DE3035485A1 - CONTINUOUS METHOD FOR GASIFYING CARBON-CONTAINING MATERIALS IN A FLUID BED SYSTEM - Google Patents

Description

DR. BERG DIPL.-INÜ. STAPF DIPL.-ING. SCHWABE DR. DR. SAIsDMAiR

PATENTANWÄLTE Postfach 860245 8000München 86 303548

Dr. Berg Dipl.-Ing. Stapf and Partner, P.O.Box 860245, 8000 Munich 86 ' Your reference Our reference Mauerkircherstraße 45

Yourref. Ourref. 22. 105 8000 MUNICH 80 Sept. 19, 1980

Lawyer file number: 31 105

ÜONSANTO COJYIPANY St. Lο u i s, Missouri / USA

Continuous process for gasifying carbon-containing materials in a fluidized bed system

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130015/0917

«(089) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850

988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

988274 TELEX: Bayet Vereinsbank Munich 453100 (bank code 70020270) 983310 0524560BERGd Postscheck Munich 65343-808 (bank code 70010080)

2O-21-0141A GW

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The present invention relates to the treatment of coals ^ · materials containing substance. On the one hand, the present invention relates to the treatment of carbon containing Materials such as coal, coke, and hydrocarbons for the production of oxides of carbon therefrom. The invention also relates to a method for Production of high purity synthesis gas, carbon monoxide, or a mixture of hydrogen and carbon monoxide, made of carbon-containing materials.

Coal and coke can be used with oxygen and / or steam at relatively high temperatures to convert the coal or the Coke is treated in hydrogen and carbon monoxide, which products are used for various purposes including the synthesis of organic compounds therefrom, are useful. If steam alone is used to gasify coal or coke is used, it is necessary to supply heat from an external source. Made by the gasification of coal Heat released with relatively pure oxygen leads to excess heat. As a result, there will be steam and oxygen normally used together in such proportions that the. Net heat of reaction is sufficient to maintain the desired temperatures for the gasification of the coal or coke. When using the combination of steam and oxygen in the

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In another way, the oxygen can be used in a substantially
pure form can be used, and by such
The procedure is continuous, thermal
appropriate and provides a gas that hydrogen and
Contains carbon monoxide.

The use of oxygen is an economic burden and increases the complexity of the process. If you put the oxygen in the process in the form of air instead of
introduces purified oxygen, the economic advantage achieved by the use of air is negated by the fact that the product gas has large amounts of diluent
Contains nitrogen. It is therefore desirable to provide a method which can purify the oxygen
eliminated, but provides a gas that is essentially free of nitrogen.

U.S. Patent No. 2,602,809 describes the gasification of solid, carbon-containing materials using metal oxides such as Fe-, 0. or Fe ~ 0 ₃ , which serve as the main source of oxygen in the reaction. The process described uses a countercurrent of coal and metal oxide in a fluidized state in a reactor
Performing the reduction of the metal oxide for release
of oxygen and causing the coal to oxidize with the

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released oxygen with formation of carbon oxides. The reduced metal oxide is reoxidized for a new one Use with air where it is heated by the heat from the exothermic air oxidation reaction. If you have a If synthesis gas product desires, some of the reduced metal oxide is taken with steam at an elevated temperature Formation of hydrogen reoxidized. This hydrogen is then combined with the carbon monoxide obtained from coal gasification mixed to form the synthesis gas.

The present invention provides a unified process for producing high purity synthesis gas from carbon containing materials. In this method, a metal-oxygen-containing material is used as a transfer agent used for oxygen and heat for the oxidative gasification of carbon-containing material. That Metal-oxygen-containing material can be characterized as a heat and oxygen carrier and is used here generally referred to as an oxidizing agent. According to a main aspect of the present invention, steam, Carbon dioxide, synthesis gas or mixtures thereof for swirling and transporting the oxidizing agent through an after above flowing direct current system used. Synthesis gas is first oxidized by the oxidizing agent and heated under Formation of carbon dioxide, or water and carbon dioxide, in

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an oxidizing agent reducing zone, prior to the contact of the oxidizing agent and gases with the carbon containing material in a gasification zone. The carbon-containing materials are predominantly turned into carbon monoxide, or carbon monoxide and hydrogen, oxidized in such a way that the nitrogen contained in the air does not contaminate the product synthesis gas. The gasification of the carbon-containing materials is carried out by accomplished alternating oxidation and reduction of a fluidized oxidizing agent. After the gassing it will reduced oxidizing agents, which are in the form of the elemental metal or in a lower oxidized state can, reoxidized in an oxidizing zone and the cycle repeated. The term reduced oxidizer, such as it is used here, refers either to the elemental metal, or to a lower oxidation state, as obtained by reducing the oxidizing agent.

