WO2018007205A1 - Method for the parallel production of synthesis gas, carbon, and low-pollutant residual coal from brown coal - Google Patents

Abstract

The invention relates to a method for the parallel production of synthesis gas, carbon, and a residual coal of a feed coal having a molar H to C ratio in the water- and ash-free coal of greater than 0.6, characterized in that in a first step, at least a part of the volatile constituents of the feed coal are thermally expelled from the feed coal at temperatures of 500 to 1000 °C. Subsequently, in a second step, said volatile constituents are thermally converted to synthesis gas and carbon at temperatures of 1000 to 1800 °C. Both reaction products of the second step are discharged from the reactor, wherein the conversion of the second step is carried out as sub-stoichiometric reforming and thermal decomposition.

Description

 Process for the parallel production of synthesis gas, carbon and low-emission residual coal from lignite

description

The present invention involves chemical utilization of coal, particularly lignite, with a lower carbon footprint than in the prior art. The current processes for the chemical use of lignite, e.g.

Coal gasification, have a high carbon footprint. The production of hydrogen from coal via coal gasification releases about twice as much carbon dioxide as the production of hydrogen from natural gas.

The present invention is intended to make it possible, in parallel, to produce so-called inferior coal having a low calorific value, e.g. Brown coal, a

Synthesis gas for the production of organic products, e.g. methanol,

 Dimethyl ether, gasoline or Fischer / Tschopp diesel as well

• High purity carbon that can replace refinery petroleum coke and one

• Coal which, compared to the starting coal, has substantially less pollutants, e.g.

 Sulfur or mercury, to generate. Furthermore, this process according to the invention is intended to sum up to the

Products have a lower carbon footprint than the combination of the known processes for the preparation of the products hydrogen, carbon and carbon, such as e.g. coal gasification and methane steam reforming to produce hydrogen, and oil refining to produce (pet) coke. The carbon footprint of

The inventive method should not be greater than when these products are made from petroleum or natural gas.

Coal is a natural product with a very different composition. In one

Reviews by D. Riedl in "deutsche-steinkohlenbergbau.de/site/- bildungsmedien / kohleheft.pdf" are the following areas for the chemical

Lignite composition indicated: carbon of 65-75% by weight, hydrogen of 8-5.5% by weight, oxygen of 30-12% by weight, volatiles of 60-43% by weight and calorific value of 7-13 MJ / kg. The Federal Association brown coal DEBRIV gives in

"Www.braunkohle.de/4-0-Zahlen-und-Fakten.html" the following further areas for the

German lignite: ash content of 2.5 - 20 wt%, water content of 40 - 60 wt% and sulfur content of 0.15 - 3.5 wt%.

Currently, lignite is used primarily for electricity generation. The lignite is burned, creating the climate-damaging carbon dioxide. Chemically, the Lignite via gasification and hydrogenation for the production of fuels, via charring and extraction as raw material for the chemistry, via coking for the

Iron production and via calcination used for the production of highly porous coals. The chemical use of lignite has, however, in recent years for reasons of cost in the background. The petroleum-based extraction of the former from coal

The product range from gasoline to waxes and tars to tar coke is more cost-effective since, for example, the handling of liquids is easier than that of

Solids. The use of lignite as a chemical raw material is currently still among many

 Reserved, seen & a. due to the relatively high carbon footprint of established methods. Therefore, there is currently a great need for methods that have a lower carbon footprint. In the future, on the one hand, due to the use of wind power and solar energy, a decline in the price of electricity will be expected and, on the other hand, the oil and gas reserves will become noticeably shorter in the foreseeable future, so that these raw materials will only be of limited use as chemicals - and

Energy resources are available. Countries such as Germany, Poland, Russia, China and the US have large coal deposits. Furthermore, for some of these countries, oil and gas are expensive import products.

In order to make use of coal as a raw material for the chemical industry, so far the following processes are described and partly combined: coal gasification, coal fumigation and coal coking. In DE 1 1 2010 003 184 T5 a method for gasifying a carbonaceous material is described in which the carbonaceous material with water vapor in

Presence of a catalyst at 650 to 700 ° C under a pressure of 35 bar. The generated gas mixture contains carbon monoxide, carbon dioxide, hydrogen and water as well as methane, which is thermally decomposed in a second stage into hydrogen and carbon. The generated carbon is returned to the gasification. The generated gas can be used after purification as a synthesis gas for methanol production or Fischer-Tropsch synthesis. A disadvantage of this method is the need for a catalyst and high pressures in the gasification reaction, which usually entail high investment costs. There is a risk that the generated

Carbon deposits on the catalyst and thus deactivates it.

From DE 2 553 760 B2 a process for the carbonization of granular coal for

Recovery of Schwelkoks, carbonization and by-products known in which the coal used pre-dried, preheated to about 300 ° C and then in a

Fluidized bed at about 600 ° C is geschwelt. Part of the resulting carbonization gas is withdrawn from the process, freed from the entrained coke dust, to a

Gas treatment plant performed in which the tar condensation and gas purification are performed. The discharged carbonization gas is used as heating gas. The other Part of the resulting carbonization is used for heating an exhaust gas stream, which serves for preheating the coal used, and then returned to the fluidized bed. The coke is in an Enderhitzer on a over the

750 ° C and then removed from the process. The exhaust gas produced during the final heating is used to pre-heat the coal to be smoldered. The produced tar oil can be used in the production of naphthalene, anthracene or phenanthrene. In this single-stage

Process is generated neither syngas nor carbon. Furthermore, DE 2 825 691 A1 discloses a process for the production of shaped coke in which a mixture of fine coal, grass and non-coke agglomerates is moved downwards in an oven and the mixture in one

Preheating section is heated to a temperature of 370 to 540 ° C to form Grus and initiate the release of the volatiles of the coal. The temperature of the preheated coal mixture is further increased within a devolatilizer furnace section to 650-1300 ° C to form discrete coke agglomerates of plastic consistency. The coke agglomerates are then cooled with carbon dioxide gases to a range of 315 to 40 ° C to cure the coke agglomerates. Then they are removed together with the grus from the oven, the coke agglomerates and the grus separated by sieves and the Grus in the oven cycle

recycled. The released in the heating of the coal or coke gases comprise at its discharge point, the volatile carbon constituents, carbon dioxide and different proportions of hydrogen and carbon monoxide depending on the gas temperature. Chemical use of the volatile carbon components is not disclosed. The parallel production of high-purity carbon is not possible with this one-step process.

EP 80 549 A2 discloses a process for obtaining pyrolysis gas from combustible materials, e.g. Plastic waste, crushed and subsequently in one

Verschwelungsreaktor be verschwelt at 400 to 600 ° C. The resulting carbonization gases are passed through a arranged in the heating of the Verschwelungsreaktors cracker and the larger gas molecules cracked in this without partial combustion at temperatures of 1000 to 1200 ° C, i. cleaved into smaller gas molecules without cleaving methane and thus without precipitating solid. The resulting cracking gases are then cooled and fed into a wet scrubber, where the impurities are deposited. These cracked gases are then energetically utilized, e.g. in a power plant. In this one-step process, the simultaneous production of syngas and high purity carbon is not possible.

From DE 10 201 1 1 13 504 A1 discloses a method for the chemical recovery of

Kokereigas known. In a coke oven coal is produced from coke, it is in the

Coke oven part of the volatile hydrocarbons in the coal by heating to a temperature of 900 to 1400 ° C pyrolyzed. The remainder of the volatile components are released and filtered off with suction. This is essentially made of carbon existing coke and a coke oven gas. The coke oven gas contains hydrogen, methane,

Nitrogen, carbon monoxide, carbon dioxide, sulfur and higher hydrocarbons. This gas is fed into a process for the formation of methanol and / or dimethyl ether. Even with this method, the production of separately from the coal, or the coke present high-purity carbon is not possible.

