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Title:
DEVICE FOR GASIFICATION OF SOLID CARBONACEOUS MATERIALS WITH A PRONOUNCED CONCENTRATION OF TARS AND THEIR CATALYTIC CONVERSION INTO CARBON MONOXIDE AND HYDROGEN
Document Type and Number:
WIPO Patent Application WO/2020/145903
Kind Code:
A1
Abstract:
The present invention discloses a device for gasification of solid carbonaceous materials with a pronounced concentration of tars and their catalytic transformation into carbon monoxide and hydrogen, containing a mixer (1) for gasification material, containing feeding systems (2, 3, 4, 5), first conveying system (6), a second conveying system (50), a gasifier (8) enclosed by a first heat exchanger (28), a catalytic reactor containing a mixing part (16), dosing systems (17, 18, 19), manifold (20), catalyst (21 ), flame arrester (22), ignition chamber (23), ignition elements (24) and catalyst core (25), which is made of a porous linear ceramic support and contains a plurality of parallel channels in form of honeycomb, second heat exchanger (30), third heat exchanger (33) and a demister (36). The device allows the use of low-quality or more complex materials with high moisture and/or dust content by allowing the formation of significantly higher tar contents in the product gas, which are then used in the catalytic reactor for the autothermal catalytic tar conversion without increasing the inert components in the resulting gas ( e.g. N2 in CO2), but at the same time a higher tar concentration linearly increases the H2/CO ratio in the synthesis gas.

Inventors:
PERNE TEOS (SI)
SELJAK TINE (SI)
ŠETINC MARKO (SI)
Application Number:
PCT/SI2020/000001
Publication Date:
July 16, 2020
Filing Date:
January 06, 2020
Export Citation:
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Assignee:
PERNE TEOS (SI)
International Classes:
C10J3/10; C10J3/30; C10J3/42; C10K3/02
Domestic Patent References:
WO2009132449A12009-11-05
Foreign References:
DE102007047931A12009-07-09
US20070212276A12007-09-13
US20070094929A12007-05-03
DE202012101271U12012-05-02
US0835847A1906-11-13
US4971599A1990-11-20
US5138957A1992-08-18
US20080196308A12008-08-21
US7459594B22008-12-02
US20070212276A12007-09-13
US8936886B22015-01-20
CN200810021485A2008-08-18
Attorney, Agent or Firm:
MARK-INVENTA D.O.O. (SI)
Download PDF:
Claims:
Claims

1. Device for gasification of solid carbonaceous materials with a pronounced concentration of tars and their catalytic conversion into carbon monoxide and hydrogen, characterized in that it consists of:

- mixer (1) for gasification material containing feeding system (2) for dosing of gasification material, feeding system (3) for dosing optional additives to gasification material, feeding system (4) for dosing adsorbent and feeding system (5) for dosing water, device for detecting the presence of S and Cl compounds in the gasification material, weighing device and grinding device;

- first conveying system (6);

second conveying system (50);

- gasifier (8), which is enclosed by a first heat exchanger (28) and comprises an upper part (14), an outlet pipe (15), a grid (9), a rotary blade (52), third conveying system (53), a cell lock (11), an ignition system (56), feeding system (12) for dosing the first oxidizer, feeding system (13) for dosing water or water vapor, a temperature sensor (57) and raw material level sensor (58);

- catalytic reactor containing a mixing part (16) configured to provide a homogeneous sub-stoichiometric mixture of product gas and oxidant with a stoichiometric ratio of 0.3 to 0.5, preferably 0.4, based on the proportion of tars expressed as Cio¾, whose partial oxidation, predominantly based on the partial oxidation of tar, takes place behind a flame arrester (22), which allows a homogeneous temperature field to be reached in the space in front of the catalyst core (25) and thus prevents the formation of unbound carbon, a feeding system (17) for dosing the second oxidant, a feeding system (18) for dosing water or water vapor, a feeding system (19) for dosing ignition gas, manifold (20), catalyst (21), flame arrester (22), ignition chamber (23), ignition elements (24) and catalyst core (25), which is enclosed by heaters (26) and has a temperature sensor (60) in the center for controlling the temperature of the catalyst core (25), - second heat exchanger (30),

- third heat exchanger (33), and

- demister (36), containing a condensation barrier (37) for removing moisture from the synthesis gas and has a reservoir (67) for condensed water collection at the bottom, which is provided with a condensate drainage valve (68) and a water level sensor (69) for water level in the condensed water tank (67) which controls the said valve (68).

2. Device according to claim 1 , characterized in that:

- the said first conveying system (6) and the said second conveying system (50) are located between the said mixer (1) and the said gasifier (8),

- between the said first conveying system (6) and the said second conveying system (50) there is a cell lock (7) through which material from the first conveying system (6), through the space (49), falls on the said second conveying system (50),

- the said first conveying system (6) and the said second conveying system are in the preferred embodiment carried out in the form of a lifting screw.

3. Device according to claim 1 or 2, characterized in that:

- the gasifier (8) is enclosed by a hollow housing representing the first heat exchanger (28) which is connected through the manifold (27) and the connecting pipe (62) to the outlet part of the catalyst (21), from which the synthesis gas enters the said first heat exchanger (28) and emits part of the heat to the fuel column (51) in the said gasifier (8)

- the gasifier (8) is connected to the second heat exchanger (30) to which a synthesis gas enters from the first heat exchanger (28), where in the said second heat exchanger (30) the said synthesis gas emits a part of the heat to the second oxidant (31), by which it is cooled to the limit of water condensation and the heated second oxidant is led to the mixing part (16) of the catalytic reactor;

- the said second heat exchanger (30) is connected to a third heat exchanger (33) into which the synthesis gas cooled to the limit of water condensation enters from the second heat exchanger (30), where the said synthesis gas emits some of the heat to the medium (34) for heat transfer and is cooled below the limit of water condensation;

- the said third heat exchanger (33) is connected to the demister (36) into which the synthesis gas cooled below the limit of water condensation enters from the third heat exchanger (33), where the said condensation barrier (37) draws condensed water from the said synthesis gas, the cooled synthesis gas, without tars and dust, S and Cl compounds and with low humidity, CH4 in CO2 concentrations, in the case when air as well as N2 are used as the first oxidant, from said demister (36) through the outlet opening (39).

