Methanol preparation device and preparation method

Abstract

The invention provides a methanol preparation device and method, and belongs to the field of methanol preparation, the methanol preparation device comprises a gasification reaction device, a reforming hydrogen production reactor, a preheater, a methanol generation device and a power generation device, the gasification reaction device, the preheater, the reforming hydrogen production reactor and the methanol generation device are connected in sequence, and the reforming hydrogen production reactor and the methanol generation device are connected with the power generation device through pipelines. The invention aims to solve the problems of high methanol preparation cost and high energy consumption in the prior art. The method has the technical effects that the energy waste is avoided while the methanol is prepared at a relatively simple and relatively low cost.

Description

Technical Field

[0001] The present invention relates to the technical field of methanol preparation, in particular to a methanol preparation device and a methanol preparation method. Background Art

[0002] Methanol has great market potential as an important chemical raw material and energy carrier. It is widely used in many industries such as chemical industry, energy, medicine and agriculture. In the chemical industry, it is a key raw material for the production of chemicals such as formaldehyde, acetic acid, and methyl tert-butyl ether (MTBE); in the energy industry, it can be used directly as a fuel. Methanol fuel used in automobiles burns more fully, produces relatively fewer pollutants, and is more environmentally friendly. It can also be used in methanol fuel cells, synthetic gasoline, power generation and other fields; in the pharmaceutical industry, it is used in drug synthesis, solvents and disinfectants; in the agricultural field, it is used to produce pesticides and fertilizers. With the continuous development of the global economy and the continuous advancement of technology in various industries, the demand for methanol is also increasing.

[0003] In the field of methanol production, traditional production processes mostly rely on fossil energy, which not only consumes a large amount of resources such as coal and natural gas, but also produces a large amount of carbon dioxide and other pollutants, causing serious impacts on the environment. In addition, the energy consumption in the methanol production process is also high, which increases production costs. Summary of the invention

[0004] The present invention provides a methanol preparation device and a methanol preparation method, which are used to solve the defects of high methanol preparation cost and high energy consumption in the prior art, and realize relatively simple and low-cost production of methanol while avoiding energy waste.

[0005] A first aspect of the present invention provides a methanol preparation device, comprising a gasification reaction device, a reforming hydrogen production reactor, a preheater, a methanol generation device and a power generation device. The gasification reaction device, the preheater, the reforming hydrogen production reactor and the methanol generation device are connected in sequence, and the reforming hydrogen production reactor and the methanol generation device are both connected to the power generation device through pipelines.

[0006] In addition, the methanol preparation device according to the present invention may also have the following additional technical features: In some embodiments of the present invention, the reforming hydrogen production reactor comprises an outer tube, a palladium-based membrane tube, an adsorbent and a catalyst, the palladium-based membrane tube is arranged inside the outer tube, and the adsorbent and the catalyst are arranged between the outer tube and the palladium-based membrane tube; An input hole and a permeation hole are provided at one end of the outer tube at intervals, and an exhaust gas output hole is provided at the other end of the outer tube. The permeation hole is communicated with the interior of the palladium-based membrane tube, and the input hole and the exhaust gas output hole are both communicated with the space between the outer tube and the palladium-based membrane tube. The tail gas output hole is connected to the power generation device, the input hole is connected to the preheater, and the permeation hole is connected to the methanol generation device.

[0007] In some embodiments of the present invention, a methanol production device includes a first compressor, a second compressor, a methanol synthesis reactor and a distillation column; The air inlet of the first compressor is connected to the exhaust gas output hole, and the air inlet of the second compressor is connected to the penetration hole; The gas outlet of the second compressor and the gas inlet of the distillation tower are connected to the methanol synthesis reactor.

[0008] In some embodiments of the present invention, the methanol production device further includes a degassing tower, and the degassing tower is arranged between the distillation tower and the methanol synthesis reactor.

[0009] In some embodiments of the present invention, the methanol synthesis reactor comprises a first reactor, a first flash evaporator, a second reactor and a second flash evaporator, and the first reactor, the first flash evaporator, the second reactor and the second flash evaporator are sequentially connected between the second compressor and the degassing tower; The liquid outlet of the first flash evaporator is connected to the degassing tower.

[0010] In some embodiments of the present invention, a first storage tank and a second storage tank are further included, the first storage tank is arranged between the first flash evaporator and the second reactor, the liquid outlet of the distillation tower is connected to the second storage tank, the gas outlet of the distillation tower is connected to the power generation device, and the gas outlet of the distillation tower is connected to the power generation device.

[0011] The second aspect of the invention provides a method for preparing methanol, using all the technical features of the methanol preparation device of the first aspect of the invention, and in addition, further comprising the following steps: Step S100: using a gasification reaction device to pyrolyze and gasify biomass; Step S200: the pyrolyzed and gasified biomass flows through a preheater and then flows into a reforming hydrogen production reactor; Step S300: using a reforming hydrogen production reactor to reform the pyrolyzed and gasified biomass to produce hydrogen and carbon dioxide; Step S400: using a methanol production device to combine hydrogen and carbon dioxide to produce methanol; Step S500: using a first compressor to input hydrocarbons after the reforming hydrogen production reactor into a power generation device to generate electricity; Step S600: After the methanol is produced by the methanol production device, the unreacted hydrocarbons are input into the power generation device to generate electricity; Step S700: methanol preparation is completed.

[0012] In some embodiments of the present invention, in step S300, part of the carbon dioxide produced by the reforming hydrogen production reactor is used to produce methanol, and the other part of the carbon dioxide is collected by a carbon capture device.

[0013] In some embodiments of the present invention, in step S400, the method of using a methanol production device to combine hydrogen and carbon dioxide to produce methanol includes the following steps: Step S410: using the first reactor and the second reactor to prepare methanol; Step S420: using the first flash evaporator and the second flash evaporator to separate the methanol, and then inputting it into a degassing tower to separate impurities, and then using a distillation tower to liquefy the methanol; Step S430: After the methanol is liquefied, it is input into the second storage tank for storage.

