CN113527052B - Methane-to-methanol process - Google Patents
Methane-to-methanol process Download PDFInfo
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- CN113527052B CN113527052B CN202110672554.6A CN202110672554A CN113527052B CN 113527052 B CN113527052 B CN 113527052B CN 202110672554 A CN202110672554 A CN 202110672554A CN 113527052 B CN113527052 B CN 113527052B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 185
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000005485 electric heating Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 82
- 238000003786 synthesis reaction Methods 0.000 claims description 82
- 238000002407 reforming Methods 0.000 claims description 24
- 238000006477 desulfuration reaction Methods 0.000 claims description 21
- 230000023556 desulfurization Effects 0.000 claims description 21
- 239000011819 refractory material Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000498 cooling water Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000629 steam reforming Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 137
- 239000000779 smoke Substances 0.000 abstract description 5
- 239000002737 fuel gas Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention relates to a methane-making technology, which is based on an electric heating type converting furnace, wherein the synthetic gas separated from the upper part of a crude methanol separator is returned to a synthetic gas compressor inlet and a raw material heat exchanger inlet in a stranding way, the effective gas in the synthetic gas is recovered, and the methane utilization rate in the methane can reach more than 95%; the temperature of the raw material gas at the inlet of the reformer can be flexibly adjusted by adopting an electric heater to preheat the raw material gas at the inlet of the reformer; the high-temperature conversion gas at the outlet of the reformer is used for producing medium-pressure steam and overheated medium-pressure steam, the self-produced medium-pressure overheated steam of the device is totally used for distributing steam, the steam ratio at the inlet of the reformer is adjusted, external steam is not required to be consumed, the energy consumption is reduced, and the energy utilization rate is improved; compared with the traditional open fire heating furnace, the reformer provided by the invention does not need to consume fuel gas and discharge smoke, so that a complex combustion control system and a smoke waste heat recovery control system of the traditional reformer are omitted, and the process flow is simplified.
Description
Technical Field
The invention relates to a process for preparing methanol from methane.
Background
Biogas is a combustible gas generated by fermenting organic matters such as straw, weeds, human and animal excreta, garbage, sludge, industrial organic wastewater and the like under anaerobic conditions through microorganisms. Biogas is a flammable mixed gas, and the main component is CH 4 (about 50% -80%) and CO 2 (about 20% to 40%) and also contains a small amount of H 2 S、H 2 N 2 Its characteristics are similar to natural gas.
China is a country with relatively rich biogas resources, and at present, biogas in China is mainly used as fuel and illumination, has low energy utilization rate and also pollutes the environment. The biogas is taken as a renewable clean energy source, expands the application field of the biogas, and produces high added value products, which is an important direction of biogas development in the future.
The traditional methanol production technology mainly comes from non-renewable natural gas, coal and other fossil raw materials, and the search for a purpose of producing methanol by using renewable biological raw materials is pursued by students at home and abroad in recent decades, and in recent years, along with the development of large-scale industrialized biogas engineering, the production of methanol by using biogas as a raw material is possible. The method for preparing hydrogen by taking methane as a raw material disclosed in the Chinese patent application with the application number of 201010521863.5 comprises the following process flows: raw material biogas preheating, desulfurization, heating, reforming reaction, CO conversion and membrane separation, wherein a shell-and-tube reactor is adopted in the process reformer, and shell pass provides heat required by the reforming reaction through burning tail gas. The invention discloses a method for producing hydrogen by using biogas biomass in China patent application with the application number of 201610698707.3, which comprises the following technological processes: raw material biogas purification, methane concentration, steam conversion hydrogen production, CO conversion and hydrogen purification, wherein a conventional top-fired furnace or bottom-fired furnace is adopted as a process conversion furnace, and heat required by conversion reaction is provided by burning tail gas and fuel gas.
The prior art realizes the utilization of methane, but is limited by the structure of heat conversion equipment, so that the whole device has large occupied area and low capacity utilization rate.
Disclosure of Invention
Aiming at the current state of the art, the invention provides a methane-to-methanol process with small occupied area and high energy utilization rate.
