CA2314094A1

CA2314094A1 - Method for gasifying organic substances and substance mixtures

Info

Publication number: CA2314094A1
Application number: CA002314094A
Authority: CA
Inventors: Heinz-Jurgen Muhlen; Christoph Schmid
Original assignee: Individual
Current assignee: Deutsche Montan Technologie GmbH
Priority date: 1997-12-16
Filing date: 1998-12-15
Publication date: 1999-06-24
Also published as: DE19755693C1; JP2002508433A; WO1999031197A1; AU2513399A; EP1053291B1; HUP0101001A3; TR200001777T2; EP1053291A1; ATE244746T1; PL341225A1; DE59809004D1; BG104615A; HUP0101001A2

Abstract

The invention relates to a method for gasifying organic substances and substance mixtures in which a) the organic substances are fed into a pyrolysis reactor and the organic substances are held in contact with a heat carrier medium; b) the solid residual containing carbon and the heat carrier medium are fed to a firing in which the residual containing carbon is burnt and the heat carrier medium is heated and fed to the pyrolysis reactor again; c) the pyrolysis gases containing tar are reheated in a second reaction zone such that a product gas having a high calorific value is obtained.

Description

METHOD FOR GASIFYING ~RGANIC SUBSTANCES AND, SUBSTANCE
MIXTURES
The invention relates to a me od for gasifying organic substances and sub-stance mixtures according to th generic terms of Claim 1.
From US-PS 4,568,362, a method for gasifying organic substances and substance mixtures is known i which the organic substances are directed into a pyrolysis reactor in which th organic substances come into contact with a heat carrier medium which ca see rapid pyrolysis in which the organic sub-stances are converted into p rolysis products, that is, pyrolysis gases with substances that can be conde sed and solid residue containing carbon. The heat energy needed for the p rolysis is generated by firing th~ solid residue containing carbon. In a second reaction zone, the pyrolysis gases that contain tar are subjected to cracking r actions and reactions with steam such that a product gas with a high caloric alue is obtained.
In this method, the pyr lysis as welt as the firing of the solid residue containing carbon take place i ' a fluidized bed. In the upper part of the pyroly sis fiuidiz~d bed r~actor, a re ction zone is provided for the pyrolysis gases containing tar.
The heat carrier media is discharged together with the solid residue containing carbon in part thro gh the reactor h~ad of the pyrolysis fluidized bed reactor and the remaining portion via a tine that is mounted on the upper fluidized bed limit, and fed to tl~e fluidized bed firing. There, the solid residue containing carbon is fired and t a heat carrier medium heated up. The heated heat carrier medium and the as e9 ere discharged from the fluidized bed firing together with the waste gas, a d separated in a gas-solid separator mounted above the fluidized bed pyroly is reactor, and fed to the reaction zone of the pyrolysis reactor from which it gain falls into the fluidized bed of the .pyrolysis reactor (heat carrier medium cy le).
It is very costly to opera ~ th~ fluidiZed beds and it is hardly possible to control the reactions of the pyrdlysis gases in the r~action zone.
The object of the inventi n is to .make available a method for generating a gas with a high caloric value hat is easy to perform. In this pmcess, a small condensation portion is preferr d. A further object of the invention is to mak~
available a simple apparatus fo carrying out the method.
With respect to the meth d, this object is resolved by the combination of features in Claim 1. According o the invention, the pyrolysis is carried out in a fluidizad bed reactor or a rota~ drum, the pyrolysis gases are mixed, if neces-sary, with a reactant such as seam, and they are fed into an indirect heat, ex-changer in which the pyrolysis ases react with the reactant. The solid residue 2o containing carbon and the heat exchanger medium are fed to a firing. The firing waste gases are fed through t a indirect heat exchanger such that their heat content is used for the reactio of the pyrolysis gases With the reactant. The ashes of the solid residue cont fining carbon and the heat carrier medium taken from the firing are fed into the ~yrolysis reactor at the entry end for the organic substance.
The invention involves t~e basic concept that gasifying methods should be divided into three method I~teps that can be carried out easily. In a first method st~p, pyrolysis of the s bstances used takes place rapidly. in the proc-ess, the goat is to have as littl as possible of the condensable substances in the pyrolysis gases. The rapid yrolysis is ensured by performing th~ pyrolysis of the substances used at a to perature of 550-850°C.

