CN104293403B - The system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction and technique - Google Patents
The system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction and technique Download PDFInfo
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Abstract
The invention belongs to the energy and chemical technology field, disclose system and the technique of the integrated carbonization gas methane of a kind of solid thermal carriers oil-shale eduction.Oil shale retorting unit that the system of the integrated carbonization gas methane of described solid thermal carriers oil-shale eduction includes being sequentially connected with, shale Oil-gas Separation unit, CO2Elimination unit, C1-C3Separative element and CO methanation unit.The present invention is by carbonization gas methanation by-product alkene, drastically increase the income of oil shale processing industry, the income relatively conventional solid heat carrier oil-shale eduction process adopting the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention improves about 9%, and total cost of production improves about 7%；Adopt C1-C3Order isolation technics, obtains chemical products alkene and the ethane of high value；Adopt low temperature methanation technology, obtain natural gas, decrease the pressure of natural gas shortage.
Description
Technical field
The invention belongs to the energy and chemical technology field, be specifically related to system and the technique of the integrated carbonization gas methane of a kind of solid thermal carriers oil-shale eduction.
Background technology
Along with the fast development of national economy, the demand of the energy is increased by people day by day.Oil can not meet the mankind as a kind of limited non-renewable energy to be continued and ever-increasing energy demand.And oil shale is as unconventional petroleum resources, its resource reserve enriches, and prior art ensure that the feasibility of its exploitation.According to statistics, China's oil shale reserves is converted to shale oil 47,600,000,000 tons, for 2 times of petroleum reserves.Greatly develop oil shale oil-refining technology to be conducive to alleviating China's oil resource supply and demand contradiction, provide practicable approach for realizing energy diversification.
Domestic industrialized oil shale retorting technology is gas heat carrier distillation process at present, mainly includes Fushun furnaceman's skill and gas complete alternation stove.Fushun furnace oil yield is generally relatively low, and only about 65%.It is primarily due in the coal gas of high temperature that stove gasification section produces and enters retort section containing a small amount of unreacting oxygen, the shale oil that a part of pyrolysis produces can be burnt.And in gas complete alternation stove, furnace bottom enters SAPMAC method gas, absorb semicoke sensible heat, no longer have air to enter.Additionally, gas complete alternation outlet of still oil gas is without oxygen, supporting condensate recovery system can adopt electric oil-trap, can improve oil yield further.Thus oil yield can reach about 90%.But, the heat needed for gas complete alternation furnace oil shale retorting, a part must be burnt by the carbonization gas of outsourcing and be supplemented, and limits the profit of this technique.
Ensureing that oil yield reaches more than 90%, how improving the economic performance of refining process further, Dalian University of Technology develops novel hot solid carrier devolatilization technique.The oily yield of this technique can reach 90%-96%, and oil shale utilization rate is up to 100%, and the water consumption of production process is little, and wastewater flow rate is few.It addition, shale oil recovery system adopts oil wash flow process, the distillate of shale oil can be directly obtained.Current Daqing oil field adopts big work hot solid carrier devolatilization technology, the commerical test device of built adult processing 600,000 t oil shale.This technology investment is little, and profit is big, utilizes lime-ash to be recycling as oil shale retorting as heat carrier and provides heat, and the discharge capacity of lime-ash is few, solves Fushun furnaceman's skill and gas complete alternation technique lime-ash is piled up, the problem such as contaminated environment and soil.
At present, the carbonization gas that big work hot solid carrier devolatilization obtains is mainly used in gas turbine power generation, and generating efficiency is relatively low, generally only has 32%-38%.But, the calorific value of the carbonization gas that big work hot solid carrier devolatilization obtains is higher, for 11-22MJ/m3.Iff for combustion power generation, reduce energy efficiency and the economic benefit of whole refining process undoubtedly；If being used for carbonization gas making some high-grade chemicals, so not only increasing energy efficiency and economic benefit, reducing carbonization gas burning CO simultaneously2Discharge serious problem.
Summary of the invention
In order to overcome shortcoming and the deficiency of prior art, the primary and foremost purpose of the present invention is in that to provide the system of the integrated carbonization gas methane of a kind of solid thermal carriers oil-shale eduction；
The technique that another object of the present invention is to provide the methane processed of the system adopting above-mentioned solid thermal carriers oil-shale eduction integrated carbonization gas methane.
The purpose of the present invention is achieved through the following technical solutions:
The system of the integrated carbonization gas methane of a kind of solid thermal carriers oil-shale eduction, including the oil shale retorting unit being sequentially connected with, shale Oil-gas Separation unit, CO2Elimination unit, C1-C3Separative element and CO methanation unit；
Described oil shale retorting unit is provided with the entrance passing into oil shale raw material, and the gas mixture outlet of oil shale retorting unit is connected by the gas mixture feed(raw material)inlet of pipeline with described shale Oil-gas Separation unit；The carbonization gas outlet of described shale Oil-gas Separation unit is by pipeline and described CO2The carbonization gas feed(raw material)inlet of elimination unit is connected；
Described CO2Elimination unit is provided with raw sorbent entrance, CO2The clean gas outlet of elimination unit is by pipeline and described C1-C3The purge gas feed(raw material)inlet of separative element is connected；C1-C3The C of separative element1The component outlet C by pipeline Yu described CO methanation unit1Feed(raw material)inlet is connected；CO methanation unit is provided with hydrogen feed entrance and methane outlet；
Preferably, described oil shale retorting unit comprises oil shale preheater, exsiccator and dry distillation reactor device；Described shale Oil-gas Separation unit comprises the first gas-solid separator, coal-char combustion device, the second gas-solid separator, heat exchanger, the first cooler, the first oil scrubber, the second cooler, the second oil scrubber, air cooler and gas-liquid separator；
Described oil shale preheater is provided with oil shale feed(raw material)inlet；Oil shale preheater, exsiccator and dry distillation reactor device are sequentially connected with by pipeline；Dry distillation reactor device is provided with the dry oil shale entrance of elimination surface water, and the gas mixture outlet of dry distillation reactor device is connected by the gas mixture entrance of pipeline and the first gas-solid separator；The gas mixture outlet of the first gas-solid separator is connected by the air-fuel mixture stream inlet of pipeline and the first oil scrubber；The washing gas outlet of the first oil scrubber is connected by the washing gas entrance of pipeline and the second oil scrubber；The washing gas outlet of the second oil scrubber is connected with the washing gas entrance of air cooler by pipeline；The cooling washing gas outlet of air cooler is connected with gas-liquid separator by pipeline；