The technical scheme adopted for solving the technical problems is as follows:
a methane-to-methanol process comprises the following steps:
the marsh gas from the marsh gas storage tank is sent into the molecular sieve desulfurization tank after being boosted by the marsh gas compressor, and H in the marsh gas is purified 2 S is removed to below 10ppm, and the methane after coarse desulfurization enters a raw material heat exchanger to be heated and then is sent into a ZnO fine desulfurization tank to remove H in the methane 2 S is removed to below 0.2ppm, methane discharged from the fine desulfurization tank is mixed with medium-pressure superheated steam self-produced by the device, the water-carbon ratio of the mixed gas is controlled to be 2.5, and raw material gas after steam distribution is sent into an electric heater for heating and then enters an electric heating type reformer for steam conversion reaction;
the method comprises the steps that raw gas flows through an electric heating type reformer from top to bottom, the residual methane volume content of reformed gas at an outlet of the electric heating type reformer is less than 12.7% of dry basis, high-temperature reformed gas enters a reformed gas steam generator, byproduct medium-pressure saturated steam is separated by a steam drum and then is sent to a medium-pressure steam superheater, the reformed gas temperature of the reformed gas steam generator is reduced and then enters the medium-pressure steam superheater, the medium-pressure steam from the steam drum is superheated and then is fed into methane as raw gas, the reformed gas is reduced and then enters a raw material heat exchanger, methane is preheated, the reduced temperature of the reformed gas is sent to a boiler water preheater, boiler water after preheating is sent to the steam drum, the converted gas is sent to a reformed gas cooler for heat exchange with circulating cooling water after the temperature of the reformed gas is reduced to 40 ℃, and then the converted gas is sent to a reformed gas liquid separating tank for condensate;
the synthesis gas after condensate liquid separation through a conversion gas liquid separation tank is sent to a No. 1 synthesis gas preheater after being boosted by a synthesis gas compressor, the synthesis gas enters a No. 2 synthesis gas preheater after being preheated, the synthesis gas enters a methanol synthesis tower after being preheated, crude methanol at the outlet of the methanol synthesis tower is sent to the No. 2 synthesis gas preheater to preheat the synthesis gas, the crude methanol enters the No. 1 synthesis gas preheater after being reduced in temperature, the crude methanol enters a crude methanol cooler to exchange heat with circulating cooling water after being reduced in temperature, the crude methanol temperature is reduced to 40 ℃, and the crude methanol is sent to a crude methanol separator to obtain crude methanol;
the synthesis gas separated from the upper part of the crude methanol separator is divided into three strands, the first strand of synthesis gas is used as purge gas to be discharged to a torch, the second strand of synthesis gas is used as first circulating gas to be returned to the inlet of the synthesis gas compressor for recycling, and the third strand of synthesis gas is used as second circulating gas to be returned to the inlet of the raw material heat exchanger for adjusting the hydrogen-carbon ratio of the conversion gas at the outlet of the electric heating type conversion furnace.
Preferably, the biogas from the biogas storage tank at 40 ℃ and 0.004MPaG is sent to a molecular sieve desulfurization tank after being boosted to 3.2MPaG by a biogas compressor, so that H in the biogas is removed 2 S is removed to below 10ppm, the methane after coarse desulfurization enters a raw material heat exchanger to be heated to 250 ℃, and then is sent into a ZnO fine desulfurization tank to remove H in the methane 2 S is removed to below 0.2ppm, methane discharged from a fine desulfurization tank is mixed with the medium-pressure superheated steam at 350 ℃ and 4.0MPaG which are self-produced by the device, the water-carbon ratio of the mixed gas is controlled to be 2.5, and the raw material gas after steam distribution is sent into an electric heater to be heated to 510 ℃ and then enters an electric heating type reformer for steam conversion reaction;
the raw material gas flows through an electric heating type reformer from top to bottom, the temperature of reforming gas at an outlet of the electric heating type reformer is 800 ℃, the residual methane volume content of the reforming gas is less than 12.7% of dry basis, high-temperature reforming gas enters a reforming gas steam generator, by-product 4.5MPaG medium-pressure saturated steam is delivered to a medium-pressure steam superheater after being separated by a steam drum, the temperature of the reforming gas steam generator is reduced to 370 ℃, the reforming gas enters the medium-pressure steam superheater, the medium-pressure steam from the steam drum is overheated to 350 ℃ and then is fed into methane as raw material gas steam, the temperature of the reforming gas is reduced to 325 ℃, the raw material heat exchanger is used for preheating methane to 250 ℃, the reforming gas temperature is reduced to 245 ℃, the boiler water is delivered to a boiler water preheater, the preheated boiler water is delivered to the steam drum, the temperature of the reforming gas is reduced to 177 ℃, and finally the reforming gas cooler and circulating cooling water are delivered to a reforming gas separating condensate after the temperature of the reforming gas is reduced to 40 ℃;
