DE2953866A1 - Catalyst compositions,their method of formation and combustion processes using the catalyst compositions - Google Patents

Description

Catalyst compositions, method for their formulation and combustion process using the catalyst * compositions

This invention relates to catalyst systems / compositions and methods for formulating such Compositions. In particular, the invention relates to catalyst systems in which the active material is homogeneously interspersed throughout a monolithic structure of ceramic composition.

Presently known catalyst systems for use in combustion devices use surface active materials in the form of pure pellets of the active material or in the form of a surface coating ^of: active material on substrates such as ceramics. For example, it is well known to engob a ceramic substrate in the form of a honeycomb or other suitable monolith structure with a catalyst material. For certain uses, such as gas turbine burners, monolithic structures are most advantageous.

The disadvantages and limitations of conventional monolithic catalyst systems close the problem the loss of active material through flaking or volatilization of substrate with consequent loss catalytic effectiveness or the problem of a change in the mechanical properties of the structure an interaction between the catalyst coating and the monolith. In certain applications, For example, in burners for gas turbines, the flaking material can cause erosion and damage to the turbine blades lead, or the weakened catalyst carrier can thermostructurally fail and enter the turbine and thereby damaging the wings.

It is an object of the present invention to provide new and improved catalyst systems and compositions and methods for formulating the compositions too

create.

Another object is to provide a catalyst system of the type described in which the active material forms an integral part of the monolith structure to solve the problems of flaking or volatilization and thus to remedy the loss of catalytic effectiveness.

Another object is to provide a catalyst system in which the integrity of the monolith structure while sustained combustion is maintained while the problem of undesirable interaction between a catalyst metal and a substrate that leads to structural weakening is fixed.

Another object is to provide a catalyst system that will have a relatively longer operating life enables, especially when used at high temperatures, and that a good performance due to relatively higher combustion sEffectiveness for a long period of time.

Another object is to create a catalyst system that exhibits relatively good catalytic effectiveness, the light-off temperature of the system compared to that of catalyst systems based on noble metals is advantageous.

Overall, the invention relates to a system in which the catalyst composition is a catalytically active material comprises, which is homogeneously interspersed throughout a monolith structure of ceramic composition. the Composition is formed into a unitary monolith that is used as a catalyst structure. In a Embodiment of the method is the active material or the active.Materials with a ceramic material, which can be either active or inactive, in fine mixed in distributed form and then shaped into their monolith structure, which is calcined. The combustion process after of the invention includes the combustion of reactants in

-A- · ■ ■ '

Presence of monolithic catalytic structures.

The foregoing and additional items and features of the invention emerge from the following description, in which various embodiments are explained are.

The catalyst systems of the invention generally comprise a catalytically active metal oxide material which is homogeneously sprinkled into or mixed with a ceramic metal oxide material. The mixture can be formed into a unitary monolith of the desired shape. The resulting monolith contains thereby continuously catalytically active material to a catalytic system with ^high: degree of structural integrity and having improved LEI.:. to create performance.

In one embodiment of the invention this is active Material a metal oxide that is homogeneous throughout with an inactive (or less active) metal oxide that is a mixed metal oxide can be mixed.

Active metal oxides suitable for this embodiment are, for example:

^Fe 3 ° 4.

LaCrO-

^CO 2 ° 3 COAl ₂ O ₄

Inactive (or less active) materials suitable for this embodiment are, for example: Zirconia spinel

Yttria-stabilized zirconium dioxide MgAl ₂ O ₄ SrZrO ₃ CaZrO-

_ ff _

From the above materials for this embodiment The catalyst systems formed are, for example:

Zirconium dioxide spinel, doped with nickel oxide (5% by weight) Yttria-stabilized zirconia doped with

Nickel oxide (5% by weight) Cerium oxide (80% by weight) with zirconium dioxide (20% by weight)

Cerium oxide (17% by weight) with zirconium dioxide (78% by weight) with

Nickel oxide doping (5% by weight) SrCrO - perovskite, doped with Co ₃ O ₃ (5% by weight) CaZrO ₃ , doped with Co O ₃ (5% by weight) CaZrO ₃ / arc plasma sprayed with CoAl ₂ O ., doped with MgAl ₃ O ₄ (5 wt.%) SrZrO ₃ , arc plasma sprayed with CoAl-O., doped with MgAl ₃ O ₄ (5 wt.) LaCrO ₃ (10 wt.%) with ZrO ₃ (90 Wt.%) ^Mg 0.25 ^Ni 0.75 ^Cr 2 ° 4