Typical objects of the present invention are to provide

(1) a process for the gasification of carbon-containing materials,

(2) a process for converting carbon-containing materials into carbon oxides,

(3) a method for producing a synthesis gas, and

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(4) an improved method for gasifying carbon-containing materials in which the heated Oxidizing agents through synthesis gas at least partially with the formation of carbon dioxide, or steam and carbon dioxide, before contact with the carbon-containing material and its gasification is reduced.

Different other tasks, goals and benefits of the present Invention will become accessible to a person skilled in the art after reading this description, the drawing and the claims have been made.

In accordance with the present invention, there is a three-zone system used in which an oxidizing agent, such as iron chromite ore, is swirled at an elevated temperature and at least partially reduced by synthesis gas in a reducing zone with the formation of carbon dioxide, or steam and carbon dioxide will. The partially reduced oxidizing agent and accompanying gases move into one under vortex conditions Gasification zone in which a contact with carbon containing Material is made under conditions by which the carbon-containing material becomes carbon oxides, is oxidized mainly to carbon monoxide. The gaseous effluent from the gasification zone is removed for purification and the reducing oxidizing agent into an oxidizing agent

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Zone transferred in which it is brought into contact with air under such conditions that the oxidizing agent reoxidized and heated. Part of the heat released by air oxidation is used as intrinsic heat in the Oxidizer stored, which provides heat for the reduction and gasification zones. That heated, reoxidized Oxidizing agent is returned to the reduction zone .

In the preferred method of operation in the various zones, particulate oxidant is in the fluidized state held and continuously circulated through the reaction system. Throughout the entire gasification zone are linear Maintain gas velocities such that the solid materials are entrained in the gases. It will Gas velocities in excess of about 3.05 m / s are used for such operation. The actual gas velocities used will depend on the size, shape and densities of the solid materials used. With this one Type of operation, means are used inside or outside the gasification zone for the separation of solid materials that are in have been entrained in the gaseous effluent will.

The oxidizing agent useful in the present invention

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will usually be a particulate material of such a size that it is capable of being vortexed, and it will contain a metal oxide that is reducible and reoxidizable under the operating conditions of the system. It can use various metal oxides and metal oxide-containing materials as oxidizing agents to supply oxygen can be used in the heduction and gasification zones. Contain materials suitable as "oxidizing agents" Oxides of iron, cobalt, nickel, molybdenum, manganese, barium, vanadium, chromium, copper, ger, uranium, and mixtures thereof. Naturally occurring ores, such as iron chromite ore, which contain iron oxide can be used as. Oxidizing agents can be used.

The temperature used in the reduction and gasification can vary over a wide range. Preferably, such reaction will be conducted in a range of 80O ⁰ C to 1200 ° C. The pressure on the system can also vary. The system can operate at pressures from 34.5 to 13.789 kPa.

As mentioned earlier, the invention uses Moving a vortex system with the flow direction upwards, wherein the oxidizing agent and the carbon-containing material flow in the same direction. The vortex

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and transportation of the materials are achieved by introducing a carrier gas into the system. The carrier gas can to be inert to the various reactions, but it is preferably steam, carbon dioxide, or synthesis gas Mixtures thereof that enter into the reaction, thereby eliminating excess gas handling. The carrier gas is introduced at such rates that it swirls and transports the materials and is turbulent Maintains flow of materials in the system. The introduction of gases at speeds from 3.05 to 9.14 m / s will usually be sufficient, however this variable is determined by the size, shape and density of the materials who move through the system is dictated.

The invention will now be described in detail with reference to the drawing. Figure 1 is a schematic Explanation of the device in the with reference to the gasification of coal using a mixture of Hydrogen and carbon monoxide synthesis gas system described.

According to Figure 1, fresh oxidizing agent is as required from the storage container 1 through the line 2 into the oxidation zone 3 introduced. Air is compressed in the compressor 4 and through the line 5 at the bottom of the oxidation zone 3

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guided. The oxidation zone 3 is based on such conditions held, in which the oxidizing agent is oxidized by the oxygen from the air in an exothermic reaction will. The exothermic reaction heats the oxidizing agent.

The oxidizing agent is transported from the oxidation zone 3 through the line 6 into the lower part of the reduction zone 7. Synthesis gas is introduced through line 8 into the bottom of the reduction zone at a rate such that the oxidant is swirled and moves up through reduction zone 7 into gasification zone 9. In the reduction zone 7, the contact of the synthesis gas with the heated oxidizing agent causes a reduction of the oxidizing agent and the formation of water and carbon dioxide from the synthesis gas milled in the range of 40 to 200 microns (40 to 200 µm) and dried to less than 2% moisture by contact with the effluent from the oxidation zone 3 introduced through line 13. The gases from the dryer pulverizer 12 are removed through line 14. The dried / pulyerized coal is transported through the line 15 into the feeder 16. The coal is metered from the feeder 16 through the line 17 and introduced into the gasification zone 9 through the line 18.

