CN223404903U - Methanol preparation system - Google Patents
Methanol preparation systemInfo
- Publication number
- CN223404903U CN223404903U CN202422838115.XU CN202422838115U CN223404903U CN 223404903 U CN223404903 U CN 223404903U CN 202422838115 U CN202422838115 U CN 202422838115U CN 223404903 U CN223404903 U CN 223404903U
- Authority
- CN
- China
- Prior art keywords
- gas
- methanol
- outlet end
- module
- inlet end
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本申请提供了一种甲醇制备系统，包括制气模块、气体净化模块和制醇模块；制气模块包括生物质气化装置，生物质气化装置的出口端与气体净化模块连接，生物质气化装置制备用于生产甲醇的合成气；气体净化模块包括脱碳装置脱碳装置的出口端分别与生物质气化装置的入口端和制醇模块连接；脱碳装置用于去除合成气中的至少部分二氧化碳，并将合成气输送至制醇模块，以供制醇模块进行制醇，以及将部分二氧化碳输送至生物质气化装置，以作为生物质气化装置的输送载气，替代原来采用的氮气或空气，从而有助于降低氮气等惰性气体进入到合成气中的含量，提升甲醇的制备效果。
The present application provides a methanol preparation system, comprising a gas production module, a gas purification module and an alcohol production module; the gas production module comprises a biomass gasification device, the outlet end of the biomass gasification device is connected to the gas purification module, and the biomass gasification device prepares synthesis gas for producing methanol; the gas purification module comprises a decarbonization device, the outlet end of the decarbonization device is respectively connected to the inlet end of the biomass gasification device and the alcohol production module; the decarbonization device is used to remove at least part of the carbon dioxide in the synthesis gas, and transport the synthesis gas to the alcohol production module for the alcohol production module to produce alcohol, and transport part of the carbon dioxide to the biomass gasification device to serve as a transport carrier gas for the biomass gasification device, replacing the nitrogen or air originally used, thereby helping to reduce the content of inert gases such as nitrogen entering the synthesis gas and improving the methanol production effect.
Description
Technical Field
The application relates to the technical field of energy and chemical industry, in particular to a methanol preparation system.
Background
In the traditional mode, the preparation mode of the methanol mainly comprises the preparation of the methanol by coal, the preparation of the methanol by natural gas, the preparation of the methanol by coke oven gas and the like, but the raw materials of the preparation mode adopt fossil fuel, so that the energy consumption and the carbon emission are very high, and the property requirements of the green methanol can not be met. Along with the continuous development of technology, a mode of preparing methanol by biomass appears in the industry, and the preparation problem of green methanol is effectively solved.
At present, biomass methanol production mainly comprises three modes of producing methanol by biomass gasification, producing methanol by synthesis gas by coupling carbon dioxide with green hydrogen and producing methanol by biomass fermentation, wherein the mode of producing methanol by carbon dioxide coupling green hydrogen has lower reliability and higher cost for producing alcohol, and the mode of producing methanol by biomass fermentation has smaller scale and higher cost, which is not beneficial to industrialized popularization and application. The method for producing the methanol by the synthesis gas through biomass gasification is more suitable for industrial popularization and application due to higher stability and better economic benefit, so that the method is focused on by industries. However, in the mode of producing methanol from synthesis gas by biomass gasification in the prior art, the content of impurities in the synthesis gas is high, which affects the preparation effect of green methanol.
Disclosure of utility model
In view of the above, the present application provides a methanol preparation system to at least solve the problems of high inert gas content and low system equipment utilization rate in the crude synthesis gas produced in the current methanol preparation system.
In order to achieve the above purpose, the technical scheme of the application is realized as follows:
The application provides a methanol preparation system, which comprises a gas making module, a gas purifying module and an alcohol making module;
The gas making module comprises a biomass gasification device, the outlet end of the biomass gasification device is connected with the gas purifying module, and the biomass gasification device is used for preparing synthetic gas for producing methanol;
The gas purification module comprises a decarbonization device, and the outlet end of the decarbonization device is respectively connected with the inlet end of the biomass gasification device and the alcohol production module;
The decarbonization device is used for removing at least part of carbon dioxide in the synthesis gas, conveying the synthesis gas to the alcohol production module and conveying part of carbon dioxide to the biomass gasification device.
Optionally, the gas purification module further comprises a carbon monoxide conversion device, wherein the outlet end of the carbon monoxide conversion device is connected with the inlet end of the decarburization device, and the carbon monoxide conversion device is used for adjusting the carbon-hydrogen ratio in the synthesis gas.
Optionally, the gas purification module further comprises a desulfurization device, wherein the outlet end of the desulfurization device is connected with the inlet end of the carbon monoxide conversion device, and the desulfurization device is used for removing sulfides in the synthesis gas.
Optionally, the desulfurization device comprises a coarse desulfurization device and a fine desulfurization device which are connected with each other, wherein the outlet end of the fine desulfurization device is connected with the inlet end of the carbon monoxide conversion device;
the coarse desulfurization device is used for removing hydrogen sulfide gas in the synthesis gas, and the fine desulfurization device is used for removing sulfide in the synthesis gas.
Optionally, the gas purification module further comprises a temperature swing adsorption device, wherein the inlet end of the temperature swing adsorption device is connected with the outlet end of the coarse desulfurization device, the outlet end of the temperature swing adsorption device is connected with the inlet end of the fine desulfurization device, and the temperature swing adsorption device is used for removing tar in the synthesis gas. Optionally, the gas purification module further comprises a first compression device, wherein the first compression device is connected between the outlet end of the temperature swing adsorption device and the inlet end of the fine desulfurization device, and the first compression device is used for boosting the synthesis gas.
Optionally, the air making module further comprises an air separation device, wherein the outlet end of the air separation device is respectively connected with the inlet end of the biomass gasification device and the inlet end of the temperature swing adsorption device, and the air separation device is used for conveying oxygen separated from air to the biomass gasification device and nitrogen separated from air
The gas is delivered to the temperature swing adsorption apparatus.
