Device for preparing methanol by gasifying, supplementing sulfur and desulfurizing biomass

Abstract

The utility model provides a device for preparing methanol by gasifying, supplementing sulfur and desulfurizing biomass, which comprises a gasification furnace used for biomass reaction to obtain crude synthesis gas; a sulfur source reservoir; the sulfur supplementing reactor is arranged at the downstream of the gasification furnace to receive the crude synthesis gas; the sulfur supplementing reactor is arranged at the downstream of the sulfur source storage device and is used for enabling a sulfur source to react with the crude synthesis gas to obtain hydrogen sulfide; the conversion reactor is arranged at the downstream of the sulfur supplementing reactor and is used for carrying out reaction on a sulfur-tolerant conversion catalyst and hydrogen sulfide to obtain a sulfurized catalyst active component and carrying out CO conversion reaction on the crude synthesis gas; the desulfurization tower is arranged at the downstream of the conversion reactor and is used for removing sulfides to respectively obtain sulfur-containing substances and synthetic reaction gas; the regenerator is arranged at the downstream of the desulfurization tower and is used for receiving the sulfur-containing substance and carrying out regeneration treatment to obtain sulfur; and the methanol synthesis tower is arranged at the downstream of the desulfurization tower and is used for receiving the synthesis reaction gas and carrying out methanol synthesis reaction to obtain methanol.

Description

Technical Field

[0001] The utility model relates to the technical field of energy conversion, and particularly relates to a biomass gasification sulfur supplementation and desulfurization methanol production device. Background Art

[0002] The syngas produced by biomass gasification includes impurity gases such as CO, CO2, CH4, and sulfides. It is necessary to carry out a sulfur-tolerant shift process to convert CO into CO2, adjust the ratio of CO to H2 in the syngas, and obtain syngas with a better ratio for synthesizing methanol. In the CO shift technology, a sulfur-tolerant shift catalyst is used to carry out the CO shift reaction under high sulfur content conditions, avoiding the "hot and cold disease" in the traditional process where the gas is first cooled, then enters wet desulfurization, and then is heated up to enter the traditional shift process, reducing heat exchange equipment, simplifying the process, saving the steam used for shifting, and reducing energy consumption.

[0003] Currently, the catalysts used for CO shift include Fe-Cr series medium temperature shift catalysts, Co-Mo series wide temperature sulfur-tolerant shift catalysts, and Cu-Zn series low temperature shift catalysts. Among them, since the active temperature range of the Fe-Cr series medium temperature shift catalyst is 300-500 °C, a relatively high water-gas ratio is required to ensure the reaction rate within the active temperature range, resulting in too high steam consumption. At the same time, due to the toxic effect of chromium compounds in the Fe-Cr series catalyst on the human body, its waste catalyst is classified as hazardous waste by the state and requires a relatively high cost for professional manufacturers to recycle and treat, so its application has gradually decreased. The Cu-Zn series low temperature shift catalyst has a too narrow operating temperature range and is prone to overheating and deactivation when applied to gases with high sulfur content. The Co-Mo series wide temperature sulfur-tolerant shift catalyst has the characteristics of a wide operating temperature range, a low starting temperature, and no side reactions during low water-gas ratio reactions, meeting the catalyst performance requirements for the biomass gasification syngas shift process.

[0004] However, in the syngas produced by biomass gasification, the sulfide content is relatively low, which causes the Co-Mo series sulfur-tolerant shift catalyst to undergo reverse sulfurization reaction, resulting in catalyst deactivation, poor CO shift effect, and the ratio of CO to H2 in the syngas not reaching the optimum, thereby leading to a relatively small amount of methanol synthesis. Summary of the Utility Model

[0005] The purpose of the utility model is to provide a biomass gasification sulfur supplementation and desulfurization methanol production device with a relatively high methanol output to solve the problems in the prior art.

