CN217418188U - System for preparing methanol and co-producing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming - Google Patents
System for preparing methanol and co-producing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming Download PDFInfo
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- CN217418188U CN217418188U CN202221313101.0U CN202221313101U CN217418188U CN 217418188 U CN217418188 U CN 217418188U CN 202221313101 U CN202221313101 U CN 202221313101U CN 217418188 U CN217418188 U CN 217418188U
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- 239000007789 gas Substances 0.000 title claims abstract description 255
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 193
- 239000001257 hydrogen Substances 0.000 title claims abstract description 185
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000000571 coke Substances 0.000 title claims abstract description 132
- 238000002407 reforming Methods 0.000 title claims abstract description 82
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000003860 storage Methods 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000746 purification Methods 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000013589 supplement Substances 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The utility model relates to a system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas, belonging to the technical field of hydrogen production by reforming industrial byproduct gas. The system comprises a chemical-looping coke oven gas reforming component, a heat exchanger and a hydrogen (H) 2 CO purification and separationThe hydrogen purification device comprises a component, a water-containing hydrogen purifier, a methanol synthesizer and a gas storage component. The utility model discloses the system can effectively improve each component's in the coke oven gas utilization ratio and hydrogen output to with CO and H 2 The separation is used for the synthesis of methanol, and high-purity nitrogen gas (more than 95%) and hydrogen gas (more than 99.5%) are simultaneously by-produced, the process is flexible, the carbon emission and the investment cost can be obviously reduced, and the energy efficiency and the economic benefit are effectively improved.
Description
Technical Field
The utility model relates to a system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas, belonging to the technical field of hydrogen production by reforming industrial byproduct gas.
Background
With the rapid development of hydrogen metallurgy, new energy automobiles and the like, the demand for hydrogen gas is rapidly increasing. However, hydrogen mainly comes from fossil fuels such as coal, natural gas and the like, and then is industrial byproduct gases such as coke oven gas, industrial chlor-alkali gas and the like, and the hydrogen production by water electrolysis accounts for less than 5%. In the transition period that fossil fuels are increasingly exhausted and clean hydrogen production technology is not mature, industrial byproduct hydrogen such as coke oven gas and the like needs to be reasonably developed and utilized.
The coke oven gas contains 50-60% of hydrogen, and the coke oven gas is separated industrially mainly by adopting physical technical means such as a pressure swing adsorption method, a cryogenic method, a membrane separation method and the like, so that the problems of complex equipment, complex operation, large investment, low utilization rate of components except the hydrogen and the like exist.
SUMMERY OF THE UTILITY MODEL
The utility model discloses to coke oven gas separation hydrogen among the prior art have equipment complicacy, complex operation, the investment is big, the not high problem of component utilization ratio beyond the hydrogen, provide an integrated chemical chain coke oven gas reformed synthesis gas system methyl alcohol coproduction hydrogen system, the device can effectively improve the utilization ratio and the hydrogen output of each component in the coke oven gas to with CO and H output 2 The separation is used for the synthesis of methanol, and high-purity nitrogen gas (more than 95%) and hydrogen gas (more than 99.5%) are simultaneously by-produced, the process is flexible, the carbon emission and the investment cost can be obviously reduced, and the energy efficiency and the economic benefit are effectively improved.