[0014] In some embodiments of the present invention, in step S420, the separated impurities are input into a power generation device to perform power generation.

[0015] The present application includes the following beneficial technical effects: a methanol production device that produces methanol by cooperating with a gasification reaction device to produce carbon dioxide and hydrogen produced by a reforming hydrogen production reactor can not only realize the resource utilization of carbon dioxide, but also effectively alleviate the greenhouse effect problem; carbon dioxide hydrogenation is a strongly exothermic reaction under standard conditions, and has a strong spontaneous tendency in thermodynamics. The power generation function of the methanol preparation process is realized by the setting of a power generation device, thereby realizing the utilization of by-products and avoiding energy waste. In addition, since a gasification reaction device is used to pyrolyze and gasify biomass, that is, biomass is used as raw material and biomass is used as energy. It is the only renewable carbon source and plays a unique role in energy conservation and emission reduction, thereby reducing costs.

[0016] Second, by setting up a gasification reaction device to achieve the coupling of solar energy and biomass, based on the principle of energy cascade utilization, the integration of hydrogen production-power multi-generation system was carried out. The gasification synthesis gas formed by gasified gaseous biomass is used as an important raw material for hydrogen production. The integrated production of high-purity hydrogen system further adsorbs carbon dioxide, and methanol is produced by combining hydrogen and carbon dioxide, opening up a new path for the development of low-energy carbon capture technology. For by-products, various by-products are used as fuel to drive gas-steam combined cycle power generation, and then connected to the grid with hydrogen power generation units to store electricity to achieve complementary power generation. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present invention. Moreover, the same reference numerals are used throughout the accompanying drawings to represent the same components. In the accompanying drawings: Figure 1 The overall structural diagram of a methanol production device according to some embodiments of the present invention is schematically shown.

[0018] Figure 2The schematic diagram shows the structure of a methanol preparation device according to some embodiments of the present invention without a gasification reaction device.

[0019] Figure 3 The structure diagram schematically shows a methanol preparation device according to some embodiments of the present invention, which is a combination of a methanol generation device, a power generation device and a reforming hydrogen production reactor.

[0020] Figure 4 The structural diagram of the carbon capture device of the methanol production device according to some embodiments of the present invention is schematically shown.

[0021] Figure 5 A cross-sectional view of a reforming hydrogen production reactor of a methanol production device according to some embodiments of the present invention is schematically shown.

[0022] Figure 6 A three-dimensional diagram of a heat collection device of a methanol production device according to some embodiments of the present invention is schematically shown.

[0023] Figure 7 A three-dimensional diagram schematically shows the connection between a motor and a base of a heat collecting device of a methanol production device according to some embodiments of the present invention.

[0024] Figure 8 A perspective view schematically shows a base of a heat collecting device of a methanol production device according to some embodiments of the present invention.

[0025] Fig. 9 A cross-sectional view schematically shows a gasification reaction tube of a heat collection device of a methanol production device according to some embodiments of the present invention.

[0026] Fig.10 A cross-sectional view schematically shows biomass disposed in a gasification reaction tube of a heat collecting device of a methanol production device according to some embodiments of the present invention.

[0027] Reference numerals: 1. Gasification reaction device, 2. Heat collection device, 21. Gasification reaction tube, 22. Heat collection mirror, 23. Support rod, 24. First splint, 25. Second splint, 26. Bottom plate, 27. Connecting seat, 28. Base, 281. Mounting shell, 29. Pipe sleeve, 210. Motor, 211. Heat absorption layer, 212. Heat storage layer, 213. Isolation layer, 214. Heat uniformity layer, 215. Reaction tube body, 3. Preheater, 4. Reforming hydrogen production reactor, 401. Outer tube, 402. Palladium-based membrane tube, 403. Adsorbent, 404. Catalyst, 405. Input hole, 406. Permeation hole, 407. Sealing flange, 408. Tail gas output hole, 5. Methanol production device, 501. First compressor, 502. Second compressor, 503. First reactor, 504. First flash evaporator, 505, first storage tank, 506, second reactor, 507, second flash evaporator, 508, degassing tower, 509, distillation tower, 510, second storage tank, 511, compressor, 6, biomass, 7, power generation device, 8, carbon capture device, 801, monoethanolamine storage tank, 802, cooler, 803, absorbent, 804, absorption tower, 805, raw gas, 806, rich liquid, 807, first pump, 808, carbon dioxide reactor, 809, second pump, 810, desorption tower, 811, heat integration device, 812, pressure sensor, 813, temperature sensor, 814, flash tank, 9, photovoltaic cell, 10, constant flow pump, 11, hydrogen storage tank, 12, vacuum pump, 13, carbon dioxide storage tank, 14, spectrum divider, 15, heat recovery device. DETAILED DESCRIPTION

[0028] The exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments of the present disclosure are shown in the accompanying drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.

[0029] It should be understood that the terms used herein are only for the purpose of describing specific example embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "one", "an" and "" as used herein may also be meant to include plural forms. The terms "include", "comprise", "contain", and "have" are inclusive and therefore specify the presence of stated features, steps, operations, elements and / or parts, but do not exclude the presence or addition of one or more other features, steps, operations, elements, parts, and / or combinations thereof. The method steps, processes, and operations described herein are not interpreted as necessarily requiring them to be performed in the specific order described or illustrated, unless the execution order is clearly indicated. It should also be understood that additional or alternative steps may be used.

[0030] Although the terms first, second, third, etc. can be used in the text to describe multiple elements, components, regions, layers and / or sections, these elements, components, regions, layers and / or sections should not be limited by these terms. These terms can only be used to distinguish an element, component, region, layer or section from another region, layer or section. Unless the context clearly indicates, terms such as "first", "second" and other numerical terms do not imply order or sequence when used in the text. Therefore, the first element, component, region, layer or section discussed below can be referred to as the second element, component, region, layer or section without departing from the teaching of the example embodiments.