[0006] To solve the above technical problems, the utility model provides a biomass gasification sulfur supplementation and desulfurization methanol production device, including:

[0007] A gasifier for supplying biomass to react to obtain raw syngas;

[0008] A sulfur source storage for storing a sulfur source;

[0009] A sulfur replenishment reactor is disposed downstream of the gasifier to receive the raw syngas; the sulfur replenishment reactor is disposed downstream of the sulfur source storage to receive the sulfur source, and is used for reacting the sulfur source with the raw syngas to obtain hydrogen sulfide;

[0010] A shift reactor is disposed downstream of the sulfur replenishment reactor. A sulfur-tolerant shift catalyst is provided in the shift reactor. The shift reactor is used for reacting the sulfur-tolerant shift catalyst with hydrogen sulfide to obtain a sulfided catalyst active component and for subjecting the raw syngas to a CO shift reaction;

[0011] A desulfurization tower is disposed downstream of the shift reactor and is used for removing sulfides to obtain sulfur-containing substances and synthesis reaction gas respectively;

[0012] A regenerator is disposed downstream of the desulfurization tower to receive the sulfur-containing substances and perform regeneration treatment to obtain sulfur;

[0013] A methanol synthesis tower is disposed downstream of the desulfurization tower to receive the synthesis reaction gas and perform a methanol synthesis reaction to obtain methanol.

[0014] In one embodiment, the sulfur source stored in the sulfur source storage includes low-molecular-weight organic sulfur compounds; the sulfur source includes at least one of ethanethiol, n-butyl mercaptan, dimethyl disulfide, dimethyl sulfide, carbon disulfide, and di-tert-nonyl polysulfide.

[0015] In one embodiment, the sulfur-tolerant shift catalyst is a Co-Mo based catalyst; and / or,

[0016] The desulfurization tower is filled with a desulfurization liquid for removing sulfides;

[0017] The desulfurization liquid is a sodium carbonate solution.

[0018] In one embodiment, the regenerator includes a flash tower, a regeneration tank, and a sulfur melting kettle arranged in sequence from upstream to downstream. The flash tower is disposed downstream of the desulfurization tower. The flash tower is used for decomposing carbon dioxide in the sulfur-containing substances and reducing the pressure of the sulfur-containing substances. The regeneration tank is used for subjecting the sulfur-containing substances to a regeneration reaction to obtain suspended sulfur particles. The sulfur melting kettle is used for converting the suspended sulfur particles into solid sulfur.

[0019] In one embodiment, the sulfur melting kettle is communicated with the desulfurization tower to return the reacted liquid to the desulfurization tower.

[0020] In one embodiment, a pressurizing device is provided between the desulfurization tower and the methanol synthesis tower for pressurizing the synthesis reaction gas; and / or,

[0021] A decarbonization tower is provided between the desulfurization tower and the methanol synthesis tower to remove carbon dioxide from the synthesis reaction gas.

[0022] In one embodiment, a methanol rectification tower is further provided downstream of the methanol synthesis tower; and / or, a heat recovery device is further provided downstream of the methanol synthesis tower, and the heat recovery device receives the purge gas output from the methanol synthesis tower.

[0023] In one embodiment, a waste heat utilization device is provided at the gas outlet of the gasifier to utilize the heat of the raw synthesis gas; and / or, a booster is provided between the gasifier and the sulfur supplementation reactor.

[0024] In one embodiment, a purification device is provided between the gasifier and the sulfur supplementation reactor to purify the raw synthesis gas.

[0025] In one embodiment, the purification device includes a separator, a dust collector, and a water washing tower arranged in sequence. The separator is arranged downstream of the gasifier and is used for gas-solid separation. The dust collector receives the gaseous substance separated by the separator and is used for dust removal. The water washing tower is used to remove tar and ammonia.