The utility model discloses a solve its technical problem and the technical scheme who adopts is:
a system for preparing methanol and hydrogen by synthesis gas integrated with chemical-looping coke oven gas reforming comprises a chemical-looping coke oven gas reforming component, a heat exchanger 1 and an H 2 a/CO purification and separation component, a hydrous hydrogen purifier 8, a methanol synthesizer 7 and a gas storage component,
the chemical-looping coke oven gas reforming component is provided with a hot air inlet, a hot coke oven gas inlet, a water vapor inlet, an oxygen-deprived air outlet, a hydrogen-rich synthetic gas outlet and a water-containing hydrogen outlet, a coke oven gas heat exchange tube, an air heat exchange tube, an oxygen-deprived air heat exchange tube and a hydrogen-rich synthetic gas heat exchange tube are arranged in the heat exchanger 1, and H is 2 the/CO purification and separation component is provided with a gas inlet and H 2 An outlet and a CO outlet, a water-vapor separation device is arranged at the bottom of the hydrous hydrogen purifier 8 and is provided with a hydrous hydrogen inlet, a condensed water outlet and a hydrogen outlet, a water vapor generation device is arranged at the top of the hydrous hydrogen purifier 8 and is provided with a water vapor outlet, a condensed water inlet and a water supplement port, and a methanol synthesizer 7 is provided with a CO inlet and an H inlet 2 An inlet and a methanol outlet, and a gas storage member comprising H 2 A storage device 10 and a CO storage device 9,
a cold coke oven gas inlet of a coke oven gas heat exchange pipe of the heat exchanger 1 is externally connected with a cold coke oven gas conveying pipe, and a coke oven gas outlet of the coke oven gas heat exchange pipe is communicated with a hot coke oven gas inlet of a chemical-looping coke oven gas reforming component through a hot coke oven gas conveying pipe; a cold air inlet of an air heat exchange tube of the heat exchanger 1 is externally connected with a cold air conveying tube, and a hot air outlet of the air heat exchange tube is communicated with a hot air inlet of a chemical-looping coke oven gas reforming component through the hot air conveying tube; an oxygen-loss air inlet of an oxygen-loss air heat exchange tube of the heat exchanger 1 is communicated with an oxygen-loss air outlet of a chemical-looping coke oven gas reforming member through an oxygen-loss air conveying tube, and a nitrogen outlet of the oxygen-loss air conveying tube is externally connected with a nitrogen conveying tube; a hydrogen-rich synthetic gas inlet of the hydrogen-rich synthetic gas heat exchange tube of the heat exchanger 1 is communicated with a hydrogen-rich synthetic gas outlet of the chemical-looping coke oven gas reforming component through a hot hydrogen-rich synthetic gas conveying tube, and a cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with the H through a cold hydrogen-rich synthetic gas conveying tube 2 CO purificationThe gas inlets of the separating members are communicated;
the hydrogen-containing outlet of the chemical-looping coke oven gas reforming component is communicated with the hydrogen-containing inlet of the water-steam separating device through a hydrogen-containing conveying pipe, the condensed water outlet of the water-steam separating device is communicated with the condensed water inlet of the water-steam generating device through a condensed water pipe, and the hydrogen outlet of the water-steam separating device is communicated with the H through a hydrogen conveying pipe I 2 The gas inlet of the/CO purification and separation component is communicated, the water supplement port of the water vapor generation device is externally connected with a water supplement pipe, and the water vapor outlet of the water vapor separation device is communicated with the water vapor inlet of the chemical-looping coke oven gas reforming component through a water vapor conveying pipe;
H 2 h of/CO purification and separation Member 2 Outlet through H 2 The delivery pipes I are respectively connected with H of a methanol synthesizer 7 2 Inlet and H 2 Storage means 10 are connected, H 2 The CO outlet of the/CO purification and separation component is respectively connected with the CO inlet of the methanol synthesizer 7 and the CO storage device 9 through a CO conveying pipe I.
The methanol synthesizer 7 is externally connected with a methanol delivery pipe H 2 Storage device 10 external connection H 2 The conveying pipe II and the CO storage device 9 are externally connected with a CO conveying pipe II.
The chemical-looping coke oven gas reforming component passes through the pipeline, the heat exchanger and the H 2 the/CO purification and separation component is communicated with the water-containing hydrogen purifier, and can continuously prepare hydrogen-rich synthesis gas, hydrogen and high-purity nitrogen;
the chemical-looping coke oven gas reforming component comprises a chemical-looping coke oven gas reforming reactor I2, a chemical-looping coke oven gas reforming reactor II3 and a chemical-looping coke oven gas reforming reactor III4 which have the same structure.
