WO2024213050A1 - Green methanol preparation process and system - Google Patents
Green methanol preparation process and system Download PDFInfo
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- WO2024213050A1 WO2024213050A1 PCT/CN2024/087260 CN2024087260W WO2024213050A1 WO 2024213050 A1 WO2024213050 A1 WO 2024213050A1 CN 2024087260 W CN2024087260 W CN 2024087260W WO 2024213050 A1 WO2024213050 A1 WO 2024213050A1
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 406
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 130
- 230000008569 process Effects 0.000 claims abstract description 121
- 239000002028 Biomass Substances 0.000 claims abstract description 114
- 238000010248 power generation Methods 0.000 claims abstract description 82
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 75
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 75
- 238000002309 gasification Methods 0.000 claims abstract description 62
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000446 fuel Substances 0.000 claims abstract description 46
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000003546 flue gas Substances 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 230000005611 electricity Effects 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 21
- 238000000605 extraction Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000002918 waste heat Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 3
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 CO2 Chemical compound 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002699 waste material 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
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J3/00—Circuit arrangements for ac mains or ac distribution networks
- H02J3/38—Arrangements for parallely feeding a single network by two or more generators, converters or transformers
- H02J3/381—Dispersed generators
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
- H02S10/10—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power including a supplementary source of electric power, e.g. hybrid diesel-PV energy systems
- H02S10/12—Hybrid wind-PV energy systems
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J2300/00—Systems for supplying or distributing electric power characterised by decentralized, dispersed, or local generation
- H02J2300/20—The dispersed energy generation being of renewable origin
- H02J2300/22—The renewable source being solar energy
- H02J2300/24—The renewable source being solar energy of photovoltaic origin
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J2300/00—Systems for supplying or distributing electric power characterised by decentralized, dispersed, or local generation
- H02J2300/20—The dispersed energy generation being of renewable origin
- H02J2300/28—The renewable source being wind energy
-
- 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
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the present invention relates to the field of new energy power generation technology, and specifically to a green methanol preparation process and system that utilizes renewable energy to produce green hydrogen and couples biomass gasification and biomass fuel power generation to achieve zero carbon emissions.
- green methanol Using renewable green electricity to produce green methanol (hereinafter referred to as green methanol) eliminates complex process steps such as coal gasification and purification, reduces fixed asset investment, and directly electrolyzes water into high-purity hydrogen and oxygen. Hydrogen reacts with carbon dioxide and carbon monoxide formed from biomass combustion to produce green methanol in one step, simplifying the production process and improving the reliability of the chemical system.
- the high-purity oxygen formed by electrolysis can be used for steelmaking and coal chemical processes, greatly reducing the energy consumption of traditional air separation oxygen production.
- green methanol products In addition to being made into zero-carbon ocean shipping, green methanol products can also be made into zero-carbon olefins, zero-carbon aromatics and other downstream chemicals, promoting the chemical industry to achieve zero-carbon transformation and upgrading.
- Chinese patent 202111286319.1 discloses a method for preparing methanol by gasifying pulverized coal waste boilers and coupling green electricity and green hydrogen to achieve near-zero carbon emissions. This method eliminates the boiler in the traditional coal-to-methanol route through a gasification process, and basically all carbon elements enter the methanol product, achieving near-zero carbon production of methanol products.
- this process uses fossil fuels as a carbon source and is equipped with a high-energy-consuming air separation device, while all electricity used in the process comes from a new energy power generation system, so this method still has the problem of volatility and imbalance in renewable power production.
- the present invention provides a green methanol preparation process and system that utilizes renewable energy to produce green hydrogen and couples it with biomass gasification and biomass fuel power generation to achieve zero carbon emissions.
- biomass gasification and biomass fuel power generation By coupling biomass gasification and biomass fuel power generation, the CO content in the green alcohol feed gas is increased, the feedstock conversion rate is improved, and energy consumption and equipment investment are reduced.
- Renewable energy power generation is combined with biomass fuel power generation to ensure the power stability and reliability of the overall process and system.
- the green methanol preparation process of the present invention comprises the following steps:
- Biomass fuel power generation Biomass is burned to generate electricity under the action of combustion aids, and flue gas and electricity are obtained, which are then transmitted to the power grid;
- renewable energy generation using wind and/or solar energy to generate electricity
- Electrolysis of water electrolysis of water generates hydrogen and oxygen; the electric energy obtained in the new energy power generation process is first supplied to the electrolysis process, and the remaining electric energy is transmitted to the power grid;
- Biomass gasification biomass is gasified under the action of a gasifying agent to generate a first synthesis gas; wherein the flue gas obtained by the biomass fuel power generation is divided into two parts, one part of the flue gas is mixed with a part of the oxygen generated in the water electrolysis process to form a combustion aid, and is returned to the biomass fuel power generation process; the remaining part of the flue gas is mixed with another part of the oxygen generated in the water electrolysis process to form a gasifying agent, and is input into the biomass gasification process;
- Methanol synthesis The hydrogen obtained in the water electrolysis process is compressed and mixed with the compressed first synthesis gas to obtain raw gas, which reacts to generate crude methanol;
- Methanol distillation The crude methanol is separated and purified to obtain high-quality green methanol products
- the method also includes inputting saturated steam produced as a by-product of the biomass gasification process and the methanol synthesis process into the biomass fuel power generation process to generate electricity after the flue gas is overheated.
- the flue gas generated by the biomass fuel power generation process includes high-purity CO2 and some unreacted oxygen.
- the generated flue gas is not discharged directly, but is divided into two streams:
- One stream is mixed with a part of the pure oxygen prepared in the water electrolysis process to form a combustion-supporting agent and is returned to the biomass fuel power generation process.
- the combustion-supporting agent includes CO2 and oxygen. Therefore, air and nitrogen contained in the air are not introduced into the biomass fuel power generation process.
- the combustion-supporting agent formed by the mixture of flue gas and pure oxygen replaces the air or oxygen-enriched air combustion-supporting agent used in the traditional coal-to-methanol process, avoiding the generation of nitrogen oxide impurities or direct discharge of flue gas into the atmosphere during the combustion process. Therefore, the present invention does not need to set up a purification device for denitrification or desulfurization, saving equipment investment and simplifying the process flow.
- Another flue gas is mixed with another part of the oxygen produced in the water electrolysis process to form a gasifying agent which is input into the biomass gasification process.
- the gasifying agent includes high-purity CO 2 , oxygen and water vapor. CO and hydrogen are generated under the action of the gasifying agent, and CO2 in the gasifying agent is also partially reduced.
- the first synthesis gas obtained by the biomass gasification process is a mixed gas rich in CO2 , including CO2 , CO and hydrogen.
- the first synthesis gas is compressed and input into the methanol synthesis process.
- the mixed gas of flue gas and oxygen is used as the gasifying agent, which avoids the introduction of nitrogen oxide impurities into the first synthesis gas due to the use of air as the gasifying agent, and further simplifies the process flow.
- the carbon source in the biomass is not discharged from the process flow but is input into the first synthesis gas and finally synthesized into green alcohol in the methanol synthesis process.
- the raw gas that is not completely reacted in the methanol synthesis process will return to the methanol synthesis process to continue to participate in the reaction. Therefore, the process flow of the present invention makes full use of the carbon source, and all the carbon sources in the biomass are used to prepare green alcohol products, which has a very high raw material utilization rate.
- the first synthesis gas is a CO2- rich mixed gas containing CO
- the methanol synthesis process will adopt a CO2 - rich methanol synthesis process.
- the single-pass conversion rate is 25% to 30%, and the methanol single-pass conversion rate of the present invention is significantly improved, reaching nearly 50%.
- the technical characteristics of the biomass fuel power generation process coupled with the biomass gasification process are further optimized.
- the molar ratio of CO in the first synthesis gas is 1% to 70%.
- the distribution of flue gas input to the biomass fuel power generation process and the biomass gasification process can be determined according to the demand for carbon source in the methanol synthesis process, and the proportion of CO in the first synthesis gas can be further adjusted.
- the molar ratio of oxygen in the combustion-supporting gas is 5% to 99%.
- the flue gas produced from the biomass fuel power generation process is divided into two streams.
- the carbon source in the flue gas can be distributed in the biomass fuel power generation process and the biomass gasification process by monitoring the oxygen content in the combustion-supporting gas.
- the mass ratio of the biomass input to the biomass fuel power generation process and the biomass gasification process is 1:(0.2-3).
- the proportion of the carbon source of the gasifying agent input to the biomass gasification process can be adjusted by adjusting the distribution of the biomass in the biomass fuel power generation process and the biomass gasification process, and the content of CO in the first synthesis gas can be further adjusted to meet the demand for carbon sources in the subsequent methanol synthesis process.
- the biomass gasification process adopts a circulating fluidized bed gasification process, with a gasification temperature of 560 to 1400° C. and a gasification pressure of 0 to 6500 KPaG.
- the biomass fuel power generation process uses an extraction condensing steam turbine generator set, and the extraction steam generated by power generation is respectively input into the methanol synthesis process and the methanol distillation process.
- the biomass fuel power generation process uses an extraction condensing steam turbine generator set, and the extraction steam generated by power generation is respectively input into the methanol synthesis process and the methanol distillation process.
- the biomass used in the present invention includes various organisms produced by photosynthesis using the atmosphere, water, land, etc., and can further be selected as biomass straw.
- reaction equations for preparing methanol using CO2 and CO as raw materials are shown in (1) and (2) respectively:
- reaction equations (1) and (2) It can be seen from reaction equations (1) and (2) that the amount of hydrogen required for the subsequent green alcohol synthesis is relatively large. Therefore, the green electricity obtained in the new energy power generation process is preferentially supplied to the water electrolysis process for electrolysis to produce hydrogen and oxygen, and the remaining electric energy is transmitted to the power grid to supply the electricity demand of other processes in the process flow of the present invention; further considering the volatility and imbalance of wind and solar power generation, a biomass fuel power generation process is set in the process of the present invention, and the obtained electric energy is transmitted to the power grid to compensate for the volatility of the electricity used by the new energy power generation to supply the water electrolysis process, the methanol synthesis process and other processes, thereby ensuring that the power consumption of the process of the present invention is continuous and stable, making the power consumption of the process more stable and safe.