Optionally, the alcohol preparation module comprises a methanol synthesis device and a methanol rectification device, wherein the inlet end of the methanol synthesis device is connected with the outlet end of the decarburization device, and the outlet end of the methanol synthesis device is connected with the inlet end of the methanol rectification device;
the methanol synthesis device is used for synthesizing crude methanol, and the methanol rectification device is used for separating the crude methanol to obtain refined methanol.
Optionally, the alcohol producing module further comprises a hydrogen recovery device, wherein the outlet end of the methanol synthesis device is also connected with the inlet end of the hydrogen recovery device, and the outlet end of the hydrogen recovery device is respectively connected with the inlet end of the methanol synthesis device and the inlet end of the temperature swing adsorption device;
The hydrogen recovery device is used for conveying usable synthesis gas separated from the recovered gas to the methanol synthesis device and conveying non-permeate gas separated from the recovered gas to the temperature swing adsorption device.
Optionally, the device also comprises a power module, wherein the power module comprises a power generation device and a biomass boiler device, and the biomass boiler device is used for driving the power generation device to generate power;
the hydrogen recovery device is also used for conveying the non-permeate gas to the biomass boiler device for blending combustion, and the temperature swing adsorption device is also used for conveying the regenerated gas to the biomass boiler device for blending combustion.
Optionally, the device also comprises a power module, wherein the power module comprises a power generation device, a gas turbine and a waste heat boiler, and the waste heat boiler is used for driving the power generation device to generate power;
The hydrogen recovery device is further used for conveying the non-permeate gas to the gas turbine for blending, and the temperature swing adsorption device is further used for conveying part of the synthesis gas to the gas turbine for blending.
Optionally, the gas purification module further comprises a washing electric capturing device, a gas holder and a second compression device, wherein the outlet end of the washing electric capturing device is connected with the inlet end of the gas holder, the outlet end of the gas holder is connected with the inlet end of the second compression device, and the outlet end of the second compression device is connected with the inlet end of the desulfurization device;
the scrubbing electric catching device is used for removing tar in the synthesis gas, the gas holder is used for carrying out buffer pressure stabilization on the synthesis gas, and the second compression device is used for boosting the synthesis gas.
Optionally, the washing electric catching device comprises a washing tower, wherein the washing tower is used for condensing tar, the washing tower is of a double-layer structure, the lower layer is a spraying layer, and the upper layer is a packing layer.
Optionally, the biomass gasification device is a biomass gasification fluidized bed or a biomass gasification fixed bed.
Compared with the related art, the methanol preparation system provided by the application has the following advantages:
In the methanol preparation system, the outlet end of the decarbonization device is respectively connected with the inlet end of the biomass gasification device and the alcohol preparation module, and carbon dioxide output by the decarbonization device can be conveyed to the biomass gasification device to serve as raw materials and ash conveying carrier gas of the biomass gasification device, so that the carbon dioxide replaces nitrogen or air adopted originally, inert gases such as nitrogen and the like are effectively prevented from entering the biomass gasification device, and the synthesis gas generated by the biomass gasification device does not contain inert gases such as nitrogen and the like, so that the methanol preparation effect is effectively improved. Of course, the carrier gas of the biomass gasification device can also adopt a part of air, and as carbon dioxide enters the biomass gasification device to occupy a part of space in the biomass gasification device, the content of air or nitrogen in the biomass gasification device is reduced, so that the content of inert gases such as nitrogen and the like entering the synthesis gas can be reduced to a certain extent, and the preparation effect of methanol is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a schematic diagram showing the connection of components of a first methanol production system according to an embodiment of the present application;
FIG. 2 is a schematic diagram showing the connection of components of a second methanol production system according to an embodiment of the present application;
FIG. 3 is a schematic diagram showing the connection of components of a third methanol production system according to an embodiment of the present application;
FIG. 4 is a component connection diagram of a power module employing a gas turbine in an embodiment of the application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The terms first, second and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged, as appropriate, such that embodiments of the present application may be implemented in sequences other than those illustrated or described herein, and that the objects identified by "first," "second," etc. are generally of a type, and are not limited to the number of objects, such as the first object may be one or more. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.
The terms "comprises," "comprising," or any other variation thereof, in the description and claims, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal device that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal device. Without further limitation, an element defined by the phrase "comprising one does not exclude the presence of additional like elements in a process, method, article, or terminal device comprising the element.
The methanol production system according to the present application will be described in detail by way of specific examples.
Referring to fig. 1, the methanol preparation system provided by the application comprises a gas preparation module 1, a gas purification module 2 and an alcohol preparation module 3, wherein the gas preparation module comprises a biomass gasification device 11, an outlet end of the biomass gasification device 11 is connected with the gas purification module 2, the biomass gasification device 11 is used for preparing synthesis gas for producing methanol, the gas purification module 2 comprises a decarbonization device 22, an outlet end of the decarbonization device 22 is respectively connected with an inlet end of the biomass gasification device and the alcohol preparation module 3, and the decarbonization device 22 is used for removing at least part of carbon dioxide in the synthesis gas and conveying the synthesis gas to the alcohol preparation module 3 and part of carbon dioxide to the biomass gasification device 11.
Specifically, the gas making module 1, the gas purifying module 2 and the alcohol making module 3 belong to three large modules of the methanol preparation system, wherein each module comprises a plurality of devices for cooperative work, each device in the gas making module 1 is mainly used for preparing synthesis gas for producing methanol, each device in the gas purifying module 2 is mainly used for purifying the synthesis gas conveyed by the gas making module 1, and each device in the alcohol making module 3 is mainly used for chemically reacting the synthesis gas conveyed by the gas purifying module 2 to generate methanol, so that the preparation of green methanol is realized. In the methanol production system, synthesis directly produced by the gas production module 1
The gas is crude synthesis gas, impurities such as dust, tar, benzene, naphthalene, hydrogen sulfide, organic sulfur and the like are not removed from the crude synthesis gas, and then the crude synthesis gas is purified by the gas purification module 2 to form usable synthesis gas, namely the usable synthesis gas is gas from which impurities such as dust, tar, benzene, naphthalene, hydrogen sulfide, organic sulfur and the like are removed, and the usable synthesis gas is conveyed to the alcohol production module 3 to prepare methanol.
