CN111039479A - Treatment method of Fischer-Tropsch synthesis recycle gas decarburization wastewater - Google Patents
Treatment method of Fischer-Tropsch synthesis recycle gas decarburization wastewater Download PDFInfo
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- CN111039479A CN111039479A CN201811189762.5A CN201811189762A CN111039479A CN 111039479 A CN111039479 A CN 111039479A CN 201811189762 A CN201811189762 A CN 201811189762A CN 111039479 A CN111039479 A CN 111039479A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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Abstract
The invention relates to a treatment method of Fischer-Tropsch synthesis recycle gas decarburization wastewater, which comprises the following steps of carrying out flash evaporation and gas stripping on the wastewater: 1) and (3) sending the decarbonized wastewater into a flash tank for reduced pressure flash evaporation, discharging the gas after flash evaporation from the upper part of the flash tower, and discharging the wastewater after flash evaporation from the bottom of the tower. 2) Feeding the flash-evaporated wastewater into a stripping tower through the upper part of the stripping tower, feeding hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide into the stripping tower through the lower part of the stripping tower, stripping the wastewater by stripping gas in the stripping tower, discharging stripped water from the bottom of the tower, discharging the stripped gas from the top of the tower, and returning the gas and the flash-evaporated gas obtained in the step 1) to the reactor. The method of the invention reduces the emission of the decarbonization waste water and simultaneously realizes the comprehensive utilization of waste water resources.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of petrochemical industry, and particularly relates to a treatment method of Fischer-Tropsch synthesis recycle gas decarburization wastewater.
Background
The Fischer-Tropsch synthesis process is to indirectly synthesize liquid fuel by using coal or natural gas as a raw material, wherein water is simultaneously generated in the reaction process while hydrocarbon products are generated on a reduction catalyst by H2 and CO in the Fischer-Tropsch reaction, and the water and the CO are subjected to water gas shift reaction to generate a large amount of CO 2. Thus, after separation of the products from the gas exiting the synthesis reactor, the remaining tail gas must be freed of CO2 before it can be recycled. Since the hot potash process is used for CO2 removal with minimal hydrocarbon losses, it is common to decarbonise fischer-tropsch synthesis recycle gas, but because of the complex gas composition, the gas is first washed with water to remove impurities in the absorber, and thus some waste water is produced in the process. At present, the conventional methods for treating such wastewater are: steam stripping, steam stripping and multi-effect evaporation concentration. For the steam stripping method, although most organic matters in the organic wastewater can be stripped, the stripped wastewater still needs to be sent to sewage for treatment, and the stripped substances also need to be designed separately, so that the treatment difficulty of the whole process requirement is high, the investment is high, and the operation cost is high; the steam stripping method with multiple-effect evaporation and concentration steps has the defects of high energy consumption and the need of sewage treatment on the evaporated wastewater. On the other hand, the current wastewater treatment process only focuses on wastewater discharge control, and the wastewater resources and organic matter components in wastewater are not effectively utilized, so that secondary discharge pollution is still inevitable. With the continuous development of economy and increasingly strict requirements on environmental protection in China, the treatment of three wastes becomes a major subject of the development of coal chemical industry. When organic wastewater is treated, how to realize reasonable utilization of wastewater resources, develop circular economy and recycle and reuse waste are also important subjects.
Disclosure of Invention
The invention aims to provide a method for treating Fischer-Tropsch synthesis recycle gas decarburization wastewater, which reduces the emission of the decarburization wastewater and realizes the comprehensive utilization of wastewater resources.
The invention provides a method for treating waste water from decarbonization of Fischer-Tropsch cycle gas, which comprises the following steps of carrying out flash evaporation and gas stripping on the waste water: and (3) sending the decarbonized wastewater into a flash tank for reduced pressure flash evaporation, discharging the gas after flash evaporation from the upper part of the flash tower, and discharging the wastewater after flash evaporation from the bottom of the tower. 2) Feeding the flash-evaporated wastewater into a stripping tower through the upper part of the stripping tower, feeding hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide into the stripping tower through the lower part of the stripping tower, stripping the wastewater by stripping gas in the stripping tower, discharging stripped water from the bottom of the tower, discharging the stripped gas from the top of the tower, and returning the gas and the flash-evaporated gas obtained in the step 1) to the reactor.
The invention provides a method for treating Fischer-Tropsch synthesis wastewater, which is based on the problems that a large amount of steam is consumed and effective resources in the wastewater cannot be fully utilized by adopting methods such as steam stripping, steam stripping and multi-effect evaporation concentration and the like in the conventional Fischer-Tropsch synthesis wastewater treatment, and a flash evaporation and gas stripping combined treatment mode is adopted, so that a large amount of energy is not consumed, the subsequent wastewater treatment difficulty can be reduced, and effective substances in the wastewater can be effectively utilized.
