DD213239A5 - METHOD AND DEVICE FOR PREPARING SYNTHESEGAS - Google Patents

Abstract

In the process for the production of synthesis gas (CO + H deep 2) by autothermal gasification of finely divided, carbon-rich materials with oxygen, wherein the carbon-rich material with a particle size of 0-0.1 mm with oxygen in a hot gasification zone Einduest, the formed flyschhealtige primaere raw synthesis gas with its inherent thermal energy through a filled with the starting materials for an endothermic carbothermic reduction reduction zone and, increased by the resulting in the carbothermal reduction synthesis gas, passes through an upwardly subsequent, filled with the same substances preheating and at a temperature deducting from 300-1500 degrees C for purification and conversion, and wherein below the reduction zone, the reaction product of the carbothermic reduction and resulting slag takes molten from a collection and post-reaction zone, produced as a gasification zone in a Ha ufwerk from the starting materials for d. carbothermic reduction means a cavity or at least a vortex zone of such loosened debris held at 1300 to 3300 degrees C; the reduction zone is produced above and to the side of the gasification zone and simultaneously undergoes gasification in the reduction zone, with water vapor and carbon dioxide contained in the primary crude synthesis gas reacting with carbon-rich material to form further synthesis gas. The invention also relates to a device for carrying out the method.

Description

Berlin, 23rd, 02. 1984 AP C 10 J / 255 057/7 62 980 11

Process and apparatus for the production of synthesis gas

Field of application of the invention

The invention relates to a method and an apparatus for producing synthesis gas (CO + H ₂ ) by autothermal gasification of finely divided, carbon-free materials with oxygen in the presence of starting materials for an endothermic carbothermic reduction.

Characteristic of the known technical solutions .

Since about 1973/74, processes for producing synthesis gas from coal and other solid fuels, especially those under increased pressure, have been intensively developed in order to make better use of domestic sources of energy and sources. Such processes are described in detail in the literature (eg Ullmanns Sncyklopadie of Technical Chemistry, 4th edition, volume 14, page 375 ff "). The future increase in large-scale application of such processes is likely to lead to an immense attack of ashes and slags and pose serious landfill problems. In the DS application P 31 32 506.8 a method and an apparatus for the production of synthesis gas was described ao, wherein the addition of aggregates at least parts of the ashes as chemical-technical products, such as a. B "ferrosilicon or calcium carbide are obtained.

Characteristic of the device described therein is that 'side of a filled with aggregate mixture shaft furnace (ubstichgenerator) gasification chambers are arranged, which are in open communication with the Reüuktionszone in the shaft furnace »In this

the carbonaceous material is injected with oxygen and optionally additional gases and transferred into a extremely hot, carbon monoxide-containing Sythesegas, which from there into the one bed of aggregate. containing reducing agent, where e.g. Forming ferrosilicon or calcium carbide as reduction products. Part of the ash from the input materials is discharged as dust with the synthesis gas, another is converted by chemical reaction and the remainder is removed with the reduction product.

The proportion of ash from the high-carbon materials discharged with the synthesis gas depends on the gasification temperature and the reaction temperature in the reduction zone. Evaporation and partial reduction of the oxides of the ash to volatile suboxides, e.g. SiO, are u.a. responsible for.

It. shows that the purity of the reduction products produced depends strongly on the purity of the feedstock, especially the carbon-rich material. Using, for example, very high ash coals as the feedstock, it may prove necessary to produce significantly higher temperatures in the gasification and / or reduction zone than would be required for the formation of the corresponding reduction products to accommodate larger amounts of ash into the gas stream convict. Preferably, temperatures between 2,000 and 3,300 ° C are desirable here.

Considering a Flugstromvergaser, which consists in principle of an empty, refractory "bricked reactor, or the device of DE application P 31 32 506.8, which, although considerably smaller, but also empty, has refractory lined gasification chambers, it can be seen easy, that when using extreme reaction temperatures, the wall of the reactor the

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simultaneous attack τοη reducing atmosphere and molten ash or slag can not withstand. This is especially true for high-ash coals where significant difficulties are observed even at conventional synthesis gas generators and gasification temperatures 1500 to 2000 ⁰ G.

Aim of the invention;

The aim of the invention is to provide an improved process for the production of synthesis gas.