The gas making module comprises a biomass gasification device 11, the outlet end of the biomass gasification device 11 is connected with the gas purifying module 2, the crude synthesis gas generated by the biomass gasification device 11 is conveyed to the gas purifying module 2 for gas purification, and the purified gas is conveyed to the alcohol making module 3 for preparing green methanol. The embodiment of the application adopts carbon monoxide and hydrogen generated by the biomass gasification device 11 as raw materials, adopts mature carbon monoxide hydrogenation to prepare green methanol, and has mature technology, excellent catalyst performance and long service life.
The gas cleaning module 2 comprises a decarbonizing device 22, wherein the decarbonizing device 22 is provided with two outlet ends, one outlet end is connected with the biomass gasification device 11, and the other outlet end is connected with the alcohol producing module 3. The decarbonization device 22 is provided with a solvent for adsorbing carbon dioxide, and after the solvent adsorbs part of carbon dioxide in the synthesis gas, the carbon dioxide content in the synthesis gas can be controlled to be about 2% -5%, so that the carbon dioxide content in the synthesis gas meets the requirement of the alcohol production module 3 on the carbon dioxide content, and the synthesis gas meeting the requirement is conveyed to the alcohol production module 3 to produce methanol. At the same time, the solvent is circulated to the regeneration system in the decarbonization device 22 to continuously desorb carbon dioxide, so as to avoid supersaturation of the solvent, and the solvent has continuous adsorption capacity, a part of carbon dioxide gas desorbed by the solvent is discharged out of the methanol preparation system, and the other part of carbon dioxide gas is conveyed to the biomass gasification device 11 as a carrier gas for conveying raw materials and ash.
In the related art, nitrogen or air is adopted as carrier gas for conveying raw materials and ash of the biomass gasification device, so that inert gases such as nitrogen and the like can enter into synthesis gas to have high content, the inert gases can influence the preparation effect of green methanol, in the embodiment of the application, carbon dioxide output by the decarburization device 22 is conveyed to the biomass gasification device 11, as carrier gas for conveying raw materials and ash of the biomass gasification device 11, carbon dioxide replaces nitrogen or air adopted originally, so that inert gases such as nitrogen and the like are effectively prevented from entering the biomass gasification device 11, and the synthesis gas generated by the biomass gasification device 11 does not contain inert gases such as nitrogen and the like, so that the preparation effect of methanol is effectively improved. Of course, the carrier gas of the biomass gasification device 11 may also adopt a part of air, and since carbon dioxide enters the biomass gasification device 11 to occupy a part of space in the biomass gasification device 11, the content of air or nitrogen in the biomass gasification device 11 is reduced, so that the content of inert gases such as nitrogen entering the synthesis gas can be reduced to a certain extent, and the preparation effect of methanol is improved.
In addition, after decarburization is carried out by the decarburization device 22, the purity of the carbon dioxide gas entering the biomass gasification device 11 is more than or equal to 96%, the purity of the gas is higher, the preparation effect of green methanol is improved, the content of the carbon dioxide in the synthesis gas entering the alcohol preparation module 3 is controlled to be about 2% -5%, the requirement of the alcohol preparation module 3 on the content of the carbon dioxide can be effectively met, and the alcohol preparation effect of the system is further ensured. In addition, the application conveys the carbon dioxide output by the decarbonization device 22 to the biomass gasification device 11 for recycling, thereby being beneficial to improving the equipment utilization rate of the decarbonization device 22 and realizing the recycling of waste gas, thereby improving the economic benefit and the environmental protection degree of the system.
Optionally, referring to FIG. 2, in some embodiments of the application, the gas cleaning module 2 further comprises a carbon monoxide shifting device 21, wherein an outlet end of the carbon monoxide shifting device 21 is connected to an inlet end of the decarbonizing device 22, and the carbon monoxide shifting device 21 is used for adjusting the hydrocarbon ratio in the synthesis gas.
Specifically, the carbon monoxide shifting device 21 is mainly used for adjusting the carbon-hydrogen ratio in the synthesis gas so as to meet the requirement of the alcohol making module 3 on the hydrogen-carbon ratio in the alcohol making process. The carbon monoxide conversion device 21 works by reacting carbon monoxide with water in a shift converter to produce hydrogen and carbon dioxide (chemical formula: CO+H 2O＝H2+CO2), thereby converting part of the carbon monoxide into hydrogen and carbon dioxide, and realizing the adjustment of the carbon-hydrogen ratio in the synthesis gas. In the related art, the hydrogen-carbon ratio is regulated unstably, the fluctuation of hydrogen and oxygen is larger, the load fluctuation is easy to occur, the system power consumption is larger, and the stability is lower, while the methanol preparation system in the embodiment of the application adopts the carbon monoxide conversion device 21 to regulate the hydrogen-carbon ratio, the technology is relatively mature, the regulation and control mode is simple, the stability of regulating the hydrogen-carbon ratio is high, and the fluctuation of the hydrogen and oxygen of the system is smaller, so that the load fluctuation in the methanol preparation process is smaller, and the system power consumption is reduced, and the system stability is improved.
In addition, the embodiment of the application adopts biomass raw materials, the biomass raw materials generally have lower sulfur content, more raw material varieties, lower content of hydrogen sulfide of the generated synthesis gas and larger fluctuation range, if sulfur-resistant transformation is adopted, catalyst reverse sulfuration is easy to cause, catalyst service life and device stability are influenced, the carbon monoxide transformation device 21 adopts sulfur-free transformation, the sulfur-free transformation needs to adopt a copper-based catalyst, and isothermal transformation is adopted because the copper-based catalyst is not high-temperature-resistant, so that the reverse sulfuration phenomenon of the traditional sulfur-resistant transformation catalyst in a low sulfur state is effectively avoided, and meanwhile, the isothermal transformation is adopted, thereby being beneficial to prolonging the service life of the catalyst.