In other embodiments of the invention, the monolithic catalytic composition of the propwskite, spinel, corundum or ilmenite crystal structure type, wherein primary, catalytically active metal oxide materials are in intimate admixture with carriers, which are inactive or active metal oxide materials capable of forming ceramics. The resulting composition includes a random scattering of different possible crystal structures, for example from the perovskites, or the spinels, or the corundum, or the ilmenite, in each case Case.

In such an embodiment, a catalytically active base metal oxide of the perovskite crystal structure ABO _{3 forms} a solid solution with another material (either active or inactive) which comprises a _{metal oxide of the perovskite structure ABO 3 capable of forming ceramics.} In general, the perovskite structure comprises cations of

different types of metals, one of type A and another of type B, the cations being of different sizes and the smaller cations in the ccp arrangement occupy the octahedral cavities formed exclusively by the oxide ions.

The following are examples of the primary active perovskite base metal oxides used in this embodiment can be used:

LaCrO ₃ LaNiO ₃ LaMnO

^La 0.5 ^{Sr 0.5 1010} S.

^ 0.8 * 0.2 ^ 0, ^ 0.9 ⁰ S. ^:

ZrXWO ₃ (X = Ni, Co) LaCoFeO ₃ LaMNiO (M = Ca or Sr)

The following are examples of perovskite type metal oxides which in this embodiment are designated as Support materials can serve.

LaAlO ₃ ^(Sr 0.4 ^La 0.6 ^{) (C} ° 0.5 ^V 0.2 ^{) O} 3 '(Sr _{0 2} ' La ₀ 3

The following are examples of catalytically active perovskite metal oxides in solid solution with perovskite metal oxides as a carrier:

LaAlO ₃ TLaCrO ₃ (3: 1 molar ratio) LaAlO ₃ : LaNiO ₃ (3: 1 molar ratio)

Another embodiment of the invention provides a primary, catalytically active metal oxide of the spinel crystal structure in solid solution with a compound with a spinel structure capable of binding ceramics. The spinel crystal structure corresponds to the form a [b] o. or the reverse structure b [ab] o ..

The following are examples of the primary spinel active metal oxides used in this embodiment can be:

Fe ₃ O ₄

NiAl ₂ O ₄

^{Ni0 (1GeW} - ^%)

^{Co (Al} 0.3 ^Cr 0.5 ^Fe 0.2 ⁾ 2 ° 4 ^{+ CO} ° ⁽⁵ MgCr ₂ O ₄

The following is an example of a spinel type metal oxide used as the support material in this embodiment can be used:

MgAl ₂ O ₄

The following are examples of the solid solutions of the catalytically active spinel materials with the carrier spinel materials:

MgAl ₃ O ₄ : NiAl ₃ O ₄ (3: 1 molar ratio) MgAl ₂ O ₄ : MgCr ₃ O ₄ (3: 1 molar ratio) MgAl ₂ O ^ Fe ₃ O ₄ (9: 1 molar ratio)

Alternatively, an oxide cermet such as the one below can be used Spinel Cermet Example can be used:

: (3: 1 molar ratio) +40 wt% Cr

O ^ Fe ₃ O

In another embodiment of the invention, a primary, catalytically active base metal oxide of either corundum B ₂ ^ 3 ~ ^or Hmenit ABO crystal structure can form a solid solution with another material (either active or inactive), which is used to form ceramic Capable metal oxide of the corundum crystal structure includes.

Primary active corundum oxides are for example:

Fe ₂ O ₃

Co 0. stabilized with yttrium oxide

Examples of primary active ilmenite oxides for these Embodiments are:

Cr ₂ O ₃

Fe Mg ₁ TiO, (χ for example between 0.85 and 0.90)

A compound with a corundum structure that is suitable for use as a ceramic carrier is, for example, aluminum oxide.

Examples of solid solutions formed from active compounds with a corundum structure and the carrier with an ilmenite structure are Cr ₃ O ₃ : Al ₃ O ₃ (1: 5 molar ratio) and Fe _{n Qc} .Mg TiO: A1 0_ (1: 9 molar ratio) .