[0031] For ease of description, spatial relative terms may be used in the text to describe the relationship of one element or feature relative to another element or feature as shown in the figure, such as "inside", "outside", "inner side", "outer side", "below", "below", "above", "above", etc. Such spatial relative terms are intended to include different orientations of the device in use or operation in addition to the orientation depicted in the figure. For example, if the device in the figure is flipped, then the element described as "below other elements or features" or "below other elements or features" will be subsequently oriented as "above other elements or features" or "above other elements or features". Therefore, the example term "below..." can include both upper and lower orientations. The device can be additionally oriented and rotated 90 degrees or in other directions and the spatial relative descriptors used in the text are interpreted accordingly.

[0032] like Figures 1 to 10 As shown, according to an embodiment of the first aspect of the present invention, a methanol preparation device is proposed, including a gasification reaction device 1, a reforming hydrogen production reactor 4, a preheater 3, a methanol generation device 5 and a power generation device 7, the gasification reaction device 1, the preheater 3, the reforming hydrogen production reactor 4 and the methanol generation device 5 are connected in sequence, and the reforming hydrogen production reactor 4 and the methanol generation device 5 are both connected to the power generation device 7 through pipelines.

[0033] In the above embodiment, it should be noted that the biomass 6 is arranged in the gasification reaction device 1, the gasification reaction device 1 is the heat collection device 2, the heat collection device 2 includes a gasification reaction tube 21, a heat collection mirror 22, a support rod 23, a first clamping plate 24, a second clamping plate 25, a bottom plate 26, a connecting seat 27, a base 28, a mounting shell 281, a pipe sleeve 29 and a motor 210, the gasification reaction tube 21 includes a heat absorption layer 211, a heat storage layer 212, an isolation layer 213, a uniform heat layer 214 and a reaction tube body 215, the heat collection mirror 22 is rotatably connected to the base 28, and the gasification reaction tube 21 is connected to the heat collection mirror 22 through a plurality of support rods 23; The gasification reaction tube 21 includes a reaction tube body 215, a heat absorption layer 211 and a heat storage layer 212. The outer periphery of the reaction tube body 215 is coated with the heat storage layer 212, and the outer periphery of the heat storage layer 212 is coated with the heat absorption layer 211. The end of each support rod 23 away from the heat collecting mirror 22 is connected to the heat absorption layer 211; an isolation layer 213 is arranged between the reaction tube body 215 and the heat storage layer 212; the thickness of the isolation layer 213 is 100 mm, and the isolation layer 213 is The heat-uniform layer 214 is made of metal material; a heat-uniform layer 214 is arranged between the reaction tube body 215 and the isolation layer 213; the heat-uniform layer 214 is made of foam metal material; the thickness of the heat-uniform layer 214 is 250 mm; the heat-uniform layer 214 is the heat transfer layer, and the isolation layer 213 separates the heat storage layer 212 from the heat-uniform layer 214 to prevent the molten salt of the heat absorption layer 211 from flowing into the heat-uniform layer 214 after melting and causing failure; the second uniform temperature heat transfer is achieved by the setting of the heat-uniform layer 214.

[0034] The mounting shell 281 is mounted in the middle of the base 28, the motor 210 is mounted in the mounting shell 281, the output shaft of the motor 210 is connected to the heat collecting mirror 22, the motor 210 is located at the center of the heat collecting mirror 22, and the output shaft of the motor 210 is connected to the heat collecting mirror 22 by screwing, welding, or clamping; the motor 210 is connected to the mounting shell 281 by screwing, welding, or clamping; one side of the connecting seat 27 is connected to the heat collecting mirror 22, and the output shaft of the motor 210 is connected to the connecting seat 2 7 is connected to the other side of the gasification reaction tube 21, and the cross-sectional shape of the connection seat 27 is "C" shaped; the connection seat 27 is connected to the heat collecting mirror 22 through the bottom plate 26; a plurality of first clamping plates 24 are arranged at intervals on the outer side of the heat collecting mirror 22, and a plurality of second clamping plates 25 are arranged at intervals on the inner side wall of the heat collecting mirror 22; the bottom plate 26 is connected to the heat collecting mirror 22 through the plurality of first clamping plates 24, and one end of each support rod 23 away from the gasification reaction tube 21 is connected to a second clamping plate 25, and each first clamping plate 24 is connected to the bottom plate 26. The bottom plate 26 and the connection seat 27 are connected by screwing, welding, riveting or bonding; each first clamping plate 24 is connected to the heat collecting mirror 22 by screwing, welding, riveting or bonding, and each second clamping plate 25 is connected to the heat collecting mirror 7 by screwing, welding, riveting or bonding; the support rod 23 and the second clamping plate 25 are connected by screwing, welding or clamping in a one-to-one correspondence; the shape of each first clamping plate 24 Each second clamping plate 25 is in the shape of an arc, and the upper surface of the bottom plate 26 is in the shape of an arc; each support rod 23 is connected to the gasification reaction tube 21 through a pipe sleeve 29. Specifically, the gasification reaction tube 21 is inserted into a plurality of pipe sleeves 29 in sequence along the axial direction. After the insertion, each pipe sleeve 29 is connected to the gasification reaction tube 21 by welding, bonding, or clamping, and each pipe sleeve 29 is connected to the corresponding support rod 23 by screwing, welding, clamping, or bonding.

[0035] The heat absorption layer 211 is made of molten salt, the reaction tube body 215 is made of high-strength alloy seamless steel pipe, the heat storage layer 212 is made of copper foam metal material with a porosity of 50%, the diameter of the tube mouth of the gasification reaction tube 21 is 2400mm, the length of the gasification reaction tube 21 is 3500mm, the reaction tube body 215 is provided with biomass 6, the minimum inner diameter of the reaction tube body 215 is 400mm, the thickness of the heat absorption layer 211 is 1500mm, and the thickness of the heat storage layer 212 is 300mm; the heat collecting mirror 22 is a trough-type solar focusing heat collecting mirror; the heat collecting mirror 22 is rotatably connected to the base 28 to realize that the heat collecting device can be rotated with the heat collecting mirror 22. The solar collector 22 rotates in the direction of the sun rising in the east and setting in the west. When the sun rises from the east in the morning, the solar collector mirror 22 of the solar collector rotates to the position facing the east and drives the gasification reaction tube 21 to rotate to the position facing the east to absorb the maximum amount of solar energy. When the sun is located in the south at noon, the solar collector mirror 22 of the solar collector rotates to the position facing the south and drives the gasification reaction tube 21 to rotate to the position facing the south to absorb the maximum amount of solar energy. When the sun is located in the west in the afternoon, the solar collector mirror 22 of the solar collector rotates to the position facing the west and drives the gasification reaction tube 21 to rotate to the position facing the west to absorb the maximum amount of solar energy.