Explanation of the essence of the invention

The invention has for its object to provide a method and a device au, which minimize the wear on the device with the same objective as in DS application P 31 32 506.8, thus extending their life dine influence on the distribution of the ash bzn. Enable slag between synthesis gas and solid Eeduktionsprodukt and cause an increased s unit of the carbothermic Seduktionsproduktes.

The present invention solves this problem in a simple manner, whereby at least partially chemical-technical products can be produced on the equilateral side from the ashes of the carbonaceous materials used.

Invention according to the prior art and the DE application P 31 32 506.8 summarize the following advantages:

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1, The reaction temperatures in the gasification zone can be varied in a wide range of 13ΟΟ to 3300 ⁰ C.

2 »Sin wear on a refractory lining of the gasification chamber is excluded. Nozzle tips and nozzle feedthroughs are sufficiently coolable,

3. Sin Wear on the constructive parts of the shaft-shaped tapping generator is minimized by a strong radial temperature drop with protective layer formation on the inner walls.

4. Heat losses are minimized.

5. The gasification zone simultaneously acts as a gas distributor.

6. The device according to the invention is substantially rotationally symmetrical and thereby ensures a largely uniform gas distribution.

7 parts of the additive mixture can also be introduced through the nozzle in the tapping generator.

8. From the rotational symmetry of the device according to the invention, it is possible to arrange them in a suitable manner rotating, slightly inclined to the perpendicular and to achieve intensive mixing of the components in the collection and post-reaction chamber.

These advantages are preferably achieved by containing in a closed reactor containing a heap of carbon-rich, solid materials such as coke, carbon coke, anthracite, charcoal or peat coke, and optionally additives such as lime, scrap iron and others, during operation creating a cavity or at least a vortex zone of loosened debris in situ by means of a nozzle a dusty carbon-rich material, for example one or more of the above or coal or lignite, together with oxygen, optionally in the presence of additional gases such as water vapor, carbon monoxide, Nitrogen or carbon dioxide blows in and ignites. In this case, the ratio of the gasification agent components (O ₂ / H ₂ O, CO ₂ ), preferably in the gasification zone with carbon to form syngas, is preferably adjusted so that the resulting primary synthesis gas has the desired flame temperature of preferably 1300-2000 ° C receives.

This ratio is at least adjusted to continuously consume a certain amount of the material surrounding the generated cavity, thereby achieving gasification of the carbonaceous materials in two stages.

1. A pre-gasification with a stoichiometric carbon subzero, based on the sum of the gasification agents (Op, COp »HpO). In principle, this is a DC or entrained flow gasification in a continuously renewing empty gasification chamber with gas-permeable boundary surfaces, which at the same time as a gas distributor acting as symmetrical gas supply ensures.

2. A post-gasification, wherein the amount of carbon gas corresponding to the Vergasungsmittelüberschuß is implemented in the manner of a fixed or moving bed gasification in countercurrent in a region enveloping the gasification zone, in the. at the same time the desired reaction of the aggregates can be carried out. The oxygen-transferring gasification agent is no longer oxygen itself, but water vapor and / or carbon dioxide. Wassergasbzw. Boudouard reaction (HpO + C -> C0 + H ₂ ; COp + C->

2TC0) as well as the reaction of the aggregates are endothermic, i. Consuming heat. Also, this Nachvergasung renewed in the operating state steadily. However, it is not sharply demarcated on the outside and contained in the actual reduction zone.

In detail, the invention now relates to a process for the production of synthesis gas (CO + H ₂ ) by autothermal gasification of finely divided, carbon-rich materials with oxygen, wherein the carbon-rich material with

a particle size of O - 0.1 mm with oxygen and possibly additional gases injected into a hot gasification zone, the fly ash-containing primary crude synthesis gas with its inherent thermal energy by a filled with the starting materials for an endothermic carbothermic reduction reduction zone, and increased by the in the carbothermal reduction resulting synthesis gas ,, passes through an upwardly subsequent, filled with the same substances preheating zone and at a temperature of 300 - 1500 ⁰ C for purification and conversion, and wherein below the reduction zone, the reaction product of the carbothermic reduction and molten slag arising from a collection and post-reaction zone, which is characterized in that as a gasification zone in a heap of the starting materials for the carbothermic reduction a cavity or at least a vortex zone of such loosened Heap produced, which is held at 1300 to 330O ⁰ C; that one generates the reduction zone above and to the side of the gasification zone; and simultaneously conducting post gasification in the reduction zone, wherein water vapor and carbon dioxide contained in the primary crude synthesis gas react with carbonaceous material to form further synthesis gas.