Optionally, referring to FIG. 2, in some embodiments of the application, the gas cleaning module 2 further comprises a desulfurization device 23, the outlet end of the desulfurization device 23 being connected to the inlet end of the carbon monoxide conversion device 21, the desulfurization device 23 being configured to remove sulfides from the syngas. The decarbonization device 22 can adopt a pre-desulfurization process to enable the gas entering the decarbonization device 22 to be free of hydrogen sulfide gas, so that the carbon dioxide gas exiting the decarbonization device 22 can meet the gas source quality requirement of the biomass gasification device 11.
Specifically, the desulfurization device 23 is used for removing sulfides in the synthesis gas, and the sulfides include two types, namely organic sulfur, such as carbon disulfide, mercaptan, carbonyl sulfide, etc., and inorganic sulfur, such as hydrogen sulfide, etc., which affect the preparation effect of green methanol, so that the removal of the sulfides is required before the synthesis gas enters the alcohol production module 3. So that the outlet end of the desulfurization unit 23 is connected to the inlet end of the carbon monoxide conversion unit 21, and the sulfide-removed synthesis gas is fed to the carbon monoxide conversion unit 21 to adjust the hydrocarbon ratio.
In the related art, a dry desulfurization technology is generally adopted in a methanol preparation system, and the dry desulfurization technology is generally suitable for a scene with lower content of hydrogen sulfide in the synthesis gas, such as less than 50mg/NH 3, while the content of hydrogen sulfide in the synthesis gas produced by the biomass gasification device 11 is higher and is far greater than 50mg/NH 3, and a large amount of absorbent is required to be consumed and needs to be replaced frequently by adopting the dry desulfurization technology, so that the cost for preparing the alcohol is higher. The desulfurization device 23 of the embodiment of the present application adopts a wet desulfurization technique, and the wet desulfurization is realized by using a desulfurizing agent (such as an alkaline solution) to chemically react with hydrogen sulfide to generate soluble sulfide. The wet desulfurization has high desulfurization efficiency, is suitable for the scene of higher content of hydrogen sulfide in the synthesis gas produced by the biomass gasification device 11, can effectively remove most of inorganic sulfur in the synthesis gas, has lower operation cost and high economic benefit, and is beneficial to controlling the overall cost of the methanol preparation system.
In addition, as shown in fig. 2, in the methanol preparation system of the embodiment of the application, the desulfurizing device 23 is located before the decarbonizing device 22, that is, a front desulfurizing and rear decarbonizing mode is adopted, so that desulfurization and decarbonizing can be independently carried out, thereby ensuring that the carbon dioxide in the decarbonizing device 22 does not contain hydrogen sulfide, effectively avoiding the problem of treating low-concentration hydrogen sulfide, being beneficial to reducing the corrosion influence of the hydrogen sulfide on equipment pipelines, and being beneficial to improving the purity of the carbon dioxide conveyed by the decarbonizing device 22 to the biomass gasification device 11, so that the quality requirements of gasification bin sealing and fly ash conveying air sources are met.
Alternatively, referring to FIG. 3, in some embodiments of the application, the desulfurization unit 23 comprises a coarse desulfurization unit 231 and a fine desulfurization unit 232 connected to each other, the outlet end of the fine desulfurization unit 232 is connected to the inlet end of the carbon monoxide conversion unit 21, the coarse desulfurization unit 231 is used for removing hydrogen sulfide gas from the synthesis gas, and the fine desulfurization unit 232 is used for removing hydrogen sulfide gas from the synthesis gas
The device 232 is used to remove sulfur compounds from the syngas.
Specifically, the coarse desulfurization device 231 mainly removes hydrogen sulfide gas in the synthesis gas, and adopts sodium carbonate as an alkali source and adopts a wet desulfurization technology, and hydrogen sulfide in the synthesis gas is absorbed and regenerated by a novel catalyst to convert the hydrogen sulfide into sulfur paste, and then the sulfur paste is melted to form byproducts with the sulfur content of more than or equal to 95%. After desulfurization by coarse desulfurization unit 231, the hydrogen sulfide content of the syngas is about 20mg/Nm 3, (unit: nm 3 is standard cubic, representing the volume of gas under standard conditions) and the syngas then enters temperature swing adsorption unit 28.
The fine desulfurization device 232 mainly adopts a secondary hydrogenation and secondary absorption technology to remove macromolecular organic sulfur in the synthesis gas so as to meet the requirement of the carbon monoxide conversion device 21 and the alcohol production module 3 on total sulfur, and in general, the requirement of the carbon monoxide conversion device 21 and the alcohol production module 3 on total sulfur needs to ensure that the sulfur content is less than or equal to 0.1ppm.
Optionally, referring to FIG. 3, in some embodiments of the application, the gas cleaning module 2 further comprises a temperature swing adsorption device 28, an inlet end of the temperature swing adsorption device 28 is connected to an outlet end of the coarse desulfurization device 231, an outlet end of the temperature swing adsorption device 28 is connected to an inlet end of the fine desulfurization device 232, and the temperature swing adsorption device 28 is used for removing tar from the syngas.
The temperature swing adsorption apparatus 28 utilizes the difference in adsorption properties of the gas components on the solid material to effect separation and purification of the gas by periodic temperature swing. In the methanol preparation system, the temperature swing adsorption device 28 utilizes the low-temperature adsorption and high-temperature desorption technology to further treat tar, benzene, naphthalene and other impurities in the synthetic gas, so that regenerated gas containing the tar, the benzene and the naphthalene enters the biomass boiler device 42 to be incinerated, and then the tar content in the synthetic gas discharged from the temperature swing adsorption device 28 is less than or equal to 1mg/Nm 3, the benzene content is less than or equal to 10mg/Nm 3, and the naphthalene content is less than or equal to 5mg/Nm 3.
Optionally, referring to FIG. 3, in some embodiments of the application, the gas cleaning module 2 further comprises a first compression device 29, the first compression device 29 being connected between the outlet end of the temperature swing adsorption device 28 and the inlet end of the fine desulfurization device 232, the first compression device 29 being configured to boost the pressure of the syngas.
