CN110182761B - Process for preparing synthesis gas by converting coke-oven gas - Google Patents
Process for preparing synthesis gas by converting coke-oven gas Download PDFInfo
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- CN110182761B CN110182761B CN201910367058.2A CN201910367058A CN110182761B CN 110182761 B CN110182761 B CN 110182761B CN 201910367058 A CN201910367058 A CN 201910367058A CN 110182761 B CN110182761 B CN 110182761B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Industrial Gases (AREA)
Abstract
The invention relates to a process for preparing synthesis gas from coke-oven gas, which comprises the steps of separating methane and unsaturated hydrocarbon from the coke-oven gas to obtain methane-rich gas, wherein the methane-poor gas is used as synthesis gas 1, and the methane-rich gas is used as hydrocarbon conversion raw material and is also used as coke-oven fuel; the regenerative chamber of the coke oven with the concentration of more than 40 percent is changed into a hydrocarbon conversion chamber, the fuel gas, combustion-supporting gas and flue gas systems of the hydrocarbon conversion chamber and a common regenerative chamber are separated, the combustion-supporting gas supply of the hydrocarbon conversion chamber is changed into oxygen-enriched air (nitrogen-containing synthetic gas) or pure oxygen (nitrogen-free synthetic gas), the gas reaction temperature of the conversion chamber is not lower than the combustion temperature before transformation by 5 ℃ and cannot be higher than the original combustion temperature, and the regenerative chamber which is not taken as the hydrocarbon conversion chamber still uses the original fuel and air system; the fuel gas of the hydrocarbon conversion chamber, the flue gas (synthesis gas 2) outlet and the regenerator fuel gas of the non-hydrocarbon conversion furnace, the flue gas and the waste heat recovery system are respectively separated, thereby realizing the purpose of hydrocarbon conversion in the coke-oven gas; the nozzle of the hydrocarbon conversion chamber is changed into a conversion nozzle, the synthesis gas 1 and the synthesis gas 2 are synthesis gas raw materials, and the total amount of oxygen-rich nitrogen is the total amount of nitrogen of the nitrogen-containing synthesis gas.
Description
Technical Field
The invention relates to the fields of chemical industry, energy conservation and environmental protection, and discloses a method for converting hydrocarbons in coke oven gas into synthesis gas.
Background
The coal cracking tail gas generated in the coke production process is called coke oven gas, and the common practice is to use 40-60% of the coke oven gas as direct fuel of the coke oven and use the other part as synthesis conversion gas.
The special converter is used for preparing the synthesis gas by converting the coke-oven gas. The investment is huge. The energy consumption in the conversion process is considerable.
The first method for preparing synthesis gas by coke oven gas conversion uses steam to catalytically convert hydrocarbons in the coke oven gas.
The second method for preparing synthesis gas by coke oven gas conversion is to use oxygen (air) to catalytically convert hydrocarbons in the coke oven gas.
The third method for preparing synthesis gas by coke oven gas conversion uses oxygen (air) to convert hydrocarbons in the coke oven gas in a non-catalytic mode.
The reports disclosed so far are all that a specially-made reformer is used, so that hydrocarbons in coke oven gas can be converted with high efficiency.
The method for preparing the synthesis gas by converting the natural gas is consistent with that of the coke oven gas.
In a common coke oven, regenerators and a carbonization chamber are arranged at intervals, the regenerators combust coke oven gas or other combustible gas, air is used as combustion-supporting gas, gas inlet pipelines and flue gas pipelines of all the regenerators are connected in parallel, all the air inlet pipelines are connected in parallel, and the combustible gas and the combustion-supporting gas enter the regenerators through different pipelines to be combusted. The temperature of the gas after combustion reaches the coking temperature or is higher than the coking temperature by within 50 ℃.
The combustion process of the reformer and the coke oven regenerator has a lot of heat loss, and the outlet temperature of the reformed gas and the flue gas of the coke oven is far higher than the inlet temperature, so the heat recovery process is accompanied with a lot of heat loss.
The coke oven gas converter has high hydrogen content of the coke oven gas, and energy waste is huge in the processes of heating the coke oven gas hydrogen and cooling the converted gas hydrogen.