U / ÖD U / J-D J a j

Examples of solid solutions of active compounds and carriers, both of which have a corundum structure, are:

Al ₂ O ₃ : Fe ₂ O (3: 1 molar ratio)

Al ₂ O: Co 0 (5: 1 molar ratio) stabilized with 2% by weight of yttrium oxide

Of the potentially large number of metal oxide compounds that are formulated into solid solutions of the above type it should be noted that those compounds that contain metals with volatile oxides, in general are unsuitable for use in burners. Thus, the many compounds that barium, lead, rhenium, Containing ruthenium, sodium and other volatile metals, not preferred. Likewise, halogen-containing Compounds for use in burners are not believed to be useful and are therefore not preferred for the invention. Additionally, compounds of the type with known melting points below about 1873 K are for use only suitable in lower temperature ranges.

One method of formulating the catalyst systems of the invention comprises selecting the starting material in a predetermined proportion according to the molecular weight formula the composition desired for the resulting monolith structure. The starting compounds are pulverized and mixed together, for example using a ball mill or other method to obtain complete dispersion and a small partial

size in the order of 10 - 20 ym. The powder mixture is then added to the respective Ceramic technique that is used to form the catalyst structure, brought into appropriate shape and then attached Fired at a temperature of at least 1000 C.

In one example a method for deforming the catalyst structure into a desired shape, for example Honeycomb shape, an aqueous or organic slurry can be made from the reactive powders and a binder formed, poured it into a mold, expelled the water and binding agent and the residue by applying heat then sintered at high temperature. Another example is by means of such a mixture coating a substrate, for example paper, which has been deformed to the desired shape, and then coating the paper to burn. Another example of use when one of the starting materials is a pure compound, for example Alumina is made up of the powder pressed together into the desired shape and then brought to reaction.

The following is a specific example of a method for formulating a perovskite based catalyst system which is a solid solution of LaAlO and LaCrO. Ammonium dichromate (NH.) »Cr ^ O- is dissolved in deionized water. The appropriate mol% La_0_ are added to this solution. A reactive aluminum oxide is added to this mixture in an appropriate mol% dosage. The resulting mixture is dried then calcined to form a slurry at about 150 ⁰ C and above a temperature of about 600 C. The powder obtained is ground in a ball mill and then calcined again at above 1300.degree. A sample of the recalcined material can then be examined by X-ray diffraction. If the reaction is not complete, the powder can be calcined again until the desired state is reached.

the.

In this state, the powder obtained is complete reacted composition of base metal oxides. The reacted powder is then mixed with water or another grind the appropriate liquid in the ball mill, in order to obtain a rheology corresponding to the selected deformation method, and then to the desired uniform Deformed shape.

Another method of making materials useful in the invention is by gelling solutions the appropriate composition of the desired metals. In this case the gel can then be turned into a powder the rheology suitable for further processing can be spray-dried.

After the powder has been brought to the appropriate rheology, the deformation can be achieved by forming a Water-based slip (with appropriate organic binders and dispersants) and subsequent Casting, extruding, molding or pressing the material into the desired shape. This step can the coating of a paper, polymer or foam substrate with the slip and subsequent removal of the substrate, for example by firing.

The final treatment in this method consists in calcining the resulting monolith material in the range of 1100 - 1600 ⁰ C. Preferably calcined wird.in oxidizing atmosphere. In the case of components with oxides such as Cr ^ O-, which are somewhat volatile, it may be necessary, however, to calcine in an inert atmosphere, for example argon. If the material is calcined under a deformation gas in order to reduce the risk of oxide evaporation, a sample must be checked by means of X-ray diffraction to ensure that no precipitated reduced phases have been introduced.

The following is a specific example of one

Method for the formation of a catalyst system with active ceramic based on corundum. In the first stage, appropriate mol% fractions of (NH) Cr 0 and Al ₃ O (reactive) are added to deionized water using appropriate dispersants. The slurry is dried to a sludge at 150.degree. C., the sludge is calcined at 600.degree. C. and the powder obtained is ground in a ball mill. The further steps are carried out as described above with respect to the perovskite-based system.

