CN105925317A - Method for improving yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases - Google Patents
Method for improving yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases Download PDFInfo
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- CN105925317A CN105925317A CN201610539825.XA CN201610539825A CN105925317A CN 105925317 A CN105925317 A CN 105925317A CN 201610539825 A CN201610539825 A CN 201610539825A CN 105925317 A CN105925317 A CN 105925317A
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- methane
- pyrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/02—Removal of water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/06—Catalysts as integral part of gasifiers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/12—Heating the gasifier
- C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for improving the yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases. The method is characterized in that: methane of which the volume ratio is 50-90% and carbon dioxide of which the volume ratio is 10-50% are used as reactant gases, methane and carbon dioxide are mixed together, then the mixed gas is introduced into a pyrolysis reactor and is subjected to co-pyrolysis with a mixture containing coal of which the mass percent is 30-90% and semi-coke of which the mass percent is 10-70% under the condition that the microwave heating temperature is 400-700 DEG C for a constant temperature time of 10-40min, volatile products after pyrolysis leave the reactor and then enter a condensing system for gas-liquid separation, and then a tar product is collected. The method disclosed by the invention has the advantages that the semi-coke is used as a catalyst, and methane and carbon dioxide replace hydrogen and serve as hydro-pyrolysis reactant gases, so that the yield of the pyrolysis tar can be obviously improved, and the hydro-pyrolysis cost is reduced; and the semi-coke is used as a catalyst for activating methane and carbon dioxide, the catalyst does not need to be recovered and separated from the product, the semi-coke is generated continuously during pyrolysis, and the problem of catalyst deactivation is avoided.
Description
Technical field
The invention belongs to energy technology field, relate to a kind of method improving coal microwave-heating tar yield with carbon dioxide for reacting gas with methane, the method can be applicable to coal microwave-heating and produces semicoke, tar and pyrolysis coal gas, especially can improve the tar yield in pyrolytic process.
Background technology
Coal pyrolysis refers to that the series of physical that coal occurs when being heated to higher temperature under inert atmosphere or isolation air conditions changes and chemical reaction.Compared with gasification or liquefaction process, pyrolytic process of coal is simple, and processing conditions is gentle, and small investment, production cost is low.Pyrolysis of coal can obtain liquid fuel and the industrial chemicals of product for the purpose of tar.Being pyrolyzed under inert atmosphere and isolation air conditions, tar yield is low；To improve pyrolysis of coal conversion ratio and the hydropyrolysis technique of tar yield, with hydrogen as reacting gas, process for making hydrogen is complicated, and equipment investment is big, and operating cost is high so that hydropyrolysis technology is difficult to industrialization.Methane is the main component of natural gas, coke-stove gas, coal bed gas, cheap, wide material sources, and H/C atomic ratio is high, is preferably to be pyrolyzed hydrogen source.But research finds, less than 800 DEG C, methane does not reacts with coal, can not improve tar yield, methane is equivalent to noble gas (periodical literature, Fuel in pyrolytic process, 1982,61:721), this is highly stable gas molecule mainly due to methane, is difficult to activate under the conditions of on-catalytic.Chinese invention patent 200510045853.8 discloses a kind of method improving pyrolysis of coal tar yield for reacting gas with methane, the method uses conventional heating mode, devise double-deck reactor, upper strata is catalyst, lower floor is coal seam, and methane first passes through catalyst layer catalytic pyrolysis with gaseous oxidant after mixing, enter back into coal seam, to pyrolysis of coal and coking, pyrolysis of coal tar yield can be improved.The deficiency of this invention is that structure of reactor is more complicated, needs load type metal catalyst, and the easy carbon distribution of catalyst inactivates；Pyrolytic reaction terminates rear catalyst to be needed to reclaim and regeneration, is unfavorable for serialization commercial production.