The process of the invention may further be optionally and preferably characterized by

a) in the gasification zone with a stoichiometric excess of oxygen with respect to the oxidation to CO

works and produces a 2000 to 330O ⁰ C hot primary crude synthesis gas;

b) injecting into the gasification zone as additional gases and gasification agent steam and / or carbon dioxide and produced by reaction with carbon I300 to 2000 ⁰ C hot primary crude synthesis gas;

c) from the top of the preheating so much carbon-rich material in excess, based on the stoichiometry of the endothermic carbothermic reduction, in which the gasification zone surrounding debris brings in that emerging from the gasification zone of water vapor and / or carbon dioxide with carbon to further synthesis gas;

d) freeing the raw synthesis gas leaving the preheat zone from dust and ash and at least partially re-injecting these solids into the gasification zone together with fresh carbonaceous material;

e) the starting materials for the carbothermic reduction in particle sizes of 10-20 mm, 20-40 mm and / or 40-60 mm is used, wherein preferably for optimal gas distribution alternately layers of different particle size ranges are poured over each other;

f) the preheating zone and reduction zone with coke, iron scrap and optionally quartz charged, wherein MAN gains as the reaction product of the carbothermal reduction at I3OO to 1800 ⁰ C ferrosilicon;

g) the preheating zone and the reduction zone with coke or anthracite and lime fed, which is obtained as the reaction product of the carbothermic reduction at 1800 ⁰ C to 2300 ⁰ C calcium carbide; 5

h) injecting a portion of the lime in the form of in the carbide gasification accumulating and then finely pulverized hydrated lime together with the finely divided carbon-rich material in the gasification zone.

i) charging the preheating zone and the reduction zone with coke and oxidic iron ore to yield metallic iron as the reaction product of the carbothermic reduction at 1300 to 1800 ^° C;

j) the preheating zone and the reduction zone are charged with coke or anthracite, lime, iron and / or iron scrap and / or iron oxide, and optionally quartz, whereby calcium carbonate and ferrosilicon are obtained as reaction products of the carbothermic reductions at 1800 to 2300 ^° C .;

k) feeding the preheating zone and reduction zone with coke, CaI-ciumphosphat and quartz, which is obtained as a reaction product of the carbothermal reduction at I300 to 1700 ⁰ C elemental phosphorus;

1) as an additional gas CO, CO ₂ , N ₂ , steam or recycled synthesis gas used;

m) in the symmetry axis of the preheating zone provides a laterally and upwardly closed pyrolysis zone through which at least a portion of the carbon-rich material intended for gasification and carbothermal reduction is degassed and coked from above

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wherein the volatile Sntgasungs- and coking products are forcibly pyrolyzed in this zone at from 400 ⁰ C to 1100 to 1500 ⁰ C increasing temperatures;

n) introducing steam from above into the pyrolysis aones and adjusting a certain hydrogen content of the crude synthesis gas by reacting it with carbon;

o) used in the pyrolysis zone as a carbon-rich material shredded old tires of motor vehicles.

The device according to the invention will be explained in more detail with reference to the figures of the enclosed drawing.

In the figures 1 to 5, various embodiments of the inventive device are shown in side view and in section. The method of the invention is explained in more detail with reference to these illustrations as follows:

FIG. 1:

Very finely ground and pre-dried gasification carbon (carbon-rich material, particle diameter: 90% less than 90 / Um) is fed via the supply line 1, the intermediate bunker 2 and 3 line to a nozzle 4-, where it is oxygen from line 5 and possibly additional gas, in particular Carbon dioxide, water vapor, carbon monoxide or crude synthesis gas, derived from