The oil export of the first oil scrubber is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the first cooler, and another passage is product oil export；The washing oil export of the first cooler is connected by the washing oil-in of pipeline and the first oil scrubber；The oil export of the second oil scrubber is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the second cooler, and another passage is product oil export；The washing oil export of the second cooler is connected by the washing oil-in of pipeline and the second oil scrubber；
Coal-char combustion device is provided with preheated air entrance, the solid material inlet of coal-char combustion device is connected by the solid matter outlet of pipeline and the first gas-solid separator, and the gas-solid mixture outlet of coal-char combustion device is connected by the gas-solid mixture entrance of pipeline and the second gas-solid separator；The waste gas outlet of the second gas-solid separator is connected with the hot waste gas entrance of oil shale preheater by pipeline；The lime-ash outlet of the second gas-solid separator is divided into two passages, and a passage is connected with the heat carrier feed(raw material)inlet of dry distillation reactor device by pipeline, and another passage is connected with the air preheat feed(raw material)inlet of heat exchanger by pipeline；
Preferably, described CO2Elimination unit includes absorbing liquid pump, absorbing liquid cooler, absorption tower, rich solution pump, lean pump, lean-rich liquid heat exchanger, lean solution cooler, regenerator, regeneration gas condenser, separator and reboiler；
Described absorption liquid pump is provided with raw sorbent entrance, and the absorption liquid outlet absorbing liquid pump is connected with the absorption liquid entrance absorbing liquid cooler by pipeline, and the enfleurage of absorption liquid cooler is received fluid outlet and is connected with the enfleurage receipts liquid entrance on absorption tower by pipeline；Absorption tower is provided with carbonization gas entrance, is connected with the carbonization gas outlet of described shale Oil-gas Separation unit by pipeline；The rich solution outlet on absorption tower is connected with the rich solution entrance of rich solution pump by pipeline, the pressurization rich liquid stream outlet of rich solution pump is connected with the feed(raw material)inlet of lean-rich liquid heat exchanger by pipeline respectively with the lean fluid outlet that pressurizes of lean pump, the rich solution outlet of lean-rich liquid heat exchanger is connected with the rich solution entrance of regenerator by pipeline, and the lean solution outlet of lean-rich liquid heat exchanger is connected with the lean solution entrance of lean solution cooler by pipeline；The cold lean solution outlet of lean solution cooler is connected with the cold lean solution entrance on absorption tower by pipeline；The regeneration gas outlet of regenerator is connected with the regeneration gas import of regeneration gas condenser by pipeline, the cold renewal gas of regeneration gas condenser is connected with the stream inlet of separator by pipeline, and the condensate outlet of separator is connected with the condensate inlet of regenerator by pipeline；The tower base stream outlet of regenerator is connected with the stream inlet of reboiler by pipeline, and the steam (vapor) outlet of reboiler is connected with the steam inlet of regenerator by pipeline；
Preferably, described C1-C3Separative element includes the first compressor, domethanizing column, dethanizer and ethylene rectifying column；
First compressor is provided with purge gas entrance, by pipeline and CO2The clean gas outlet of elimination unit connects；The clean gas outlet of the first compressor is connected with the purge gas entrance of domethanizing column by pipeline；The C of domethanizing column1Component outlet is connected with CO methanation unit by pipeline；Domethanizing column elimination C1C after component2-C3Stream outlet is by the C of pipeline with dethanizer2-C3Stream inlet is connected；C after dethanizer elimination propylene2The component streams outlet C by pipeline Yu ethylene rectifying column2Stream inlet is connected；
Preferably, described CO methanation unit includes the second compressor, heater, methanator, water cooler, cooling water pump, drum and methane separation device；
Described second compressor is provided with C1Component and fresh hydrogen mixture inflow entrance, C1Component raw material pipeline and hydrogen feed pipeline are connected to the C of the second compressor after converging1Component and fresh hydrogen mixture inflow entrance；The mixture flow export of the second compressor is connected with the mixture inflow entrance of heater by pipeline, the hot mixt flow export of heater is connected with the stream inlet of methanator by pipeline, the product gas outlet of methanator is connected with the gas product entrance of water cooler by pipeline, and the product gas outlet of water cooler is connected with the gas product entrance of separator by pipeline；
Cooling water pump is provided with cooling water inlet, the pressure-raising coolant outlet of cooling water pump is connected with the cooling water inlet of drum by pipeline, the coolant outlet of drum is connected with the shell side cooling water inlet of methanator by pipeline, and the shell side steam (vapor) outlet of methanator is connected with the steam inlet of drum by pipeline.
The system adopting the integrated carbonization gas methane of above-mentioned solid thermal carriers oil-shale eduction prepares the technique of methane, comprises the steps:
Oil shale after crushing passes into oil shale retorting unit generation dry distillation reactor and obtains shale oil gas mixture and lime-ash, and lime-ash discharges system, and obtained shale oil gas mixture passes into the separation of shale Oil-gas Separation unit and obtains shale oil and carbonization gas；
Gained carbonization gas enters CO2Elimination unit, is purified gas and CO after being undertaken absorbing-resolve reaction by absorbent2；Gained purge gas is passed into C1-C3Separative element is easily separated and obtains C1Component and C2-C3Blending ingredients, C1Pass into CO methanation unit after component and hydrogen mixing and carry out methanation reaction, obtain gas product methane.
Preferably, described broken after oil shale particle diameter be not more than 10mm；
Preferably, in described oil shale retorting unit, the temperature of dry distillation reactor is 460～560 DEG C, and pressure is 0.1MPa；
It is furthermore preferred that the temperature of dry distillation reactor is 510 DEG C in described oil shale retorting unit；
Preferably, described absorbent is ethanolamine；
Preferably, described CO2The temperature carrying out absorption reaction in elimination unit is 25～50 DEG C, and pressure is 110～120kPa；Described CO2The temperature carrying out resolving reaction in elimination unit is 100～130 DEG C, and pressure is 101～110kPa；
It is furthermore preferred that described CO2The temperature carrying out absorption reaction in elimination unit is 40 DEG C, and pressure is 120kPa；Described CO2The temperature carrying out resolving reaction in elimination unit is 120 DEG C, and pressure is 103kPa；
Preferably, the temperature carrying out methanation reaction in described CO methanation unit is 250～350 DEG C, and pressure is 300～500kPa, and air speed is 5000～7000h-1；
It is furthermore preferred that the temperature carrying out methanation reaction in described CO methanation unit is 300 DEG C, pressure is 400kPa.