- the water electrolysis process is carried out in an alkaline electrolytic cell; the temperature of the alkaline solution in the alkaline electrolytic cell is 80-100° C., and the operating pressure is 1.6-1.8 MPaG.
- the process of the present invention further comprises delivering part of the oxygen generated in the water electrolysis step as a product.
- the process of the present invention further includes a hydrogen storage process, in which the hydrogen generated in the water electrolysis process is stored, and hydrogen is input into the methanol synthesis process to ensure that hydrogen is continuously and stably input into the subsequent methanol synthesis process.
- a hydrogen storage process in which the hydrogen generated in the water electrolysis process is stored, and hydrogen is input into the methanol synthesis process to ensure that hydrogen is continuously and stably input into the subsequent methanol synthesis process.
- a hydrogen storage device is used in the hydrogen storage process to store and output hydrogen, and the storage capacity of the hydrogen storage device will be matched and calculated according to the load curve of the local wind power generator set and/or photovoltaic generator set and the allowable load of the downstream chemical device to ensure that in actual production, when the output of the new energy power generation process is small and the hydrogen production is reduced or insufficient, the green hydrogen is output through the hydrogen storage process to ensure the high-load operation of the process of the present invention, thereby increasing the operating load and annual operating hours of the overall process, increasing production and thus improving economic benefits.
- the present invention proposes a green methanol preparation system, which includes: a biomass fuel power generation device, a new energy power generation device, a water electrolysis device, a biomass gasification device, a methanol synthesis device and a methanol distillation device, wherein:
- the biomass fuel power generation device comprises a circulating fluidized bed boiler and an extraction condensing steam turbine generator set.
- the biomass is burned in the circulating fluidized bed boiler to generate steam to drive the extraction condensing steam turbine generator set to generate electricity, thereby obtaining flue gas and electric energy, which is then transmitted to the power grid.
- the new energy power generation device includes a wind power generator set and/or a photovoltaic generator set, which uses wind energy and/or solar energy to generate electricity.
- the electric energy obtained by the device is first supplied to the water electrolysis device, and the remaining part is transmitted to the power grid;
- the water electrolysis device comprises an electrolytic cell, in which water is electrolyzed to obtain hydrogen and oxygen;
- the biomass gasification device comprises a circulating fluidized bed gasifier, a high-temperature gasification stage furnace and a waste heat boiler connected in sequence, and the biomass undergoes a gasification reaction under the action of a gasifying agent to obtain a first synthesis gas;
- the methanol synthesis device comprises a methanol synthesis tower, the hydrogen generated by the electrohydrolysis device is compressed by a first compressor and mixed with the first synthesis gas compressed by a second compressor, and crude methanol is generated in the methanol synthesis tower;
- the methanol distillation device is used to purify and separate the crude methanol to obtain high-quality green methanol products
- the circulating fluidized bed boiler is provided with a flue gas output pipeline, and the water electrolysis device is provided with an oxygen output pipeline; the first branch of the flue gas output pipeline merges with the first branch of the oxygen output pipeline to form an combustion-aiding agent input pipeline, and the combustion-aiding agent input pipeline is connected to the circulating fluidized bed boiler; the second branch of the flue gas output pipeline merges with the second branch of the oxygen output pipeline to form a gasifying agent input pipeline, and the gasifying agent input pipeline is connected to the circulating fluidized bed gasifier; the biomass gasification device and the methanol synthesis device are connected to the extraction-condensing steam turbine generator set after heat exchange with the flue gas output pipeline through pipelines, respectively, so as to input saturated steam for power generation into the extraction-condensing steam turbine generator set.
- the green methanol preparation system of the present invention further includes a hydrogen storage device for storing hydrogen produced by the water electrolysis device and inputting hydrogen into the methanol synthesis device.
- the hydrogen storage device is a high-pressure gaseous hydrogen storage device or a liquid hydrogen storage device; further optionally, it is a high-pressure gaseous hydrogen storage device.
- the steam after extraction and condensation is connected to the methanol synthesis device and the methanol distillation device respectively through pipelines.
- the extraction-condensing steam turbine generator set is a double extraction-condensing steam turbine generator set.
- the oxygen output pipeline is further provided with a third branch for externally delivering oxygen products generated by electrolysis of the water electrolysis device.
- electrolyzers there are multiple electrolyzers; further, 4-5 electrolyzers may be arranged as a group, and the electrolyzers may be grouped and controlled, so that the operation and start and stop of the water electrolysis device are more flexible, thereby improving the green hydrogen production efficiency.
- the electrolytic cell is an alkaline electrolytic cell.
- the green methanol preparation process and system of the present invention couples the production of green hydrogen from renewable energy power generation with biomass fuel power generation and biomass gasification, and has the following beneficial effects:
- the saturated steam produced by the biomass gasification and methanol synthesis is input into the biomass fuel power generation process, and the power generation is carried out after the flue gas is superheated; and the steam condensed by the extraction condensing steam turbine generator set is respectively input into the methanol synthesis process and the methanol distillation process through pipelines. In this way, there is no need to set up another steam production system separately, which can reduce equipment investment and land occupation, and realize the cascade utilization of energy.
- FIG1 is a schematic diagram of the structure of the green methanol production system of the present invention.
- connection should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two components.
- connection should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two components.
- a green methanol preparation system includes: a biomass fuel power generation device 1, a new energy power generation device 2, a water electrolysis device 3, a biomass gasification device 4, a methanol synthesis device 5 and a methanol distillation device 6, wherein:
- Biomass fuel power generation device 1 including a circulating fluidized bed boiler and an extraction condensing steam turbine generator set. Biomass is burned in the circulating fluidized bed boiler to generate steam to drive the extraction condensing steam turbine generator set to generate electricity, thereby obtaining flue gas and electric energy, which is then transmitted to the power grid.
- New energy power generation device 2 including a wind turbine generator set and/or a photovoltaic generator set, using wind energy and/or solar energy to generate electricity.
- the electric energy obtained by the device is first supplied to the water electrolysis device 3, and the rest is transmitted to the power grid;
- the water electrolysis device 3 comprises an electrolytic cell, in which water is electrolyzed to obtain hydrogen and oxygen;
- Biomass gasification device 4 comprising a circulating fluidized bed gasifier, a high-temperature gasification stage furnace and a waste heat boiler connected in sequence, wherein the biomass undergoes a gasification reaction under the action of a gasifying agent to obtain a first synthesis gas;
- Methanol synthesis device 5 comprising a methanol synthesis tower, the hydrogen generated by the electrohydrolysis device is compressed by the first compressor 51 and mixed with the second synthesis gas compressed by the second compressor 52, and crude methanol is generated in the methanol synthesis tower;
- Methanol distillation unit 6 used to purify and separate crude methanol to obtain high-quality green methanol products
- the circulating fluidized bed boiler is provided with a flue gas output pipeline, and the electrolytic water device is provided with an oxygen output pipeline;
- the first branch of the flue gas output pipeline merges with the first branch of the oxygen output pipeline to form an combustion-aiding agent input pipeline, and the combustion-aiding agent input pipeline is connected to the circulating fluidized bed boiler;
- the second branch of the flue gas output pipeline merges with the second branch of the oxygen output pipeline to form a gasifying agent input pipeline, and the gasifying agent input pipeline is connected to the circulating fluidized bed gasifier;
- the biomass gasification device 4 and the methanol synthesis device 5 are connected to the extraction-condensing steam turbine generator set after heat exchange with the flue gas output pipeline through pipelines, respectively, so as to input saturated steam for power generation to the extraction-condensing steam turbine generator set.
- steam from three sources namely, the biomass gasification device 4, the methanol synthesis device 5 and the circulating fluidized bed boiler, is superheated by the flue gas output by the circulating fluidized bed boiler and then enters the extraction-condensing steam turbine generator set to generate electricity.
- FIG1 shows a connection mode in which the saturated steam output pipelines of the biomass gasification device 4 and the methanol synthesis device 5 are combined, exchanged with the flue gas, and then input into the biomass fuel power generation device 1.
- a person skilled in the art can, through non-creative labor, set up a connection mode in which the saturated steam output pipelines of the biomass gasification device 4 and the methanol synthesis device 5 are respectively exchanged with the flue gas, and then enter into the biomass fuel power generation device 1 for power generation.
- the technical solution thus formed is within the protection scope of the present invention.
- the green methanol preparation system of the present invention further includes a hydrogen storage device 7 for storing hydrogen produced by the water electrolysis device 3 and inputting the hydrogen into the methanol synthesis device 5 .
- the steam after extraction and condensation is connected to the methanol synthesis device 5 and the methanol distillation device 6 through pipelines respectively.
- the oxygen output pipeline is also provided with a third branch for externally delivering oxygen products.
- the extraction-condensing steam turbine generator set is a double extraction-condensing steam turbine generator set.
- This embodiment shows the process flow of green methanol production under specific working conditions using the green methanol production system shown in Example 1. It should be noted that this process flow is only a demonstration of a better process and does not limit the scope of protection of the present invention.
- Biomass fuel power generation The equipment used in this process includes circulating fluidized bed boilers and double-extraction condensing steam turbine generator sets.
- the low-heat calorific value of the biomass input into this process is about 13-15MJ/kg, and the consumption of the biomass boiler is 20,000-30,000kg/h.
- the steam produced by direct combustion of biomass is 80-100t/h.
- the 5.0MPaG steam produced as a by-product of biomass gasification is about 70-90t/h
- the 5.0MPaG steam produced as a by-product of methanol synthesis is about 60-80t/h.
- the steam from the above three sources is superheated by the flue gas output by the circulating fluidized bed boiler and enters the double-extraction condensing steam turbine generator set to generate electricity, with a power generation capacity of 30-50MW.
- the first-stage extraction steam of the double-extraction condensing steam turbine generator set is 1.1MPaG, 50-60t/h
- the second-stage extraction steam is 0.5MPaG, 10-15t/h.