4. Device according to claim 1, 2 or 3, characterized in that the said catalyst core (25) is made of a linear ceramic support that is resistant to temperature shocks and is sufficiently porous to allow a catalytic layer such as a layer of suitable metal to be applied and that the catalyst core (25) comprises a plurality of parallel channels in form of honeycomb extending in the direction of the product gas stream, wherein the cross section of said channels is large enough to allow the passage of solid inorganic particles, or ash, which the product gas may contain.

5. Catalytic reactor, characterized in that it comprises a mixing part (16), a feeding system (17) for dosing the second oxidant, a feeding system (18) for dosing water or water vapor, a feeding system (19) for dosing ignition gas, a manifold (20 ), further characterized in that it comprises two or more catalyst units (21) connected in parallel, in which each catalyst unit contains a flame arrester (22), an ignition chamber (23), ignition elements (24), a catalyst core (25) according to claim 4, which is enclosed by heaters (26) and has in the center a temperature sensor (60) for controlling the temperature of the catalyst core (25), where the mixing part of the catalytic reactor (16) is configured to provide a homogeneous sub-stoichiometric mixture of product gas and of an oxidant, having a stoichiometric ratio of 0.3 to 0.5, preferably 0.4, based on the proportion of tars expressed as CioHg, whose partial oxidation, predominantly based on the partial oxidation of tar, takes place behind a flame arrester (22), which allows a homogeneous temperature field to be reached in the space in front of the catalyst core (25) and thus prevents the formation of unbound carbon.

6. Device according to any one of the claims from 1 to 4, characterized in that it contains a catalytic reactor according to claim 5.

7. Device according to any one of the claims from 1 to 5, characterized in that it is configured to allow carrying out a process of the gasification of solid carbonaceous materials by the transformation of tars into carbon monoxide and hydrogen, where the device:

due to the higher permissible concentration of tars in the product gas, allows gasification of low-quality or complex materials with high moisture and/or dust content, which significantly extends the usefulness of the said device; allows slow gasification of materials at lower temperatures in the presence of moisture and proper filling of material, which creates a filter (adsorption) zone and allows chemical reaction of the adsorbent with S and/or Cl compounds, thereby removing S and/or Cl compounds in gasification of materials which contain these two elements;

- due to the catalytic transformation of the product with higher tar content, the device allows the use of an updraft gasifier, which is the simplest type of gasifier;

- allows the carrying out of the process of partial tar oxidation as main source of the internal heating of the catalytic reactor, followed by the catalytic steam reforming process, which with a higher tar content also linearly increases the H2/CO ratio in the synthesis gas and thus favors a higher tar content at the outlet from the gasifier;

enables catalytic transformation in a wide-channel catalyst, which also allows the treatment of dust-laden gas from the downdraft gasifier;

does not cause the formation of charcoal or soot that would be emitted into ash or product/synthesis gas because the carbon is converted to a gaseous state by the partial oxidation process before catalytic conversion; - allows the carrying out of the process that produces lower emissions compared to incineration and the residues after gasification are inorganic ash and condense water, which is used as process water in the process itself.

AMENDED CLAIMS

received by the International Bureau on 28 May 2020 (28.05.2020)

1. Device for gasification of solid carbonaceous materials with a pronounced concentration of tars and their catalytic conversion into carbon monoxide and hydrogen, characterized in that it consists of:

mixer (1) for gasification material containing feeding system (2) for dosing of gasification material, feeding system (3) for dosing optional additives to gasification material, feeding system (4) for dosing adsorbent and feeding system (5) for dosing water, device for detecting the presence of S and Cl compounds in the gasification material, weighing device and grinding device;

first conveying system (6);

second conveying system (50);

gasifier (8), which is enclosed by a first heat exchanger (28) and comprises an upper part (14), an outlet pipe (15), a grid (9), a rotary blade (52), third conveying system (53), a cell lock (11), an ignition system (56), feeding system (12) for dosing the first oxidizer, feeding system (13) for dosing water or water vapor, a temperature sensor (57) and raw material level sensor (58);

catalytic reactor containing a mixing part (16) configured to provide a homogeneous sub-stoichiometric mixture of product gas and oxidant with a stoichiometric ratio of 0.3 to 0.5, preferably 0.4, based on the proportion of tars expressed as CioHg, whose partial oxidation, predominantly based on the partial oxidation of tar, takes place behind a flame arrester (22), which allows a homogeneous temperature field to be reached in the space in front of the catalyst core (25) and thus prevents the formation of unbound carbon, a feeding system (17) for dosing the second oxidant, a feeding system (18) for dosing water or water vapor, a feeding system (19) for dosing ignition gas, manifold (20), catalyst (21), flame arrester (22), ignition chamber (23), ignition elements (24) and catalyst core (25), which is enclosed by heaters (26) and has a temperature sensor (60) in the center for controlling the temperature of the catalyst core (25),

second heat exchanger (30),

- third heat exchanger (33), and

demister (36), containing a condensation barrier (37) for removing moisture from the synthesis gas and has a reservoir (67) for condensed water collection at the bottom, which is provided with a condensate drainage valve (68) and a water level sensor (69) for water level in the condensed water tank (67) which controls the valve (68);

wherein:

- the first conveying system (6) and the second conveying system (50) are located between the mixer (1) and the gasifier (8),

- between the first conveying system (6) and the second conveying system (50) there is a cell lock (7) through which material from the first conveying system (6), through the space (49), falls on the second conveying system (50),

- the first conveying system (6) and the second conveying system are in the preferred embodiment carried out in the form of a lifting screw; and further

wherein:

- the gasifier (8) is enclosed by a hollow housing representing the first heat exchanger (28) which is connected through the manifold (27) and the connecting pipe (62) to the outlet part of the catalyst (21), from which the synthesis gas enters the first heat exchanger (28) and emits part of the heat to the fuel column (51) in the gasifier (8)

- the gasifier (8) is connected to the second heat exchanger (30) to which a synthesis gas enters from the first heat exchanger (28), where in the second heat exchanger (30) the synthesis gas emits a part of the heat to the second oxidant (31), by which it is cooled to the limit of water condensation and the heated second oxidant is led to the mixing part (16) of the catalytic reactor; - the second heat exchanger (30) is connected to a third heat exchanger (33) into which the synthesis gas cooled to the limit of water condensation enters from the second heat exchanger (30), where the said synthesis gas emits some of the heat to the medium (34) for heat transfer and is cooled below the limit of water condensation;

- the third heat exchanger (33) is connected to the demister (36) into which the synthesis gas cooled below the limit of water condensation enters from the third heat exchanger (33), where the condensation barrier (37) draws condensed water from the synthesis gas, the cooled synthesis gas, without tars and dust, S and Cl compounds and with low humidity, CH4 in CO2 concentrations, in the case when air as well as N2 are used as the first oxidant, from said demister (36) through the outlet opening (39).

2. Device according to claim 1, characterized in that the catalyst core (25) is made of a linear ceramic support that is resistant to temperature shocks and is sufficiently porous to allow a catalytic layer such as a layer of suitable metal to be applied and that the catalyst core (25) comprises a plurality of parallel channels in form of honeycomb extending in the direction of the product gas stream, wherein the cross section of said channels is large enough to allow the passage of solid inorganic particles, or ash, which the product gas may contain, when produced from a material such as coal of all kinds, wood biomass or biomass of vegetable origin, municipal or industrial waste, sludge from treatment plants or biogas plants or any other combustible materials, preferably in the form of sawdust, pellets or chips.

3. Catalytic reactor, characterized in that it comprises a mixing part (16), a feeding system (17) for dosing the second oxidant, a feeding system (18) for dosing water or water vapor, a feeding system (19) for dosing ignition gas, a manifold (20 ), further characterized in that it comprises two or more catalyst units (21) connected in parallel, in which each catalyst unit contains a flame arrester (22), an ignition chamber (23), ignition elements (24), a catalyst core (25) according to claim 4, which is enclosed by heaters (26) and has in the center a temperature sensor (60) for controlling the temperature of the catalyst core (25), where the mixing part of the catalytic reactor (16) is configured to provide a homogeneous sub-stoichiometric mixture of product gas and of an oxidant, having a stoichiometric ratio of 0.3 to 0.5, preferably 0.4, based on the proportion of tars expressed as CioHg, whose partial oxidation, predominantly based on the partial oxidation of tar, takes place behind a flame arrester (22), which allows a homogeneous temperature field to be reached in the space in front of the catalyst core (25) and thus prevents the formation of unbound carbon.

4. Device according to any one of the claims 1 and 2, characterized in that it contains a catalytic reactor according to claim 3.

5. Device according to any one of the claims from 1 to 4, characterized in that it is configured to allow carrying out a process of the gasification of solid carbonaceous materials by the transformation of tars into carbon monoxide and hydrogen, where the device:

due to the higher permissible concentration of tars in the product gas, allows gasification of low-quality or complex materials with high moisture and/or dust content, which significantly extends the usefulness of the said device; allows slow gasification of materials at lower temperatures in the presence of moisture and proper filling of material, which creates a filter (adsorption) zone and allows chemical reaction of the adsorbent with S and/or Cl compounds, thereby removing S and/or Cl compounds in gasification of materials which contain these two elements;

due to the catalytic transformation of the product with higher tar content, the device allows the use of an updraft gasifier, which is the simplest type of gasifier;

allows the carrying out of the process of partial tar oxidation as main source of the internal heating of the catalytic reactor, followed by the catalytic steam reforming process, which with a higher tar content also linearly increases the H2/CO ratio in the synthesis gas and thus favors a higher tar content at the outlet from the gasifier;

enables catalytic transformation in a wide-channel catalyst, which also allows the treatment of dust-laden gas from the downdraft gasifier;

does not cause the formation of charcoal or soot that would be emitted into ash or product/synthesis gas because the carbon is converted to a gaseous state by the partial oxidation process before catalytic conversion;

allows the carrying out of the process that produces lower emissions compared to incineration and the residues after gasification are inorganic ash and condense water, which is used as process water in the process itself.

Description:
Device for gasification of solid carbonaceous materials with a pronounced concentration of tars and their catalytic conversion into carbon monoxide and hydrogen

The field of invention:

The subject of the invention is a device for gasification of carbonaceous materials, for the production of pure synthesis gas.

Description of the technical problem

The technical problem solved by the present invention is to provide a device for gasification of a wide variety of solid carbonaceous materials that produces a product gas with a high concentration of tars and can use materials with a high content of volatile hydrocarbons (such as for example biomass of all kinds, bio-waste, plastics, rubber, mixed municipal waste and the like) as well as low content of volatile hydrocarbons (such as coal or charcoal) without the need for special preparation of these gasification materials, in the sense of dust or moist elimination, or their homogenization, and which may also contain materials with S and Cl components.