the synthesis gas after condensate liquid separation by a conversion gas liquid separation tank is boosted to 5.1MPaG by a synthesis gas compressor and then is sent to a No. 1 synthesis gas preheater, the synthesis gas temperature is preheated to 170 ℃, then the synthesis gas enters a No. 2 synthesis gas preheater, the synthesis gas is preheated to 235 ℃ and then enters a methanol synthesis tower, crude methanol with the outlet temperature of 260 ℃ of the methanol synthesis tower is sent to the No. 2 synthesis gas preheater to preheat the synthesis gas, the temperature of the crude methanol is reduced to 200 ℃, then enters the No. 1 synthesis gas preheater, the temperature of the crude methanol is reduced to 130 ℃, finally enters a crude methanol cooler to exchange heat with circulating cooling water, the temperature of the crude methanol is reduced to 40 ℃, and the crude methanol is sent to a crude methanol separator to obtain crude methanol;
the synthesis gas separated from the upper part of the crude methanol separator is divided into three strands, the first strand of synthesis gas with the concentration of 5% is used as purge gas, the purge gas is discharged to a torch, the second strand of synthesis gas with the concentration of 76% is used as first circulating gas, the first circulating gas is returned to the inlet of the synthesis gas compressor for recycling, and the third strand of synthesis gas with the concentration of 19% is used as second circulating gas, is returned to the inlet of the raw material heat exchanger and is used for adjusting the hydrogen-carbon ratio of the converted gas at the outlet of the electric heating type reformer.
In the above scheme, the electric heating type reformer comprises a furnace body and a reformer tube arranged in the furnace body, a central supporting structure arranged along the height direction of the furnace body is arranged at the central position of the furnace body, a first refractory material layer is arranged on the inner wall of the furnace body, a first heating wire is arranged on the inner side of the first refractory material layer, a second refractory material layer is arranged on the outer wall of the central supporting structure, a second heating wire is arranged on the outer side of the second refractory material layer, a heating cavity is formed between the first heating wire and the second heating wire, and the reformer tube is formed by arranging a plurality of reformer tubes in the heating cavity at intervals.
Preferably, the first heating wire and the second heating wire are separated into a first heating zone, a second heating zone and a third heating zone from top to bottom along the height of the furnace body, and the first heating wire and the second heating wire of each heating zone are independently controlled.
Preferably, the height ratio of the first heating area, the second heating area and the third heating area is 3:6:4.
Preferably, the first heating zone, the second heating zone and the third heating zone are respectively provided with a plurality of heating loops which can independently control temperature from top to bottom, the temperature of each heating loop in the first heating zone and the second heating zone is gradually increased from top to bottom, the temperature of each heating loop in the third heating zone is gradually reduced from top to bottom, and the temperature of the heating loop at the bottommost end of the third heating zone is higher than the temperature of the heating loop at the topmost end of the first heating zone.
Preferably, the temperature of the first heating zone is controlled between 40 ℃ and 1000 ℃, the temperature of the second heating zone is controlled between 40 ℃ and 1500 ℃, and the temperature of the third heating zone is controlled between 40 ℃ and 1200 ℃.
Preferably, three heating loops with sequential heating control are arranged in the first heating area from top to bottom, six heating loops with sequential heating control are arranged in the second heating area from top to bottom, and four heating loops with sequential cooling control are arranged in the third heating area from top to bottom.
Preferably, each heating zone is correspondingly provided with a plurality of thermocouple thermometers for detecting the furnace temperature, the thermocouple thermometers of each heating zone are arranged at intervals along the circumferential direction of the heating cavity, the number ratio of the thermocouple thermometers corresponding to the first heating zone, the second heating zone and the third heating zone is 1:2:1, and the thermocouple thermometer score corresponding to the second heating zone is arranged in an upper row and a lower row.
By adopting the heating control structure, the reformer is divided into three areas from top to bottom, each area is provided with a plurality of groups of heating wires which can be independently controlled, each group of heating wires is an independent loop, an independent temperature control system is arranged, the temperature is respectively controlled according to the reaction requirement, the power consumption can be reduced, the temperature of a hearth can be accurately controlled, and the device is more suitable for the characteristics of hydrocarbon steam reforming reaction and is beneficial to improving the depth of the reforming reaction.