The present invention has such advantages as relative to prior art and effect:
(1) general carbonization gas is for combustion power generation, and generating efficiency is relatively low, is 32%～36%；The carbonization gas that additionally big work new distillation process technique produces, calorific value is significantly high, for 21.6MJ/m3.The present invention is by carbonization gas methanation by-product alkene, drastically increase the income of oil shale processing industry, the income relatively conventional solid heat carrier oil-shale eduction process adopting the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention improves about 9%, and total cost of production improves about 7%.
(2) present invention adopts MEA process to absorb CO in carbonization gas2, CO2Removal efficiency can reach 99%；Adopt C1-C3Order isolation technics, obtains chemical products alkene and the ethane of high value；Adopt low temperature methanation technology, obtain natural gas, decrease the pressure of natural gas shortage.
Accompanying drawing explanation
Fig. 1 is the process schematic representation of conventional solid heat carrier oil-shale eduction process.Wherein 1 is oil shale retorting unit, and 2 is shale Oil-gas Separation unit；3-7 is logistics numbering, and wherein 3 is oil shale, and 4 is shale oil gas mixture, and 5 is lime-ash, and 6 is shale oil, and 7 is carbonization gas.
Fig. 2 is the process schematic representation of the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention.Wherein 8 is CO2Elimination unit, 9 is C1-C3Separative element, 10 is CO methanation unit；11-17 is logistics numbering, and wherein 11 is absorbent, and 12 is purge gas, and 13 is CO2Product, 14 is C1Component, 15 is C2-C3Blending ingredients, 16 is hydrogen, and 17 is methane.
Fig. 3 is the specific embodiment figure of oil shale retorting unit 1 and shale Oil-gas Separation unit 2 in system of the present invention.Wherein 73 is oil shale preheater, and 74 is exsiccator, and 75 is dry distillation reactor device, 76 is the first gas-solid separator, 84 is coal-char combustion device, and 85 is the second gas-solid separator, and 86 is heat exchanger, 77 is the first cooler, 78 is the first oil scrubber, and 79 is the second cooler, and 80 is the second oil scrubber, 81 is air cooler, and 82 is gas-liquid separator；18-42 is logistics numbering, wherein 18 is hot waste gas, 19 is preheating oil shale, 20 is discharge waste gas, 21 is dry oil shale, 22 is appearance moisture content, 23 is circulation lime-ash, 24 is shale oil-carbonization gas mixture, 25 is solids stream, 26 is SAPMAC method heavy oil, 27 is heavy oil at the bottom of tower, 28 is circulation heavy oil, 29 is the first shale oil, 30 attach most importance to separating of oil gas mixture, 31 is SAPMAC method light oil, 32 is light oil at the bottom of tower, 33 is circulation light oil, 34 is the second shale oil, 35 is light oil separation oil and gas mixture, 36 is air cooling gas mixture, 37 is page 3 rock oil, 38 is fresh air, 39 is preheated air, 40 is gas slag mixture, 41 is total lime-ash, 42 is discharge lime-ash.The logistics that all the other numberings are identical with same reference numeral in Fig. 1.
Fig. 4 is CO in system of the present invention2The process chart of elimination unit.Wherein 87 for absorbing liquid pump, and 88 for absorbing liquid cooler, and 89 is absorption tower, and 90 is rich solution pump, and 91 is lean pump, and 92 is lean-rich liquid heat exchanger, and 93 is lean solution cooler, and 94 is regenerator, and 95 is regeneration gas condenser, and 96 is separator, and 97 is reboiler；44-56 is logistics numbering, and wherein, 44 is cold absorbent, and 45 is cold lean solution, and 46 is rich solution, and 48 is lean solution, and 50 is heat exchange rich solution, and 51 is absorbent condensed fluid, and 52 is rich solution steam, and 53 is regeneration gas, 55 lean solutions, and 56 is regenerator rich solution.The logistics that all the other numberings are identical with same reference numeral in Fig. 2.
Fig. 5 is C in system of the present invention1-C3The process chart of separative element.Wherein 98 is the first compressor, and 99 is domethanizing column, and 100 is dethanizer, and 101 is ethylene rectifying column；57-61 is logistics numbering, and wherein 57 is pressurized purge gas, and 58 is C2Component, 59 is propylene product, and 60 is ethylene product, and 61 is ethane product.All the other number logistics identical with same reference numeral in Fig. 2.
Fig. 6 is CO methanation unit process chart in system of the present invention.Wherein 102 is the second compressor, and 103 is heater, and 104 is methanator, and 105 is water cooler, and 106 is cooling water pump, and 107 is drum, and 108 is methane separation device；62-72 is logistics numbering, and wherein 62 is methanation mixing gas, and 65 cool down water for drum, and 66 is gas product, and 67 is steam, and 68 is cooling water, and 72 for separating water.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Solid thermal carriers oil-shale eduction system of the prior art, including oil shale retorting unit 1 and shale Oil-gas Separation unit 2, process schematic representation is as shown in Figure 1.Oil shale 3 after break process passes into oil shale retorting unit 1 and carries out dry distillation reactor, obtains lime-ash 5 and shale oil gas mixture 4, and lime-ash 5 is discharged, and shale oil gas mixture 4 passes into shale Oil-gas Separation unit 2 and is easily separated and obtains shale oil 6 and carbonization gas 7.
Embodiment 1
The system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention, including the oil shale retorting unit 1 being sequentially connected with, shale Oil-gas Separation unit 2, CO2Elimination unit 8, C1-C3Separative element 9 and CO methanation unit 10；
Described oil shale retorting unit 1 is provided with the entrance passing into oil shale raw material, and the gas mixture outlet of oil shale retorting unit 1 is connected by the gas mixture feed(raw material)inlet of pipeline with described shale Oil-gas Separation unit 2；The carbonization gas outlet of described shale Oil-gas Separation unit 2 is by pipeline and described CO2The carbonization gas feed(raw material)inlet of elimination unit 8 is connected；
Described CO2Elimination unit 8 is provided with raw sorbent entrance, CO2The clean gas outlet of elimination unit 8 is by pipeline and described C1-C3The purge gas feed(raw material)inlet of separative element 9 is connected；C1-C3The C of separative element 91The component outlet C by pipeline Yu described CO methanation unit 101Feed(raw material)inlet is connected；CO methanation unit 10 is provided with hydrogen feed entrance and methane outlet.