DE 10 201 1 106 645 A1 describes a process for producing and / or curing coke, in which a hydrocarbon-containing gas, preferably natural gas, is introduced into a reaction space. There it will be in the presence of a carbon-rich

Granules, e.g. Coal thermally decomposed into carbon and hydrogen. Of the

Deposited carbon deposits for the most part on the carbon-rich granules. In this document, the coal is used as an inert material for the deposition of thermally produced carbon. A utilization of coal as a chemical raw material is not described. There is no indication that the gas to be used would be coal carbonization or coal vaporization gas.

EP 2 987 769 describes a process for the production of synthesis gas in which carbon and hydrogen are obtained from hydrocarbon by thermal decomposition, wherein at least a part of the carbon obtained in a coal power plant for electricity production oxidizes and at least part of the hydrogen obtained with

Carbon dioxide is converted to carbon monoxide and water. Again, one will

Utilization of coal as a chemical raw material not described. There is no suggestion that the gas to be used in the thermal decomposition would be coal carbonization gas or coal vaporization gas.

In the book by Jörg Schmalfeld, The refinement and conversion of coal, technologies and projects 1970 to 2000 in Germany, German scientific society for oil, natural gas and coal registered association, P. 37, a procedure is described, with the uncleaned Kokereigas in the reactor a Kokstrockenkühlung system is initiated. at

Temperatures of 900 ° C, the higher hydrocarbons, but not methane and benzene, are split on the hot coke. The purified gas leaving the reactor is free of tarry components. The carbon excreted in the crude gas fission deposits on the coke. Thereafter, the coke oven gas is cooled, giving off its heat in a steam boiler, and subsequently partially returned to the reactor. The other part is delivered as a cleaned coke oven gas. With this method, it is not possible to cleave and chemically utilize the methane and benzene contained in the coking gas, e.g. as synthesis gas for the production of organic products. Furthermore, it is not possible to produce high-purity carbon present separately from the coal or the coke. In WO 2014/95661, the utilization of carbon dioxide and / or

Hydrogen-containing dome gases, such as or blast furnace gas from a blast furnace, converter gas from the crude steel production and / or coke oven gas from the pyrolysis of hard coal,

described. These gases are thermally converted to synthesis gas and possibly carbon, which attaches to a submitted carrier. There is no indication that the gas to be used would be coal carbonization or coal vaporization gas.

US 4,039,392 describes the charring of coal for the production of aromatics, tar acid and elemental sulfur. The charcoal produced after smoldering is burned. There is no description of a second thermal treatment of the carbonization gases that could provide synthesis gas and solid carbon.

WO 2013/2691 describes a combination of gasification and pyrolysis of

Substance mixtures containing organic components. That in the gasification of the

 Substance mixture resulting raw gas is introduced into a cracking reactor. In the cracking reactor, the raw gas is reacted in the presence of pyrolysis coke and the ash from the gasification with the aid of steam in synthesis gas. The pyrolysis coke is burned in a third step with air. Accordingly, no pyrolysis coke is discharged.

In the cited prior art, the residual coal and the volatile constituents obtained from it are partially thermally utilized, so that the carbon footprint is high, analogous to combustion of the feed coal. Only in the case of chemical utilization of the volatiles, e.g. DE 10 201 1 1 13 504 A1 discloses a reduced carbon footprint.

The invention is based on the object to develop a method that makes it possible from the large incidence of low-rank coal with low Kohlenohlungsgrad, especially with a molar H to C ratio in the water and ash-free coal greater than 0.6 , eg Brown coal, three high quality, separately available products such as

 Synthesis gas, high-purity carbon and a low-emission residual carbon with a total on the products related lower carbon footprint (carbon dioxide emissions) to produce than with the combination of known methods such. Coal gasification, coal coking, methane team reforming, oil refining. The synthesis gas can be used for example for the production of organic products, such as methanol, dimethyl ether, gasoline or diesel. The high-purity carbon can replace, for example, refinery petroleum coke.

The degree of coalification characterizes the chemical and physical properties of the coals such as water content, carbon content, volatile content, calorific value and vitreous reflection (Maceral). In general, the higher the carbon content in the water- and ash-free coal, the higher the rank of coal will be.

"High purity carbon" in this context means that the carbon content is greater than 99.9 mol%, preferably greater than 99.95 mol%.

In particular, it is intended to make it possible to produce liquid products such as methanol, dimethyl ether, gasoline or Fischer / Tropsch diesel with an at least equivalent carbon footprint than when produced from crude oil or natural gas. Thus, due to the According to the invention, the imports of crude oil or natural gas and hard coal for the production of electricity can be reduced. Hard coal mining has been gradually reduced in recent years in Germany and is scheduled to be fully phased out by 2018. However, as there is still a need for hard coal, coal is currently being imported.

Technically, the object is achieved according to the invention with a process for the parallel production of synthesis gas, carbon and a residual coal from a charcoal with a molar H to C ratio in the water and ash-free coal of greater than 0.5, achieved in that a first stage at least a portion of the volatile constituents of the feed coal are thermally expelled from the feed coal at temperatures of 500 to 1000 ° C and at least a portion of these volatile constituents in a second stage thermally at temperatures of 1000 to 1800 ° C to synthesis gas and carbon reacted and both reaction products of the second stage are discharged from the reactor, wherein the reaction of the second stage as

substoichiometric reforming and thermal decomposition is performed.

The temperatures in the first stage may be between 400 and 1200 ° C, advantageously between 600 and 900 ° C, preferably between 600 and 800 ° C, more preferably between 700 and 800 ° C, in particular about 750 ° C. With higher Verschwelungstemperatur the carbon content of the carbonization tends to decrease and the hydrogen content of the carbonization tends to increase; the oxygen content of the carbonization gas tends to be temperature independent (see "Experimental results of the dry distillation of a

Brown coal at various temperatures "by A. Naumann after experiments by W. Weber, Journal of Electrochemistry, Vol. 22, 1916, page 109).

The pressure in the first stage is preferably 1 to 25 bar, preferably 1 to 5 bar, in particular 1 to 2 bar.

Advantageously, 10 to 100%, preferably 30 to 70%, in particular 40 to 60%, of the volatile constituents expelled in relation to the anhydrous and ash-free feed coal. The content of volatiles to be driven can be adjusted by the temperature and pressure range, as well as the size of the

Charcoal particles and the degree of predrying of the coal used. Advantageously, the feed coal has a molar H to C ratio in the water- and ash-free coal of greater than 0.55, preferably greater than 0.6.

Since the oxygen present in the charcoal forms predominantly water in the smoldering with consumption of hydrogen, the charcoal can generally be given the formula CHxOy = CHx-2y + y H20 with: advantageously x - 2y = 0.50 to 0.75 are given. The "x-2y" value of the feed coal is preferably 0.55 to 0.7, in particular 0.6 to 0.65, and particularly preferred is lignite with an "x-2y" value of = 0.64. In general, the highest yield of volatile components is achieved for coals having the highest "x-2y" value, ie, for example, charcoal with x-2y = 0.72 However, since flame coal is significantly more expensive than eg lignite, the economic optimum is advantageous a mean "x - 2y" value. Advantageously, the residual coal has a molar H: C ratio of 0.3 to 0.8, preferably from 0.4 to 0.8, in particular from 0.5 to 0.7.