Specifically, the synthesis gas output from the outlet end of the temperature swing adsorption device 28 enters the first compression device 29, the first compression device 29 boosts the pressure of the synthesis gas to meet the pressure requirements of the fine desulfurization device 232 and the carbon monoxide conversion device 21, and meanwhile, the temperature of the synthesis gas is increased after the pressure of the synthesis gas is boosted by the first compression device 29, so that the temperature requirement of the fine desulfurization device 232 on the synthesis gas is met, and the energy consumption of a system is reduced. Optionally, referring to FIG. 3, in some embodiments of the application, the gas making module further comprises an air separation device 12, wherein an outlet end of the air separation device 12 is connected to an inlet end of the biomass gasification device 11 and an inlet end of the temperature swing adsorption device 28, respectively, and the air separation device 12 is used for conveying oxygen separated from air to the biomass gasification device 11 and nitrogen separated from air to the temperature swing adsorption device 28.
Specifically, the air separation unit 12 is an industrial unit for separating each component gas in the air and producing each gas such as oxygen, nitrogen, and argon in the air component. In the embodiment of the application, the air separation device 12 is mainly used for separating oxygen and nitrogen in the air component, and the outlet end of the air separation device 12 is connected with the inlet end of the biomass gasification device 11, so that the oxygen separated from the air component can be conveyed to the biomass gasification device 11 for the biomass gasification device 11 to prepare the raw synthesis gas for producing methanol. Therefore, the biomass gasification device 11 in the embodiment of the application adopts the oxygen separated from the air separation device 12 and the carbon dioxide from the decarburization device 22, so that inert gases such as nitrogen and the like can be effectively prevented from entering the system, and the preparation effect of green methanol is further improved.
The air separation unit 12 can supply the nitrogen gas to the temperature swing adsorption unit 28 in addition to the oxygen gas to the biomass gasification unit 11, and the nitrogen gas plays a role of regenerating the adsorbent, so that the adsorbent which is adsorbed and saturated in the temperature swing adsorption unit 28 can be regenerated and analyzed to be in an adsorption state again, and the regenerated gas containing impurities such as tar, benzene and naphthalene enters the biomass boiler unit 42 for doping and burning, or the nitrogen gas required for other devices to work is supplied, thereby improving the equipment utilization rate and helping to avoid excessive synthesis gas consumption of the temperature swing adsorption unit 28.
Meanwhile, the oxygen used by the biomass gasification device 11 comes from the air separation device 12, the carbon dioxide used by the carbon dioxide comes from the decarburization device 22, so that the purity of the gas is improved, inert gases such as nitrogen and the like are effectively prevented from entering the biomass gasification device 11, the stability of synthesis gas used for preparing methanol is improved, and the stability of the system and the preparation effect of green methanol are improved. Meanwhile, the nitrogen generated by the air separation device 12 can be used by the temperature swing adsorption device 28 or used by other devices, so that the recycling of waste gas is realized, the utilization rate of equipment is improved, the preparation cost of green methanol is controlled, and the economic benefit and the environmental protection degree of the system are improved. While also helping to avoid excessive consumption of synthesis gas by the temperature swing adsorption apparatus 28 and to maximize the use of the synthesis gas for the production of methanol, thereby increasing the production efficiency of methanol to some extent.
Alternatively, referring to fig. 3, in some embodiments of the present application, the alcohol producing module 3 includes a methanol synthesizing device 31 and a methanol rectifying device 32, an inlet end of the methanol synthesizing device 31 is connected to an outlet end of the decarbonizing device 22, an outlet end of the methanol synthesizing device 31 is connected to an inlet end of the methanol rectifying device 32, the methanol synthesizing device 31 is used for synthesizing crude methanol, and the methanol rectifying device 32 is used for separating the crude methanol to obtain refined methanol.
Specifically, the methanol synthesis device 31 is used for making synthesis gas chemically react to generate methanol, the chemical reaction includes that carbon monoxide reacts with hydrogen to generate methanol (chemical formula: CO+2H2H 2＝CH3 OH) and carbon dioxide reacts with hydrogen to generate methanol and water (chemical formula: CO 2+3H2＝CH3OH+H2 O), but the methanol produced by the methanol synthesis device 31 is a crude methanol product, the methanol is required to be separated for the second time by the methanol rectification device 32, and the methanol rectification device 32 mainly adopts a rectification method to separate the crude methanol, water and other impurities, so as to finally obtain a refined methanol product meeting the requirements. In addition, a methanol storage device 34 may be disposed after the methanol rectifying device 32 to store and seal the obtained refined methanol product, so as to facilitate subsequent loading and transportation.
Optionally, referring to fig. 3, in some embodiments of the present application, the alcohol producing module 3 further includes a hydrogen recovery device 33, the outlet end of the methanol synthesis device 31 is further connected to the inlet end of the hydrogen recovery device 33, the outlet end of the hydrogen recovery device 33 is respectively connected to the inlet end of the methanol synthesis device 31 and the inlet end of the temperature swing adsorption device 28, and the hydrogen recovery device 33 is configured to deliver the usable synthesis gas separated from the recovered gas to the methanol synthesis device 31 and the non-permeate gas separated from the recovered gas to the temperature swing adsorption device 28.
Specifically, the outlet end of the methanol synthesis device 31 is also connected to the inlet end of the hydrogen recovery device 33, and the hydrogen recovery device 33 adopts a permeable membrane device, and is mainly used for recovering hydrogen in the purge gas of methanol synthesis, so that the hydrogen recovery rate is improved, and the yield of crude methanol products is improved. Meanwhile, the hydrogen recovery device 33 can also recycle the permeated gas obtained by permeation back to the methanol synthesis device 31 for secondary alcohol production so as to improve the utilization of waste gas and the alcohol production efficiency, wherein the permeated gas mainly comprises effective gas containing hydrogen. The hydrogen reclamation apparatus 33 may also be capable of delivering non-permeate gas that does not permeate the permeable membrane to the temperature swing adsorption apparatus 28 for use by the temperature swing adsorption apparatus 28, wherein the non-permeate gas includes primarily methane gas of high heating value, and possibly a portion of hydrogen, carbon monoxide, and the like. The gas used by the temperature swing adsorption apparatus 28 is thus derived from the nitrogen separated by the air separation unit 12 and the non-permeate separated by the hydrogen recovery unit 33, effectively avoiding the adverse effects of the temperature swing adsorption apparatus 28 consuming synthesis gas during operation. Optionally, referring to fig. 3, in some embodiments of the present application, the methanol preparation system further includes a power module, where the power module includes a power generation device 41 and a biomass boiler device 42, where the biomass boiler device 42 is configured to drive the power generation device 41 to generate power, an inlet end of the biomass boiler device 42 is connected to an outlet end of the hydrogen recovery device 33 and an outlet end of the temperature swing adsorption device 28, respectively, and the hydrogen recovery device 33 is further configured to deliver the non-permeate gas to the biomass boiler device 42 for co-firing, and the temperature swing adsorption device 28 is further configured to deliver the regeneration gas to the biomass boiler device 42 for co-firing.