n tung 6 in the gasification zone of the Seaktorraumes

(bay-shaped Abstichgenerator) 8 injected and

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is gasified autothermally. The shaft-shaped Abstichgenerator 8 is designed so that the nozzle 4 is located at: a recess 9 of the soil in the symmetry and that by carbothermal leduktion and / or a post gasification in a debris layer with the respective aggregate mixture a cavity, but at least a vortex zone from loosened up debris, gasification zone 7 is produced and stabilized. In the adjoining areas of the debris layer, gasification then takes place in the forming operation zone 10. The grain size of the aggregates of this mixture is preferably 10 to 20 mm or 20 to 40 mm. Above the debris layer, a preheating zone 11 is arranged, which also contains a debris layer of aggregate mixture, so that by gravity flow the aggregate mixture according to the consumption in the Heduktionszone 10 moves down, below the Beduktionszone 10 is an annular collecting and Nachreektionszone 12 arranged »in the into drops dripping from the reduction zone 10, molten slag and Beduktionsprodukt with a (temperature 1200-2200 ⁰ O. the collection and ÜTachreaktionszone 12 is provided with at least one closable tap opening, so that molten slag and molten Beduktionsprodukt than d ^ e lines can be peeled 13 and / or 14 · is then granulated or cooled in vessels. While in the gasification zone 7, the temperature ⁰ C is adjusted by means of excess oxygen at about 2000 to 3300, resulting in the Eeduktionszone 10 a temperature of e twa 2 200 ⁰ C. Large parts of the ashes from the gasification coal are therefore already in the

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Gasification zone 7 is evaporated and removed with the forming primary crude synthesis gas. The aggregate mixture contains a reducing agent, preferably coke, carbon coke, anthracite, charcoal or peat coke, and other specific materials for the desired reaction. The resulting in the gasification zone 7 gasification products Y ^ earth forcibly passed through the reduction zone 10 and the preheating zone 11, where they give the inherent heat to the aggregate mixture and even emerge at the top of the reactor chamber 8 at temperatures between 350 and 1 500 ⁰ C. Depending on the requirement of the amount of reduction product produced or the desired outlet temperature of the raw gas, the aggregate mixture can be metered according to the amount and composition. Minimum raw synthesis gas temperatures result when the preheating zone 11 is designed such that the bulk surface available for heat exchange becomes very large and the energy consumption through reduction reactions corresponds to the energy released by the autothermal gasification reaction. At the top of the tapping generator 8 there is provided a suitable device for introducing the aggregate mixture supplied via line 15, preferably in the form of chutes which are sealed against gas or gout closures. In line 16, a waste heat boiler 17 may be provided at high outlet temperatures of Hohsynthesegases so that the raw synthesis gas in the hot dedusting 18 can be dedusted and discharged via line 19. The dust removed from the hot dedusting 18 can be removed.

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neither returned via the line 20 and the isμ isehenbunker 2 back into the gasification zone 7 and the Seduktionszone 10 or removed via line 21 or in certain proportions simultaneously over 20 and 21 out. In this quiet you can either peel off all Bestasche and fiber from the Sinsatzmaterialien as slag via line 13 or 14 or parts thereof as dust from the Heißentstaübung 18 via line 21. If calcium carbide is produced as a reduction product, which can be hydrolyzed to acetylene and hydrated lime, the latter, which accumulates in dust form with about 4% by weight moisture from dry gasifiers, can be added via line 22 and injected via the nozzle 4 so that a Part of the lime component is substituted in the aggregate mixture.

As a result, a reduction of the raw material and energy consumption is effected because a lime recirculation would otherwise be possible only 'with briquetted and calcined material. A special feature is that the Schuttungsmantel performs a protective function for the wall of the reactor space in the tapping generator 8. The passage of the nozzle 4 through the Binnülpung 9 at the bottom of the tapping generator 8 is cooled by cooling chambers with the incoming and outgoing lines 23 and 24 respectively.

FIG. 2:.

In a further embodiment of the device according to the invention may be provided in contrast to Fig. 1, a component of the additive mixture via line 25 of the remaining aggregate mixture separately in the reactor space .des Abstichgenerators 8 and with auxiliary installations in the form of separating plates 26th

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to achieve a columnar or annular distribution of the components in the bed.

The gasification zone 7 can be charged with either excess oxygen, which sets higher gas temperatures, or with excess carbon dioxide or water vapor, which results in lower gas temperatures, as gasifying agents, when the aggregate mixture is enriched with high-carbon material.

FIG. 3:

Likewise, unlike in FIGS. 1 and 2, the device according to the invention can have a gradient in the collecting and after-reaction chamber 12, making it possible to achieve better phase separation of slag and reduction product or of two treatment products and separate tapping via lines 13 and 14 to reach.