The "x-2y" value of the residual carbon is likewise advantageously 0.1 to 0.8, preferably from 0.2 to 0.7, in particular from 0.3 to 0.6. Reduces the value of the residual coal by 10 to 60%, preferably by 30 to 60% and in particular by 40 to 50% with respect to the "x - 2y" value of the feed coal.

As volatile constituents, also called carbonization gases, in particular hydrogen, methane, heavy hydrocarbons such as e.g. Brown coal smolder, carbon monoxide and carbon dioxide. In particular, gasoline, yellow oil, creosote oil, gas oil, paraffin oil, hard paraffin, soft paraffin, tar pitch and tar coke can be obtained from lignite smelters.

Due to the different composition of the starting educt "Einsatzkohle" the product yields and compositions are highly dependent on the type of carbon used and may possibly vary considerably.

In addition to the said preferred lignite, which is strictly speaking lignite, there are the following other possible carbons with the following compositions

(Water and ash-free calculated):

 c H O

 mol% mol% molar

Lignite: CHl, 20o, 28 40,9 47,3 1 1, 4

 Hard lignite CHo, 80o, 14 50.2 42.2 7.2

 Charcoal CHo, gOo, 09 50.9 44.1 4.6

 Gas flame coal CHo, 80o, 08 52.9 42.7 4.0

 Gas coal CHo, 60o, 05 56.1 40.7 2.9

 Charcoal CHo, 60o, 03 59.7 38.0 1, 9

Advantageously, the carbonization gas after the first stage has the following composition: hydrogen in the range from 30 to 50 mol% with respect to the total amount of carbonization gas, preferably from 30 to 45 mol%, in particular from 40 to 45 mol%; Methane in the range from 25 to 15 mol%, preferably from 20 to 25 mol%, heavy hydrocarbons in the range from 4 to 1 mol%, preferably from 3 to 4 mol%, carbon monoxide in the range from 10 to 20 mol%, preferably from 10 to 15 mol%, carbon dioxide in the range from 5 to 15 mol%, preferably in the range from 5 to 10 mol%.

The oxygen content of the carbonization gas is advantageously from 1 to 25 mol .-%, preferably from 2 to 20 mol .-%, in particular from 5 to 15 mol .-%.

In the first stage, less than 25 mol% of steam is preferably fed in relation to the optionally predried charge coal, preferably less than 10 mol%, particularly preferably less than 5 mol%; In particular, no water vapor is added in the first stage.

Furthermore, it is preferred that in the first stage less than 10 mol% of oxygen, with respect to the optionally pre-dried feed coal, is fed, preferably less than 5 mol%; In particular, no oxygen is added in the first stage.

Advantageously, the feed coal used in the first stage consists of predried lignite whose water content after drying is preferably between 0 and 25% by weight, more preferably between 1 and 15% by weight, most preferably between 2 and 12% by weight, in particular between 5 and 10% by weight. Pre-drying is advantageously carried out with the aid of a vapor compression, as in the

 Fluidized bed drying with integrated waste heat recovery, developed by the Rheinische Braunkohlewerke in Cologne (see www.rwe.com/web/cms/mediablob/en/535344/.../Stand- der-Entwicklung.pdf). The smoldering in the first stage advantageously converts the char to a low-emission residual coal that has a calorific value between 22 and 28 MJ / kg ashless, typically 24 to 26 MJ / kg. The low-emission residual coal is advantageously discharged from the Verschwelungsreaktor or the reactor region of the carbonization.

With this residual carbon, e.g. Imported coal with a typical calorific value of 28 to 30 MJ / kg or dried lignite be substituted. Low-pollutant in this context means that the residual carbon based on the initial amount of pollutants contains at least 10% less pollutants, preferably at least 30% less, especially at least 50% less than the feed coal.

Contain e.g. 1000g coal initially pollutant content of 5% by weight, so that is 1000 g x 0.05 = 50 g of pollutants. If 30% of the initially existing amount of pollutants escape from the coal during smoldering, the remaining coal contains only 50 g x 70% = 35 g pollutants.

A summary of pollutants and their concentrations in hard coal gives an "Analysis of heavy metal flows in hard coal mining - influence of coal species and of the load condition "by O. Rentz and Ch. Martel, www.fachdokumente.lubw.- badenwürtemberg.de After that, the pollutants As, Cd, Co, Cr, Cu, F, Hg, Mn, Ni, Pb, Sb , Se, V and Zn are also found in the ppm range, and lignites always contain as much as a few percent by weight of sulfur, and these pollutants are now at least partially used in power plants in coal-fired power plants

The atmosphere.

The first stage, the smoldering, can advantageously be carried out in a rotary kiln, shaft furnace fluidized bed or moving bed reactor. The production bed of the first stage is advantageously a packed bed of the coal used.

The term "fixed bed" is understood to mean when the solid reactor contents are not fluidized and at rest, the term "moving bed" when the solid reactor contents are not fluidized but move through the reactor, and the term "fluidized bed" the solid reactor contents are at least partially fluidized at least in the reaction zone and move through the reactor

Production bed understood when the solid reactor content in the reaction zone is at least partially fluidized and above and / or below the reaction zone of the solid

Reactor contents are moving, but no longer fluidized.

A preferred embodiment of the method according to the invention further provides that in the first stage the expulsion of the volatile constituents from the advantageous

Pre-dried feed coal in the presence of a moving from top to bottom bed from the feed coal and in countercurrent to from bottom to top, a gaseous recycle stream is performed. Advantageously, this circulation stream consists of the volatile constituents of the feed coal and, when starting the carbonization, has methane as the base gas, superheated steam and / or carbon dioxide, preferably methane and / or superheated steam, in particular methane. Before leaving the coal bed, this circulatory stream, which at this point with the volatile

Components enriched, by the entering advantageous pre-dried coal, preferably lignite, cooled, whereby this coal is heated. The cooling of the recycle stream enriched with the volatile components is expediently carried out only to the extent that no appreciable amounts of volatile components condense, the temperature to be selected depending on the gas composition and the pressure.

This enriched circulation stream, advantageously with a ratio of cycle gas to gas, which is introduced into the second stage, from 0.1 to 10, preferably 0.5 to 5, more preferably 0.75 to 2.5, in particular 1 to 2, is then advantageously separated into the recycle stream, which is recycled back into the lower end of the coal bed and into a stream which is advantageously fed without further treatment of the second stage. Further

Treatments could be targeted separations of components or compression of the gas stream. The recycle stream is advantageously further cooled to a temperature of advantageously 20 to 80 ° C. This condense water and the condensable organic components. The thus cooled and dried recycle stream occurs as a circulating stream at the lower end of the coal bed back into this and cools there the exiting residual coal.

The condensate from the recycle stream is advantageously separated in a phase separator into a water phase and an organic phase, wherein the organic phase is fed to the second stage in a suitable manner. The first stage energy supply can be both direct and indirect. The type of energy supply can be both electrical and thermal. Advantageously, the endothermic charring in the first stage is maintained by thermal energy.

In the case of direct thermal energy supply, part of the carbonization gases is advantageously oxidized. However, it is also possible that part of the hydrocarbon

Fill in the first stage is also oxidized. Serves as an oxidizing agent

For example, pure oxygen or oxygen-enriched air having an O 2 content of greater than 80% mol%, wherein pure oxygen is understood as meaning strongly enriched air having an O 2 content greater than 99 mol%.

A favorable embodiment is the following process: Gas is withdrawn from the hot area of the bed, burned in a combustion chamber with the oxygen and the hot flue gases back into the hot area of the bed

returned and distributed.

With the heat of combustion released during the oxidation, the heat of the carbonization is advantageously provided.