In a second method step, the pyralysis gases are heated and reacted with steam to adjust the pro uct gas quality. The reaction of the pyrolysis gases is carried out with steam at a temperature of 900-1000°C.
In a third method step, the solid pyrolysis residue containing carbon is fired. The heat generated in th process is used for the pyrolysis and the reac-tion of the pyrolysis gases. Fu hermore, the heat carrier medium is heated up in the firing and then is conv yed back into the pyrolysis reactor. The, heat transfer for the reaction of the yrolysis gases with steam taken place in a heat exchanger that is heated by th waste gases from the .firing.
The advantage of this ~ivision of the three m~thod steps is that each method step and the combine ion of the method steps can be arranged ac-cording to the s~t standard of g s product quality.
The set standard for the as product quality is first of all, a higher caloric value. Furthermore, the steam ontent is increased by the second method step so that the gas product is very well suited for use as a synthesis gas, and en-ergy use in connection with fue cells can also be considered. Naturally, use to obtain energy via a gas motor ~r gas turbine is also possible.
The reactant is steam. It is possible to avoid the addition of steam when sufficient water vapor is conta~ned in the feedstock used, for example, when the material used is not dried of only to a limited extent. Furthermore, it is pos~
sible that the pyrolysis gases t at form contain sufficient water vapor when suf-ficient steam develops in the p rolysis of the substances used. It is also possi-ble to provide the addition of st am in the pyrolysis step.
with the method accor~ing to the invention, basically all organic sub-stances and substance mixtur~s can be gasified. However, it is preferable to gasify biomasses.
The substances used m ~ st be pretreated before they are fed to the py-rolysis. The pretreatment is ge orally limited to drying and if necessary, to pul-verization. In the process, no g eat restrictions are set for the lumpiness of the substances used because the Ipyrolysis is carried out in a fluidized bed with a heat carrier medium.

To improve the cracking of the noncondensable substances in the py-rolysis gas, a catalyst can be rovided in the reaction of the pyrolysis gases with steam. Preferr~d catalysts rB dolomite, calcite, nickel, nick~I oxid~, nickel aluminate, or nickel spinal, When dolomite is used, t is advantag~ous to calcinate the, dolomite at the reaction temperature of 90 -1000°C, and the resulting calcium/magnesium oxide has particularly high catal~tic activity.
The reaction temperatur of 9DD-'1000°C is advantageous for the reac-tion of the pyrolysis gas with team, because in this temperature range, the sulfur sensitivity of the named~catalysts is very much reduced. There is the possibility of regenerating the c talysts from time to time in. situ by the addition of a small amount of air at temc~~ratures abov~ 1000°C.
The catalysts can also b~e used as a heat carrier medium. This manner of proceeding has the advantage that the catalysts are periodically regener-1 b ated in the heat carrier cycle.
To prevent the catalyst from being deactivated by dust, if is recom-mended that the hot pyrolysis g ses be dedusted before addition of the steam.
In cases in which, beca se of the substances used, there is only mini-mal development of pyrolysis c ke and thus the heat developing in the firing is not sufficient for pyrolysis and reaction with steam, a portion of the pyrolysis gas can be fired to generate he~t.
The firing of a portion o the pyrolysis gas to generate heat is also re-quired when the pyrolysis coke is used as a material, for example, for the pro-duction ofi activated charcoal or grilling charcoal or charcoal briquettes. So that the pyralysis cok~ can be traps erred out wall, the grain size of the heat carrier medium must be small enough that the heat carrier medium can be separated from the pyrolysis coke without zany problem.
For th~ device according to the invention, simple and cost-effective components can be used that dare known as such and easily available. With these components, the device according to the invention can easily be con-structed.