[0026] As can be seen from the above technical solutions, the advantages and positive effects of the present utility model are as follows:

[0027] The biomass gasification sulfur supplementation desulfurization methanol production device of the present utility model realizes the sulfur supplementation, conversion, and desulfurization processes through a sulfur supplementation reactor, a converter, and a desulfurization tower, forms qualified synthesis reaction gas, and enters the methanol synthesis tower to produce methanol. Due to sulfur supplementation, the activity of the catalyst is ensured, so that the CO conversion of the raw synthesis gas can fully react, and then a synthesis reaction gas with a better hydrogen-carbon ratio is obtained, improving the methanol production.

[0028] At the same time, the subsequent sulfur-containing substances are regenerated to produce sulfur, and sulfur is a high-value-added product, which can increase the income and thus reduce the cost of preparing methanol. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a schematic structural diagram of one embodiment of the biomass gasification sulfur supplementation desulfurization methanol production device of the present utility model.

[0030] The description of the reference numerals is as follows:

[0031] 11. Gasifier; 12. Sulfur source storage; 13. Sulfur replenishment reactor; 14. Shift reactor; 15. Desulfurization tower; 17. Methanol synthesis tower; 18. Raw material storage bin; 19. Conveyor; 20. Lock hopper; 21. Feed hopper; 22. Feeder; 23. Separator; 24. Dust collector; 25. Water washing tower; 26. Waste heat utilization equipment; 27. Booster; 28. Decarbonization tower; 29. Methanol distillation column; 30. Pressurization equipment; 31. Heat recovery equipment; 32. Flash tower; 33. Regeneration tank; 34. Sulfur melting kettle. Detailed implementation manners

[0032] Although the present utility model can be easily embodied in different forms of embodiments, only some specific embodiments are shown in the drawings and will be described in detail in this specification. At the same time, it can be understood that this specification should be regarded as a demonstration of the principle of the present utility model and is not intended to limit the present utility model to what is described herein.

[0033] Thus, a feature pointed out in this specification will be used to illustrate one of the features of one embodiment of the present utility model, rather than implying that each embodiment of the present utility model must have the described feature. In addition, it should be noted that this specification describes many features. Although some features can be combined to show possible system designs, these features can also be used in other combinations not explicitly described. Thus, unless otherwise stated, the described combinations are not intended to be limiting.

[0034] In the embodiments shown in the drawings, the indication of directions (such as up, down, left, right, front and back) is used to explain that the structures and movements of various elements of the present utility model are not absolute but relative. When these elements are in the positions shown in the drawings, these explanations are appropriate. If the description of the positions of these elements changes, then the indication of these directions also changes accordingly.

[0035] It should be noted that before the Co-Mo series sulfur-tolerant shift catalyst is used, its active components exist in the oxidized state, that is, in the form of CoO and MoO3, and the activity at this time is relatively low. Therefore, the catalyst needs to be pre-sulfurized before production to obtain the active composition of the sulfided catalyst, CoS and MoS2.

[0036] The reactions that occur during the pre-sulfurization of the Co-Mo series sulfur-tolerant shift catalyst are as follows:

[0037] CoO + H2S → CoS + H2O, MoO3 + 2H2S → MoS2 + 3H2O.

[0038] The active components of the Co-Mo series sulfur-tolerant shift catalyst require a certain concentration of H2S to maintain their sulfided state. If used in a low-sulfur environment for a long time, the catalyst will undergo reverse sulfidation, resulting in a decrease in activity, and further affecting the activity of the sulfur-tolerant shift catalyst. This reverse sulfidation phenomenon is mainly related to three operating conditions: the hot spot temperature of the catalyst bed, the H2S concentration, and the steam / gas ratio. The active component MoS2 is relatively easy to hydrolyze, and there is the following equilibrium reaction with the H2S content in the process gas:

[0039]

[0040] It can be seen from this that the minimum allowable H2S content of the catalyst is related to the hot spot temperature of the bed and the partial pressure of water vapor. That is, under certain reaction hot spot temperature and water / gas conditions, a certain content of H2S must be present in the process gas to ensure that the catalyst is in a sulfided state and has high activity.

[0041] However, the sulfur content in the syngas produced by biomass gasification is relatively low. Therefore, the Co-Mo series sulfur-tolerant shift catalyst is prone to reverse sulfidation reaction, resulting in catalyst deactivation.