In the indirect thermal heat supply are beneficial in the beds

Heat exchanger installed. These heat exchangers may advantageously have both a plate shape and tubes. In the case of pipes, the beds can flow both in the pipes and around the pipes. In the case that the tubes are lapped by the beds, flows in the tubes, a hot flue gas, which gives off its heat through the tube wall to the beds and thereby cools when flowing through the tubes.

The advantage of indirect thermal heat input is that a low cost fuel can be burned at ambient pressure with air outside the reaction spaces.

Alternatively, advantageously, the heat required in the first stage to drive off the volatiles from the coal may be supplied by electric current. This can be done by electromagnetic induction or by passing electrical current through the bed of the feed coal, which serves as a resistor and thereby heated. Furthermore, the energy input can be effected by indirect electrical heating. A preferred variant of the method according to the invention consists in that the heat required in the first stage for expelling the volatile constituents from the coal is effected by indirect thermal heat supply by combustion of the feed coal or of the residual coal with air.

Particularly preferred is the indirect heating by hot flue gases. there

hot flue gases flow through heat exchanger tubes, which are lapped by the charcoal on the outside. The carbonization gases formed in the first stage are advantageously carried out without further cooling outside the reactor of the carbonization or the reactor region of the carbonization and advantageously without further work-up in the second stage. The sulfur compounds and other pollutants contained in the carbonization gases are also advantageously carried to the second stage, in which the thermal reaction takes place.

Advantageously, the volatiles cooled by the feed coal bed are removed at the top of the carbonization reactor. An alternative advantageous process control is to remove the volatile constituents from the hot region of the feed coal bed.

In a second stage, the volatile constituents, in particular the methane and the higher hydrocarbons, advantageously thermally reacted at temperatures preferably between 1000 to 1600 ° C and at pressures between 1 and 25 bar, in synthesis gas and carbon (see, for example, WO 2013/004398) ,

The temperatures in the second stage are advantageously between 1000 and 1600 ° C, in particular between 1 100 and 1300 ° C.

The pressure in the second stage is preferably 1 to 10 bar, in particular 1 to 5 bar. Advantageously, the pressure in the second stage is 0.01 to 2 bar, preferably 0.01 to 1 bar, preferably 0.01 to 0.5 bar lower than the pressure in the first stage. Advantageously, the first and second stages are thus carried out at a similar pressure level.

Advantageously, the thermal reaction of the second stage in the presence of solid

Support materials, preferably heat transfer materials carried out, on which the carbon formed in the cleavage reaction of the hydrocarbons primarily, in particular greater than 90% with respect to the maximum pyrolyzable

Carbon content of the carbonization gas, adsorbs. These solid supports can be used for regenerative heat integration.

The production bed is advantageously a packed bed of solid support materials. The second stage, the thermal decomposition, can advantageously be carried out in a fixed bed, fluidized bed or moving bed reactor, wherein the term "fluidized bed" also includes a Production bed is understood when the solid reactor content in the reaction zone is at least partially fluidized and above and / or below the reaction zone of the solid reactor contents moves, but no longer fluidized. The support materials of the production bed are advantageously temperature-resistant in the range from 1000 to 1800 ° C., preferably from 1300 to 1800 ° C., more preferably from 1500 to 1800 ° C., in particular from 1600 to 1800 ° C.

As temperature-resistant carrier materials advantageously come e.g. ceramic

Carrier particles, in particular materials according to DIN EN 60 672-3 such. Alkali aluminum silicates, magnesium silicates, titanates, alkaline earth aluminum silicates, aluminum and magnesium silicates, mullite, aluminum oxide, magnesium oxide and / or zirconium oxide. Furthermore, non-standard high performance ceramic materials such as e.g. Quartz glass, silicon carbide, boron carbide and / or nitrides serve as a temperature-resistant support materials. These heat transfer materials can be compared to the deposited thereon

Carbon have a different expansion capacity.

Furthermore, the use of carbonaceous material, as granules, is advantageous. In the present invention, a carbonaceous granulate is to be understood as meaning a material which advantageously consists of solid grains which are at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of carbon, more preferably at least 95 wt .-%, in particular at least 98 wt .-% carbon. The carbonaceous granules are advantageously spherical. In the method according to the invention, a multiplicity of different carbonaceous granules can be used. For example, such granules may consist predominantly of coal, coke, coke breeze and / or mixtures thereof. Further, the carbonaceous granules 0 to 15 wt .-% based on the total mass of the granules, preferably 0 to 5 wt .-%, metal, metal oxide and / or ceramic.

The ammonia contained in the carbonization gases is advantageously decomposed in the second stage into nitrogen and hydrogen. In the thermal reaction, the methane and the higher hydrocarbons are largely reacted in an endothermic reaction, advantageously greater than 90% in synthesis gas and carbon due to the high temperatures. To the higher ones

Hydrocarbons include, but are not limited to, crude tar, naphthalene and BTX (mixture of benzene, toluene and xylenes). These products are preferably reacted in a thermal conversion to methane.

The area in which the methane conversion is to be adjusted depends primarily on the nature of the subsequent processes. The methane conversion can be controlled by the selected pressure and Setting the temperature. It may be advantageous, for example, to not react methane in pyrolysis above 95% and then to discharge the unreacted methane in the subsequent process step. This may be advantageous, for example, if the subsequent process requires a cycle gas process, such as the methanol synthesis or the Fischer-Tropsch process, or the separation of the methane from the pyrolysis in the subsequent process, for example by a pressure swing absorption or a temperature swing absorption, with a lower Effort is possible, as in pyrolysis.

The thermal conversion in the second stage is advantageously a "substoichiometric reforming." Here, sub-stoichiometric reforming means that the O content of the process gas, including the carbonization gases (volatile constituents of the feed coal) and optionally oxygen for autothermal heating, is not in the second stage In substoichiometric reforming, the molar C: O ratio is greater than 1: 1. The choice of the concrete substoichiometric ratio depends on the desired synthesis gas product stream Synthesis gas (consisting of H2, CO, C02, H20) always also a solid carbon-containing phase

Reaction products are discharged from the reactor or the reaction zone of the thermal reaction.

In the thermal reaction of the second stage, the oxygen-containing react

Components of the carbonization partially, depending on the selected pressure, with the carbonaceous components according to the reaction equations:

H ₂ 0 + C = CO + H ₂ gasification x H ₂ 0 + CxHy = x CO + (x + y / 2) H ₂ reforming

C0 ₂ + C = 2 CO Boudouard reaction

In the equation for reforming, x may advantageously be between 1 and 30 and y advantageously between 2 and 60.

The carbonaceous components due to the substoichiometric

Ratio were not reformed, are thermally decomposed according to the following reaction equation:

-►CH ₄ C + 2 H ₂

- ^► Cx H _Y x C + y / 2 H ₂

The ammonia is decomposed during the thermal reaction at least partially, depending on the selected temperature and the pressure in nitrogen and hydrogen.

- ^► 2 NH 2 N ₂ + 3 H ₂

At the selected temperatures of 1000 to 1600 ° C in the second stage, the balance of the Boudouard reaction is on the side of carbon monoxide. To the Reverse reaction of the carbon monoxide to avoid carbon dioxide, the hot product gas of the second stage is advantageously cooled as quickly as possible; this cooling can be carried out particularly preferably by a direct heat transfer from the hot product gas to the cold bed of support materials.