The pyrolysis takes place in a moving bed reactor using a heat carrier medium. A shaft kiln is primarily used for this into which the mixture consisting of the material to be gasified and tha heat carrier m~dium is loaded from above. The mixture travets thro~gh the shaft kiln. Rapid pyrolysis occurs due to 5 the intimate contact of the matehial used with the heat carrier medium.
So that even with heter geneous materials, transport through the shaft kiln is ensured; built-in structu es or spiral conveyors can be provided inside the shaft kiln. The built-in stru ures also have the advantage that the pyrolysis gases developing can better a cape upwards through the moving bed. Never-theless, the equipment expens is increased in this way.
Basically, the' pyrolysis an also be carried out in a rotary drum or a double-deck oven, although he a as well, the equipment cost would be greater.
The mixture consisting ~f the heat carrier medium and the pyrolysis residue can be transferred into he firing via commercially available aggregat~s such as conveyor worms, s vel grates, rotating grates or cellular wheel sluices. In combination with a rate firing, however, the use of feeding rams is pref~rred. When an underfeeds stoker is used, the use of conveyor worms is preferred. The firing waste gales are fed through an indirect heat exchang~r that simultaneously serves as hemical reactor in which the pyrolysis gases react with st~am. Such heat ~a hangers are known, for example, in refineries as steam reformers or Also for the convayance~ of th6 heat carrier medium from the firing into the shaft kiln, conventional conveyance devices can be used, such as vibrating conveyors, bucket conveyors, r chain conveyors. The demands on convey-ance technique also corraspon to the requirements that appear in the steel industry or in the field of cvkin , so that excessive expense is not required for layout of the aggregates.
The heat. carrier medium must have sufficient mechanical, chemical, and thermal stability in the ,temperature range of 500-1000°C. Fire-resistant sub-stances such as sand, silicon,~rit, aluminum silicates, corundum, graywacke, quartzite, or cvrdierite are us~~1 Th~ use of molded bodies of metallic or non-metallic materials or combinati ns of them, such as steel or ceramic balls is also possible..
With respect to the parti le size, the heat carrier medium must be fine enough to b~ able to make int mete contact with the material used so that a good transfer of heat can tak~ place. On' the other hand, the particles of the heat carrier medium must be bi enough that there is sufficient empty volume through which the pyrolysis gas s can flow.
These requirements are eat fulfilled when the heat carrier medium has a grain size of 1-~40 mm. This rain size also has the adwantag~ that th~ h~at carrier medium can be separat d well from the ash of the pyrolysis residue af ter the firing.
As mentioned above, a talyst can be provided for the reaction of the pyrolysis gases with steam. For this purpose, a catalyst bed can be mounted in the heat exchan~er. Depending on whether the pyrolysis gases are fed through the pipes of the heat exchange or outside the pipes through heat exchanger, the catalyst bed is mounted i side or outside of the pipes of the heat ex-changer. It is also possible to se a catalytically active material for the heat exchanger pipes such as corun um with nickel or nickel oxide. It is also possi-ble to provide a solid bed re ctor with a catalyst bed behind the heat ex-changer.
If the reaction of the pyr lysis gases with steam is to be supported by a catalyst, it is recommended tha the hot pyrolysis gases be dedusted with a fil-ter before contact with the catal st.
The method steps name above as well as those claimed and described in the embodiment example, w ich are to be used according to the invention, as well as structural componen s are not subject to any special excsptional re strictions with respect to their ethod restrictions, their size, shape, material selection, and technical conception, so that the selection criteria known in tt,e particular area of application in ' ach case can be used without any limitations.
Further details, features,~and advantages of th~ obj~ct of the invention result from the following descrl~tion of the related illustration in which, as an example, a preferred ~mbodim nt of th~ gasifying of organic materials is repre-sented. Shown in the illustratio are:
Figure 1, a diagram of th method according to the invention, Figure 2, the mass an energy ba4ance of the pyrolysis and reaction steps, Figure 3, the mass and nergy balance of the firing, and Figure 4, a, schematic presentation of a device for carrying out the method according to the on.
invent It is evident from Figure 1 that the material tv be gasified is fed into pretreatment step 2. Dependig on the material, this can be a drying and/or pulverization device in a which t material is prepared for the subsequent py~

rolysis. The pretreated 1 material is brought into pyrolysis step 3.
The.pyrolysis step 3 leaves a pyrolysis nd gas 5 a pyro(ysis coke Sa.