Disclosure of Invention
In order to reduce the total heat loss, the methane and the unsaturated hydrocarbon in the coke oven gas are separated into methane-rich gas and methane-poor gas, the methane-rich gas is used for conversion and coke oven heating, and the methane-poor gas is directly used as synthesis gas. The invention changes the regenerative chamber of the coke oven more than 40% into a hydrocarbon conversion chamber, the fuel gas of the hydrocarbon conversion chamber is separated from the regenerative chamber, the supply is changed into methane-rich gas, superheated steam is not used to participate in the conversion process, the air supply of the hydrocarbon conversion chamber is changed into oxygen-rich air or pure oxygen, the gas reaction temperature of the regenerative chamber is at most 5 ℃ lower than the combustion temperature before the conversion and can not be higher than the original combustion temperature, and the regenerative chamber which is not used as the hydrocarbon conversion chamber still uses the original fuel, air and flue gas system; the flue gas (converted gas) outlet of the hydrocarbon converter is separated from the flue of the regenerative chamber of the non-hydrocarbon converter and the waste heat recovery system, thereby achieving the purpose of hydrocarbon conversion in the coke oven. The method has the greatest advantage of reducing the cost for independently building the reformer, and simultaneously changing the heat loss of the reformer and the heat loss of the coke oven into the heat loss of only the coke oven, thereby saving energy. To minimize the amount of oxygen used in the hydrocarbon gas, the operating temperature of the regenerator has previously been reduced to as low as 5 ℃ below the original combustion temperature. Because the process of reforming gas belongs to oxygen-deficient combustion, the original regenerator nozzle needs to be changed into a reformer nozzle.
The flue gas of the conversion chamber becomes nitrogen-containing synthetic gas, and the flue gas of the conversion chamber becomes nitrogen-free synthetic gas.
This process converts all hydrocarbons in the coke oven gas to synthesis gas.
Detailed Description
Example 1: methane and unsaturated hydrocarbon are separated from coke oven gas to form methane-rich gas and methane-poor gas, the methane-poor gas is used as synthesis gas 1, a heat storage chamber with 22 holes in the middle of a coke oven with 40 holes is changed into a hydrocarbon conversion chamber, and air in the hydrocarbon conversion chamber is used. The flue gas system is separated from the other 18-hole regenerators. The hydrocarbon conversion chamber is changed to send 100% pure oxygen, the fuel system is kept consistent, but the oxygen flow control valve is independently arranged, but the fuel gas flow control valve is independently arranged, so that the total heat supply of the hydrocarbon conversion chamber is equal to the heat release + conversion heat of other regenerative chambers. The hydrocarbon conversion chamber burner is separately located. The flue for hydrocarbon conversion is set up separately from the flue for the other regenerators. This converts all the hydrocarbons in the methane-rich gas to synthesis gas 2. This process converts all hydrocarbons in the coke oven gas to synthesis gas.
Example 2: methane and unsaturated hydrocarbon are separated from coke oven gas to form methane-rich gas and methane-poor gas, the methane-poor gas is used as synthesis gas 1, a heat storage chamber with 36 holes in the middle of a coke oven with 48 holes is changed into a hydrocarbon conversion chamber, fuel gas, a combustion-supporting system and flue gas of the hydrocarbon conversion chamber are separated from other heat storage chambers with 28 holes, combustion supporting is changed into 60% of oxygen enrichment, a fuel system is separately arranged, an oxygen enrichment flow control valve is independently arranged, the fuel gas of the common heat storage chamber is mixed gas of blast furnace gas and a coke oven, the raw material of the hydrocarbon conversion chamber is purified hydrogen tail gas by using the coke oven gas containing 48% of methane, and the flow control valves of the common heat storage chamber and the hydrocarbon conversion chamber are respectively and independently arranged, so that the total heat of the hydrocarbon conversion chamber is equal to the heat release and conversion heat of other heat storage chambers. The hydrocarbon conversion chamber burner is additionally configured as a reforming burner. The flue for converting the hydrocarbon is separated from the flue of other heat storage chambers, and the waste heat recovery systems are independent. This allows the methane-rich gas to be converted into synthesis gas 2.
This process converts all hydrocarbons in the coke oven gas into synthesis gas.
Example 3: the middle 48-hole regenerator in the 48-hole coke furnace is completely changed into a hydrocarbon conversion chamber, air is changed into oxygen rich gas with the concentration of 60 percent, the raw material of the fuel system uses methane rich gas with the concentration of 78 percent methane, and a burner of the hydrocarbon conversion chamber is additionally arranged. This allows the hydrocarbon-rich gas to be converted into synthesis gas.
