CN110950305A - Purification method and purification system of semi-coke gas - Google Patents
Purification method and purification system of semi-coke gas Download PDFInfo
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- CN110950305A CN110950305A CN202010033076.XA CN202010033076A CN110950305A CN 110950305 A CN110950305 A CN 110950305A CN 202010033076 A CN202010033076 A CN 202010033076A CN 110950305 A CN110950305 A CN 110950305A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
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- C01B2203/0465—Composition of the impurity
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
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Abstract
The invention discloses a method and a system for purifying semi-coke gas, wherein the method for purifying the semi-coke gas comprises the following steps: s1, washing with water; s2, cooling; s3, removing oil; s4, heating; s5, detoxification; s6, humidifying; s7, sulfur tolerance transformation; s8, recovering heat; s9, cooling, namely, finishing the purification and ventilation operation of the semi-coke gas after cooling; the semi-coke gas purification system comprises a washing tower, a gas water cooler, an oil removal furnace, a preheating exchanger, a main heating exchanger, a detoxification furnace, a humidifier, a shift converter and a shift converter water cooler; the air inlet of the washing tower is connected with the air outlet of the semi-coke production device, and the washing tower, the gas water cooler, the oil removing furnace, the preheating exchanger, the main heating exchanger, the detoxifying furnace, the humidifier, the shift converter and the shift gas water cooler are sequentially connected through the air duct.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a method and a system for purifying semi coke gas.
Background
In the semi-coke production process, about 700m3 semi-coke gas is generated for each 1 ton of semi-coke produced. At present, a large amount of semi coke gas is mostly discharged in an empty or direct combustion mode, so that the environment is seriously polluted, and a large amount of energy is wasted. Typical semi-coke gas has main component H220-28%、CO9-18%、CO28-12%、O20.5-2.0%、N237-43%、CH47-10% of carbon tetrachloride, CmHn1-3% of carbon tetrachloride, and in addition, the carbon tetrachloride also contains tar, benzene, naphthalene, phenol, dust, sulfide, ammonia, fluorine, chlorine, heavy metals and other impurities. Because the nitrogen content in the gas is high, the hydrogen content is low, the heat value is low, and impurities are more, the gas is not suitable to be directly used as fuel gas. But wherein H2CO and CH4Are all valuable chemical raw materials. If the semi-coke gas exchange device is effectively utilized, not only can the environmental pollution caused by direct discharge be reduced, but also waste can be changed into valuable to create certain economic benefit for enterprises, but the direct air exchange operation of the semi-coke gas can cause the deoxidant and the conversion catalyst to be poisoned and inactivated in a short time, so that the stable operation of the semi-coke gas exchange operation is influenced.
Disclosure of Invention
The invention aims to solve the above requirements and provide a method and a system for purifying semi-coke gas, which can be stably operated.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for purifying semi coke gas comprises the following steps:
s1, carrying out water washing operation on semi-coke gas discharged in semi-coke production to remove ammonia gas in the semi-coke gas;
s2, cooling the semi-coke gas from which the ammonia gas is removed and separating oil and water in the semi-coke gas;
s3, further removing tar from the cooled semi-coke gas through an oil remover;
s4, heating the semi-coke gas after tar removal through a heat exchange device;
s5, removing poison in the semi-coke gas and the oxygen content in the semi-coke gas through a detoxification furnace after the temperature is raised;
s6, spraying water to the detoxified semi-coke gas, cooling, and supplementing steam to the semi-coke gas;
s7, performing one-stage or two-stage CO sulfur-tolerant transformation on the semi-coke gas after steam supplementation to obtain the semi-coke gas containing H2And CO;
s8, recycling heat of the obtained conversion gas through a heat recycling device;
and S9, cooling the converted gas after heat recovery, and finishing the purification and ventilation operation of the semi-coke gas after cooling.
Further, in step S1, a circulation water washing operation is performed by using the condensate and supplementing fresh water.
Further, the degreaser in the step S3 is filled with a degreaser.
Further, the detoxification furnace in the step S5 is filled with a protective agent and a sulfur-tolerant detoxification agent.
