• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for obtaining synthesis gas by heating with organic substrates with microwaves. The process to produce synthesis gas by heating with organic waste microwaves is based on the production of synthesis gas by microwave heating in two stages. Initially, the organic substrate, together with a microwave susceptor, is subjected to microwave heating, in the absence of oxygen, at temperatures between 400ºC and 800º c. A synthesis gas, a carbonaceous residue and a liquid fraction of pyrolysis oils are obtained. Subsequently, the oils from the first stage are mixed and heated in a microwave oven, in the absence of oxygen, at a temperature higher than 700º c, obtaining a synthesis gas and the susceptor enriched in carbon. The process as a whole gives rise only to synthesis gas and a carbonaceous waste. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2646546A1
    申请号:ES201630602
    申请日:2016-05-10
    公开日:2017-12-14
    发明作者:José Ángel MENÉNDEZ DÍAZ；Ana Arenillas De La Puente；Daniel BENEROSO VALLEJO；José Miguel BERMÚDEZ MENÉNDEZ；Miguel Ángel MONTES MORÁN
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    SECTOR OF THE TECHNIQUE
    The object of the present invention is a process for the production of a gas mixture, called synthesis gas, composed mostly of H2 and CO, in proportions greater than 70% by volume, from biomass or organic waste (organic substrate) . The process is based on a microwave heating in two stages.
    Therefore, the present invention is framed within the chemical, environmental and particularly the energy sector, more specifically in the field of fuel production procedures that are more environmentally friendly. BACKGROUND OF THE INVENTION
    The social concern about climate change and its relationship with CO2 emissions from energy generation processes is growing. However, fossil resources continue to be the primary source for energy generation, so it is necessary to develop competitive technologies based on renewable sources. Pyrolysis of biomass is one of the technologies that have a key role in such development.
    Pyrolysis is a process in which an organic material (for example, an organic substrate) is subjected to high temperatures (between 400 ° C and 800 ° C) using an inert atmosphere. These conditions allow to obtain three fractions with a remarkable energy content: a carbonaceous solid residue, a liquid fraction rich in organic compounds and a gaseous fraction, rich in H2 and CO, which can be used as a starting material for the synthesis of chemical products as alcohols, olefins or even biodegradable plastics [Griffin et al., Environmental Progress & Sustainable Energy, 31 (2), 219-224 (2012)].
    Microwave-induced organic waste pyrolysis has been proposed as an alternative to produce synthesis gas (H2 + CO) compared to conventional gasification processes, in order to avoid the use of gasifying agents, such as water vapor.


    The production of synthesis gas by microwave-induced pyrolysis of organic urban solid wastes has shown promise (0.64 Synthetic Lgas / gresiduo), with a gas yield of 48.3% by mass, in addition to reducing the yield in oils up to 7.8% by mass [D. Beneroso et al., Journal of Analytical and Applied Pyrolysis, 111, 55-63 (2015)]. In the case of agricultural waste, such as rice straw, gas yields of up to 53.9% by mass have been obtained, with a proportion of synthesis gas of 70% by volume [Zhang et al., Bioresource Technology, 191 , 17-23 (2015)]. However, these processes produce a certain amount of liquids or pyrolysis oils.
    The use of microwave radiation to induce a pyrolysis process of organic waste is set out in US8354005 and US8808507. These inventions propose a system for carrying out microwave-induced flash pyrolysis on an industrial scale. However, these systems are not designed for the production of synthesis gas, since they produce a stream consisting of the liquid fraction of pyrolysis oils.
    The production of a hydrogen-rich gas from biomass pyrolysis using a fluidized bed reactor followed by a microwave-heated catalytic bed is collected in the document of the CN patent 102963866. In this process, the pyrolysis of the biomass takes place in a fluidized bed reactor and the generated volatiles (oils and synthesis gas) are introduced into a catalytic bed based on nickel oxides, which is heated by microwave radiation and which, together with the feeding of a stream of water vapor, It allows reforming the liquid fraction of pyrolysis oils into synthesis gas.
    The study collected in the scientific article by Zhang et al. [Zhang et al., Bioresource Technology, 191, 17-23 (2015)] proposes the use of nickel-copper-based carbon catalysts during microwave-induced pyrolysis of rice straw, which has reduced oil yield from 22% to 10% by mass.
    The study collected in the scientific article by Xie et al. [Xie et al., Bioresource Technology, 156, 291-296 (2014)] makes use of water vapor in the conversion of biomass into synthesis gas by microwave-induced pyrolysis, allowing a reduction in oil yield up to 5.1% by mass during the catalytic pyrolysis of corn stubble on Ni / Al2O3.


