DE202017005327U1 - Device for gasification of biomass - Google Patents

Abstract

Apparatus for carrying out the process according to claims 1-36, consisting of a synthesis reactor (1), in which two sliding floor grates (2, 3) arranged above one another and in opposite directions, arranged in the upper region of the synthesis reactor (1), with a water supply (13) and synthesis gas outlet (16) provided superheater (4) and • in the lower part of the synthesis reactor (1) arranged discharge screw (7) and • with a synthesis gas recirculation line (15) connected to the gas inlet (14), • wherein the discharge screw (7) with an active - coal quench (5) and a fermenter (6), • the superheater (4) via a pipe (15) for returning the synthesis gas with a gas inlet (14) in the synthesis reactor (1) and • the synthesis gas discharge (15) of the Synthesis reactor (1) with a dust separator (8), • the dust collector (8) with a filter (9) connected to return the catalyst to the sliding bottom grid (3) of the synthesis reactor (1) , • the filter (9) with a water inlet (19) and with a cation exchanger or anion exchanger or with a cation exchanger and anion exchanger in the mixed bed, filled ammonia scrubbers (10), • the ammonia scrubber (10) with a Hg filter (11) and • the Hg filter (11) is connected to a synthesis gas utilization device.

Description

The invention relates to a catalytic process and apparatus for the thermochemical production of synthesis gas, ammonia and ammonium salts, carbon dioxide water as process water and drinking water and plants as activated carbon and as fertilizer or soil substrate of carbonaceous energy sources, in particular of biomass.

Biomass is understood to mean all substances of biological origin. Synthesis gas consists predominantly of hydrogen, carbon dioxide, carbon monoxide and methane. Ammonia and ammonium salts are formed during the thermochemical decomposition of proteins present in the biomass. The carbon dioxide is produced during the combustion of the synthesis gas. Water as process water is formed in the condensation of water from the synthesis gas, in the condensation of the exhaust gas stream and in the inventive use of ammonia or ammonium ion as a regenerating agent for an ion exchange process for the desalination of waters, especially seawaters. Excess ammonia is extracted with mineral ion exchangers or as magnesium ammonium phosphate as fertilizer. Drinking water is desalinated water that is mixed with calcium bicarbonate by reaction of calcium carbonate and carbon dioxide. Biochar is the coal obtained from the biomass, which becomes activated carbon when it reaches 300 m2 / a. If this coal is biologically activated and lactated with biomass, for example molasses, Terra Preta is obtained as an anthropogenic soil substrate with fertilising effect and humus thawing effect. The pyrolysis is therefore better suited for this task than a combustion, since this targeted coal from biomass and activated carbon can be produced, which later as TerraPreta do Indio a similar substrate further use in agriculture and horticulture and so in a simple way the Phosphate can be made available to plants again.

Essentially, three methods are known for the thermochemical production of synthesis gas from biomass.

The fixed bed gasification is used in the small power range for high quality biomass and gas mainly with air, which is why only a low-quality gas is produced. From 1 GW power so-called entrained flow gasifier are used, which mainly gas largely dry biomass gas at very high temperatures with pure oxygen. For decentralized small systems, the entrained flow gasifier is not suitable because of the high investment costs. Because of the high temperatures, the ash melting point is below, so it would be possible only with very high equipment and chemical effort to recover phosphates and other fertilizers. Between 1 MW and 1 GW, a fluidized bed reactor can be used. This is operated in two variants; once allothermic and once autothermal. In autothermal gasification, a portion of the biomass is burned to provide the energy for the ongoing endothermic reactions. In the allothermal gasification, the necessary energy is supplied from the outside. This can be achieved by electrical heating of the system or by circulating heat transfer medium, such. As sand, which are heated by burning the biomass happen. Such a gasifier is operated in Güssing, Austria. If burnt lime is used as a circulating heat transfer medium, the heat of reaction can be used in addition to the conversion to calcium carbonate, as in the DE 10 2004 045 772 A1 is disclosed. Since the fluidized bed reactor is operated below the ash melting point, the ash can be used as a mineral fertilizer.

The DE 20 2012 101 271 U1 describes a device for the thermal workup of organic waste, consisting of the material supply, the reactor block), the tar separation, the gas cleaning, the evaporator and the Aktivkoksaufbereitung, the material supply consists of a predominantly funnel-shaped feeding device and a feed screw arranged underneath, the output in the lower end of the main reactor opens, and in the material supply further facilities for introducing an aggregate mixture and tar derived from the process open. The reactor block consists of a heated with synthesis gas to temperatures of 500 to 550 ° C combustion chamber through which extends the vertically arranged main reactor having an internal conveyor. In the DE 20 2006 016 442 U1 An installation for carrying out a process for the gasification of biomass with continuous feed, subsequent comminution and gas purification is described.

The biomass is fed through a plug screw and thereby continuously compressed so that a gas-impermeable plug is formed, whereby steam and gases can not escape opposite to the conveying direction. In a screw extruder is heated by a defibration screw, which feeds the biomass either continuously under pressure, and in which the biomass is gradually heated by the addition of water vapor or pure oxygen or a combination of both from 100 ° C to about 200-250 ° C. , or the biomass shortly after the inlet of the screw extruder by the addition of water vapor or pure oxygen or a combination of both to a temperature of about 200-250 ° C. heated and brought to a pressure of about 25-30 bar, wherein (in both cases) by heating the lignin contained in the biomass (putty between the plant fibers) softens or becomes liquid. In addition, the biomass (in particular the epidermis shell and the nodules of grasses) is partially decomposed chemically by the oxygen supplied. The shearing forces generated by the shearing elements of the defibration screw, the biomass fibers are separated from each other and finely divided epidermis and Noden due to the embrittlement by the oxygen. Water vapor is additionally added shortly before the exit into the screw extruder, which leads to a drifting apart of the fiber-vapor mixture due to the resulting larger volume. At the outlet of the screw extruder, the oxygen required for gasification is added to the biomass. Through a combustion chamber, either the evenly mixed biomass-oxygen mixture is supplied, so that it comes to a homogeneous explosion (optimal partial combustion) at about 900 ° C, or it is alternatively necessary for the gasification of oxygen only within the combustion chamber added separately, whereby the mixture is then inhomogeneous and therefore gassed unevenly. By an extruder or an arrangement of several extruders, through which the biomass (or the gasification mixture) is fed to the gasification chamber, is passed through high-temperature filter (metallic membrane filter) through which the resulting gas at 900 ° C and thereby cleaned in several stages, and by a catalytic device in which finally the remaining pollutants in the gas passing through are rendered harmless.

In the DE 10 2015 107 491 A1 a process and a plant for rapid pyrolysis of biomass, in particular lignocellulosic biomass are given, in which the biomass provided is reacted with a solid heat carrier under pyrolysis conditions. In the subsequent separation of the pyrolysis products, a liquid product, the pyrolysis tar get. According to the invention, at least a portion of the flue gas used for heating the heat carrier or the pyrolysis gas obtained as a further product or mixtures of both gases is recycled to the pyrolysis reactor or into the hot region of the product work-up.

The invention according to the DE 10 2013 017 854 A1 relates to a reactor and a method for the gasification of fuels, in particular of biomass, in which a muffle tube arranged above the grate is provided in the interior of the reactor, in which the fuel to be gasified is received. The muffle tube opens into a lower reactor region designed as an autothermal gasification zone in which the fuel to be gasified oxidizes. With an upper muffle tube region, the muffle tube is accommodated in an annular reactor region forming a muffle housing in such a way that the gas entering the annular gap at least partially flows along and / or around the upper muffle tube region with heat release that this forms an allothermal gasification zone for heating, pyrolysis and reduction of the fuel to be gasified. In the prior art, the synthesis gas reactor, which is pronounced as a fluidized bed, takes the biomass directly on. Here, the pyrolysis reactions with resulting tar and gasification reactions with resulting synthesis gas take place side by side. Consequently, the tar content in the synthesis gas is very high. To avoid system failure, the tar content must be removed consuming.

• • das Brenngas oder auch Synthesegas
• • das verbrannte Abgas – also hauptsächlich Kohlendioxid und Wasser Ammoniak, und
• • Pflanzenkohle oder Kohle aus anderen Biomassen ausgeprägt als Aktivkohle (je nach Einsatzstoff)

zur erreichen.Object of the invention to develop a device for the gasification of biomass, which avoids the disadvantages in the production of synthesis gas, as well as the harnessing of all material flows that leave the thermochemical reactor, such as

• • the fuel gas or syngas
• • the burned exhaust - so mainly carbon dioxide and water ammonia, and
• • Biochar or coal from other biomasses pronounced as activated carbon (depending on input material)

to reach.

The present invention is intended to make a contribution to converting energy from biomass in such a way that all coming from a pyrolysis or gasification material flows can be harnessed and the plants can be used decentralized to avoid the transport of biomass, as the Energy density of the biomass is too low for a wide transport.

• • Austragsschnecke (7) mit einer Aktiv-Kohle-Quensche (5) und einem Fermenter (6),
• • der Überhitzer (4) ist über eine Rohrleitung (15) zur Rückführung des Synthesegases mit einem Gaseingang (14) in den Synthesereaktor (1),
• • die Synthesegasableitung (15) des Synthesereaktors (1) mit einem Staubscheider (8),
• • der Staubabscheider (8) mit einem Filter (9),
• • das Filter (9) zur Rückführung des Katalysators mit dem Schubbodenrost (3) des Synthesereaktors (1) und mit Ammoniakwäschern (10), gefüllt mit einem Kationentauscher oder Anionentauscher oder einem Katioinentauscher und Anionentauscher im Mischbett,
• • der Ammoniakwäscher (10) mit einem Hg-Filter (11) und
• • der Hg-Filter (11) mit einer Verwendungsvorrichtung für das Synthesegas verbunden sind.

The object of the invention is achieved by a device for the catalytic gasification of biomass to biochar and to a combustible, mainly CO, CO2 water vapor, hydrogen, methane and ammonia-containing gas with exclusion of air, wherein the device from a synthesis reactor ( 1 ), in which two superimposed and counter-rotating sliding floor grates ( 2 . 3 ) are arranged. In the upper part of the synthesis reactor ( 1 ), there is a superheater ( 4 ) with a water supply 13 ) and synthesis gas discharge ( 16 ). In the lower part of the synthesis reactor ( 1 ) is a discharge screw ( 7 ) and a gas inlet ( 14 ), which via a synthesis gas recirculation line ( 15 ) with the synthesis gas discharge ( 16 ) of the superheater ( 4 ), wherein the

• • discharge screw ( 7 ) with an active coal quencher ( 5 ) and a fermenter ( 6 )
• • the superheater ( 4 ) is via a pipeline ( 15 ) for recycling the synthesis gas with a gas inlet ( 14 ) in the synthesis reactor ( 1 )
• The synthesis gas discharge ( 15 ) of the synthesis reactor ( 1 ) with a dust separator ( 8th )
• • the dust collector ( 8th ) with a filter ( 9 )
• • the filter ( 9 ) for the return of the catalyst with the sliding bottom grid ( 3 ) of the synthesis reactor ( 1 ) and with ammonia scrubbers ( 10 ), filled with a cation exchanger or anion exchanger or a catalyst exchanger and anion exchanger in the mixed bed,
• • the ammonia scrubber ( 10 ) with a Hg filter ( 11 ) and
• • the Hg filter ( 11 ) are connected to a use apparatus for the synthesis gas.

The ammonia scrubber ( 10 ) has a water supply ( 19 ), an ammonia feed ( 20 ) with the calciner ( 21 ) is connected to the return of the liberated ammonia, and a discharge ( 22 ), which is used to remove the ammonium ion-loaded cation exchanger from the ammonia scrubber ( 10 ) with the calciner ( 21 ) and one with an ion exchanger ( 12 ) associated removal ( 23 ) of the water from the ammonia scrubber ( 10 )

The ammonia scrubber ( 10 ) is equipped with a calciner ( 21 ), in which the ammonium-loaded cation exchanger is calcined, the calciner ( 21 ) via an ammionic feedback line ( 20 ) with the ammonia scrubber ( 10 ) connected is.

In a further embodiment of the invention, the ammonia scrubber ( 10 ) which is filled with a cation exchanger and an anion exchanger in the mixed bed, via the ion exchanger ( 12 ) with a separator ( 17 ) to separate the cation exchanger from the anion exchanger.

The calciner ( 21 ) and the ion exchanger ( 12 ) are equipped with a desalination plant ( 18 ) connected.

The invention will now be explained in more detail with reference to an example, wherein the 1 a schematic representation of the device, 1a a schematic representation of the ammonia scrubber ( 10 ) loaded with cation and anion exchangers in the mixed bed, the 2 a schematic representation of the calciner, 3 a schematic representation of seawater desalination with the aid of the H + -loaded cation exchanger from the calcination and the OH ion-loaded anion exchanger from the separator ( 17 ) 4 a schematic representation of seawater desalination with the aid of NH4 loaded separator ( 17 ) and the OH ion-loaded anion exchanger from the separator ( 17 ), the 5 a schematic representation of the use of carbon dioxide and the 6 show a schematic representation of the magnesium salt production plant from the sea water, wherein

LIST OF REFERENCE NUMBERS

1

Syntheseraktor

2

Sliding floor grate for the biomass

3

Sliding floor grate for the catalyst

4

superheater

5

Activated carbon Quensche

6

fermenter

7

discharge screw

8th

dust collector

9

filter

10

ammonia scrubber

11

Hg filter

12

ion exchanger

13

water supply

14

gas input

15

Synthesis gas recirculation line

16

Synthesis gas discharge

17

separator

18

Desalination

19

water supply

20

Ammonia feed for ammonia from the calcination

21

calciner

22

Removal of the cation exchanger from the ammonia scrubber ( 10 )

23

Discharge of water from the ammonia scrubber ( 10 )

The amounts of water present in the biomass are sufficient to produce a hydrogen-rich gas by gasification with the carbon from the biomass. If this gas is returned, then the biomass can be heated by the gas and the water released and evaporated in the pyrolysis and the resulting carbon dioxide can be used as a gasification agent in a synthesis gas reactor.

The use of air, oxygen and carbon dioxide are known per se. The synthesis gas reactor ( 1 ) is pronounced so that two opposing sliding floor grates ( 2 . 3 ) are arranged one above the other. The lower z. B. from right to left promoting sliding floor grid ( 2 . 3 ) is fed with biomass and catalyst from the upper 3 ) after serving for gas purification, falls, charges. The upper sliding floor grate ( 3 ) becomes loaded with carbonate minerals, which are heated and calcined by the recirculated syngas. However, already calcined minerals can also be used in mixtures with carbonates, if the temperatures of the process do not exceed 900 ° C. The generated gas flows through the upper moving-bed bed with the catalyst where tars are eliminated by cracking up to 99.99%, and by chemical reaction, hydrochloric acid and hydrogen sulfide are bound as their calcium salts. The catalyst continues to function when it falls into the biomass as a pyrolysis inhibitor and catalyst for the desired gasification reactions. Tar formation is thus largely avoided and promoting the formation of synthesis gas. Furthermore, the quality and quality of the obtained biochar, activated carbon or graphite is determined by the choice and the amount of catalyst, as these other properties z. B. with respect to the change in pH when irrigated as a plant substrate, if instead of dolomite, burned or semi-calcined dolomite is used.

Heat transfer occurs by recirculating the synthesis gas over the biomass and catalyst bed. The synthesis gas flows into a superheater ( 4 ) directly above the synthesis gas reactor ( 1 ) where the synthesis gas is partially combusted to maintain the synthesis gas at the desired temperature. Thus, the process is independent of the exact composition of the biomass with respect to the energy required for the process.

The coal produced here has a larger internal surface area (several thousandths) due to the gas recirculation and the additional injection of water and / or steam or the additional addition of CO2 by the calcination of the catalyst, which leads to further gasification reactions on the surface of the coal qm per g) than usual biochar used in Terra-Preta (50 to 300 g per square meter). The activation of this coal with nitrifying bacteria and a yeast-bacterial mixture from the beer production of Lambic surprisingly shows a much higher uptake of nitrate (up to 200% more) than conventional biologically activated plant carbon.

The biochar, which can also be used here as activated carbon, plays a central role in this entire process: the water produced in the process and water evaporating by drying the biomass is condensed in a targeted manner and purified with the self-generated activated carbon, so that ultimately it can as drinking water at least but as process water becomes usable. Likewise, the water vapor which forms when the synthesis gas is formed can be condensed and purified via the activated carbon, so that at least one service water is also produced here.

Another use of this water is the washing of the exhaust gas stream in the ammonia washers ( 10 . 11 ), whereby ammonia and carbon dioxide dissolve in the water. In addition, the dissolution in the presence of an anion exchanger occurs in the chloride form, so that the hydroxyl ions and the hydrogen carbonate ions, which form when dissolving ammonia and carbon dioxide in water, bind to the anion exchanger and thus ensure that much more ammonia and Let carbon dioxide dissolve in this water. In a subsequent step, the ammonium ion formed from the ammonia in the reaction with carbon dioxide and water is removed from the water by means of a zeolite-based or bentonite-based mineral cation exchanger in the sodium form. In this way, one obtains an anion exchanger which is loaded with hydroxyl ions and hydrogen carbonate ions, and a cation exchanger which is loaded with ammonium ions, and a concentrate of sodium chloride-containing water.

Due to the pyrolysis process, high temperatures> 360 ° C are available for calcination of the ammonium-loaded cation exchanger. Therefore, it becomes possible in this way to recover the ammonia as a regeneration agent for a mineral cation exchanger in the sodium form. An ion exchanger system for the demineralization of water is now available with the anion exchanger charged with hydroxyl ions and hydrogen carbonate ions and with the mineral cation exchanger charged with hydrogen cations after calcination.

The fact that the regenerant can be recovered by the calcination, it is now possible for the first time to use ion exchangers for the desalination of seawater, which previously failed because of the need for the provision of regenerants, all of which would lead to further salification.

In a further process according to the invention, the ammonia is dissolved in water. The hydroxyl ions exchanged with an anion exchanger for chloride ions and the ammonium exchanged for sodium, which is located on a strong or weakly acidic cation exchanger, also of non-mineral origin. Thus, the ion exchangers are regenerated and saline water can be desalinated over it, so that in the produced water now ammonium ions and hydroxyl ions are. The water will now Magnesiummonohydrogenphosphat add and so solid magnesium ammonium phosphate precipitated. Thus, the hydrogenation of phosphate exchanges with the Ammonium ion from and with the hydroxyl anion in the water is again water and the salt water is desalted. The obtained magnesium ammonium phosphate is filtered and roasted so that ammonia is released as gas and magnesium monohydrogen phosphate is formed again.

In the desalting process used here, the seawater is first filtered through the coal produced in the pyrolysis to retain algae, plankton, oil and other impurities. Once saturated coal is returned to the pyrolysis.

The seawater is then treated in a second step with cation exchangers in the sodium form and anion exchangers in the chloride form in order to obtain a water in which only sodium ions and chloride ions are present. Other ions such as magnesium, potassium, sulfate, heavy metal ions, barium, strontium, etc. are then in a concentrate that can be further processed to obtain magnesium and other substances. The ion exchangers are z. B. regenerated by the concentrate from the ion exchange with ammonium-containing Ammonikawaschwasser.

In the third step, the chloride ion in the water is exchanged for the hydroxyl ion or the bicarbonate ion. The solution now contains sodium hydroxide or sodium bicarbonate. This solution is treated with the calcined cation exchanger, which now exchanges hydrogen cations for sodium ions, producing water and carbonic acid.

In the fourth step, there is the possibility to trickle the water to expel the carbon dioxide as carbon dioxide or to pass the water over a calcium carbonate bed to dissolve calcium bicarbonate. Here, there is also the option to enrich the water beforehand with more carbon dioxide from the exhaust gas of the combustion of the pyrolysis gas, so that more calcium carbonate can dissolve as calcium hydrogencarbonate and the water thus becomes drinking water.

The amount of carbon dioxide and ammonia are more by the entry of biomass, so that these substances can also be used for other processes:
With the help of these substances dissolved in water algae can be bred. Algae have a threefold higher carbon dioxide turnover per hectare than maize and are thus of great interest for energy production. They also need phosphate. The biomass phosphate in this process is available in the biochar by biologically activating it and then filtering the water for algae cultivation enriched with carbon dioxide and ammonium ions. This makes it possible to grow the input material for pyrolysis through its own residues carbon dioxide, ammonia and biochar.

It is easy to use magnesium ammonium phosphate. The same applies to the operation of greenhouses, which can be heated on the one hand with waste heat from the pyrolysis, on the other hand, with the biologically activated biochar, the ammonia and carbon dioxide can be fertilized.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102004045772 A1 [0004]
• DE 202012101271 U1 [0005]
• DE 202006016442 U1 [0005]
• DE 102015107491 A1 [0007]
• DE 102013017854 A1 [0008]

Claims (5)

Apparatus for carrying out the process according to claims 1-36, consisting of a synthesis reactor ( 1 ), In which two sliding floor grates ( 2 . 3 ), • in the upper part of the synthesis reactor ( 1 ), with a water supply ( 13 ) and synthesis gas discharge ( 16 ) provided superheater ( 4 ) and • in the lower part of the synthesis reactor ( 1 ) arranged discharge screw ( 7 ) and • with a synthesis gas recirculation line ( 15 ) connected gas inlet ( 14 ), • whereby the discharge screw ( 7 ) with an active coal quencher ( 5 ) and a fermenter ( 6 ), • the superheater ( 4 ) via a pipeline ( 15 ) for recycling the synthesis gas with a gas inlet ( 14 ) in the synthesis reactor ( 1 ) and • the synthesis gas discharge ( 15 ) of the synthesis reactor ( 1 ) with a dust separator ( 8th ), • the dust collector ( 8th ) with a, for the return of the catalyst with the sliding floor grid ( 3 ) of the synthesis reactor ( 1 ), filters ( 9 ), • the filter ( 9 ) with a water supply ( 19 ) and with a cation exchanger or anion exchanger or with a cation exchanger and anion exchanger in the mixed bed, filled ammonia scrubbers ( 10 ), • the ammonia scrubber ( 10 ) with a Hg filter ( 11 ) and • the Hg filter ( 11 ) are connected to a use apparatus for the synthesis gas. Apparatus according to claim 1, characterized in that the ammonia scrubber ( 10 ) via a water supply ( 19 ), an ammonia feed ( 20 ) with the calciner ( 21 ) for the return of the liberated ammonia, and via a discharge ( 22 ), which is used to remove the ammonium ion-loaded cation exchanger from the ammonia scrubber ( 10 ) with the calciner ( 21 ) and via one with an ion exchanger ( 12 ) associated removal ( 23 ) of the water from the ammonia scrubber ( 10 ). Device according to claim 1, characterized in that the Amoniakwäscher ( 10 ) with a calciner ( 21 in which the ammonium-loaded cation exchanger is calcined, the calciner ( 21 ) via an ammionic feedback line ( 20 ) with the ammonia scrubber ( 10 ) connected is. Apparatus according to claim 1, characterized in that the ammonia scrubber ( 10 ), which is filled with a cation exchanger and an anion exchanger in the mixed bed, with a separator ( 17 ) is connected to the separation of the cation exchanger from the anion exchanger. Device according to claims 1-3, characterized in that the calciner ( 21 ) and the ion exchanger ( 12 ) with a desalination plant ( 18 ) connected is

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