Said H 2 The CO purifying and separating member comprises a double pressure swing adsorption tower I5 and a double pressure swing adsorption tower II6, the bottom end of the double pressure swing adsorption tower I5 is provided with a hydrogen-rich synthetic gas inlet, the top end of the double pressure swing adsorption tower I5 is provided with a CO outlet and H 2 The cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with the hydrogen-rich synthetic gas inlet of the double pressure swing adsorption tower I5 through a cold hydrogen-rich synthetic gas conveying tube; h of double pressure swing adsorption tower I5 2 Outlet through H 2 The transfer pipe I is respectively synthesized with methanolH of vessel 7 2 Inlet and H 2 The storage device 10 is communicated, and a CO outlet of the double pressure swing adsorption tower I5 is respectively communicated with a CO inlet of the methanol synthesizer 7 and the CO storage device 9 through a CO conveying pipe I; the bottom end of the double pressure swing adsorption tower II6 is provided with a hydrogen inlet, the top end of the double pressure swing adsorption tower II6 is provided with a hydrogen outlet, and the hydrogen outlet of the water vapor separation device passes through the hydrogen conveying pipe I and the H of the double pressure swing adsorption tower II6 2 The inlet is communicated with the H of the double pressure swing adsorption tower II6 2 Outlet through H 2 The delivery pipes I are respectively connected with H of a methanol synthesizer 7 2 Inlet and H 2 The storage device 10 is communicated;
the cold coke oven gas conveying pipe, the hot coke oven gas conveying pipe, the cold air conveying pipe, the hot air conveying pipe, the oxygen-deprived air conveying pipe, the nitrogen conveying pipe, the hot hydrogen-rich synthetic gas conveying pipe, the cold hydrogen-rich synthetic gas conveying pipe, the water-containing hydrogen conveying pipe, the condensate pipe, the hydrogen conveying pipe I, the water replenishing pipe, the water vapor conveying pipe, the H gas conveying pipe and the hydrogen-rich synthetic gas conveying pipe 2 The conveying pipe I and the CO conveying pipe I are both provided with one-way control valves;
chemical chain coke oven gas reforming member passes through pipeline, heat exchanger and H 2 the/CO purification and separation component is communicated with the water-containing hydrogen purifier, and can continuously prepare hydrogen-rich synthesis gas, hydrogen and high-purity nitrogen;
the use method of the system for preparing methanol and coproducing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming comprises the following specific steps:
s1: preheating coke oven gas through a heat exchanger, then conveying the coke oven gas into a chemical-looping coke oven gas reforming reactor, and reacting the coke oven gas with an oxidation-state oxygen carrier to generate hydrogen-rich synthesis gas;
s2: the hydrogen-rich synthetic gas is sent to a heat exchanger, exchanges heat with the working medium in the heat exchanger and then is sent to H 2 A double pressure swing adsorption tower I of a CO purification and separation component;
s3: warp H 2 The CO purification and separation component (double pressure swing adsorption tower I) separates two gas flows, one is H 2 One stream, CO, is sent to a gas storage means (H) 2 Storage and CO storage) or methanol synthesizer;
s4: the water vapor from the water vapor generating device is conveyed to a chemical-looping coke oven gas reforming reactor and reacts with a reduced-state oxygen carrier to generate hydrogen, and the oxygen carrier can be oxidized into a non-complete oxidation state only due to the weak oxidizing capability of the water;
s5: the hydrogen containing water vapor in the S4 returns to the hydrogen containing water purifier, condensed water and hydrogen are separated by a water-vapor separation device (condenser) through condensation, the condensed water enters the water-vapor generation device again to be vaporized to form water vapor, and when the water in the water-vapor generation device is insufficient, water is supplemented through a water supplementing pipe;
s6: the hydrogen separated in S5 enters H 2 The hydrogen deeply purified by the double pressure swing adsorption tower II is sent to a hydrogen storage device or a methanol synthesizer;
s7: the cold air is preheated into hot air by a heat exchanger and then is sent to a chemical-looping coke oven gas reforming component (a chemical-looping coke oven gas reforming reactor I2, a chemical-looping coke oven gas reforming reactor II3 and a chemical-looping coke oven gas reforming reactor III4) to react with the oxygen carrier in the incomplete oxidation state, so that the oxygen carrier in the incomplete oxidation state is completely oxidized and regenerated, and oxygen-deprived air is generated at the same time;
s8: the oxygen-deprived air generated in S7 is sent to a heat exchanger for heat exchange, and high-purity nitrogen gas (> 95%) is generated at the same time;
s9: products CO and H 2 Introducing the mixture into a methanol synthesizer according to the ratio of 1:2 to synthesize methanol; the reaction conditions for synthesizing the methanol are that the reaction temperature in the prior art is 200-300 ℃, and the reaction pressure is 2.0-5.0 MPa.
