Mixing fine coal powder with particle size less than 200 μm generated in the process of drying pulverized coal and fine coke powder with particle size less than 200 μm generated by cooling and separating high-temperature oil gas, and sending the mixture to a pulverized coal dry powder gasification device to prepare synthetic coal gas, wherein the gasification temperature is 1600 ℃, and (CO + H) in the synthetic coal gas2) The content reaches more than 90 percent; the obtained synthetic coal gas is used for providing fuel gas for a pulverized coal pyrolysis hot air system and fuel gas for other heating furnaces in the system after being desulfurized. The synthetic coal gas comprises the following components:
| composition (I) | O2+Ar | N2 | CO | CO2 | CH4 | H2 |
| Content (wt.) | 0.05 | 0.67 | 62.71 | 8.59 | 0.1 | 27.88 |
And (3) sending pyrolysis water obtained by high-temperature oil-gas separation to a sewage treatment device, and treating to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water can be directly used for supplementing water to industrial circulating cooling water.
Carrying out acidic water stripping on acidic water generated in the processes of coal tar hydrogenation, delayed coking, crude gas purification, synthesis gas desulfurization and gasification reaction to prepare sulfur, liquid ammonia and purified water, wherein the purified water is reused for process water replenishing; the sulfur is prepared by performing a Claus sulfur recovery process on acid gas generated in the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
The fine coal powder produced in the process of drying pulverized coal and the fine coke powder produced by cooling and separating high-temperature oil gas have the granularity of below 200 mu m generally, wherein the grain diameter of 20-90 mu m accounts for more than 90%, the moisture is less than 2%, the fine coke powder is the most suitable raw material of a dry powder gasification furnace, the raw material of the grain diameter does not need to be ground, the use of a coal grinding and drying system is avoided, the synthetic coal gas is prepared by gasifying and producing 4.0MPa high-pressure coal, the effective gas component is more than 90%, the fine coke powder is the best raw material for preparing hydrogen, and the carbon monoxide conversion does not need pressurizing power equipment.
Example 2
Feeding raw material pulverized coal with granularity less than or equal to 30mm into an internal heat and external heat type rotary drying furnace with dust removal function, and introducing high-temperature smoke at 450 ℃ into the furnace and a jacketHeating the pulverized coal to 110 ℃ to obtain fine pulverized coal with the granularity less than 200 mu m, dried pulverized coal with the granularity of 0.2-30 mm and dried water, wherein the water content of the dried pulverized coal is 0.5 wt%; feeding the dried pulverized coal into an external heating type rotary reaction furnace to carry out pyrolysis reaction at 600 ℃ and in an oxygen-free environment to generate high-temperature oil gas at 550 ℃ and high-temperature upgraded coke powder at 600 ℃, dedusting the high-temperature oil gas by a filter type dust remover, then feeding the high-temperature oil gas into an oil gas cooling washing tower, and spraying and washing the high-temperature oil gas by using coal tar and pyrolysis water, wherein the spraying density is 20m3/(m2H), the gas velocity of the empty tower is 0.5m/s, and crude gas at the top of the tower, pyrolysis water and coal tar at the bottom of the tower are obtained.
The crude gas separated by the oil-gas cooling tower is compressed and pressurized to 0.5MPa for the first time, then Temperature Swing Adsorption (TSA) is carried out to remove benzene, naphthalene, ammonia, HCN and coal tar in the gas, the gas is pressurized to 3.2MPa for the second time and then is sent into a hydrolysis tower for organic sulfur hydrolysis, a demercuration tower carries out sulfur-carrying activated carbon to adsorb mercury, wet desulfurization is carried out to deacidify, and H in a solvent is regenerated by the solvent2S and CO2And (4) regenerating. The purified coal gas is sent to temperature swing adsorption for drying and dehydration, other impurities in the dried coal gas are adsorbed and removed by using a molecular sieve so as to meet the requirement of LNG cryogenic liquefaction separation, and finally LPG, LNG, C2 products, hydrogen-rich gas and CO-rich gas are obtained by using circulating coolant refrigeration and a four-stage rectifying tower for separation. PSA pressure swing adsorption is carried out on the hydrogen-rich gas to obtain high-purity H2CO conversion of the CO-rich gas to produce H2。
The coal tar obtained by cooling and separating high-temperature oil gas is 125 ℃ and has the water content of 0.35 wt%, the coal tar is sent to a disc separator for centrifugal separation, so that the content of mechanical impurities is less than 1 wt%, and then the coal tar after centrifugal separation is sent to a delayed coking device for asphaltene extraction and delayed coking treatment to obtain needle coke and crude oil products; sending part of the high-phenol-content crude oil product to a crude phenol extraction device to extract crude phenol, and refining the crude phenol in a fine phenol device to obtain phenol products such as phenol, o-cresol, m-cresol and p-cresol; and (4) sending the rest crude oil products to a coal tar hydrogenation device for carrying out hydrofining and hydrocracking reactions to obtain naphtha and diesel oil. And conveying the centrifugally separated tar residues to a rotary reactor through a residual oil conveying device for pyrolysis to obtain high-temperature oil gas and upgraded coke powder.