The next technical problem solved by the present invention is to provide a device for transforming high concentrations of tars in the product gas, which may also contain particulate matter as well as high molecular weight tars, into CO and ¾ or into synthesis gas by catalytic reaction of a partial oxidation, which runs with the increased concentration of tars in the product gas that serve as a reactant in the reaction.

State of the art

Devices for gasification of the carbonaceous materials for the production of synthesis gas are well known, developed and regularly used and can be divided into:

- fixed bed gasifiers. There are two subgroups of these: a) downdraft gasifier (cocurrent fixed bed gasifier), in which the gasification material is fed from the top or at the side of the gasifier and the gas is discharged in parallel with the material flow, and b) updraft gasifier (counter-current fixed bed gasifier), where the material is fed from above, from the side or from below, and the gas is discharged from the gasifier at the top.

- fluidized bed gasifier, wherein, with intense mixing and heat transfer in the layer, no distinct direction of air and fuel inflow is present. Sub-groups of this technology are: a) bubbling fluidized bed gasifier, where air is supplied at a rate of about 1 m/s, and part of the gasification reactions takes place entirely in a free layer above the layer of inert material, and b) gasifiers with a circulating layer where the velocities of the air movement is higher (> 3 m/s) and most of the gasification reactions take place inside the floating layer, whose inert material from the product gas is filtered and returned to the base layer.

Updraft gasifiers with a stable fuel layer according to the state of the art are described in patents US 835.847, US 4.971.599 and US 5.138.957. In mentioned cases, these are the gasifiers where the fuel is fed through the center of the grid from below. The grid is a fixed plate with openings for air intake and ash discharge. The gasification process is carried out over the entire column of material formed in the gasifier, namely in the upper layer is the drying zone, followed by the pyrolysis zone, and the reduction zone, and below, just above the grid is the oxidation zone. The product gas that forms in the pile of smoldering material is discharged through an opening at the top of the gasifier. Such gasifiers allow the use of a wide range of gasification materials which do not need to be specially prepared and may contain dust or may be in the form of sawdust and with high moisture content. The characteristic of the described type of gasifiers is that the product gas contains high concentrations of tars, so they are mostly used as preheating furnaces of boilers, where the product gas combusts and uses only thermal energy, as well as the possibility of using worse fuels that are not suitable for the combustion process directly in the boiler. Gasifiers of this type are robust and the process cannot be precisely controlled, so they are very rarely used for producing synthesis gas.

Patent US 2008/0196308 presents a technological solution of a double wall housing gasifier that acts as a regenerative heater of the gasification tank. It produces high- energy synthesis gas with low tar concentrations, which are still too high for further gas use. Due to the heating of the gasification tank, the process is in great deal a pyrolysis, causing a considerable portion of carbon to remain unbound in the form of charcoal in the ash as an unwanted by-product.

Transformation of tars

If the purpose of gasification is the production of pure synthesis gas from solid gasification materials, the removal of tars is solved by primary or secondary measures. The primary measures are those within the gasifier, namely the appropriate construction or type of gasifier and/or properly prepared fuel. However, existing types of gasifiers are not sufficient for production of completely pure synthesis gas. For this reason, the purification of product gas is provided by secondary measures (after the gasifier) by additional procedures. Secondary measures can be divided into the physical removal of tars (filtration, water washing) and the transformation (breaking, cracking, reforming) of tars (thermal or catalytic), which represents a significant advantage over the physical extraction of tars. Catalytic processes for the conversion of tars or long chain hydrocarbons to shorter compounds or CO and ¾ are well-established process in the petrochemical industry. In the field of gasification of solid materials, a number of studies on the use of catalysts are underway. Basically, the catalytic reaction of partial oxidation and/or steam transformation of tars are used. The catalytic reactions take place at a certain high temperature and use an internal or external heat source to maintain the operating temperature. The advantage of catalytic transformation of tars compared to thermal cracking is the speed of reaction and thus the lower consumption of external energy sources.

A technical problem with the investigated systems of catalytic transformation with partial oxidation is the use of product gas with very low tar concentrations. If the product gas contains small quantities of tars, the complete oxidation of a part of the already formed synthesis gas is used to maintain the catalyst operating temperature, thereby increasing the content of inert components (e.g. CO 2 in N 2 ) and reducing its calorific value and efficiency of the entire system. For this reason, the energy balance of the system is significantly better, if the product gas contains the highest possible concentration of tars, which are itself a high caloric fuel. The use of gas with higher tar concentrations is described in patent US 7.459.594. It is a catalyst with partial oxidation where the product gas and oxidant are mixed just above the catalytic layer, the oxidant being fed through a layer of cold plasma, which immediately ignites the mixture. The system works well at lower flow rates where sufficient homogenization of the mixture can be ensured. However, at higher flow rates, anomalies occur, which means that, in some parts of the catalyst, intense oxidation take place and some do not. This is mainly due to the action of the plasma and point feed of the oxidant, which are, by increasing the flow rate, limited to an ever narrower zone or cross section, so that the oxidant and the product gas do not allow provision of a sufficiently homogeneous mixture before entering the catalyst. As a result, high temperatures are reached at certain parts of the catalyst, where large quantities of fixed carbon begin to form in the form of soot or charcoal dust, and part of the product gas and/or air passes through the catalyst in unreacted form, i.e. with the tar present.