The utility model has the advantages that:
(1) the system for preparing methanol and coproducing hydrogen by using the synthesis gas reformed by the integrated chemical chain coke oven gas can simultaneously produce three raw material gases of hydrogen, nitrogen and carbon monoxide and chemical product methanol, thereby effectively improving the production capacity;
(2) the utility model discloses the system for preparing methanol and coproducing hydrogen from the synthesis gas of integrated chemical chain coke oven gas reforming can realize the effective utilization of each component gas in the coke oven gas, reduce carbon emission, reduce environmental pollution and resource waste;
(3) the process of the system for preparing methanol and coproducing hydrogen by using the synthesis gas integrated with the chemical-looping coke oven gas reforming is flexible, the demand of hydrogen and methanol can be flexibly adjusted according to the outside, the market adaptability is improved, and the product methanol is convenient to store and transport;
(4) the utility model discloses a heat exchanger utilizes to preheat focusing furnace gas and air and preheats, utilizes condensing equipment to carry out cyclic utilization to vapor, has reduced the energy consumption.
Drawings
FIG. 1 is a schematic diagram of a system for co-production of methanol and hydrogen from synthesis gas by integrated chemical looping coke oven gas reforming;
in the figure, a 1-heat exchanger, a 2-chemical chain coke oven gas reforming reactor I, a 3-chemical chain coke oven gas reforming reactor II, a 4-chemical chain coke oven gas reforming reactor III, a 5-double pressure swing adsorption tower I, a 6-double pressure swing adsorption tower II, a 7-methanol synthesizer, an 8-water-containing hydrogen purifier, a 9-CO storage device and a 10-H 2 A storage device.
Detailed Description
The present invention will be further described with reference to the following detailed description.
Example 1: as shown in figure 1, a system for preparing methanol and hydrogen by synthesis gas integrated with chemical-looping coke oven gas reforming comprises a chemical-looping coke oven gas reforming component, a heat exchanger 1 and an H 2 a/CO purification and separation component, a hydrous hydrogen purifier 8, a methanol synthesizer 7 and a gas storage component,
the chemical-looping coke oven gas reforming component is provided with a hot air inlet, a hot coke oven gas inlet, a water vapor inlet, an oxygen-deprived air outlet, a hydrogen-rich synthetic gas outlet and a water-containing hydrogen outlet, a coke oven gas heat exchange tube, an air heat exchange tube, an oxygen-deprived air heat exchange tube and a hydrogen-rich synthetic gas heat exchange tube are arranged in the heat exchanger 1, and H is 2 the/CO purification and separation component is provided with a gas inlet and H 2 An outlet and a CO outlet, a water-vapor separation device is arranged at the bottom of the hydrous hydrogen purifier 8, the water-vapor separation device is provided with a hydrous hydrogen inlet, a condensed water outlet and a hydrogen outlet, a water vapor generation device is arranged at the top of the hydrous hydrogen purifier 8, and the water vapor generation device is arrangedHas a steam outlet, a condensed water inlet and a water supplement port, and the methanol synthesizer 7 is provided with a CO inlet and an H 2 An inlet and a methanol outlet, and a gas storage member comprising H 2 A storage device 10 and a CO storage device 9,
a cold coke oven gas inlet of a coke oven gas heat exchange pipe of the heat exchanger 1 is externally connected with a cold coke oven gas conveying pipe, and a coke oven gas outlet of the coke oven gas heat exchange pipe is communicated with a hot coke oven gas inlet of a chemical-looping coke oven gas reforming component through a hot coke oven gas conveying pipe; a cold air inlet of an air heat exchange tube of the heat exchanger 1 is externally connected with a cold air conveying tube, and a hot air outlet of the air heat exchange tube is communicated with a hot air inlet of a chemical-looping coke oven gas reforming component through the hot air conveying tube; an oxygen-loss air inlet of an oxygen-loss air heat exchange tube of the heat exchanger 1 is communicated with an oxygen-loss air outlet of a chemical-looping coke oven gas reforming member through an oxygen-loss air conveying tube, and a nitrogen outlet of the oxygen-loss air conveying tube is externally connected with a nitrogen conveying tube; a hydrogen-rich synthetic gas inlet of the hydrogen-rich synthetic gas heat exchange tube of the heat exchanger 1 is communicated with a hydrogen-rich synthetic gas outlet of the chemical-looping coke oven gas reforming component through a hot hydrogen-rich synthetic gas conveying tube, and a cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with the H through a cold hydrogen-rich synthetic gas conveying tube 2 The gas inlets of the/CO purification and separation components are communicated;