    The production of synthesis gas by biomass gasification using a fixed bed reactor with microwave plasma is set out in patent application document US20140306161A1. This system uses water vapor or oxygen as gasifying agents.
    The use of carbonaceous materials as catalytic bed material for microwave-induced toluene pyrolysis has allowed a conversion of 92.8% of said compound [L. Li et al., Chemical Engineering Journal, 284, 1308-1316 (2016)]. However, toluene is a model compound of pyrolysis oils; in this study a real pyrolysis oil has not been used which is composed of a complex mixture of dozens of organic compounds as in the case of the process proposed in the present invention. Furthermore, said process is not intended to treat solid organic substrates as the process proposed in this invention, but toluene. On the other hand, toluene is not a good model for biomass oils that have a high oxygen content.
    Other documents that also describe microwave heating for the production of synthesis gas are: -the patent ES2310127 includes a procedure for obtaining synthesis gas from a gas rich in CH4 and CO2. -in the utility model CN202482282 describes an installation formed by various microwave equipment for pyrolysis and gasification that interconnect with each other and allow the reuse of by-products from one unit to another. -in the article by A. Domínguez et al. “Investigations into the characteristics of oils produced from microwave pyrolysis of sewage sludge”; Fuel Processing Technology, Vol. 86, Issue 9 (2005), 1007-1020, describes the composition of oils obtained by microwave pyrolysis of sewage sludge, using carbonaceous residues as a catalyst. In this case the heating process is in a single stage and the temperature of 1000º. Water, solids, oil and gases are obtained. -in the article by Su Shiung Lama et al. "Production of hydrogen and light hydrocarbons as a potential gaseous fuel from microwave-heated pyrolysis of waste automotive engine oil"; International Journal of Hydrogen Energy, Vol. 37, Issue 6, (2012), 5011–5021, describes the microwave pyrolysis of used oils from vehicles for obtaining synthesis gas. Carbon particles are used as a microwave susceptor and the pyrolysis process takes place in a single stage at a temperature. The comments included in section 3.2 of this document are interesting, indicating that the older


    temperatures a higher proportion of synthesis gas and a lower amount of residual material in the rector is obtained, 700 ° being the temperature at which a higher gas yield is obtained, although it is not used because at this temperature PAHs (polycyclic aromatic hydrocarbons are obtained ) and metals. -in the review article, "A Review on Waste to Energy Processes Using Microwave Pyrolysis"; Su Shiung Lam et al. Energies 2012, 5 (10), 4209-4232, includes an extensive list of technologies and projects that are being developed for the application of microwaves in the treatment of waste and obtaining by-products with energy value such as bio-fuels or synthesis gas. No project with a double pyrolysis is mentioned. -in the publication of D. Beneroso et al. “Oil fractions from the pyrolysis of diverse organic wastes: The different effects of conventional and microwave induced pyrolysis”, Journal of Analytical and Applied Pyrolysis, Vol. 114 (2015), 256–264 compares the production of synthetic oils and gases a from various types of organic waste (agroresiduos, sewage sludge, municipal waste) from a microwave pyrolysis treatment at 800º in the presence of a microwave susceptor.
    In conclusion, in the state of the art no references have been found to processes that combine a double pyrolysis and allow to obtain exclusively synthesis gas and solid waste, without the presence of oils. A process of these characteristics would avoid the use of metal catalysts and gasifying agents. EXPLANATION OF THE INVENTION
    Different terms used throughout the description of the present invention are defined below:
    Organic substrate is defined as any residue or by-product composed mostly of organic compounds, such as fractions from lignocellulosic biomass or organic fractions from urban solid waste.
    Pyrolysis is defined as the process in which thermal decomposition of an organic substrate occurs at high temperatures (400 ° C - 800 ° C) in the absence of an oxidizing atmosphere.


