CN202762409U - Reactor for operation of periodic flow reversal in syngas methanation - Google Patents
Reactor for operation of periodic flow reversal in syngas methanation Download PDFInfo
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- CN202762409U CN202762409U CN2012203633515U CN201220363351U CN202762409U CN 202762409 U CN202762409 U CN 202762409U CN 2012203633515 U CN2012203633515 U CN 2012203633515U CN 201220363351 U CN201220363351 U CN 201220363351U CN 202762409 U CN202762409 U CN 202762409U
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Abstract
The utility model discloses a reactor for operation of periodic flow reversal in syngas methanation and belongs to the field of coal chemical industries. The reactor comprises a reactor unit and a heat exchanger. The reactor unit comprises a three-layer packed bed catalytic reactor, a two-position four-way valve, two two-way stop valves and a connecting pipeline. The heat exchanger comprises a feed-preheating heat exchanger and a recovery heat exchanger, wherein the recovery heat exchanger is connected to the feed-preheating heat exchanger through the pipeline, and accordingly feed gas is preheated by residual heat brought by product gas. According to requirements in practice, three reactor units can be connected in three combination manners to increase content of methane in product gas and improve stability of the whole process. The reactor is stable in performance, low in reactor investment and operation costs and longer in the service life of catalyst.
Description
Technical field
The utility model belongs to coal chemical technology, particularly a kind of flow-reversal cycleoperation reaction unit of synthesis gas methanation.
Background technology
Natural gas is a kind of cleaning, convenient, safe high-grade energy, and its main component is methane.Expect 2020, the consumption demand of China's natural gas year will reach 3000 billion cubic meters, have about 1500 billion cubic meter breach, and externally interdependency will reach 50%.The price of international energy is upheaval sharply, will bring Chinese energy safety to have a strong impact on.The energy resource structure characteristics of oil-poor, the weak breath of China, rich coal have determined that coal will occupy the main status of Chinese primary energy consumption for a long time.Utilize the relatively abundant coal resources of China or biomass resource to prepare synthetic natural gas and have more transport economic specific property and utilize usefulness, be conducive to focus on pollutant, environmental contamination reduction, for the town dweller provides gaseous fuel efficient, cleaning with industry.
Compare with other coal chemical technology routes such as generating, coal liquefaction, coal methyl alcohol processed, coal derived DMEs, coal or biomass-making synthetic natural gas have the energy conversion efficiency height, water consumes less, invests the advantages such as low, good in economic efficiency, are the optimization approach of coal conversion.Synthesis gas full methanation technology is the core technology of coal preparing natural gas.
Coal or living beings get synthesis gas through vaporizing system and are converted into synthetic natural gas through the full methanation process again, and following reaction mainly occurs:
2CO?+?2H
2?→?CH
4?+?H
2O
CO
2?+?4H
2?→?CH
4?+?2H
2O
CO?+?H
2O?→?CO
2?+H
2
The catalyzing methanation of synthesis gas reaction is a strong heat release reversible reaction, and existing synthesis gas methanator mainly contains following three major types.
The first kind is the plural serial stage insulation fix bed reactor, and the mode by external heat exchanger realizes that heat pipettes.Representational technology has the multistage insulation fix bed reaction process technology of German Lurgi company and South Africa SASOL company joint development, and this technology has realized many cover industrial production devices.U.S. Fuelcell Energy, Inc. discloses a kind of multistage fixed bed reaction process (CN1957076) of improved series and parallel connections combination, further reduces the load of each reactor, and with the unstripped gas of product as fuel cell.This class technique usually needs a plurality of reactors, and adopts the CO up to the circulating air diluting reactor import more than 5 times, and the temperature rise with in the control reactor had both increased equipment investment, had increased again the power consumption of circulating air, had reduced its economy.