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Additional synthesis gas and steam are fed in through lines 31 and 32 to move the coal into gasification zone 9 to move. In the gasification zone 9, the coal is by contact and turbulent mixing with the upward flowing Mixing of heated oxidizing agent and gases from the reduction zone 7 to predominantly carbon monoxide and hydrogen oxidized. The reaction gases and the oxidizing agent are separated. Such a separation can be through a cyclone separator can be accomplished, which is arranged in the upper part of the gasification zone 9. That reduced Oxidant is removed from the top of gasification zone 9 through line 19 and into the oxidation zone 3 introduced for reoxidation and reheating. The gaseous effluent is from the gasification zone 9 through the line 20 removed and introduced into the cyclone 21. Optionally, the reaction gases and the oxidizing agent removed together from gasification zone 9 through line 20 and separated in a first cyclone (not shown) will. In this case, the line 19 would be the first cyclone with the oxidation zone 3 for conveying the oxidizing agent yerbind and the gaseous effluent would be directed into the cyclone 21. In the cyclone 21 are carried away Solids such as grayling and fine debris separated and removed by line 22 for disposal. The gaseous waste stream is then through line 23 into the

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Sulfur removal zone 24 out. The desulphurized gaseous The effluent is fed to the gas compressor 26 through line 25. The desulfurized effluent is passed through line 27 passed into a zone 28 for the removal of acidic gas, from which carbon dioxide by line 29, and substantially pure synthesis gas can be withdrawn through line 30. A portion of the gaseous effluent from the sulfur removal zone 24 becomes the reduction zone through lines 31 and 8 7, and passed through the lines 31 and 18 into the gasification zone 9 for transporting the coal. Like in the drawing indicated, a heat exchange of the various gas streams can take place. Likewise (not shown) the fixed Oxidizer and the coal with a gas, such as carbon dioxide, between the various zones to remove Gases such as nitrogen are stripped off.

If steam, carbon dioxide, or mixtures thereof are to be used, these gases can be supplied through line 32 in introduce line 18 instead of or in addition to synthesis gas from line 31. If steam, carbon dioxide, or Mixtures of these are to be used as the only gas for swirling and reducing the oxidizing agent, these gases are in the reduction zone 7 through the line 8 introduced from line 31 instead of synthesis gas. Various levels and auxiliary functions, such as

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the dryer-pulverizer 12, the feeder 16, the compressors 4 and 26, cyclone 21, sulfur removal and acid gas removal 28 are well known to those skilled in the art Standard functions and do not need to be described further here.

The particle size of the carbon-containing material, if this is a solid, and that in the material according to the invention Process used "oxidizing agent" can be used within vary over a wide range. However, the solids are usually in the 40 particle size range up to 200 microns (40 to 200 jam) used.

According to the present invention, any material containing carbon can be gasified. The inventive Process is particularly useful for gasification of solid, carbon-containing materials, such as of coal, including a wide range of coal from lignites to anthracites, animal charcoal, Peat, coke, coke dust, wood chips, KeIp, and the like. Also liquid and gaseous hydrocarbons, for example Crude oils as such, or fractions, such as asphalt and vacuum residues, shale oil, refined oils, such as heating oil, cycle oil, bunker C-oil and tar, Products from chemical plants, such as aromatic and heavy oils

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Tars, and tars from the tar sands, can be considered the carbon containing material can be used as a feed for the process according to the invention.

In summary, in the process according to the invention, carbon containing materials with the formation of synthesis gas, carbon monoxide, or a mixture of hydrogen and carbon monoxide, in a unified three-zone system (oxidation zone, reduction zone and gasification zone) using a metal oxide as a source of oxygen and heat for gasification with carbon monoxide, or steam and carbon monoxide, gasified. The synthesis gas comes with the metal oxide before gasification to release the oxygen and converting the synthesis gas to carbon dioxide, or steam and carbon dioxide, as a gasification medium in contact.

The practice of the present invention will now be explained in detail in the following examples.

In the following examples there was the one to carry out of the special coal gasification experiments used a reactor made of a 61 cm long pipe made of stainless steel list 40 with a main section with an inner diameter of 5.2 cm, which at the bottom with a conical section with a inscribed angle of 40, and at the top with an enlarged

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terten section with an inner diameter of 6.4 cm and 24.1 cm long, was provided with a conical, flanged connecting portion. That Fluidizing gas is passed through the bottom of the conical section of the reactor and the coal at one in the center Point of the conical section introduced. The gasifying agents are supplied through a gas distributor extending from the top of the reactor extending down through the fluidized bed and into the conical section. the Product gases are withdrawn through the top of the reactor for analysis. The reactor is insulated with a sheathed electrical resistance heating.

B e i s ρ i e 1 1

This example illustrates the gasification of various coals using steam as the gasification agent and iron chromite ore from the Transvaal Mines South Africa as an oxidizing agent.