The following is a specific example of a method of forming a spinel-based metal oxide catalyst system which is a solid solution of MgAl ₅ O ₄ and NiAl-O ₄ . Basic magnesium carbonate MgCO -Mg (OH) '3H ₂ Q is dispersed in deionized water, and the appropriate proportions of reactive AlNO and Ni (CO-) are added to the mixture. The product is dried to a sludge at 150.degree. C. and this sludge is calcined at a temperature in the range from 1000-1300.degree. The further steps are carried out as described above in relation to the perovskite-based system.

The following is a specific example of a method of formulating another spinel-based system in the form of a solid solution of MgAl ₂ O ₄ and MgCr-O ₄ . In the first stage (NH ₄ ) _Cr “O_ is dispersed in deionized water. Appropriate proportions of basic magnesium carbonate and reactive Al ₉ O-, as well as a dispersant, are added to this mixture.

The further steps are carried out as described in the example immediately above.

In the method for the formation of catalyst systems based on the ceramic materials described above becomes a common catalytic to the material prior to monolith formation Substrate with several% (preferably 1 - 10%, but up to 25%) of a catalytically active metal oxide

added. For example, nickel oxide in yttrium-stabilized zirconium oxide; Nickel oxide or chromium oxide in mullite or cordierite or zirconium mullite; LaCrO and mullite; MgCr ₃ O and alumina; or nickel oxide or Co ₃ O ₃ and aluminum oxide. The material is then deformed as described above in relation to the perovskite-based system. An extended period of time at calcining temperature may be necessary to ensure that any solid state reaction is complete during formulation.

Another preferred embodiment of the present Invention is the use of catalytically active oxide compositions as both catalytic and structural Material. Although various advantages can be obtained by mixing active materials with it less active materials, it is often desirable to use the active oxide composition for catalytic and structural To use material. An example of this is the use of LaCrO as a catalytically active, electrically conductive monolith material.

Example I.

Oxide powders of MgAl 0 and NiAl 0 (3: 1 molar ratio) were prepared by pressing the powders. Disks and calcination in the manner described above. The disks had a diameter of 57 mm and a height of 32 mm and 18-30 axial bores of 6.35 mm internal width as gas passages. The obtained monlithic structure was grown in a combustion chamber using air and natural gas as reactants under fuel-lean conditions

checked down to a minimum preheat to 16 3 ° C.

At the highest, with a space velocity of 849 ¹ OOO throughput achieved h no extinction took place of the catalyst bed. The catalytic converter was also tested with a lean diesel mixture and maintained combustion up to a minimum preheating of 310 C. When tested with this! fuel did not extinguish at maximum throughput

with a space velocity of l'152'OOO h

The results of the tests of the first example are given in Table I. The CO emission was less than 50 ppm and from NO 1-30 ppm.

Example II

Powders of LaAlO and LaCrO (3: 1 molar ratio) were made pressed into disks and calcined as described in Example 1. The catalyst was in a combustion chamber tested using the reactants air and natural gas as well as diesel oil. The test results obtained are in Table II listed.

Example III

Powders of MgAl ₃ O ₄ and Fe ₃ O (3: 1 molar ratio) were pressed into pellets and calcined as described in Example I. The catalytic converter was tested for a lean natural gas mixture and a lean diesel mixture in a combustion chamber. The test results are listed in Table III.

Example IV

Powders of MgAl ₃ O ₄ and MgCr ₃ O ₄ (3: 1 molar ratio) were pressed into tubes 5 cm in length with 6.35 mm outside diameter and 3.2 mm inside diameter and calcined. Forty-four of the resulting tubes were bundled, wrapped in insulating material and placed vertically in a support tube on a disk of "Torvex" alumina 25.4 mm thick and 50.8 mm in diameter in a honeycomb shape with cells of 4.76 mm in diameter. The catalyst structure was tested with lean and rich mixtures of air with natural gas and diesel oil, respectively. The test results are given in Table IV. The test showed that with a lean natural gas mixture there was no passage of CO and NO or less than 18 or 10 ppm. There was no loss of catalytic effectiveness during the 5 h test period.

Example V

Powders of Al ₃ O ₃ and Cr O ₃ (9: 1 molar ratio) were shaped into tubes and these were arranged to form a catalyst.

net as described in Example 4. Platinum was added to the front segment in order to stimulate starting. The catalyst structure was tested with a mixture of air and natural gas. The test results are listed in Table V.