Homogenization of mixtures for partial oxidation

In the catalytic tar transformation by the partial oxidation process, the product gas is mixed with an appropriate amount of oxidant (oxygen or air) before entering the catalyst. There is usually an extremely low amount of oxygen in this mix, from 1 to 3 percent. It is extremely important that the mixture is as homogeneous as possible before initiating partial oxidation reactions in the catalyst. The homogeneity of the mixture prevents the occurrence of hot spots described above without causing the problems described above. The solution is to separate the mixing part from the reaction area with the corresponding flame arrester, as described by the patent US 2007/0212276, where the catalyst consists of a chamber to which the product gas and oxidizer is fed, stirrers with an integrated flame arrester in the form of a metal foam sponge, stationary stirrers and a tank with the catalyst. The described solution is used for the transformation of pure long chain hydrocarbons into shorter products, as well as for the production of H 2 in CO (synthesis gas), for example from methane, but is not suitable for the production of product gas from a gasification plant containing higher or lower concentration of tars and which is laden with dust as the flame arrester or stirrer described in this patent would be quickly blocked by tar and dust, and such a device also represents a large pressure barrier and a site with intense heat dissipation, which is undesirable. Integration of device components

Usually, pure synthesis gas production systems are set up as a set of standalone devices that follow the process flow. Integration of the components into a whole is presented, for example, in the patent US 8.936.886, which describes a system for the production of pure synthesis gas using an updraft gasifier, followed at the outflow tube immediately by a device for the thermal cracking of tars in the product gas and thereby the production of pure synthesis gas. The operating temperature in the second reactor is achieved by recovery, and in particular by the addition of an oxidant to the (unpurified) product gas, which in the gas flow itself triggers the complete oxidation of part of the product gas. Due to the long retention times required, a relatively large amount of oxidant is required to feed to the process of thermal cracking of the tars, thus significantly reducing the calorific value of the synthesis gas purified in this way, making the mentioned system more useful for heat production.

An example of the integration of a gasifier and a catalyst is also presented by the patent CN 2008/10.021.485, where the catalyst part is located directly above the gasifier and is separated only by the funnel construction of the container. An S-resistant catalyst (dolomite, added CaO) is used. Immediately after the gasification phase is the phase of catalytic transformation followed by gas purification. The described system produces a product gas with as little tar content as possible, which limits the range of gasification material used. Also, the catalyst cannot work with the partial oxidation process, since the optimal oxidant feed and preparation of a homogeneous mixture is practically unfeasible.

Explanation of terms used

In the following description of the invention, the terms "product gas" and "synthesis gas" are used. For the purpose of the description of present invention, "product gas" is gas coming from a gasifier to a catalytic reactor where it is converted into "synthesis gas".

The essential difference between the product gas and the synthesis gas is that the product gas contains tars and dust particles, while the synthesis gas consists essentially of CO and !¾ it is without tar and dust particles and does not need to be further purified.

Furthermore, the term "pure synthesis gas free of water or moisture" means a gas mixture which is tar free and consists of CO, H2 and additionally CO2, C¾ and a minimum of moisture content.

Short description of the figures

The present invention is described below by means of the accompanying figures showing:

Figure 1 : schematic illustration of the gasification line according to the present invention;

Figure 2: the first part of the line according to the present invention (feeding of the gasification material and updraft gasifier);

Figure 3: the second part of the line according to the present invention (catalytic reactor and technological preparation of synthesis gas);

Figure 4: schematic illustration of the integration of the catalytic reactor and the downdraft gasifier;

Figure 5: schematic illustration of the integration of the catalytic reactor with a single catalyst outside the updraft gasifier according to the present invention;

Figure 6: schematic illustration of the integration of the catalytic reactor with multiple catalysts outside the updraft gasifier according to the present invention;

Figure 7: schematic illustration of the integration of the catalytic reactor with multiple catalysts in the cover of updraft gasifier according to the present invention;

Short description of the invention

The present technical solution solves the given technical problem by introducing a device that allows the gasification of solid carbonaceous materials and the transformation of tars to CO and H 2 or synthesis gas. The device for gasification of solid carbonaceous materials according to the present invention combines two types of reactors that can be constructed and enlarged in any size, namely:

- gasifier for carbonaceous materials, such as coal, wood and biomass, municipal and special waste, sludge from wastewater treatment plants or biogas plants, materials containing S and/or Cl, such as brown coal or rubber producing product gas with high concentration of tars or hydrocarbons

- catalytic reactor allowing the transformation of the resulting tars/hydrocarbons in the product gas to CO and ¾ and at the outlet providing a synthesis gas with substantially higher hydrogen content and no tar presence so that the synthesis gas meets the qualitative standards for future use, for example in internal combustion engines or as a raw material for the synthesis of hydrocarbons.

The device according to the present invention is shown schematically in Figure 1 and in detail in Figure 2 and Figure 3 and consists of the following essential parts:

- mixer,

first conveying system,

- second conveying system,

- gasification reactor,

- catalytic reactor and

system for technological treatment of synthesis gas.

The device according to the present invention consists of:

- a mixer 1 for gasification material, comprising feeding systems 2, 3, 4, 5, a device for detecting the presence of S and Cl compounds in the gasification material, a weighing device and a grinding device;;

first conveying system 6,

second conveying system 50,

a gasifier 8, which is enclosed by a first heat exchanger 28 and comprises an upper part 14, an outlet pipe 15, a grid 9, a rotary blade 52, third conveying system 53, a cell lock 1 1, an ignition system 56, dosing systems 12, 13, a temperature sensor 57 and raw material level sensor 58, - a catalytic reactor consisting of a mixing part 16 having inlets 17, 18, 19, a manifold 20, a catalyst 21, a flame arrester 22, an ignition chamber 23, firing elements 24 and a catalyst core 25 surrounded by heaters 26,

- second heat exchanger 30,

- third heat exchanger 33, and

- a demister 36,

wherein the second heat exchanger 30, the third heat exchanger 33 and the demister 36, form a system for the technological treatment of the synthesis gas. The aforementioned elements of the device are interconnected in such a way that the device makes it possible to carry out a process of gasification of solid carbonaceous materials.