The pyrolysis coke 5a i fired in firing 6.
The heat from firing is di-rected via a heat couplingyrolysis 7 to step and via a heat coupling 7a to a reaction zone 4 for pyrolysiss.
The waste gases of firing are cooled and diverted in a flue ning gas cle and cooling step 17.
The waste heat ob-tained writh the flue gas and cleanin cooling step can be used, for example, for the drying in pretreatmentp s 2.

Depending on the meth d conditions, more heat may develop in firing than is needed for heat g coupli 7 and 7a.
Steam can be generated with this heat. For this, feed waterb~
9 can fed via water treatment and pump into heat exchanger 12 which nted is mo in firing 6.
The steam generated is fed into reaction zone 4. The re press of the unneeded portion can be released via turbine 7 3 and further waste utilized a steam 16a.

The pyrolysis gas 5 is into fs reaction zon~

with steam 16.
In this re-action zone, the pyrolysisnd gas the crack products of the condensable sub-stances are reacted with to steam the desired gas product 15.
The gas product 15 is then purified in g a dedusti 8 and fine dedustin~
and quenching 14.
It is also possible to feed a 9 portion~ of the gas product into pyrolysis 3.

The addition of air an~ I_or oxygen can be provided in the individual method steps to influenc~ the method steps of pyrolysis, firing, arsd reaction with steam.
Figure 2 shows the ma s and energy balance of a pyrolysis st~p 101 and a reaction step 102 in the ~xample of gasifying wood. Wood 104 and heat carrier medium.104a ar~ introd cad into pyrolysis ~ste~p 101. Furthermor~, h~at flow 111 a, that results from the size and consistency of the material filows con-sisting of wood 104 and heat c rrier medium 104a, as well as the targeted py-rolysls temperature, is added. Pyrolysis step 101 leaves a mixture 105 con-sisting of wood charcoal and h at carrier msdium, and pyrolysis gas 106.
Pyrolysis gas 106 ante reaction step 102. Furthermore, a heat loss 108 occurs. Additionally, the reaction heat of the wood charcoal formation 109 and steam 112 are fed into re ction step 102. In addition, another heat loss 110 occurs. Resulting from the~heat and material streams fed in and diverted out, is still the heat quantity 11 to be fed in.
In Figure 3, the mass a d energy .balance of the wood charcoal Erring 103 is represented. The mate ial streams, mixture 105, (consisting of wood charcoal and heat carrier medi m 104a}, water 117, and air 113 enter into the firing, and also the material streams, waste gas 116, steam 112, and mixture 118 (consisting of heat carrier fnedium 104a and ash), exit. Heat streams that appear are heat stream 111 t at is fed into reaction step 102, h~at str~am 111 a that is fed into pyrolysis step 101, heat excess 114, and heat loss 115.
Figure 4 shows a devic for carrying out the method according to the invention. A material 401 is me~ered via sluice 402 into shaft kiln 403.
Simulta-neously, heat carrier medium 4~4 is fed into shaft kiln 403 by conveyor 409 via sluice 410. Mat~rial 401 and the heat carrier medium 414 travel downwards in shaft kiln 403 and mix, whereb by means of the heat contained in heat carrier medium 414, material 401 is py olyzed at approximately 600°C.
At the lower end of shaf kiln 403, the mixture consisting of heat carrier medium 474 and pyrolysis cok 426 forming from material 401 through pyroly..
sis is fed onto grate 405 of br ck-lined firing 407 through feeding 404.
Firing 407 has starting booster 406. n grate 405, pyrvlysis coke 426 burns, giving off heat. In this way, heat carrier medium 414 is heated to approximately 1000°C. Heat carrier medium X14 consists of a coarse grained material such as sand, grav~I, yr split. During the firing, heat carrier m~dium 414 and pyroly-sis coke 426 travel as far as rm 408 at the end of grate 405, by which the ash of pyrolysis coke 426 and heat carrier medium 414 are discharged. The majority of this mixture consisting of heat carrier medium 414 and ash is re-turned to shaft kiln 403 via con eyance 409 and sluice 410, where heat carrier medium 414 dischar~es the heat absorbed in firing 407 to material 401.