    Synthesis gas is defined as a mixture of gases composed mostly of hydrogen (H2) and carbon monoxide (CO). It is generally understood that the proportion of H2 + CO is greater than 70% by volume. However, this mixture of gases may also minorly include other compounds such as: CO2, CH4 or light hydrocarbons such as ethane or ethylene.
    Pyrolysis oil is defined as a liquid product derived from the pyrolysis process, which consists of a multitude of organic compounds, such as organic acids, alcohols, ketones, aldehydes or phenols. In addition, it can also contain an appreciable amount in water.
    Microwave susceptor is defined as a material capable of converting microwave radiation into heat. For example, activated carbons, graphite, carbonized or carbonaceous residue obtained in the present process are microwave susceptor materials.
    Carbonic or carbonized residue is defined as a solid product derived from the pyrolysis process, which consists mainly of carbon (20% - 70% by mass) and inorganic compounds, generally oxides and metal salts (30% - 80% by mass). The carbonaceous residue is a microwave susceptor material, which allows the temperature of the medium to be raised to the pyrolysis temperature when mixed with the organic substrate to be pyrolyzed.
    Gasifying agent is defined as a reagent capable of partially oxidizing an organic substrate and allowing the production of synthesis gas. For example, water vapor, oxygen, air or carbon dioxide are gasifying agents.
    Microwave oven is defined as a device capable of generating microwaves with sufficient power to reach the temperatures of the pyrolysis process and which are transmitted to a cavity where the organic substrate to be pyrolyzed.
    Thermal cracking is defined as the process of breaking bonds of molecules by the action of high temperatures and which results in lighter molecules.


    The present invention describes a process based on heating with microwave energy, by means of which synthesis gas (H2 + CO) can be produced from an organic substrate, without using gasifying agents and without generating pyrolysis oils as a byproduct.
    The process consists of two stages of microwave-induced pyrolysis to carry out, during the first stage, the pyrolysis of an organic substrate and, later in the second stage, the pyrolysis of the oils produced to convert them into synthesis gas.
    The process allows the maximum use of the volatile matter of an organic substrate for conversion into synthesis gas. This is a great advantage over other processes, since it is not necessary to use gasifying agents, as in conventional gasification processes, and unwanted oils are not produced. In addition, the use of metal catalysts is not necessary. On the other hand, this process has a greater versatility than conventional gasification processes since it has a greater tolerance to moisture of an organic substrate, as well as to its degree of grinding.
    The process consists in subjecting an organic substrate to a microwave radiation of controlled intensity for a certain time. This causes the pyrolysis of the organic material to take place and a carbonaceous residue and a fraction of volatiles are produced which, after passing through a condenser, provides a fraction of synthesis gas and a liquid fraction of pyrolysis oils. Subsequently, the pyrolysis oils are passed through a bed irradiated with microwave containing the carbonaceous residue obtained above. This causes thermal cracking of the organic compounds contained in the pyrolysis oils to take place, resulting in more synthesis gas.
    In a first aspect, the object of the present invention constitutes a process for obtaining synthesis gas from an organic substrate, which comprises the following steps:
    a) microwave-induced pyrolysis of the organic substrate to obtain synthesis gas, a carbonaceous residue and a liquid fraction of oils
    b) microwave-induced pyrolysis of the liquid fraction of oils obtained in the previous stage to produce synthesis gas.


    The organic substrate is any material that contains mostly organic compounds and is particularly selected from urban solid waste and lignocellulosic biomass or mixture of both.
    5 In each of the stages a bed of microwave susceptor material is used whichselect from activated carbon, graphite, carbonized, metal particles or residuecarbonaceous produced in the process stages.
    In a preferred embodiment, the pyrolysis step of the organic substrate is brought to
    10 carried out at a temperature between 400 and 800 ° C, more preferably at 400 ° C. As for the pyrolysis stage of the liquid fraction of oils, it is preferably carried out at temperatures above 700 ° C, more preferably at a temperature of 800 ° C.
    In another preferred embodiment, in the pyrolysis stage of the organic substrate the carbonaceous residue of a previous pyrolysis is used as a susceptor in a mass proportion equal to or greater than 0.3 microwave susceptor / 1 organic substrate and in the stage The carbonaceous residue of an earlier pyrolysis in a mass proportion equal to or less than 0.3 liquid fraction of pyrolysis is used as a pyrolysis of the liquid oil fraction.
    20 oils / 1 microwave susceptor.
    The pyrolysis stages, both of the organic substrate and the liquid fraction of oils are carried out in a microwave oven, which can be operated at any frequency band allowed between 9 kHz and 400 Ghz. Preferably, the frequency bands a
    25 those operated by the microwave are 915 MHz and 2.45 GHz.
    Optionally, a preliminary step of mixing the organic substrate and the microwave susceptor material before the pyrolysis of the organic substrate is included. 30 BRIEF DESCRIPTION OF THE DRAWINGS
    To complement the description and in order to help a better understanding of the features of the invention, it is accompanied as an integral part of said description:
    35 Figure 1.- Shows the diagram of the global process. 8