[0042] Therefore, the present utility model provides a biomass gasification sulfur supplementation and desulfurization methanol production device. This biomass gasification methanol production device creatively realizes the conversion of syngas components through sulfur supplementation and desulfurization methods to obtain syngas with a suitable hydrogen-carbon ratio. At the same time, after the syngas is converted, it enters the desulfurization process, and wet oxidation desulfurization is used to produce high-value-added product sulfur.

[0043] Figure 1 The schematic diagram of one embodiment of the biomass gasification sulfur supplementation and desulfurization methanol production device is shown. Refer to Figure 1 , the biomass gasification methanol production device includes a gasifier 11, a sulfur source storage 12, a sulfur supplementation reactor 13, a shift reactor 14, a desulfurization tower 15, a regenerator, and a methanol synthesis tower 17.

[0044] The gasifier 11 is used for the biomass to react to obtain raw syngas. The raw syngas is obtained through biomass gasification reaction. Among them, the raw syngas mainly includes CO, CO2, H2, and a small amount of H2S and CH4, etc.

[0045] The gasifier 11 is provided with an air outlet at the top and a slag outlet at the bottom. The side of the lower part of the gasifier 11 is provided with a feed inlet.

[0046] In this embodiment, the upstream of the gasifier 11 includes a raw material storage bin 18, a conveyor 19, and a feeder. The raw material storage bin 18 is used for storing biomass. The conveyor 19 is used to convey the biomass in the raw material storage bin 18 to the feeder. The feeder is connected to the feed inlet of the gasifier 11 to send the biomass into the gasifier 11.

[0047] Specifically, the conveying member 19 is a conveyor belt. The feeding member includes a lock hopper 20, a feeding hopper 21 disposed below the lock hopper 20, and a feeder 22 disposed below the feeding hopper 21. The lock hopper 20 is disposed downstream of the conveying member 19 to receive the biomass conveyed by the conveying member 19. The feeding hopper 21 is used to receive biomass. The feeder 22 is communicated with the feed inlet of the gasifier 11 to convey the biomass in the feeding hopper 21 into the gasifier 11.

[0048] The number of the feeding hoppers 21 can be multiple, and the multiple feeding hoppers 21 are arranged in parallel downstream of the lock hopper 20. At this time, corresponding feed inlets can also be opened on the gasifier 11. In this embodiment, there are two feeding hoppers 21. The feeder 22 is arranged in one-to-one correspondence with the feeding hopper 21.

[0049] A purification device is provided between the gasifier 11 and the sulfur addition reactor 13 to purify the raw syngas.

[0050] Specifically, the purification device includes a separator 23, a dust collector 24, and a water washing tower 25 arranged in sequence. The separator 23 is disposed downstream of the gasifier 11 for gas-solid separation. The separator 23 is communicated with the gas outlet of the gasifier 11. The solid substances separated by the separator 23 are returned to the gasifier 11. The outlet at the bottom of the separator 23 is used to discharge the solid substances, which is communicated with the reflux port on the side of the lower part of the gasifier 11.

[0051] The dust collector 24 receives the gaseous substances separated by the separator 23 and is used for dust removal. The top of the dust collector 24 is the gas outlet, and the bottom is the dust discharge port.

[0052] The water washing tower 25 is used to remove tar and ammonia. That is, the tar and ammonia contained in the gas are dissolved in water, thereby achieving the purpose of removal. The inlet of the water washing tower 25 is arranged at the lower part, which is communicated with the outlet at the top of the dust collector 24. The outlet of the water washing tower 25 is arranged at the top, which is communicated with the sulfur addition reactor 13.

[0053] Furthermore, a waste heat utilization device 26 is provided at the gas outlet of the gasifier 11 to utilize the heat of the raw syngas. Specifically, the waste heat utilization device 26 is disposed between the gasifier 11 and the dust collector 24.

[0054] Among them, the waste heat utilization device 26 includes a first channel and a second channel that can perform heat exchange with each other. The first channel is connected to the gas outlet of the gasifier 11 and the dust collector 24. There is water in the second channel, and it absorbs the heat of the raw syngas and is converted into steam.

[0055] A booster 27 is provided between the gasifier 11 and the sulfur addition reactor 13 to be used for pressurization so that the gas entering the sulfur addition reactor 13 has pressure. Specifically, the booster 27 is located between the water washing tower 25 and the sulfur addition reactor 13.

[0056] The sulfur source storage 12 stores a sulfur source. Among them, the sulfur source includes low-molecular-weight organic sulfur compounds. Specifically, the sulfur source includes at least one of ethanethiol, n-butyl mercaptan, dimethyl disulfide, dimethyl sulfide, carbon disulfide, and di-tert-nonyl polysulfide. Low molecular weight means a molecular weight less than 1000.

[0057] The sulfur source can react with hydrogen in the raw syngas to obtain hydrogen sulfide. The following are several specific substances that exemplarily provide the sulfur source.

[0058] Ethyl mercaptan (abbreviated as EM) is an organic compound with the chemical formula C2H6S and is a colorless transparent liquid. Ethyl mercaptan reacts with hydrogen to generate hydrogen sulfide, and the reaction formula is as follows:

[0059] C2H6S + H2 → C2H6 + H2S.

[0060] n-Butyl mercaptan (abbreviated as NBM) is an organic compound with the chemical formula C4H 10 S and is a colorless transparent liquid. n-Butyl mercaptan reacts with hydrogen to generate hydrogen sulfide, and the reaction formula is as follows:

[0061] C4H 10 S + H2 → C4H 10 + H2S.

[0062] Dimethyl disulfide (abbreviated as DMDS) is a dimethyl disulfide with the chemical formula C2H6S2. It reacts with hydrogen to generate hydrogen sulfide, and the reaction formula is as follows:

[0063] C2H6S2 + 3H2 → 2CH4 + 2H2S.

[0064] Dimethyl sulfide (abbreviated as DMS) is a dimethyl sulfide with the chemical formula C2H6S. It reacts with hydrogen to generate hydrogen sulfide, and the reaction formula is as follows:

[0065] C2H6S + H2 → 2CH2 + H2S.

[0066] The chemical formula of di-tert-nonyl polysulfide (abbreviated as TNPS) can be (t-C9H 19 )2S 4.5 , and it reacts with hydrogen to generate hydrogen sulfide, and the reaction formula is as follows:

[0067] (t-C9H 19 )2S 4.5 + 5.5H2 → (t-C9H20 ) 2 + 4.5H2S。

[0068] The chemical formula of carbon disulfide is CS2. It reacts with hydrogen to produce hydrogen sulfide, and the reaction formula is as follows:

[0069] CS2 + 4H2 = CH4 + 2H2S。

[0070] In other embodiments, the sulfur source can also be inorganic solid sulfur. Exemplarily, such as elemental sulfur.

[0071] The addition amount of the sulfur source, that is, the amount of the sulfur source entering the sulfur replenishment reactor 13, is specifically calculated based on the complete sulfidation of the active components in the sulfur-tolerant shift catalyst.

[0072] The sulfur replenishment reactor 13 is arranged downstream of the gasifier 11 to receive the raw syngas, and the sulfur replenishment reactor 13 is arranged downstream of the sulfur source storage 12 to receive the sulfur source. The sulfur replenishment reactor 13 is used for the sulfur source to react with the raw syngas to obtain hydrogen sulfide.

[0073] In the sulfur replenishment reactor 13, the sulfur source reacts with the hydrogen in the raw syngas, and the reaction can refer to the foregoing.