For each run, the reactor contained 1200 g [75 to 350 microns (75 to 350 pounds)] of the nitrogen spun oxidizer . The oxidizing agent is kept at a temperature of 1050 ° C and a pressure of 34.5 kPa. In 3.0 pounds / min of nitrogen entrained coal is fed into the reactor together with approximately 3.6 g / min of water as steam as a

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gassing agent introduced. Each attempt takes about 30 minutes carried out long, the reaction gases are periodically removed and analyzed. The gas velocity on Coal inlet is approximately 0.2 m / s and at the reaction gas outlet approximately 0.36 m / s. The results for each particular coal tested are in the table below I stated in which the production is the cubic meters of gas produced per kilogram of converted coal, the selectivity the mole percent of carbon converted to CO and productivity is the kilograms of carbon, converted per hour per cubic meter of oxidant bed mean.

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T a b e 1 1 e

attempt

Time (min)

Production (m ³ / kg)

H ₂ / CO-

Molar ratio

selectivity
(Mole percent)

Productivity (kg / h / m ³ )

4 6 8

10 15 20 25 30

4 6 8

10 15 20

1.77 2.45 3.30 2.80 3.03 3.18 3.05 3.08

1.68 2.18 2.23 2.24 2.30 2.32

0.4

1.1 2.0 1.4 1.5 1.5 1.5 1.6

0.8 1/2 1.2 1.2 1.3 1.3

64.8
73.1
71.9
77.7
81.9
86.0
82.6
81.1

63.8
80.0
81.1

82.5
83.8
83.8

209.6 219.2 204.8 208.0 198.4 188.8 201.6 200.0

232.0 212.8 232.0

233.6 230.4 225.6

Table I - continued

attempt

Time (min)

Production (m ³ / kg)

H ₂ / CO-Mo! Ratio

selectivity
(Mole percent) productivity
(kg / h / m ³ ) f
J 83.8 225.6 ··
ι 84.4 224.0 16.8 153.6 61.3 160.0 71.6 156.8 O
CO 75.0 150.4 OO
4M 76.9 145.6 78.5 163.2 79.2 168.0 81.3 160.0 75.5 158.4 76.4
76.7 158.4
164.8 79.0 169.6

CjO
CD

25th 2.31 30th 2.32 4th 1.34 6th 1.92 8th 2.46 10 2.76 15th 2.90 20th 2.74 25th 2.71 30th 2.73 8th - 10 - 15th - 20th _

1.3 1.3

0.6 1.0 1.5 1.6 1.6 1.6!, Β 1.6

1.8 1.8

1.9 1.8

Table I - continued

attempt

Time (min)

Production (ItI ³ Ag)

H ₂ / CO molar ratio

Selectivity (mole percent)

Productivity (kg / h / m ^J )

25 30

1.8

79.5 78.5

176.0 176.0

attempt

money

Coal feed rate (g / min)

A. Wyoming Bog Coal 3.4 B. Texas lignite 3.9 C. Illinois # 6 coal 3.7 D. Indiana coal 3.4

A6-

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B 'e i s ρ i e 1 2

This example illustrates the gasification of coal in the presence of an inert heat carrier and, consequently, the improvement the use of an oxidizing agent when the results of this example compare with those of Experiment A of Example 1 can be compared.

The procedure was as in Example 1, Experiment A, with the exception that the reactor contained 1000 g of ct-aluminum oxide instead of an oxidizing agent. The Wyoming bog coal was fed at a rate of 3.5 g / min and water in the form of steam at a rate of 3.7 g / min.

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T a b "e '1 1' e '

II

Time
(min)

production

H ₂ / C0 molar ratio

selectivity
(Mole percent)

Productivity (kg / h / _m 3)

4th
6th
8th

10
15th
20th
25th
30th

2.36 2.98 3.03 2.95 2.90 2.86 2.84 2.83

1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6

71.9
73.5
73.7
73.5
74.0
75.2
74.3
75.4

163.2 188.8 193.6 190.4 193.6 187.2 185.6 184.0

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B e i s ρ i e 1 3

This example illustrates the gasification of coal using steam and CO ~ as gasification agents, in contrast to steam alone as shown in Example 1.

The procedure was as in Experiments A and B of Example 1, with the exception that 1.8 g /
min of water in the form of steam and 2.24 Jl / min CO _{2 were} fed.

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T a b e '1 1 e

III

attempt

Time (min)

Production (m ³ / kg)

H ₂ / CO-Mo! Ratio

Selectivity (mole percent)

Productivity (kg / h / m ³ )

4 6 8

10 15 20 25 30

4 6 G

10 15 20

25 30

2.65 2.83 2.91 3.02 2.90 2.98 2.95 2.93

0.4 0.5 0.6 0.6 0.6 0.2 0.1 0.1

0.5 0.5 0.5 0.5 0.5 0.1

0.1 0.1

74.6 80.2 82.2 83.0 82.5 82.5 82.6 83.8

83.1 83.4 83.0 85.4 85.2 84.6

84.6 84.9

228.8 220.8 211.2 214.4 219.2 288.8 225.6 225.6

232.0 232.0 228,

^24O '° € O 241.6

243.2 243.2

B e i s ρ i e 1 4

This example explains the gasification of coal using repeated reoxidations of iron chromite ore as an oxidizing agent .