    Figure 2.- It shows the balance of process material when operating at 800ºC in the first stage and at 800ºC in the second stage.
    Figure 3.- Shows the balance of process material when operating at 400ºC in the first stage and at 800ºC in the second stage. PREFERRED EMBODIMENT OF THE INVENTION
    The present invention relates to a synthesis gas production process, characterized in that the pyrolysis steps of an organic substrate and the subsequent pyrolysis of the oils produced take place by a microwave heating process.
    The described process is represented in the flowchart shown in Figure 1.
    The synthesis gas production process consists of two main stages:
    i) Microwave induced pyrolysis, where an organic substrate (1.1) is thermally degraded with the assistance of a microwave susceptor material (1.7), to produce a carbonaceous residue (1.2), a liquid fraction of pyrolysis oils (1.5) and a fraction of synthesis gas (1.4), represented in block 1.A.
    ii) Microwave-induced pyrolysis of the liquid fraction of pyrolysis oils produced in the previous stage (1.5), where it is thermally cracked on a bed containing the carbonaceous residue obtained in the previous stage (1.9), to produce a fraction of synthesis gas (1.6), represented in block 1.B.
    In a preferred embodiment, the first stage of the process (1.A) is carried out at a temperature between 400 ° C and 800 ° C. More preferably, the first stage of the process (1.A) is carried out at a temperature of 400 ° C.
    Preferably, during the first stage of the process (1.A) the carbonaceous residue from a previous pyrolysis process (1.7) is used as a microwave susceptor material in a proportion equal to or greater than 0.3 kg per 1 kg of substrate Organic fed to the process. More preferably, the carbonaceous residue of a previous pyrolysis process (1.7) is used in a mass ratio of 0.3 kg of susceptor per 1 kg of organic substrate.


    In another preferred embodiment, the second stage of the process (1.B) is carried out at a temperature greater than 700 ° C. More preferably, the second stage of the process (1.B) is carried out at a temperature of 800 ° C.
    In a preferred embodiment, the liquid fraction mass of pyrolysis oils (1.5) fed to the second stage (1.B) is 0.3 kg per 1 kg of bed formed by the carbonaceous residue (1.9). More preferably, the liquid fraction mass of pyrolysis oils (1.5) fed to the second stage (1.B) is less than 0.3 kg per 1 kg of bed formed by the carbonaceous residue (1.9).
    First, the organic substrate (1.1) is mixed with a microwave susceptor material (1.7), from a solids distribution system (1.D), in a suitable mass ratio in a reactor that has to be able to withstand the temperature at which the pyrolysis will occur, normally below 1000 ° C. Although it would not be necessary in certain devices, it is advisable that the reactor be made of a microwave-transparent material, for example, quartz or alumina. It is convenient to subject this mixture to stirring before introducing it into the reactor, so that the mixture is as homogeneous as possible.
    The proportions in which the organic substrate is mixed with the microwave susceptor material, which will lead to the production of synthesis gas, are important. The organic substrate and the microwave susceptor material must normally be mixed in predetermined proportions for maximum synthesis gas production to take place.
    In the next stage of the process object of the present invention the mixture of an organic substrate and microwave susceptor material is subjected to the action of the microwaves, which produces a heating thereof and induces the pyrolysis process. For this, a device is used, a microwave oven (1.A). Normally the microwave oven operates at a frequency of 2.45 GHz, although it can also operate at a frequency of 915 MHz.
    Preferably, in said step the microwave-induced pyrolysis process (1.A) is carried out at a temperature between 400 ° C and 800 ° C. More preferably, in said step the microwave-induced pyrolysis process (1.A) is carried out at a temperature of 400 ° C. The temperature used directly influences the energy consumption of the