Summary of the invention
The purpose of the present invention provides a kind of method improving coal microwave-heating tar yield with carbon dioxide for reacting gas with methane just for the weak point in the presence of above-mentioned prior art.The method of the present invention is using methane and carbon dioxide gaseous mixture replacement pure hydrogen as reacting gas, to improve the new method of pyrolysis of coal tar yield.The method can reduce tradition hydropyrolysis cost；Used catalyst is the solid product semicoke of pyrolysis of coal, and catalyst directly mixes with coal, and reaction terminates rear catalyst without separating with product and reclaiming；Use microwave heating, the activity of catalyst can be improved.
It is an object of the invention to be realized by techniques below measure:
The present invention with methane and carbon dioxide be reacting gas improve the method for coal microwave-heating tar yield using methane that volume ratio is 50%～90% and 10%～50% carbon dioxide as reaction gas, pyrolysis reactor is entered after methane and carbon dioxide mix, semicoke (semicoke is as microwave absorption and catalyst) mixture copyrolysis under conditions of microwave heating temperature is 400～700 DEG C with the coal that the mass percent in reactor is 30-90% Yu 10-70%, constant temperature time 10～40min, pyrolysis devolatilization product (tar and water through) enters condenser system (B-grade condensation system) after leaving reactor and carries out gas-liquid separation, collect tar product.
Beneficial effects of the present invention is as follows:
The present invention utilizes semicoke for methane and carbon dioxide activated catalyst, and semicoke is the product of pyrolytic process itself, it is not necessary to separates with product and reclaims；Pyrolysis uses microwave heating, can improve the activity of catalyst, reduces catalytic reaction temperature；Utilize methane and carbon dioxide to substitute hydrogen for reacting gas and coal is carried out hydropyrolysis, tradition hydropyrolysis cost can be reduced, increase substantially the tar yield during pyrolysis of coal.
Detailed description of the invention
The present invention is further described below with reference to embodiment:
Embodiment 1
Raw coal and semicoke gross mass be 20g(semicoke addition be 70%), be sufficiently mixed in quartz reactor, reactor be placed in microwave oven pyrolysis；Flow is 0.5L/min methane and flow is to enter reactor after 0.5L/min carbon dioxide mix, be pyrolyzed final temperature 700 DEG C, be pyrolyzed constant temperature time 30min；Thermal decomposition product carries out gas-liquid separation through-25 DEG C of B-grade condensation systems, carries out oil-water separation according to GB/T 480-2010.Thus obtaining tar yield is 32.03%, and semi-coke yield is 24.97%.
Embodiment 2
Raw coal and semicoke gross mass 20g(semicoke addition 30%), quartz reactor is sufficiently mixed, reactor is placed in microwave oven pyrolysis, flow is 0.5L/min methane and flow is to enter reactor after 0.5L/min carbon dioxide mix, pyrolysis final temperature 700 DEG C, is pyrolyzed constant temperature time 30min；Thermal decomposition product carries out gas-liquid separation through-25 DEG C of B-grade condensation systems, carries out oil-water separation according to GB/T 480-2010.Thus obtaining tar yield is 17.14%, and char yeild is 58.59%.
Comparative example 1(is without methane and carbon dioxide)
Raw coal and semicoke gross mass be 20g(semicoke addition be 70%), be sufficiently mixed in quartz reactor, reactor be placed in microwave oven pyrolysis.N2 flow is that 1L/min(is without methane and carbon dioxide), it is pyrolyzed final temperature 700 DEG C, is pyrolyzed temperature retention time 30min.Thermal decomposition product carries out gas-liquid separation through-25 DEG C of B-grade condensation systems, carries out oil-water separation according to GB/T 480-2010.Thus obtaining tar yield is 9.35%, semi-coke yield 32.33%.