The reactor was filled with 1200 g of oxidizing agent and heated to 1050 C. 3.6 g / min Wyoming bog coal, entrained in 3.0 Å / min nitrogen along with 3.5 g / min steam into the reactor over a period of 20 minutes introduced during which time samples of the reaction gases were taken and analyzed. The reactor runs on steam and purged with nitrogen. To reoxidize the oxidizing agent, air is fed into the reactor for a period of Initiated 30 minutes. Coal, nitrogen and steam are returned to the reactor in the same amounts during one A period of 30 minutes is supplied and samples of the reaction gases are taken and analyzed. The reactor was turned on Purged with steam and nitrogen, and air passed in for 30 minutes to reoxidize the oxidizing agent again. Again, equal amounts of coal, nitrogen and steam were added to the reactor, and samples of the reaction gases were taken and analyzed. The results are set out in Table IV below.

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T file IV

attempt

Time
(min)

Production (m ³ / kg)

H ₂ / CO molar ratio

selectivity
(Mole percent)

Productivity (kg / h / m ³ )

approx ο ο

18th
20th

20th 30th

0.89 0.82

0.99 0.98

1.7 1.8

1.4 1.4

78.6
79.0

79.9
83.1

228.8 211.2

252.8 251.2

20th 30th

0.74 0.78

1.5 1.6

86.0
81.1

188.8 200.0

B e j 's ρ i e 1 5

This example illustrates the reduction of oxidizing agent with a gaseous fluid in the absence of coal.

The reactor is filled with 1160 g Eisenchromiterz and held at 1050 ⁰ C and 5 psig (34.5 kPa). A mixture of 3.65 Jl / min H ₂ and 3.50 Å / min CO is fed into the reactor. Samples of the product gases and the oxidizing agent are taken at 1 minute intervals and analyzed. The results are set out in Table V below.

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T a b e 1 1 e

I. Time
(min) co ₂ Product gas, Mole percent H ₂ O * Oxidizing agent oxidation
O / Fe t \
to
co 0 - CO ^Η 2 - 1.50 0> 1 48.7 - 47.1 1.42 co 2 45.8 4.0 0.3 48.9 1.34 O
O 3 41.1 4.3 I ₁ I 48.6 1.27 O
OO
cn tn 4th 26.4 8.1 2.3 41.8 1.22 CO O 5 14.6 22.5 9.4 26.5 1.19 -j 6th 12.4 33.6 25.4 21.7 1.16 7th
8th 11.5
6.7 35.3 30.6 17.2
13.7 1.14
1.12 9 4.7 37.9
40.9 33.4
38.7 8.4 1.11 * As steam 45.1 42.0

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Example 1 game 6

This example explains the reoxidation of the example 5 reduced oxidizing agent obtained.

Air is introduced at a rate of 7.2 pounds per minute into the reactor, which contains 1160 g of reduced iron chromite ore and is kept at 105O ⁰ C and at a pressure of 34.5 kPa. Samples of the reactor gases and the oxidizing agent are periodically taken and analyzed. The results are set out in table yi below:

Ta b e 1 1 e

VI

Air, Mole percent Oxidizing agent oxidation
O / Fe Time
(min) ° 2 ^N 2 1.20 0 - 1.22 1 1.4 98.6 1.34 5 1.5 98.5 1.39 7th 6.5 93.5 1.41 9 12.4 87.6 1.43 11 16.1 83.9 1.46 19th 18.4 81.6 1.46 21st 18.8 81.2

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B e i s ρ i el '7

This example illustrates the gasification of coal using steam, CO ₂ , and steam and CO 2, as gasification agents.

The procedure is as in Example 1, Experiment A, with the exception that 1.8 g / min of water in the form of steam and 2.24 Å / min of CO _{2 are} fed in as the gasification agent in Experiment A. In experiment B, 3.6 g / min of water are fed in in the form of steam and in experiment C, 4.48 Å / min of CO ₂ . The results of the analyzes of periodically taken samples of the product gas are set out in Table VII below.

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T a b e Γ 1 e

VII

attempt

Time
(min) production
(m ^J / kg) 5 2.89 10 2.91 15th 2.93 5 3.02 10 2.90 5 2.98 10 2.95

H ₂ / C0 molar ratio

selectivity
(Mole percent)

1.4 1.4 1.4

0.6 0.6

0.2 0.1

79.9
81.0
83.1

83.0
82.5

82.5
82.6

Productivity (kg / h / m ³ )

196.8 192.0 198.4

214.4 219.2

228.8 225.6

B e i s ρ i e 1 8

This example illustrates the advantages of the present invention in the pre-reduction of the oxidizing agent in FIG Gasification product distribution.