The gasification material mixer 1 comprises feeding systems, namely the feeding system 2 for the dosing of the gasification material, the feeding system 3 for dosing optional additives to the gasification material (such as wood sawdust, sewage sludge or heavy fraction of municipal waste), the feeding system 4 for dosing the adsorbent for binding S and Cl, and the feeding system 5 for dosing water consisting of a dosing valve with a nozzle. Each feeding system 4, 5 has its own tank 40 with a dosing valve 41. Further, the gasification material mixer 1 comprises a device for detecting the presence of S and Cl compounds in the gasification material, a device for weighing of the dosed materials, and a device for optional grinding of the gasification material (not shown).

The aforementioned gasification material mixer 1 has an outlet opening in the lower part, which is closed by a flap 43, through which a prepared raw material for

gasification is poured into the inlet part 44 of the first conveying system 6, which in the described embodiment is a lifting screw which raises the raw material above the cell lock 7. The cell lock 7 consists of an upper valve 45 and a lower valve 46, one of which is always closed when the gasification raw material is passing through the cell lock. The operation of valves 45, 46 is controlled by the upper 47 and lower 48 level switches.

The cell lock 7 prevents the return fire from spreading to the stock of the gasification raw material and prevents the product gas from escaping from the device.

The gasification raw material is falling through the said cell lock and through the space 49 below the cell lock onto the second conveying system 50, which is in a preferred embodiment a feeding screw. The said space 49 below the cell lock is carried out conically in such a way that it broadens downwards and therefore there is no clogging by the gasification raw material. The said feeding screw 50 feeds the gasification raw material into the gasifier 8 and is inclined so that its highest point is located in the gasifier 8, thus preventing backfire from the gasifier 8.

The feeding screw 50 feeds the gasification raw material onto the grid 9 of the gasifier 8 through the center of the grid 9 so that the material moves upwards in the middle of the gasifier 8 and back downwards at the walls of the gasifier 8 toward the grid 9.

The said gasifier 8 has a rotating blade 52 in the space 10 below the grid 9, which pushes the ash produced during gasification falling through the grid 9 onto the third conveying system 53, which is in the preferred embodiment a screw, which through the appropriate cell lock 11 discharges the ashes from device to the appropriate collector 54. The said gasifier 8 further comprises an ignition system 56 such as, for example, a hot air blower system mounted above the grid 9.

The gasifier 8 further comprises a system 12 for dosing the first oxidizer located below the grid and equipped with a dozing nozzle 55 and a system for dosing water or water vapor 13 located below the grid and equipped with a dozing nozzle 55.

The gasifier 8 further comprises, a temperature sensor 57 located below the grid for regulating the amount of water or water vapor introduced into the gasifier 8 and a level sensor for the raw material 58 in the gasifier 8 for controlling the amount of gasification raw material on the grid 9 of the gasifier 8.

The gasifier 8 is designed as a pressure vessel so that the gasification process is carried out in the overpressure mode. This provides better possibilities for managing process conditions. Passages of the gasification raw material into and out of the gasifier 8 are provided with cell locks 7 and 11 , which allow the passage of said raw material under pressure regime.

The gasifier 8 double wall housing is hollow and serves as the first heat exchanger 28, as will be described below.

The described embodiment of the gasifier 8 allows the use of a wide range of carbon- containing gasification materials, such as coal of all kinds, wood biomass or biomass of vegetable origin, municipal or industrial waste, sludge from treatment plants or biogas plants or any other combustible materials. Gasification materials must be of a suitable particle size and are therefore usually in the form of sawdust, pellets or chips and in that the heterogeneity of material composition is desirable. The dust itself cannot be gasified, but certain portion of it can be added to the gasification material. There is also a restriction on liquid or highly inflammable substances that must be properly mixed with a dry support, such as wood sawdust or other suitable absorbent substance. The gasification materials do not need to be specially dried; the water is added as needed.

In the gasification process which takes place in the gasifier, a product gas is generated, which is collected in the upper part 14 of the gasifier 8 and is discharged through the outlet pipe 15 on the gasifier cover 8 into the mixing part of the catalyst 16.

The said mixing part 16 of the catalytic reactor is equipped with a system 17 for feeding the second oxidant, a system 18 for feeding water or water vapor, and a system 19 for feeding ignition gas. The entire mixing part of catalytic reactor 16 is designed to provide a homogeneous sub-stoichiometric mixture of product gas and oxidant. A homogeneous post-stoichiometric mixture of product gas and oxidant provides a stoichiometric ratio of 0.3-0.5 (preferably 0.4) based on the proportion of tars expressed as Cio¾ consumed during partial oxidation for achieving a homogeneous temperature field in the space in front of the catalyst core 25.

A mixture of product gas and oxidant is passed through a manifold 20, through a flame arrester 22 and through the ignition chamber 23 to a catalyst core 25 of a catalyst 21 , where homogeneous partial oxidation of the tars in the product gas is established, the tars are converted to CO and ¾, or a pure synthesis gas is formed providing a sufficient rise in the temperature of the product gas, which can then support the endothermic process of catalytic steam reforming of the remaining tars.

The catalyst core 25 is made of a linear ceramic support that is resistant to temperature shocks and is sufficiently porous to allow a catalytic layer such as a layer of suitable metal to be applied. The catalyst core 25 comprises a plurality of parallel channels in form of honeycomb extending in the direction of the product gas stream, wherein the cross section of said channels is large enough to allow the passage of solid inorganic particles, or ash, which the product gas may contain.