Because the decarbonization of the circulating gas is operated under a certain pressure, the circulating water of the washing tower also has a certain pressure, the discharged wastewater with pressure is sent into a flash tank to be directly subjected to reduced pressure flash evaporation, and hydrocarbon-containing gas flashed at the tower top can be returned to be synthesized to be used as a synthetic raw material. The main raw materials of the Fischer-Tropsch synthesis are hydrogen and carbon monoxide, the hydrogen or the carbon monoxide or the mixture of the hydrogen and the carbon monoxide is used for stripping the organic wastewater generated in the decarbonization process of the circulating gas, the effective substances in the wastewater are brought out of the tower top in a gaseous state, simultaneously, the stripping gas can also return to the synthesis tower together with flash evaporation gas in a flash evaporation section, and as the dissolved substances in the wastewater are removed from the wastewater, the discharge concentration of the wastewater is reduced, so that the resource reutilization is realized while the wastewater discharge is reduced.
In the scheme of the invention, after the flash evaporation and the gas stripping are completed, the gas at the top of the flash evaporation tower and the gas stripping tower is pressurized and sent into the synthesis tower, and the organic wastewater discharged from the bottom of the tower is sent into the subsequent water treatment process.
In the embodiment of the invention, the wastewater after flash evaporation can be preheated before entering the gas stripping, and the preheating temperature is 50-150 ℃.
In the above embodiment of the present invention, the wastewater may be wastewater discharged from a process of decarbonizing fischer-tropsch (F-T) synthesis cycle gas in coal-to-oil production, and the wastewater generally contains various hydrocarbons, has complex components, is energy-consuming to treat by a conventional method, and cannot effectively utilize resources. According to the embodiment of the present invention, the hydrocarbon substances dissolved in the wastewater can be utilized as resources to the maximum extent while the wastewater is treated, and therefore, the embodiment of the present invention has a significant meaning in terms of reduction of organic matter emission pollution and recycling of organic matter resources.
In the technical scheme, the used stripping gas is hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide, the two gases are Fischer-Tropsch synthesis raw materials, and the gas extracted by the two gases can still be returned for synthesis. The total amount of hydrocarbons in the waste water discharged after gas stripping is reduced, and the waste water is directly discharged if the water quality condition can meet the discharge standard, and the content of the hydrocarbons in the waste water is also obviously reduced even if the waste water cannot be discharged, and the difficulty and the treatment cost of the subsequent water treatment process are also reduced.
The embodiment of the invention has no special requirements on the arrangement of the used flash tower, flash system and stripping tower and stripping system, namely, the structures of the flash tower and the stripping tower and the selection and arrangement of the filler can be implemented according to the conventional means in the chemical field and the wastewater treatment industry without additional investment and design.
In summary, the technical scheme of the invention has the following beneficial effects:
1. according to the invention, the wastewater is subjected to flash evaporation by adopting a flash evaporation mode, the operation is simple, part of hydrocarbon gas which is flashed can be returned and synthesized to be used as a raw material, resources are reasonably utilized, the hydrocarbon content in the flash evaporation wastewater is reduced, and the flash evaporation wastewater is sent to a gas stripping process;
2. in the process of stripping the wastewater by using hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide, hydrocarbons in the wastewater also leave the wastewater in a gaseous state, so that the discharge amount of the hydrocarbons in the wastewater is reduced, the concentration is reduced, and the load and the difficulty of subsequent treatment are reduced;
3. no matter the flash evaporation process, the gas stripping process or the subsequent water treatment and synthesis gas preparation process, no special limitation and requirement are provided for equipment selection, so that the method is beneficial to industrial application.
Drawings
FIG. 1 is a schematic process flow diagram of a treatment method according to an embodiment of the present invention.
In the figure, 1-flash column, 2-stripping column and 3-pump.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Example 1
Referring to FIG. 1, a process of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-liquids plant (A) as an example.
The hydrocarbon-containing waste water (components are shown in table 1) with the pressure of 3.0MPa (a) and the temperature of 50 ℃ discharged from the bottom of a water washing tower of a circulating gas decarbonization device of a certain coal-to-liquid plant is sent into a flash tower, the treated waste water is discharged from the bottom of the flash tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the flash tower are discharged, thus finishing the first step. The composition of the flash-evaporated wastewater is shown in Table 1. The wastewater after flash evaporation treatment is continuously sent to the upper part of a stripping tower, stripping gas (hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide) is sent to the bottom of the stripping tower, gas and liquid materials are in countercurrent contact in the tower to realize stripping of the wastewater, after stripping, unvaporized wastewater is discharged from the bottom of the tower, hydrocarbon-containing gas components are discharged from the top of the tower, the second step is completed, the wastewater components after stripping are shown in table 1, most of hydrocarbons dissolved in water by circulating gas in the washing process are separated from the wastewater, and the treated wastewater can be directly discharged or can be discharged after being properly treated by a wastewater treatment system, so that the difficulty of wastewater treatment is reduced. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 1 composition table before and after wastewater treatment in coal-to-liquids plant (A)
Example 2
Referring to FIG. 1, the wastewater from coal-to-liquids plant (B) is taken as an example to briefly show the flow of the embodiment of the present invention.