- the molar ratio of oxygen in the combustion aid is 5% to 99%.
- the electricity used in the methanol synthesis and methanol distillation processes of this embodiment is about 30-50Mw.
- the power generation capacity of the bed boiler can meet the normal load electricity consumption of these processes.
- New energy power generation using wind turbines and photovoltaic generators to generate electricity.
- Electrohydrolysis The process uses the electricity produced by the new energy power generation process to electrolyze water. This process is carried out in an alkaline electrolytic cell.
- the optimal operating temperature of the alkaline solution in the electrolytic cell is about 90°C, and the operating pressure of the electrolytic cell is 1.6-1.8MPaG.
- the amount of pure hydrogen produced by electrolyzing water to produce hydrogen is 130,000-150,000Nm3 / h.
- Biomass gasification The equipment used in this process includes a circulating fluidized bed gasifier, a high-temperature gasification section furnace and a waste heat boiler, wherein the operating pressure of the circulating fluidized bed gasifier is about 0-6500KPaG, the operating temperature of the circulating fluidized bed gasifier is 560-1400°C, and the operating temperature of the high-temperature gasification section is 560-1400°C.
- the biomass mass required for biomass gasification is 50000-80000kg/h, and the gas production of biomass gasification is about 100000-130000Nm3 /h.
- the first synthesis gas is mainly composed of hydrogen, CO and CO2 , of which the molar ratio of CO is 1%-70%.
- Methanol synthesis and methanol distillation The first synthesis gas is compressed and mixed with green hydrogen produced by compressed electrolyzed water, and reacted in the methanol synthesis tower to prepare crude methanol.
- the crude methanol is separated and purified by the methanol distillation process to obtain high-quality green methanol products.
- the methanol synthesis process and the methanol distillation process can be set up with multiple production series according to the output requirements. Among them, the green alcohol production capacity of a single series is 20,000-35,000 kg/h, and the total methanol synthesis and methanol distillation production capacity of green alcohol is 60,000-105,000 kg/h.
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Abstract
Disclosed are a system and a green methanol preparation process that achieves zero carbon emissions by utilizing renewable energy source-produced green hydrogen and biomass gasification and biomass fuel power generation coupling. The process comprises the procedures of biomass fuel power generation, new energy power generation, water electrolysis, biomass gasification, methanol synthesis, and methanol rectification; by means of coupling biomass fuel power generation and biomass gasification, air is prevented from being used as a combustion improver or a gasification agent, which cuts the investment on a purification device and simplifies operations; zero carbon emissions is achieved; and a process of making methanol from a CO2-rich raw material gas is utilized, which enables the single-pass conversion rate of the process of the present invention to be improved by 60% or more. By combining new energy power generation and biomass fuel power generation, the problem of new energy power generation stability being affected by weather, climate, etc. when new energy is utilized alone for power generation to produce green hydrogen is overcome, enabling the process and the system of the present invention to operate stably for longer periods, and thus enhancing economic benefits.
Description
本发明涉及新能源发电技术领域,具体涉及一种利用可再生能源制绿氢与生物质气化、生物质燃料发电耦合实现零碳排放的绿色甲醇制备工艺及系统。The present invention relates to the field of new energy power generation technology, and specifically to a green methanol preparation process and system that utilizes renewable energy to produce green hydrogen and couples biomass gasification and biomass fuel power generation to achieve zero carbon emissions.
随着我国可再生新能源的大规模开发,可再生电力的发展主要受到了两方面因素的限制:其一,可再生电力生产的波动性和不平衡性,将导致电网平衡和消纳难度持续增加,尽管通过电化学储能可以提供系统平衡容量,但系统成本持续升高;其二,可再生电力的开发高度依赖用电负荷,我国可再生资源和电力需求逆向分布矛盾突出,解决可再生能源丰富的边远地区的绿电送出难题。但大规模特高压输电成本较高,且可再生能源波动对送和受端电网均构成压力。With the large-scale development of renewable energy in my country, the development of renewable electricity is mainly restricted by two factors: first, the volatility and imbalance of renewable electricity production will lead to increasing difficulty in grid balance and absorption. Although electrochemical energy storage can provide system balancing capacity, the system cost continues to rise; second, the development of renewable electricity is highly dependent on electricity load, and the contradiction between the reverse distribution of renewable resources and electricity demand in my country is prominent. The problem of green electricity transmission in remote areas with abundant renewable energy is solved. However, the cost of large-scale ultra-high voltage transmission is high, and the fluctuation of renewable energy puts pressure on both the sending and receiving power grids.
将新能源发电与电化学结合,将绿色电力转化为化学产品,将储电、输电变成化学品储运,可以在扩展绿电消纳空间的同时,极大降低储电输电成本,为偏远地区优质可再生能源开发创造有利条件。相比于抽水蓄能、电化学储能等传统储能方式,氢能是一种优质清洁的大规模储能载体,而甲醇被视为是一种理想的氢气载体。Combining new energy generation with electrochemistry, converting green electricity into chemical products, and transforming power storage and transmission into chemical storage and transportation can greatly reduce the cost of power storage and transmission while expanding the space for green electricity consumption, creating favorable conditions for the development of high-quality renewable energy in remote areas. Compared with traditional energy storage methods such as pumped storage and electrochemical energy storage, hydrogen energy is a high-quality, clean, large-scale energy storage carrier, and methanol is considered an ideal hydrogen carrier.
利用可再生绿电制绿色甲醇(以下简称为绿醇),省去煤气化和净化等复杂工艺环节,降低固定资产投资,将水直接电解成高纯度氢气和氧气,氢气与从生物质燃烧形成的二氧化碳和一氧化碳气发生加氢反应可一步制成绿色甲醇,简化了生产工艺,提高了化工系统可靠性。电解形成的高纯度氧气可供炼钢、煤化工工艺用氧,极大的降低传统的空分制氧能耗。绿色甲醇产品除可制成零碳远洋海运外,还可制成零碳烯烃、零碳芳烃等下游化学品,推动化工产业实现零碳化转型升级。Using renewable green electricity to produce green methanol (hereinafter referred to as green methanol) eliminates complex process steps such as coal gasification and purification, reduces fixed asset investment, and directly electrolyzes water into high-purity hydrogen and oxygen. Hydrogen reacts with carbon dioxide and carbon monoxide formed from biomass combustion to produce green methanol in one step, simplifying the production process and improving the reliability of the chemical system. The high-purity oxygen formed by electrolysis can be used for steelmaking and coal chemical processes, greatly reducing the energy consumption of traditional air separation oxygen production. In addition to being made into zero-carbon ocean shipping, green methanol products can also be made into zero-carbon olefins, zero-carbon aromatics and other downstream chemicals, promoting the chemical industry to achieve zero-carbon transformation and upgrading.
中国专利202111286319.1公开了一种粉煤废锅气化耦合绿电绿氢实现近零碳排放制备甲醇的方法,该方法通过气化工艺取消了传统煤制甲醇路线中的锅炉,将碳元素基本全部进入甲醇产品中,实现了甲醇产品的近零碳生产。但该工艺以化石燃料作为碳来源,且设置了高耗能的空气分离装置,而工艺过程中的用电全部来自新能源发电系统,故该方法仍存在再生电力生产的波动性和不平衡性的问题。
Chinese patent 202111286319.1 discloses a method for preparing methanol by gasifying pulverized coal waste boilers and coupling green electricity and green hydrogen to achieve near-zero carbon emissions. This method eliminates the boiler in the traditional coal-to-methanol route through a gasification process, and basically all carbon elements enter the methanol product, achieving near-zero carbon production of methanol products. However, this process uses fossil fuels as a carbon source and is equipped with a high-energy-consuming air separation device, while all electricity used in the process comes from a new energy power generation system, so this method still has the problem of volatility and imbalance in renewable power production.
发明内容Summary of the invention
针对上述问题,本发明的提供一种利用可再生能源制绿氢与生物质气化、生物质燃料发电耦合实现零碳排放的绿色甲醇制备工艺及系统,通过耦合生物质气化和生物质燃料发电,提高了绿醇原料气中CO的含量,提高了原料转化率,同时减少了能耗和设备投资;通过可再生能源发电与生物质燃料发电组合以保障整体工艺和系统的用电稳定性和可靠性。In view of the above problems, the present invention provides a green methanol preparation process and system that utilizes renewable energy to produce green hydrogen and couples it with biomass gasification and biomass fuel power generation to achieve zero carbon emissions. By coupling biomass gasification and biomass fuel power generation, the CO content in the green alcohol feed gas is increased, the feedstock conversion rate is improved, and energy consumption and equipment investment are reduced. Renewable energy power generation is combined with biomass fuel power generation to ensure the power stability and reliability of the overall process and system.
一方面,本发明绿色甲醇制备工艺包括以下工序:On the one hand, the green methanol preparation process of the present invention comprises the following steps:
生物质燃料发电:生物质在助燃剂作用下燃烧发电,得到烟气和电能,该部分电能输送至电网;Biomass fuel power generation: Biomass is burned to generate electricity under the action of combustion aids, and flue gas and electricity are obtained, which are then transmitted to the power grid;
新能源发电:采用风能和/或太阳能进行发电;Renewable energy generation: using wind and/or solar energy to generate electricity;
电解水:电解水生成氢气和氧气;所述新能源发电工序得到的电能优先供给电解水工序,剩余的电能输送至电网;Electrolysis of water: electrolysis of water generates hydrogen and oxygen; the electric energy obtained in the new energy power generation process is first supplied to the electrolysis process, and the remaining electric energy is transmitted to the power grid;
生物质气化:生物质在气化剂作用下气化生成第一合成气;其中,所述生物质燃料发电得到的烟气分为两部分,一部分烟气与所述电解水工序生成氧气中的一部分混合后形成助燃剂,并返回所述生物质燃料发电工序;剩余部分烟气与所述电解水工序生成氧气中的另一部分混合后形成气化剂,并输入所述生物质气化工序;Biomass gasification: biomass is gasified under the action of a gasifying agent to generate a first synthesis gas; wherein the flue gas obtained by the biomass fuel power generation is divided into two parts, one part of the flue gas is mixed with a part of the oxygen generated in the water electrolysis process to form a combustion aid, and is returned to the biomass fuel power generation process; the remaining part of the flue gas is mixed with another part of the oxygen generated in the water electrolysis process to form a gasifying agent, and is input into the biomass gasification process;
甲醇合成:电解水工序得到的氢气压缩后与经压缩后的第一合成气混合得到原料气,该原料气反应生成粗品甲醇;Methanol synthesis: The hydrogen obtained in the water electrolysis process is compressed and mixed with the compressed first synthesis gas to obtain raw gas, which reacts to generate crude methanol;
甲醇精馏:所述粗品甲醇经分离提纯得到高品质的绿色甲醇产品;Methanol distillation: The crude methanol is separated and purified to obtain high-quality green methanol products;
还包括将所述生物质气化工序和甲醇合成工序副产的饱和蒸汽输入所述生物质燃料发电工序,经烟气过热后进行发电。The method also includes inputting saturated steam produced as a by-product of the biomass gasification process and the methanol synthesis process into the biomass fuel power generation process to generate electricity after the flue gas is overheated.