FIG. 4:

In Figure 4, the method is performed unlike Figure in a rotating device. Essential here is an intimate mixing of the reactants of the carbothermic reduction, caused by a resulting during rotation flow in the collection and post-reaction chamber 12. The lid 27 of the tapping generator 8 and the nozzle 4 remain fixed and are the tapping generator 8 back against gas passage z * B. with stuffing boxes, Labyrinthdichtungoa or other known devices 28 movably sealed. The dividers 26 are tracked virtually endless. At the end

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Stitch generator 8 is a support ring 29 »which is rotated by a gear 30 equipped with a drive gear. The rotation preferably takes place at 0.2-2 rpm,

FIG. 5:

Figure 5 shows schematically a section of the shaft-shaped Abstichgenerator 8 in the region of the indentation 9 of the bottom with the arrangement of two nozzles 4-,

The wall of the ifcstichgenerators 8 in the region of the bottom invagination and the tips of the nozzles 4 are by cooling chambers 3Λ through which a cooling medium, for. B. water or a heat transfer oil flows, designed coolable. The inside of the wall of the tapping generator 8 is lined with refractory material 32, which protects against the attack of the molten slag or the molten reduction product.

The invention thus also relates to an apparatus for carrying out a process for the production of synthesis gas (CO + H ₂ ) by autothermal gasification of finely divided, carbon-rich materials with * oxygen in the presence of starting materials for an endothermic carbothermic reduction, containing a shaft furnace which in the Operating state, viewed from top to bottom, an elongated preheating zone, a reduction zone and a collecting and Eachreaktionszone, the open into one another, as well as with the reduction zone open connected gasification zone comprises} nozzles for the joint supply of coal dust, oxygen and possibly additional gases, Feed lines for the starting materials of the carbothermic reduction and a discharge line for crude synthesis gas at the top of the shaft furnace; and withdrawal lines from the collection and ITachreak

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tion zone at the bottom of the shaft furnace for the withdrawal of molten slag and molten reaction product from the carbothermic reduction, which is characterized in that the shaft furnace is a shaft-shaped Abstichgenerator with a circular cross-section and centrally upwardly inverted bottom; that in the operating state, the reduction zone 10 encloses the gasification zone 7; that the collecting and Hachreaktionszone 12 surrounds the bottom invagination 9 annular; that at least one nozzle 4 is inserted through the bottom invagination 9 with connected lines 3; 5; 6 for the joint supply of finely divided, carbon-rich material, oxygen and, if appropriate, additional gases and pulverulent starting materials for the carbothermal reduction.

The device of the invention may further be optionally and preferably characterized in that

a) they are arranged in the upper part of the tapping generator 8 vertically and circularly arranged separating plates 26 for demarcation

.__: zju2jg ^ eme; g ^ ss ^ in the symmetry axis

the tapping generator 8 above the gasification zone 7; a Transportieitung 25 for charging the columnar space with the carbon component of the starting materials for the carbothermic reduction; and at least 2 transport lines 15 for the supply of further starting materials for the carbothermic reduction to form an inner wall of the Abstichgenerators 8 protective annular Schüttungsmantels;

b) the separating plates 26 through the head of the tapping generator 8 from outside to inside by applying shots quasi endless until melting above the Verga-

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- 16 sungszone 7 are consumption-dependent trackable;

c) the entirety of the circular separating plates 26 has the shape of a tube;

d) the dividing plates 26 are broken open like a lattice and are gas-impermeable;

e) the bottom of the tapping generator 8 is provided with the Samuel and post-reaction zone 12 with a slope;

f) the tapping generator 8 provided with a lateral support ring 29 and on a sprocket, equipped with drive 30 and 1 to 20 degrees inclined to the vertical, is rotatably disposed; that the tapping generator stones cover. 27 carries; that the lid 27, nozzle 4- and guided through the lid 27 and, respectively, connected to the nozzle 4 supply and discharge lines are fixed and sealed to the tapping generator 8 with seals 28 against gas passage;

g) surrounded by the bottom invagination 9 nozzle 4 is surrounded by a coolant-loaded cooling chamber;

h) at least 2 nozzles 4 are provided, wherein the tips and the wall of the tapping generator 8 are protected in the region of the Bodenausstülpung 9 by coolant flowing through the cooling chambers 31 from heat;

i) the inner wall of the collection and post-reaction zone 12 is lined with refractory material 32.

Execution e spi el

The invention will be described in more detail below with reference to some examples

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- 17 explained.

In the following examples, the volume data refer to the normal state at 273 K and 1.013 bar.