the hydrogen-containing outlet of the chemical-looping coke oven gas reforming component is communicated with the hydrogen-containing inlet of the water-steam separating device through a hydrogen-containing conveying pipe, the condensed water outlet of the water-steam separating device is communicated with the condensed water inlet of the water-steam generating device through a condensed water pipe, and the hydrogen outlet of the water-steam separating device is communicated with the H through a hydrogen conveying pipe I 2 The gas inlet of the/CO purification and separation component is communicated, the water supplement port of the water vapor generation device is externally connected with a water supplement pipe, and the water vapor outlet of the water vapor separation device is communicated with the water vapor inlet of the chemical-looping coke oven gas reforming component through a water vapor conveying pipe;
H 2 h of/CO purification and separation Member 2 Outlet through H 2 The delivery pipes I are respectively connected with H of a methanol synthesizer 7 2 Inlet and H 2 Storage means 10 are connected, H 2 The CO outlet of the/CO purification and separation component is respectively connected with the CO inlet of the methanol synthesizer 7 through a CO conveying pipe IA mouth and CO storage 9;
the methanol synthesizer 7 is externally connected with a methanol delivery pipe H 2 Storage device 10 external connection H 2 A conveying pipe II and a CO storage device 9 are externally connected with the CO conveying pipe II;
chemical chain coke oven gas reforming member passes through pipeline, heat exchanger and H 2 the/CO purification and separation component is communicated with the water-containing hydrogen purifier, and can continuously prepare hydrogen-rich synthesis gas, hydrogen and high-purity nitrogen;
the use method of the system for preparing methanol and coproducing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming specifically comprises the following steps:
s1: preheating coke oven gas through a heat exchanger, then conveying the coke oven gas into a chemical-looping coke oven gas reforming reactor, and reacting the coke oven gas with an oxidation-state oxygen carrier to generate hydrogen-rich synthesis gas;
s2: the hydrogen-rich synthetic gas is sent to a heat exchanger, exchanges heat with the working medium in the heat exchanger and then is sent to H 2 A CO purification and separation member;
s3: warp H 2 the/CO purification and separation component separates two gas flows, one is H 2 One stream, CO, is sent to a gas storage means (H) 2 Storage and CO storage) or methanol synthesizer;
s4: the water vapor from the water vapor generating device is conveyed to a chemical-looping coke oven gas reforming reactor and reacts with a reduced-state oxygen carrier to generate hydrogen, and the oxygen carrier can be oxidized into a non-complete oxidation state only due to the weak oxidizing capability of the water;
s5: the hydrogen containing water vapor in the S4 returns to the hydrogen containing water purifier, condensed water and hydrogen are separated by a water-vapor separation device (condenser) through condensation, the condensed water enters the water-vapor generation device again to be vaporized to form water vapor, and when the water in the water-vapor generation device is insufficient, water is supplemented through a water supplementing pipe;
s6: the hydrogen separated in S5 enters H 2 a/CO purification and separation component, wherein the deeply purified hydrogen is sent to a hydrogen storage device or a methanol synthesizer;
s7: the cold air is preheated into hot air by a heat exchanger and then is sent to a chemical-looping coke oven gas reforming component to react with the oxygen carrier in the incomplete oxidation state, so that the oxygen carrier in the incomplete oxidation state is completely oxidized and regenerated, and oxygen-losing air is generated at the same time;
s8: the oxygen-deprived air generated in S7 is sent to a heat exchanger for heat exchange, and high-purity nitrogen gas (> 95%) is generated at the same time;
s9: products CO and H 2 Introducing the mixture into a methanol synthesizer according to the ratio of 1:2 to synthesize methanol.