The system adopting the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention prepares the technique of methane, and process schematic representation is as in figure 2 it is shown, specifically include following steps:
Oil shale 3 after crushing passes into oil shale retorting unit 1 and occurs dry distillation reactor to obtain shale oil gas mixture 4 and lime-ash 5, and lime-ash 5 discharges system, and obtained shale oil gas mixture 4 passes into the separation of shale Oil-gas Separation unit 2 and obtains shale oil 6 and carbonization gas 7；
Gained carbonization gas 7 enters CO2Elimination unit 8, is purified gas 12 and CO after being undertaken absorbing-resolve reaction by absorbent 112Product 13；Gained purge gas 12 is passed into C1-C3Separative element 9 is easily separated and obtains C1Component 14 and C2-C3Blending ingredients 15, C1Pass into CO methanation unit 10 after component 14 and hydrogen 16 mixing and carry out methanation reaction, obtain gas product methane 17.
Contrasted from the system of solid thermal carriers oil-shale eduction system of the prior art with the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention, carbonization gas is separated methane processed and by-product alkene by system of the present invention, it is achieved that the utilization of resource high-efficiency economy.
In the system of solid thermal carriers oil-shale eduction of the present invention integrated carbonization gas methane, the concrete equipment of oil shale retorting unit 1 and shale Oil-gas Separation unit 2 and technical process are as shown in Figure 3:
Described oil shale retorting unit comprises oil shale preheater 73, exsiccator 74 and dry distillation reactor device 75；Described shale Oil-gas Separation unit comprises the first gas-solid separator 76, coal-char combustion device the 84, second gas-solid separator 85, heat exchanger the 86, first cooler the 77, first oil scrubber the 78, second cooler the 79, second oil scrubber 80, air cooler 81 and gas-liquid separator 82；
Described oil shale preheater 73 is provided with oil shale feed(raw material)inlet；Oil shale preheater 73, exsiccator 74 and dry distillation reactor device 75 are sequentially connected with by pipeline；Dry distillation reactor device 75 is provided with the dry oil shale entrance of elimination surface water, and the gas mixture outlet of dry distillation reactor device 75 is connected by the gas mixture entrance of pipeline and the first gas-solid separator 76；The gas mixture outlet of the first gas-solid separator 76 is connected by the air-fuel mixture stream inlet of pipeline and the first oil scrubber 78；The washing gas outlet of the first oil scrubber 78 is connected by the washing gas entrance of pipeline and the second oil scrubber 80；The washing gas outlet of the second oil scrubber 80 is connected with the washing gas entrance of air cooler 81 by pipeline；The cooling washing gas outlet of air cooler 81 is connected with gas-liquid separator 82 by pipeline；
The oil export of the first oil scrubber 78 is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the first cooler 77, and another passage is product oil export；The washing oil export of the first cooler 77 is connected by the washing oil-in of pipeline and the first oil scrubber 78；The oil export of the second oil scrubber 80 is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the second cooler 79, and another passage is product oil export；The washing oil export of the second cooler 79 is connected by the washing oil-in of pipeline and the second oil scrubber 80；
Coal-char combustion device 84 is provided with preheated air entrance, the solid material inlet of coal-char combustion device 84 is connected by the solid matter outlet of pipeline and the first gas-solid separator 76, and the gas-solid mixture outlet of coal-char combustion device 84 is connected by the gas-solid mixture entrance of pipeline and the second gas-solid separator 85；The waste gas outlet of the second gas-solid separator 85 is connected with the hot waste gas entrance of oil shale preheater 73 by pipeline；The lime-ash outlet of the second gas-solid separator 85 is divided into two passages, and a passage is connected with the heat carrier feed(raw material)inlet of dry distillation reactor device 75 by pipeline, and another passage is connected with the air preheat feed(raw material)inlet of heat exchanger 86 by pipeline；
Concrete technology flow process is:
Oil shale 3 after crushing preheats through oil shale preheater 73, after preheating oil shale 19 drying device 74 removes appearance moisture content 22, the dry oil shale 21 of elimination surface water enters dry distillation reactor device 75, carries out dry distillation reactor and generates the shale oil gas mixture 4 containing shale oil, carbonization gas and semicoke；Shale oil gas mixture 4 enters the first gas-solid separator 76 and is separated into shale oil-carbonization gas mixture 24 and the solids stream 25 containing inorganic mineral and semicoke；
Shale oil-carbonization gas mixture 24 washs separation through the first oil scrubber 78 and obtains heavy oil 27 at the bottom of heavy oil separation oil and gas mixture 30 and tower；Heavy oil 27 at the bottom of tower is divided into circulation heavy oil 28 and the first shale oil 29, and circulation heavy oil 28 forms SAPMAC method heavy oil 26 after the first cooler 77 cooling and returns to the first oil scrubber 78；Heavy oil separation oil and gas mixture 30 enters the second oil scrubber 80 and washs separation and obtain light oil 32 at the bottom of light oil separation oil and gas mixture 35 and tower；Light oil 32 at the bottom of tower is divided into circulation light oil 33 and the second shale oil 34, and circulation light oil 33 forms SAPMAC method light oil 31 after the second cooler 79 cooling and returns to the second oil scrubber 80；Light oil separation oil and gas mixture 35 forms air cooling gas mixture 36 after air cooler 81 cools down, and air cooling gas mixture 36 enters gas-liquid separator 82 separation and obtains carbonization gas 7 and page 3 rock oil 37；
Shale oil 6 is obtained after first shale oil the 29, second shale oil 34 and the blended device mixing of page 3 rock oil 37；
Fresh air 38 enters heat exchanger 86 to carry out preheating and obtains preheated air 39, and preheated air 39 passes into coal-char combustion device；Solids stream 25 enters coal-char combustion device 84 and preheated air 39 mixed combustion, gas slag mixture 40 after burning enters the second gas-solid separator 85 and obtains hot waste gas 18 and total lime-ash 41, and hot waste gas 18 enters and discharges outside system as discharge waste gas 20 after oil shale preheater provides heat；Total lime-ash 41 is divided into circulation lime-ash 23 and discharge lime-ash 42, and circulation lime-ash 23 is passed directly to dry distillation reactor device 75, provides heat for oil shale retorting, and discharge lime-ash 42 provides heat for heat exchanger 86, obtains lime-ash 5 and discharges system；
In described dry distillation reactor device, the temperature of dry distillation reactor is 60～560 DEG C, and pressure is 0.1MPa；Preferably, the temperature of described dry distillation reactor is 510 DEG C.