[0036] The heat collecting mirror 22 can accurately reflect and focus sunlight onto a long and narrow focal line through its parabolic shape design. This focusing effect significantly increases the energy density of sunlight, so that the gasification reaction tube 21 located on the focal line can absorb and utilize solar energy more effectively. Since the sunlight is efficiently focused, the gasification reaction tube 21 located on the focal line can heat up rapidly, thereby improving the efficiency of converting solar energy into thermal energy; secondly, the light and heat reflected by the heat collecting mirror 22 are transferred to the heat storage layer 212 for heat collection, so that the working medium halogenated molten salt of the heat absorption layer 211 melts, and the foam metal of the large-aperture heat storage layer 212 strengthens heat transfer and accelerates the phase change rate of the molten salt of the heat absorption layer 211; the molten salt of the melted heat absorption layer 211 can flow in the pores of the foam metal of the heat storage layer 212 to achieve uniform temperature heat transfer; thirdly, the setting of the rotatable connection between the heat collecting mirror 22 and the base 28 realizes that the heat collection device can collect heat according to the direction of the sun to ensure the heat collection temperature.

[0037] The process of hydrogen production by the reforming hydrogen production reactor 4 is to use a heat collection device 2 to provide heat energy for the reforming hydrogen production reactor 4.

[0038] The composition of the biomass 6 gasified by the gasification reaction device 1 includes 60% CO+H 2 , 10% hydrocarbons and 30% CO 2 .

[0039] Gasification reaction device 1 uses solar radiation heat source 800W / m 2, copper / water vapor convection heat exchange is adopted in the reaction chamber (i.e., the reaction tube body 215).

[0040] When hydrogen is produced using the reforming hydrogen production reactor 4 , water vapor is injected into the reforming hydrogen production reactor 4 .

[0041] It also includes a compressor 511 , which is connected to the power generation device 7 .

[0042] The arrangement of the compressor 511 can provide other fuels to the power generation device 7 to meet the power supply demand if the amount of by-products in the methanol manufacturing process is small and insufficient to provide sufficient electricity.

[0043] The power generation device 7 is a thermal power generation device in the prior art.

[0044] The working process of preparing methanol in this device is as follows: biomass is added to the gasification reaction device 1 to realize the gasification of biomass to form biomass gasification synthesis gas, and then the biomass gasification synthesis gas is input into the reforming hydrogen production reactor 4 so that the methane and carbon monoxide in the biomass gasification synthesis gas are produced into hydrogen and carbon dioxide, and then the unreacted biomass gasification synthesis gas, i.e., the by-product, is directly input into the power generation device 7 as a power generation raw material for power generation, hydrogen and carbon dioxide are input into the methanol generation device to generate methanol, and then the by-product 38 of the methanol synthesis device is input into the power generation device 7 as a power generation raw material for power generation; the power generation device 7 can adopt the thermal energy power generation device of the existing technology.

[0045] The technical effects achieved by the above embodiments are as follows: First, the methanol production device 5 that produces methanol by cooperating with the carbon dioxide and hydrogen generated by the gasification reaction device 1 in cooperation with the reforming hydrogen production reactor 5 can not only realize the resource utilization of carbon dioxide, but also effectively alleviate the greenhouse effect problem; carbon dioxide hydrogenation is a strong exothermic reaction under standard conditions, and has a strong spontaneous tendency in thermodynamics. The power generation function of the methanol preparation process is realized by the setting of the power generation device 7, thereby realizing the utilization of by-products and avoiding energy waste. In addition, since the gasification reaction device 1 is used to pyrolyze and gasify biomass, that is, biomass is used as raw material and biomass is used as energy. It is the only renewable carbon source and plays a unique role in energy conservation and emission reduction, thereby reducing costs.

[0046] Second, by setting up a gasification reaction device 1 to achieve the coupling of solar energy and biomass, based on the principle of energy cascade utilization, a hydrogen production-power multi-generation system integration was carried out. The gasified synthesis gas formed by the gasified gaseous biomass 6 was used as an important raw material for hydrogen production. The integrated production system of high-purity hydrogen was used to convert CO 2Further adsorption, through the combination of hydrogen and carbon dioxide to produce methanol, has opened up a new path for the development of low-energy carbon capture technology. As for by-products, various by-products are used as fuel to drive gas-steam combined cycle power generation, and then connected to the grid with hydrogen power generation units to achieve complementary power generation.

[0047] Optional, such as Figure 1 , Figure 2 , Figure 3 and Figure 5 As shown, the reforming hydrogen production reactor 4 includes an outer tube 401, a palladium-based membrane tube 402, an adsorbent 403 and a catalyst 404. The palladium-based membrane tube 402 is arranged inside the outer tube 401, and the adsorbent 403 and the catalyst 404 are arranged between the outer tube 401 and the palladium-based membrane tube 402; An input hole 405 and a permeation hole 406 are provided at one end of the outer tube 401 at intervals, and an exhaust gas output hole 408 is provided at the other end of the outer tube 401. The permeation hole 406 is communicated with the interior of the palladium-based membrane tube 402, and the input hole 405 and the exhaust gas output hole 408 are both communicated with the space between the outer tube 401 and the palladium-based membrane tube 402; The tail gas output hole 408 is connected to the power generation device 7 , the input hole 405 is connected to the preheater 3 , and the permeation hole 406 is connected to the methanol production device 5 .