Equations of The Second Kind is to adopt fluidized-bed reactor.Not only can promote unstripped gas and the effective of catalyst to contact with unstripped gas as the fluidized-bed reaction technique of catalyst fluidization medium, can also significantly improve the heat transfer efficiency of built-in heat exchanger, it is even to be conducive to shifting out with reaction bed temperature of heat of reaction, can under high reaction velocity, move continuously, improve the production capacity of device.Patent CN1960954 discloses a kind of methanation reaction process based on fluidized-bed reactor, comes balance but this technology depends in the unstripped gas heat absorption of reforming synchronously of additional aromatic hydrocarbon.The price of aromatic hydrocarbon own is higher, and the benzene in the claim, toluene or naphthalene etc. all are the end products of market demand, and the material heat-obtaining that consumes these high values does not have economy and universality.Patent CN10817716A discloses the technique of fluid bed and fixed bed coupling; Patent CN102180756A discloses gas-solid-gas-solids reactors, but all have the serious and serious problem of catalyst abrasion of back-mixing in the reactor.
The 3rd class reaction process is to adopt paste state bed reactor.Patent CN101979476A discloses the technology that adopts paste state bed reactor, solved shifting out of reaction heat, but the diabatic process step is many, and whole efficiency remains further to be improved during large-scale industrial application.
Based on the prior art feature, the utility model proposes a kind of packed bed catalytic reactor and method of the flow-reversal cycleoperation for methanation.By the periodically-varied feed flow direction, methanation catalytic reactor and heat exchanger are integrated, increase the integrated level of process and improved efficient, reached the conversion ratio and selective that under traditional stationary state operating condition, is beyond one's reach, reduced the speed of catalysqt deactivation.
The utility model content
The purpose of this utility model provides a kind of flow-reversal cycleoperation reaction unit of synthesis gas methanation, and described reaction unit structure is as follows:
(1) reactor unit 19 comprises a packed bed catalytic reactor 5, two position four-way valve, two two-way stop valves and connecting pipe:
Described packed bed catalytic reactor 5 is divided into three layers: the upper strata is be used to loading inert filler or having the heat transfer zone 8 of the solid catalyst of reactivity; The intermediate layer is the reaction zone 7 that filling has the solid catalyst of reactivity; Lower floor is be used to loading inert filler or having the heat transfer zone 6 of the solid catalyst of reactivity; Packed bed catalytic reactor 5 upper/lower terminals respectively have the opening of a supplied gas turnover;
The h port of two position four-way valves 13 and second two-way stop valve 18 link to each other by pipeline, and i port and first two-way stop valve 17 link to each other by pipeline, and the g port links to each other with pipeline respectively with the j port; The other end of first two-way stop valve 17 and second two-way stop valve 18 is respectively by pipeline be positioned at the opening of supplied gas turnover of described packed bed catalytic reactor 5 lower ends and the opening of the supplied gas turnover of upper end directly links to each other;
(2) heat-exchanger rig comprises a raw material preheating heat exchanger 9 and a recovery heat heat exchanger 10:
Described raw material preheating heat exchanger 9 is installed in unstripped gas and enters on the reactor unit pipeline before; Described recovery heat heat exchanger 10 is installed in gas product from the pipeline of reactor unit after out, and is connected on the raw material preheating heat exchanger 9 by pipeline, thereby utilizes waste heat that gas product is with preheating to unstripped gas.
Described inert filler refers to the high temperature resistant fillers of inert inorganic such as silica, carborundum or alundum (Al2O3).
Also can as required three reactor units be connected in the practice, with the content that improves methane in the gas product and the stability of improving whole technical process, the mode of connection has following three kinds:
The first connected mode: an end of first reactor unit 14 has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of second reactor unit 15; The outlet of second reactor unit 15 is connected by pipeline with the import of the 3rd reactor unit 16, perhaps directly by pipeline output products gas; The outlet of the 3rd reactor unit 16 is connected by the import of pipeline with second reactor unit 15;
The second connected mode: an end of the 3rd reactor unit 16 has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of second reactor unit 15 and the import of first reactor unit 14; Gas product is by the outlet of first reactor unit 14 and the outlet output of second reactor unit 15;
The third connected mode: an end of second reactor unit 15 has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of the 3rd reactor unit 16; The outlet of the 3rd reactor unit 16 is connected by pipeline with the import of first reactor unit 14, perhaps directly by pipeline output products gas; The outlet of first reactor unit 14 is connected by the import of pipeline with the 3rd reactor unit 16.