The catalyst core 25 may also be in the form of a granulate, which is not suitable for gases containing solid inorganic particles. The catalyst core 25 of the device according to the present invention has a uniform temperature in all parts, which is achieved by a homogeneous mixture of oxygen, product gas and water vapor in the mixing part 16 of the catalytic reactor, which is separated from the catalyst core 25 by a flame arrester 22, which is made in honeycomb form as described above for catalyst core 25.

Flame retention in the flame arrester 22 is achieved solely by increasing the speed of the mixture of product gas and oxidant, for which the proper homogeneity of said mixture is of great importance, since it fully maintains the product gas temperature.

A high concentration of tars and/or dust in the product gas is also adapted to the mixing part of the catalytic reactor 16, which is carried out without passive stirrers only by properly shaping the inlet (manifold 20) of the mixture into the catalyst 21 and ensuring adequate homogeneity of the mixture.

The length of the mixing part of the catalytic reactor 16 without passive stirrers is significantly shortened by dividing the catalyst 21 into several smaller units, and the manifold 20 provides a homogeneous mixture already with its shape, which is also reflected in the smaller heat losses.

The said outlet pipe 15 is surrounded by heaters 59 provided with temperature sensors. Before the beginning of the process, the outlet pipe 15, the mixing part of the catalyst 16 and the manifold 20 are heated with the said heaters 59 to an operating temperature between 300 °C and 400 °C.

The said catalyst core 25 of catalyst 21 is surrounded by heaters 26 which, before the beginning of the process heat the catalyst core 25 to a catalytic reaction operating temperature of about 700 °C.

The said catalyst core 25 has a temperature sensor 60 in the center for controlling the temperature of catalyst core 25.

For heating the catalyst core 25, a mixture of ignition gas and of the second oxidant, which is fed into the outlet pipe 15 via the said dosing systems 17, 19, can be used instead of the heaters 60. The said mixture is ignited after passing through the flame arrester 22 on the ignition elements 24 and just above the catalyst core 25.

The said ignition gas is also used to clean away possible soot from the catalyst core 25. When the catalyst core 25 is heated to the initial operating temperature, a mixture of product gas and oxidant is started to be introduced into the catalyst 21 , where it is, by the action of the ignition elements 24 in the ignition chamber 23, ignited just above the catalyst core 25, where the catalytic conversion process takes place. In an atmosphere with a low oxygen content, which depends on the concentration of tars in the product gas, and usually ranges from 1 to 2 volume percent (but also more or less), two reactions relevant to the process itself are taking place:

1. partial oxidation (exothermic process),

2. steam reforming (endothermic process),

The first reaction provides a sufficiently high operating temperature and is a leading reaction, while the second reaction provides the conditions for the production of higher quality synthesis gas with higher concentrations of CO and ¾ and higher H2/CO ratio. The tar content of the product gas must be at least sufficient to meet the energy requirements of the catalyst operating temperature maintenance system.

The higher tar concentration also eliminates the significant drawback of using low-tar product gases, where oxygen, in the deficiency of tars during the phase of providing the heat for the catalytic steam reforming process, begins to bind to the already formed ¾ and CO in the full oxidation reaction to CO2 and ¾0, which causes deterioration of the calorific value of the gas, higher temperatures develop, which may also be unevenly distributed, and unbound carbon in the form of soot occurs that blocks the catalyst operation (catalyst clogging). At an appropriate concentration of tars, the process is leaded so that it is auto-thermal. The catalyst 21 is adequately insulated 61 to reduce heat loss.

The synthesis gas from the catalyst 21 passes through the connecting pipe 62 into the manifold 27 and further into the first heat exchanger 28 enclosing the gasifier 8, where the said synthesis gas transfers some of the heat to the fuel column 51 in the gasifier 8. The device according to the present invention further comprises a second heat exchanger 30 to which the synthesis gas is led from the first heat exchanger 28.

The said second heat exchanger 30 is connected to the first heat exchanger 28, the third heat exchanger and has an opening 63 for the inlet of the fresh oxidant 3 1 and an opening 64 for the discharge of the heated oxidant which is connected to the inlet 17 of the second oxidant on the mixing part 16 of the catalytic reactor.

In the second heat exchanger 30, the synthesis gas transfers some of the heat to the oxidant 31 , such as the air used in the process as the second oxidant 17 for the catalytic reaction. The oxidant 31 enters the second heat exchanger 30 in the opposite direction to the synthesis gas stream in the case described above through the inlet opening 63 and leaves it below through the outlet opening 64, and then it is fed through the inlet of the second oxidant 17 into the mixing part of the catalyst 16.

The synthesis gas, cooled to the limit of water condensation, is led from the second heat exchanger 30 through the pipe 32 to the third heat exchanger 33, where it is cooled below the limit of water condensation.

The said third heat exchanger 33 is coupled to second heat exchanger 30, the demister 36, and has an opening 64 for the inlet of the medium 34 for heat dissipation and an opening 66 for the outlet of the heat dissipation medium.

The said heat dissipation medium 34 in the third heat exchanger 33 is a fluid, such as, for example, water, which in the case described, enters the third heat exchanger 33 below through the inlet opening 65 and exits above through the outlet opening 66, while the synthesis gas travels in the opposite direction.

The synthesis gas cooled below the water condensation limit is then though the line 35 led to the demister 36.

The upper part of the gasifier, the product gas outlet pipe, the catalyst mixing part, the catalyst, the catalyst outlet pipe, and the second and third heat exchangers are thermally insulated.