A small portion of the fixture consisting of ash of pyrolysis coke 426 and heat carrier medium 414~s discharged via cooling 411 and sieve 412.
Through sieve 412, the ,ash of yrolysis coke 426 is separated as fine material 413 from the coarser heat carri~r medium 414 and heat carrier medium 414 is returned to the process. This separation is superfluous when the material to be gasified does net contain any a h-forming constituents. , The pyrolysis gas formin during the pyrolysis in shaft kiln 403 is with-drawn from the upper area of s aft kiln 403 via line 403a ahd fed into heat ex-changer 417. Aside from wate , carbon monoxide, carbon dioxide, hydrogen, and methane, the pyroiysis gas also contains higher hydrocarbons and tars as w~II as other organic, especiall~r aromatic compounds as condensable compo-nents. Heat exchanger 417 is heated to a temperature of approximately 950°C
by the waste gases of firing 40 . At this temperature, th~ pyrolysis gas and the condensable substances react with steam that is contained in the pyrolysis gas. In addition, steam 416 is ed into line 403a for the reactions in heat ex-changer 417. To further increase the temperature ih heat exchanger 417, air 415 can also be added for a p ~ rtial firing of the pyrolysis gas. To improve the cracking of the accompanying ~ars, a catalyst can be provided in the heat ex-changer.
It is also possible to add the catalyst in the flow stream to the pyrolysis gas stream and to separate it main after heat exchanger 417 and reuse it.
Heat exchanger 417 leaves a gas product whose portions of carbon monoxide and hydrogen have been maximized. This gas is fed to heat ex-changer 421 for utilization of w~ste heat and into washer 422 for gas purifica tion.
Gas product 425 is withd wn via induced draught ventilator 423.
The waste heat from he t exchanger 421 can be used to heat the py-5 rolysis gas to reaction temperat re for the reaction with steam.
After it has flowed throw h heat exchanger 417, the waste gas of firing 407 is fed through heat exchan er 418 for waste heat utilization. After gas pu-rification 419, waste gas 424 s discharg~d to the surroundings via induced draught ventilator 420.
1 O Both firing 407 and also eat exchanger 417 are operated at a pressure that only slightly deviates from atmospheric pressure and generally is some-what less than the latter. Indu ed draught ventilator 423 for gas product 425 and 420 for waste gas 424 are regulated and coordinated with one another so that the pyrolysis gas is fed t rough heat exchanger 417 and is not sucked through the shaft oven feed int firing 407.
Embodiment example 1000 kg/h wood are ga ified in the device according to Figure 4. The wood contains 3% ash (free fr m water) and otherwise consists essentially of 50% carbon, 6°~ hydrogen, 42° oxygen, and 1.9% nitrogen, calculated without water or ash. The upper caloric value is 17.9 MJlkg in .the anhydrous state.
The thermal gasification gfficicncy is 4.97 MW. Ths pyrolysis is carried out at fi00°C and the reaction with st am at 950°C. The workin~
pressure is atmos-pheric pressure.
Gravel with a grain size om 3 mm to 15 mm is used as heat carrier me-dium. The gravel is heated fr m 600°C to 950°C. Because of the required thermal performance of 380 k , the cycling quantity of the heat carrier medium is five times that of the wood i put, that is, 5000 kg per hour. The shaft kiln is 4.5 m high and has a diameter of 1,5 m, corresponding to a fluidized bed vol-ume of 7.5 m3. The residence ti a in the shaft kiln is two hours.
fn the pyrolysis, the woo is reacted so that 20 wt°i6 of the ~ivood remains as wood charcoal. In the following table, the quantities and compositions of the wood and pyrolysis coke (wood charcoal) are listed:
' Material flow Wood Wood charcoal m [kglh] 1000 200 Hu [MJlkg] dry 17,9 33,5 C [wt%] daf 52,1 82,2 H [wtr6] daf T 4,8 2,6 O [wt~] daf 42,4 5,2 Ash cwt~J d(y __ _ 3 4 I 17,0 The following gas produ t is obtained:
Caloric valueJINm J 10,5 [