From the above it can be seen that the catalyst system compositions of the present invention performs well with high combustion efficiency during have a long period of time. The catalytic monolith maintains its structural integrity during operation without loss of catalytic effectiveness due to flaking or volatilization. There is no problem of changing ': effect between base metal catalysts with the substrate still a problem of degradation on the surface due to Crystal growth of the active component during operation, so that a relatively longer life, especially when Use at high temperatures results. In addition, the manufacturing process is relatively less expensive because the Forming the monolith structure requires fewer steps compared to known methods of making one Substrate, application of a primer coat and then the catalyst. -

While the embodiments described above At the present time, it should be noted that numerous variations will be apparent to those skilled in the art and modifications are possible, and the intent is for all such variations in the following claims and modifications that fall within the spirit and scope of the invention.

In the following tables, the information in the table header has the following meaning:

Test point

TA,% =

SV, l / h = space velocity of the fuel mixture gas flow through the catalyst bed

fuel / lb / h - unit of weight of fuel in the fuel

substance mixture gas flow / h weight unit Lx mixture gas flow / h

m. , lb / h = weight units of air in the fuel

T. , F = preheating temperature of the catalyst

T, ,, F = operating temperature of the catalyst bed

Velocity, ft / s = flow velocity of the gas stream

CO, NO and UHC,

ppm = residual CO, NO and unburned

te hydrocarbons Q, Btu / h = heat flow

Table I.

IeU TA 5 « * »Ucl (Ibm / hr) V. 'lH-il Velocity approx NO UiIC Q Ρτίί-fa v-h paint {-.) (1 / hr) (Itw / hr) //.4 ("F) ("f) (ft / l «) (| · Ι «» 1 (PP ") (pi"") (Btu / hr) XrLLtLdX. L. 41-6 191 307,000 2.36 66 » 2000 9.0 10 4th 0 50,700 Stabilizing 41-7 6ΙΠ 2025 tion on 41-9 6I)
610 2020 natural gas 41-10 610 2020 41-11 609 2010 41-12 610 13th I. 41-1) 60S IO 0 41-14 607 41-15 60 / 41-16 609 41-17 575 41-18 550 2005 41-19 500 2005 B. 41-20 475 2010 I. 5 41-21 450 2010 6th <l-22 425 2010 8th 41-23 400 2005 8th 41-24 3/5 IO 0 minimal pre 41-25 188 77.4 350 5 warming, 41-26 1B6 381,000 2.36 75.2 3? P 8.6 50,700 lean earth 41-27 in) 376,000 74.2 335 β.7 gas mixture 41-34 181 172,000 /3.3 523 8.6 41-37 174 36 /, 0OO 70.4 658 8.5 9 41-40 172 353,000 69.4 801 2015 8.2 IO 41-41 169 349,000 en.4. / 93 2005 8.1 41-42 162 344,000 65.5 790 2005 8.0 6th 41-4) 160 330,000 64.5 79) 2015 7.7 41-44 157 326,000 63.6 / fl9 1960 7.5 41-47 152 321,000 61.6 708 2030- 7.4 41-48
41-19
ä I ΚΛ 52 312,000 38.4 692
66)
642 2035 /.2 7th * I · Vj
41-51 $ 2 219,000 JU.4 676 20KO 5.1 - 8th 41-52 193 219,000 80.0 CO) 20 O 5.1 B. 11-53 204 399,000 99.4 594 2OÜ5 9.2 ■ 9 41-58 193 495,000 101. 8> 6 2025 11.5 4) 2 41-59
41-60 212 545,000 130 06.1
860 2090 12.6 43 I. rich natural gas 41-61 249 687.0 ounces) 172. 8/2 2115
2115
91 in 15.9 40 5 mixed, unstable 41-62 17) 849,000 /7.1 B / n C III /
2100 11.Z 0 4th maximum 41-63 365,000 89S 20/5 8.5 45
43 5 Throughput, 41-64 867 2025 45 3 6βΟΟ lean earth 41-65 BAQ 2140 40 2 3100 92,200 gas mixture 4.29 2200
2100 25th 16 (1 92,200 I. 170 4.29 75.2 2260 44 SO.700 minimal preheating 170 356,000 2.36 /5.2 2) 25 8.2 40 61,100 mung »lean» condensate
ized diesel oil mixture 164 356,000 2.84 75.2 2) 50 8.2 40 15th /1,000 171
181 356,000 3.30 81.7
119. 2240 8.2 - IC 82,000 1b8 425,000
512.01) 0 3.1) 1 143. 2340 9.8
I). 0 I) 1/ 86,400 I / O 677,000 4.02 15). IS.7 15th 30th (2.100 194 723,000 2. «9 ine. 16./ 30th 25th 200 80) .000 24). 20 5 23 0 maximum 185 I.I52.OOO 21). 26.7 3) Throughput,
lean diesel oil I.I52.OOO 26.7 24 mixture 18th 21 54,100 2.97 62,200
/ 7.700 3.41
4.26 O.S. 89./OO 4.92 0.5 ΙΟΙ. / OO 5.58 113,600 6.2) 143,500 7.8 / ISS.SOO 8.5)