    process. The organic substrate mixture with the microwave susceptor material is subjected to a heating process in the microwave oven. Within minutes, sometimes seconds, the organic substrate begins to degrade as the microwave susceptor material absorbs microwave energy and transforms it into heat, which is transmitted by conduction to said organic substrate. A part of the organic substrate remains as a carbonaceous solid fraction (1.2), transported to the solids distribution system (1.D), which is, in turn, a microwave susceptor material, whereby the microwave-induced pyrolysis process can hold on Another part of the organic substrate is transformed into volatile compounds leaving the reactor (1.3). These volatile compounds are passed through a condenser (1.C) at a temperature below 20 ° C, so that they are separated into a fraction of synthesis gas (1.4), which is stored in a tank, and in a liquid fraction of pyrolysis oils (1.5).
    The second stage of the process object of the present invention consists in subjecting the liquid fraction of pyrolysis oils obtained at the exit of the condenser (1.5) to the action of the microwaves, which will produce a thermal cracking thereof. For this, a device is used, a microwave oven (1.B), in which there is a reactor made of a microwave transparent material; for example, quartz or alumina. Said reactor contains a bed formed by the carbonaceous residue obtained in the previous step (1.9), which is a microwave susceptor material that acts as a catalyst for the microwave induced pyrolysis of the liquid oil fraction. The liquid fraction of oils is circulated through the bed formed by the carbonaceous residue, which reaches very high local temperatures that favor the decomposition reactions of organic molecules, present in the liquid fraction of oils in: a solid or coke residue, which is essentially carbon (C); and a mixture of gases, among which are mostly (more than 70% by volume) hydrogen (H2) and carbon monoxide (CO) and, minority form (less than 30% by volume) carbon dioxide (CO2 ), methane and other light hydrocarbons. In this way the liquid stream is completely eliminated from the whole process and converted into synthesis gas (1.6). This synthesis gas is stored in another tank, and can be mixed totally or partially with the synthesis gas produced in the first stage 1.A. On the other hand, the carbonaceous residue of the bed, whose carbon content has increased during the microwave-induced pyrolysis of the oils in said stage, is extracted therefrom (1.10) and replaced by fresh carbonaceous solid fraction from the distributor system. of solids (1.9). The residue


    The carbonaceous extracted from step 1.B can be mixed, in whole or in part, with the carbonaceous residue from stream 1.8.
    Preferably, the microwave-induced pyrolysis process of the liquid fraction of
    5 oils (1.B) is made at a temperature above 700 ° C. More preferably, the processof microwave-induced pyrolysis of the liquid fraction of oils (1.B) is performed at atemperature of 800 ° C.
    Preferably, the liquid fraction mass of pyrolysis oils (1.5) fed to said
    The stage (1.B) is 0.3 kg per 1 kg of bed formed by the carbonaceous residue (1.9). Most preferably, the mass of the liquid fraction of pyrolysis oils (1.5) fed to said stage (1.B) is less than 0.3 kg per 1 kg of bed formed by the carbonaceous residue (1.9).
    As a result of the process proposed in the present invention, two streams of synthesis gas (gas1, gas2) that can be mixed, totally or partially (gas3), and two streams of carbonaceous solid fraction (solid1, solid2) that can be mixed are obtained , totally or partially (solid3).
    The process object of the present invention, based on the use of microwave radiation to produce synthesis gas, is clearly superior to conventional processes in regard to the full utilization of an organic substrate, without detriment to the quality of the synthesis gas obtained. In addition, no gasifying agents typical of conventional processes or metal catalysts are used to convert
    25 pyrolysis oils in synthesis gas. EXAMPLES
    Example 1
    The present example describes the process of producing synthesis gas from an organic fraction of urban solid waste subjected to the process described in the present invention (Figure 2). The currents are referred to a base of 1 kg of organic fraction of urban solid waste, although the experimental process was carried out with 5 g. Figure 2 represents the material balances of the entire process and Table 1 shows the
    35 energy balances of the entire process.