The temperature of high-temperature upgraded coke powder generated by pyrolysis in the pyrolysis reactor is 600 ℃, the high-temperature upgraded coke powder is cooled to be below 250 ℃ through rotary dividing wall type heat exchange, and then dried water generated by drying pulverized coal is used for humidifying and passivating to obtain a passivated upgraded coke powder product with the temperature of 85 ℃ and the water content of 9 wt%. The dry gas obtained by evaporation of the drying furnace is dedusted, cooled and washed to obtain fine coal powder and dry water, the dry water contains trace suspended coal powder and has low impurity content, and the fine coal powder and the dry water are used for cooling, humidifying and recycling upgraded coke powder, so that the effect of cooling the upgraded coke powder is achieved, the storage and transportation of the upgraded coke powder are facilitated, the treatment capacity of wastewater is reduced, and the wastewater is effectively recycled.
Mixing fine coal powder with particle size less than 200 μm generated in the process of drying pulverized coal and fine coke powder with particle size less than 200 μm generated by cooling and separating high-temperature oil gas, and sending the mixture to a pulverized coal dry powder gasification device to prepare synthetic coal gas, wherein the gasification temperature is 1600 ℃, and (CO + H) in the synthetic coal gas2) The content reaches more than 90 percent; the obtained synthetic coal gas provides H for coal tar hydrogenation through CO conversion and PSA pressure swing adsorption2. The synthetic coal gas comprises the following components:
| composition (I) | O2+Ar | N2 | CO | CO2 | CH4 | H2 |
| Content (wt.) | 0.04 | 0.68 | 62.69 | 8.54 | 0.21 | 27.84 |
And (3) sending pyrolysis water obtained by high-temperature oil-gas separation to a sewage treatment device, and treating to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water can be directly used for supplementing water to industrial circulating cooling water.
Carrying out acidic water stripping on acidic water generated in the processes of coal tar hydrogenation, delayed coking, crude gas purification, synthetic gas desulfurization and gasification reaction to prepare sulfur, liquid ammonia and purified water, wherein the purified water is reused for process water replenishing; the sulfur is prepared by performing a Claus sulfur recovery process on acid gas generated in the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
Example 3
Feeding raw material pulverized coal with the particle size of less than or equal to 30mm into an internal heating type rotary drying furnace with a dust removal function, introducing 580 ℃ high-temperature flue gas into the furnace, and heating until the pulverized coal reaches 200 ℃ to obtain fine pulverized coal with the particle size of less than 200 mu m, dried pulverized coal with the particle size of 0.2-30 mm and dried water, wherein the water content of the dried pulverized coal is 0.1 wt%; sending the dried pulverized coal into an external heating type rotary reaction furnace for carrying out pyrolysis reaction at 650 ℃ and in an oxygen-limited environment to generate high-temperature oil gas at 600 ℃ and high-temperature upgraded coke powder at 620 ℃, removing dust of the high-temperature oil gas through a gravity settling chamber and a dust filter, then feeding the high-temperature oil gas into an oil gas cooling washing tower, and carrying out spray washing on the high-temperature oil gas by using coal tar, wherein the spray density is 25m3/(m2H), the gas velocity of the empty tower is 1.2m/s, and crude gas at the top of the tower, pyrolysis water and coal tar at the bottom of the tower are obtained.