Further, the heat recovery device in step S8 is one or a combination of several of a heat exchanger, a waste heat boiler, a boiler water heater, and a desalted water heater.
Further, in step S9, the cooling operation is performed by using one of air cooling and water cooling or a combination of both.
A semi-coke gas purification system comprises a washing tower, a gas water cooler, an oil removal furnace, a preheating exchanger, a main heating exchanger, a detoxification furnace, a humidifier, a shift converter and a shift gas water cooler; the air inlet of the washing tower is connected with the air outlet of the semi-coke production device, and the washing tower, the gas water cooler, the oil removing furnace, the preheating exchanger, the main heating exchanger, the detoxifying furnace, the humidifier, the shift converter and the shift gas water cooler are sequentially connected through the air duct.
Furthermore, a heat exchange outlet is arranged on the shift converter and is connected with a hot gas inlet of the main heating exchanger through a ventilation pipeline, the hot gas outlet of the main heating exchanger is connected with a hot gas inlet of the waste heat boiler, and the hot gas outlet of the waste heat boiler is connected with a heat exchange inlet of the shift converter.
Furthermore, ventilation pipelines between the shift converter and the shift converter water cooler are respectively connected with a preheating exchanger, a boiler water heater and a desalted water heater; the exhaust port of the shift converter is respectively connected with the hot gas inlet of the preheating exchanger and the air inlet of the boiler water heater, the hot gas outlet of the preheating exchanger and the air outlet of the boiler water heater are both connected with the air inlet of the desalted water heater, and the air outlet of the desalted water heater is connected with the air inlet of the shift gas water cooler.
Furthermore, the washing tower and the desalted water heater are both connected with an external desalted water pipe; the boiler water heater, the humidifier and the waste heat boiler are all connected with an external deoxidizing water pipe; and the steam discharge pipeline of the waste heat boiler and an external steam pipeline are connected with a ventilation pipeline between the air outlet of the humidifier and the air inlet of the shift converter.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention provides a method and a system for purifying semi-coke gas, which use a proper process, a degreasing agent, a protective agent and a catalyst, and carry out the steps of water washing, dehydration, oil removal, temperature rise, detoxification, oxygen removal, water supplement, conversion, heat recovery, cooling and the like, so that the semi-coke gas purification and conversion operation can be stably operated for a long time, the problem of poisoning and inactivation in the conversion process of the deoxidant and the conversion catalyst is solved, stable and qualified gas is provided for extracting hydrogen or producing synthetic ammonia in the downstream process, and the heat generated in the conversion process is recycled, so that the resource utilization is maximized, the consumption of semi-coke gas purification and gas exchange is reduced, and the condition of energy waste is avoided.
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 only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a purification system for semi-coke gas.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
In order to solve the problem of long-period stable operation of semi-coke gas conversion, the invention provides a semi-coke gas purification technology, which uses a proper process and uses special oil removal agents, protective agents and catalysts for semi-coke gas and coke oven gas, and comprises the steps of water washing, dehydration, oil removal, temperature rise, detoxification, water supplement, conversion, heat recovery and cooling, and the specific steps are as follows:
(1) washing with water: washing semi-coke gas from an exhaust port of the semi-coke with water to remove ammonia;
(2) and (3) dehydrating: cooling and dehydrating the ammonia-removed semi-coke gas through a water cooler;
(3) oil removal: removing tar from the cooled semi-coke gas through an oil remover;
(4) and (3) heating: heating after deoiling;
(5) detoxification and deoxidization: heating the semi-coke gas, then removing oxygen after detoxification in a detoxification furnace;
(6) water replenishing: after the semi-coke gas is deoxidized, spraying water to cool and humidify and supplying steam;
(7) and (3) transformation: the semi-coke gas is subjected to one-stage or two-stage CO sulfur-tolerant shift to obtain part of CO and H in the semi-coke gas2O reaction to transform hydrogen to obtain H2: shift gas of CO ratio;
(8) and (3) heat recovery: the heat of the converted gas is recovered by a heat recovery device;
(9) and (3) cooling: and cooling the converted gas after heat recovery by a cooler to finish the purification and ventilation operation.