Example 1 (Figure 2)

Il's gasification coal is a dry coal with 22 wt.% Ash, which in turn contains 45 wt.% SiO 2, 26 wt.% Al ₂ O and 12 wt.% CaO as main constituents. The dry coal has 65 wt.% C and 3.5 wt.% H, balance 9.5 wt.%. 0, N, S, H some has a lower heating value (Hu) of 25 KJoule / g. As a slag-absorbing ineduction product, calcium carbide is produced. For this purpose, a mixture of coke and quicklime in the. Heaktor filled. The coke contains about 13% by weight ash, 0.5% by weight water, 81% by weight C, 1% by weight H (best 4-5% by weight 0, IT, S) and has a lower calorific value ( Hu) of 29 KJoules / g. The calcined lime is about 95 wt.% Total CaO (CaO, Ca (OH) ₂ , CaCO ^, CaSO ₂ ^) is set.

If, according to the general description of FIG. 2, 94 t / h of gasification coal together with 56,000 nr / h of oxygen (99.5% by volume of pure) are introduced into the gasification zone 7 through the nozzle 4, a primary synthesis gas (approx -8,000 m ^ h) with a temperature of about 2 500 ⁰ C and a composition (Vol.%) Of about 21% H ₂ , 1% H ₂ , 70% CG, 4.5% CO ₂ , - 2.5% H ₂ O and 1% argon, CH ₂ , H ₂ S and COS. In addition, about 21 t / h of molten ash together with about 1.2 t / h of unreacted coal are discharged from the gasification zone 7 into the reduction zone 10. After entering the reduction zone 10, the COp contained in the primary crude synthesis gas reacts with carbon in the manner of the Boudouard reaction. The primary crude synthesis gas cools down and the existing water vapor

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acts with a corresponding excess of coke. 7 »1 t / h of excess coke are introduced via line 25 into the reduction zone 10. Via line 15 and the ring-shaped preheating unit 11, 38.9 t / h of lime and 23 t / h of coke are introduced into the reduction zone 10 as the additive mixture. The carbide formation reaction and lifting reactions, such as 2. Binding of sulfur from sulfur-containing components to the basic CaO component of the aggregate mixture (R = S- + C + CaO - ^ GaS +00 + H) ₁ Deacidification of residual carbonate (CaCOo + C -) > CaO + 2 CO) or dehydration of Hesthydroxid (Ca (OH) ₀ + C - > CaO + H ₀ + CO) release carbon monoxide. This produces about 177,000 nr / h of crude synthesis gas with about 22% H ₂ , 76% CO, 1 % U ₂ and 1 % CO ₂ , argon, H ₂ O, and (% by volume). Together with the crude, 450 to 500 ⁰ C hot synthesis gas about 18 t / h of dust with about 32 ü ew.% CaO, 29 wt.% SiO ₂ and 14 wt.% Al ₂ O .. discharged via line 16 and separated from the gas in the hot dedusting 18. The aggregates for the carbide are continuously introduced via the lines 15 and 25 from above in countercurrent to the rising synthesis gas and reacted in the reduction zone 10 to 49 t / h of carbide with a littleness of ca, 248 1 acetylene per kg of carbide, from the collection and Bach reaction zone 12 is discontinuously tapped »

Example 2 (FIG. 3)

Assuming the same raw materials as in Example 1, 135 »5 t / h gasification coal together with

78 000 m - ^ / h of oxygen through the nozzle 4 into the held at ca · 2 500 ⁰ C gasification zone 7, fed via the lines 15 and 25, the tap generator 8 with a mixture of 38.9 t / h of lime and 37, 6 t / h coke for the carbothermic reactions and the Hachvergasung and with

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8.8 t / h iron scrap (98% by weight iron), so via line 13 15 »3 t / h 4-5 wt,% ferro silicon, via line 14- 45.3 t / h calcium carbide with a Litrigkeit of about 266 1 acetylene per kg of carbide and on line 16 257 000 nr / h of crude synthesis gas having a temperature of 400 to 500 ⁰ C, the latter 16.1 t / h leads dust, which in the hot dedusting 18th is separated. The crude deducted syngas contains about 22 % hydrogen, 77 % CO and 1 % CH ₄ , GO ₂ , H ₃ O ₁ N _2, and argon (7%,%). The dust contains about 42 % CaO, 4 % SiO ₂ and 23% AlpO 3 (% by weight). The total amount of ash introduced from the feed materials of 35t3 t / h is opposed by the amount of 16.1 t / h of dust removed via line 21.

