Patent Application
20210087481
The present invention relates to a method for the production of synthesis gas. In particular, the present invention is directed to a synthesis gas production method using a hot plasma, such as a microwave plasma, gasification of solid or liquid waste, including biomass.
Gasification is commonly defined as thermochemical conversion of solid or liquid carbon-based materials into a combustible gaseous product. Established gasification technologies, such as air or oxygen blown fixed bed, fluidized bed or entrained flow gasifiers, are operated in a range of 800° C. to 1400° C. and use a gasification agent for conversion. The product, commonly known as synthesis gas, contains carbon monoxide (CO) and hydrogen (H2) as well as impurities such as tars, volatile or semi-volatile organic compounds, sulfur, ammonia, nitrogen oxides, sulfur oxides, hydrogen chloride and ashes. High levels of impurities require cost-intense synthetic gas clean-up for further processing. Common gasification technologies are dedicated to material species and narrow particle size distribution as well as low moisture content, increasing pretreatment costs and complexity. Further, the operation at high temperatures requires a burner, fuel, pipes and other installations. Required preheating of common gasifiers result in significant start-up times and are therefore only efficient when operated constantly over long-term period.
One alternative is the gasification by means of plasma, which is generated by an external power source. Plasma, as highly ionized gas, contains a significant number of electrically charged particles and is classified as the fourth state of matter. As plasma contains an equal number of free positive and negative charges, it is electrically neutral.
Plasma processes may be largely classified into thermal and hot plasma processes. Thermal plasma and arc torch plasmas are operated at very high temperature or require the use of electrodes with a limited lifetime, increasing material requirements and maintenance intervals (WO 2012/39751 A2, US 2010/0199557 A1).
Hot plasma systems, such as microwave plasma, can be far away from thermodynamic equilibrium by providing extremely high concentrations of chemically active species at concurrent low bulk temperatures. Other advantages of microwave plasma are the operation without electrodes or additional fuels and a conversion in an atmosphere of low oxygen content (EP 2 163 597 A1).
Common gasification technologies convert fossil raw materials, such as coal, to synthesis gas. The incineration of hazardous waste for mass reduction or destruction of pathogens and toxins prior to landfill is commonly known including the application of plasma (CN 204824145 U, WO 2011/14118 A2). Waste to energy concepts utilize the thermal energy of the conversion process as heat or convert the combustibles to electricity in a power plant. However, with regard to global changing raw material situation, the interest in utilization of novel material and energy sources as alternative to fossil materials is increasing. The primary utilization of biomass, as CO2-neutral energy, through combustion for energy and heat as well as conversion to bio-based fuels such as biodiesel are actively conducted. A method for using biomass or waste to produce conversion products, such as synthesis gas for value-added products, is still challenging because of the above mentioned draw-backs of gasification technologies and the variations in bio-based raw material quality as well as the need for an additional hydrogen source, required for following conversion processes.
In existing biofuel processes, a large amount of biomass consisting mainly of lignin is difficult to become converted into fuel and is utilized e.g. thermally by intensive drying prior burning. A value-added conversion through gasification to syngas and potentially further conversion to fuel or electricity would be beneficial for the overall performance of such biofuel plants.
Several methods and devices for the plasma-catalytic conversion of materials are already known.
WO 2015/051893 A1 discloses such method and device for converting hydrocarbon-containing educts, such as gaseous or liquid hydrocarbons, by means of a plasma into chemical base materials.
WO 2016/040969 A1 discloses a method and a device for the production of synthesis gas from carbon-containing waste material, for example from solid organic waste material. In this method said waste material is introduced into a reaction chamber and is subjected therein to thermal pyrolysis. The synthesis gas and the solid residual materials are discharged from the reaction chamber and are further processed by subjecting these to plasma treatment.
EP 2 915 869A1 discloses an entrained flow gasifier using an integrated plasma temperatures below 3500° C. in the gasification compartment. This system can be used to process solid or liquid materials, such as sawdust, and to convert this material into synthesis gas.