Table II

IA

5 »" fuM

(l / hr) (him / hr)

-air (Ita / hr)

P (T)

Vd Cf)

Velocity (fl / wc)

NQ

(ρι-Ί

UIlC Q

(PP-) (nto / hr)

Test type

41-11 42-tf 42-11 42-14 4J-I5 42- U 42-1 / 42-la

42-19 42-20 42-21 42-22 42-21

42-2S 42-26 42-27 42-28

29 42-M 42.} l 42-12 42-Jl 42-14 42. "

191

191 181 181 IN THE 169 162 ISi 157

52 56 56 60 61

206 210 207 214

IB4

182 172 161

460,000

2.16

460,000 4.42.000 417,000 421,000 410,000 391,000 182,000 1H2.0I.H)

260,000 277,000 277,000 211,000 2B4.OOO

580,000 701,000 JHI .000 874,000

000

420,000 19H.000 171,000

751,000

944,000

I.I24.OOH

2.16

4.29

1.05 1.21 1.40 1.50

2.6 "

4.4] 5.74 6.76

77.4

77 75. 71

70 68. 65 61 61

18th 41 41 44,

46.

99.4 119. 111

148.

75.5

74.5 70.6 65.8

111.5

IK /.

191.

610 610 610 611 611

tv.

614

570 548 525 500 450 425 4 (X) 177

500 474 4SO 190 175

690 689 6R9 691

790 766 725 700 6S0 671 600

750 772 792

2120 2110

2120

2110 2110 2100 2100 2090 21OD 2110 2100

2120 2110 2100 1170 2025

2125 2100 2160 2160

2140 2140 2160 2IM) 2140 2IS0 1770

2240 2140 1650

7 8 9 β

16

7 7 7 6

11 12 Il 12 15 20

12th

18 16

0 50,700 I.