The hydrocarbon-containing wastewater (components shown in table 2) with the pressure of 2.6MPa (a) and the temperature of 35 ℃ discharged from the bottom of the water washing tower of the plant circulating gas decarburization device is sent into a flash tower, the treated wastewater is discharged from the bottom of the tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the tower are discharged, thus completing the first step. The composition of the flash-evaporated wastewater is shown in Table 2. The wastewater after flash evaporation treatment is continuously sent to the upper part of a stripping tower, stripping gas (hydrogen or carbon monoxide or a mixture of the hydrogen and the carbon monoxide) is sent to the bottom of the stripping tower, gas and liquid materials are in countercurrent contact in the tower to realize stripping of the wastewater, after stripping, unvaporized wastewater is discharged from the bottom of the tower, hydrocarbon-containing gas components are discharged from the top of the tower, the second step is completed, the stripped wastewater components are shown in a table 2, most of hydrocarbons dissolved in water by circulating gas in the table in the washing process are separated, the treated wastewater can be directly discharged or can be discharged after being properly treated by a wastewater treatment system, and the difficulty of wastewater treatment is reduced. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 2 composition table before and after wastewater treatment in coal-to-liquids plant (B)
Example 3
Referring to fig. 1, a process flow of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-oil plant (C) as an example.
The hydrocarbon-containing wastewater (components shown in table 3) with the pressure of 3.2MPa (a) and the temperature of 50 ℃ discharged from the bottom of the water washing tower of the plant circulating gas decarburization device is sent into a flash tower, the treated wastewater is discharged from the bottom of the tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the tower are discharged, thus completing the first step. The composition of the flash-evaporated wastewater is shown in Table 3. The wastewater after flash evaporation treatment is heated to 90 ℃ by adopting steam and then is continuously sent to the upper part of a stripping tower, hydrogen is taken as stripping gas and sent to the bottom of the stripping tower, gas and liquid materials are in countercurrent contact in the tower to realize stripping of the wastewater, after stripping, unvaporized wastewater is discharged from the bottom of the tower, hydrocarbon-containing gas components are discharged from the top of the tower, the second step is completed, the stripped wastewater components are shown in a table 3, most of hydrocarbons dissolved in water by circulating gas in the table are separated in the water washing process, the treated wastewater can be directly discharged or can be discharged after being properly treated by a wastewater treatment system, and the difficulty of wastewater treatment is reduced. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 3 composition table before and after wastewater treatment in coal-to-liquids plant (C)
Example 4
Referring to FIG. 1, a process flow of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-liquids plant (D) as an example.
The hydrocarbon-containing waste water (components are shown in table 4) with the pressure of 3.0MPa (a) and the temperature of 50 ℃ discharged from the bottom of a water washing tower of a circulating gas decarbonization device of a certain coal-to-liquid plant is sent into a flash tower, the treated waste water is discharged from the bottom of the flash tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the flash tower are discharged, thus finishing the first step. The composition of the flash-evaporated wastewater is shown in Table 4. And (3) continuously feeding the wastewater subjected to flash evaporation treatment into the upper part of a stripping tower, heating the wastewater to 100 ℃ by adopting steam, continuously feeding the wastewater into the upper part of the stripping tower, taking carbon monoxide as stripping gas, discharging unvaporized wastewater from the bottom of the tower after stripping, discharging hydrocarbon-containing gas components from the top of the tower, finishing the second step, wherein the components of the wastewater subjected to stripping are shown in a table 4, most of hydrocarbons dissolved in water in circulating gas in a water washing process are separated from the wastewater, and the treated wastewater can be directly discharged or can be properly treated by a wastewater treatment system and then discharged, so that the difficulty of wastewater treatment is reduced. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 4 composition table before and after wastewater treatment in coal-to-liquids plant (D)
Example 5
Referring to FIG. 1, a process flow of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-liquids plant (E) as an example.
The hydrocarbon-containing waste water (components are shown in table 5) with the pressure of 3.5MPa (a) and the temperature of 50 ℃ discharged from the bottom of a water washing tower of a circulating gas decarbonization device of a certain coal-to-liquid plant is sent into a flash tower, the treated waste water is discharged from the bottom of the flash tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the flash tower are discharged, thus finishing the first step. The composition of the flash-evaporated wastewater is shown in Table 5. And continuously feeding the wastewater subjected to flash evaporation treatment into the upper part of a stripping tower, heating to 80 ℃ by adopting steam, continuously feeding the wastewater into the upper part of the stripping tower, adopting 50% (mol) of carbon monoxide and 50% (mol) of hydrogen as stripping gas, carrying out gas stripping, discharging unvaporized wastewater from the bottom of the tower, discharging hydrocarbon-containing gas components from the top of the tower, and finishing the second step. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 5 composition table before and after wastewater treatment in coal-to-liquids plant (E)
Example 6
Referring to FIG. 1, a process flow of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-liquids plant (E) as an example.