[0048] In the above optional embodiment, it should be noted that it also includes a sealing flange 407, and the sealing flange 407 is covered on the palladium-based membrane tube 402 by interference fit, gluing, screwing, welding or the like.

[0049] The reaction tube body 215 of the heat collecting device 2 is sleeved on the outer tube 401 to provide heat for the reforming hydrogen production reactor 4. The outer tube 401, palladium-based membrane tube 402, adsorbent 403 and catalyst 404 of the reforming hydrogen production reactor 4 are arranged in coordination to achieve directional separation of multiple products, thereby achieving a methane reforming hydrogen production conversion rate of nearly 100% and a hydrogen yield of more than 99%.

[0050] Membrane separation is often used to separate hydrogen. Depending on the separation principle, it can be divided into porous membranes and dense membranes; depending on the separation principle, it can be divided into metal membranes, polymer membranes, etc.; a typical hydrogen membrane separation methane reforming hydrogen production reactor consists of an inner tube and an outer tube, and a catalyst is filled between the inner and outer tubes to catalyze methane reforming; the inner tube is a hydrogen permeable tube, and hydrogen can pass through the inner tube under the drive of pressure difference to achieve product separation; the particle adsorption method is often used to separate carbon dioxide. For the separation of carbon dioxide in the methane reforming hydrogen production reaction, the adsorbent is required to be able to maintain adsorption characteristics at high temperatures above 400°C.

[0051] The palladium-based membrane tube 402 is a 3μm palladium-silver alloy membrane plated on the outside of a porous α-alumina tube. The palladium-based membrane tube 402 is coaxially arranged with the outer tube 401. One end of the palladium-based membrane tube 402 is flange-sealed, and the other end is connected to a vacuum pump to form a negative pressure environment on the vacuum side, thereby separating and pumping out the hydrogen. The catalyst 404, i.e., the SMR catalyst, and the adsorbent 403, i.e., the carbon dioxide adsorbent, are alternately filled in the annular space sandwiched between the palladium-based membrane tube 402 and the outer tube 401. The effective functional area of ​​the palladium-based membrane is located on the outer surface of the tubular membrane, and the reaction side flow is in countercurrent to the permeation side flow.

[0052] The reforming hydrogen production reactor 4 is operated in a "reaction + dwell + regeneration" cycle mode, with a reaction step time of 90s, a dwell step time of 60s, and a regeneration step time of 120s. When the reaction gas flow passes through the reforming hydrogen production reactor 4, a reforming reaction occurs in the catalyst 404 section, carbon dioxide is separated in the adsorbent 403 section, and hydrogen is separated in the radial direction of the gas flow under the action of the pressure difference, thereby achieving the effect of directional separation of multiple products. The directional separation of the products realizes the complete coordination of hydrogen production and decarbonization, and then enters the dwell step, stops the introduction of the reaction gas flow, and allows the hydrogen to be fully separated. Finally, water vapor is introduced in the dwell step for purging to achieve adsorbent regeneration. Catalyst 404, i.e., the SMR catalyst, uses a nickel (40wt%) catalyst based on active magnesium aluminum spinel, and the chemical formula is Ni / MgO-Al 2 O 3 ; Adsorbent 403, i.e., carbon dioxide adsorbent, is K 2 CO 3 Modified magnesium aluminum hydrotalcite, chemical formula K 2 CO 3 promotedγ-Al 2 O 3 / Mg 2 CO 3 (OH) 16 For each combination of catalyst and adsorbent, the filling volume of catalyst 404 is 5 ml, and the filling volume of adsorbent 403 is 35 ml. Both catalyst 404 and adsorbent 403 are ground into fine particles.

[0053] In addition, as an option, it also includes a photovoltaic cell 9, a constant flow pump 10, a hydrogen storage tank 11, a vacuum pump 12, a carbon dioxide storage tank 13 and a spectrum divider 14. The air inlet of the vacuum pump 12 is connected to the permeation hole 406 of the reforming hydrogen production reactor 4 through a pipeline, and the air outlet of the vacuum pump 12 is connected to the hydrogen storage tank 11 through a pipeline. The carbon dioxide adsorbed by the adsorbent 403 of the reforming hydrogen production reactor 4 is discharged to the carbon dioxide storage tank 13 through the input hole 405 after the tail gas by-product is output from the tail gas output hole 408 to the power generation device 7. The constant flow pump 10 is connected between the gasification reaction device 1 and the preheater 3; the preheater 3, the vacuum pump 12 and the and the constant current pump 10 are electrically connected to the photovoltaic cell 9, and the photovoltaic cell 9 is provided with a spectrum divider 14, so that the sunlight transmits high-frequency light to the photovoltaic cell 9 through the spectrum divider 9 to generate electricity, power the constant current pump 10 and the vacuum pump 12, and the low-frequency light is reflected to the preheater 3 to preheat the raw materials; the raw gas at about 400°C is reformed in the reforming hydrogen production reactor under the energy supply of concentrated solar energy to produce hydrogen. When methanol needs to be produced, the hydrogen in the hydrogen storage tank 11 and the carbon dioxide in the carbon dioxide storage tank 13 can also be injected into the methanol production device 5 as methanol preparation raw materials to prepare methanol; in addition, hydrogen and carbon dioxide can also be used for other purposes.

[0054] The beneficial effects of the above optional embodiments are as follows: by coordinating the outer tube 401 of the reforming hydrogen production reactor 4, the palladium-based membrane tube 402, the adsorbent 403 and the catalyst 404, the hydrogen in the radial direction of the gas flow is separated under the action of the pressure difference, thereby achieving the effect of directional separation of multiple products. The directional separation of the products realizes the complete coordination of hydrogen production and decarbonization, so that the hydrogen is fully separated, and finally water vapor is introduced for purging to achieve adsorbent regeneration.

[0055] Optional, such as Figure 3 As shown, the methanol production device 5 includes a first compressor 501, a second compressor 502, a methanol synthesis reactor and a distillation tower 509; The air inlet of the first compressor 501 is connected to the exhaust gas output hole 408, and the air inlet of the second compressor 502 is connected to the penetration hole 406; The gas outlet of the second compressor 502 and the gas inlet of the distillation tower 509 are connected to the methanol synthesis reactor.