H: [upl.-% 51,1 dry]

CO [Vol.-r6 _ ___ _____ _39 ?
dry] __-CH4 [Vol.-% 0,01 d COz [Vol.-% 9,2 d HzO [Vol.-%] 14,8 ~~

Chemical. Ipy flow [MW] 3,9 enth Quantity [Nm 1.338 Ih The enthalpy flow of the wood charcoal in the firing is 1.86 MW. This is sufficient to generate a steam flow of 0.45 MW (360 kglh at 950°C and atrnos-pheric pressure) as well as tv c ver the heat requirement of the reaction of the pyrolysis gas with steam at the level of 0.84 MW. The firing efficiency is 85%.
After accounting fvr tha heat ( ss and Icss through the waste gas flow, only 0.26 MW remain. With this, 32~ kg/h.supsrheated steam ~rvere generated that were relaxed via a turbine and sed as heatin~ steam. The cold gas efificiency IS 7g%.

List of reference numbers:
1 Mat~rial us~d 2 Pretreatment step 3 Pyrolysis 4 Reaction zone 5 Pyrolysis gas 5a Pyrolysis coke 6 Firing 7 Heat coupling 7a Heat coupling 8 Deducting 9 Feed water 10 Water treatment 11 Pump 12 Heat exchanger 13 Turbine 14 Fine dedusting/quenchin 15 Gas product 16 Steam 16a Waste steam 17 Heat exchang~r/flueleaning gas 18 Waste gas 19 Gas product 20 Air 101 Pyrolysis step 102 Reaction step 103 Firing 104 Wood 3D 104a Heat carrier msdium 105 Mixture 1a '106 Pyrolysis gas 107 Gas product 108 Lost heat 109 Formation heat 110 Lost heat 111 Heat feed reaction step 111 a Heat feed pyrolysis step 112 Superheated steam 113 Air 1 D 114 Excess heat 115 Heat loss 116 Waste gas 117 Water 118 Mixtur~

401 Material used 402 Sluice 403 Shaft kiln 403a Line 404 Feeding 405 Grate 406 Booster 407 Firing 408 Worm 409 Conveyor 410 Sluice 411 Cooling 412 Sieve 413 Fine material 414 Heat carrier medium 415 Air 416 Steam 417 Heat exchanger 41 B Heat exchanger 419 Gas purification 420 Induced draught ventil 5 421 Heat exchanger 422 Washer 423 Induced draught ventil 424 Waste gas 425 Gas product 1 O 426 Pyralysis cake