In the step (1), the conversion condensate is utilized and part of fresh water is supplemented for circular water washing, and the ammonia content after water washing is lower than 50 PPm.
In the step (2), the semi-coke gas needs to be indirectly cooled to less than 35 ℃ by using low-temperature water.
And (4) filling an oil removing agent into the oil remover in the step (3).
And (5) filling a protective agent and a sulfur-resistant deoxidant into the detoxification furnace.
In the step (7), one-stage or two-stage CO sulfur-tolerant shift is set for the semi-coke gas according to the process requirements, and a sulfur-tolerant shift catalyst is used in the shift process.
In the step (8), the heat recovery device includes one or a combination of a heat exchanger, a waste heat boiler, a boiler water heater and a desalted water heater.
In the step (9), the cooling may be one of air cooling and water cooling or a combination of the two.
As shown in fig. 1, the semi-coke gas purification system of the present invention operates as follows:
the semi-coke gas enters a gas water cooler 2 after passing through a washing tower 1 and washing ammonia with conversion condensate and supplemented desalted water, and the semi-coke gas is cooled to below 35 ℃ for dehydration; then the semi-coke enters an oil removing furnace 3, a special oil removing agent is filled in the oil removing furnace 3, tar in the semi-coke gas is removed and is less than or equal to 1PPm, then the semi-coke gas is heated to 170-250 ℃ by a preheating exchanger 4 and a main heating exchanger 5 in sequence and enters a detoxification furnace 6, a protective agent I, a protective agent II and a sulfur-resistant deoxidant are filled in the detoxification furnace 6, the oxygen content is removed to be less than 50PPm after heavy metal and other impurities in the semi-coke gas are removed, and the relatively clean semi-coke gas is obtained through the steps.
Clean semi-coke gas is sprayed with water by a humidifier 7 for cooling, steam is supplemented and then enters a shift converter 8 for shift reaction, reaction heat is recovered by a main heating exchanger 5 and a waste heat boiler 9, and the primary shift gas enters the shift converter 8 for second-stage reaction to complete shift reaction, so that the content of CO in the shift gas is reduced to 0.5%.
The conversion gas at the outlet of the conversion furnace 8 is sent to the downstream after entering a conversion gas water cooler 12 and being cooled to the temperature of less than or equal to 40 ℃ after the heat of the conversion gas is recovered by a preheating exchanger 4, a boiler water heater 10 and a desalted water heater 11.
The invention provides a method and a system for purifying semi-coke gas, which use a proper process, a degreasing agent, a protective agent and a catalyst, and carry out the steps of water washing, dehydration, oil removal, temperature rise, detoxification, oxygen removal, water supplement, conversion, heat recovery, cooling and the like, so that the semi-coke gas purification and conversion operation can be stably operated for a long time, the problem of poisoning and inactivation in the conversion process of the deoxidant and the conversion catalyst is solved, stable and qualified gas is provided for extracting hydrogen or producing synthetic ammonia in the downstream process, and the heat generated in the conversion process is recycled, so that the resource utilization is maximized, the consumption of semi-coke gas purification and gas exchange is reduced, and the condition of energy waste is avoided.
Claims (10)
1. A method for purifying semi coke gas is characterized in that: the method comprises the following steps:
s1, carrying out water washing operation on semi-coke gas discharged in semi-coke production to remove ammonia gas in the semi-coke gas;
s2, cooling the semi-coke gas from which the ammonia gas is removed and separating oil and water in the semi-coke gas;
s3, further removing tar from the cooled semi-coke gas through an oil remover;
s4, heating the semi-coke gas after tar removal through a heat exchange device;
s5, removing poison in the semi-coke gas and the oxygen content in the semi-coke gas through a detoxification furnace after the temperature is raised;
s6, spraying water to the detoxified semi-coke gas, cooling, and supplementing steam to the semi-coke gas;
s7, performing one-stage or two-stage CO sulfur-tolerant transformation on the semi-coke gas after steam supplementation to obtain the semi-coke gas containing H2And CO;
s8, recycling heat of the obtained conversion gas through a heat recycling device;
and S9, cooling the converted gas after heat recovery, and finishing the purification and ventilation operation of the semi-coke gas after cooling.