Accordingly, the hydrogen to carbon ratio can be adjusted by the pressure chosen due to the reforming reactions to the requirements of the subsequent processes. Depending on the heating concept, the carbon formed in the pyrolysis forms in the gas phase or on the support materials and settles on these and is discharged from the pyrolysis reactor. The carbon is now in a high purity state and may be e.g. Replace refinery petroleum coke. The process of the second stage is advantageously carried out without the presence of a technical catalyst, wherein a technical catalyst is characterized in that it is produced and used in a targeted manner.

The energy supply to the second stage, the thermal conversion, can also be done both directly and indirectly. Moreover, the type of energy input can be both electrical and thermal.

The direct electrical energy supply can be done both inductively and ohmic. In both cases, the respective carbonaceous beds represent a corresponding resistance. It is preferable in the case of the invention, the ohmic variant, since in this case all electrical losses that arise from the end of the external power supply, directly benefit the heating of the beds.

The beds can be designed both as a fluidized bed, moving bed or as a fixed bed, in the case of direct electrical heating, the fixed bed variant is preferable.

In a preferred embodiment, two electrodes are installed in the beds, between which the beds act as an electrical resistance and heat up as the current passes through the electrical feedthrough losses. Of the

Current flow can take place both transversely to the flow directions of the beds and longitudinally thereto.

In the indirect electrical energy supply electric heating elements are lapped by the respective beds. These electric heating elements heat up when electricity flows through them and release this heat to the surrounding beds.

In the direct thermal energy supply, a portion of the pyrolysis or reforming gases is mainly oxidized. But it can not be ruled out that part of the carbonaceous bed in the second stage is also oxidized. The oxidizing agent used is, for example, pure oxygen or oxygen-enriched air having an O 2 content of greater than 80 mol%, where pure oxygen is understood as meaning strongly enriched air having an O 2 content greater than 99 mol%.

The heat of combustion of the above-mentioned endothermic reactions is advantageously provided by the heat of combustion released during the oxidation.

A favorable embodiment is the following process: Gas is withdrawn from the hot area of the respective bed, burned in a combustion chamber with the oxygen and the hot flue gases are redistributed into the hot area of the bed.

In the indirect thermal heat supply are beneficial in the beds

Heat exchanger installed. These heat exchangers may advantageously have both a plate shape and tubes. In the case of pipes, the beds can flow both in the pipes and around the pipes.

In the case that the tubes are lapped by the beds, flows in the tubes, a hot flue gas, which gives off its heat through the tube wall to the beds and thereby cools when flowing through the tubes.

The advantage of indirect thermal heat input is that a low cost fuel can be burned at ambient pressure with air outside the reaction spaces. The detailed description of the electric heating of the second stage, the thermal conversion, also applies to the first stage, the smoldering.

Furthermore, it is advantageous that the heat required in the second stage for thermal conversion of the components expelled from the coal is supplied by electric current and / or oxygen addition for an oxidation process. Also in this case, the heat supply can be done by electromagnetic induction or by

Passing electrical current through the carbon-rich granules, which acts as a resistor and heats up. Another possibility of heat supply is the heating of a gas in an outside of the reaction space

arranged heating device by means of an arc and subsequent introduction of the heated gas stream into the reaction space.

A further embodiment of the method according to the invention provides that in the second stage, the thermal conversion of methane and the higher

Hydrocarbons, used heat transfer material advantageously from a

carbon-rich granules, which is recycled.

Conveniently, the bed of carbonaceous granules is designed as a moving or fluidized bed. This bed is called carbon bed in the following. A further variant of the process according to the invention provides that the conversion of the volatiles expelled from the coal into synthesis gas and high-purity carbon takes place in the presence of a bed of carbon-rich granules moving from top to bottom, which at least partially recirculates becomes. In countercurrent to the expelled from the feed coal volatile components are passed whose gaseous reaction products after pyrolysis and gasification or reforming at the upper end of the carbon bed through the

incoming carbon are cooled and discharged there, the

Carbon at the lower end is discharged more or less hot.

In this case, it is again expedient that the hot carbon emerging at the lower end of the second stage is cooled by an inert gas stream which flows to the

Predrying the coal used and is used in the circuit after condensation of the water again to cool the hot carbon.

However, the hot inert gas stream for cooling the exiting hot carbon can also be used to generate steam. This steam can be used on the one hand in the workup process of the process for the conversion of the synthesis gas to methanol or dimethyl ether or for the production of electricity.

Since all conversion processes require energy, it is advantageous to have that

Inventive process according to the invention as a hybrid process, so that it can be operated with regenerative excess current (see WO

2014/090914). In the hybrid process, the reactors, or reaction areas for both stages (charring and thermal conversion, i.

 Pyrolysis, gasification, reforming, Boudouard reaction) each equipped with two heating systems, in particular with an electric and a non-electric heating system. In times of surplus regenerative electricity both stages are heated electrically. In the remaining time by any of the above

described heating systems. This can reduce the carbon footprint of the

Overall procedure be further reduced.

A further embodiment of the method according to the invention provides that the synthesis gas leaving the second stage is desulfurized and purified (in "Chemische Technik, Prozesse und Produkte, Volume 4, Winnacker-Kuchler, 5th edition, Wiley-VCH, p. 353 et seq. ). In this case, the sulfur compounds and the other in the

Gas mixture present pollutants, such as mercury, from the

Gas mixture removed. The present after the desulfurization and purification gas consists mainly of hydrogen and carbon monoxide and possibly partially back-reacted

Carbon dioxide, preferably greater than 80 mol%, more preferably greater than 90 mol%, in particular greater than mol 95% of hydrogen and carbon monoxide or

Carbon dioxide, wherein the content of re-reacted carbon dioxide is less than 5% of

Carbon monoxide exists in terms of the anhydrous gas after the exhaust gas purification. An improvement of the method according to the invention is that the process is operated by controlling, inter alia, water content of the feed coal, temperature and pressure of the respective stages such that the gas present after desulfurization and purification has a hydrogen-carbon monoxide ratio corresponding to the requirement of greater than 2. For this purpose, this gas is additionally supplied with carbon dioxide when used for the synthesis of, for example, methanol, dimethyl ether, gasoline or Fischer / T ropsch condensate, so that this process represents a carbon dioxide sink. Through the extraction of solid carbon and its discharge from the

 Processes, it is possible that the products of the synthesis gas (e.g., fuels) and the products of the residual coal (e.g., electricity) have an overall lower carbon footprint than products from coal fuming and / or coal gasification without pyrolysis.

Due to the low carbon footprint, the inventive method allows new opportunities for the use of lignite. Thus, in the production of synthesis gas from lignite less carbon dioxide is released than in the known processes of coal gasification (see Figure 6).

A further advantage of the method according to the invention is the possibility of producing, on the one hand, highly pure carbon and, on the other hand, low-emission residual coal with a relatively high calorific value (about 26 GJ / t ashless). As with the

Smoldering a part of the volatile pollutants such as sulfur and mercury are expelled with the volatile components from the dry coal, the remaining carbon is more environmentally friendly than the lignite used. Due to the volatility of mercury and hydrogen sulfide or COS, they remain

Pollutants in the pyrolysis in the gas phase and can be separated in the following from this by known methods.

The process according to the invention offers a long-term perspective for low carbon dioxide production of chemical products, liquid fuels, pure carbon as

Petcoke replacement for coking plants or electrode production for the aluminum industry and low-emission coals for power generation to offset fluctuating renewable energies. The value of the invention is not the highest

 But to create value from lignite without polluting the environment with C02.

That it is theoretically possible to convert lignite into liquid products such as methanol,

Dimetyl ether, gasoline or Fischer's T ropsch condensate, and thereby to reduce the C02 content of the atmosphere, shows Example 1, in which methanol, ie CH30H, the product is (see Figure 1). Methanol (shown in the top left of FIG. 1) requires the preparation thereof

Input materials carbon and hydrogen. The carbon may e.g. by CO2 to

Are provided (in Figure 1 top left), which is withdrawn from the atmosphere and the hydrogen can be withdrawn from the brown coal (bottom left in Figure 1).