The crude gas separated by the oil gas cooling tower is compressed for the first time and is boosted to 0.5MPa, removing benzene, naphthalene, ammonia, HCN and coal tar in the coal gas by Temperature Swing Adsorption (TSA), increasing the pressure of the coal gas to 3.2MPa for the second time, feeding the coal gas into a hydrolysis tower for organic sulfur hydrolysis, adsorbing mercury by sulfur-carrying activated carbon in a demercuration tower, removing acid by wet desulfurization, and regenerating the solvent to remove H in the solvent2S and CO2And (4) regenerating. The purified coal gas is sent to temperature swing adsorption for drying and dehydration, other impurities in the dried coal gas are adsorbed and removed by using a molecular sieve so as to meet the requirement of LNG cryogenic liquefaction separation, and finally LPG, LNG, C2 products, hydrogen-rich gas and CO-rich gas are obtained by using circulating coolant refrigeration and a four-stage rectifying tower for separation. PSA pressure swing adsorption is carried out on the hydrogen-rich gas to obtain high-purity H2CO conversion of the CO-rich gas to produce H2。
The coal tar obtained by cooling and separating high-temperature oil gas is 130 ℃, the water content is less than 0.25 wt%, the coal tar is sent to a horizontal screw centrifuge for centrifugal separation, the mechanical impurity content is less than 1 wt%, and the coal tar separated by a disc separator is sent to a delayed coking device for asphaltene extraction and delayed coking treatment to obtain needle coke and crude oil products; sending part of the high-phenol-content crude oil product to a crude phenol extraction device to extract crude phenol, and refining the crude phenol in a fine phenol device to obtain phenol products such as phenol, o-cresol, m-cresol and p-cresol; and (4) sending the rest crude oil products to a coal tar hydrogenation device for carrying out hydrofining and hydrocracking reactions to obtain naphtha and diesel oil. And conveying the centrifugally separated tar residues to a rotary reactor through a residual oil conveying device for pyrolysis to obtain high-temperature oil gas and upgraded coke powder.
The temperature of high-temperature upgraded coke powder generated by pyrolysis in the pyrolysis reactor is 600 ℃, the high-temperature upgraded coke powder is cooled to be below 250 ℃ by dividing wall type heat exchange, and then dried water generated by drying pulverized coal is used for humidifying and passivating to obtain a passivated upgraded coke powder product with the temperature of 90 ℃ and the water content of 9.5 wt%. The dry gas obtained by evaporation of the drying furnace is dedusted, cooled and washed to obtain fine coal powder and dry water, the dry water contains trace suspended coal powder and has low impurity content, and the fine coal powder and the dry water are used for cooling, humidifying and recycling upgraded coke powder, so that the upgraded coke powder is cooled, the storage and transportation of soot-free coke powder are facilitated, the treatment capacity of waste water is reduced, and the waste water is effectively recycled.
The fine coal powder with the granularity less than 200 mu m generated in the process of drying the fine coal, the fine coke powder with the granularity less than 200 mu m generated by cooling and separating the high-temperature oil gas and the raw coal are mixed, and the mixture is ground and then sent to a coal powder boiler to generate 9.8MPa superheated steam which is used for a steam turbine driving steam source of high-power equipment, so that a large amount of power consumption can be saved, and the steam is recycled for system process production and production heat tracing.
And (3) sending pyrolysis water obtained by high-temperature oil-gas separation to a sewage treatment device, and treating to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water can be directly used for supplementing water to industrial circulating cooling water.
Carrying out acidic water stripping on acidic water generated in the processes of coal tar hydrogenation, delayed coking, crude gas purification, synthetic gas desulfurization and gasification reaction to prepare sulfur, liquid ammonia and purified water, wherein the purified water is reused for process water replenishing; the sulfur is prepared by performing a Claus sulfur recovery process on acid gas generated in the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
Example 4
Feeding raw material pulverized coal with the particle size of less than or equal to 30mm into an internal heating type rotary drying furnace with a dust removal function, introducing high-temperature flue gas at 500 ℃ into the furnace, and heating until the pulverized coal reaches 140 ℃ to obtain fine pulverized coal with the particle size of less than 200 mu m, dried pulverized coal with the particle size of 0.2-30 mm and dried water, wherein the water content of the dried pulverized coal is 0.25 wt%; sending the dried pulverized coal into an external heating type rotary reaction furnace for carrying out pyrolysis reaction at 610 ℃ and in an oxygen-limited environment to generate high-temperature oil gas at 550 ℃ and high-temperature upgraded coke powder at 550 ℃, dedusting the high-temperature oil gas by a cyclone oil-gas separator and a gravity settling chamber, then feeding the high-temperature oil gas into an oil-gas cooling washing tower, and spraying and washing the high-temperature oil gas by using coal tar and pyrolysis water, wherein the spraying density is 10m3And (m 2. h), wherein the gas velocity of the empty tower is 0.5m/s, and crude gas at the top of the tower, pyrolysis water and coal tar at the bottom of the tower are obtained.