[0074] The shift reactor 14 is arranged downstream of the sulfur replenishment reactor 13. A sulfur-tolerant shift catalyst is provided in the shift reactor 14. The shift reactor 14 is used for the sulfur-tolerant shift catalyst to react with hydrogen sulfide to obtain the sulfided catalyst active components and for the raw syngas to carry out the CO shift reaction. That is, in the shift reactor 14, there is not only the pre-sulfidation reaction of the catalyst, but also the CO shift reaction of the raw syngas.

[0075] Furthermore, in the shift reactor 14, a reaction between the organic sulfur and the hydrogen in the raw syngas also occurs, and this reaction produces hydrogen sulfide. The organic sulfur can be the unreacted sulfur source transported by the sulfur replenishment reactor 13 or the organic sulfur generated after the reaction of the sulfur source.

[0076] Specifically, the sulfur-tolerant shift catalyst is a Co-Mo series catalyst.

[0077] The desulfurization tower 15 is arranged downstream of the shift reactor 14 and is used for removing sulfides to obtain sulfur-containing substances and synthesis reaction gas respectively. The desulfurization tower 15 not only needs to remove the generated hydrogen sulfide, but also needs to remove various sulfides generated during the biomass gasification process. The sulfides include organic sulfur and inorganic sulfur.

[0078] The desulfurization tower 15 is filled with a desulfurization liquid for removing sulfides, that is, the desulfurization tower 15 uses the wet oxidation method for desulfurization. The upper part of the desulfurization tower 15 is provided with a gas outlet, and the bottom is provided with a liquid outlet.

[0079] Specifically, the desulfurization liquid is a sodium carbonate solution. The reaction formula of the desulfurization liquid and hydrogen sulfide is as follows:

[0080] H2S + Na2CO3 = NaHS + NaHCO3.

[0081] The gaseous substance after passing through the desulfurization liquid and the synthesis reaction gas enter the downstream through the gas outlet. The liquid substance formed after passing through the desulfurization liquid, i.e., the sulfur-containing substance, enters the regenerator through the liquid outlet.

[0082] The methanol synthesis tower 17 is arranged downstream of the desulfurization tower 15 to receive the synthesis reaction gas and carry out the methanol synthesis reaction to obtain methanol.

[0083] A decarbonization tower 28 is provided between the desulfurization tower 15 and the methanol synthesis tower 17 to remove carbon dioxide from the synthesis reaction gas. That is, the synthesis reaction gas output from the gas outlet of the desulfurization tower 15 enters the decarbonization tower 28.

[0084] A pressurizing device 30 is provided between the desulfurization tower 15 and the methanol synthesis tower 17 to pressurize the synthesis reaction gas. Specifically, the pressurizing device 30 is arranged between the decarbonization tower 28 and the methanol synthesis tower 17 to pressurize the gas entering the methanol synthesis tower 17.

[0085] That is, CO with pressure and H2 react in the methanol synthesis tower 17 to obtain methanol.

[0086] Further, a methanol rectification tower 29 is also provided downstream of the methanol synthesis tower 17. The methanol rectification tower 29 receives the crude methanol synthesized by the methanol synthesis tower 17 and conducts rectification treatment.

[0087] A heat recovery device 31 is also provided downstream of the methanol synthesis tower 17. The heat recovery device 31 receives and burns the purge gas output from the methanol synthesis tower 17, and at the same time recovers the heat generated by the combustion to make full use of the heat generated by the combustion of the purge gas.

[0088] The regenerator is arranged downstream of the desulfurization tower 15 to receive the sulfur-containing substance and carry out regeneration treatment to obtain sulfur.

[0089] Specifically, the regenerator includes a flash tower 32, a regeneration tank 33, and a sulfur melting kettle 34 arranged in sequence from upstream to downstream.

[0090] The flash tower 32 is arranged downstream of the desulfurization tower 15. The flash tower 32 is used to analyze the carbon dioxide in the sulfur-containing substance and reduce the pressure of the sulfur-containing substance. Since the liquid output from the desulfurization tower 15 is a high-pressure liquid and the inside of the flash tower 32 is at normal pressure, the sudden drop in pressure causes the carbon dioxide in the liquid to be analyzed. The liquid after pressure reduction enters the regeneration tank 33.