Compared with the prior art, the invention has the advantages that: on the basis of relying on an electric heating type converting furnace, the invention returns the synthetic gas separated from the upper part of the crude methanol separator to the inlet of the synthetic gas compressor and the inlet of the raw material heat exchanger in a stranding way, and recovers the effective gas in the synthetic gas, and the utilization rate of methane in methane can reach more than 95 percent; the temperature of the raw material gas at the inlet of the reformer can be flexibly adjusted by adopting an electric heater to preheat the raw material gas at the inlet of the reformer; the high-temperature conversion gas at the outlet of the reformer is used for producing medium-pressure steam and overheated medium-pressure steam, the self-produced medium-pressure overheated steam of the device is totally used for distributing steam, the steam ratio at the inlet of the reformer is adjusted, external steam is not required to be consumed, the energy consumption is reduced, and the energy utilization rate is improved; compared with the traditional open flame heating furnace, the reformer provided by the invention does not need to consume fuel gas, does not need to discharge smoke, protects the environment, does not need a burner, a complex smoke heat recovery system and a chimney, effectively reduces the investment and occupied area of the device, simultaneously omits the complex combustion control system and the smoke waste heat recovery control system of the traditional reformer, and simplifies the process flow.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention;
FIG. 2 is a schematic diagram of an electrically heated reformer in accordance with an embodiment of the present invention;
fig. 3 is a cross-sectional view taken along the direction A-A in fig. 2.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
As shown in fig. 1 to 3, the method for preparing methanol from biogas in this embodiment comprises the following steps:
biogas 1 from a biogas storage tank at 40 ℃ and 0.004MPaG is boosted to 3.2MPaG by a biogas compressor 2 and then is sent into a molecular sieve desulfurization tank 3 to treat H in the biogas 2 S is removed to below 10ppm, the methane after coarse desulfurization enters a raw material heat exchanger 4 to be heated to 250 ℃, and then is sent into a ZnO fine desulfurization tank 5 to remove H in the methane 2 S is removed to below 0.2 ppm. The marsh gas from the fine desulfurization tank 5 is mixed with the medium-pressure superheated steam at 350 ℃ and 4.0MPaG which is self-produced by the device, the water-carbon ratio of the mixed gas is controlled to be 2.5, and the raw gas after steam distribution is sent into an electric heater 6 to be heated to 510 ℃ and then enters an electric heating type reformer 7 for steam conversion reaction. The composition of the feed gas is (V%): h 2 ：21.87％、N 2 ：0.3％、CH 4 ：16.94％、CO 2 ：6.79％、CO：3.15％、H 2 O：50.7％、CH 3 OH：0.25％。
The raw material gas flows through an electric heating type reformer 7 from top to bottom, the temperature of the reformed gas at the outlet of the electric heating type reformer 7 is 800 ℃, and the components are as follows (V%): h 2 ：40.17％、N 2 ：0.256％、CH 4 ：8.126％、CO 2 ：7.334％、CO：7.887％、H 2 O：36.01％、CH 3 OH:0.217%. The residual methane content of the converted gas is less than 10% (V) dry basis. The high-temperature conversion gas enters a conversion gas steam generator 8, and byproduct 4.5MPaG medium-pressure saturated steam is delivered to a medium-pressure steam superheater 10 after being separated by a steam drum 9. The temperature of the converted gas from the converted gas steam generator 8 is reduced to 370 ℃, the converted gas enters the medium pressure steam superheater 10, the medium pressure steam from the steam drum 9 is superheated to 350 ℃ and then is fed into methane as raw material gas steam, the temperature of the converted gas is reduced to 325 ℃, the methane enters the raw material heat exchanger 4, the methane is preheated to 250 ℃, the temperature of the converted gas is reduced to 245 ℃, the converted gas is fed into the boiler water preheater 11, the boiler water is preheated to 230 ℃, and the preheated boiler water is fed into the steam drum 9. The temperature of the converted gas is reduced to 177 ℃, and finally the converted gas is sent to a converted gas cooler 12 to exchange heat with circulating cooling water, and the converted gas is sent to a converted gas liquid separating tank 13 to separate condensate after the temperature of the converted gas is reduced to 40 ℃.