CO in the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention2The elimination concrete equipment of unit 8 and technical process be as shown in Figure 4:
Described CO2Elimination unit 8 includes absorbing liquid pump 87, absorbing liquid cooler 88, absorption tower 89, rich solution pump 90, lean pump 91, lean-rich liquid heat exchanger 92, lean solution cooler 93, regenerator 94, regeneration gas condenser 95, separator 96 and reboiler 97；
Described absorption liquid pump 87 is provided with raw sorbent entrance, the absorption liquid outlet absorbing liquid pump 87 is connected with the absorption liquid entrance absorbing liquid cooler 88 by pipeline, and the enfleurage of absorption liquid cooler 88 is received fluid outlet and is connected with the enfleurage receipts liquid entrance on absorption tower 89 by pipeline；Absorption tower 89 is provided with carbonization gas entrance, is connected with the carbonization gas outlet of described shale Oil-gas Separation unit 2 by pipeline；The rich solution outlet on absorption tower 89 is connected with the rich solution entrance of rich solution pump 90 by pipeline, the pressurization rich liquid stream outlet of rich solution pump 90 is connected with the feed(raw material)inlet of lean-rich liquid heat exchanger 92 by pipeline respectively with the lean fluid outlet that pressurizes of lean pump 91, the rich solution outlet of lean-rich liquid heat exchanger 92 is connected with the rich solution entrance of regenerator 94 by pipeline, and the lean solution outlet of lean-rich liquid heat exchanger 92 is connected with the lean solution entrance of lean solution cooler 93 by pipeline；The cold lean solution outlet of lean solution cooler 93 is connected with the cold lean solution entrance on absorption tower 89 by pipeline；The regeneration gas outlet of regenerator 94 is connected with the regeneration gas import of regeneration gas condenser 95 by pipeline, the cold renewal gas of regeneration gas condenser 95 is connected by the stream inlet of pipeline with separator 96, and the condensate outlet of separator 96 is connected by the condensate inlet of pipeline with regenerator 94；The tower base stream outlet of regenerator 94 is connected by the stream inlet of pipeline with reboiler 97, and the steam (vapor) outlet of reboiler 97 is connected by the steam inlet of pipeline with regenerator 94；
Concrete technology includes as follows:
Carbonization gas 7 is entered by the bottom of the tower on absorption tower 89；Absorbent 11 entrance absorption liquid cooler 88 after absorbing liquid pump 87 pressurization carries out cooling and obtains cold absorbent 44, and cold absorbent 44 is entered absorption tower 89 by tower top；By regenerator 94 lean solution 55 out through lean pump 91 pressure-raising, obtaining cold lean solution 45 after cooling down then through lean-rich liquid heat exchanger 92 and lean solution cooler 93, cold lean solution 45 is entered absorption tower 89 by tower top；Carbonization gas 7, cold absorbent 44 and cold lean solution 45 react in absorption tower 89, and reacted purge gas 12 is gone out from absorption tower 89 tower top, enter C1-C3Separative element；Rich solution 46 out at the bottom of the tower of absorption tower 89 is sent to lean-rich liquid heat exchanger 92 through rich solution pump 90 to carry out heat exchange and obtains heat exchange rich solution 50, heat exchange rich solution 50 enters regenerator 94 from tower top, regenerator rich solution 56 is heated by the reboiler 97 at the bottom of regenerator 94 tower, completes absorbent and CO2Separation；Lean solution 55 is discharged at the bottom of regenerator 94 tower；Regenerator 94 tower top outlet is discharged containing absorbing liquid and CO2Regeneration gas 53, regeneration gas 53 through regeneration gas condenser 95 condensation and separator 96 separate after obtain the CO that purity is more than 99%2Product 13, separator 96 separates the absorbent condensed fluid 51 containing absorbent and water obtained and is entered regenerator 94 by tower top.
Preferably, described CO2In elimination unit, the temperature in absorption tower 89 is 25～50 DEG C, and pressure is 110～120kPa；Temperature in regenerator 94 is 100～130 DEG C, and pressure is 101～110kPa；
It is furthermore preferred that the temperature in described absorption tower 89 is 40 DEG C, pressure is 120kPa；Temperature in regenerator 94 is 120 DEG C, and pressure is 103kPa.
C in the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention1-C3The concrete equipment of separative element 9 and technical process be as shown in Figure 5:
Described C1-C3Separative element 9 includes the first compressor 98, domethanizing column 99, dethanizer 100 and ethylene rectifying column 101；
First compressor 98 is provided with purge gas entrance, by pipeline and CO2The clean gas outlet of elimination unit 8 connects；The clean gas outlet of the first compressor 98 is connected with the purge gas entrance of domethanizing column 99 by pipeline；Domethanizing column 99 removes C1C after component2-C3Stream outlet is by the C of pipeline with dethanizer 1002-C3Stream inlet is connected；Dethanizer 100 removes the C after propylene2The component streams outlet C by pipeline Yu ethylene rectifying column 1012Stream inlet is connected；
Concrete technology includes as follows:
Elimination CO2After purge gas 12 compress through compressor 98, the pressurized purge gas 57 after compression enters domethanizing column 99, C1Component 14 is gone out from tower top, enters CO methanation unit 10；C at the bottom of tower2-C3Blending ingredients 15 enters dethanizer 100 and reacts, and obtains C2Component 58 and propylene product 59；C2Component 58 is discharged by dethanizer 100 tower top, enters ethylene rectifying column 101 and reacts；Ethylene rectifying column 101 tower top obtains ethylene product 60, obtains ethane product 61 at the bottom of tower.