DE 10 2011 051 906 A1 discloses a method and a device for the gasification of coal or of carbon-containing solid materials together with water vapor and carbon dioxide. This method comprises introduction of water vapor and carbon dioxide into a gasification reactor, introduction of the solid particulate material into said reactor and forming a fluidized bed from these materials, and treating said materials in said reactor with a rotating plasma.
EP 1 419 220 B1 discloses a plasma pyrolysis and vitrification of organic material, such as solid waste material from different sources. The reactor comprises a carbon-catalyst bed which is heated by means of a plasma that is generated by several plasma arc generators which are arranged in a circle around said carbon-catalyst bed.
While these known methods and devices allow the generation of synthesis gas from waste material there is still a need of a highly efficient gasification technology that is flexible towards feedstock quality and quantity, particle size and moisture content.
Accordingly, a method for flexibly conversion of waste material into synthesis gas, preferably of biomass into synthesis gas through plasma gasification is desired.
Furthermore, a method of conversion of waste material into synthesis gas which is easy to implement and uses readily available reactors is desired.
The present invention relates to a process for the production of synthesis gas by plasma gasification of solid or liquid carbon-containing or hydro-carbon-containing material comprising the steps:
In the process of this invention various solid and/or liquid carbon-containing or hydrocarbon-containing materials may be used. Examples of possible feedstock are biomass, coal, hydrocarbons, organic matter, municipal waste, polymers, cellulose-containing materials, lignin-containing materials, such as Sunliquid® raw lignin, and mixtures thereof.
Examples of preferred feedstock materials are
Pure lignin:
The feedstock used in the method of this invention is particulate. Typically, the mean particle size of the solid or liquid feedstock is between 0.01 mm and 10 mm, preferably between 0.01 mm and 2 mm, even more preferred between 0.02 mm and 2 mm and most preferably between 0.05 mm to 1 mm.
The feedstock used in the method of this invention may be dry or humid. Preferably a humid feedstock, especially a water-containing feedstock is used. Typically, the water-content or other liquid content of the feedstock is between 0.05 wt.-% and 95 wt.-%, preferably between 0.05 wt.-% and 80 wt.-%, even more preferred between 0.05 wt.-% and 50 wt.-%, and most preferably between 0.1 wt.-% and 30 wt.-%, referring to the total amount of feedstock.
In a preferred embodiment of the process of the invention the solid and/or liquid carbon- or hydrocarbon-containing feedstock is combined with a liquid which is selected from the group consisting of water, organic solvents or combinations thereof. Preferably water is added to the solid and/or liquid carbon- or hydrocarbon-containing feedstock.
In another preferred embodiment of the process of the invention the solid or liquid feedstock is guided through a vaporizer which is arranged upstream to the reaction chamber. In this embodiment preferably liquid feedstock is used which is vaporized prior to the plasma treatment in the reaction chamber.
The particulate solid and/or liquid carbon- or hydrocarbon-containing feedstock is combined with a carrier gas. This gas has the function to carry the particulate feedstock into the reactor. Various types of carrier gas can be used. Examples of carrier gas are inert gases, oxygen-containing gases or synthesis gas. Preferably, oxygen-containing gases are used. These are typically oxygen ore preferably air. Other preferred gases are gases comprising oxygen and other gases, such as nitrogen, carbon dioxide, carbon monoxide, hydrocarbons, syngas, preferably gas derived from the product stream of the inventive process, or water-vapor containing air.
The carrier gas may be combined with the feedstock prior to introduction thereof into the reactor or at the reactor intake. The carrier gas may be added to the feedstock via one or more pipes which discharge the carrier gas into the feedstock stream. The pipe(s) may be equipped with nozzles at the discharge location.