50,700

5100

2500

3000

900

400

18 17 IS

92

200

60,600 71,000 80,600 86,400

48 500

Stabilization on natural gas

minimal preheating, lean natural gas mixture

minimal preheating, rich natural gas mixture

80,800

10,500

121,000

maximum throughput, lean natural gas mixture

minimal preheating, lean diesel oil mixture

maximum flow rate, lean diesel

oil mixtures

Table III

Ittt
point lh
(D 9 SY
(l / tir) "FuM
(Ibra / hr) "iir
(lto »/i.r) (V, CM 40 Velocity
IH / itc) 0 co
(PP-) HU ■ Ulic
(P? -) Q
(Btu / hr) Test type 4S-Z 191 U9 '19S.0O0 Line 36 77.4 7) 0 2760 2240 11.4 4th 0 SO. 700 stabilization 4S-)
4S-4 US 2200 3
0 on natural gas 4S-S 172 2740 - 4S-S UO 2250 4S-It 167 2250 25th 4S-U 191 2) 10 ZO 4S-U ZII 2100
2320 20th 0 minimal preheating 45-14 191 214 195,000 2.16 77.4 778 2280 2300 11.4 25th SO 700 mung, lean earth 45-IS Zl) 774 2280 0 gas mixture 45-16 187 700 2250 4S-U 182
182 675 2240 45-18 I. 182 7th 675 2250 45-19 180 600 45-20 176 S7S 4S-Z6 Ul 171,000 SSO 10.R ZS.S. 4S-Z7 167 171,000 S2S 2 10.8 8.4 45-28 162 362,000 72. SOO 10.5 12.6 4S-29 IN THE 357,000 70. 860 10.) 12.6 ' 4SO0 ISl 351,000 69. 824 2320 10.2 4SOI
4SO2 ISl 148,000 68. 817 23SO 10.1 0 45-)) 149 195.003 67. 806 2) 00 11.4 45-34 144 (04.000 77 794 2HO U.S 4SO5 142 702,000 119 750
700 2) 40 . 20.1 maximum through
rate, natural gas gas 45-16 142 751,000 1) 8 650 2140 21.8 mix 4SO7 140 188,000 148 62S Z) 40 11.2 45-18 137 179,000
179,000 80. 600 2) 00 II.0
ii.o 0 45-19 U2 179,000 Line 16 78.
78. 57S 2270 11.0 .. SO.700 minimal preheating, 45-40 IU 174,000 1.10 78. SSO 22SO 10. » ■ · 71,000 lean diesel oil
miscn 4S-4I 182 165,000 3.78 77 525 2150 IO .. 81,300 4S-42 20)
194 155,000 4.05 7S. 490 2280 10. .. 87.100 45-4] 174 146,000 Line 79 7). 47S 2150
2) 00 10. .. 50,900 45-44 140 117,000 71. < 450 2000 9 .. 45-4S 111 127,000 69. 425 2170 .. 0 45-46 119 1IA.0OO 67. 395 2250 4S-47 118,000 65.1 375 ZZ20 9, .. 4S-48 109.Ot) O 65.1 348 .. IS 4S-49 299,000 63.ί 125 6th ·· 14th
IS 45-52 295,000 61.5 300 .. 45-53
45-54 29S.OOO 275 β t .. 4S-SS 290.0 (10 2SS .. 45-56 285,000 794 a. .. I. 4S-S7 251,000 701
794 7th - .. 45-58 241.OQO 793 J 174,000 351 ok 669,000
B U, 0OO 321 19th
Z). • * 879,000 304 U 290,000 - 10 415,000 - 21 415,000 2) ·. 22nd ·. Z) E.g. 28 28- 26th 21 26th 20th Il 8th
IS 30th maximum throughput, 61.0 E.g. Diesel oil mixture 61.0 .. 60.0 .. S9.0 minimal preheating, 52.) lean diegel oil
mixed Bex nonerem SO.) Throughput 2.81 77.4 527,000 4.42
P.64 I) B.
lea. 806,000
101,000 6.7) m. Z 124,000 2.79 60.0 1
Z 50,900 4.92 90.0 89,700 4.92 90.0 1 89,700

CO ♦ 30 CD CO

Table IV

Tett TA SV "fuel ".Ir ¹ Ph ^T bed Velocity I. CO NO HC q Prurart point (X) (1 / hrl (lbm / hr) (Ibn / hr) Cr) cn (ri / iec) (Pl-) (PP "O (PP *) (etu / hr) minimal preheating 46-2 222 121,000 2.36 90.0 724 2450 14. < ϊ ■ 4th 0 $ 0.700 mung, lean era 46 1 222 121,000 90.0 694 2450 14 / 10 S. gas mixture 46-4 21 « 115,000 88.1 640 2450 14.1 10 7th 46-S 201 295,000 8t.3 611 2400 13th U 46-6 »9 288,000 80.1. 575 2425 13. ' Il 46-7 196 285,000 79.4 550 2150 11 .. . ■ IS 46-8 191 279,000 77.4 S25 .. 12 / " «6-9 187 272,000 75.5 500 2400 12.1 IS 46-10 182 265,000 71.S 475 2550 12 .. 46-11 I. 450 2620 I. ... 46-12 425 2600 B. 46-11 I. 400 2550 46-14 179 3 »5 2500 ll.l 46-15 V » 150 2550 12th 46-16 179 325 2525 12th Il 46-17 175 262,000 72.6 300 2525 ll.l 46-18 175 262,000 72.6 27S 2500 U.I 15th 46-19 175 262,000 72.6 250 2S (OK U.I 7.0 IO 46-20 170 255,000 70.6 178 2450 II. 15th 46-21 SO 255,000 70.6 674 2620 15.7 255,000 70.6 18.1
19.7 46-25 214 249,000 68.7 824 2450 22.2 46-26
46-27 227
212 152,000 36.8 700
780 2450
2460 24.5 46-28 208 789 2525 14.2 46-29 2 Tea spoons 118,000 94.8 780 2500 14.2 46-12 207 390,000
426,000 109.
119. 780 2550 21.9 46-)] 20? 479,000 114. 804 25Ot) 12.9 46-15 175 510,000 Με. 850 - · 12.9 18th 46-17 111 107,000 90.0 575 2450 IS
11th 46-18 191 107,000 90.0 497 2450 IS 472,000 133. IO 279,000 77.4 20th 279,000 77.4 10 10 6th unstable with rich S. Natural gas mixture S. 10 maximum throughput, lean natural gas
mix 4.29 6000 92,000 2.16 I. 0 50,700 with diesel oils 2.82
J.27 60,600
70,300 mixed unstable 1.75 SO.600 4.05 7th 87.100 2.82 8th 60,600 with natural gas mixture
still catalytic
effective 2.82 9 60,600 P.12 S. ΙΙ2.6ΠΟ 2.16 S. 0 SO.700 2.16 1 50,700 10 0