The hydrocarbon-containing waste water (components are shown in table 5) with the pressure of 3.5MPa (a) and the temperature of 50 ℃ discharged from the bottom of a water washing tower of a circulating gas decarbonization device of a certain coal-to-liquid plant is sent into a flash tower, the treated waste water is discharged from the bottom of the flash tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the flash tower are discharged, thus finishing the first step. The composition of the flash-evaporated wastewater is shown in Table 5. And continuously feeding the wastewater subjected to flash evaporation treatment into the upper part of a stripping tower, heating to 100 ℃ by adopting steam, continuously feeding the wastewater into the upper part of the stripping tower, adopting 50% (mol) of carbon monoxide and 50% (mol) of hydrogen as stripping gas, carrying out gas stripping, discharging unvaporized wastewater from the bottom of the tower, discharging hydrocarbon-containing gas components from the top of the tower, and finishing the second step. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 6 ingredient table before and after wastewater treatment in coal-to-liquids plant (E)
Example 7
Referring to FIG. 1, a process flow of an embodiment of the present invention is schematically shown, taking wastewater from a coal-to-liquids plant (E) as an example.
The hydrocarbon-containing waste water (components are shown in table 5) with the pressure of 3.5MPa (a) and the temperature of 50 ℃ discharged from the bottom of a water washing tower of a circulating gas decarbonization device of a certain coal-to-liquid plant is sent into a flash tower, the treated waste water is discharged from the bottom of the flash tower after decompression flash evaporation, and the hydrocarbon-containing gas components flashed from the top of the flash tower are discharged, thus finishing the first step. The composition of the flash-evaporated wastewater is shown in Table 5. And continuously feeding the wastewater subjected to flash evaporation treatment into the upper part of a stripping tower, heating to 150 ℃ by adopting steam, continuously feeding the wastewater into the upper part of the stripping tower, adopting 50% (mol) of carbon monoxide and 50% (mol) of hydrogen as stripping gas, carrying out gas stripping, discharging unvaporized wastewater from the bottom of the tower, discharging hydrocarbon-containing gas components from the top of the tower, and finishing the second step. And the exhaust gases from the top of the first step and the second step are returned to the synthesis for reuse after being summed together.
TABLE 6 ingredient table before and after wastewater treatment in coal-to-liquids plant (E)
Claims (9)
1. The method for treating the decarbonization wastewater of the Fischer-Tropsch synthesis recycle gas is characterized by comprising the following flash evaporation and stripping steps:
1) sending the decarbonized wastewater into a flash tank for reduced pressure flash evaporation, discharging the gas after flash evaporation from the upper part of the flash tank, and discharging the wastewater after flash evaporation from the bottom of the flash tank; 2) feeding the flash-evaporated wastewater into a stripping tower through the upper part of the stripping tower, feeding stripping gas into the stripping tower through the lower part of the stripping tower, stripping the wastewater by the stripping gas in the stripping tower, discharging stripped water from the bottom of the tower, discharging the stripped gas from the top of the tower, and returning the gas and the flash-evaporated gas obtained in the step 1) to the reactor.
2. The process according to claim 1, wherein after the completion of the flash evaporation and the stripping, the top gas of the flash evaporation tower and the top gas of the stripping tower are pressurized and fed into the synthesis tower, and the organic wastewater discharged from the bottom of the tower is fed into the subsequent water treatment process.
3. The treatment method according to claim 1, wherein the wastewater is wastewater discharged from a Fischer-Tropsch synthesis cycle gas decarbonization process in coal-to-liquids production.
4. The process of claim 1, wherein the stripping gas is hydrogen.
5. The process of claim 1, wherein the stripping gas is carbon monoxide.
6. The process of claim 1, wherein the stripping gas is a mixture of hydrogen and carbon monoxide in any ratio.
7. The process according to claim 1, characterized in that the flashed and stripped gases are returned as feed for the Fischer-Tropsch synthesis.
8. The process of claim 1, wherein the flashed wastewater is preheated prior to entering the gas stripping section.
9. The process according to claim 8, characterized in that the preheating temperature is comprised between 50 and 150 ℃.
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| CN114853591A (en) * | 2022-06-13 | 2022-08-05 | 扬州大学 | Resource utilization method of acetone and carbon dioxide in sodium phenolate carboxylation reaction |
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