In the process of this invention a swirl gas is used which protects the walls of the gasification device from the reactive species generated by the plasma treatment in the feedstock material. The composition of the swirl gas may be the same as the composition of the carrier gas. Preferably, the swirl gas should be inert as it does not participate in the reaction. That would decrease NOx-content and CO2-content of the product stream and would also reduce thermal losses, because CO2 and water vapor absorb/emit radiation. Preferred inert gases are nitrogen or noble gases, e.g. argon. But also air or a combination of water-vapor and air may be used as a swirl gas.
In the process of this invention the swirl gas may be introduced into the reactor at the reactor intake or at a position downstream thereof but above the location at which the feedstock is treated with the hot plasma. The swirl gas may be added to the reactor via one or more pipes which discharge the swirl gas into the reactor in a manner, that the feedstock-carrier-gas-stream is encased by the swirl gas. Preferably several pipes are available which introduce the swirl gas into the reactor in a circular manner, so that the swirl gas develops an encasement of the feedstock-carrier-gas-stream and moves in a helical manner between the inner reactor wall and the feedstock-carrier-gas-stream. Preferably the pipes introducing the swirl gas into the reactor are equipped with nozzles at the discharge location.
Typical conditions for the carrier gas and the swirl gas used in preferred embodiments of the process of this invention are as follows:
The plasma used in the process of this invention is a hot plasma which is far away from thermodynamic equilibrium, either because the ion temperature is different from the electron temperature, or because the velocity distribution of one of the species does not follow a Maxwell-Boltzmann distribution.
A hot plasma may be generated by using various methods, such as by using a gliding arc discharge, a plasma pencil, a plasma needle, a plasma jet, a dielectric barrier discharge, a resistive barrier discharge, a piezoelectric direct discharge, a glow discharge or preferably by using a microwave plasma generation.
A microwave plasma can be a hot plasma at about atmospheric pressure or above but not at low pressure.
Preferably the hot plasma is a microwave generated plasma within a pressure range between 1 and 5 bar, preferably between 1.1 and 2 bar.
In a preferred embodiment of the inventive process the plasma is energized with a microwave field contained in a waveguide.
Typical conditions for the gasification conditions in preferred embodiments of the process of this invention using microwave generated plasma are as follows:
After treatment of the feed stream with the hot plasma the produced synthesis gas, the carrier gas, the swirl gas and the non-reacted material is removed from the reaction chamber followed by removal of non-reacted material from the gaseous ingredients of the medium streaming through the reactor.
This may be performed by guiding the streaming medium through a filter means separating the solid ingredients from the gaseous ingredients or by reversing the flow direction of the gaseous ingredients and collecting the solid ingredients.
Preferably, the reactor is a tube reactor with an inner tube enveloped by an outlet tube. The inner tube is preferably arranged vertically, that means in plumb line direction. So a preferred reactor has a vertical inner tube through which the feedstock-carrier-gas-stream encased by the swirl gas is streaming from top to bottom and is treated with the hot plasma during this passage. At the bottom of this inner tube the flow direction of the gaseous ingredients of this stream is reversed and the gaseous ingredients are introduced into the outlet tube which envelops the inner reactor tube. The gaseous ingredients leave the reactor by streaming from the lower portion of the outlet tube to the upper portion of the outlet tube and are discharged therefrom. The solid ingredients of the stream, for example ash and unconverted solids, leaving the inner reactor tube, however, are collected below the outlet of said inner reactor tube. These solid ingredients are moving from top to bottom controlled by gravity and are discharged at the bottom of the reactor assembly.
In a preferred embodiment of the process of this invention the feedstock gas stream and the carrier gas-stream are introduced into a tubular reactor through a feedstock feeding means and through a carrier gas feeding means which are installed at the top of the tubular reactor, downstream of the feedstock feeding means and of the carrier gas feeding means the swirl gas is introduced into the tubular reactor through a swirl gas feeding means and downstream to the swirl gas feeding means the gas streams are treated by a hot plasma. The tubular reactor is preferably arranged vertically.