The flow-reversal cycleoperation reaction unit that has respectively the synthesis gas methanation with three reactor units of above-mentioned three kinds of connected modes all contains a raw material preheating heat exchanger 9 and a recovery heat heat exchanger 10 separately; Described raw material preheating heat exchanger 9 is installed in unstripped gas and enters first on the reactor unit pipeline before; Described recovery heat heat exchanger 10 is installed in gas product and goes out at last on the reactor unit pipeline afterwards, and is connected on the raw material preheating heat exchanger 9 by pipeline, thereby utilizes waste heat that gas product is with preheating to unstripped gas.
The beneficial effects of the utility model are:
1, the solid catalyst bed has " sandwich " formula structure in the multistage packed bed catalytic reactor, the inert filler large in beds two end regions filling thermal capacity, that intensity is high, allow inert filler serve as the heat exchanger of bed two end regions, and bear the air-flow that causes owing to flow-reversal periodically to the impact of beds, reduce the efflorescence of catalyst, prolonged catalyst service life;
2, pass through the method for flow-reversal cycleoperation, with the packed bed catalytic reactor by simple function reaction zone commonly used, expand to that two ends can be recovered, the reaction zone three functions district of the heat transfer zone of reproducibility and middle part, the alternate heat exchange with gas-solid of gas-solid catalysis is organically integrated, reach the purpose of process intensification;
3, the heat transfer zone at packed bed catalytic reactor two ends both can be loaded inert filler, also can load the solid catalyst with reactivity;
4, the packed bed catalytic reactor with single hop flow-reversal cycleoperation just can replace existing multistage insulation fixed bed reactor and heat exchanger, greatly simplified the technological process of whole synthesis gas methanation, the utilization rate of reaction heat is high, increase substantially the thermal efficiency of process, reduced equipment investment and operating cost;
5, be suitable for processing the low-temperature and low-concentration unstripped gas: even unstripped gas temperature and concentration are lower, reaction also can self-heating be carried out.
Description of drawings
Fig. 1 is synthesis gas methanation flow-reversal cycleoperation reaction unit structural representation of the present utility model;
Fig. 2 is the first connected mode schematic diagram that three reactor units are connected;
Fig. 3 is the second connected mode schematic diagram that three reactor units are connected;
Fig. 4 is the third connected mode schematic diagram that three reactor units are connected.
The specific embodiment
The utility model is described in more detail below in conjunction with the drawings and specific embodiments:
Fig. 1 is seen in embodiment 1(technological process)
Unstripped gas enters reactor unit after raw material preheating heat exchanger 9 is preheating to 120 ℃; The g-h port of two position four-way valves is communicated with, and the i-j port is communicated with, and naturally disconnects simultaneously the connected relation between g-i port, the h-j port, and unstripped gas flows in packed bed catalytic reactor 5 from top to bottom; Reach time half period t
1/2The time, being communicated with by the g-i port of computer control with two position four-way valves, the h-j port is communicated with, and naturally disconnects simultaneously the connected relation between g-h port, the i-j port, and at this moment unstripped gas flows in packed bed catalytic reactor 5 from bottom to top; By setting time half period t
1/2, the regularly alternately automatically periodicity conversion of switching realization gas flow direction in packed bed catalytic reactor 5 of four valves of control two position four-way valves;
The time half period t that adopts
1/2Value be 10 minutes; Used methanation catalyst be nickel content at the industrialization nickel catalyst of 15wt%, reaction temperature is 300 ℃, pressure is 0.6MPa, the air speed of unstripped gas is 5000 h
-1In order to take full advantage of the heat of methanation reaction, from the superheated steam of first process recovery of reactor gas product out heat heat exchanger 10 recovery heats and by-product 4.0 MPa, and then process raw material preheating heat exchanger 9 is with the unstripped gas preheating.Use these apparatus and method can make the conversion ratio of unstripped gas reach 93%, the volume fraction of methane reaches more than 94% in the gas product.