This method is simple and feasible, but the hydrocarbon gas flow rate and the oxygen purity, the flow rate need to be designed and optimized separately, and the safety design needs to be calculated in detail.
This method reduces the investment in the hydrocarbon reformer and at the same time reduces the heat loss of the hydrocarbon reformer.
Claims (1)
1. A process for preparing synthetic gas from coke-oven gas is characterized by comprising the following steps: separating methane and unsaturated hydrocarbon from the coke-oven gas to obtain methane-rich gas, wherein the methane-poor gas is used as synthesis gas 1, and the methane-rich gas is used as hydrocarbon conversion raw material and is also used as coke-oven fuel; the method is characterized in that a coke oven regenerator with the mass percent of more than 40% is changed into a hydrocarbon conversion chamber, a fuel gas system, a combustion-supporting gas system and a flue gas system of the hydrocarbon conversion chamber are arranged in a separated mode, the combustion-supporting gas supply of the hydrocarbon conversion chamber is changed into oxygen-enriched air to finally obtain nitrogen-containing synthetic gas, or pure oxygen to finally obtain nitrogen-free synthetic gas, the gas reaction temperature of the hydrocarbon conversion chamber is not lower than the combustion temperature before transformation by 5 ℃ and cannot be higher than the original combustion temperature, and the original fuel and air system is still used as the regenerator which is not used as the hydrocarbon conversion chamber; the fuel gas and the flue gas of the hydrocarbon conversion chamber are the synthesis gas 2, and the outlet is separated from the regenerative chamber fuel gas, the flue gas and the waste heat recovery system of the non-hydrocarbon conversion furnace, thereby realizing the purpose of hydrocarbon conversion in the coke-oven gas; the nozzle of the hydrocarbon conversion chamber is changed into a conversion nozzle, the synthesis gas 1 and the synthesis gas 2 are synthesis gas raw materials, and the total nitrogen supply amount of the oxygen-rich air is the total nitrogen amount of the nitrogen-containing synthesis gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367058.2A CN110182761B (en) | 2019-05-05 | 2019-05-05 | Process for preparing synthesis gas by converting coke-oven gas |
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| CN201910367058.2A CN110182761B (en) | 2019-05-05 | 2019-05-05 | Process for preparing synthesis gas by converting coke-oven gas |
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| Publication Number | Publication Date |
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| CN110182761A CN110182761A (en) | 2019-08-30 |
| CN110182761B true CN110182761B (en) | 2023-03-21 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649449A (en) * | 1992-07-29 | 1994-02-22 | Nippon Steel Corp | Method for reducing oxygen in combustion off-gas after collection of small flue by mechanism for changing coke oven gas |
| CN103303863A (en) * | 2013-06-13 | 2013-09-18 | 黄家鹄 | Method for producing ammonia synthesis gas from coke-oven gas |
| CN104232195A (en) * | 2013-06-18 | 2014-12-24 | 中国石油化工股份有限公司 | Method for jointly producing methanol and synthetic natural gas by utilizing coke oven gas |
| CN104419483A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Coke-oven gas methane synthetic technology with product quality being finely controlled |
| JP2015157896A (en) * | 2014-02-24 | 2015-09-03 | Ｊｆｅスチール株式会社 | Operation method of coke oven |
| CN106315510A (en) * | 2015-06-30 | 2017-01-11 | 甘肃宏汇能源化工有限公司 | Coke oven gas hydrogen production technology |
-
2019
- 2019-05-05 CN CN201910367058.2A patent/CN110182761B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649449A (en) * | 1992-07-29 | 1994-02-22 | Nippon Steel Corp | Method for reducing oxygen in combustion off-gas after collection of small flue by mechanism for changing coke oven gas |
| CN103303863A (en) * | 2013-06-13 | 2013-09-18 | 黄家鹄 | Method for producing ammonia synthesis gas from coke-oven gas |
| CN104232195A (en) * | 2013-06-18 | 2014-12-24 | 中国石油化工股份有限公司 | Method for jointly producing methanol and synthetic natural gas by utilizing coke oven gas |
| CN104419483A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Coke-oven gas methane synthetic technology with product quality being finely controlled |
| JP2015157896A (en) * | 2014-02-24 | 2015-09-03 | Ｊｆｅスチール株式会社 | Operation method of coke oven |
| CN106315510A (en) * | 2015-06-30 | 2017-01-11 | 甘肃宏汇能源化工有限公司 | Coke oven gas hydrogen production technology |
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| CN110182761A (en) | 2019-08-30 |
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