Specifically, the power module is used for providing green electricity for the methanol preparation system, the power module comprises a power generation device 41 and a biomass boiler device 42, the power generation device 41 is mainly used for providing green electricity for the whole system, a steam turbine power generation device is adopted, the power module has the characteristics of high single machine power, high rotating speed, safe and stable operation and the like, and the green methanol attribute requirement can be met by using biomass fuel. The outlet end of the biomass boiler device 42 is connected with the power generation device 41, and is mainly used for providing steam for the whole system, wherein most of the steam is used for driving the steam turbine power generation device 41 to generate power, and the other part of the steam is used for steam balance.
The inlet end of the biomass boiler device 42 is connected with the outlet end of the hydrogen recovery device 33 and the outlet end of the temperature swing adsorption device 28, respectively, the non-permeate gas output by the hydrogen recovery device 33 can be conveyed to the biomass boiler device 42 for blending combustion, and the regenerated gas output by the temperature swing adsorption device 28 can be conveyed to the biomass boiler device 42 for blending combustion, wherein blending combustion refers to burning the mixed gas entering the biomass boiler device 42. The raw materials of the biomass boiler are mainly biomass materials, and the biomass boiler further comprises non-seepage air from the hydrogen recovery device 33, regenerated gas from the temperature swing adsorption device 28 and the like, and the biomass boiler device 42 can generate high-temperature steam after reaction, so that the waste heat utilization efficiency is improved.
In addition, an exhaust gas treatment device 43 may be disposed at the outlet end of the biomass boiler device 42 to remove impurities such as nitrogen oxides, sulfur dioxide, dust, etc. in the gas, so that the discharged gas meets the environmental emission requirements.
Still or referring to FIG. 4, in other embodiments of the application, the power module includes a power plant 41, a gas turbine 44, and a heat recovery boiler 45, the heat recovery boiler 45 is configured to drive the power plant 41 to generate power, the inlet end of the gas turbine 44 is connected to the outlet end of the hydrogen recovery device 33 and the outlet end of the temperature swing adsorption device 28, respectively, the hydrogen recovery device 33 is further configured to deliver non-permeate gas to the gas turbine 44 for co-firing, and the temperature swing adsorption device 28 is further configured to deliver a portion of the synthesis gas to the gas turbine 44 for co-firing, wherein co-firing refers to burning a mixture of gases entering the gas turbine 44.
Specifically, the power module includes a pressurizing device 46 in addition to the gas turbine 44 and the waste heat boiler 45 of the power generation device 41, wherein the power generation device 41 may be a steam turbine power generation device that generates power mainly using steam sent from the waste heat boiler 45. The inlet end of the gas turbine 44 is connected to the outlet end of the hydrogen recovery device 33 and the outlet end of the temperature swing adsorption device 28, respectively, and mainly uses the synthesis gas from the temperature swing adsorption device 28 and the non-permeate gas from the hydrogen recovery device 33 as fuel to perform combustion power generation. The exhaust-heat boiler 45 is connected to the outlet end of the gas turbine 44, and mainly exchanges heat between the high-temperature flue gas at the outlet of the gas turbine 44 and boiler feed water to generate medium-pressure high-temperature steam, part of the high-temperature steam is used for steam balance, and most of the high-temperature steam is conveyed to the power generation device 41 for power generation. The pressurization device 46 primarily boosts the syngas from the temperature swing adsorption device 28 to meet the inlet pressure requirements of the gas turbine 45.
Optionally, referring to FIGS. 2 and 3, in some embodiments of the application, the gas cleaning module 2 further comprises a scrubbing electric capture device 24, a gas holder 25, and a second compression device 26, wherein the outlet end of the scrubbing electric capture device 24 is connected to the inlet end of the gas holder 25, the outlet end of the gas holder 25 is connected to the inlet end of the second compression device 26, and the outlet end of the second compression device 26 is connected to the inlet end of the desulfurization device 23;
The scrubbing electric catching device 24 is used for removing tar in the synthesis gas, the gas holder 25 is used for carrying out buffer pressure stabilization on the synthesis gas, and the second compression device 26 is used for boosting the synthesis gas.
Specifically, the washing electric tar precipitator 24 is composed of a washing tower, an electric tar precipitator and other parts, and the process method is that the crude synthetic gas of the coming biomass gasification device 11 enters the washing tower, fresh water and circulating cooling water outside the washing tower transfer mass and heat in the washing tower, so that most of tar, benzene, naphthalene and other impurities are condensed in the washing tower, the crude synthetic gas leaving the washing tower is cooled to 40 ℃ and enters the electric tar precipitator, tar in the crude synthetic gas is further supplemented, the tar content in the synthetic gas leaving the electric tar precipitator is less than or equal to 20mg/Nm 3, the electric tar precipitator is connected with the inlet end of the gas holder 25, and the synthetic gas leaving the electric tar precipitator enters the gas holder 25.
The gas holder 25 adopts a dry rare gas holder, and mainly performs short-time buffer pressure stabilization on the synthesis gas so as to facilitate pressure control of a front system and a rear system. The outlet end of the gas holder 25 is connected to the inlet end of the second compression device 26, and the synthesis gas from the gas holder 25 enters the second compression device 26.