“Vertical” or “vertically” means in plumb line direction. So the longitudinal tube axis of a vertical tube reactor is arranged in plumb line direction. Solid ingredients can move easily from the top of the tube to the bottom controlled by gravity in a vertical tube reactor or a vertical reactor tube. Preferred are tube reactors where the longitudinal tube axis differs from vertical direction (plumb line direction) by up to 10°, more preferred by less than 5° and most preferred by less than 1°.
The gaseous ingredients discharged from the reactor comprise syngas, carrier gas, swirl gas and optionally other gaseous ingredients of the stream, for example water vapor. After the gaseous stream has been discharged from the reactor this stream is worked-up. For example, the discharged gaseous stream may be treated in a gas cleaning operation removing residual dust particles and/or may be treated to remove residual oxygen by using a part of the hydrogen present in the syngas.
The process of the present invention provides several benefits. Surprisingly, it has now been found that
In a preferred embodiment of the process of the invention a solid feedstock comprising particulate hydrocarbon-containing material is used, preferably lignin or a lignin-containing material, most preferably wood.
In another preferred embodiment of the process of the invention a particulate carbon-containing material or a particulate hydrocarbon-containing material is fed from a storage vessel via a transportation means, preferably via a screw conveyer, is combined with air as a carrier gas and it introduced into the top of a vertical reactor tube.
In another preferred embodiment of the process of the invention a carbon-containing material or a hydrocarbon-containing material is comminuted before introduction of this into the reactor and/or said material is humidified by adding water or the water content of said material is reduced by drying said material.
In another preferred embodiment of the process of the invention the product stream after treatment with the hot plasma is subjected to rapid cooling, for example by introduction of said product stream into a cooling tube. Such tube may be equipped, for example, with cooling means at the outside of said tube, for example by using a finned tube or by using a tube being equipped with heat exchanger means.
In another preferred embodiment of the inventive process synthesis gas is produced from solid or liquid waste material, including biomass, through microwave plasma gasification using a vertical tube reactor. The utilized waste material is fed from a storage vessel with a screw conveyer and enters the microwave plasma setup via top with a carrier gas. The waste material potentially requires milling, drying or moistening to the aspired composition prior to processing. A swirl gas is blown inside the reactor via a set of nozzles to centrifugally contain the plasma. The plasma is energized with a microwave field, contained in a waveguide. The waste material is converted into syngas by contacting the plasma. Unconverted solids and ash are collected below the reactor, while the gaseous products exit the reactor and are subjected to gas cleaning.
The process of the present invention can be performed in a reactor which is generally known from the prior art. An example of a reactor is disclosed in www.tudelft.nl/reinventthetoilet (flyer: syngas/gas cleaning).
The synthesis gas stream produced in the process of the present invention may be used in a solid oxide fuel cell, in other thermal, chemical or catalytic conversion processes or in combinations thereof.
The examples which follow are intended to illustrate the subject matter of the invention without restricting it thereto.
Feedstock composition examples are presented in the following table 1.
The feedstock compositions of Examples Ex. 1 to 4 can be gasified by using the following exemplary gasification conditions.
The gasification described in table 2 has been carried out in a gasification reactor with the following set-up:
Biomass enters the reactor via the top with a carrier gas. The reactor is a vertically arranged inner tube. Inside the reactor a swirl gas is blown in via a set of nozzles to centrifugally contain the plasma. The plasma is energized with a microwave field contained in a waveguide. Contacting the plasma with the biomass converts the biomass feedstock into syngas. Ash and unconverted solids are collected below the reactor, while the gaseous products exit the reactor through an outer tube which envelops the inner tube. The gaseous products are processed through simple gas cleaning, then the gas is conditioned for offline GC analysis.
The following table shows the N2-free transient results for fast start-up and steady state conditions.
In the following table the N2-, O2- and CH4-free composition of synthetic gas product stream after gasification using feedstock material of Ex. 2 from table 1 and using gasification conditions from table 2 is shown.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17208262.0 | Dec 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/084731 | 12/13/2018 | WO | 00 |