Claims (26)

IP οίο J / 255 057/7 62 980 11 - 20 - Claim 1. Process for the production of synthesis gas (CO + H ₂ ). by autothermic gasification of finely divided, carbon-rich materials with oxygen, wherein the carbon-rich material with a particle size of 0 0.1 mm with oxygen and possibly additional gases injected into a hot gasification zone, the fly ash-containing primary crude synthesis gas with its inherent 'thermal energy through ? a column filled with ds n precursors for an endothermic carbothermal reduction reduction zone and, aggravated by the resulting in the carbothermal reduction synthesis gas by a subsequent upward, filled with the same materials preheating zone passes and a "temperature of 300 - 15OO ⁰ G deducted for purification and conversion, and wherein below the reduction zone, the reaction product of carbothermic see reduction and resulting slag molten from a collection and post-reaction zone, characterized in that the gasification zone in a Haufvjerk from the Starting materials for the carbothermic reduction, a cavity or at least a .foirbelzone produced from such loosened heap, which is maintained at 13OO to 3300 ⁰ ; that the reduction zone is generated above and to the side of the gasification zone} and that gasification is carried out simultaneously in the reduction zone, with water vapor and carbon dioxide contained in the primary crude synthesis gas reacting with carbon-rich material to form further synthesis gas. AP C 10 j / 255 057/7 62 980 11 2 A method according to item 1, characterized in that in the gasification zone with a stoichiometric excess of acid in relation to the oxidation to GO and produces a 2000 to 3300 ⁰ C hot primary raw synthesis gas., 3. The method according to item 1, characterized in that is injected into the gasification zone as additional gases and gasification water vapor and / or carbon dioxide and produced by reaction with carbon 1300 to 2000 ⁰ C hot primary crude synthesis gas. 4. The method according to any one of items 1 to 3 », characterized in that from the top of the preheating so much carbon-rich material in excess, based on the stoichiometry of the endothermic carbothermic reduction, in the surrounding the gasification zone heap introduces that emerging from the gasification zone steam and / or carbon dioxide react with carbon to further synthesis gas. 5. The method according to any one of items 1 to 4, characterized in that freed the preheating zone upwards leaving raw synthesis gas from dust and ash and these pesticides at least partially in the circuit together with fresh carbonaceous material again into the gasification zone, 6. Method according to one of the items 1 to 5i, characterized in that the starting materials for carbo- thermal reaction in particle sizes of 10 ».20 mm, 20 - 4-0 mm and / or 40 - 60 mm sets, preferably for optimal gas distribution layers of different particle size ranges one above the other AP C 10 j / 255 057/7 52 980 11 7. The method according to any one of items 1 to 6, characterized in that the preheating zone and the Eeduktionszone with coke, iron scrap and · possibly quartz fed, -wobei wins as the reaction product of the carbothermic reduction at 1300 to 1800 ⁰ C ferro silicon. 8 «method according to one of the items 1 to 6, characterized in that the preheating zone and the reduction zone with coke or anthracite and lime fed, which is obtained as the reaction product of the carbothermic reduction at 1800 ⁰ C to 2300 ⁰ C calcium carbide. 9. The method according to item 8, characterized in that one injects a portion of the lime in the form of at the Carbidvergäsung accumulating and then feinpulveriäertem hydrated lime together with the finely divided carbon-rich material in the gasification zone. 10. Method according to one of the items 1 to 6, characterized in that the preheating zone and the reduction zone are charged with coke and oxidic iron ore, • where it is obtained as the reaction product of the carbothermic reduction at 13ΟΟ to 1800 ⁰ C metallic iron. 11. The method according to any one of items 1 to 6, characterized in that laan the preheating zone and the reduction zone with coke or anthracite, lime, iron and / or scrap iron and / or iron oxide, and ggfl. Supplied quartz, wherein the reaction product of the carbothermic reductions at 1800 to 2300 ⁰ C. σ ίο j / 255 057/7 62 980 11 - 23 Calcium Carbide and Ferro Silicon Wins, 12. The method according to any one of items 1 to 6, characterized in that the preheating zone and the Heduktionszone charged with coke, calcium phosphate and quartz, wherein mantis heath product of the carbothermic reduction at 13ΟΟ to 1700 ⁰ G elemental phosphorus wins, Method according to one of the items 1 to 12, characterized in that the additional gas used is CO, COo, Np, steam or recycled synthesis gas, 14. The method according to any one of items 1 to 13, characterized in that one provides in the symmetry axis of the preheating a laterally closed and top pyrolysis zone, supplied by the above at least a portion of the gasification and carbothermic reduction specific carbon-rich material and degassed therein and is carbonized, the coke and volatile JSntgasungs- pyroly.siert be forced into this zone at from 400 ⁰ C. to 1100 to 15ΟΟ ⁰ C rising temperatures. Method according to item 14, characterized in that water vapor is introduced into the pyrolysis zone from above and, by its reaction with carbon, a certain hydrogen content of the crude synthesis gas is established. 