Example 2: the system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas in the embodiment is basically the same as the system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas in the embodiment 1, and the difference is that: the chemical-looping coke oven gas reforming component comprises a chemical-looping coke oven gas reforming reactor I2, a chemical-looping coke oven gas reforming reactor II3 and a chemical-looping coke oven gas reforming reactor III4 which have the same structure;
H 2 the CO purifying and separating member comprises a double pressure swing adsorption tower I5 and a double pressure swing adsorption tower II6, the bottom end of the double pressure swing adsorption tower I5 is provided with a hydrogen-rich synthetic gas inlet, the top end of the double pressure swing adsorption tower I5 is provided with a CO outlet and H 2 The cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with the hydrogen-rich synthetic gas inlet of the double pressure swing adsorption tower I5 through a cold hydrogen-rich synthetic gas conveying tube; h of double pressure swing adsorption tower I5 2 Outlet through H 2 The delivery pipes I are respectively connected with H of a methanol synthesizer 7 2 Inlet and H 2 The storage device 10 is communicated, and a CO outlet of the double pressure swing adsorption tower I5 is respectively communicated with a CO inlet of the methanol synthesizer 7 and the CO storage device 9 through a CO conveying pipe I; the bottom end of the double pressure swing adsorption tower II6 is provided with a hydrogen inlet, the top end of the double pressure swing adsorption tower II6 is provided with a hydrogen outlet, and the hydrogen outlet of the water-steam separation device passes through the hydrogen conveying pipe I and the H of the double pressure swing adsorption tower II6 2 The inlet is communicated with the H of the double pressure swing adsorption tower II6 2 Outlet through H 2 The delivery pipes I are respectively connected with H of a methanol synthesizer 7 2 Inlet and H 2 The storage device 10 is communicated;
the use method of the system for preparing methanol and coproducing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming specifically comprises the following steps:
s1: preheating coke oven gas through a heat exchanger, then conveying the coke oven gas into a chemical-looping coke oven gas reforming reactor, and reacting the coke oven gas with an oxidation-state oxygen carrier to generate hydrogen-rich synthesis gas;
s2: the hydrogen-rich synthetic gas is sent to a heat exchanger, exchanges heat with the working medium in the heat exchanger and then is sent to H 2 A double pressure swing adsorption tower I of a CO purification and separation component;
s3: warp H 2 The CO purification and separation component (double pressure swing adsorption tower I) separates two gas flows, one is H 2 One stream, CO, is sent to a gas storage means (H) 2 Storage and CO storage) or methanol synthesizer;
s4: the water vapor from the water vapor generating device is conveyed to a chemical-looping coke oven gas reforming reactor and reacts with a reduced-state oxygen carrier to generate hydrogen, and the oxygen carrier can be oxidized into a non-complete oxidation state only due to the weak oxidizing capability of the water;
s5: the hydrogen containing water vapor in the S4 returns to the hydrogen containing water purifier, condensed water and hydrogen are separated by a water-vapor separation device (condenser) through condensation, the condensed water enters the water-vapor generation device again to be vaporized to form water vapor, and when the water in the water-vapor generation device is insufficient, water is supplemented through a water supplementing pipe;
s6: the hydrogen separated in S5 enters H 2 The hydrogen deeply purified by the double pressure swing adsorption tower II is sent to a hydrogen storage device or a methanol synthesizer;
s7: the cold air is preheated into hot air by a heat exchanger and then is sent to a chemical-looping coke oven gas reforming component (a chemical-looping coke oven gas reforming reactor I2, a chemical-looping coke oven gas reforming reactor II3 and a chemical-looping coke oven gas reforming reactor III4) to react with the oxygen carrier in the incomplete oxidation state, so that the oxygen carrier in the incomplete oxidation state is completely oxidized and regenerated, and oxygen-deprived air is generated at the same time;
s8: the oxygen-deprived air generated in S7 is sent to a heat exchanger for heat exchange, and high-purity nitrogen gas (> 95%) is generated at the same time;
s9: products CO and H 2 Introducing the mixture into a methanol synthesizer according to the ratio of 1:2 to synthesize methanol; first of allThe reaction conditions for synthesizing the alcohol are that the reaction temperature in the prior art is 200-300 ℃, and the reaction pressure is 2.0-5.0 MPa.