Lignite has approximately twice as high hydrogen content as hard coal in terms of carbon content. Thus lignite typically have a molar ratio of H to C-1, 2 (hence the formula CH1 2) and coal of only 0.6 (hence the formula CH _0, 6). If the brown coal is withdrawn half of its hydrogen, a residual carbon remains (bottom right in the figure), which has about a molar H to C ratio as hard coal.

If the residual coal is sequestered (i.e., returned to the earth) as shown in Figure 1, then fossil CO2 is not produced from lignite production. CO2 is even consumed in relation to the entire process up to methanol.

The present inventive method is shown abstracted in Figures 7 and 8.

With regard to the carbon footprint, it basically makes no difference whether the pure carbon and the low-emission residual coal are ultimately re-sequestered or whether they can replace other fossil raw materials in other processes and that these fossil raw materials can remain in the earth. For example, could be the high purity carbon

replace petroleum-based petcoke in coking plants or during electrode production. Furthermore, it could be useful, e.g. In coal-fired power plants, residual coal with low-emission emissions takes place

Imported coal can be used. For this, the not yet subsidized import coal could be left in the earth. Because only in the promotion and transport of

Imported coal become It. European Reference Life Cycle Database (ELCD 3.0,

http://eplca.jrc.ec.europa.eu/7pape_id126) released an average of 0.43 t of CO2 per ton of imported coal. This value applies to Germany.

Examples:

 1 a) Carbon footprint compared to coal gasification:

This is illustrated by a comparison (FIG. 2a). In this computational comparison, the principle should be clarified, so that no losses and no conversion energies are taken into account, but only the atomic balance.

The mathematical comparison is based on experimental results, which in the Journal of Electrochemistry, Vol. 22, 1916, "Experimental results of the dry distillation of a

Brown coal at different temperatures "by Alexander Naumann, published after experiments by Wilhelm Weber An evaluation of the results shows that a smoldering temperature of 750 ° C is particularly advantageous for the investigated brown coal of the Ludwigshoffnung mine near Wölfersheim in the Wetterau Experimental evaluation shows that lower carbonization temperatures lead to a lower carbon footprint overall, but also to lower yields in terms of gasoline and high-purity carbon. Higher carbonization temperatures have the opposite effect.

Considering only the atoms C, H and O, the evaluation of the tests for the lignite used the chemical formula CH1 2O 0.3 and at a

750 ° C for the remaining carbon the chemical formula CH ₀ , 6O 0.2, wherein in the experiment at 750 ° C molar about 70% of the C ^' s remained in the remaining coal.

Fuel, such as diesel, consists mainly of molecules with the chemical formula (CH2) n. As the smallest characteristic molecule piece for a liquid fuel, therefore, CH 2 can be used. By way of example, 1 mol of CH ₂ should now be prepared from CH ₂ O, 0.3, in comparison once by the process according to the invention and once by coal gasification:

It is assumed that the carbonization gases consist only of CH4, H2 and CO. Taking into account only the material balance, then theoretically required for the process according to the invention 5.45 mol CHi, 20 0.3. Since 70% of the C ^' s remain in the remaining coal, this results in a residual carbon amount of 5.45 x 0.7 = 3.82 with the chemical formula CH ₀ , 6O 0.2. This results in the molar material balance for the smoldering

5.45 CHi, ₂ 0 0.3 = 3.82 CH ₀ , ₆ O 0.2 + x CH ₄ + y H ₂ + z CO.

The atomic balances result in the following values: x = 0.76

y = 0.60

z = 0.87 The volatile components are then pyrolytically decomposed to 0.76 mol C and to a synthesis gas with the composition of 0.87 mol CO and 2.12 mol H2.

However, the preparation of 1 mol of CH ₂ requires a molar ratio of CO: H 2 of 1: 2. This molar ratio can be achieved by adding 0.13 mol of CO 2 (eg from the atmosphere). This results in the following reaction equations:

0.13 mol CO ₂ + 0.87 mol CO + 2.12 mol H ₂ = 1, 00 mol CO + 2.00 mol H ₂ + 0.12 mol H ₂ 0

And finally 1 mol CO + 2 mol H ₂ = 1 mol CH ₂ + 1 mol H ₂ 0.

3.82 mol of residual carbon and 0.76 mol of C together give 4.58 mol of a mixture with the chemical formula CHo, 50o, i7. Sequestrate this mixture of solid

Coal components, then from 0.87 mol (= 5.45 mol - 4.58 mol) of fossil C and from 0.13 mol C0 ₂ theoretically 1, 00 mol CH2 can be prepared. For example, the C0 ₂ is removed from the atmosphere. Coal gasification:

For comparison, one theoretically requires for the preparation of 1, 00 mol CH ₂ over

Coal gasification 1, 30 mol brown coal with the composition CHi, ₂ 0 0.3. In order to reach the required molar ratio of CO: H ₂ = 1: 2 by gasification one needs additionally 1, 22 mol H ₂ 0 according to the gross reaction equation:

1, 30 mol CHi, ₂ 0 0.3 +1, 22 mol H20 = 1, 00 mol CO + 2.00 mol H2 + 0.30 mol CO2

That is, for the production of a synthesis gas by coal gasification, which theoretically yields 1 mol of CH ₂ , you need 1.30 mol of fossil C and generates at least 0.30 mol of CO ₂ , which is released into the atmosphere.

Thus, while the coal gasification theoretically releases 0.3 mol of CO ₂ into the atmosphere per mol of CH ₂ , in the process according to the invention, 0.13 mol of CO ₂ can theoretically be

Atmosphere be withdrawn.

Table 1: Preparation of 1 mol CH 2

1 b) Cost comparison for coal gasification without carbon footprint (carbon dioxide emission = 0)

The value of the invention is not in the highest value added, or proceeds from

But to achieve a value added from lignite, without polluting the environment with C02. It is also possible to chemically utilize the coal without a carbon footprint with the help of coal gasification, but in addition to 1 mole of CH1, 20 0.3 per mole of CH2, in addition to water it also requires 0.7 mol of hydrogen without a carbon footprint. This variant is shown in FIG. 2b. Comparing the novel process with coal gasification with the addition of hydrogen without a carbon footprint, a simple economic comparison shows that the process according to the invention has a higher added value or revenue. This comparison is shown in Table 2.

If the values in FIGS. 2a and 2b are not based on 1 mol of the end product CH2 but on 1 mol of the charcoal CH1, 20 0.3, the process according to the invention gives 0.18 mol CH2 (= 1 / 5.45) , 14 mol pyrolysis C (= 0.76 / 5.45) and 0.70 mol residual carbon (= 3.82 / 5.45).

In the case of conventional coal gasification (with CO 2 production) are from 1 mol

CM, 20 0.3 0.77 mol CH2 (= 1/1, 30) and in the case of coal gasification without C02-

Production are won 1, 00 mol CH2. Taking usual prices for the products, e.g. 600 € / t petroleum, 200 € / t pyrolysis-C and 50 € / t residual coal can be calculated for 1 Mmol coal application.