[0056] The methanol production device 5 further includes a degassing tower 508 , and the degassing tower 508 is arranged between the distillation tower 509 and the methanol synthesis reactor.

[0057] Optional, such as Figure 3As shown, the methanol synthesis reactor includes a first reactor 503, a first flash evaporator 504, a second reactor 506 and a second flash evaporator 507, and the first reactor 503, the first flash evaporator 504, the second reactor 506 and the second flash evaporator 507 are sequentially connected between the second compressor 502 and the degassing tower 508; The liquid outlet of the first flash evaporator 504 is connected to the degassing tower 508 .

[0058] It also includes a first storage tank 505 and a second storage tank 510 . The first storage tank 505 is arranged between the first flash evaporator 504 and the second reactor 506 . The liquid outlet of the distillation tower 509 is connected to the second storage tank 510 , and the gas outlet of the distillation tower 509 is connected to the power generation device 7 .

[0059] In the above optional embodiment, it should be noted that the first reactor 503 and the second reactor 506 are both methanol synthesis towers in the prior art.

[0060] Specifically, carbon dioxide and hydrogen are then fed into the first reactor 503 for methanol synthesis reaction, and then fed into the first flash evaporator 504 for gas-liquid separation, and the liquid mixture is fed into the first storage tank 505 for storage; the gas mixture is pressurized and preheated, and then fed into the second reactor 506 for methanol synthesis reaction to obtain a synthetic product; the synthetic product is fed into the second flash evaporator 507 for gas-liquid separation, and then fed into the degassing tower 508 and the distillation tower 509 to obtain methanol; part of the gas separated by the second flash evaporator 507 is fed into the combustion furnace for combustion, and the other part is fed into the first storage tank 505 for circulation. By feeding a part of the gas synthetic product into the combustion furnace as fuel for catalytic combustion to heat the heat transfer oil, and heating other equipment through the heat transfer oil, heat self-sufficiency is achieved; the other part of the gas synthetic product is circulated as circulating gas, thereby improving the utilization rate of raw materials.

[0061] It also includes a heat recovery device 15, which is arranged between the preheater 3 and the reforming hydrogen production reactor 4; the heat recovery device 15 adopts a waste heat boiler or a waste heat recovery device in the prior art, and the waste heat carried by the gasified biomass 6 is recovered through the setting of the heat recovery device 15, thereby increasing the energy utilization rate.

[0062] The technical effect achieved by the above embodiment is that the preparation of methanol by hydrogenation of carbon dioxide can not only realize the resource utilization of carbon dioxide, but also effectively alleviate the greenhouse effect problem. Carbon dioxide hydrogenation is a strong exothermic reaction under standard conditions and has a strong tendency to proceed spontaneously in thermodynamics.

[0063] In addition, based on the principle of cascade utilization of the full spectrum of solar energy, this device integrates a multi-generation system for complementary utilization of multiple energy sources. Sunlight transmits high-frequency light to the photovoltaic cell 9 through the spectrum divider 14 to generate electricity, power the constant current pump 10 and the vacuum pump 12, and reflects low-frequency light to the collector surface of the preheater 3 to preheat the gaseous biomass 6 synthesis gas raw material; the raw gas at about 400°C is reformed in the reforming hydrogen production reactor 4 under the energy supply of concentrated solar energy to produce hydrogen. In the "reaction + stay" step of reforming hydrogen production, the vacuum pump 12 continuously extracts hydrogen, and in the "regeneration" step of reforming hydrogen production, carbon dioxide is desorbed by steam purging.

[0064] The main product of hydrogen production through reforming hydrogen production reactor 4 is synthesis gas, which is CO 2 +H 2 It is an important raw material for chemical production. In order to achieve efficient storage and transportation of hydrogen and cogeneration of hydrogen, the production of high value-added products - methanol is integrated; a distributed hydrogen energy supply system, hydrogen-heat combined power generation, and a small energy conversion device are proposed to construct a multi-generation system method. The specific process is: hydrocarbon organic matter, coke and other by-products and gasification medium water vapor are used as fuel or working medium for the gas-steam combined cycle to drive two Brayton cycles to generate electricity, and at the same time, it is combined with wind turbines to directly supply electricity to users. This method solves the defects of intermittent and instability in the process of wind power generation, and realizes the self-production and sales of biomass gasification reaction by-products. The waste heat of the circulating exhaust gas is used as a low-temperature heat source, and a heat pump circulation heating system is integrated, which greatly improves energy utilization.

[0065] According to an embodiment of the second aspect of the present invention, a method for preparing methanol is provided, which uses all the technical features of the methanol preparation device of the embodiment of the first aspect of the present invention, and in addition, further comprises the following steps: Step S100: using the gasification reaction device 1 to pyrolyze and gasify the biomass 6; Step S200: the pyrolyzed and gasified biomass 6 flows through the preheater 3 and then flows into the reforming hydrogen production reactor 4; Step S300: using the reforming hydrogen production reactor 4 to reform the pyrolyzed and gasified biomass 6 to produce hydrogen and carbon dioxide; Step S400: using the methanol production device 5 to combine hydrogen and carbon dioxide to produce methanol; Step S500: using the first compressor 501 to input the hydrocarbons after the reforming hydrogen production reactor 4 into the power generation device 7 to generate electricity; Step S600: After the methanol is produced by the methanol production device 5, the unreacted hydrocarbons are input to the power generation device 7 for power generation; Step S700: methanol preparation is completed.