The second compression device 26 mainly adopts a screw compressor to boost the pressure of the crude synthetic gas so as to meet the pressure requirement of the temperature swing adsorption device 28, the outlet end of the second compression device 26 is connected with the inlet end of the desulfurization device 23, and the boosted synthetic gas enters the crude desulfurization device 231.
In addition, a sewage pretreatment device 27 is arranged at the outlet end of the washing electric catching device 24, and the sewage pretreatment device 27 is used for pretreating the oily wastewater produced by the washing electric catching device 24, and the pretreated wastewater is sent to a sewage treatment station.
Optionally, in some embodiments of the present application, the scrubber is a double layer structure, wherein the lower layer is a spray layer and the upper layer is a packing layer. The washing tower realizes separation by utilizing the interaction of liquid and gas, and when the gas passes through the washing tower, the liquid can be sprayed on the packing layer to form a layer of liquid film. When the liquid film moves, the gas will react with the liquid physically or chemically and be absorbed or adsorbed by the liquid, and after some time of reaction, the pollutant in the liquid is separated, while the clean gas is discharged from the outlet of the tower top. In the related art, a packed tower is generally adopted as a washing tower of the methanol preparation system, and is easy to block, while the washing tower in the methanol preparation system provided by the embodiment of the application adopts a double-layer structure, wherein the lower layer is a spraying layer for spraying the crude synthesis gas, the upper layer is a packing layer for separating pollutants, and the packing layer is positioned on the upper layer, so that impurities such as tar, naphthalene, dust and the like in the crude synthesis gas can be effectively prevented from blocking the packing layer of the washing tower, and the effect of washing and cooling the synthesis gas can be improved.
Alternatively, in some embodiments of the present application, the biomass gasification device 11 is a biomass gasification fluidized bed or a biomass gasification fixed bed. The biomass gasification fluidized bed can adopt normal pressure or pressurized circulating pure oxygen biomass gasification fluidized bed, and the biomass gasification fixed bed can also adopt normal pressure or pressurized circulating pure oxygen biomass gasification fixed bed. The biomass gasification fluidized bed has the internal circulation formed in the fluidized bed, and the external circulation that the material carried out of the bed by the air flow and returned to the bed, and the material in the system has multiple circulation, so that the gasification reaction is more complete, the carbon conversion rate is higher, the temperature of the whole reaction system is uniform, the tar content in the product gas can be greatly reduced, and the environmental protection performance is improved. Meanwhile, the technology is more suitable for biomass characteristics, namely, the characteristics of high cellulose, low heat value, low ash melting point, large fly ash, high volatile matters and the like, and is beneficial to improving the output effect of the synthesis gas.
In addition, the outlet of the fluidized bed biomass gasification device or the fixed bed biomass gasification device is provided with a high-temperature cracking furnace so as to reduce the content of tar, benzene and naphthalene in the crude synthesis gas, the high-temperature crude synthesis gas at the outlet of the cracking furnace enters a waste boiler to exchange heat with boiler water to generate medium-pressure high-temperature steam, and the rest of the high-temperature crude synthesis gas is sent out of a gasification boundary zone for use except the gasification system.
It should be appreciated that reference throughout this specification to "some embodiments" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. Thus, the appearances of the phrase "in some embodiments" in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Finally, it should be understood that the foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the application to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, alternatives, and alternatives falling within the spirit and scope of the application.
Claims (12)
1. The methanol preparation system is characterized by comprising a gas preparation module (1), a gas purification module (2) and an alcohol preparation module (3);
The gas making module comprises a biomass gasification device (11), wherein the outlet end of the biomass gasification device (11) is connected with the gas purifying module (2), and the biomass gasification device (11) is used for preparing synthetic gas for producing methanol;
The gas purification module (2) comprises a decarbonization device (22), wherein the outlet end of the decarbonization device (22) is respectively connected with the inlet end of the biomass gasification device (11) and the alcohol production module (3), and the decarbonization device (22) is used for removing at least part of carbon dioxide in the synthesis gas, conveying the synthesis gas to the alcohol production module (3) and conveying part of carbon dioxide to the biomass gasification device (11).
2. Methanol production system according to claim 1, wherein the gas purification module (2) further comprises a carbon monoxide shift device (21);
the outlet end of the carbon monoxide conversion device (21) is connected with the inlet end of the decarburization device (22), and the carbon monoxide conversion device (21) is used for adjusting the carbon-hydrogen ratio in the synthesis gas.
3. Methanol production system according to claim 2, wherein the gas cleaning module (2) further comprises a desulphurisation device (23);
The outlet end of the desulfurization device (23) is connected with the inlet end of the carbon monoxide conversion device (21), and the desulfurization device (23) is used for removing sulfide in the synthesis gas.
4. A methanol production system according to claim 3, characterized in that the desulfurizing device (23) comprises a coarse desulfurizing device (231) and a fine desulfurizing device (232), the outlet end of the fine desulfurizing device (232) being connected to the inlet end of the carbon monoxide shifting device (21);
The coarse desulfurization device (231) is used for removing hydrogen sulfide gas in the synthesis gas, and the fine desulfurization device (232) is used for removing sulfide in the synthesis gas.
5. The methanol production system of claim 4, wherein the gas purification module (2) further comprises a temperature swing adsorption device (28);
the inlet end of the temperature swing adsorption device (28) is connected with the outlet end of the coarse desulfurization device (231), the outlet end of the temperature swing adsorption device (28) is connected with the inlet end of the fine desulfurization device (232), and the temperature swing adsorption device (28) is used for removing tar in the synthesis gas.
6. A methanol production system according to claim 5, characterized in that the gas purification module (2) further comprises a first compression means (29);
The first compression device (29) is connected between the outlet end of the temperature swing adsorption device (28) and the inlet end of the fine desulfurization device (232), and the first compression device (29) is used for boosting the synthesis gas.
7. The methanol production system of claim 5, wherein the gas making module further comprises a space division device (12);
The outlet end of the air separation device (12) is respectively connected with the inlet end of the biomass gasification device (11) and the inlet end of the temperature swing adsorption device (28), and the air separation device (12) is used for conveying oxygen separated from air to the biomass gasification device (11) and nitrogen separated from air to the temperature swing adsorption device (28).