Claims

1. Method for the gasifying of organic substances and substance mixtures in which a) the organic substance are fed into a pyrolysis reactor in which the organic substances are kept in contact with a heat carrier medium whereby a rapid pyrolysis takes place in which the organic substances are reacted into pyrolysis products whereby the pyrolysis products consist of pyrolysis gases with condensable substances and a solid residue containing carbon, b) the solid residue containing carbon and the heat carrier medium are fed to a firing in which the residue containing carbon is fired and the heat carrier medium heated and fed again to the pyrolysis reaction (heat carrier medium cycle) c) the pyrolysis gases containing tar are reheated in a second reaction zone so that a gas product is obtained with at high caloric value, characterized in that d) the pyrolysis is carried out in a moving bed reactor or a rotary drum, e) if necessary, a reactant such as steam is mixed in with the pyrolysis gases and then f) are fed into an indirect neat exchanger in which the pyrolysis gases react with the reactant, g) the firing waste gases are fed through the indirect heat exchanger such that their heat content is utilized for the reaction of the pyrolysis gases with the reactant, and h) the ash of the solid residue containing carbon and the heat carrier medium is removed from the firing and recycled into the pyrolysis reactor at the input end for the organic material.

2. Method according to Claim 1, characterized in that the pyrolysis is carried out at a temperature of 550-650°C.

3. Method according to Claims 1 and 2, characterized in that the reaction of the pyrolysis gases with steam is carried out at a temperature of 900-1000°C.

4. Method according to on of Claims 1-3, characterized in that the reaction of the pyrolysis gases with steam is carried out in the presence of a catalyst.

5. Method according to Claim 4, characterized in that, dolomite, calcite, nickel, nickel oxide, nickel aluminate, or nickel spinal is used as catalyst.

6. Method according to Claim 5, characterized in that the catalysts are used simultaneously as heat carrier medium for the heat carrier medium cycle.

7. Method according to one of Claims 1-6, characterized in that the hot pyrolysis gases are dedusted before the addition of steam.

8. Method according to one of Claims 1-7, characterized in that the catalyst is fed to the hot pyrolysis gases in an entrained flow mode and is separated out after the reaction with steam, and returned to the hot pyrolysis gases in the cycle.

9. Method according to one or more of Claims 1-8, characterized in that the pyrolysis gases are dedusted and quenched after the reaction with steam.

10. Method according to one of Claims 1-9, characterized in that a portion of the pyrolysis gas is fired and the heat is utilized for the pyrolysis and/or the reaction with steam.

11. Method according to one of Claims 1-10, characterized in that the solid residue containing carbon and the heat carrier medium are fed, to a grate firing.

12. Apparatus for carrying the method according to Claims 1-11 with a pyrolysis reactor, a firing for the pyrolysis residue, a reaction zone for the pyrolysis gases, a heat carrier cycle between the pyrolysis reaction and the firing, characterized in that a shaft kiln (403) or a rotary drum is equipped with a sluice (402) for a material used (401) and a sluice (410) for a heat carrier medium (414) in addition to a firing (407) with a grate (405), and the shaft kiln (403) has a feed (404) for the firing (407), and the waste gases (424) of the firing (407) can be fed to a heat exchanger (417) that is connected with the shaft kiln (403) via a line (403a) for the pyrolysis gases, and the firing (407) is connected via a discharge apparatus, such as a worm (408) to a conveyor (409) for the heat carrier medium (414).

13. Apparatus according to Claim 12, characterized in that the heat carrier medium consists of fire-resistant materials such as sand, gravel, split, aluminum silicate, corundum, graywacke, quartzite, or cordierite.

14. Apparatus according to Claim 12, characterized in that the heat carrier medium consists of molded bodies composed of metallic or nonmetallic substances such as steel or ceramic balls.

15. Apparatus according to Claims 13 and 14, characterized in that the heat carrier medium has a grain size of 1-40 mm.

16. Apparatus according to one or more or maims 12-15, characterized in that the firing (407) is performed as a grate firing.

17. Apparatus according to one or more of Claims 12-16, characterized in that the heat exchanger (417) has a catalyst filling.

18. Apparatus according to one or more of Claims 10-17, characterized in that the pipes of the heat exchanger (417) consist of catalytically active material.

19. Apparatus according to one or more of Claims 12-18, characterized in that the heat exchanger (417) is assigned to a solid bed reactor with catalyst feed.

20. Apparatus according to one or more of Claims 12-19, characterized in that the heat exchanger (417) is first connected to a filter for dedusting.