    Table 1. Energy consumptions and balances of the process when operating at 800ºC in the first stage and 800ºC in the second stage.
    Stage 1 kWh per kg of feedkWh per m3 of gas produced
    Energy consumed 3.004.43
    Energy contained in gas he2.633.89
    Energy contained in solid he0.32-
    Balance -0.05-0.54
    Stage 2
    Energy consumed 0.859.61
    Energy contained in gas he0.252.82
    Energy contained in solid he0.55-
    Balance -0.05-6.79
    Global process
    Energy consumed 3.855.04
    Energy contained in gas he2.883.77
    Energy contained in solid he0.88-
    Balance -0.09-1.27
    1 kg of the organic fraction of urban solid waste is fed to the first stage of the
    5 process together with 0.30 kg of the carbonaceous residue, from a solids distribution system, which is used as microwave susceptor material. In other experiments (not shown) it has been determined that the 0.3 / 1 mass ratio (organic susceptor / fraction) is the minimum and preferable ratio to maximize the production of synthesis gas. The temperature at this stage is 800ºC and the energy used is 3 kWh / kgresiduo, although this
    10 energy consumption depends on the scale of the process and the equipment used. As a result of this process, 0.48 kg of synthesis gas are obtained (with an H2 + CO ratio> 80% by volume) and 0.08 kg of the liquid fraction of pyrolysis oils that are fed to the second stage of the process. In other experiments (not shown) it has been


    determined that below 700 ° C the conversion of oils is not complete and that the preferred temperature for carrying out this stage is 800 ° C. In other experiments (not shown) it has been determined that the 0.3 / 1 mass ratio (oil / carbonaceous residue) is the maximum ratio for the conversion of the oils to be complete, the ratio being
    5 preferred of 0.3 / 1. The temperature in this stage is 800ºC and the energy used is 0.85 kWh / kgresiduo, although this energy consumption depends on the scale of the process and the equipment used. As a result of said step, 0.06 kg of synthesis gas fraction is obtained (with a proportion H2 + CO = 90% by volume).
    10 In summary, from 1 kg of organic fraction of urban solid waste, 0.54 kg of synthesis gas fraction (having a calorific value of 2.88 kWh / kgresiduo) and 0.46 kg of fraction are obtained solid carbonaceous (which has a calorific value of 0.88 kWh / kgresiduo). The production cost of the synthesis gas is 5.04 kWh / m3.
    Example 2 The present example describes the process of producing synthesis gas from an organic fraction of urban solid waste subjected to the process described in the present invention (Figure 3). The currents are referred to a base of 1 kg of organic fraction of urban solid waste, although the experimental process was carried out with 5 g. The
    20 Figure 3 represents the material balances of the entire process and Table 2 shows the energy balances of the entire process.
    Table 2. Energy consumptions and balances of the process when operating at 400ºC in the first stage and at 800ºC in the second stage.
    Stage 1 kWh per kg of feedkWh per m3 of gas produced
    Energy consumed 0.832.35
    Energy contained in the gas 1.524.32
    Energy contained in the solid 0.49-
    Balance +1.18+1.97
    Stage 2
    Energy consumed 1.369.18


    Energy contained in gas he0.342.35
    Energy contained in solid he1.32-
    Balance +0.30-6.83
    Global process
    Energy consumed 2.194.42
    Energy contained in gas he1.853.75
    Energy contained in solid he1.80-
    Balance +1.46-0.67
    1 kg of the organic fraction of urban solid waste is fed to the first stage of the process together with 0.30 kg of the carbonaceous residue, from a solid distributor system, which is used as microwave susceptor material. The temperature in said 5 stage is 400 ° C and the energy used is 0.83 kWh / kgresiduo, although this energy consumption depends on the scale of the process and the equipment used. As a result of this process, 0.27 kg of synthesis gas are obtained (with a ratio H2 + CO = 79% by volume) and 0.13 kg of the liquid fraction of pyrolysis oils that are fed to the second stage of the process. The temperature in said stage is 800 ° C and the energy
    10 used of 1.36 kWh / kgresiduo, although this energy consumption depends on the scale of the process and the equipment used. As a result of said step, 0.10 kg of synthesis gas fraction is obtained (with an H2 + CO ratio> 90% by volume).
    In summary, from 1 kg of organic fraction of urban solid waste, they are obtained
    0.37 kg of synthesis gas fraction (which has a calorific value of 1.85 kWh / kgresiduo) and 0.63 kg of carbonaceous solid fraction (which has a calorific value of 1.80 kWh / kgresiduo). The production cost of the synthesis gas is 4.42 kWh / m3.
    Comparison between Examples 1 and 2
    20 When comparing Example 1 and Example 2, the energy cost for the production of synthesis gas is 14% higher when using 800 ° C in the first stage (4.42 kWh / m3 versus 5.04