The synthesis gas after condensate liquid separation by the conversion gas liquid separation tank 13 is boosted to 5.1MPaG by the synthesis gas compressor 14 and then is sent to the No. 1 synthesis gas preheater 15, the synthesis gas is preheated to 170 ℃, then enters the No. 2 synthesis gas preheater 16, the synthesis gas is preheated to 235 ℃ and then enters the methanol synthesis tower 17, the crude methanol with the outlet temperature of 260 ℃ of the methanol synthesis tower 17 is sent to the No. 2 synthesis gas preheater 16 to preheat the synthesis gas, the crude methanol temperature is reduced to 200 ℃, then enters the No. 1 synthesis gas preheater 15, the crude methanol temperature is reduced to 130 ℃, finally enters the crude methanol cooler 18 to exchange heat with circulating cooling water, the crude methanol temperature is reduced to 40 ℃, and the crude methanol is sent to the crude methanol separator 19 to obtain the crude methanol.
The synthesis gas separated from the upper part of the crude methanol separator 19 is divided into three strands, the first strand of synthesis gas 20 with the concentration of 5 percent is used as purge gas to be discharged to a torch, the second strand of synthesis gas 21 with the concentration of 76 percent is used as first circulating gas to be returned to the inlet of the synthesis gas compressor 14 for recycling, and the third strand of synthesis gas 22 with the concentration of 19 percent is used as second circulating gas to be returned to the inlet of the raw material heat exchanger 4 for adjusting the hydrogen-carbon ratio of the converted gas at the outlet of the electric heating reformer 7.
In this embodiment, the electric heating reformer 7 is a square box structure or a cylindrical structure, and includes a furnace body 1' and a reformer tube 3' disposed in the furnace body 1', a central supporting structure 2' disposed along the height direction of the furnace body 1' is disposed at the central portion of the furnace body 1', a first refractory material layer 61' is disposed on the inner wall of the furnace body 1', a first heating wire 4' is disposed on the inner side of the first refractory material layer 61', a second refractory material layer 62' is disposed on the outer wall of the central supporting structure 2', a second heating wire 5' is disposed on the outer side of the second refractory material layer 62', and a heating cavity 100' is formed between the first refractory material layer 61' and the first heating wire 4' and the second heating wire 5' on the second refractory material layer 62', and the reformer tube 3' is disposed in the heating cavity 100' in a plurality and equidistant manner.
The first heating wire 4', the second heating wire 5' are separated from top to bottom along the height direction of the furnace body 1 'into a first heating zone 10', a second heating zone 20', and a third heating zone 30', and the first heating wire 4 'and the second heating wire 5' of each heating zone are independently controlled.
The height ratio of the first heating zone 10', the second heating zone 20', and the third heating zone 30' is 3:6:4. The furnace body 1' of this embodiment has a height of 13000mm, the first heating zone 10' has a height of 3000mm, the second heating zone has a height of 6000mm, and the third heating zone 30' has a height of 4000mm.
The first heating zone 10', the second heating zone 20', and the third heating zone 30' respectively have a plurality of heating loops with independent temperature control from top to bottom, the temperature of each heating loop in the first heating zone 10', the second heating zone 20' gradually increases from top to bottom, the temperature of each heating loop in the third heating zone 30' gradually decreases from top to bottom, and the temperature of the heating loop at the lowest end of the third heating zone 30 is higher than the temperature of the heating loop at the highest end of the first heating zone 10 '.
Specifically, the temperature of the first heating zone is controlled to be 40-1000 ℃, and three heating loops for sequentially heating and controlling are arranged in the first heating zone 10' from top to bottom; the temperature of the second heating zone 20 'is controlled to be 40-1500 ℃, and six heating loops for sequentially heating and controlling are arranged in the second heating zone 20' from top to bottom; the temperature of the third heating zone 30 'is controlled to be 40-1200 ℃, and four heating loops for sequentially cooling and controlling are arranged in the third heating furnace 30' from top to bottom.
The reformer is divided into three areas from top to bottom, each area is provided with a plurality of groups of heating wires which can be independently controlled, each group of heating wires is an independent loop, an independent temperature control system is arranged, the temperature is respectively controlled according to the reaction requirement, the power consumption can be reduced, the temperature of a hearth can be accurately controlled, and the reformer is more suitable for the characteristics of hydrocarbon steam reforming reaction and is beneficial to improving the depth of the reforming reaction.
Each heating zone is correspondingly provided with a plurality of thermocouple thermometers 15' for detecting the furnace temperature, the thermocouple thermometers 15' of each heating zone are arranged at intervals along the circumferential direction of the heating cavity 100', and the ratio of the numbers of the thermocouple thermometers 15' corresponding to the first heating zone 10', the second heating zone 20', the third heating zone 30' is 1:2:1. Twelve thermocouple thermometers 15 'are arranged on the first heating zone 10' and are respectively and equally arranged around the furnace body 1 'along the circumferential direction, twenty-four thermocouple thermometers 15' are arranged on the second heating zone 20 'and are respectively arranged on the furnace body 1' in an upper layer and a lower layer, and twelve thermocouples are arranged on each layer; the third heating zone 30 'is provided with twelve thermocouple thermometers which are respectively and equally arranged around the furnace body 1' along the circumferential direction.