8. The methanol production system according to claim 5, wherein the alcohol production module (3) comprises a methanol synthesis device (31) and a methanol rectification device (32);
The inlet end of the methanol synthesis device (31) is connected with the outlet end of the decarburization device (22), and the outlet end of the methanol synthesis device (31) is connected with the inlet end of the methanol rectification device (32);
The methanol synthesis device (31) is used for synthesizing crude methanol, and the methanol rectification device (32) is used for separating the crude methanol to obtain refined methanol.
9. The methanol production system according to claim 8, wherein the alcohol production module (3) further comprises a hydrogen recovery device (33);
The outlet end of the methanol synthesis device (31) is also connected with the inlet end of the hydrogen recovery device (33), and the outlet end of the hydrogen recovery device (33) is respectively connected with the inlet end of the methanol synthesis device (31) and the inlet end of the temperature swing adsorption device (28);
The hydrogen recovery unit (33) is configured to deliver the separated usable synthesis gas in the recovered gas to the methanol synthesis unit (31) and to deliver the separated non-permeate gas in the recovered gas to the temperature swing adsorption unit (28).
10. The methanol production system according to claim 9, further comprising a power module including a power generation device (41) and a biomass boiler device (42), the biomass boiler device (42) being configured to drive the power generation device (41) to generate power;
The inlet end of the biomass boiler device (42) is respectively connected with the outlet end of the hydrogen recovery device (33) and the outlet end of the temperature swing adsorption device (28);
The hydrogen recovery device (33) is also used for conveying the non-permeate gas to the biomass boiler device (42) for blending combustion, and the temperature swing adsorption device (28) is used for conveying the regenerated gas to the biomass boiler device (42) for blending combustion.
11. The methanol production system according to claim 9, further comprising a power module including a power generation device (41), a gas turbine (44), and a waste heat boiler (45), the waste heat boiler (45) being for driving the power generation device (41) to generate power;
The inlet end of the gas turbine (44) is respectively connected with the outlet end of the hydrogen recovery device (33) and the outlet end of the temperature swing adsorption device (28), and the outlet end of the gas turbine (44) is connected with the waste heat boiler (45);
The hydrogen recovery device (33) is further configured to deliver the non-permeate gas to the gas turbine (44) for co-combustion, and the temperature swing adsorption device (28) is further configured to deliver a portion of the synthesis gas to the gas turbine (44) for co-combustion.
12. The methanol preparation system according to any one of claims 3 to 11, wherein the gas purification module (2) further comprises a scrubbing electric capturing device (24), a gas holder (25) and a second compression device (26);
The outlet end of the washing electric catching device (24) is connected with the inlet end of the gas holder (25), the outlet end of the gas holder (25) is connected with the inlet end of the second compression device (26), and the outlet end of the second compression device (26) is connected with the inlet end of the desulfurization device (23);
The scrubbing electric catching device (24) is used for removing tar in the synthesis gas, the gas holder (25) is used for carrying out buffer pressure stabilization on the synthesis gas, and the second compression device (26) is used for boosting the synthesis gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202422838115.XU CN223404903U (en) | 2024-11-20 | 2024-11-20 | Methanol preparation system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202422838115.XU CN223404903U (en) | 2024-11-20 | 2024-11-20 | Methanol preparation system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN223404903U true CN223404903U (en) | 2025-10-03 |
Family
ID=97206078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202422838115.XU Active CN223404903U (en) | 2024-11-20 | 2024-11-20 | Methanol preparation system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN223404903U (en) |
-
2024
- 2024-11-20 CN CN202422838115.XU patent/CN223404903U/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kadam et al. | Recent advancement in biogas enrichment and its applications | |
| CN1880412B (en) | Process for cleaning gases from gasification units | |
| CN101434879B (en) | Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal | |
| AU2010241062B2 (en) | Process for producing purified synthesis gas | |
| CN101125796B (en) | Method for producing alcohol ether fuel from hydrogen prepared from coke oven gas and synthesis gas prepared from scorched particles | |
| CN104232195B (en) | Method for jointly producing methanol and synthetic natural gas by utilizing coke oven gas | |
| US5069685A (en) | Two-stage coal gasification and desulfurization apparatus | |
| EP1207132A1 (en) | Process and apparatus for production of hydrogen by gasification of combustible material and method for electric power generation using fuel cell and electric power generation system using fuel cell | |
| JP2019172595A (en) | Method for methanation of carbon dioxide in combustion exhaust gas and methane production facility | |
| CA2585391A1 (en) | Method for satisfying variable power demand | |
| CN106554831B (en) | Equipment and process for purifying methane and synchronously methanation-transforming carbon dioxide | |
| JP2012522089A (en) | Method for generating a purified syngas stream | |
| KR20120007020A (en) | Process of producing purified syngas | |
| CN110590501B (en) | Processing technology for co-production of methanol and ethylene glycol from coal-based natural gas | |
| CN1057322C (en) | Method for continuously gasifying coal (coke) and purifying synthesized gas | |
| CN115924845B (en) | Polygeneration method of circulating IGCC with complete capture of carbon dioxide and recovery of flue gas water | |
| AU638543B2 (en) | Process for purifying high-temperature reducing gases and integrated coal gasification combined cycle power generation plant | |
| EP1195353A1 (en) | Method and apparatus for production of hydrogen by gasification of combusible material | |
| CN223404903U (en) | Methanol preparation system | |
| CN120776334A (en) | Wind-solar hydrogen production coupling CO2Polygeneration system and method for trapping and utilizing | |
| CN106635165A (en) | Method and device for preparing clean synthesized gas by gasifying carbon-containing raw material | |
| EP1390456A1 (en) | Method for converting hydrocarbon-containing material to a methane-containing gas | |
| CN221822122U (en) | System for preparing methanol and acetic acid and coproducing LNG (liquefied Natural gas) by using blast furnace gas and coke oven gas | |
| CN109776260A (en) | A method of methanol is prepared using volatile matter in low-order coal | |
| CN116924331B (en) | Natural gas hydrogen production system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |