DE102017009622A1 - Process for the gasification of biomass - Google Patents

Abstract

A process for the catalytic gasification of biomass to biochar and a combustible, mainly CO, C02 steam, hydrogen, methane and ammonia-containing gas with exclusion of air, characterized in that in a synthesis gas reactor (1) the biomass is mixed with a countercurrent catalyst, wherein
• The biomass on a sliding floor grate (2) in countercurrent to a likewise on a lying above the sliding floor grate (2) of the biomass moving soil grid (3) mounted catalyst and the catalyst through the sliding floor grate (3) distributed to the biomass and with the from the Burning the biomass resulting and heated in a superheater (4) synthesis gas from the synthesis loop brought by recycling at least a portion of the synthesis gas in contact,
The synthesis gas which is produced and not required for combustion of the biomass is fed to the water via a dust separator (8), via a filter (9), via an ammonia scrubber (10) filled with an ion exchanger and used as a quench, and via a HG filter (12) is supplied for use in the form of a fuel gas or for driving a turbine or for use in the Fischer-Tropsch synthesis.
and
• the biochar produced during the pyrolysis by means of a discharge screw (7) via a biochar quencher (5) in a fermenter (6) and subjected to a biological activation.

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 carriers, 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 service water is formed here during the condensation of the water from the synthesis gas, in the condensation from the exhaust stream and in the inventive use of ammonia or ammonium ion as a regenerating agent for an ion exchange process for desalination of water, especially seawater. Excess ammonia is with mineral ion exchangers or magnesium Ammonium phosphate obtained as fertilizer. Drinking water is desalinated water which is enriched with calcium bicarbonate by the reaction of calcium carbonate and carbon dioxide. Biochar is the coal extracted 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-building effect. The pyrolysis is therefore better suited for this task than a combustion because this targeted coal from biomass and activated carbon, which later as Terra Preta do Indio similar substrate continues to use in agriculture and horticulture, can be produced and so in a simple way 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 undercut, which is why it would be possible to recover phosphates and other fertilizers only with very high equipment and chemical effort. 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 done by electrical heating of the system or by circulating heat transfer media, such as sand, which are heated by burning the biomass. 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 an underlying feed screw, 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 synthesis gas heated to temperatures of 500 to 550 ° C combustion chamber through which extends the vertically arranged main reactor. which has 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 is heated 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 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 017854 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, und
• • Pflanzenkohle oder Kohle aus anderen Biomassen ausgeprägt als Aktivkohle (je nach Einsatzstoff)

zur erreichen.The object of the invention is to develop a gasification process of biomass, which avoids the disadvantages in the production of synthesis gas, as well as making it possible to use all material flows leaving the thermochemical reactor, such as

• • the fuel gas or syngas
• • the burnt exhaust gas - mainly carbon dioxide and water, 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.

The object of the invention is achieved by a method for catalytic gasification of biomass to biochar and to a combustible, mainly CO, C02 steam, hydrogen, methane and ammonia-containing gas with exclusion of air, wherein in a synthesis gas reactor ( 1 ) the biomass is mixed with a catalyst in a countercurrent principle, and on a Sliding floor grate ( 2 ) in countercurrent to a likewise over the sliding floor grid ( 2 ) the biomass lying moving floor grid ( 3 ) carried catalyst and the catalyst through the sliding floor grid ( 3 ) is distributed to the biomass. With the resulting from the combustion of the biomass and in a superheater ( 4 ) heated synthesis gas from the synthesis loop is brought into contact by recycling at least a portion of the synthesis gas with the biomass. The synthesis gas is in the superheater ( 4 ) brought to a temperature of 360 ° C to 1000 ° C. The resulting synthesis gas, which is not required for combustion of the biomass, is passed through a dust separator ( 8th ), via a filter ( 9 ), via an ammonia scrubber filled with an ion exchanger and used as a quencher ( 10 ,), to which water is supplied and over a Hg filter ( 11 ) is supplied to a use in the form of a fuel gas or to drive a turbine or for use in the Fischer-Tropsch synthesis.

• • wobei der Kationenaustauscher den Ammoniak in Form seines Ammoniumions, das sich beim Lösen des Ammoniaks in Wasser bildet, gegen ein anderes Kation, insbesondere das Natriumion tauscht und der Anionenaustauscher, die bei der Lösung des Ammoniaks in Wasser entstehenden Hydroxylanionen gegen andere Ionen, insbesondere Chloridionen tauscht,
• • die Hydrogencarbonatanionen, die durch Lösen von Kohlensäure im Ammoniakwäscher entstehen, gegen Chloridionen getauscht werden, und
• • der mineralische Kationenaustauscher von dem Anionenaustauscher separiert und im Kalzinator kalziniert sowie der freiwerdende Ammoniak aus dem Kalzinator dem Ammoniakwäscher (10) wieder als Regeneriermittel des Kationenaustauschers zugeführt und recycelt wird.

Das Wasser des Ammoniakwäschers (10) wird über einen weiteren lonentauscher (12), der als Anionenaustauscher ausgeprägt ist, geführt und der Anionentauscher wird dabei mit Hydroxylanionen und Hydrogencarbonatanionen beladen.The biochar produced during the gasification is produced by means of a discharge screw ( 7 ) about a biochar quencher ( 5 ) in a fermenter ( 6 ) and subjected to biological activation. The catalyst used is calcined or unfired or semi-calcined dolomite, in particular semi-calcined, quicklime, chalk, magnesium carbonate, magnesium oxide or potassium salts such as potassium carbonate, iron salts and oxides, manganese salts and oxides in a mass ratio of 0.1 to 5% based on the biomass or a mixture of these used. The ammonia scrubber ( 10 ) is filled with a cation exchanger and the ammonium ion-exchanged cation exchanger is fed to a calciner ( 19 ) and calcined to form a cation exchanger loaded with hydrogen cations. The water of the ammonia scrubber ( 10 ) is passed through another ion exchanger ( 12 ), which is expressed as an anion exchanger, out and the anion exchanger is loaded with hydroxyl anions and bicarbonate anions. In the ammonia scrubber ( 10 ), in a further embodiment of the invention the ammonia can be washed with water which is fed to the ammonia scrubber in the presence of an anion exchanger and a cation exchanger in the mixed bed,

• • wherein the cation exchanger exchanges the ammonia in the form of its ammonium ion, which forms when dissolving the ammonia in water, against another cation, in particular the sodium ion and the anion exchanger, the resulting in the solution of ammonia in water hydroxyl anions against other ions, in particular chloride ions exchanges,
• • the bicarbonate anions, which are formed by dissolving carbonic acid in the ammonia scrubber, are exchanged for chloride ions, and
• The mineral cation exchanger is separated from the anion exchanger and calcined in the calciner, and the liberated ammonia from the calciner is added to the ammonia scrubber ( 10 ) is recycled as a regenerating agent of the cation exchanger and recycled.

The water of the ammonia scrubber ( 10 ) is passed through another ion exchanger (12), which is pronounced anion exchanger, and the anion exchanger is loaded with hydroxyl anions and bicarbonate anions.

The cation exchanger is a weakly acidic cation exchanger or a strongly acidic cation exchanger, also of non-mineral origin. The ammonium ion-loaded cation exchanger or the magnesium ammonium phosphate is used as fertilizer or fertilizer additive. The anion exchangers used are both weakly basic and strongly basic anion exchangers, and weakly acidic and strongly acidic cation exchangers based on mineral zeolite. The zeolite material is a material that conforms to one of the following structural types: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD , AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO , CON, CZP, DAC, GDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EON, EPI, ERI, ESV, ETR, EUO, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME , GON, GOO, HEU, IFR, IHW, ISV, ITE, ITH, ITW, IWR, IVW, IWW, JBW, KFI, LAU, LEV, LIO, LIT, LOT, LOV, LTA, LTL, LTN, MAR, MAZ , MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MSE, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NES, NON, NPO, NSI, OBW, OFF, OSI , OSO, OWE, PAR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG , SFH, SFN, SFO, SGT, SIV, SOD, SOS, SSY, STF, STI, STT, SZR, TER, THO, TONE, TSC, TUN, UEI, UFI, UOZ, USI, UTL, VET, VFL VNI, VSV, WEI, WEN, YUG and ZON.

The cation exchanger obtained from the calcination and the anion exchanger loaded with hydroxyl anions and bicarbonate anions exchanged in a seawater desalination plant in which the seawater is preferably mixed in a mixed bed of cation and anion exchangers by exchanging the anions and cations contained in the seawater for hydrogen cations and hydroxyl anions Getting released in the water to desalinate the seawater. The carbon dioxide from the combustion of the synthesis gas is dissolved in the desalting water and over a bed of calcium carbonate passed, wherein the water is hardened by dissolving the calcium carbonate as calcium bicarbonate to drinking water.

The salty water is pre-cleaned with the biochar and the waste gas from the combustion of the synthesis gas is. before it serves to harden the saline water, also purified over the biochar. The synthesis gas is in the filter ( 9 ) of long-chain hydrocarbons, tars, hydrochloric acid, sulfur dioxide and trioxide passed through a bed of calcined dolomite, quicklime, magnesia or potassium salts or a mixture thereof and the long chain hydrocarbons and tars are cracked to carbon monoxide and hydrogen, and the hydrochloric acid to calcium chloride and / or as magnesium chloride, the sulfur oxides as calcium sulfate and the hydrogen sulfide as calcium sulfide deposited.

In a further embodiment of the invention, the ammonia can load a non-sinterable cation exchanger and exchange ammonium ions for sodium ions when producing deionized water and the ammonium ions are precipitated by adding magnesium monohydrophosphate or magnesium dihydrogen phosphate as magnesium ammonium phosphate and the resulting magnesium ammonium phosphate is sintered, whereby ammonia and magnesium hydrogen phosphate regress.

The gasification can be controlled by the external addition of water vapor and / or carbon dioxide to the extent that either biochar, activated carbon or inorganic carbon in the form of graphite is produced. The biochar or activated carbon or the inorganic carbon is combined with the excess ammonium-loaded cation exchanger on a mineral basis and fermented lactic acid together with biomass, in particular lactic acid bacteria, thus producing a further fertilizer or a soil substrate.

In the case of the gasification of sewage sludge, this has the particular advantage when the carbon has become completely inorganic and thus electrically conductive, that the sewage sludge can lose its sewage sludge properties in terms of sewage sludge regulation and can be used as fertilizer

The fermentation involves lactic acid bacteria, yeasts, fungi, archaebacteria and algae, in particular symbioses of these microorganisms, e.g. in foods such as kefir, lambic (Belgian beer), nukazuke (Japanese pickles), natto (fermented soybeans), tempeh, water kefir, kombucha, sauerkraut, kimchi, yogurt Skye, cheese, raw sausage, silage, sourdough, bread drink, miso, quark etc , especially preferred are the microorganisms of kefir and larmbic. Probiotics from animal and human nutrition may also be involved in the fermentation, e.g. Enterococcus faecium, Enterococcus faecalis, Lactobacilli, Bifidobacteria, Escherichia coli, Saccharomyces boulardi, Saccharomyces cerevisia. The carbon dioxide is introduced into a water - drinking water, drinking water or seawater to grow algae.

Process of ammonia from calcination or pyrolysis can be added to the carbon dioxide and thus serve for the fertilization of algae. The fermented activated carbon is added to the water used for algae cultivation in order to obtain further fertilizers needed for the cultivation of algae, such as e.g. To introduce phosphate into the water.

1

Synthesereaktor

2

Schubbodenrost für die Biomasse

3

Schubbodenrost fü den Katalysator

4

Überhitzer

5

Aktivkohle- Quensche

6

Fermenter

7

Austragsschnecke

8

Staubabscheider

9

Filter

10

Ammoniakwäscher

11

Hg- Filter

12

lonentauscher

13

Wasserzuführung

14

Gaseingang

15

Gasrückführungsleitung

16

Synthesegasableitung

17

Separator

18

Meerwasserentsalzung

19

Kalzinator

The invention will now be explained in more detail with reference to an example, wherein the 1 is a flow chart of the method, the 1a a flow chart of the ammonia scrubber ( 10 ) with mixed bed, 2 a flow chart of calcination 3a a flow chart 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 ( 14 ) 4 a flow chart of seawater desalination and the OH ion-loaded anion exchanger from the separator ( 17 ), the 5 a flow chart of the use of carbon dioxide and the 6 show a flow chart of the magnesium salt recovery from the sea water, where

1

synthesis reactor

2

Sliding floor grate for the biomass

3

Sliding floor grate for the catalyst

4

superheater

5

Activated carbon quenching

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

Gas recirculation line

16

Synthesis gas discharge

17

separator

18

Desalination

19

calciner

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, for example, from right to left promoting sliding floor grate ( 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 ) is charged with carbonate-containing 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. Further, the choice and the amount of catalyst determine the quality of the obtained biochar, activated carbon or graphite, since these have different properties, e.g. with regard to the change in pH when irrigated as a plant substrate, if instead of dolomite, burnt 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 of thousands) due to the gas recirculation and the additional injection of water and / or steam or the additional addition of CO.sub.2 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 the 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 ), 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.

With the anion exchanger loaded with hydroxyl ions and hydrogen carbonate ions and the mineral cation exchanger loaded after the calcination with hydrogen cations, an ion exchange system for the demineralisation of water is now available.

The fact that the regenerant can be recovered by the calcination, it is now possible for the first time to use ion exchanger for the desalination of sea water, which previously failed because of the need to provide 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 desalted 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 hydrogen cation of the phosphate exchanges with the ammonium ion, and with the hydroxyl anion in the water, water again results and the salt-containing water is desalted. The resulting magnesium ammonium phosphate is filtered off 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 e.g. regenerated by the concentrate from the ion exchange with ammonium-containing ammonia wash water.

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 [0006]
• DE 102015107491 A1 [0008]
• DE 102013017854 A1 [0009]

Claims (14)

A process for the catalytic gasification of biomass to biochar and a combustible, mainly CO, C02 steam, hydrogen, methane and ammonia-containing gas with exclusion of air, characterized in that in a synthesis gas reactor (1) the biomass is mixed with a countercurrent catalyst, wherein • The biomass on a sliding floor grate (2) in countercurrent to a likewise on a lying above the sliding floor grate (2) of the biomass moving soil grid (3) mounted catalyst and the catalyst through the sliding floor grate (3) distributed to the biomass and with the from the Combustion of biomass resulting and heated in a superheater (4) synthesis gas from the synthesis loop brought by recycling at least a portion of the synthesis gas in contact, • the resulting and not required for combustion of the biomass synthesis gas via a dust separator (8), via a filter (9 ), via a ge with an ion exchanger filled and serving as a quenching ammonia scrubber (10), the water is supplied and via a HG filter (12) for use in the form of a fuel gas or for driving a turbine or for use in the Fischer-Tropsch synthesis is supplied. and • the biochar resulting from the pyrolysis is transported by means of a discharge screw (7) via a biochar quencher (5) into a fermenter (6) and subjected to biological activation. Method according to Claim 1 characterized in that the ammonia scrubber (10) is filled with a cation exchanger and the cation exchanger loaded with ammonium ions is fed to a calciner and calcined to form a cation exchanger loaded with hydrogen cations and ammonia which is returned to the ammonia scrubber (10). Method according to Claim 1 and 2 , characterized in that the water of the ammonia scrubber (10) via a further ion exchanger (12), which is pronounced as an anion exchanger, is performed and the anion exchanger is loaded with hydroxyl anions and bicarbonate anions. Method according to Claim 1 , characterized in that the ammonia scrubber (10) is filled with an anion exchanger and the ion exchanger (12) with a cation exchanger Method according to Claim 1 characterized in that in the ammonia scrubber (10) the ammonia is washed with water supplied to the ammonia scrubber in the presence of an anion exchanger and a cation exchanger in the mixed bed, the cation exchanger containing the ammonia in the form of its ammonium ion resulting from dissolution of the ammonia forms in water, exchanged for another cation, in particular the sodium ion and the anion exchanger, which exchanges the formation of ammonia in water hydroxyl anions against other ions, in particular chloride ions, • the bicarbonate anions formed by dissolving carbonic acid in the ammonia scrubber, against chloride ions • The mineral cation exchanger is separated from the anion exchanger in the separator (17) and calcined in the calciner, and the ammonia liberated from the calciner is returned to the ammonia scrubber (10) as a regenerating agent of the cation exchanger and recycled. Method according to Claim 1 characterized in that the biomass is added as a catalyst of fired or unfired or semi-calcined dolomite in a mass ratio of 0.1 to 5% based on the biomass, Method according to Claim 2 characterized in that the catalyst is lime, chalk, magnesium carbonate, magnesium oxide or potassium salts, such as potassium carbonate, iron salts and oxides, manganese salts and oxides or a mixture of these. Method according to Claim 1 characterized in that the synthesis gas in the superheater (4) is brought to a temperature of 360 ° C to 1000 ° C. Method according to Claim 1 - 7 , characterized in that both weakly basic and strongly basic anion exchangers, as well as weakly acidic and strongly acidic cation exchangers, are used on a mineral zeolite base or non-mineral base. Method according to Claim 1 - 5 characterized in that the cation exchanger obtained from the calcination and the anion exchanger loaded with hydroxyl anions and bicarbonate anions desalt from the separator (17) in a seawater desalination plant in which the seawater preferably in a mixed bed of cation and anion exchangers by exchange of the anions contained in the seawater and Cations against hydrogen cations and hydroxyl anions, which react at the moment of release in the water to desalinate the sea water, exchanges. Method according to Claim 1 - 6 characterized in that the carbon dioxide from the combustion of the synthesis gas is dissolved in the desalting water and passed over a bed of calcium carbonate, wherein the water is hardened by dissolving the calcium carbonate as calcium bicarbonate to drinking water. Method according to Claim 1 - 7 , characterized in that the saline water pre-cleaned with the biochar and the exhaust gas from the combustion of the synthesis gas. before it is used to harden the saline water, is also purified on the biochar. Method according to Claim 1 - 9 characterized in that the synthesis gas in the filter (9) of long chain hydrocarbons, tars, hydrochloric acid, sulfur dioxide and trioxide is passed through a bed of calcined dolomite, quicklime, magnesia or potassium salts or a mixture thereof and the long chain hydrocarbons and tars cracked to carbon monoxide and hydrogen, and the hydrochloric acid to calcium chloride and / or as magnesium chloride, the sulfur oxides as calcium sulfate and the hydrogen sulfide as calcium sulfide are deposited. Method according to Claim 1 - 10 characterized in that the ammonia loads a non-sinterable cation exchanger and that ammonium ions are exchanged for sodium ions in the production of deionized water and the ammonium ions are precipitated by adding Magnesiummonohydrogenphophat or Magensiumdihydrogenphosphat as magnesium ammonium phosphate and the resulting magnesium ammonium phosphate is sintered , where ammonia and magnesium hydrogen phosphate regress.

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