上述技术方案中,设置了生物质燃料发电工序耦合生物质气化工序的技术特征。In the above technical solution, a technical feature of coupling a biomass fuel power generation process with a biomass gasification process is provided.
所述生物质燃料发电工序所生成烟气中包括高纯度的CO2和部分未反应完全的氧气,生成的烟气不直接排放,而是分为两股:The flue gas generated by the biomass fuel power generation process includes high-purity CO2 and some unreacted oxygen. The generated flue gas is not discharged directly, but is divided into two streams:
一股与所述电解水工序制备的纯氧中的一部混合和后形成助燃剂并返回生物质燃料发电工序,该助燃剂中包括CO2和氧气,由此,所述生物质燃料发电工序中未引入空气以及空气中所包含的氮气,由烟气和纯氧混合形成的助燃剂代替了传统煤制甲醇工艺中采用的空气或者富氧空气助燃气,避免在燃烧过程中产生氮氧化物杂质或将烟气直排大气,因此本发明无需设置脱硝或脱硫用的净化装置,节省了设备投资并简化了工艺流程。One stream is mixed with a part of the pure oxygen prepared in the water electrolysis process to form a combustion-supporting agent and is returned to the biomass fuel power generation process. The combustion-supporting agent includes CO2 and oxygen. Therefore, air and nitrogen contained in the air are not introduced into the biomass fuel power generation process. The combustion-supporting agent formed by the mixture of flue gas and pure oxygen replaces the air or oxygen-enriched air combustion-supporting agent used in the traditional coal-to-methanol process, avoiding the generation of nitrogen oxide impurities or direct discharge of flue gas into the atmosphere during the combustion process. Therefore, the present invention does not need to set up a purification device for denitrification or desulfurization, saving equipment investment and simplifying the process flow.
另一股烟气与所述电解水工序制备的氧气中的另一部混合后形成气化剂输入所述生物质气化工序,该气化剂中包括高纯度CO2、氧气和水蒸气。在所述生物质气化工序,生物质在
气化剂的作用下生成CO和氢气,同时气化剂中的CO2也会发生部分的还原。经生物质气化工序得到的第一合成气为富CO2的混合气体,包括CO2、CO和氢气。第一合成气被压缩后输入所述甲醇合成工序。本发明中以烟气和氧气混合气作为气化剂,避免了使用空气作为气化剂而导致在第一合成气中引入氮氧化物杂质,进一步简化了工艺流程。Another flue gas is mixed with another part of the oxygen produced in the water electrolysis process to form a gasifying agent which is input into the biomass gasification process. The gasifying agent includes high-purity CO 2 , oxygen and water vapor. CO and hydrogen are generated under the action of the gasifying agent, and CO2 in the gasifying agent is also partially reduced. The first synthesis gas obtained by the biomass gasification process is a mixed gas rich in CO2 , including CO2 , CO and hydrogen. The first synthesis gas is compressed and input into the methanol synthesis process. In the present invention, the mixed gas of flue gas and oxygen is used as the gasifying agent, which avoids the introduction of nitrogen oxide impurities into the first synthesis gas due to the use of air as the gasifying agent, and further simplifies the process flow.
上述技术方案中,无论是输入生物质燃料发电工序或生物质气化工序,生物质中的碳源均未排出本工艺流程而是输入第一合成气中并最终在甲醇合成工序中合成绿醇,在甲醇合成工序中未反应完全的原料气将返回甲醇合成工序继续参与反应。因此,本发明工艺流程充分利用碳源,将生物质中的碳源全部用于制备绿醇产品,具有极高的原料利用率。此外,本领域内普通技术人员将理解,第一合成气为包含CO的富CO2混合气体,因此所述甲醇合成工序将采用富CO2甲醇合成工艺,相对于纯CO2制甲醇工艺的单程转化率为25%~30%而言,本发明的甲醇单程转化率显著提高,达到了接近50%。In the above technical scheme, whether it is input into the biomass fuel power generation process or the biomass gasification process, the carbon source in the biomass is not discharged from the process flow but is input into the first synthesis gas and finally synthesized into green alcohol in the methanol synthesis process. The raw gas that is not completely reacted in the methanol synthesis process will return to the methanol synthesis process to continue to participate in the reaction. Therefore, the process flow of the present invention makes full use of the carbon source, and all the carbon sources in the biomass are used to prepare green alcohol products, which has a very high raw material utilization rate. In addition, it will be understood by ordinary technicians in this field that the first synthesis gas is a CO2- rich mixed gas containing CO, so the methanol synthesis process will adopt a CO2 - rich methanol synthesis process. Compared with the pure CO2 methanol production process, the single-pass conversion rate is 25% to 30%, and the methanol single-pass conversion rate of the present invention is significantly improved, reaching nearly 50%.
上述技术方案中,进一步优化了生物质燃料发电工序耦合生物质气化工序的技术特征。In the above technical solution, the technical characteristics of the biomass fuel power generation process coupled with the biomass gasification process are further optimized.
可选的,所述第一合成气中CO所占摩尔比为1%~70%。实际生产过程中,可根据所述甲醇合成工序中碳源的需求量来确定输入所述生物质燃料发电工序和所述生物质气化工序的烟气分配,进一步调控第一合成气中CO的占比。Optionally, the molar ratio of CO in the first synthesis gas is 1% to 70%. In the actual production process, the distribution of flue gas input to the biomass fuel power generation process and the biomass gasification process can be determined according to the demand for carbon source in the methanol synthesis process, and the proportion of CO in the first synthesis gas can be further adjusted.
可选的,所述助燃气中氧气所占摩尔比为5%~99%。本发明中从所述生物质燃料发电工序生产的烟气分为两股,在实际生产过程中还可通过对助燃气中氧气含量的监测,来实现对烟气中的碳源在生物质燃料发电工序和生物质气化工序中的分配。Optionally, the molar ratio of oxygen in the combustion-supporting gas is 5% to 99%. In the present invention, the flue gas produced from the biomass fuel power generation process is divided into two streams. In the actual production process, the carbon source in the flue gas can be distributed in the biomass fuel power generation process and the biomass gasification process by monitoring the oxygen content in the combustion-supporting gas.
可选的,输入所述生物质燃料发电工序和所述生物质气化工序的生物质的质量比为1:(0.2-3)。在实际生产过程中,还可通过调节生物质在所述生物质燃料发电工序和所述生物质气化工序分配情况,来调控输入生物质气化工序中气化剂的碳源的占比,进一步调控第一合成气中CO的含量,以满足后续甲醇合成工序中碳源的需求。Optionally, the mass ratio of the biomass input to the biomass fuel power generation process and the biomass gasification process is 1:(0.2-3). In the actual production process, the proportion of the carbon source of the gasifying agent input to the biomass gasification process can be adjusted by adjusting the distribution of the biomass in the biomass fuel power generation process and the biomass gasification process, and the content of CO in the first synthesis gas can be further adjusted to meet the demand for carbon sources in the subsequent methanol synthesis process.
可选的,所述生物质气化工序采用循环流化床气化工艺,气化温度为560~1400℃,气化压力为0~6500KPaG。Optionally, the biomass gasification process adopts a circulating fluidized bed gasification process, with a gasification temperature of 560 to 1400° C. and a gasification pressure of 0 to 6500 KPaG.
可选的,所述生物质燃料发电工序采用抽凝式汽轮发电机组,发电产生的抽汽蒸汽分别输入甲醇合成工序和甲醇精馏工序。由此无需单独设置产汽系统,可减少设备投资和占地,实现能量的梯级利用。Optionally, the biomass fuel power generation process uses an extraction condensing steam turbine generator set, and the extraction steam generated by power generation is respectively input into the methanol synthesis process and the methanol distillation process. In this way, there is no need to set up a separate steam production system, which can reduce equipment investment and land occupation, and realize the cascade utilization of energy.
可选的,本发明所用生物质包括利用大气、水、土地等通过光合作用而产生的各种有机体,进一步可选为生物质秸秆。Optionally, the biomass used in the present invention includes various organisms produced by photosynthesis using the atmosphere, water, land, etc., and can further be selected as biomass straw.
在上述技术方案中,设置了再生能源发电与生物质燃料发电组合供电的技术特征。In the above technical solution, a technical feature of combined power supply of renewable energy power generation and biomass fuel power generation is set.