The crude gas separated by the oil gas cooling tower is compressed and pressurized to 0.5MPa for the first time, then Temperature Swing Adsorption (TSA) is carried out to remove benzene, naphthalene, ammonia, HCN and coal tar in the gas, the gas is pressurized to 3.2MPa for the second time and then is sent into a hydrolysis tower for organic matterHydrolyzing sulfur, adsorbing mercury by sulfur-carrying activated carbon in a demercuration tower, deacidifying by wet desulfurization, and regenerating solvent to remove H in the solvent2S and CO2And (4) regenerating. The purified coal gas is sent to temperature swing adsorption for drying and dehydration, other impurities in the dried coal gas are adsorbed and removed by using a molecular sieve so as to meet the requirement of LNG cryogenic liquefaction separation, and finally LPG, LNG, C2 products, hydrogen-rich gas and CO-rich gas are obtained by using circulating coolant refrigeration and a four-stage rectifying tower for separation. PSA pressure swing adsorption is carried out on the hydrogen-rich gas to obtain high-purity H2CO conversion of the CO-rich gas to produce H2。
The coal tar obtained by cooling and separating high-temperature oil gas is 120 ℃ and the water content is less than 0.45 wt%, the coal tar is sent into a horizontal screw centrifugal separator and a disc separator for centrifugal separation, so that the mechanical impurity content is less than 1 wt%, and then the coal tar after centrifugal separation is sent into a delayed coking device for asphaltene extraction and delayed coking treatment to obtain needle coke and crude oil products; sending part of the high-phenol-content crude oil product to a crude phenol extraction device to extract crude phenol, and refining the crude phenol in a fine phenol device to obtain phenol products such as phenol, o-cresol, m-cresol and p-cresol; and (4) sending the rest crude oil products to a coal tar hydrogenation device for carrying out hydrofining and hydrocracking reactions to obtain naphtha and diesel oil. And conveying the centrifugally separated tar residues to a rotary reactor through a residual oil conveying device for pyrolysis to obtain high-temperature oil gas and upgraded coke powder.
The temperature of high-temperature upgraded coke powder generated by pyrolysis in the pyrolysis reactor is 550 ℃, the high-temperature upgraded coke powder is cooled to be below 250 ℃ by dividing wall type heat exchange, and then dried water generated by drying pulverized coal is used for humidifying and passivating to obtain a passivated upgraded coke powder product with the temperature of 80 ℃ and the water content of 10 wt%. The dry gas obtained by evaporation of the drying furnace is dedusted, cooled and washed to obtain fine coal powder and dry water, the dry water contains trace suspended coal powder and has low impurity content, and the fine coal powder and the dry water are used for cooling, humidifying and recycling upgraded coke powder, so that the upgraded coke powder is cooled, the storage and transportation of soot-free coke powder are facilitated, the treatment capacity of waste water is reduced, and the waste water is effectively recycled.
The fine coal powder with the granularity less than 200 mu m generated in the process of drying the fine coal, the fine coke powder with the granularity less than 200 mu m generated by cooling and separating the high-temperature oil gas and the raw coal are mixed, and the mixture is ground and then sent to a fine coal boiler to generate 9.8MPa superheated steam which is used for a steam turbine driving steam source of high-power equipment, so that a large amount of power consumption can be saved, and the steam is recycled for system process production and production heat tracing.
And (3) sending pyrolysis water obtained by high-temperature oil-gas separation to a sewage treatment device, and treating to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water can be directly used for supplementing water to industrial circulating cooling water.
Carrying out acidic water stripping on acidic water generated in the processes of coal tar hydrogenation, delayed coking, crude gas purification, synthetic gas desulfurization and gasification reaction to prepare sulfur, liquid ammonia and purified water, wherein the purified water is reused for process water replenishing; the sulfur is prepared by performing a Claus sulfur recovery process on acid gas generated in the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
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 therefrom are within the scope of the invention.