Fig. 2 is seen in embodiment 2(technological process)
Unstripped gas enters first reactor unit 14 after raw material preheating heat exchanger 9 is preheating to 200 ℃, enter second reactor unit 15 from first reactor unit 14 gas out and further react; 50% of second reactor unit 15 gas out enters next technical process as gas product, and remaining 50% enters reactor unit 16 and further react; Entering second reactor unit 15 from the 3rd reactor unit 16 gas out further reacts again.
Three time half period t that reactor unit adopts
1/2Be 15 minutes, used methanation catalyst be nickel content at the industrialization nickel catalyst of 10wt%, reaction temperature is 400 ℃, pressure is 0.6MPa, the air speed of unstripped gas is 5000 h
-1Use these apparatus and method can make the conversion ratio of unstripped gas reach 95%, the volume fraction of methane reaches more than 97% in the gas product.
The reactor network that present embodiment adopts three reactor units to form " product " word configuration replaces the single-reactor unit, has further reduced the disturbance to downstream process and equipment, improves the content of methane in conversion ratio and the gas product; And realize easily the needs that any one reactor unit stops separately, as long as first two-way stop valve 17 and second two-way stop valve 18 are all closed, g-h-j port or g-i-j with two position four-way valves 13 is communicated with simultaneously, just can realize that whole system is not stopped and change the catalyst of a certain reactor unit, guarantee the continuity of production process.
Fig. 3 is seen in embodiment 3(technological process)
Unstripped gas enters the 3rd reactor unit 16 after raw material preheating heat exchanger 9 is preheating to 250 ℃; Enter first reactor unit 14 from 50% of the 3rd reactor unit 16 gas out, remaining 50% enters second reactor unit 15 and further reacts; After first reactor unit 14 and second reactor unit 15 gas mixing out, enter next technical process as gas product.
Three time half period t that reactor unit adopts
1/2Be 20 minutes, used methanation catalyst be nickel content at the industrialization nickel catalyst of 10wt%, reaction temperature is 350 ℃, pressure is 0.6MPa, the air speed of unstripped gas is 5000h
-1Use these apparatus and method can make the conversion ratio of unstripped gas reach 94%, the volume fraction of methane reaches more than 96% in the gas product.
The reactor network that present embodiment adopts three reactor units to form " product " word configuration replaces the single-reactor unit, has further reduced the disturbance to downstream process and equipment, improves the content of methane in conversion ratio and the gas product; And realize easily the needs that any one reactor unit stops separately, as long as first two-way stop valve 17 and second two-way stop valve 18 are all closed, g-h-j port or g-i-j with two position four-way valves 13 is communicated with simultaneously, just can realize that whole system is not stopped and change the catalyst of a certain reactor unit, guarantee the continuity of production process.
Fig. 4 is seen in embodiment 4(technological process)
Unstripped gas enters second reactor unit 15 after raw material preheating heat exchanger 9 is preheating to 200 ℃; Entering the 3rd reactor unit 16 from second reactor unit 15 gas out further reacts, 60% of the gas of the 3rd reactor unit 16 outlets enters next technical process as gas product, 40% entering first reactor unit 14 and further react in addition; Entering the 3rd reactor unit 16 from first reactor unit 14 gas out further reacts again.
Three time half period t that reactor unit adopts
1/2Be 25 minutes, used methanation catalyst be nickel content at the industrialization nickel catalyst of 10wt%, reaction temperature is 500 ℃, pressure is 0.6MPa, the air speed of unstripped gas is 4000 h
-1Use these apparatus and method can make the conversion ratio of unstripped gas reach 98%, the volume fraction of methane reaches more than 98% in the gas product.