Said demister 36 is connected to third heat exchanger 33, contains a condensation barrier 37 for removing moisture from the synthesis gas and has a reservoir 67 for condensed water collection at the bottom, which is provided with a valve 68 for draining of the condensed water 38, and a water level sensor 69 for water level in the condensed water tank 67 which controls the said valve 68.

Further, said demister 36 has at its top an opening 39 for the outlet of the synthesis gas. The condensed water collected is filtered and used in the process which takes place in the described device for adding water to the mixer 1, to the gasifier 13, to the mixing part of the catalyst 18 and for cooling 34. Tar-free synthesis gas with low moisture content exits the device through the opening at the top of the demister 39. The obtained synthesis gas is then used as a raw material, in chemical synthesis processes (for example, in Fischer - Tropsch reactors, methanation or methanol synthesis), as industrial gases or as an energy source for energy production. The complete device construction according to the present invention is carried out in overpressure mode, and it is also possible to implement the described device in depression mode. All components of the device are equipped with safety outlets.

Figures 4 to 7 schematically show embodiments of the device according to the present invention regarding the different types or sizes of gasifiers 8 and catalysts 21.

Figure 4 shows the installation of catalyst 21 in configuration B, with several catalyst units connected in parallel on the downdraft gasifier 70 for the gasification of wood biomass. The gasification material enters through the upper part of the gasifier 70. The first oxidant is blown through the inlet 12 into the lower part of the gasifier 70 from which the part of ash and product gas are exiting at the lower part 71 and the product gas is discharged through the outlet 15 into the cyclone 72, which is added to the system because the product gas is laden with dust or unreacted carbon in the form of soot. From the said cyclone 72, the remainder of the ash exits at the bottom 73. The product gas is led to a mixing part 16 of the catalytic reactor into which a second oxidant is fed through inlet 17. In the manifold 20, the mixture is distributed into individual catalysts 21, where the tars are converted to CO and !¾. The synthesis gas is collected in the manifold 27 and cooled in the heat exchanger 33, and exits through the outlet opening 39.

Figures 5 and 6 show the integration of the updraft gasifier 8 according to the present invention and the catalyst 21 in configuration A (Figure 5) and configuration B (Figure 6). In both cases, the gasification material 2 enters through the cell block 7 the gasifier 8. In the lower part of the gasifier 8, the first oxidant is fed through the inlet 12, water or water vapor through the inlet 13, and ash is removed through the outlet 71. The tar-rich product gas is mixed with the second oxidant in the mixing part of the catalytic reactor 16. Figure 5 shows the installation of catalyst 21 in the embodiment with a single catalyst unit, and Figure 6 shows the embodiment with multiple catalyst units connected in parallel, where the mixture of gas and oxidant is distributed into several units in the manifold 20 and, after the transformation in the individual units, when the synthesis gas is formed, collected the manifold 27. The hot synthesis gas is led to the first heat exchanger 28, which encloses the gasifier 8, where it emits a part of the heat. From the first heat exchanger 28, the synthesis gas is then led 29 to the synthesis gas cooling device.

Figure 7 shows the complete integration of the updraft gasifier 8 according to the present invention and the catalyst 21 in configuration B, that is, with several parallel connected catalyst units where the catalyst is positioned just above the gasifier 8. Here, too, the gasification material 2 enters through the cell lock 7 the gasifier 8. Through the inlet 12, the first oxidant and through the inlet 13 water or water vapor is fed into the lower part of the gasifier, and ash is removed through the outlet 71. The product gas enters in the middle of the gasifier directly into the mixing part of the catalyst 16, to which a second oxidant is fed through the inlet 17. The mixture is then in the manifold

20, which is at the extreme top of the device, distributed into individual catalyst units

21. The resulting synthesis gas is led to the first heat exchanger 28, which encloses the gasifier 8, where it emits a part of the heat and is led 29 forward to the gas cooling device.

The advantages of the device according to the present invention are as follows:

- due to the higher permissible concentration of tars in the product gas, the device allows gasification of low-quality or complex materials with high moisture and/or dust content, which significantly extends the usefulness of the said device;

- the device allows slow gasification of materials at lower temperatures in the presence of moisture and proper filling of material, which creates a filter (adsorption) zone and allows chemical reaction of the adsorbent with S and/or Cl compounds, thereby removing S and/or Cl compounds in gasification of materials which contain these two elements;

due to the catalytic transformation of the product with higher tar content, the device allows the use of an updraft gasifier, which is the simplest type of gasifier;

- the device allows the carrying out of the process of partial tar oxidation for the internal heating of the catalytic reactor without increasing the content of inert components in the gas (e.g. CO 2 ), followed by the catalytic steam reforming process, which with a higher tar content also linearly increases the H 2 /CO ratio in the synthesis gas. This enables that the tar transformation process is auto-thermal;

- the device enables catalytic transformation in a wide-channel catalyst, so it is also possible to process dust-laden gas from the updraft gasifier;

- the device does not cause the formation of charcoal or soot that would be emitted into ash or product/synthesis gas because the carbon is converted to a gaseous state by the partial oxidation process before catalytic conversion;

- the device allows the carrying out of the process that produces lower emissions compared to incineration and the residues after gasification are inorganic ash and condense water, which is used as process water in the process itself;

- the device allows the carrying out of a process whose product is pure synthesis gas, free of tars, S and Cl compounds and dust particles and with low concentrations of moisture, C¾ in CO 2 , in the case when air is used as the first oxidant, as well as N 2 , where the said synthesis gas is ready for further use.

The device according to the present invention is described and shown in the accompanying figures by means of specific embodiments, which in no way limit the invention itself. Various derived versions of the described device are also possible, which will be immediately clear to those skilled in the art.