以CO2和CO为原料制备甲醇的反应式分别如(1)和(2)所示:
The reaction equations for preparing methanol using CO2 and CO as raw materials are shown in (1) and (2) respectively:
The reaction equations for preparing methanol using CO2 and CO as raw materials are shown in (1) and (2) respectively:
由反应式(1)和(2)可知,后续绿醇合成需要的氢气的量较大,因此,所述新能源发电工序得到的绿电优先供给电解水工序,用于电解制氢气和氧气,剩余的电能输送至电网供给本发明工艺流程中其他工序的用电需求;进一步考虑到风能和太阳能发电的波动性和不平衡性,本发明工艺中设置生物质燃料发电工序,得到的电能输送至电网用于补偿新能源发电供给电解水工序、甲醇合成工序等工序用电的波动性,从而能保证本发明工艺用电持续、稳定,使得工艺用电更为平稳和安全。It can be seen from reaction equations (1) and (2) that the amount of hydrogen required for the subsequent green alcohol synthesis is relatively large. Therefore, the green electricity obtained in the new energy power generation process is preferentially supplied to the water electrolysis process for electrolysis to produce hydrogen and oxygen, and the remaining electric energy is transmitted to the power grid to supply the electricity demand of other processes in the process flow of the present invention; further considering the volatility and imbalance of wind and solar power generation, a biomass fuel power generation process is set in the process of the present invention, and the obtained electric energy is transmitted to the power grid to compensate for the volatility of the electricity used by the new energy power generation to supply the water electrolysis process, the methanol synthesis process and other processes, thereby ensuring that the power consumption of the process of the present invention is continuous and stable, making the power consumption of the process more stable and safe.
可选的,所述电解水工序在碱性电解槽中进行;所述碱性电解槽内碱液的温度为80~100℃,操作压力为1.6~1.8MPaG。Optionally, the water electrolysis process is carried out in an alkaline electrolytic cell; the temperature of the alkaline solution in the alkaline electrolytic cell is 80-100° C., and the operating pressure is 1.6-1.8 MPaG.
可选的,本发明工艺中还包括将部分所述电解水工序生成的氧气作为产品外送。Optionally, the process of the present invention further comprises delivering part of the oxygen generated in the water electrolysis step as a product.
可选的,本发明工艺中还包括储氢工序,该工序中对所述电解水工序生成的氢气进行储存,以及向所述甲醇合成工序输入氢气,以保证持续稳定地向后续甲醇合成工序输入氢气。可选的,储氢工序中采用储氢设备储存并输出氢气,储氢装置的存储能力将根据当地的风能发电机组和/或光伏发电机组发电的负荷曲线和下游化工装置的允许负荷进行匹配计算,以确保在实际生产中,当新能源发电工序出力较小、产氢量下降或不足的情况下,通过储氢工序输出绿氢来保证本发明工艺高负荷运行,从而提高整体工艺的操作运行负荷和全年运行小时数,提高产量进而提升经济效益。Optionally, the process of the present invention further includes a hydrogen storage process, in which the hydrogen generated in the water electrolysis process is stored, and hydrogen is input into the methanol synthesis process to ensure that hydrogen is continuously and stably input into the subsequent methanol synthesis process. Optionally, a hydrogen storage device is used in the hydrogen storage process to store and output hydrogen, and the storage capacity of the hydrogen storage device will be matched and calculated according to the load curve of the local wind power generator set and/or photovoltaic generator set and the allowable load of the downstream chemical device to ensure that in actual production, when the output of the new energy power generation process is small and the hydrogen production is reduced or insufficient, the green hydrogen is output through the hydrogen storage process to ensure the high-load operation of the process of the present invention, thereby increasing the operating load and annual operating hours of the overall process, increasing production and thus improving economic benefits.
另一方面,本发明提出了一种绿色甲醇制备系统,该系统包括:生物质燃料发电装置、新能源发电装置、电解水装置、生物质气化装置、甲醇合成装置和甲醇精馏装置,其中,On the other hand, the present invention proposes a green methanol preparation system, which includes: a biomass fuel power generation device, a new energy power generation device, a water electrolysis device, a biomass gasification device, a methanol synthesis device and a methanol distillation device, wherein:
所述生物质燃料发电装置:包括循环流化床锅炉和抽凝式汽轮发电机组,生物质在所述循环流化床锅炉中燃烧产生蒸汽带动抽凝式汽轮发电机组发电,得到烟气和电能,该部分电能输送至电网;The biomass fuel power generation device comprises a circulating fluidized bed boiler and an extraction condensing steam turbine generator set. The biomass is burned in the circulating fluidized bed boiler to generate steam to drive the extraction condensing steam turbine generator set to generate electricity, thereby obtaining flue gas and electric energy, which is then transmitted to the power grid.
所述新能源发电装置:包括风力发电机组和/或光伏发电机组,采用风能和/或太阳能发电,该装置得到的电能优先供给电解水装置,剩余部分输送至电网;The new energy power generation device includes a wind power generator set and/or a photovoltaic generator set, which uses wind energy and/or solar energy to generate electricity. The electric energy obtained by the device is first supplied to the water electrolysis device, and the remaining part is transmitted to the power grid;
所述电解水装置:包括电解槽,在所述电解槽中电解水得到氢气和氧气;The water electrolysis device comprises an electrolytic cell, in which water is electrolyzed to obtain hydrogen and oxygen;
所述生物质气化装置:包括依次连接的循环流化床气化炉、高温气化段炉和余热锅炉,生物质在气化剂作用下发生气化反应得到第一合成气;The biomass gasification device comprises a circulating fluidized bed gasifier, a high-temperature gasification stage furnace and a waste heat boiler connected in sequence, and the biomass undergoes a gasification reaction under the action of a gasifying agent to obtain a first synthesis gas;
所述甲醇合成装置:包括甲醇合成塔,所述电水解装置生成的氢气经第一压缩机压缩后与经第二压缩机压缩后的第一合成气混合,并在所述甲醇合成塔中生成粗品甲醇;The methanol synthesis device comprises a methanol synthesis tower, the hydrogen generated by the electrohydrolysis device is compressed by a first compressor and mixed with the first synthesis gas compressed by a second compressor, and crude methanol is generated in the methanol synthesis tower;
所述甲醇精馏装置:用于提纯分离所述粗品甲醇,得到高品质的绿色甲醇产品;
The methanol distillation device is used to purify and separate the crude methanol to obtain high-quality green methanol products;
所述循环流化床锅炉设置烟气输出管路,所述电解水装置设置氧气输出管路;所述烟气输出管路的第一支路与所述氧气输出管路的第一支路汇合形成助燃剂输入管路,该助燃剂输入管路连接所述循环流化床锅炉;所述烟气输出管路的第二支路和所述氧气输出管路的第二支路汇合形成气化剂输入管路,该气化剂输入管路连接所述循环流化床气化炉;所述生物质气化装置和甲醇合成装置分别经管路与所述烟气输出管路换热后连接所述抽凝式汽轮发电机组,用于向所述抽凝式汽轮发电机组输入发电用的饱和蒸汽。The circulating fluidized bed boiler is provided with a flue gas output pipeline, and the water electrolysis device is provided with an oxygen output pipeline; the first branch of the flue gas output pipeline merges with the first branch of the oxygen output pipeline to form an combustion-aiding agent input pipeline, and the combustion-aiding agent input pipeline is connected to the circulating fluidized bed boiler; the second branch of the flue gas output pipeline merges with the second branch of the oxygen output pipeline to form a gasifying agent input pipeline, and the gasifying agent input pipeline is connected to the circulating fluidized bed gasifier; the biomass gasification device and the methanol synthesis device are connected to the extraction-condensing steam turbine generator set after heat exchange with the flue gas output pipeline through pipelines, respectively, so as to input saturated steam for power generation into the extraction-condensing steam turbine generator set.
可选的,本发明绿色甲醇制备系统还包括储氢装置,用于储存所述电解水装置生产的氢气,以及将氢气输入所述甲醇合成装置。Optionally, the green methanol preparation system of the present invention further includes a hydrogen storage device for storing hydrogen produced by the water electrolysis device and inputting hydrogen into the methanol synthesis device.
进一步可选的,所述储氢装置为高压气态储氢装置或液态储氢装置;更进一步可选为高压气态储氢装置。Further optionally, the hydrogen storage device is a high-pressure gaseous hydrogen storage device or a liquid hydrogen storage device; further optionally, it is a high-pressure gaseous hydrogen storage device.
进一步可选的,经抽凝后的蒸汽经管路分别连接所述甲醇合成装置和所述甲醇精馏装置。Further optionally, the steam after extraction and condensation is connected to the methanol synthesis device and the methanol distillation device respectively through pipelines.
可选的,所述抽凝式汽轮发电机组为双抽凝式汽轮发电机组。Optionally, the extraction-condensing steam turbine generator set is a double extraction-condensing steam turbine generator set.
可选的,所述氧气输出管路还设有第三支路,用于外送由电解水装置电解生成的氧气产品。Optionally, the oxygen output pipeline is further provided with a third branch for externally delivering oxygen products generated by electrolysis of the water electrolysis device.
可选的,所述电解槽的数量为多台;进一步可选为设置每4-5台为一组,对所述电解槽进行分组控制,使得所述电解水装置的操作和启停更为灵活,提高绿氢生产效率。Optionally, there are multiple electrolyzers; further, 4-5 electrolyzers may be arranged as a group, and the electrolyzers may be grouped and controlled, so that the operation and start and stop of the water electrolysis device are more flexible, thereby improving the green hydrogen production efficiency.
可选的,电解槽为碱性电解槽。Optionally, the electrolytic cell is an alkaline electrolytic cell.
与现有技术相比,本发明绿色甲醇制备工艺和系统将新能源发电制绿氢与生物质燃料发电、生物质气化耦合,具有以下有益效果:Compared with the prior art, the green methanol preparation process and system of the present invention couples the production of green hydrogen from renewable energy power generation with biomass fuel power generation and biomass gasification, and has the following beneficial effects:
1.通过设置生物质燃料发电和生物质气化耦合技术特征,避免产生氮氧化物杂质或将烟气直排大气,节省脱硝或脱硫用的净化装置投入并简化流程;生物质中的碳源均未排出本发明工艺流程,充分利用碳源,具有极高的原料利用率;与现有技术中纯富CO2制甲醇工艺相比提高了原料气中CO的占比,使得本发明工艺的单程转化率可提高60%以上。1. By setting up the coupling technical features of biomass fuel power generation and biomass gasification, the generation of nitrogen oxide impurities or direct discharge of flue gas into the atmosphere is avoided, the investment in purification devices for denitrification or desulfurization is saved and the process is simplified; the carbon source in the biomass is not discharged from the process flow of the present invention, the carbon source is fully utilized, and the raw material utilization rate is extremely high; compared with the pure CO2 - rich methanol production process in the prior art, the proportion of CO in the raw gas is increased, so that the single-pass conversion rate of the process of the present invention can be increased by more than 60%.