[0091] The regeneration tank 33 is used to supply sulfur-containing substances to undergo a regeneration reaction to obtain suspended sulfur particles. The liquid and air undergo the oxidative regeneration of the desulfurization catalyst in the regeneration tank 33. At the same time, the suspended sulfur particles in the liquid are floated by the air to form foam and float on the upper part of the regeneration tank 33. Among them, a DSH high-sulfur-capacity salt-inhibiting catalyst is provided in the regeneration tank 33, and this catalyst is a composite catalyst with a multi-metal catalytic center.

[0092] Under the action of the catalyst, the generated sodium hydrosulfide reacts with the oxygen in the solution to undergo an oxidative sulfur precipitation reaction:

[0093] NaHS + NaHCO3 + 1 / 2O2 = S + Na2CO3 + H2O.

[0094] The sulfur melting kettle 34 is used to convert the suspended sulfur particles into solid sulfur. In the sulfur melting kettle 34, the sulfur foam is broken by heating, so that the elemental sulfur in the form of fine particles sinks to the bottom of the kettle. As the temperature rises, the sulfur particles gradually aggregate and grow and are separated from the solution.

[0095] The solid in the sulfur melting kettle 34 enters the lower high-temperature zone for further melting. When it reaches an appropriate molten state, the liquid sulfur is discharged out of the kettle through devices such as a heat preservation valve, and finally solidifies into solid sulfur after cooling.

[0096] The amount of sulfur obtained comes partly from the sulfur recovered after the pre-sulfidation of the Co-Mo series catalyst, and partly from the sulfur removed from the raw syngas, and is continuously produced.

[0097] Furthermore, the sulfur melting kettle 34 is connected to the desulfurization tower 15 to return the reacted liquid to the desulfurization tower 15 for continued use. This not only reduces the discharge of waste liquid, but also fully saves raw materials and reduces costs.

[0098] The working principle of the biomass gasification sulfur supplementation and desulfurization methanol production device in this embodiment is as follows:

[0099] The biomass raw material enters the gasification furnace 11 and is converted into raw syngas mainly composed of CO, H2, and CO2. The raw syngas is then processed through sulfur supplementation, conversion, desulfurization, and decarbonization processes to form qualified synthesis reaction gas, which enters the methanol synthesis tower 17 to produce methanol.

[0100] The hydrogen in the raw syngas reacts with the sulfur source in the sulfur supplementation reactor 13 to obtain hydrogen sulfide. The hydrogen sulfide converts the Co-Mo series sulfur-tolerant conversion catalyst in the conversion reactor 14 into a sulfided state, thus ensuring the catalyst activity, enabling the CO conversion of the raw syngas to react fully, and further obtaining synthesis reaction gas with a better hydrogen-carbon ratio, thereby increasing the methanol yield.

[0101] At the same time, the subsequent sulfur-containing substances are regenerated to produce sulfur. Sulfur is a high-value-added product, which can increase the income and thus reduce the cost of preparing methanol.

[0102] The biomass gasification sulfur supplementation and desulfurization methanol production device in this embodiment has the following advantages:

[0103] The biomass gasification sulfur supplementation and desulfurization methanol production device realizes the sulfur supplementation, conversion, and desulfurization processes through a sulfur supplementation reactor, a converter, and a desulfurization tower, forms qualified synthesis reaction gas, and enters the methanol synthesis tower to produce methanol. Due to the sulfur supplementation, the activity of the catalyst is ensured, enabling the CO conversion of the raw synthesis gas to react fully, and then obtaining a synthesis reaction gas with a better hydrogen-carbon ratio, thereby increasing the methanol production.

[0104] Meanwhile, the subsequent sulfur-containing substances are regenerated to produce sulfur, which is a high-value-added product, thus being able to increase the revenue and further reduce the cost of methanol production.