In the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention, the concrete equipment of CO methanation unit 10 and technical process are as shown in Figure 6:
Described CO methanation unit 10 includes the second compressor 102, heater 103, methanator 104, water cooler 105, cooling water pump 106, drum 107 and methane separation device 108；
Described second compressor is provided with C1Component and fresh hydrogen mixture inflow entrance, C1Component raw material pipeline and hydrogen feed pipeline are connected to the C of the second compressor after converging1Component and fresh hydrogen mixture inflow entrance；The mixture flow export of the second compressor is connected with the mixture inflow entrance of heater by pipeline, the hot mixt flow export of heater is connected with the stream inlet of methanator by pipeline, the product gas outlet of methanator is connected with the gas product entrance of water cooler by pipeline, and the product gas outlet of water cooler is connected with the gas product entrance of separator by pipeline；
Cooling water pump is provided with cooling water inlet, the pressure-raising coolant outlet of cooling water pump is connected with the cooling water inlet of drum by pipeline, the coolant outlet of drum is connected with the shell side cooling water inlet of methanator by pipeline, and the shell side steam (vapor) outlet of methanator is connected with the steam inlet of drum by pipeline.
Concrete technology includes as follows:
C1Methanation mixing gas 62 is obtained after component 14 and hydrogen 16 mixing；Methanation mixing gas 62 compresses through compressor 102, enters methanator 104 and carry out methanation reaction after heating then through heater 103；The gas product 66 containing methane that methanation reaction obtains, after being cooled down by water cooled for gas product 66 device 105, enters separator 108 separation and obtains methane 17 and separate water 72；The heat produced in methanation is cooled down water 65 by the drum from drum 107 and absorbs heat, and produces steam 67, takes away heat；
From outside cooling water 68 by entering drum 107 after cooling water pump 106 pressurization, the water yield regulates valve by liquid level of steam drum and is controlled；The steam 67 that methanator 104 obtains enters drum 107, and steam pressure passes through drum pressure governor valve control；Drum cooling water 65 carries out methanator 104 and cools down；Byproduct steam 70 can send into steam pipe system；
In described CO methanation unit 10, the reaction temperature of methanator 104 is 250～350 DEG C, and pressure is 300～500kPa, and air speed is 5000-7000h-1；Preferably, described methanation reaction temperature is 300 DEG C, and pressure is 400kPa.In methanation reaction, CO conversion ratio can reach to 100%.
Embodiment 2
Being embodied as of the system of solid thermal carriers oil-shale eduction of the present invention integrated carbonization gas methane is as follows:
Oil shale retorting unit 1 that the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction of the present invention includes being sequentially connected with, shale Oil-gas Separation unit 2, CO2Elimination unit 8, C1-C3Separative element 9 and CO methanation unit 10.The concrete equipment of each process section is as described in Example 1.
The material flow entering system of the present invention is 418t/h, and fresh absorbent flow is 0.03t/h, and fresh hydrogen flow is 0.012t/h.The Industrial Analysis of oil shale and elementary analysis are in Table 1, and the composition of carbonization gas is in Table 2, and process chart is Fig. 2 such as.
The Industrial Analysis of table 1 oil shale and elementary analysis
(in table, M, FC, V, and A represent the content of moisture in oil shale, fixed carbon, volatile matter and ash respectively, and ar represents that As-received, ad represent air-dried basis, and wt represents mass fraction).
The composition (mol%) of table 2 carbonization gas
| CH4 | CO | H2 | CO2 | C2H4 | C2H6 | C3H6 | Low heat value (MJ/m3) 8 --> |
| 19.23 | 8.17 | 24.08 | 33.38 | 4.8 | 5.09 | 5.25 | 21.62 |
The specific embodiment of oil-shale eduction is:
Oil shale 3 after crushing preheats through oil shale preheater 73, after preheating oil shale 19 drying device 74 removes appearance moisture content 22, the dry oil shale 21 of elimination surface water enters dry distillation reactor device 75, carries out dry distillation reactor and generates the shale oil gas mixture 4 containing shale oil, carbonization gas and semicoke；Shale oil gas mixture 4 enters the first gas-solid separator 76 and is separated into shale oil-carbonization gas mixture 24 and the solids stream 25 containing inorganic mineral and semicoke；
Shale oil-carbonization gas mixture 24 washs separation through the first oil scrubber 78 and obtains heavy oil 27 at the bottom of heavy oil separation oil and gas mixture 30 and tower；Heavy oil 27 at the bottom of tower is divided into circulation heavy oil 28 and the first shale oil 29, and circulation heavy oil 28 forms SAPMAC method heavy oil 26 after the first cooler 77 cooling and returns to the first oil scrubber 78；Heavy oil separation oil and gas mixture 30 enters the second oil scrubber 80 and washs separation and obtain light oil 32 at the bottom of light oil separation oil and gas mixture 35 and tower；Light oil 32 at the bottom of tower is divided into circulation light oil 33 and the second shale oil 34, and circulation light oil 33 forms SAPMAC method light oil 31 after the second cooler 79 cooling and returns to the second oil scrubber 80；Light oil separation oil and gas mixture 35 forms air cooling gas mixture 36 after air cooler 81 cools down, and air cooling gas mixture 36 enters gas-liquid separator 82 separation and obtains carbonization gas 7 and page 3 rock oil 37；
Shale oil 6 is obtained after first shale oil the 29, second shale oil 34 and the blended device mixing of page 3 rock oil 37；
Fresh air 38 enters heat exchanger 86 to carry out preheating and obtains preheated air 39, and preheated air 39 passes into coal-char combustion device；Solids stream 25 enters coal-char combustion device 84 and preheated air 39 mixed combustion, gas slag mixture 40 after burning enters the second gas-solid separator 85 and obtains hot waste gas 18 and total lime-ash 41, and hot waste gas 18 enters and discharges outside system as discharge waste gas 20 after oil shale preheater provides heat；Total lime-ash 41 is divided into circulation lime-ash 23 and discharge lime-ash 42, and circulation lime-ash 23 is passed directly to dry distillation reactor device 75, provides heat for oil shale retorting, and discharge lime-ash 42 provides heat for heat exchanger 86, obtains lime-ash 5 and discharges system；
In described dry distillation reactor device, the temperature of dry distillation reactor is 510 DEG C, and pressure is 0.1MPa.