2.采用新能源发电与生物质燃料发电相结合的电力组合方案,有效克服了单独采用新能源发电制绿氢时因天气、气候等影响新能源发电稳定性的问题,提高了工艺流程用电的稳定性和可靠性,使得本发明工艺和系统平稳运行时间更长,增加产量进而提升经济效益。2. The use of a power combination scheme that combines renewable energy power generation with biomass fuel power generation effectively overcomes the problem of weather, climate, etc. affecting the stability of renewable energy power generation when renewable energy power generation is used alone to produce green hydrogen, improves the stability and reliability of electricity consumption in the process, and allows the process and system of the present invention to operate stably for a longer time, thereby increasing production and improving economic benefits.
3.将所述生物质气化和甲醇合成副产的饱和蒸汽输入所述生物质燃料发电工序,经烟气过热后进行发电;并将经抽凝式汽轮发电机组抽凝后的蒸汽经管路分别输入甲醇合成工序和甲醇精馏工序。由此无需单独设置另外的产汽系统,可减少设备投资和占地,实现能量的梯级利用。
3. The saturated steam produced by the biomass gasification and methanol synthesis is input into the biomass fuel power generation process, and the power generation is carried out after the flue gas is superheated; and the steam condensed by the extraction condensing steam turbine generator set is respectively input into the methanol synthesis process and the methanol distillation process through pipelines. In this way, there is no need to set up another steam production system separately, which can reduce equipment investment and land occupation, and realize the cascade utilization of energy.
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:
图1为本发明绿色甲醇制备系统结构示意图。FIG1 is a schematic diagram of the structure of the green methanol production system of the present invention.
其中,上述附图包括以下附图标记:
1-生物质燃料发电装置,2-新能源发电装置,3-电解水装置,4-生物质气化装置,5-甲醇
合成装置、51-第一压缩机、52-第二压缩机,6-甲醇精馏装置,7-储氢装置,8-电网。The above drawings include the following reference numerals:
1-Biomass fuel power generation device, 2-new energy power generation device, 3-water electrolysis device, 4-biomass gasification device, 5-methanol synthesis device, 51-first compressor, 52-second compressor, 6-methanol distillation device, 7-hydrogen storage device, 8-power grid.
1-生物质燃料发电装置,2-新能源发电装置,3-电解水装置,4-生物质气化装置,5-甲醇
合成装置、51-第一压缩机、52-第二压缩机,6-甲醇精馏装置,7-储氢装置,8-电网。The above drawings include the following reference numerals:
1-Biomass fuel power generation device, 2-new energy power generation device, 3-water electrolysis device, 4-biomass gasification device, 5-methanol synthesis device, 51-first compressor, 52-second compressor, 6-methanol distillation device, 7-hydrogen storage device, 8-power grid.
下面通过具体实施方式结合附图对本发明作进一步详细说明。需说明的是,本实施例中诸如“第一”“第二”等之类的关系术语仅仅用来将一个与另一个具有相同名称的部件区分开来,而不一定要求或者暗示这些部件之间存在任何这种实际的关系或者顺序。限定有“第一”“第二”等的特征可以明示或者隐含地包括一个或者更多个该特征。The present invention is further described in detail below through specific embodiments in conjunction with the accompanying drawings. It should be noted that in this embodiment, relational terms such as "first", "second", etc. are only used to distinguish one component with the same name from another, and do not necessarily require or imply any actual relationship or order between these components. Features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features.
在本发明创造的描述中,除非另有明确的规定和限定,术语“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。对于本领域的普通技术人员而言,可以通过具体情况理解上述术语在本发明创造中的具体含义。In the description of the present invention, unless otherwise clearly specified and limited, the term "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
实施例1Example 1
一种绿色甲醇制备系统,如图1所示,该系统包括:生物质燃料发电装置1、新能源发电装置2、电解水装置3、生物质气化装置4、甲醇合成装置5和甲醇精馏装置6,其中,A green methanol preparation system, as shown in FIG1 , includes: a biomass fuel power generation device 1, a new energy power generation device 2, a water electrolysis device 3, a biomass gasification device 4, a methanol synthesis device 5 and a methanol distillation device 6, wherein:
生物质燃料发电装置1:包括循环流化床锅炉和抽凝式汽轮发电机组,生物质在循环流化床锅炉中燃烧产生蒸汽带动抽凝式汽轮发电机组发电,得到烟气和电能,该部分电能输送至电网;Biomass fuel power generation device 1: including a circulating fluidized bed boiler and an extraction condensing steam turbine generator set. Biomass is burned in the circulating fluidized bed boiler to generate steam to drive the extraction condensing steam turbine generator set to generate electricity, thereby obtaining flue gas and electric energy, which is then transmitted to the power grid.
新能源发电装置2:包括风力发电机组和/或光伏发电机组,采用风能和/或太阳能发电,该装置得到的电能优先供给电解水装置3,剩余部分输送至电网;New energy power generation device 2: including a wind turbine generator set and/or a photovoltaic generator set, using wind energy and/or solar energy to generate electricity. The electric energy obtained by the device is first supplied to the water electrolysis device 3, and the rest is transmitted to the power grid;
电解水装置3:包括电解槽,在电解槽中电解水得到氢气和氧气;The water electrolysis device 3 comprises an electrolytic cell, in which water is electrolyzed to obtain hydrogen and oxygen;
生物质气化装置4:包括依次连接的循环流化床气化炉、高温气化段炉和余热锅炉,生物质在气化剂作用下发生气化反应得到第一合成气;Biomass gasification device 4: comprising a circulating fluidized bed gasifier, a high-temperature gasification stage furnace and a waste heat boiler connected in sequence, wherein the biomass undergoes a gasification reaction under the action of a gasifying agent to obtain a first synthesis gas;
甲醇合成装置5:包括甲醇合成塔,电水解装置生成的氢气经第一压缩机51压缩后与经第二压缩机52压缩后的第二合成气混合,并在甲醇合成塔中生成粗品甲醇;Methanol synthesis device 5: comprising a methanol synthesis tower, the hydrogen generated by the electrohydrolysis device is compressed by the first compressor 51 and mixed with the second synthesis gas compressed by the second compressor 52, and crude methanol is generated in the methanol synthesis tower;
甲醇精馏装置6:用于提纯分离粗品甲醇,得到高品质的绿色甲醇产品;
Methanol distillation unit 6: used to purify and separate crude methanol to obtain high-quality green methanol products;
所述循环流化床锅炉设置烟气输出管路,所述电解水装置设置氧气输出管路;所述烟气输出管路的第一支路与所述氧气输出管路的第一支路汇合形成助燃剂输入管路,该助燃剂输入管路连接所述循环流化床锅炉;所述烟气输出管路的第二支路和所述氧气输出管路的第二支路汇合形成气化剂输入管路,该气化剂输入管路连接所述循环流化床气化炉;生物质气化装置4和甲醇合成装置5分别经管路与烟气输出管路换热后连接抽凝式汽轮发电机组,用于向抽凝式汽轮发电机组输入发电用的饱和蒸汽。The circulating fluidized bed boiler is provided with a flue gas output pipeline, and the electrolytic water device is provided with an oxygen output pipeline; the first branch of the flue gas output pipeline merges with the first branch of the oxygen output pipeline to form an combustion-aiding agent input pipeline, and the combustion-aiding agent input pipeline is connected to the circulating fluidized bed boiler; the second branch of the flue gas output pipeline merges with the second branch of the oxygen output pipeline to form a gasifying agent input pipeline, and the gasifying agent input pipeline is connected to the circulating fluidized bed gasifier; the biomass gasification device 4 and the methanol synthesis device 5 are connected to the extraction-condensing steam turbine generator set after heat exchange with the flue gas output pipeline through pipelines, respectively, so as to input saturated steam for power generation to the extraction-condensing steam turbine generator set.
本发明绿色甲醇制备系统中,由生物质气化装置4、甲醇合成装置5和循环流化床锅炉产生的共三个来源的蒸汽经循环流化床锅炉输出的烟气过热后,将进入抽凝式汽轮发电机组发电。In the green methanol preparation system of the present invention, steam from three sources, namely, the biomass gasification device 4, the methanol synthesis device 5 and the circulating fluidized bed boiler, is superheated by the flue gas output by the circulating fluidized bed boiler and then enters the extraction-condensing steam turbine generator set to generate electricity.
需注意,图1示出了生物质气化装置4和甲醇合成装置5的饱和蒸汽输出管路汇合后与烟气换热,再输入生物质燃料发电装置1的连接方式,本领域的普通技术人员可通过非创造性的劳动设置生物质气化装置4和甲醇合成装置5的饱和蒸汽输出管路分别与烟气换热后,再进入生物质燃料发电装置1进行发电的连接方式,由此形成的技术方案在本发明保护范围内。It should be noted that FIG1 shows a connection mode in which the saturated steam output pipelines of the biomass gasification device 4 and the methanol synthesis device 5 are combined, exchanged with the flue gas, and then input into the biomass fuel power generation device 1. A person skilled in the art can, through non-creative labor, set up a connection mode in which the saturated steam output pipelines of the biomass gasification device 4 and the methanol synthesis device 5 are respectively exchanged with the flue gas, and then enter into the biomass fuel power generation device 1 for power generation. The technical solution thus formed is within the protection scope of the present invention.
可选的,本发明绿色甲醇制备系统还包括储氢装置7,用于储存电解水装置3生产的氢气,以及将氢气输入甲醇合成装置5。Optionally, the green methanol preparation system of the present invention further includes a hydrogen storage device 7 for storing hydrogen produced by the water electrolysis device 3 and inputting the hydrogen into the methanol synthesis device 5 .