    kWh / m3). However, when using 800 ° C in the first stage, the production of synthesis gas is 1.5 times higher (0.54 kg vs. 0.37 kg).
    On the other hand, and without taking into account the heat energy of the carbonaceous residue produced, when using a temperature of 400 ° C in the first stage (Example 2), the energy contained in the synthesis gas is 85% of the energy consumed in the complete process However, when using a temperature of 800 ° C in the first stage (Example 1), the energy contained in the synthesis gas decreases to 75% of the energy consumed in the entire process. This energy recovery is positive if the solid waste is recovered.
    This makes it possible to establish the preferable operating conditions for carrying out the process between 400 ° C, a temperature below which the pyrolysis would not take place or the volatile yields would be very low and 800 ° C, a temperature above which the energy costs would be too high. high.
    Conversions and energy efficiency of the second stage or thermal cracking stage of oils
    The second stage of this process deserves particular attention since it could be used to crack other oils or other complex mixtures of hydrocarbons, not necessarily from the first stage of the process of this invention.
    Under the conditions of temperature and ratio oil / carbonaceous residue described above (ie:> 700 ° C and <0.3 / 1 by mass) the process converts all oils into gases and carbonaceous residue, so that it occurs approximately between 75% and 77% by mass of gases and between 23% and 25% by mass of coke or carbonaceous residue. In addition, the proportion of synthesis gas (H2 + CO) of these oils is greater than 90% by volume, with an H2 / CO molar ratio of approximately 1.4. On the other hand, the energy consumed in the microwave oven to produce this synthesis gas is 3.2 kWh per kg of bed of carbonaceous residue, although this energy consumption depends on the scale of the process and the equipment used, and the energy contained in the gas produced is between 2.3 -2.8 kWh per m3 of synthesis gas produced.

    权利要求:
    Claims (10)
    [1]
    1. Process for obtaining synthesis gas from an organic substrate, which comprises the following stages:
    5 a) microwave-induced pyrolysis of the organic substrate to obtain synthesis gas,a carbonaceous residue and a liquid fraction of oilsb) microwave-induced pyrolysis of the liquid fraction of oils obtained in the stageabove to produce synthesis gas.
    2. Process according to claim 1, wherein the organic substrate is any material containing mostly organic compounds.
    [3]
    3. Process according to claim 2 wherein the organic substrate is selected from
    urban solid waste and lignocellulosic biomass or mixture of both. fifteen
    [4]
    Four. Process according to any one of claims 1 to 3, wherein a bed of microwave susceptor material is used in each of the stages.
    [5]
    5. Process according to claim 4, wherein the microwave susceptor is selected
    20 between activated carbon, graphite, carbonized, metallic particles or carbonaceous residue produced in the process stages.
    Process according to any one of claims 1 to 5, wherein the pyrolysis step of the organic substrate is carried out at a temperature between 400 and 800 ° C.
    [7]
    7. Process according to claim 6, wherein the pyrolysis step of the organic substrate is carried out at a temperature of 400 ° C.
    Process according to any one of claims 1 to 7, wherein the pyrolysis step of the liquid oil fraction is carried out at temperatures above 700 ° C.
    [9]
    9. Process according to claim 8, wherein the pyrolysis step of the liquid fraction of oils is carried out at a temperature of 800 ° C.

    [10]
    10. Process according to any one of claims 1 to 9, wherein in the pyrolysis step of the organic substrate the carbonaceous residue of a previous pyrolysis is used as a susceptor in a mass proportion equal to or greater than 0.3 susceptor of
    5 microwaves / 1 organic substrate.
    [11]
    11. Process according to any one of claims 1 to 10, wherein the carbonaceous residue of a previous pyrolysis in a mass proportion equal to or less than 0.3 liquid fraction is used as a susceptor in the pyrolysis step of the liquid oil fraction
    10 oils / 1 microwave susceptor.
    [12]
    12. Process according to any one of claims 1 to 11, wherein the pyrolysis step of the organic substrate is carried out in a microwave oven operating at a frequency that is selected between 915 MHz and 2.45 GHz.
    [13]
    13. Process according to any one of claims 1 to 12, wherein the pyrolysis step of the liquid oil fraction is carried out in a microwave oven operating at a frequency selected from 915 MHz to 2.45 GHz.
    14. Process according to any one of claims 1 to 13, wherein a previous step of mixing the organic substrate and the microwave susceptor material before the pyrolysis of the organic substrate is included.