In this embodiment, the furnace body 1 'includes an upper cover plate 8', a lower cover plate 9', and a box 14' disposed between the upper cover plate 8 'and the lower cover plate 9', the upper ends of the conversion tubes 3 'are connected with an upper tail tube 11' through the upper cover plate 8', the upper tail tube 11' is connected with an upper distribution tube 10', the lower ends of the conversion tubes 3' are connected with a lower tail tube 12 'through the lower cover plate 9', and the lower tail tube 12 'is connected with a lower gas collecting tube 13'.
The cross section of the box body 14' is rectangular or circular, the central supporting structure 2' is made of high-temperature-resistant alloy steel plates with the thickness of 14mm, and the width or the diameter of the central supporting structure 2' is 500-1000 mm. The heating chamber 100' has a width L of 1400-2400 mm and the first and second refractory layers 61', 62' have a thickness of 200-500 mm.
The periphery of the furnace body 1 'is provided with a supporting lug 7' for supporting and fixing equipment.
The working principle of the electric heating type reformer of the embodiment is as follows:
the feed gas firstly enters the upper distributing pipe 10', then is distributed to each converting pipe 3' through the upper pigtail pipe 11', flows through the converting pipes 3' from top to bottom, each converting pipe 3' is filled with a converting catalyst, and hydrocarbon steam conversion reaction occurs under the action of the catalyst to generate H 2 And CO, the first electric heating wire 4 'and the second electric heating wire 5' on the surfaces of the box body 14 'and the central supporting structure 2' provide heat required by the reaction, and the power of each group of electric heating wires is regulated to control the temperature of a hearth, so that the depth of the conversion reaction is controlled;
in this embodiment, the reformed gas is heated to 510 ℃ and then enters the electric heating reformer, and in order to avoid that the raw material does not cause cracking carbon deposition when entering the preheating section of the reformer for overheating, the heating temperature of the first heating zone 10 'cannot be too high, the temperature of the heating wires in the first heating zone 10' is controlled to be 700 ℃, 750 ℃ and 800 ℃ from top to bottom, and the temperature of the heating wires is sequentially increased according to a temperature gradient, so that the bed temperature of the reactor is gradually increased; the second heating zone 20 'is a main reaction zone, the required reaction temperature is higher, and the temperature of the heating wires in the second heating zone 20' is controlled to be 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ and 1100 ℃ from top to bottom in sequence; the third heating zone 30 'is used for further reacting the unreacted raw material gas, improving the conversion rate of the converted gas, and controlling the temperature of the heating wires in the third heating zone 30' to be 1100 ℃, 1050 ℃ and 1000 ℃ from top to bottom. The temperature of the reformed gas of the electric heating reformer 7 was 800 ℃.
In the description and claims of the present invention, terms indicating directions, such as "front", "rear", "upper", "lower", "left", "right", "side", "top", "bottom", etc., are used to describe various example structural parts and elements of the present invention, but these terms are used herein for convenience of description only and are determined based on the example orientations shown in the drawings. Because the disclosed embodiments of the invention may be arranged in a variety of orientations, the directional terminology is used for purposes of illustration and is in no way limiting, such as "upper" and "lower" are not necessarily limited to being in a direction opposite or coincident with the direction of gravity.