Example 1, experiment A is repeated in a 30 minute experiment, the reaction gas composition and the oxidation of the oxidizing agent being analyzed periodically. The results are set out in Table VIII below.

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Day 1 T e 'VIII

Time
(min)

Oxidizing agent Oxidation O / Pe

CO,

CH ₄ CO (mole percent)

H,

CO
CD
O

JO
20th
30th

1.5 J, 3 J, 2 J, 1 1.1 J, O 0.9 0.8

79.2 1.8 14.2 4.8 . U)
IO 28.9 2.4 49.5 20.1 GJ
Oo 13.1 1.7 40.2 45.2 10.1 1.5 29.4 59.0 9.3 1.5 37.4 51.8 5.8 1.8 36.4 56.0 ο 6.3 2.0 35.5 56.2 ΟΙ CQ

Example 9

This example illustrates, with reference to the drawing, the continuous gasification of coal according to the present invention. Iron chromite ore is circulated through oxidation zone 3, line 6, reduction zone 7, gasification zone 9 and line 19 at a rate of 190 g / min. The ore-containing FeO which enters the oxidation zone 3 through line 19 is brought into contact with air introduced at the bottom of the oxidation zone 3 at a rate of 11.2 Å / iain and 8.9 Å / min nitrogen at the top of the Oxidation zone 3 withdrawn through line 13. The exothermic oxidation taking place in the oxidation reactor 3 supplies 65.8 kcal / mol of oxidized PeO and heats the ore to 1150 ° C., and oxidizes the FeO to Fe ₃ O ₃ . The ore containing ^ e ₃ O ₃ is removed from the oxidation reactor 3 through the line 6 and introduced into the reduction zone 7. Synthesis gas, consisting of equal volumes of H ₃ and CO, is fed through line 8 into the reduction zone 7 at a rate of 4.48 5 / min. The Fe ₃ O ₃ is reduced by the synthesis gas with the formation of steam and CO ₂ . The reduction is endothermic and requires 4.6 kcal / mole of reduced Fe ₃ O ₃ , which means that the temperature in the reduction zone is 7J.125 ° C. The reduced ore and the gases flow into the gasification zone 9, into which 3.4 g / iuin finely divided coal is fed through the line 18.

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leads to be. The gasification of the coal with the ore and steam and CO 2 is endothermic and requires 36.2 kcal / mol, whereby the temperature in the gasification zone 9 is 1025 ° C. The reduced ore-containing PeO is withdrawn from gasification zone 9 and reintroduced into oxidation zone 3 through line 19. The effluent from the gasification zone 9 is passed through line 20 at a rate of 10.3 £ / min removed and contains .10 mole percent CO _2/1 -Molprozent CH _4, 54 mole percent CO and 35 mole percent H ". The term PeO, as used in this example, and the present invention used is a mixture of iron oxides having an average ratio of oxygen to iron of about 1.0 to l, 2j, the term Pe ₀ O., means a mixture of iron oxides with an average oxygen to iron ratio of 1.4 to 1.6.

B e i s 'ρ j' e 1 10

This example illustrates the continuous gasification of No. 6 fuel oil according to the present invention.

Example 9 is repeated using 2.8 g / min No. 6 fuel oil as a feed instead of the 3.4 g / min coal. Iron chromite ore is circulated at a rate of 200 g / min instead of 190 g / min and requires the gasification reaction 48 kcal / mole instead of 36.2 kcal / mole. The drain

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from gasification zone 9 is removed at a rate of 12.1 Å / min instead of 10.3 Å / min and contains 13 mole percent CO ₂ , 1 mole percent CH ₄ , 42 mole percent CO and 44 mole percent H ₂

In Example 11, the reactor used to carry out the particular gasification experiments consists of one 48.3 cm long stainless steel pipe list 40 with a Main section with an inner diameter of 4.1 cm, which at the bottom with a conical section made of stainless steel, Type 310, 3.2 cm long, gradually tapering to 0.63 cm in diameter, and the one at the top Flange carries. Fluidizing gas and carbon-containing material is drawn through the bottom of the conical section of the Reactor introduced. The product gases are removed through the top of the reactor for analysis. The reactor is with encased in an insulated, electrical resistance heater.

B e 'is ρ ie 1 1 1

This example illustrates the gasification of various carbon containing materials using Carbon monoxide as a gasifying agent and iron chromite ore from the Transvaal Mines of South Africa as an oxidizing agent.