Example 3: the system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas in the embodiment is basically the same as the system for preparing methanol and hydrogen by synthesis gas by reforming integrated chemical-looping coke oven gas in the embodiment 2, and the difference is that:
a cold coke oven gas delivery pipe, a hot coke oven gas delivery pipe, a cold air delivery pipe, a hot air delivery pipe, an oxygen-deprived air delivery pipe, a nitrogen delivery pipe, a hot hydrogen-rich synthetic gas delivery pipe, a cold hydrogen-rich synthetic gas delivery pipe, a water-containing hydrogen delivery pipe, a condensate pipe, a hydrogen delivery pipe I, a water supplement pipe, a water vapor delivery pipe, an H gas delivery pipe, a hydrogen-rich synthetic gas delivery pipe, a hydrogen-rich gas delivery pipe, a hydrogen-rich gas delivery pipe, a 2 The conveying pipe I and the CO conveying pipe I are both provided with one-way control valves; since the reactions of the chemical looping coke oven gas reforming reactors I2, II3 and III4 may be in different stages, the gas inlet pipeline and the gas outlet pipeline can be adjusted through the one-way control valve, so that gas cross-flow is prevented.
While the present invention has been particularly shown and described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. The system for preparing methanol and coproducing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming is characterized by comprising the following steps: comprises a chemical chain coke oven gas reforming component, a heat exchanger (1) and H 2 a/CO purification and separation component, a hydrous hydrogen purifier (8), a methanol synthesizer (7) and a gas storage component,
the chemical-looping coke oven gas reforming component is provided with a hot air inlet, a hot coke oven gas inlet, a water vapor inlet, an oxygen-deprived air outlet, a hydrogen-rich synthetic gas outlet and a water-containing hydrogen outlet, a coke oven gas heat exchange tube, an air heat exchange tube, an oxygen-deprived air heat exchange tube and a hydrogen-rich synthetic gas heat exchange tube are arranged in the heat exchanger (1), and H 2 the/CO purification and separation component is provided with a gas inlet and H 2 A water-vapor separation device is arranged at the bottom of the outlet, the CO outlet and the hydrous hydrogen purifier (8)The water-vapor separation device is provided with a hydrous hydrogen inlet, a condensed water outlet and a hydrogen outlet, the top of the hydrous hydrogen purifier (8) is provided with a water vapor generation device, the water vapor generation device is provided with a water vapor outlet, a condensed water inlet and a water supplement port, and the methanol synthesizer (7) is provided with a CO inlet and an H inlet 2 An inlet and a methanol outlet, and a gas storage member comprising H 2 A storage device (10) and a CO storage device (9),
a cold coke oven gas inlet of a coke oven gas heat exchange pipe of the heat exchanger (1) is externally connected with a cold coke oven gas conveying pipe, and a coke oven gas outlet of the coke oven gas heat exchange pipe is communicated with a hot coke oven gas inlet of a chemical-looping coke oven gas reforming component through a hot coke oven gas conveying pipe; a cold air inlet of an air heat exchange tube of the heat exchanger (1) is externally connected with a cold air conveying tube, and a hot air outlet of the air heat exchange tube is communicated with a hot air inlet of a chemical-looping coke oven gas reforming member through the hot air conveying tube; an oxygen-loss air inlet of an oxygen-loss air heat exchange tube of the heat exchanger (1) is communicated with an oxygen-loss air outlet of a chemical-looping coke oven gas reforming member through an oxygen-loss air conveying tube, and a nitrogen outlet of the oxygen-loss air conveying tube is externally connected with a nitrogen conveying tube; a hydrogen-rich synthetic gas inlet of a hydrogen-rich synthetic gas heat exchange tube of the heat exchanger (1) is communicated with a hydrogen-rich synthetic gas outlet of a chemical-looping coke oven gas reforming component through a hot hydrogen-rich synthetic gas conveying tube, and a cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with an H hydrogen-rich synthetic gas conveying tube through a cold hydrogen-rich synthetic gas conveying tube 2 The gas inlets of the/CO purification and separation components are communicated;
the hydrogen-containing outlet of the chemical-looping coke oven gas reforming component is communicated with the hydrogen-containing inlet of the water-steam separating device through a hydrogen-containing conveying pipe, the condensed water outlet of the water-steam separating device is communicated with the condensed water inlet of the water-steam generating device through a condensed water pipe, and the hydrogen outlet of the water-steam separating device is communicated with the H through a hydrogen conveying pipe I 2 The gas inlet of the/CO purification and separation component is communicated, the water supplement port of the water vapor generation device is externally connected with a water supplement pipe, and the water vapor outlet of the water vapor generation device is communicated with the water vapor inlet of the chemical-looping coke oven gas reforming component through a water vapor conveying pipe;
H 2 h of/CO purification and separation Member 2 Outlet through H 2 Delivery pipeH of I and methanol synthesizer (7) respectively 2 Inlet and H 2 The storage devices (10) are communicated with each other H 2 The CO outlet of the/CO purification and separation component is respectively connected with the CO inlet of the methanol synthesizer (7) and the CO storage device (9) through a CO conveying pipe I.