CO2The specific embodiment of elimination unit 8 is:
Carbonization gas 7 is entered by the bottom of the tower on absorption tower 89；Absorbent 11 entrance absorption liquid cooler 88 after absorbing liquid pump 87 pressurization carries out cooling and obtains cold absorbent 44, and cold absorbent 44 is entered absorption tower 89 by tower top；By regenerator 94 lean solution 55 out through lean pump 91 pressure-raising, obtaining cold lean solution 45 after cooling down then through lean-rich liquid heat exchanger 92 and lean solution cooler 93, cold lean solution 45 is entered absorption tower 89 by tower top；Carbonization gas 7, cold absorbent 44 and cold lean solution 45 react in absorption tower 89, and reacted purge gas 12 is gone out from absorption tower 89 tower top, enter C1-C3Separative element；Rich solution 46 out at the bottom of the tower of absorption tower 89 is sent to lean-rich liquid heat exchanger 92 through rich solution pump 90 to carry out heat exchange and obtains heat exchange rich solution 50, heat exchange rich solution 50 enters regenerator 94 from tower top, regenerator rich solution 56 is heated by the reboiler 97 at the bottom of regenerator 94 tower, completes absorbent and CO2Separation；Lean solution 55 is discharged at the bottom of regenerator 94 tower；Regenerator 94 tower top outlet is discharged containing absorbing liquid and CO2Regeneration gas 53, regeneration gas 53 through regeneration gas condenser 95 condensation and separator 96 separate after obtain the CO that purity is more than 99%2Product 13, separator 96 separates the absorbent condensed fluid 51 containing absorbent and water obtained and is entered regenerator 94 by tower top；
Described CO2In elimination unit, the temperature in absorption tower 89 is 40 DEG C, and pressure is 120kPa；Temperature in regenerator 94 is 120 DEG C, and pressure is 103kPa.
C1-C3The specific embodiment of separative element 9 is:
Elimination CO2After purge gas 12 compress through compressor 98, the pressurized purge gas 57 after compression enters domethanizing column 99, C1Component 14 is gone out from tower top, enters CO methanation unit 10；C at the bottom of tower2-C3Blending ingredients 15 enters dethanizer 100 and reacts, and obtains C2Component 58 and propylene product 59；C2Component 58 is discharged by dethanizer 100 tower top, enters ethylene rectifying column 101 and reacts；Ethylene rectifying column 101 tower top obtains ethylene product 60, obtains ethane product 61 at the bottom of tower.
The specific embodiment of CO methanation unit 10 is:
C1Methanation mixing gas 62 is obtained after component 14 and hydrogen 16 mixing；Methanation mixing gas 62 compresses through compressor 102, enters methanator 104 and carry out methanation reaction after heating then through heater 103；The gas product 66 containing methane that methanation reaction obtains, after being cooled down by water cooled for gas product 66 device 105, enters separator 108 separation and obtains methane 17 and separate water 72；The heat produced in methanation is cooled down water 65 by the drum from drum 107 and absorbs heat, and produces steam 67, takes away heat；
From outside cooling water 68 by entering drum 107 after cooling water pump 106 pressurization, the water yield regulates valve by liquid level of steam drum and is controlled；The steam 67 that methanator 104 obtains enters drum 107, and steam pressure passes through drum pressure governor valve control；Drum cooling water 65 carries out methanator 104 and cools down；Byproduct steam 70 can send into steam pipe system；
In described CO methanation unit 10, the reaction temperature of methanator 104 is 300 DEG C, and pressure is 400kPa, and air speed is 6000h-1；In methanation reaction, CO conversion ratio can reach 100%.
Comparing existing solid thermal carriers oil-shale eduction process, the new method oil-shale eduction process of the bigger work of income of the system of solid thermal carriers oil-shale eduction of the present invention integrated carbonization gas methane improves about 9%, and total cost of production improves about 7%.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. the technique that the system adopting the integrated carbonization gas methane of solid thermal carriers oil-shale eduction prepares methane, it is characterised in that: oil shale retorting unit that the system of the integrated carbonization gas methane of described solid thermal carriers oil-shale eduction includes being sequentially connected with, shale Oil-gas Separation unit, CO2Elimination unit, C1-C3Separative element and CO methanation unit；
Described oil shale retorting unit is provided with the entrance passing into oil shale raw material, and the gas mixture outlet of oil shale retorting unit is connected by the gas mixture feed(raw material)inlet of pipeline with described shale Oil-gas Separation unit；The carbonization gas outlet of described shale Oil-gas Separation unit is by pipeline and described CO2The carbonization gas feed(raw material)inlet of elimination unit is connected；Described CO2Elimination unit is provided with raw sorbent entrance, CO2The clean gas outlet of elimination unit is by pipeline and described C1-C3The purge gas feed(raw material)inlet of separative element is connected；C1-C3The C of separative element1The component outlet C by pipeline Yu described CO methanation unit1Feed(raw material)inlet is connected；CO methanation unit is provided with hydrogen feed entrance and methane outlet；
Described oil shale retorting unit comprises oil shale preheater, exsiccator and dry distillation reactor device；Described shale Oil-gas Separation unit comprises the first gas-solid separator, coal-char combustion device, the second gas-solid separator, heat exchanger, the first cooler, the first oil scrubber, the second cooler, the second oil scrubber, air cooler and gas-liquid separator；
Described oil shale preheater is provided with oil shale feed(raw material)inlet；Oil shale preheater, exsiccator and dry distillation reactor device are sequentially connected with by pipeline；Dry distillation reactor device is provided with the dry oil shale entrance of elimination surface water, and the gas mixture outlet of dry distillation reactor device is connected by the gas mixture entrance of pipeline and the first gas-solid separator；The gas mixture outlet of the first gas-solid separator is connected by the air-fuel mixture stream inlet of pipeline and the first oil scrubber；The washing gas outlet of the first oil scrubber is connected by the washing gas entrance of pipeline and the second oil scrubber；The washing gas outlet of the second oil scrubber is connected with the washing gas entrance of air cooler by pipeline；The cooling washing gas outlet of air cooler is connected with gas-liquid separator by pipeline；
The oil export of the first oil scrubber is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the first cooler, and another passage is product oil export；The washing oil export of the first cooler is connected by the washing oil-in of pipeline and the first oil scrubber；The oil export of the second oil scrubber is divided into two passages, and a passage is connected by the washing oil-in of pipeline and the second cooler, and another passage is product oil export；The washing oil export of the second cooler is connected by the washing oil-in of pipeline and the second oil scrubber；