For each experiment, the reactor contained 580 grams [75 to 350 microns (75 to 350 µm)] of nitrogen-swirled oxide

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130015/0917

media. The oxidizer is at one temperature kept at 1050 ° C. The carbon containing material is fed into the reactor together at approximately 1.5 pounds / min Carbon dioxide fed in as a gasification agent. Each experiment is carried out for approximately 15 minutes, taking samples the reaction gases are periodically removed and analyzed. The gas velocity in the reactor is approximately 0.3 ft / s (9.1 cm / s) and the gas / solid contact time approximately 1.9 sec. The results for each particular material tested are given in Table IX below, in which production means the cubic meters of gas that are formed per kilogram of converted material will.

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130015/0917 i-

Tab e 1 1 e IX

attempt

Time (min)

Production ³

Product (mole percent)

CO

CO,

Carbon conversion (mole percent)

CO O O

1 3 5 7 9

11 13

1 3 5 7 9

0.60 0.61 0.55 0.58 0.58 0.65

0.55 0.59 0.57 0.47

0.46 99.54 6.88 93.12 6.56 93.44 10.11 89.31 32.99 67.01 49.29 50.71 51.58 47.75 0.55 99.45 3.41 96.59 4.64 95.36 5.83 93.78 33.85 66.15

29.8 55.8 52.2 44.7 41.0 37.3 41.0

15.8 25.0 46.5 50.1 55.0

O CO Vi

00

Table IX - continued

product

. Time production of carbon conversion

test _(min) (m ³ / kg) CO CO ₃ (mole percent)

0.49 45.22 54.78 50.0

0.72 51.44 48.27 39.3

45 , 22 54, 78 51 , 44 48, 27 57 , 50 42, 50

O 15 0.64 57.50 42.50 35.8

ο try carbon material

A Ken tucky coal 1.06

(75.8% by weight carbon - 1.2% by weight hydrogen)

B U.S. Steel pure coke 1.005

(83.5 wt% carbon - 1.4 wt% hydrogen) O

CO Cn

CXD .CT)

U) «3

CO 03

· Ίι5 ·

After removal of CO _? the product gases in experiment A contained 93% CO and 7% H ₂ and in experiment B 95% CO and 5% H 2.

Example 12

This example explains, with reference to the drawing, the continuous gasification of charcoal according to the present invention. Iron chromite is circulated at a rate of 190 g / min through the oxidation zone 3, the line 6, the reduction zone 7, the gasification zone 9 and the line 19. The ore-containing FeO which enters the oxidation zone 3 through line 19 is contacted with air supplied at the bottom of the oxidation zone 3 at a rate of 11.2 Å / min and 8.9 liters / min nitrogen from the top of the oxidation zone 3 withdrawn through line 13. The exothermic oxidation taking place in the oxidation reactor 3 supplies 65.8 kcal / mol oxidized PeO and heats the ore to 1150 ° C. and oxidizes the FeO to Fe ₃ O ₃ . The ore-containing Fe ₃ O ₃ is removed from the oxidation reactor 3 through the line 6 and introduced into the reduction zone 7. Carbon monoxide is fed through line 8 into reduction zone 7 at a rate of 4.48 Å / min. The Fe ₃ O ₃ is reduced by the carbon monoxide with the formation of CO ₃ . The reduction is almost thermoneutral, which means that the temperature in the reduction zone

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ne 7 is 1135 C. The reduced ore and gases flow into gasification zone 9, into which 2.94 g / min finely divided Illinois # 6 charcoal is introduced through line 18. The gasification of the charcoal with the ore and CO ₂ is endothermic and requires 40.0 kcal / mol, whereby the temperature in the gasification zone 9 is 1025 C. The reduced FeO containing ore is withdrawn from the gasification zone 9 and reintroduced into the oxidation zone 3 through the line 19. The effluent from gasification zone 9 is removed through line 20 at a rate of 9 Å / iain and contains 15 mole percent CO ₂ / 84.8 mole percent CO and 0.2 mole percent H ₂ . The term PeO as used in this example and the invention means a mixture of iron oxides with an average ratio of oxygen to iron of 1.0 to 1.2; the term Fe ₂ Oo means a mixture of iron oxides with an average ratio of oxygen to iron of 1.4 to 1.6.

130015 / Q917

Claims (10)