[0066] In the above optional embodiment, it should be noted that in step S100, the solar thermal chemical reaction is a strongly endothermic reduction reaction, and the heat required for the reaction is provided by the high-temperature heat collecting device 2; water vapor is introduced into the heat collecting device 2 as a gasification medium, and there is no need to introduce an oxidizing medium such as air or pure oxygen. The reaction formula mainly includes the synthesis gas reaction of the gasification subsystem of solar energy and biomass 6, and the specific reaction formulas are mainly the following: Reaction 1: C+H 2 O→CO+H 2 △Hr, 298k = 131.29KJ / mol (1) Reaction 2: C+CO 2 →2CO△Hr, 298k=172.46KJ / mol(2) Reaction 3: C+2H 2 →CH 4 △Hr, 298k = -74.81KJ / mol (3) Reaction 4: CH 4 +H 2 O→CO+3H 2 △Hr, 298k = 206.10KJ / mol Reaction 5: CO + H 2 O→CO 2 +H 2 △Hr, 298k = -41.17KJ / mol (5) In step S400: In the carbon dioxide hydrogenation to methanol reaction system, if the side reactions such as the generation of alkanes and higher carbon alcohols and the small amount of inert gas that may exist in the system are not considered, the main chemical reactions are as follows: Reaction 1: CO 2 (g) +3H 2 (g) → CH 3 OH(g)+H 2 0 (g) △ r H m *(298K)=-49.01kJ / mol Reaction 2: CO + 2H 2 →CH 3 OH △ r H m *(298K)=-90.00kJ / mol Reaction 3: CO 2 (g) + H 2 (g) → CO (g) + H 2 O(g) △ r Hm *(298K)=+49.43kJ / mol The beneficial effects of the above optional embodiments are as follows: the methanol produced by this method can be used in industry and agriculture; the gasification medium water vapor and the by-product synthesis gas and the unreacted carbon monoxide-hydrogen synthesis gas can be sent to the gas-steam combined system, and after one Brayton cycle and two Rankine cycles to generate electricity, it can complement the wind turbine to supply power to the energy storage station; the waste heat of the circulating exhaust gas is used as the heat source of the heat pump cycle for heating, thereby forming a multi-generation system that complements the use of solar energy, biomass, and hydrogen energy.

[0067] In step S400: in the carbon dioxide hydrogenation to methanol reaction system, the reaction temperature is in the temperature range of 200 to 280° C. to increase the reaction rate of carbon dioxide and hydrogen to synthesize methanol, thereby obtaining the maximum methanol absorption rate.

[0068] In step S300: the reforming hydrogen production reactor 4 is operated in a "reaction + dwell + regeneration" cycle mode, with a reaction step time of 90s, a dwell step time of 60s, and a regeneration step time of 120s. When the reaction gas flow passes through the reforming hydrogen production reactor 4, a reforming reaction occurs in the catalyst section, carbon dioxide is separated in the adsorbent section, and hydrogen is separated under the action of pressure difference in the radial direction of the gas flow, thereby achieving the effect of multi-product directional separation. The directional separation of the products realizes the complete coordination of hydrogen production and decarbonization, and then enters the dwell step, stops the introduction of the reaction gas flow, and fully separates the hydrogen. Finally, water vapor is introduced in the dwell step for purging to achieve adsorbent regeneration; the temperature of the hydrogen production step of step S300 is 400°C, the water-carbon ratio is 4.0, the pressure is 1 bar, and the hydrogen separation ratio is 0.95.

[0069] Optional, such as Figure 2 and Figure 3 As shown, in step S300 , part of the carbon dioxide produced by the reforming hydrogen production reactor 4 is used to produce methanol, and the other part of the carbon dioxide is collected by the carbon capture device 8 .

[0070] In the above optional embodiments, it should be noted that the carbon capture device 8 may adopt a device using the prior art CCUS carbon capture technology.

[0071] Optionally, the carbon capture device 8 may include a monoethanolamine storage tank 801, a cooler 802, an absorption tower 804, a first pump 807, a carbon dioxide reactor 808, a second pump 809 and a desorption tower 810 connected in sequence. An absorbent 803 is arranged in the absorption tower 804. The absorbent 803 is a carbon dioxide absorbent. The carbon dioxide obtained by the reaction of the reforming hydrogen production reactor 4 is adsorbed by the liquid monoethanolamine in the monoethanolamine storage tank 801. The adsorbed carbon dioxide enters the cooler 802 to be cooled to form liquid carbon dioxide. After the carbon dioxide is absorbed by the absorbent 803 in the absorption tower 804, the first pump 809 is used to absorb the carbon dioxide. The rich liquid 806 that absorbs carbon dioxide is injected into the carbon dioxide reactor 808 for sufficient chemical reaction to further increase the carbon dioxide content, and then enters the desorption tower 810, where the heat provided by the heat integration device 811 desorbs the carbon dioxide, so that the gaseous carbon dioxide is discharged from the top of the desorption tower 810. The desorbed liquid rich liquid 806 is pumped into the carbon dioxide reactor 808 through the second pump 809 for cyclic chemical reaction to increase the carbon dioxide concentration. The flash tank 814 is arranged between the absorption tower 804 and the carbon dioxide reactor 808, and is used to separate the low-concentration carbon dioxide discharged from the absorption tower 804 from other gases.

[0072] In addition, multiple pressure sensors 812 and multiple temperature sensors 813 are included to detect the temperature and pressure of each step of the carbon dioxide capture process to ensure the smooth capture of carbon dioxide.

[0073] Optional, such as Figure 2 and Figure 3 As shown, in step S400, the method of using the methanol generating device 5 to combine hydrogen and carbon dioxide to produce methanol includes the following steps: Step S410: using the first reactor 503 and the second reactor 506 to prepare methanol; Step S420: using the first flash evaporator 504 and the second flash evaporator 507 to separate the methanol, and then inputting it into the degassing tower to separate the impurities, and then using the distillation tower 509 to liquefy the methanol; Step S430: After the methanol is liquefied, it is input into the second storage tank 510 for storage.

[0074] In the above optional embodiment, it should be noted that, in step S410 and step S420, carbon dioxide and hydrogen, synthesis gas of biomass 6 and gaseous hydrocarbons react in the first reactor 503 and the second reactor 506 to generate methanol, water and side reaction products. Subsequently, gas-liquid separation is performed in the first flash evaporator 504 and the second flash evaporator 507 to obtain a crude methanol product, and finally a methanol product with a higher purity is obtained by distillation in the distillation tower 509.