Coal-char combustion device is provided with preheated air entrance, the solid material inlet of coal-char combustion device is connected by the solid matter outlet of pipeline and the first gas-solid separator, and the gas-solid mixture outlet of coal-char combustion device is connected by the gas-solid mixture entrance of pipeline and the second gas-solid separator；The waste gas outlet of the second gas-solid separator is connected with the hot waste gas entrance of oil shale preheater by pipeline；The lime-ash outlet of the second gas-solid separator is divided into two passages, and a passage is connected with the heat carrier feed(raw material)inlet of dry distillation reactor device by pipeline, and another passage is connected with the air preheat feed(raw material)inlet of heat exchanger by pipeline；
Described CO2Elimination unit includes absorbing liquid pump, absorbing liquid cooler, absorption tower, rich solution pump, lean pump, lean-rich liquid heat exchanger, lean solution cooler, regenerator, regeneration gas condenser, separator and reboiler；
Described absorption liquid pump is provided with raw sorbent entrance, and the absorption liquid outlet absorbing liquid pump is connected with the absorption liquid entrance absorbing liquid cooler by pipeline, and the enfleurage of absorption liquid cooler is received fluid outlet and is connected with the enfleurage receipts liquid entrance on absorption tower by pipeline；Absorption tower is provided with carbonization gas entrance, is connected with the carbonization gas outlet of described shale Oil-gas Separation unit by pipeline；The rich solution outlet on absorption tower is connected with the rich solution entrance of rich solution pump by pipeline, the pressurization rich liquid stream outlet of rich solution pump is connected with the feed(raw material)inlet of lean-rich liquid heat exchanger by pipeline respectively with the lean fluid outlet that pressurizes of lean pump, the rich solution outlet of lean-rich liquid heat exchanger is connected with the rich solution entrance of regenerator by pipeline, and the lean solution outlet of lean-rich liquid heat exchanger is connected with the lean solution entrance of lean solution cooler by pipeline；The cold lean solution outlet of lean solution cooler is connected with the cold lean solution entrance on absorption tower by pipeline；The regeneration gas outlet of regenerator is connected with the regeneration gas import of regeneration gas condenser by pipeline, the cold renewal gas of regeneration gas condenser is connected with the stream inlet of separator by pipeline, and the condensate outlet of separator is connected with the condensate inlet of regenerator by pipeline；The tower base stream outlet of regenerator is connected with the stream inlet of reboiler by pipeline, and the steam (vapor) outlet of reboiler is connected with the steam inlet of regenerator by pipeline；
Described C1-C3Separative element includes the first compressor, domethanizing column, dethanizer and ethylene rectifying column；
First compressor is provided with purge gas entrance, by pipeline and CO2The clean gas outlet of elimination unit connects；The clean gas outlet of the first compressor is connected with the purge gas entrance of domethanizing column by pipeline；The C of domethanizing column1Component outlet is connected with CO methanation unit by pipeline；Domethanizing column elimination C1C after component2-C3Stream outlet is by the C of pipeline with dethanizer2-C3Stream inlet is connected；C after dethanizer elimination propylene2The component streams outlet C by pipeline Yu ethylene rectifying column2Stream inlet is connected；
Described CO methanation unit includes the second compressor, heater, methanator, water cooler, cooling water pump, drum and methane separation device；
Described second compressor is provided with C1Component and fresh hydrogen mixture inflow entrance, C1Component raw material pipeline and hydrogen feed pipeline are connected to the C of the second compressor after converging1Component and fresh hydrogen mixture inflow entrance；The mixture flow export of the second compressor is connected with the mixture inflow entrance of heater by pipeline, the hot mixt flow export of heater is connected with the stream inlet of methanator by pipeline, the product gas outlet of methanator is connected with the gas product entrance of water cooler by pipeline, and the product gas outlet of water cooler is connected with the gas product entrance of separator by pipeline；
Cooling water pump is provided with cooling water inlet, the pressure-raising coolant outlet of cooling water pump is connected with the cooling water inlet of drum by pipeline, the coolant outlet of drum is connected with the shell side cooling water inlet of methanator by pipeline, and the shell side steam (vapor) outlet of methanator is connected with the steam inlet of drum by pipeline；
The described technique preparing methane comprises the steps:
Oil shale after crushing passes into oil shale retorting unit generation dry distillation reactor and obtains shale oil gas mixture and lime-ash, and lime-ash discharges system, and obtained shale oil gas mixture passes into the separation of shale Oil-gas Separation unit and obtains shale oil and carbonization gas；Gained carbonization gas enters CO2Elimination unit, is purified gas and CO after being undertaken absorbing-resolve reaction by absorbent2；Gained purge gas is passed into C1-C3Separative element is easily separated and obtains C1Component and C2-C3Blending ingredients, C1Pass into CO methanation unit after component and hydrogen mixing and carry out methanation reaction, obtain gas product methane.
2. the technique that the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction according to claim 1 prepares methane, it is characterised in that: described broken after oil shale particle diameter be not more than 10mm；Described absorbent is ethanolamine.
3. the technique that the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction according to claim 1 prepares methane, it is characterised in that: in described oil shale retorting unit, the temperature of dry distillation reactor is 460～560 DEG C, and pressure is 0.1MPa；Described CO2The temperature carrying out absorption reaction in elimination unit is 25～50 DEG C, and pressure is 110～120kPa；Described CO2The temperature carrying out resolving reaction in elimination unit is 100～130 DEG C, and pressure is 101～110kPa；The temperature carrying out methanation reaction in described CO methanation unit is 250～350 DEG C, and pressure is 300～500kPa, and air speed is 5000～7000h-1。
4. the technique that the system of the integrated carbonization gas methane of solid thermal carriers oil-shale eduction according to claim 3 prepares methane, it is characterised in that: in described oil shale retorting unit, the temperature of dry distillation reactor is 510 DEG C；Described CO2The temperature carrying out absorption reaction in elimination unit is 40 DEG C, and pressure is 120kPa；Described CO2The temperature carrying out resolving reaction in elimination unit is 120 DEG C, and pressure is 103kPa；The temperature carrying out methanation reaction in described CO methanation unit is 300 DEG C, and pressure is 400kPa.
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