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR PATENTANWÄLTE Postfach 860245 · 8000 Munich 86 Dr. Berg Dipl.-Ing. Stapfund Partner, P.O.Box 860245, 8000 Munich 86 'Your reference Our reference Mauerkircherstraße 45 Yourref. Ourref. 32 105 8000 MUNICH 80 19th S ept. 1980 Attorney's file no .: 31 105 Monsanto Company P ä t e h t a η s ρ r ü c h e 1. Continuous "process for gasifying carbon containing materials in a fluidized bed system containing a reduction zone and a gasification zone, characterized in that one (a) a particulate, solid oxidizing agent at a introduces elevated temperature into the reduction zone, (b) a substantially oxygen-free carrier gas is introduced into the reduction zone in such an Eate that the Oxidizing agent is swirled and caused to move up through the system, (c) maintaining the reduction zone under conditions such that the oxidizing agent is reduced and the carrier gas too _{x / si} 130015/091? »(089) 988272 Telegrams: Bank accounts: Hype-Bank Munich 4410122850 988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM 988274 TELEX: Bayet Vereinsbank Munich 453100 (BLZ 70020270) 983310 0524560 BERG d Postscheck Munich 65343-808 (BLZ 70010080) 20-21-0141A GW Carbon dioxide, or a mixture of gaseous water and carbon dioxide, is oxidized, (d) introducing carbon-containing material into the gasification zone, whereby the carbon-containing material in the upward moving oxidizer and carbon dioxide, or in the mixture of gaseous Water and carbon dioxide is carried along and mixed with it, (e) maintains the gasification zone under conditions such that the carbon-containing material and the carbon dioxide, or the mixture of steam and carbon dioxide endothermic to carbon monoxide, or a mixture of carbon monoxide and hydrogen, and (f) withdrawing a gaseous effluent from the gasification zone, which contains carbon monoxide, or carbon monoxide and hydrogen. 2. The method according to claim 1, characterized in that the carbon-containing material Is charcoal, coal, coke, peat, or oil. 3. The method according to claim 1, characterized ge indicates that the oxidizing agent is a natural, or synthetic, metal oxide-containing material. 130015/0917 3035481 4. The method according to claim 3, characterized in that that the material is iron chromite ore. 5. The method according to claim 3, characterized in that that the material contains iron oxide, copper oxide, cobalt oxide, cerium oxide or manganese oxide. 6. The method according to claim i, characterized in that the temperatures maintained in the reduction zone and the gasification zone are in the range from 80O ⁰ C to 1200 ⁰ C. 7. The method according to claim I _7, characterized in that the carrier gas is carbon monoxide. 8. The method according to claim 1, characterized in that the surface velocity in the reduction zone and the gasification zone is greater than 3 meters per second is. 9. Continuous process for gasifying carbon containing materials with low hydrogen content in a fluidized bed system, containing a reduction zone and a gasification zone, and an associated oxidation zone, characterized in that one 13001S / U917 . 3035481 (a) a particulate, solid oxidizing agent at a introduces elevated temperature into the reduction zone, (b) a substantially oxygen-free carrier gas in a introduces such a rate into the reduction zone that the Oxidizing agent is swirled and caused to move up through the system, (c) maintaining the reduction zone under conditions such that the oxidizing agent is reduced and the carrier gas is oxidized to gaseous carbon dioxide, (d) Carbon containing material into the gasification zone introduces, causing the carbon-containing material in the upward moving oxidizer and is carried along with the carbon dioxide and mixed with it, (e) maintains the gasification zone under conditions such that the carbon-containing material and the carbon dioxide are converted endothermically to carbon monoxide, (f) withdrawing a gaseous effluent containing carbon monoxide from the gasification zone, (g) withdrawing the reduced oxidizing agent from the gasification zone and introducing it into the oxidation zone, (h) introducing an oxidizing gas into the oxidation zone, (i) maintaining the oxidizing zone under exothermic conditions such that the oxidizing agent is more highly oxidized State is reoxidized and reheated to an elevated temperature that is sufficient to 130015/0917 303549 dation of the carrier gas and the gasification of the carbon-containing material, and (j) withdraws the reoxidized, heated oxidizing agent from the Oxidationsζone and introduces it into the reduction zone. 10. Continuous process for the gasification of carbon-containing materials in a fluidized bed system, containing a reduction zone and a gasification zone, and an associated oxidation zone, characterized in that that he (a) introduces a particulate, solid oxidizing agent into the reduction zone at an elevated temperature, (b) introduces a substantially oxygen-free carrier gas into the reduction zone at a rate such that the Oxidizing agent is swirled and caused to move up through the system, (c) maintaining the reduction zone under conditions such that the oxidizing agent is reduced and the carrier gas is oxidized to gaseous water and carbon dioxide, (d) Carbon containing material and steam into the gasification zone introduces the carbon-containing material into the upward moving oxidizer, the gaseous water and carbon dioxide is fed in and mixed with it, (e) maintains the gasification zone under conditions such that 130015/0917 0354 the carbon containing material, steam and carbon dioxide are endothermic to a mixture of carbon monoxide and hydrogen, (f) a gaseous effluent containing carbon monoxide and hydrogen, withdraws from the gasification zone, (g) the reduced oxidant from the gasification zone withdraws and introduces into the oxidation zone, (h) introducing an oxidizing gas into the oxidation zone, (i) the oxidation zone under exothermic conditions in such a way maintains that the oxidizer reoxidizes to an oxidized state and at an elevated temperature is reheated, which is sufficient for the oxidation of the carrier gas and the gasification of the carbon to effect containing material, and (j) withdraws the reoxidized, heated oxidizing agent from the oxidation zone and introduces it into the reduction zone . 130015/0917