Claims (3)
1. The methane-to-methanol process is characterized by comprising the following steps of:
the marsh gas from the marsh gas storage tank is sent into the molecular sieve desulfurization tank after being boosted by the marsh gas compressor, and H in the marsh gas is purified 2 S is removed to below 10ppm, and the methane after coarse desulfurization enters a raw material heat exchanger to be heated and then is sent into a ZnO fine desulfurization tank to remove H in the methane 2 S is removed to below 0.2ppm, methane discharged from the fine desulfurization tank is mixed with medium-pressure superheated steam self-produced by the device, the water-carbon ratio of the mixed gas is controlled to be 2.5, and raw material gas after steam distribution is sent into an electric heater for heating and then enters an electric heating type reformer for steam conversion reaction;
the method comprises the steps that raw gas flows through an electric heating type reformer from top to bottom, the residual methane volume content of reformed gas at an outlet of the electric heating type reformer is less than 12.7% of dry basis, high-temperature reformed gas enters a reformed gas steam generator, byproduct medium-pressure saturated steam is separated by a steam drum and then is sent to a medium-pressure steam superheater, the reformed gas temperature of the reformed gas steam generator is reduced and then enters the medium-pressure steam superheater, the medium-pressure steam from the steam drum is superheated and then is fed into methane as raw gas, the reformed gas is reduced and then enters a raw material heat exchanger, methane is preheated, the reduced temperature of the reformed gas is sent to a boiler water preheater, boiler water after preheating is sent to the steam drum, the converted gas is sent to a reformed gas cooler for heat exchange with circulating cooling water after the temperature of the reformed gas is reduced to 40 ℃, and then the converted gas is sent to a reformed gas liquid separating tank for condensate;
the synthesis gas after condensate liquid separation through a conversion gas liquid separation tank is sent to a No. 1 synthesis gas preheater after being boosted by a synthesis gas compressor, the synthesis gas enters a No. 2 synthesis gas preheater after being preheated, the synthesis gas enters a methanol synthesis tower after being preheated, crude methanol at the outlet of the methanol synthesis tower is sent to the No. 2 synthesis gas preheater to preheat the synthesis gas, the crude methanol enters the No. 1 synthesis gas preheater after being reduced in temperature, the crude methanol enters a crude methanol cooler to exchange heat with circulating cooling water after being reduced in temperature, the crude methanol temperature is reduced to 40 ℃, and the crude methanol is sent to a crude methanol separator to obtain crude methanol;
the synthesis gas separated from the upper part of the crude methanol separator is divided into three strands, the first strand of synthesis gas is used as purge gas to be discharged to a torch, the second strand of synthesis gas is used as first circulating gas to be returned to the inlet of a synthesis gas compressor for recycling, and the third strand of synthesis gas is used as second circulating gas to be returned to the inlet of a raw material heat exchanger for adjusting the hydrogen-carbon ratio of the conversion gas at the outlet of the electric heating type conversion furnace;
the electric heating type reformer comprises a furnace body and a reformer tube arranged in the furnace body, wherein a central supporting structure which is arranged along the height direction of the furnace body is arranged at the central part of the furnace body, a first refractory material layer is arranged on the inner wall of the furnace body, a first heating wire is arranged on the inner side of the first refractory material layer, a second refractory material layer is arranged on the outer wall of the central supporting structure, a second heating wire is arranged on the outer side of the second refractory material layer, a heating cavity is formed between the first heating wire and the second heating wire, and a plurality of reformer tubes are arranged in the heating cavity at intervals; the first heating wire and the second heating wire are separated into a first heating zone, a second heating zone and a third heating zone from top to bottom along the height of the furnace body, and the first heating wire and the second heating wire of each heating zone are independently controlled; the height ratio of the first heating area to the second heating area to the height ratio of the third heating area to the first heating area to the second heating area to the height ratio of the first heating area to the third heating area to the first heating area to the height ratio of 3:6:4; the first heating zone, the second heating zone and the third heating zone are respectively provided with a plurality of heating loops which can independently control temperature from top to bottom, the temperatures of the heating loops in the first heating zone and the second heating zone are gradually increased from top to bottom, the temperatures of the heating loops in the third heating zone are gradually reduced from top to bottom, and the temperature of the heating loop at the bottommost end of the third heating zone is higher than the temperature of the heating loop at the topmost end of the first heating zone;
each heating zone is correspondingly provided with a plurality of thermocouple thermometers for detecting the furnace temperature, the thermocouple thermometers of each heating zone are arranged at intervals along the circumferential direction of the heating cavity, the number ratio of the thermocouple thermometers corresponding to the first heating zone, the second heating zone and the third heating zone is 1:2:1, and the thermocouple thermometer corresponding to the second heating zone is arranged in two rows up and down;
the height of the furnace body is 13000mm, the height of the first heating area is 3000mm, the height of the second heating area is 6000mm, and the height of the third heating area is 4000mm; the temperature of the heating wires in the first heating zone is controlled to be 700 ℃, 750 ℃ and 800 ℃ from top to bottom in sequence, and the temperature of the heating wires is increased in sequence according to a temperature gradient, so that the temperature of the reactor bed layer is increased gradually; the second heating zone is a main reaction zone, the required reaction temperature is high, and the temperature of the heating wires in the second heating zone is controlled to be 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ and 1100 ℃ from top to bottom in sequence; the third heating zone is used for further reacting unreacted raw material gas, improving the conversion rate of the converted gas, and controlling the temperature of the heating wires in the third heating zone to 1100 ℃, 1050 ℃ and 1000 ℃ from top to bottom.