Table 2: Comparison of revenues

Products Prices Mmol per t Total price C02- Mmol output per

Charcoal Mmol

 carbon charge

inventive

 example

 Remaining coal 50 € / t 0,70 1 1, 1 555 € / t

 Pyrolysis- 200 € / t 0.14 1, 7 340 € / t

 carbon

 Fuel 600 € / t 0,18 2,5 1500 € / t (CH2)

 Total 2395 € / t -24 km ol

Gasification with

 C02 emissions

 Fuel € 600 / t 0,77 10,8 6468 € / t +230 kmol (CH2)

 gasification

without CO 2 emission Electrolysis 4700 -0.70 -1, 4 -6580 € / t

 Hydrogen € / t

 (Wind park)

 Fuel 600 € / t 1, 00 14.0 8400 € / t

 (CH2)

 Total 1820 € / t 0 kmol

In the case of the method according to the invention, the proceeds after this calculation is 2395 €.

For conventional gasification, this revenue is much higher after this calculation, namely € 6468. In this conventional gasification, however, large amounts of CO2 are released into the atmosphere, which is why this process is also heavily criticized by the public.

For coal gasification without C02 production, 0.7 mol of hydrogen without carbon footprint is required. Such a hydrogen would have to be obtained 100% from regenerative energy. Hydrogen obtained electrolytically directly on site at a wind farm would be e.g. such a. After a publication in Chem. Eng. Technol. 2016, 39, no. 6, 1 185-1 193 The cost of such a hydrogen without the considerable logistical costs of 4,700 € / t costs such a large amount of hydrogen because the storage and transport of hydrogen is very costly is expensive.

Even without considering the expensive hydrogen logistics, in the case of CO 2 -free coal gasification according to this calculation, only a revenue of 1820 € / mol

In contrast to the process according to the invention, the use of charcoal yields proceeds of € 2,395 (~ 30% more) and, moreover, has the potential to even remove CO 2 from the atmosphere.

2) Carbon footprint compared with oil-based processes:

The fact that the method according to the invention with respect to the carbon footprint is at least comparable with oil-based methods should be clarified by a further mathematical comparison (see FIG. 3). This comparison is based on the one hand on the experimental results as in the example in Figure 2, on the other hand on simulation results, which was created using a thermodynamic simulator (analog ASPEN).

The carbon footprint value for electric current corresponds to 0.30 t C02 / MWh _e i the expected value, which was calculated by the Federal Ministry for the Environment, Nature Conservation and Nuclear Safety, Berlin 2007 (J. Nitsch, Renewable Energy Saving Strategy - Leistudie 2007)

Mains electricity in 2030 in Germany was predicted. The carbon footprint values for the upstream chains are taken from the European Reference Life Cycle Database (ELCD 3.0, http://eplca.jrc.ec.europa.eu/7pape_id126).

In the comparison, in both cases, both in the method according to the invention and in the reference method which is the state of the art, the same quantities of product and energy, i. the sum of combustibles with one

Total calorific value of 4.68 SKE, produced 1, 0 t of gasoline and 4.68 t

Hard coal units (SKE).

 According to the invention, 20.48 tons of wet brown coal are used, from which 1.00 tons of gasoline are produced in a methanol to gasoline (MTG) process, 0.57 tons of pyrolysis coke and 5.94 tons of residual coal. In total, the pyrolysis coke and the residual coal correspond to 4.30 t hard coal units. This produces 1, 23 t of carbon dioxide. According to a comparative example with a known method, refinery of 1, 09 t of crude oil produces 1, 00 t of gasoline. This fall with the comparative provision of 4.30 t

Coal units totaling 2.62 tons of carbon dioxide, i. over 1 13% more than in the method according to the invention. This high carbon dioxide attack is mainly due to the

Attributed to the extraction and transport of imported coal and to the emission of carbon dioxide in the extraction of oil, the partial burning of the associated associated gas and the long transport routes for the oil in the pipeline or by ship.

Table 3: CO2 comparison of production for each 1, 0 t of gasoline and 4.68 t

coal equivalent

The process according to the invention also opens up the possibility of excess current

to be used profitably. In the present case, the process requires 3.81 MWh _e i. With a carbon footprint of 0.35 t CO MWhei for grid current, this results in 1.33 t of CO2, which can be saved if the process is operated with purely regenerative electricity. In total, the process then becomes a C02 sink, because 1, 33 - 1, 23 = 0.10 t of CO2 have to be fed into the process from the outside.

Embodiment:

An embodiment of the invention is shown schematically in the accompanying drawings (Figure 4) and is explained in more detail below with reference to the material balances (Figures 4a to 4c). The example is based on simulation results obtained with the help of a thermodynamic simulator (similar to ASPEN) as well as on the ones already cited above

experimental results published in the Zeitschrift für Elektrochemie, Vol. 22, 1916, "Experimental Results of the Dry Distillation of a Lignite at Various Temperatures" by Alexander Naumann, after experiments by Wilhelm Weber.

About the coal feed 1 1000.7 kg wet lignite with a water content of about 58% are promoted in the dryer 2. In the dryer 2, the largest part, i. 529.8 kg of 578.5 kg = 92%, of the water physically bound in the feed coal. This leaves the dryer 2 via the steam line 3. About the dry coal feed 4 are 470.9 kg of dried coal, which now has a water content of 46.7 kg, a carbon content of 225.0 kg, an ash content of 83.3 kg and a calorific value of 19.0 GJ / t, promoted in the Schwelreaktor 5.

In the carbonization reactor 5 is a coal bed, which moves due to gravity from top to bottom. Since the migrating coal is simultaneously fluidized by flowing gas, the carbon bed is a fluidized bed. Countercurrent to the downwardly moving coal, it flows against a recycle gas. This enters the carbonization reactor 5 at its lower part, heats up in the flow, wherein it cools the exiting residual carbon. At the upper part of the carbonization reactor 5, the hot recycle gas, which now also contains the volatile components, heats the incoming charge coal, cooling itself to such an extent (see FIG. 4b, 239 ° C.) that no appreciable amounts of volatile components condense out.

In the carbonization reactor 5 is at a pressure of 5.0 bar and a temperature of 750 ° C, a carbonization process, which can also be referred to as a distillation process, instead. In order to generate the heat required for the smoldering process, 59 kWh of electrical energy are supplied to the smoldering process. At a temperature of 750 ° C, the volatiles are expelled from the coal. This produces 290.2 kg low-emission

 Residual coal with an ash content of 83.3 kg, a sulfur content of 0.2 kg and a calorific value of 18.7 GJ / t. This corresponds to 26.2 GJ / t ashless. This residual coal is removed via the residual coal discharge 6 from the carbonization reactor 5. The residual coal can be used for the substitution of hard coal or dried lignite.

The smoldering process takes place in the carbonization reactor 5 under exclusion of air and without

Water vapor addition instead. The smoldering process produces 151, 9 kg of carbonization gas. This consists of hydrogen, methane, higher hydrocarbons such as BTX (mixture of benzene, toluene and xylenes), carbon monoxide, carbon dioxide, oxygen, nitrogen,

Water vapor, hydrogen sulfide, ammonia, mercury and other pollutants.

At the upper part of the carbonization reactor 5, the carbonization gas is removed together with the recycle gas (349.7 kg) via the carbonization line 7. Of these, 215.8 kg are diverted and after drying to give 46.8 kg of carbon monoxide, recycled as recycle gas (168.9 kg) back into the lower part of the carbonization reactor 5. 133.9 kg of carbonization are passed directly into the pyrolysis reactor 8 at a pressure of 5 bar without cooling or other treatment. The carbon black condensate is separated in a phase separator into 28.8 kg of condensate water containing carbon dioxide and ammonia and 18.0 kg of organic condensate consisting of higher hydrocarbons. The organic condensate is fed into the pyrolysis reactor 8 together with the carbonization gas. In the pyrolysis reactor 8 is a heat transfer material, which consists in a variant of the method of ceramic balls and is used for heat integration. In this pyrolysis reactor 8, the supplied carbonization gases are thermally at a temperature of 1400 ° C and a pressure of 5 bar in a second stage of the process

pyrolyzed endothermic reaction. Due to the high temperatures, the methane and the higher hydrocarbons, such as BTX (mixture of benzene, toluene and xylenes) and tar, are decomposed into hydrogen and carbon. Ammonia contained in carbonization gas is also decomposed into nitrogen and hydrogen. Since the carbonization gas also contains oxygen-containing components such as H ₂ 0 and CO ₂ , gasification and reforming reactions take place in the pyrolysis reactor.