[0075] Optional, such as Figure 2 and Figure 3 As shown, in step S420, the separated impurities are input into the power generation device 7 to perform power generation.

[0076] In the above optional embodiment, it should be noted that the separated impurities are hydrocarbon by-products and the synthesis gas of unreacted carbon monoxide and hydrogen.

[0077] In addition, an appropriate amount of water can promote the transient synthesis of methanol by hydrogenation of carbon dioxide. 1 / ZnO single atom model catalyst, catalytic test results show that CO 2 The conversion rate and methanol selectivity show a volcano-like change trend with the change of water content. After the introduction of the optimal content of water, the selectivity of methanol shows a trend of first increasing and then decreasing over time, but the catalyst can be effectively regenerated through in-situ hydrogen reduction. With the help of in-situ mechanism research and theoretical calculations, the mechanism of action of water is revealed at the atomic scale: water acts as a bridge for hydrogen atoms, promotes the conversion of relatively stable intermediates, improves transient catalytic activity, and thus produces more water. The produced water will consume the by-product carbon monoxide through the water gas shift reaction, further improving the selectivity of methanol in the product.

[0078] This has enabled the Cu-ZnO-ZrO 2 CO on catalyst 2 Adding a small amount of water during the hydrogenation process to produce methanol can increase the absorption rate of methanol.

[0079] These are only preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A methanol production device, characterized in that: The invention comprises a gasification reaction device (1), a reforming hydrogen production reactor (4), a preheater (3), a methanol production device (5) and a power generation device (7), wherein the gasification reaction device (1), the preheater (3), the reforming hydrogen production reactor (4) and the methanol production device (5) are connected in sequence, and the reforming hydrogen production reactor (4) and the methanol production device (5) are both connected to the power generation device (7) through pipelines.

2. The methanol production device according to claim 1, characterized in that: The reforming hydrogen production reactor (4) comprises an outer tube (401), a palladium-based membrane tube (402), an adsorbent (403) and a catalyst (404); the palladium-based membrane tube (402) is arranged inside the outer tube (401), and the adsorbent (403) and the catalyst (404) are arranged between the outer tube (401) and the palladium-based membrane tube (402); An input hole (405) and a permeation hole (406) are provided at one end of the outer tube (401) at intervals, and an exhaust gas output hole (408) is provided at the other end of the outer tube (401), the permeation hole (406) is communicated with the interior of the palladium-based membrane tube (402), and the input hole (405) and the exhaust gas output hole (408) are both communicated with the space between the outer tube (401) and the palladium-based membrane tube (402); The tail gas output hole (408) is connected to the power generation device (7), the input hole (405) is connected to the preheater (3), and the permeation hole (406) is connected to the methanol generation device (5).

3. The methanol production device according to claim 2, characterized in that: The methanol production device (5) comprises a first compressor (501), a second compressor (502), a methanol synthesis reactor and a distillation tower (509); The air inlet of the first compressor (501) is connected to the exhaust gas output hole (408), and the air inlet of the second compressor (502) is connected to the permeation hole (406); The gas outlet of the second compressor (502) and the gas inlet of the distillation tower (509) are both connected to the methanol synthesis reactor.

4. The methanol production device according to claim 3, characterized in that: The methanol production device (5) further comprises a degassing tower (508), and the degassing tower (508) is arranged between the distillation tower (509) and the methanol synthesis reactor.

5. The methanol production device according to claim 4, characterized in that: The methanol synthesis reactor further comprises a first reactor (503), a first flash evaporator (504), a second reactor (506) and a second flash evaporator (507), wherein the first reactor (503), the first flash evaporator (504), the second reactor (506) and the second flash evaporator (507) are sequentially connected between the second compressor (502) and the degassing tower (508); The liquid outlet of the first flash evaporator (504) is connected to the degassing tower (508).

6. The methanol production device according to claim 5, characterized in that: The invention also comprises a first storage tank (505) and a second storage tank (510), wherein the first storage tank (505) is arranged between the first flash evaporator (504) and the second reactor (506), the liquid outlet of the distillation tower (509) is connected to the second storage tank (510), and the gas outlet of the distillation tower (509) is connected to the power generation device (7).

7. A method for preparing methanol, characterized in that: Using the methanol preparation device as described in any one of claims 1 to 6, in addition, it also includes the following steps: Step S100: using a gasification reaction device (1) to pyrolyze and gasify the biomass (6); Step S200: the pyrolyzed and gasified biomass (6) flows through the preheater (3) and then flows into the reforming hydrogen production reactor (4); Step S300: using a reforming hydrogen production reactor (4) to reform the pyrolyzed and gasified biomass (6) to produce hydrogen and carbon dioxide; Step S400: using the methanol production device (5) to combine hydrogen and carbon dioxide to produce methanol; Step S500: using the first compressor (501) to input the hydrocarbons after the reforming hydrogen production reactor (4) into the power generation device (7) to perform power generation; Step S600: After the methanol is produced by the methanol production device (5), the unreacted hydrocarbons are input to the power generation device (7) to generate electricity; Step S700: methanol preparation is completed.

8. The method for preparing methanol according to claim 7, characterized in that: In step S300, part of the carbon dioxide produced by the reforming hydrogen production reactor (4) is used to produce methanol, and the other part of the carbon dioxide is collected by a carbon capture device (8).

9. The method for preparing methanol according to claim 7, characterized in that: In step S400, the method of using the methanol production device (5) to combine hydrogen and carbon dioxide to produce methanol comprises the following steps: Step S410: using the first reactor (503) and the second reactor (506) to prepare methanol; Step S420: using the first flash evaporator (504) and the second flash evaporator (507) to separate the methanol, and then inputting it into a degassing tower to separate impurities, and then using a distillation tower (509) to liquefy the methanol; Step S430: After the methanol is liquefied, it is input into the second storage tank (510) for storage.

10. The method for preparing methanol according to claim 9, characterized in that: In step S420, the separated impurities are input into the power generation device (7) to perform power generation.

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