2. The methane-to-methanol process according to claim 1, wherein: the biogas from the biogas storage tank at 40 ℃ and 0.004MPaG is boosted to 3.2MPaG by a biogas compressor and then is sent into a molecular sieve desulfurization tank, so that H in the biogas is purified 2 S is removed to below 10ppm, the methane after coarse desulfurization enters a raw material heat exchanger to be heated to 250 ℃, and then is sent into a ZnO fine desulfurization tank to remove H in the methane 2 S is removed to below 0.2ppm, methane discharged from a fine desulfurization tank is mixed with super-heated steam in the middle pressure of 4.0MPaG at 350 ℃ which is self-produced by a device, the water-carbon ratio of the mixed gas is controlled to be 2.5, and the mixed gas is matchedThe raw material gas after the steam is sent into an electric heater to be heated to 510 ℃ and then enters an electric heating type reformer to carry out steam reforming reaction;
the raw material gas flows through an electric heating type reformer from top to bottom, the temperature of reforming gas at an outlet of the electric heating type reformer is 800 ℃, the residual methane volume content of the reforming gas is less than 12.7% of dry basis, high-temperature reforming gas enters a reforming gas steam generator, by-product 4.5MPaG medium-pressure saturated steam is delivered to a medium-pressure steam superheater after being separated by a steam drum, the temperature of the reforming gas steam generator is reduced to 370 ℃, the reforming gas enters the medium-pressure steam superheater, the medium-pressure steam from the steam drum is overheated to 350 ℃ and then is fed into methane as raw material gas steam, the temperature of the reforming gas is reduced to 325 ℃, the raw material heat exchanger is used for preheating methane to 250 ℃, the reforming gas temperature is reduced to 245 ℃, the boiler water is delivered to a boiler water preheater, the preheated boiler water is delivered to the steam drum, the temperature of the reforming gas is reduced to 177 ℃, and finally the reforming gas cooler and circulating cooling water are delivered to a reforming gas separating condensate after the temperature of the reforming gas is reduced to 40 ℃;
the synthesis gas after condensate liquid separation by a conversion gas liquid separation tank is boosted to 5.1MPaG by a synthesis gas compressor and then is sent to a No. 1 synthesis gas preheater, the synthesis gas temperature is preheated to 170 ℃, then the synthesis gas enters a No. 2 synthesis gas preheater, the synthesis gas is preheated to 235 ℃ and then enters a methanol synthesis tower, crude methanol with the outlet temperature of 260 ℃ of the methanol synthesis tower is sent to the No. 2 synthesis gas preheater to preheat the synthesis gas, the temperature of the crude methanol is reduced to 200 ℃, then enters the No. 1 synthesis gas preheater, the temperature of the crude methanol is reduced to 130 ℃, finally enters a crude methanol cooler to exchange heat with circulating cooling water, the temperature of the crude methanol is reduced to 40 ℃, and the crude methanol is sent to a crude methanol separator to obtain crude methanol;
the synthesis gas separated from the upper part of the crude methanol separator is divided into three strands, the first strand of synthesis gas with the concentration of 5% is used as purge gas, the purge gas is discharged to a torch, the second strand of synthesis gas with the concentration of 76% is used as first circulating gas, the first circulating gas is returned to the inlet of the synthesis gas compressor for recycling, and the third strand of synthesis gas with the concentration of 19% is used as second circulating gas, is returned to the inlet of the raw material heat exchanger and is used for adjusting the hydrogen-carbon ratio of the converted gas at the outlet of the electric heating type reformer.
3. The methane-to-methanol process according to claim 2, wherein: three heating loops controlled by sequential heating are arranged in the first heating area from top to bottom, six heating loops controlled by sequential heating are arranged in the second heating area from top to bottom, and four heating loops controlled by sequential cooling are arranged in the third heating area from top to bottom.
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| CN103804138A (en) * | 2014-03-11 | 2014-05-21 | 太原理工大学 | Technology for producing methanol through coke oven gas |
| CN112368235A (en) * | 2018-06-29 | 2021-02-12 | 国际壳牌研究有限公司 | Electrically heated reactor and gas conversion process using said reactor |
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