[0105] Although the present utility model has been described with reference to several exemplary embodiments, it should be understood that the terms used are illustrative and exemplary, rather than restrictive. Since the present utility model can be embodied in many forms without departing from the spirit or essence of the utility model, it should be understood that the above-described embodiments are not limited to any of the foregoing details, but should be broadly construed within the spirit and scope defined by the appended claims. Therefore, all changes and modifications falling within the scope of the claims or their equivalents should be covered by the appended claims.

Claims

1. A biomass gasification sulfur supplementation and desulfurization methanol production device, characterized in that Comprising: A gasifier for biomass reaction to obtain raw syngas; A sulfur source storage for storing a sulfur source; A sulfur addition reactor disposed downstream of the gasifier to receive the raw syngas; the sulfur addition reactor is disposed downstream of the sulfur source storage to receive the sulfur source and is used for the reaction of the sulfur source with the raw syngas to obtain hydrogen sulfide; A shift reactor disposed downstream of the sulfur addition reactor, with a sulfur-tolerant shift catalyst provided therein, and the shift reactor is used for the reaction of the sulfur-tolerant shift catalyst with hydrogen sulfide to obtain a sulfided catalyst active component and for the CO shift reaction of the raw syngas; A desulfurization tower disposed downstream of the shift reactor and used for removing sulfides to obtain sulfur-containing substances and synthesis reaction gas respectively; A regenerator disposed downstream of the desulfurization tower to receive the sulfur-containing substances and perform regeneration treatment to obtain sulfur; A methanol synthesis tower disposed downstream of the desulfurization tower to receive the synthesis reaction gas and perform methanol synthesis reaction to obtain methanol.

2. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, wherein The sulfur source stored in the sulfur source storage includes low-molecular-weight organic sulfur compounds; the sulfur source includes at least one of ethanethiol, n-butyl mercaptan, dimethyl disulfide, dimethyl sulfide, carbon disulfide, and di-tert-nonyl polysulfide.

3. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, characterized in that, The sulfur-tolerant shift catalyst is a Co-Mo series catalyst; and / or, The desulfurization tower is filled with a desulfurization liquid for removing sulfides; The desulfurization liquid is a sodium carbonate solution.

4. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, characterized in that, The regenerator includes a flash tower, a regeneration tank, and a sulfur melting kettle arranged in sequence from upstream to downstream. The flash tower is disposed downstream of the desulfurization tower and is used for decomposing carbon dioxide in the sulfur-containing substances and reducing the pressure of the sulfur-containing substances. The regeneration tank is used for the regeneration reaction of the sulfur-containing substances to obtain suspended sulfur particles, and the sulfur melting kettle is used for converting the suspended sulfur particles into solid sulfur.

5. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 4, characterized in that, The sulfur melting kettle is connected to the desulfurization tower to return the reacted liquid to the desulfurization tower.

6. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, wherein, A pressurizing device is provided between the desulfurization tower and the methanol synthesis tower for pressurizing the synthesis reaction gas; and / or, A decarbonization tower is provided between the desulfurization tower and the methanol synthesis tower for removing carbon dioxide from the synthesis reaction gas.

7. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, wherein, A methanol distillation tower is further provided downstream of the methanol synthesis tower; and / or, a heat recovery device is further provided downstream of the methanol synthesis tower, and the heat recovery device receives the purge gas output from the methanol synthesis tower.

8. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, wherein, A waste heat utilization device is provided at the gas outlet of the gasifier to utilize the heat of the raw syngas; and / or, a booster is provided between the gasifier and the sulfur addition reactor.

9. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 1, characterized in that, A purification device is provided between the gasifier and the sulfur addition reactor to purify the raw syngas.

10. The biomass gasification sulfur supplementation and desulfurization methanol production device according to claim 9, characterized in that, The purification device includes a separator, a dust collector, and a water washing tower arranged in sequence. The separator is disposed downstream of the gasifier and is used for gas-solid separation. The dust collector receives the gaseous substances separated by the separator and is used for dust removal. The water washing tower is used for removing tar and ammonia.

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