可选的,经抽凝后的蒸汽经管路分别连接甲醇合成装置5和甲醇精馏装置6。Optionally, the steam after extraction and condensation is connected to the methanol synthesis device 5 and the methanol distillation device 6 through pipelines respectively.
可选的,所述氧气输出管路还设有第三支路,用于外送氧气产品。Optionally, the oxygen output pipeline is also provided with a third branch for externally delivering oxygen products.
可选的,抽凝式汽轮发电机组为双抽凝式汽轮发电机组。Optionally, the extraction-condensing steam turbine generator set is a double extraction-condensing steam turbine generator set.
实施例2Example 2
本实施例展示特定工况下采用实施例1所示绿色甲醇制备工系统进行绿色甲醇制备的工艺流程。需注意,该工艺流程仅为较优流程的展示,并不限定本发明的保护范围。This embodiment shows the process flow of green methanol production under specific working conditions using the green methanol production system shown in Example 1. It should be noted that this process flow is only a demonstration of a better process and does not limit the scope of protection of the present invention.
生物质燃料发电:该工序所用设备包括循环流化床锅炉及双抽凝式汽轮发电机组。输入本工艺的生物质的低位热热值约为13-15MJ/kg,生物质锅炉的消耗量为20000-30000kg/h。生物质直燃自产的蒸汽为80-100t/h,此外,生物质气化副产的5.0MPaG蒸汽量约为70-90t/h,甲醇合成副产的5.0MPaG蒸汽量约为60-80t/h,以上三个来源的蒸汽经循环流化床锅炉输出的烟气过热后进入双抽凝式汽轮发电机组发电,发电量为30-50MW。Biomass fuel power generation: The equipment used in this process includes circulating fluidized bed boilers and double-extraction condensing steam turbine generator sets. The low-heat calorific value of the biomass input into this process is about 13-15MJ/kg, and the consumption of the biomass boiler is 20,000-30,000kg/h. The steam produced by direct combustion of biomass is 80-100t/h. In addition, the 5.0MPaG steam produced as a by-product of biomass gasification is about 70-90t/h, and the 5.0MPaG steam produced as a by-product of methanol synthesis is about 60-80t/h. The steam from the above three sources is superheated by the flue gas output by the circulating fluidized bed boiler and enters the double-extraction condensing steam turbine generator set to generate electricity, with a power generation capacity of 30-50MW.
双抽凝式汽轮发电机组一级抽汽为1.1MPaG、50-60t/h,二级抽汽为0.5MPaG、10-15t/h,此两部分抽汽将用于甲醇精馏和甲醇合成工序,蒸汽回用工艺经过计算完全耦合。The first-stage extraction steam of the double-extraction condensing steam turbine generator set is 1.1MPaG, 50-60t/h, and the second-stage extraction steam is 0.5MPaG, 10-15t/h. These two parts of extraction steam will be used for methanol distillation and methanol synthesis processes. The steam recovery process is fully coupled after calculation.
助燃剂中氧气所占摩尔比为5%~99%。The molar ratio of oxygen in the combustion aid is 5% to 99%.
本实施例工艺正常工况下甲醇合成、甲醇精馏等工序所用电量约为30-50Mw,循环流化
床锅炉发电容量能满足这些工序的正常负荷用电。Under normal working conditions, the electricity used in the methanol synthesis and methanol distillation processes of this embodiment is about 30-50Mw. The power generation capacity of the bed boiler can meet the normal load electricity consumption of these processes.
新能源发电:采用风力发电机组和光伏发电机组进行发电。New energy power generation: using wind turbines and photovoltaic generators to generate electricity.
电水解:利用新能源发电工序所生产的电能进行电解水,该工序在碱性电解槽中进行,电解槽内碱液的最佳操作温度约为90℃,电解槽的操作压力为1.6~1.8MPaG。电解水制氢产生的纯氢氢气量为130000-150000Nm3/h。Electrohydrolysis: The process uses the electricity produced by the new energy power generation process to electrolyze water. This process is carried out in an alkaline electrolytic cell. The optimal operating temperature of the alkaline solution in the electrolytic cell is about 90°C, and the operating pressure of the electrolytic cell is 1.6-1.8MPaG. The amount of pure hydrogen produced by electrolyzing water to produce hydrogen is 130,000-150,000Nm3 / h.
生物质气化:该工序所用设备包括循环流化床气化炉、高温气化段炉和余热锅炉,其中循环流化床气化炉的操作压力约为0-6500KPaG,循环流化床气化炉运行温度未560-1400℃,高温气化段运行温度为560-1400℃。生物质气化所需生物质量为50000-80000kg/h,生物质气化产气量约为100000-130000Nm3/h,第一合成气的成分主要为氢气、CO和CO2气,其中CO所占摩尔比为1%-70%。Biomass gasification: The equipment used in this process includes a circulating fluidized bed gasifier, a high-temperature gasification section furnace and a waste heat boiler, wherein the operating pressure of the circulating fluidized bed gasifier is about 0-6500KPaG, the operating temperature of the circulating fluidized bed gasifier is 560-1400℃, and the operating temperature of the high-temperature gasification section is 560-1400℃. The biomass mass required for biomass gasification is 50000-80000kg/h, and the gas production of biomass gasification is about 100000-130000Nm3 /h. The first synthesis gas is mainly composed of hydrogen, CO and CO2 , of which the molar ratio of CO is 1%-70%.
甲醇合成及甲醇精馏:第一合成气经压缩后与经压缩后的电解水所制绿氢混合,在甲醇合成塔中反应制备粗品的甲醇,粗品甲醇经甲醇精馏工序分离提纯后得到高品质绿色甲醇产品。甲醇合成工序和甲醇精馏工序可根据产量需求分别设置多个生产系列,其中,单个系列产绿醇能力为20000-35000kg/h,总的甲醇合成和甲醇精馏生产绿醇能力为60000-105000kg/h。Methanol synthesis and methanol distillation: The first synthesis gas is compressed and mixed with green hydrogen produced by compressed electrolyzed water, and reacted in the methanol synthesis tower to prepare crude methanol. The crude methanol is separated and purified by the methanol distillation process to obtain high-quality green methanol products. The methanol synthesis process and the methanol distillation process can be set up with multiple production series according to the output requirements. Among them, the green alcohol production capacity of a single series is 20,000-35,000 kg/h, and the total methanol synthesis and methanol distillation production capacity of green alcohol is 60,000-105,000 kg/h.
以上内容是结合具体的实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单改进和润饰,都应当视为属于本发明保护的范围。
The above contents are further detailed descriptions of the present invention in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple improvements and modifications can be made without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.
Claims (17)
- 一种绿色甲醇制备工艺,其特征在于,包括以下工序A green methanol preparation process, characterized in that it includes the following steps生物质燃料发电:生物质在助燃剂作用下燃烧发电得到烟气和电能,该部分电能输送至电网;Biomass fuel power generation: Biomass is burned under the action of combustion aid to generate flue gas and electricity, which is then transmitted to the power grid;新能源发电:采用风能和/或太阳能发电得到绿电;Renewable energy generation: Green electricity is generated by wind and/or solar power;电解水:电解水生成氢气和氧气;所述新能源发电工序得到的绿电优先供给电解水工序,剩余的电能输送至电网;Electrolysis of water: electrolysis of water generates hydrogen and oxygen; the green electricity obtained in the new energy power generation process is first supplied to the electrolysis process, and the remaining electric energy is transmitted to the power grid;生物质气化:生物质在气化剂作用下气化生成第一合成气;其中,所述生物质燃料发电得到的烟气分为两部分,一部分烟气与所述电解水工序生成氧气中的一部分混合后形成助燃剂,并返回所述生物质燃料发电工序;剩余部分烟气与所述电解水工序生成氧气中的另一部分混合后形成气化剂,并输入所述生物质气化工序;Biomass gasification: biomass is gasified under the action of a gasifying agent to generate a first synthesis gas; wherein the flue gas obtained by the biomass fuel power generation is divided into two parts, one part of the flue gas is mixed with a part of the oxygen generated in the water electrolysis process to form a combustion aid, and is returned to the biomass fuel power generation process; the remaining part of the flue gas is mixed with another part of the oxygen generated in the water electrolysis process to form a gasifying agent, and is input into the biomass gasification process;甲醇合成:电解水工序得到的氢气压缩后与经压缩后的第一合成气混合得到原料气,该原料气反应生成粗品甲醇;Methanol synthesis: The hydrogen obtained in the water electrolysis process is compressed and mixed with the compressed first synthesis gas to obtain raw gas, which reacts to generate crude methanol;甲醇精馏:所述粗品甲醇经分离提纯得到高品质的绿色甲醇产品;Methanol distillation: The crude methanol is separated and purified to obtain high-quality green methanol products;还包括将所述生物质气化工序和甲醇合成工序副产的饱和蒸汽输入所述生物质燃料发电工序,经烟气过热后进行发电。The method also includes inputting saturated steam produced as a by-product of the biomass gasification process and the methanol synthesis process into the biomass fuel power generation process to generate electricity after the flue gas is overheated.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,所述第一合成气中包括CO2、CO和氢气,其中CO所占摩尔比为1%~70%。The green methanol production process according to claim 1 is characterized in that the first synthesis gas comprises CO 2 , CO and hydrogen, wherein the molar ratio of CO is 1% to 70%.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,所述助燃气中氧气所占摩尔比为5%~99%。The green methanol preparation process according to claim 1 is characterized in that the molar ratio of oxygen in the combustion-supporting gas is 5% to 99%.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,输入所述生物质燃料发电工序和所述生物质气化工序的生物质的质量比为1:(0.2-3)。The green methanol preparation process according to claim 1 is characterized in that the mass ratio of the biomass input into the biomass fuel power generation process and the biomass gasification process is 1:(0.2-3).