Claims (11)
1. A pulverized coal quality-based comprehensive utilization method is characterized by comprising the following steps:
(1) heating pulverized coal with the particle size of less than or equal to 30mm to 110-200 ℃, and removing dust to obtain fine pulverized coal with the particle size of less than 200 mu m, dried pulverized coal with the particle size of 0.2-30 mm and dried water;
(2) heating the dried pulverized coal obtained in the step (1) to 600-650 ℃ under the anaerobic or oxygen-limited condition for carrying out pyrolysis reaction to obtain upgraded coke powder and high-temperature oil gas;
(3) cooling and separating the high-temperature oil gas to obtain crude gas, fine coke powder with the granularity less than 200 mu m, pyrolysis water and coal tar;
(4) for the crude gas in the step (3)Performing primary compression, temperature swing adsorption, secondary compression, primary purification, drying, secondary purification and cryogenic separation to obtain LPG, LNG and C2 products, hydrogen-rich gas and CO-rich gas; PSA pressure swing adsorption of the hydrogen-rich gas and/or CO shift of the CO-rich gas to produce H2；
Performing asphaltene extraction and delayed coking treatment on the coal tar obtained in the step (3) to obtain a needle coke product and a crude oil product; extracting crude phenol from the crude oil to obtain a phenol product and/or hydrogenating the crude oil to obtain a fuel oil product;
burning at least one of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) or a mixture of the fine coal powder obtained in the step (1) and the fine coke powder obtained in the step (3) and raw coal to prepare superheated steam; and/or performing gasification reaction on at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) or a mixture of at least one of the fine coal powder in the step (1) and the fine coke powder in the step (3) and raw coal with steam and oxygen to prepare synthetic coal gas, and then desulfurizing the synthetic coal gas to obtain fuel gas; and/or preparing H from the synthetic coal gas by CO conversion and PSA adsorption2。
2. The method according to claim 1, wherein the medium used for heating in step (1) is flue gas at 450-580 ℃.
3. A method according to claim 1 or 2, characterized in that the water content of the dried pulverized coal is < 0.5 wt.%.
4. The method as claimed in any one of claims 1 to 3, wherein the step (2) further comprises the step of cooling the upgraded coke powder from 550-650 ℃ to 80-250 ℃, and then spraying water to humidify the dried water in the step (1) to obtain the passivated upgraded coke powder product with the water content of 8-10 wt% and the temperature of 80-100 ℃.
5. The method according to any one of claims 1-4, characterized in that step (3) further comprises the step of dedusting the high-temperature oil gas before the cooling separation.
6. The method according to claim 5, characterized in that the cooling separation in the step (3) is to send the high-temperature oil gas after dust removal into an oil gas cooling washing tower for spray washing, so that the temperature of the oil gas is reduced from 550-600 ℃ to 70-115 ℃; at least one part of the tower plate in the oil-gas cooling washing tower is arranged in a herringbone structure.
7. The method of claim 6, wherein the spray washed medium is at least one of coal tar and pyrolysis water; the spraying density is 10-30 m3/m2H, the air velocity of the empty tower is 0.5-2 m/s.
8. The method according to any one of claims 1 to 7, further comprising the step of performing sewage treatment on the pyrolysis water obtained in the step (3) to obtain crude phenol, coal tar, liquid ammonia and reuse water, wherein the reuse water is used for supplementing water to industrial circulating cooling water.
9. The process of any one of claims 1 to 8, wherein step (4) further comprises separating the coal tar of step (3) to a mechanical impurities content of < 1 wt% prior to the delayed coking process; and returning the separated tar residue to the pyrolysis reaction equipment for pyrolysis to prepare coal tar and upgraded coke powder.
10. The method according to any one of claims 1 to 9, wherein the temperature of the gasification reaction in step (4) is 1200 to 1600 ℃, and the method further comprises the step of grinding the raw coal to a particle size of less than 200 μm before the gasification reaction.
11. The method of any one of claims 1 to 10, further comprising performing acidic water stripping on acidic water generated in at least one of coal tar hydrogenation, delayed coking, raw gas purification, synthesis gas desulfurization and gasification reactions to prepare acidic gas, liquid ammonia and purified water; and/or the step of preparing the sulfur by performing a Claus sulfur recovery process on the acid gas generated in at least one of the processes of raw gas purification, synthetic gas desulfurization and acid water stripping.
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