Comparative example 2(is without methane and carbon dioxide)
Raw coal and semicoke gross mass be 20g(semicoke addition be 30%), be sufficiently mixed in quartz reactor, reactor be placed in microwave oven pyrolysis.N2 flow is that 1L/min(is without methane and carbon dioxide), it is pyrolyzed final temperature 700 DEG C, is pyrolyzed temperature retention time 30min.Thermal decomposition product carries out gas-liquid separation through-25 DEG C of B-grade condensation systems, carries out oil-water separation according to GB/T 480-2010.Thus obtaining tar yield is 8.36%, semi-coke yield 59.78%.
Claims (1)
1. the method improving coal microwave-heating tar yield with carbon dioxide for reacting gas with methane, it is characterized in that: described method using methane that volume ratio is 50%～90% and 10%～50% carbon dioxide as reaction gas, pyrolysis reactor is entered after methane and carbon dioxide mix, semicoke mixture copyrolysis under conditions of microwave heating temperature is 400～700 DEG C with the coal that the mass percent in reactor is 30-90% Yu 10-70%, constant temperature time 10～40min, pyrolysis devolatilization product enters condenser system after leaving reactor and carries out gas-liquid separation, collect tar product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610539825.XA CN105925317A (en) | 2016-07-11 | 2016-07-11 | Method for improving yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases |
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| CN201610539825.XA CN105925317A (en) | 2016-07-11 | 2016-07-11 | Method for improving yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases |
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| CN201610539825.XA Pending CN105925317A (en) | 2016-07-11 | 2016-07-11 | Method for improving yield of coal microwave pyrolysis tar by using methane and carbon dioxide as reactant gases |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180273846A1 (en) * | 2017-03-24 | 2018-09-27 | Terrapower, Llc | Method and system for recycling pyrolysis tail gas through conversion into formic acid |
| US10787609B2 (en) | 2013-03-15 | 2020-09-29 | Terrapower, Llc | Method and system for performing thermochemical conversion of a carbonaceous feedstock to a reaction product |
| US10787610B2 (en) | 2017-04-11 | 2020-09-29 | Terrapower, Llc | Flexible pyrolysis system and method |
Citations (4)
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| CN1664069A (en) * | 2005-02-02 | 2005-09-07 | 大连理工大学 | Method for increasing tar yield of coalite pyrolysis with methane as reaction gas |
| CN101747922A (en) * | 2010-01-05 | 2010-06-23 | 大连理工大学 | Method for increasing yield of coal-pyrolysis-based tar in reaction atmosphere of methane-rich gas mixture in fluidized bed |
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2016
- 2016-07-11 CN CN201610539825.XA patent/CN105925317A/en active Pending
Patent Citations (4)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10787609B2 (en) | 2013-03-15 | 2020-09-29 | Terrapower, Llc | Method and system for performing thermochemical conversion of a carbonaceous feedstock to a reaction product |
| US11542437B2 (en) | 2013-03-15 | 2023-01-03 | Terrapower, Llc | Method and system for performing thermochemical conversion of a carbonaceous feedstock to a reaction product |
| US20180273846A1 (en) * | 2017-03-24 | 2018-09-27 | Terrapower, Llc | Method and system for recycling pyrolysis tail gas through conversion into formic acid |
| WO2018176026A1 (en) * | 2017-03-24 | 2018-09-27 | Terrapower, Llc | Method and system for recycling pyrolysis tail gas through conversion into formic acid |
| CN110461810A (en) * | 2017-03-24 | 2019-11-15 | 泰拉能源公司 | For recycling the method and system of pyrolysis tail gas by conversion formic acid |
| US10760004B2 (en) | 2017-03-24 | 2020-09-01 | Terrapower, Llc | Method for recycling pyrolysis tail gas through conversion into formic acid |
| CN110461810B (en) * | 2017-03-24 | 2022-05-13 | 泰拉能源公司 | Method and system for recycling pyrolysis tail gas by conversion to formic acid |
| US10787610B2 (en) | 2017-04-11 | 2020-09-29 | Terrapower, Llc | Flexible pyrolysis system and method |
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Application publication date: 20160907 |