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,所述生物质气化工序采用循环流化床气化工艺,气化温度为560-1400℃,气化压力为0~6500KPaG。The green methanol preparation process according to claim 1 is characterized in that the biomass gasification process adopts a circulating fluidized bed gasification process, the gasification temperature is 560-1400°C, and the gasification pressure is 0-6500KPaG.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,所述生物质燃料发电工序采用抽凝式汽轮发电机组,发电产生的抽汽蒸汽分别输入甲醇合成工序和甲醇精馏工序。The green methanol preparation process according to claim 1 is characterized in that the biomass fuel power generation process adopts an extraction-condensing steam turbine generator set, and the extraction steam generated by power generation is respectively input into the methanol synthesis process and the methanol distillation process.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,所述电解水工序在碱性电解槽中进行;所述碱性电解槽内碱液的温度为80~100℃,操作压力为1.6~1.8MPaG。The green methanol preparation process according to claim 1 is characterized in that the water electrolysis process is carried out in an alkaline electrolytic cell; the temperature of the alkaline solution in the alkaline electrolytic cell is 80-100°C, and the operating pressure is 1.6-1.8MPaG.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,还包括储氢工序,对所述电解水工序生成的氢气进行储存,以及向所述甲醇合成工序输入氢气。The green methanol preparation process according to claim 1 is characterized in that it also includes a hydrogen storage process for storing the hydrogen generated by the water electrolysis process and inputting hydrogen into the methanol synthesis process.
- 根据权利要求1所述的绿色甲醇制备工艺,其特征在于,还包括将部分所述电解水工 序生成的氧气作为产品外送。The green methanol preparation process according to claim 1 is characterized in that it also includes the step of: The oxygen generated in the process is delivered as a product.
- 一种绿色甲醇制备系统,其特征在于,包括生物质燃料发电装置、新能源发电装置、电解水装置、生物质气化装置、甲醇合成装置和甲醇精馏装置,其中,A green methanol preparation system, characterized by comprising a biomass fuel power generation device, a new energy power generation device, a water electrolysis device, a biomass gasification device, a methanol synthesis device and a methanol distillation device, wherein:所述生物质燃料发电装置:包括循环流化床锅炉和抽凝式汽轮发电机组,生物质在所述循环流化床锅炉中燃烧产生蒸汽带动抽凝式汽轮发电机组发电,得到烟气和电能,该部分电能输送至电网;The biomass fuel power generation device comprises a circulating fluidized bed boiler and an extraction condensing steam turbine generator set. The biomass is burned in the circulating fluidized bed boiler to generate steam to drive the extraction condensing steam turbine generator set to generate electricity, thereby obtaining flue gas and electric energy, which is then transmitted to the power grid.所述新能源发电装置:包括风力发电机组和/或光伏发电机组,采用风能和/或太阳能发电;该装置得到的电能优先供给电解水装置,剩余部分输送至电网;The new energy power generation device includes a wind power generator set and/or a photovoltaic generator set, which uses wind energy and/or solar energy to generate electricity; the electric energy obtained by the device is first supplied to the water electrolysis device, and the remaining part is transmitted to the power grid;所述电解水装置:包括电解槽,在所述电解槽中电解水得到氢气和氧气;The water electrolysis device comprises an electrolytic cell, in which water is electrolyzed to obtain hydrogen and oxygen;所述生物质气化装置:包括依次连接的循环流化床气化炉、高温气化段炉和余热锅炉,生物质在气化剂作用下发生气化反应得到第一合成气;The biomass gasification device comprises a circulating fluidized bed gasifier, a high-temperature gasification stage furnace and a waste heat boiler connected in sequence, and the biomass undergoes a gasification reaction under the action of a gasifying agent to obtain a first synthesis gas;所述甲醇合成装置:包括甲醇合成塔,所述电水解装置生成的氢气经第一压缩机压缩后与经第二压缩机压缩后的第一合成气混合,并在所述甲醇合成塔中生成粗品甲醇;The methanol synthesis device comprises a methanol synthesis tower, the hydrogen generated by the electrohydrolysis device is compressed by a first compressor and mixed with the first synthesis gas compressed by a second compressor, and crude methanol is generated in the methanol synthesis tower;所述甲醇精馏装置:用于提纯分离所述粗品甲醇,得到高品质的绿色甲醇产品;The methanol distillation device is used to purify and separate the crude methanol to obtain high-quality green methanol products;其中,所述循环流化床锅炉设置烟气输出管路,所述电解水装置设置氧气输出管路;所述烟气输出管路的第一支路与所述氧气输出管路的第一支路汇合形成助燃剂输入管路,该助燃剂输入管路连接所述循环流化床锅炉;所述烟气输出管路的第二支路和所述氧气输出管路的第二支路汇合形成气化剂输入管路,该气化剂输入管路连接所述循环流化床气化炉;所述生物质气化装置和甲醇合成装置分别经管路与所述烟气输出管路换热后连接所述抽凝式汽轮发电机组,用于向所述抽凝式汽轮发电机组输入发电用的饱和蒸汽。Among them, the circulating fluidized bed boiler is provided with a flue gas output pipeline, and the electrolytic water device is provided with an oxygen output pipeline; the first branch of the flue gas output pipeline merges with the first branch of the oxygen output pipeline to form a combustion-aiding agent input pipeline, and the combustion-aiding agent input pipeline is connected to the circulating fluidized bed boiler; the second branch of the flue gas output pipeline and the second branch of the oxygen output pipeline merge to form a gasifying agent input pipeline, and the gasifying agent input pipeline is connected to the circulating fluidized bed gasifier; the biomass gasification device and the methanol synthesis device are connected to the extraction-condensing steam turbine generator set after heat exchange with the flue gas output pipeline through pipelines, respectively, so as to input saturated steam for power generation to the extraction-condensing steam turbine generator set.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,还包括储氢装置,用于储存所述电解水装置生产的氢气,以及将氢气输入所述甲醇合成装置。The green methanol preparation system according to claim 10 is characterized in that it also includes a hydrogen storage device for storing hydrogen produced by the water electrolysis device and inputting hydrogen into the methanol synthesis device.
- 根据权利要求11所述的绿色甲醇制备系统,其特征在于,所述储氢装置为高压气态储氢装置或液态储氢装置。The green methanol production system according to claim 11 is characterized in that the hydrogen storage device is a high-pressure gaseous hydrogen storage device or a liquid hydrogen storage device.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,经抽凝后的蒸汽经管路分别连接所述甲醇合成装置和所述甲醇精馏装置。The green methanol preparation system according to claim 10 is characterized in that the steam after extraction and condensation is connected to the methanol synthesis device and the methanol distillation device respectively through pipelines.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,所述抽凝式汽轮发电机组为双抽凝式汽轮发电机组。The green methanol preparation system according to claim 10 is characterized in that the extraction-condensing steam turbine generator set is a double extraction-condensing steam turbine generator set.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,所述氧气输出管路还设有用于外送氧气产品的第三支路。 The green methanol production system according to claim 10 is characterized in that the oxygen output pipeline is also provided with a third branch for externally delivering oxygen products.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,所述电解槽的数量为多台。The green methanol production system according to claim 10 is characterized in that there are multiple electrolytic cells.
- 根据权利要求10所述的绿色甲醇制备系统,其特征在于,所述电解槽为碱性电解槽。 The green methanol production system according to claim 10 is characterized in that the electrolytic cell is an alkaline electrolytic cell.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1362393A (en) * | 2000-12-28 | 2002-08-07 | 三菱重工业株式会社 | Method and apparatus for prparing methanol using biomass material |
US20120238645A1 (en) * | 2009-11-20 | 2012-09-20 | Ruedlinger Mikael | Thermal and chemical utilization of carbonaceous materials, in particular for emission-free generation of energy |
WO2017060704A1 (en) * | 2015-10-06 | 2017-04-13 | Heptonstall William B | Sustainable energy system |
CN113187571A (en) * | 2021-05-28 | 2021-07-30 | 西安热工研究院有限公司 | Biomass pure oxygen combustion power generation system and method |
CN116496141A (en) * | 2023-04-14 | 2023-07-28 | 中国天辰工程有限公司 | Green methanol preparation process and system |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103232857B (en) * | 2013-04-24 | 2015-10-28 | 华东理工大学 | A kind of CO 2the coal-based electric power of zero release and chemicals joint process |
CN103897736B (en) * | 2014-03-17 | 2015-11-18 | 中国科学院工程热物理研究所 | Hydrogen Energy based on sun power and gasifying biomass produces the defeated integral system of storage |
CN112725034A (en) * | 2020-12-30 | 2021-04-30 | 中国电力科学研究院有限公司 | Renewable energy power-to-gas system coupled with biomass gasification |
CN113583712B (en) * | 2021-07-12 | 2022-05-24 | 浙江大学 | Multi-energy coupling complementary and sequential conversion system and method |
CN113956131A (en) * | 2021-10-08 | 2022-01-21 | 华陆工程科技有限责任公司 | Method for realizing co-production of methanol/ethylene glycol through coupling of coal chemical industry and green hydrogen |
CN114394883A (en) * | 2021-11-02 | 2022-04-26 | 华陆工程科技有限责任公司 | Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission |
CN115466637B (en) * | 2022-09-15 | 2024-03-22 | 西安交通大学 | Fuel cell power generation system and method for coupling biomass energy and solar energy |
CN115784840A (en) * | 2022-12-05 | 2023-03-14 | 山东省科学院能源研究所 | Methanol preparation process coupling organic solid waste gasification and water electrolysis hydrogen production |
-
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-
2024
- 2024-04-11 WO PCT/CN2024/087260 patent/WO2024213050A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1362393A (en) * | 2000-12-28 | 2002-08-07 | 三菱重工业株式会社 | Method and apparatus for prparing methanol using biomass material |
US20120238645A1 (en) * | 2009-11-20 | 2012-09-20 | Ruedlinger Mikael | Thermal and chemical utilization of carbonaceous materials, in particular for emission-free generation of energy |
WO2017060704A1 (en) * | 2015-10-06 | 2017-04-13 | Heptonstall William B | Sustainable energy system |
CN113187571A (en) * | 2021-05-28 | 2021-07-30 | 西安热工研究院有限公司 | Biomass pure oxygen combustion power generation system and method |
CN116496141A (en) * | 2023-04-14 | 2023-07-28 | 中国天辰工程有限公司 | Green methanol preparation process and system |
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