16, method according to item 14, characterized in that one enters the pyrolysis zone as a carbon-rich material AP C 10 J / 255 057/7 62 980 11 used shredded old tires of motor vehicles. 17. Apparatus for carrying out a process for the production of synthesis gas (GO + Hp) by autothermal gasification of finely divided, carbon-rich materials with oxygen in the presence of starting materials for an endothermic carbothermic reduction, comprising a shaft furnace which, in the operating state, viewed from top to bottom, an elongate preheat zone, a reduction zone, and a collection and post-reaction zone which openly merge into one another so as to comprise a gasification zone openly connected to the reduction zone; Nozzles for the joint supply of pulverized coal, oxygen and possibly additional gases, feed lines for the starting materials of the thermal reduction and a discharge line for crude synthesis gas at the top of the shaft furnace; and withdrawal conduits from the collection and post-reaction zone at the bottom of the shaft furnace for withdrawing molten slag and molten reaction product from the carbothermic reduction, characterized in that the shaft furnace is a shaft-shaped tapping generator (8) of circular cross section and centrally upwardly inverted bottom; that in the operating state, the reduction zone (10) encloses the gasification zone (7); that the collection and Hachreaktionszone (12) surrounds the bottom invagination (9) annularly; that at least one, nozzle (4) through the bottom invagination (9) is introduced with connected lines (3; 5; 6) for the common supply of finely divided, carbon-rich material, oxygen and optionally, additional gases and pulverulent starting materials for the carbothermic reduction. AP G 10 J / 255 057/7 62 98υ 11 18. Device nach'Punkt 17, characterized in that in the upper part of the Abstichgenerators (8) vertically and circularly arranged separating plates (26) for delimiting a columnar tree in the axis of symmetry of the Abstichgenerators (8) above the Yergasungszone (7); a transport line (25) for feeding the columnar tree with the carbon component of the starting materials for the carbothermic reduction, and at least 2 transport lines (15) for the supply of further starting materials for the carbothermic? Reduction to form a the inner wall of the tapping generator (8) protective annular bulkhead on-points. 19. The device according to item 18, characterized d _a by that the partitions (26) by the head of the tapping generator (8) from outside to inside by applying shots quasi endless until melting above the gasification zone (7) consumption-dependent nach-feasible , 20. The device according to item 18 or 19, characterized in that the entirety of the circularly arranged separating plates (26) has the shape of a Hohres. 21. Device according to one of the points 18 to 20, characterized in that the separating plates (26) are perforated like a lattice and are permeable to gas. 22. Device according to one of the points 17 to 21, characterized in that the bottom of the Abstichgenerators (8) with the Semmel- and Hachreaktionszone (12) is provided with a slope. AP σ .10 J / 255 057/7 62 980 11 - 26 - - 22 are poured. 23 * Device according to one of the points 17 to 22, characterized in that the tapping generator (8) provided with a lateral support ring (29) and rotatably mounted on a sprocket, with drive (30) and 1 to 20 degrees inclined to the vertical is · that the Abstichgenerator (8; DINEN cover (27) bears, that the cover (27) _fixed's nozzle (4) and (through the cover 27) or out (to the nozzle 4) connected to supply and exhaust lines, and towards the tapping generator (8) are sealingly sealed against gas passage with seals (28). 24, device according to one of the points 17 to 23 », characterized in that the nozzle (^) introduced through the bottom invagination (9) is surrounded by a cooling chamber charged with coolant, Device according to one of the points 17 to 23 »characterized in that at least 2 nozzles (4) are provided, the tips of which and the wall of the tapping generator (8) being in the area of the bottom invagination (9) by cooling chambers (31 ) are protected from heat. 26. Gate direction according to one of the points 17 to 25 »characterized in that the inner wall of the collecting and Nachreektionszone (12) with refractory material (32) is lined. Ropes drawings