2. The system for preparing methanol and coproducing hydrogen from synthesis gas by integrated chemical looping coke oven gas reforming as claimed in claim 1, wherein the system comprises: the methanol synthesizer (7) is externally connected with a methanol delivery pipe H 2 The storage device (10) is externally connected with H 2 The conveying pipe II and the CO storage device (9) are externally connected with a CO conveying pipe II.
3. The system for preparing methanol and coproducing hydrogen from synthesis gas by integrated chemical looping coke oven gas reforming as claimed in claim 1, wherein the system comprises: the chemical-looping coke oven gas reforming component comprises a chemical-looping coke oven gas reforming reactor I (2), a chemical-looping coke oven gas reforming reactor II (3) and a chemical-looping coke oven gas reforming reactor III (4) which have the same structure.
4. The system for preparing methanol and coproducing hydrogen from synthesis gas by integrated chemical looping coke oven gas reforming as claimed in claim 1, wherein the system comprises: h 2 The CO purification and separation component comprises a double pressure swing adsorption tower I (5) and a double pressure swing adsorption tower II (6), the bottom end of the double pressure swing adsorption tower I (5) is provided with a hydrogen-enriched synthesis gas inlet, the top end of the double pressure swing adsorption tower I (5) is provided with a CO outlet and an H outlet 2 The cold hydrogen-rich synthetic gas outlet of the hydrogen-rich synthetic gas heat exchange tube is communicated with the hydrogen-rich synthetic gas inlet of the double pressure swing adsorption tower I (5) through a cold hydrogen-rich synthetic gas conveying tube; h of double pressure swing adsorption tower I (5) 2 Outlet through H 2 The delivery pipe I is respectively connected with H of a methanol synthesizer (7) 2 Inlet and H 2 The storage device (10) is communicated, and a CO outlet of the double pressure swing adsorption tower I (5) is respectively communicated with a CO inlet of the methanol synthesizer (7) and the CO storage device (9) through a CO conveying pipe I; the bottom end of the double pressure swing adsorption tower II (6) is provided with a hydrogen inlet, the top end of the double pressure swing adsorption tower II (6) is provided with a hydrogen outlet, and the hydrogen outlet of the water-vapor separation device passes through the hydrogen conveying pipe I and the H of the double pressure swing adsorption tower II (6) 2 The inlets are communicated with each other, and H of the double pressure swing adsorption tower II (6) 2 Outlet through H 2 The delivery pipe I is respectively connected with H of a methanol synthesizer (7) 2 Inlet and H 2 The storage devices (10) are communicated.
5. The system for preparing methanol and coproducing hydrogen from synthesis gas by integrated chemical looping coke oven gas reforming as claimed in claim 1, wherein the system comprises: a cold coke oven gas delivery pipe, a hot coke oven gas delivery pipe, a cold air delivery pipe, a hot air delivery pipe, an oxygen-deprived air delivery pipe, a nitrogen delivery pipe, a hot hydrogen-rich synthetic gas delivery pipe, a cold hydrogen-rich synthetic gas delivery pipe, a water-containing hydrogen delivery pipe, a condensate pipe, a hydrogen delivery pipe I, a water supplement pipe, a water vapor delivery pipe, an H gas delivery pipe, a hydrogen-rich synthetic gas delivery pipe, a hydrogen-rich gas delivery pipe, a hydrogen-rich gas delivery pipe, a 2 The conveying pipe I and the CO conveying pipe I are both provided with one-way control valves.
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| CN202221313101.0U CN217418188U (en) | 2022-05-30 | 2022-05-30 | System for preparing methanol and co-producing hydrogen from synthesis gas by integrating chemical-looping coke oven gas reforming |
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