The reactor network that present embodiment adopts three reactor units to form " product " word configuration replaces the single-reactor unit, has further reduced the disturbance to downstream process and equipment, improves the content of methane in conversion ratio and the gas product; And realize easily the needs that any one reactor unit stops separately, as long as first two-way stop valve 17 and second two-way stop valve 18 are all closed, g-h-j port or g-i-j with two position four-way valves 13 is communicated with simultaneously, just can realize that whole system is not stopped and change the catalyst of a certain reactor unit, guarantee the continuity of production process.
Claims (5)
1. the flow-reversal cycleoperation reaction unit of a synthesis gas methanation is characterized in that, described reaction unit structure is as follows:
(1) reactor unit (19) comprises a packed bed catalytic reactor (5), two position four-way valve, two two-way stop valves and connecting pipe:
Described packed bed catalytic reactor (5) is divided into three layers: the upper strata is be used to loading inert filler or having the heat transfer zone (8) of the solid catalyst of reactivity; The intermediate layer is the reaction zone (7) that filling has the solid catalyst of reactivity; Lower floor is be used to loading inert filler or having the heat transfer zone (6) of the solid catalyst of reactivity; Packed bed catalytic reactor (5) upper/lower terminal respectively has the opening of a supplied gas turnover;
(h) port of two position four-way valves (13) links to each other by pipeline with second two-way stop valve (18), and (i) port links to each other by pipeline with first two-way stop valve (17), and (g) port links to each other with pipeline respectively with (j) port; The other end of first two-way stop valve (17) and second two-way stop valve (18) is respectively by pipeline be positioned at the opening of supplied gas turnover of described packed bed catalytic reactor (5) lower end and the opening of the supplied gas turnover of upper end directly links to each other;
(2) heat-exchanger rig comprises a raw material preheating heat exchanger (9) and a recovery heat heat exchanger (10):
Described raw material preheating heat exchanger (9) is installed in unstripped gas and enters on the reactor unit pipeline before; Described recovery heat heat exchanger (10) is installed in gas product from the pipeline of reactor unit after out, and is connected on the raw material preheating heat exchanger (9) by pipeline, thereby utilizes waste heat that gas product is with preheating to unstripped gas.
2. reaction unit according to claim 1 is characterized in that, described inert filler is silica, carborundum or alundum (Al2O3).
3. the flow-reversal cycleoperation reaction unit of a synthesis gas methanation is characterized in that, contains three reactor units, and the structure of the structure of described three reactor units and reactor unit (19) is identical; The structure of the flow-reversal cycleoperation reaction unit of described synthesis gas methanation is as follows:
(1) three reactor unit, their connected mode is as follows:
One end of first reactor unit (14) has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of second reactor unit (15); The outlet of second reactor unit (15) is connected by pipeline with the import of the 3rd reactor unit (16), perhaps directly by pipeline output products gas; The outlet of the 3rd reactor unit (16) is connected by the import of pipeline with second reactor unit (15);
(2) heat-exchanger rig comprises a raw material preheating heat exchanger (9) and a recovery heat heat exchanger (10):
Described raw material preheating heat exchanger (9) is installed in unstripped gas and enters on first reactor unit (14) pipeline before; Described recovery heat heat exchanger (10) is installed in gas product from the pipeline of second reactor unit (15) after out, and is connected on the raw material preheating heat exchanger (9) by pipeline, thereby utilizes waste heat that gas product is with preheating to unstripped gas.