2. The method for purifying semi-coke gas as claimed in claim 1, wherein: in step S1, a circulation water washing operation is performed using the condensate and the make-up fresh water.
3. The method for purifying semi-coke gas as claimed in claim 1, wherein: the degreaser in step S3 is filled with a degreaser.
4. The method for purifying semi-coke gas as claimed in claim 1, wherein: the detoxification furnace in the step S5 is filled with a protective agent and a sulfur-tolerant detoxification agent.
5. The method for purifying semi-coke gas as claimed in claim 1, wherein: the heat recovery device in the step S8 is one or a combination of several of a heat exchanger, a waste heat boiler, a boiler water heater and a desalted water heater.
6. The method for purifying semi-coke gas as claimed in claim 1, wherein: in step S9, cooling operation is performed by using one or a combination of air cooling and water cooling.
7. A semi-coke gas purification system for implementing the semi-coke gas purification method of claim 1, characterized in that: the semi-coke gas purification system comprises a washing tower, a gas water cooler, an oil removal furnace, a preheating exchanger, a main heating exchanger, a detoxification furnace, a humidifier, a shift converter and a shift converter water cooler; the air inlet of the washing tower is connected with the air outlet of the semi-coke production device, and the washing tower, the gas water cooler, the oil removing furnace, the preheating exchanger, the main heating exchanger, the detoxifying furnace, the humidifier, the shift converter and the shift gas water cooler are sequentially connected through the air duct.
8. The semi-coke gas purification system of claim 7, wherein: the conversion furnace is provided with a heat exchange outlet, the heat exchange outlet is connected with a hot gas inlet of the main heating exchanger through a ventilation pipeline, a hot gas outlet of the main heating exchanger is connected with a hot gas inlet of the waste heat boiler, and the hot gas outlet of the waste heat boiler is connected with a heat exchange inlet of the conversion furnace.
9. The semi-coke gas purification system of claim 7, wherein: the ventilation pipeline between the shift converter and the shift gas water cooler is respectively connected with the preheating exchanger, the boiler water heater and the desalted water heater; the exhaust port of the shift converter is respectively connected with the hot gas inlet of the preheating exchanger and the air inlet of the boiler water heater, the hot gas outlet of the preheating exchanger and the air outlet of the boiler water heater are both connected with the air inlet of the desalted water heater, and the air outlet of the desalted water heater is connected with the air inlet of the shift gas water cooler.
10. The semi-coke gas purification system of claim 9, wherein: the washing tower, the desalted water heater and the shift gas water cooler are all connected with an external desalted water pipe; the shift gas water cooler is connected with a circulating water pipe; the boiler water heater, the humidifier and the waste heat boiler are all connected with an external deoxidizing water pipe; and the steam discharge pipeline of the waste heat boiler and an external steam pipeline are connected with a ventilation pipeline between the air outlet of the humidifier and the air inlet of the shift converter.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910041223.5A CN110054154A (en) | 2019-01-16 | 2019-01-16 | A kind of purification method and its purification system of semi-coke gas |
| CN2019100412235 | 2019-01-16 |
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| CN110950305A true CN110950305A (en) | 2020-04-03 |
| CN110950305B CN110950305B (en) | 2020-11-27 |
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| CN202010033076.XA Active CN110950305B (en) | 2019-01-16 | 2020-01-13 | Purification method and purification system of semi-coke gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114367182A (en) * | 2022-01-17 | 2022-04-19 | 湖北禾谷环保有限公司 | Low-hydrogen low-pressure sulfur-resistant deoxidation process for tail gas of submerged arc furnace |
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2019
- 2019-01-16 CN CN201910041223.5A patent/CN110054154A/en not_active Withdrawn
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2020
- 2020-01-13 CN CN202010033076.XA patent/CN110950305B/en active Active
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| RU2094447C1 (en) * | 1994-12-28 | 1997-10-27 | Саратовский государственный технический университет | Method of thermal processing of sulfurous shales |
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Also Published As
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| CN110054154A (en) | 2019-07-26 |
| CN110950305B (en) | 2020-11-27 |
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