    Figure 1

    Figure 2
     Figure 3
    类似技术:
    公开号 | 公开日 | 专利标题
    Peng et al.2017|Hydrogen and syngas production by catalytic biomass gasification
    Yuan et al.2019|Pyrolysis and combustion kinetics of lignocellulosic biomass pellets with calcium-rich wastes from agro-forestry residues
    JP4187851B2|2008-11-26|Biomass-based carbon production equipment
    Déparrois et al.2019|Syngas production from co-pyrolysis and co-gasification of polystyrene and paper with CO2
    CA2523318C|2012-03-13|Method to recapture energy from organic waste
    JP2017502159A|2017-01-19|Pyrolysis oil by microwave system
    CA2609103A1|2007-01-11|Method for gasifying solid fuel with unified gas purification and gasifier using said method
    JPWO2010119972A1|2012-10-22|BTL manufacturing system and BTL manufacturing method
    Gan et al.2018|Kinetics and thermodynamic analysis in one-pot pyrolysis of rice hull using renewable calcium oxide based catalysts
    Foong et al.2021|Progress in waste valorization using advanced pyrolysis techniques for hydrogen and gaseous fuel production
    Su et al.2020|Production of H2-rich syngas from gasification of unsorted food waste in supercritical water
    JP2006205135A|2006-08-10|Complex waste disposal system
    JP2016535815A|2016-11-17|Char by microwave system
    CA2731376A1|2011-06-03|Enhancement of fischer-tropsch process for hydrocarbon fuel formulation
    JP6200711B2|2017-09-20|Hydrogen production apparatus and hydrogen production method
    Moneim et al.2018|Direct conversion of an agricultural solid waste to hydrocarbon gases via the pyrolysis technique
    ES2646546B1|2018-09-18|PROCESS FOR OBTAINING SYNTHESIS GAS BY WARMING WITH MICROWAVES OF ORGANIC SUBSTRATES
    KR101397378B1|2014-05-19|Apparatus for two-stage pyrolysis and gasfication and method thereof
    Kang et al.2011|Gasification and its emission characteristics for dried sewage sludge utilizing a fluidized bed gasifier
    Lee et al.2020|Offering a new option to valorize hen manure by CO2-assisted catalytic pyrolysis over biochar and metal catalysts
    Hrabovsky2011|Plasma aided gasification of biomass, organic waste and plastics
    Wang et al.2021|Synergistic effects of lanthanum ferrite perovskite and hydrogen to promote ammonia production during microalgae catalytic pyrolysis process
    Zhu et al.2021|Catalytic microwave pyrolysis of orange peel: Effects of acid and base catalysts mixture on products distribution
    AU2013220142B2|2017-07-20|Fuel processing
    Xian et al.2020|Release characteristics of gaseous products during CO2 gasification of char
    同族专利:
    公开号 | 公开日
    ES2646546B1|2018-09-18|
    WO2017194805A1|2017-11-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES2310127B1|2007-06-01|2009-12-03|Consejo Superior De Investigaciones Cientificas|SYNTHESIS GAS PRODUCTION PROCEDURE, DEVICE FOR ITS EXECUTION AND ITS APPLICATIONS.|
    CN202482282U|2012-02-04|2012-10-10|王俊|Multi-bin microwave heating continuous industry gas preparation device|
    法律状态:
    2018-09-18| FG2A| Definitive protection|Ref document number: 2646546 Country of ref document: ES Kind code of ref document: B1 Effective date: 20180918 |
    2019-03-06| FA2A| Application withdrawn|Effective date: 20190228 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201630602A|ES2646546B1|2016-05-10|2016-05-10|PROCESS FOR OBTAINING SYNTHESIS GAS BY WARMING WITH MICROWAVES OF ORGANIC SUBSTRATES|ES201630602A| ES2646546B1|2016-05-10|2016-05-10|PROCESS FOR OBTAINING SYNTHESIS GAS BY WARMING WITH MICROWAVES OF ORGANIC SUBSTRATES|
    PCT/ES2017/070288| WO2017194805A1|2016-05-10|2017-05-09|Process for producing synthesis gas by means of the microwave heating of organic substrates|
    [返回顶部]