4. the flow-reversal cycleoperation reaction unit of a synthesis gas methanation is characterized in that, contains three reactor units, and the structure of the structure of described three reactor units and reactor unit (19) is identical; The structure of the flow-reversal cycleoperation reaction unit of described synthesis gas methanation is as follows:
(1) three reactor unit, their connected mode is as follows:
One end of the 3rd reactor unit (16) has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of second reactor unit (15) and the import of first reactor unit (14); The outlet of the outlet of first reactor unit (14) and second reactor unit (15) converges rear output products gas by pipeline;
(2) heat-exchanger rig comprises a raw material preheating heat exchanger (9) and a recovery heat heat exchanger (10):
Described raw material preheating heat exchanger (9) is installed in unstripped gas and enters on the 3rd reactor unit (16) pipeline before; Described recovery heat heat exchanger (10) is installed on the pipeline after gas product out converges from first reactor unit (14) and second reactor unit (15), and be connected on the raw material preheating heat exchanger (9) by pipeline, thereby utilize waste heat that gas product is with preheating to unstripped gas.
5. the flow-reversal cycleoperation reaction unit of a synthesis gas methanation is characterized in that, contains three reactor units, and the structure of the structure of described three reactor units and reactor unit (19) is identical; The structure of the flow-reversal cycleoperation reaction unit of described synthesis gas methanation is as follows:
(1) three reactor unit, their connected mode is as follows:
One end of second reactor unit (15) has raw material gas inlet, and the outlet of its other end is connected by pipeline with the import of the 3rd reactor unit (16); The outlet of the 3rd reactor unit (16) is connected by pipeline with the import of first reactor unit (14), perhaps directly by pipeline output products gas; The outlet of first reactor unit (14) is connected by the import of pipeline with the 3rd reactor unit (16);
(2) heat-exchanger rig comprises a raw material preheating heat exchanger (9) and a recovery heat heat exchanger (10):
Described raw material preheating heat exchanger (9) is installed in unstripped gas and enters on second reactor unit (15) pipeline before; Described recovery heat heat exchanger (10) is installed in gas product from the pipeline of the 3rd reactor unit (16) after out, and is connected on the raw material preheating heat exchanger (9) by pipeline, thereby utilizes waste heat that gas product is with preheating to unstripped gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012203633515U CN202762409U (en) | 2012-07-25 | 2012-07-25 | Reactor for operation of periodic flow reversal in syngas methanation |
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| CN2012203633515U CN202762409U (en) | 2012-07-25 | 2012-07-25 | Reactor for operation of periodic flow reversal in syngas methanation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755864A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
-
2012
- 2012-07-25 CN CN2012203633515U patent/CN202762409U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755864A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
| CN102755864B (en) * | 2012-07-25 | 2014-10-29 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
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| C14 | Grant of patent or utility model | ||
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| ASS | Succession or assignment of patent right |
Owner name: DATANG INTERNATIONAL CHEMICAL TECHNOLOGY INSTITUTE Effective date: 20130807 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Honggang Inventor after: Liu Xuewu Inventor after: Wang Tengda Inventor after: Zhang Jie Inventor after: Niu Yuguang Inventor after: Yang Yongping Inventor after: Li Anxue Inventor after: Li Chunqi Inventor after: Mei Changsong Inventor after: Zuo Yubang Inventor before: Chen Honggang Inventor before: Wang Tengda Inventor before: Zhang Jie Inventor before: Niu Yuguang Inventor before: Yang Yongping |
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| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHEN HONGGANG WANG TENGDA ZHANG KAI NIU YUGUANG YANG YONGPING TO: CHEN HONGGANG WANG TENGDA ZHANG KAI NIU YUGUANG YANG YONGPING LI ANXUE LI CHUNQI MEI CHANGSONG ZUO YUBANG LIU XUEWU |
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| TR01 | Transfer of patent right |
Effective date of registration: 20130807 Address after: 102206 Beijing city Changping District Zhu Daxinzhuang North Agricultural Road No. 2 Patentee after: North China Electric Power University Patentee after: Datang International Chemical Technology Institute Co., Ltd. Address before: 102206 Beijing city Changping District Zhu Daxinzhuang North Agricultural Road No. 2 Patentee before: North China Electric Power University |
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| AV01 | Patent right actively abandoned |
Granted publication date: 20130306 Effective date of abandoning: 20141029 |
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| RGAV | Abandon patent right to avoid regrant |