The precipitated in the pyrolysis of the gas mixture carbon settles on the heat transfer material. Since the heat transfer material another

 Thermal expansion behavior than the carbon deposited thereon, this can be relatively easily removed from the heat transfer material. This carbon is now in a highly purified form as a pyrolysis coke. It is a high-quality product that can replace refinery petroleum coke and be used, for example, for electrode production. It is removed via the carbon line 1 1 from the pyrolysis reactor 8.

In the pyrolysis reactor 8, the heat transfer material moves by gravity from top to bottom. It is being circulated. The carbonization gas coming from the carbonization reactor 5 is passed into the lower part of the pyrolysis reactor 8 and flows upwards in this in countercurrent to the heat transfer material. Since that in the upper part of the

 Pyrolysis reactor 8 abandoned heat transfer material is relatively cold, the present after the pyrolysis gas mixture cools and thereby heats the heat exchange

Heat transfer material. In contrast, the carbon that is at the bottom of the

Pyrolysis reactor 8 exits through the carbon line 9, still hot. He has one

Temperature of about 292 ° C on. It is cooled by a recirculated inert gas, for example nitrogen.

Since the pyrolysis reaction is endothermic, heat must be constantly supplied to the pyrolysis reactor 8. This is done via an electric heater, which converts 73 kWh _e i into heat.

Alternatively, it is possible outside of the pyrolysis reactor 8 to heat a gas stream by means of an electric arc and the heated gas stream in the Initiate pyrolysis reactor 8. Another economically and ecologically interesting

Possibility of heat supply is to burn a part of the reactants with pure oxygen. Modification of the example:

In another variant of the method, the heat transfer material used in the pyrolysis consists not of ceramic balls, but of a carbon-rich granules, e.g. consists of pyrolysis and is recycled. This 235 kg pyrolysis are recycled. This pyrolysis coke forms in the pyrolysis reactor 8 a coke bed, which is designed as a moving or fluidized bed. The pyrolysis coke is charged at the top of the pyrolysis reactor 8 and moves downwards during pyrolysis due to gravity. The carbonization gas, which at the lower part of the

Pyrolysis reactor 8 is abandoned, flows upwards. It will be up to

Decomposition temperature of the hydrocarbons heated. After reaching the

Decomposition temperature, the hydrocarbons decompose almost completely into carbon and hydrogen. The carbon which separates out deposits on the pyrolysis coke. The pyrolysis coke consists of a pure and high-quality carbon. It is removed via the carbon line 9 from the pyrolysis reactor 8. This will be 28.1 kg

Pyrolysis coke with a calorific value of 34.0 GJ / t and a temperature of 292 ° C

led away. The heat of the hot pyrolysis coke is used to dry the feed coal in the dryer 2.

The present in the second stage after the pyrolysis gas mixture contains mainly hydrogen, carbon monoxide, ammonia, water vapor, hydrogen sulfide, residual methane and other pollutants, such as mercury u. Like. 137.8 kg of this gas mixture are compressed to about 71 bar and then with a temperature of 190 ° C over the

Gas mixture line 10 to the pollutant separation 1 1 out. There, the gas mixture is desulfurized and purified, the pollutants 12 are separated. This 3.4 kg of pollutants 12 are removed. The purified gas mixture is now a synthesis gas. This is conducted via the synthesis gas line 13 to the synthesis reactor 14. The

Synthesis gas is the starting material for syntheses for the production of various organic products, such as methanol, dimethyl ether, gasoline and diesel via Fischer / Tschopsch synthesis.

In order for the necessary for the syntheses hydrogen carbon monoxide ratio of 2 is present, 13.0 kg of additional carbon dioxide from a foreign source on the

Carbon dioxide line 15 introduced into the synthesis reactor 14. Including the

Carbon dioxide are passed a total of 150.8 kg of synthesis gas in the synthesis reactor 14. The synthesis products, such as methanol, dimethyl ether, gasoline and diesel, are led away from the synthesis reactor 14 through the product line 16.

Claims

claims:

1. A process for the parallel production of synthesis gas, carbon and carbon from a charcoal with a molar H to C ratio in the water and ashless coal greater than 0.5, characterized in that in a first stage, at least a portion of the volatile Components of the feed coal are thermally expelled from the feed coal at temperatures of 500 to 1000 ° C and at least a portion of these volatile components are subsequently thermally reacted in a second stage at temperatures of 1000 to 1800 ° C to synthesis gas and carbon and both reaction products of the second stage be discharged from the reactor, wherein the implementation of the second stage as

 substoichiometric reforming and thermal decomposition is performed.

2. The method according to claim 1, characterized in that the temperatures of the first stage are 600 to 800 ° C.

3. The method according to claim 1, characterized in that the temperatures of the first stage are 700 to 800 ° C.

4. The method according to at least one of claims 1 to 3, characterized in that the coal used in the first stage consists of pre-dried lignite whose water content is between 0 and 25%.

5. The method according to at least one of claims 1 to 4, characterized in that the second stage in the presence of a heat carrier, which is temperature resistant in the range of 1000 to 1800 ° C.

6. The method according to at least one of claims 1 to 5, characterized in that in the second stage, a non-catalytic substoichiometric reforming is carried out.

7. The method according to at least one of claims 1 to 6, characterized in that in the first stage, the expulsion of the volatile constituents from the

 Charcoal in the presence of a moving from top to bottom, possibly partially fluidized bed of feed coal takes place and in

 Countercurrent to from bottom to top, a gaseous circulation stream is performed.

8. The method according to claim 7, characterized in that the circulation stream consists of a part of the expelled volatile constituents in which a part of the volatile constituents of the feed coal is cooled to a temperature of 20 to 80 ° C, wherein the thereby condensable components are separated and the remaining residual gas is recirculated as a recycle stream to the first stage.

9. The method according to claim 7 or 8, characterized in that the moving bed of feed coal is designed as a moving bed or as a fluidized bed, wherein in the case of a fluidized bed of the heat transfer medium is at least partially fuidisiert in the reaction zone.

10. The method according to at least one of claims 1 to 9, characterized in that in the second stage, the thermal conversion of the volatile constituents from the feed coal in the presence of a moving from top to bottom bed of heat transfer and countercurrently thereto from bottom to top the volatiles from the feed coal and the condensable components of the

 Circulatory power to be performed.

1 1. A method according to claim 10, characterized in that the moving bed of the second stage is designed as a moving bed.

12. The method according to at least one of claims 1 to 1 1, characterized in that the discharged carbon in the second stage is cooled by an inert gas stream, which is used for predrying the feed coal and is used in the cycle after condensation of the water again to cool the carbon ,

13. The method according to at least one of claims 1 to 1 1, characterized in that the discharged in the second stage carbon is cooled by an inert gas stream, which is used to generate energy and used in the circuit again for cooling the carbon.

14. The method according to at least one of claims 1 to 13, characterized in that the reactors of both stages are equipped with at least one electrical and at least one non-electric heating system.