* Ambient temperature

K) CO cn co co CD co

Table V

lilt IA SY 000 ^A CH ₄ 06 ".Ir .7 IN THE 'bed (T) CO ■ I. NO IIC Test type 12-10 U) (l / hr) (IWM (Him / hr) 6 * 1 1X1 1 · 2 (Pl ") 30th (PP ") 32-12 180 116,000 2.44 75.7 685 7520 800 20th 28 8th Aging (uneven bed) 32-14 19 / 116,000 2.23 (M 2600 1560 16 22nd 12th 32-IS 207 115,000 2.12 U.N 25/5 1775 18th 23 9 32-16 I. among others 25/5 1840 20th 21 32-17 689 2560 1850 20th -21 12-18 690 2575 1910 25th 22nd 32-20 zh 2 689 26W 2I2S 19th 20th 32-21 205 111 7th I. 2590 2100 16 19th 32-73 7570 1900 16 IS 32-24 7560 1810 20th IS 32-25 1890 21 20th 12-26 1950 19th 20th .. 32-27 2100 21 18th .. 12-28 2100 22nd IO .. 32-29 123,000 81.5 2580 7110 23 16 .. 37-30 123,000 1.91 1200 21 16 ., 32-31 124,000 1.96 1690 20th 14th . · 32-32 2.01 690 1/50 20th 14th .. 32-33 2.01 690 1740 20th 14th 1 32-34 2.17 611 2575 ΠΙΟ 21 14th I. 32-35 2.31 2S7S 1740 20th 14th 2 12-36 2.31 2580 1810 • 21 ' Il 2 32-41 2.36 1640 20th 2 32-42 2.41 2560 2 32-43 2.41 690 2550 2 32-45 125,000 2.57 778 2560 1 32-4 / 125,000 2.87 761 2525 - 1 32-48 123,000 2.95 745 2550 I. 32-49 126,000 775 2580 0 32-50 141,000 IW 2560 0 32-51 126,000 675 2525 2570 1 32-52 137,000 80.1 646 25/5 2550 0 32-54 137,000 2 55 82. 621 7560 2550 0 37-56 171,000 2.13 91. S99 2560 25? Ο O 32-57 107,000 2.79 81. S / 4 2550 2590 ■ 0 32-58 154,000 1.82 09 S82 2575 2550 1 32-59 219,000 4.05 89 550 7600 2490 2 32-61 229,000 4.05 78. SOO 2580 2490 2 32-62 245 232,000 69. 440 2510 2575 I. 1 32-65 242 400 2575 - 2 32-66 23S /so· 25/0 - I. 32-67 235 762 * 260O 2560 2 17-68 218 645 2600 0 205 6 * 9 2575 0 205 6S6 2560 0 minimal preheating, lean mixture 201 64 · 75/0 0 196 101 7500 0 191 144 2500 0 190 ISO 2600 0 180 152 0 160 0 176 176 179 173 210 217 216 218 maximum throughput

cn co oo σ)

Claims (11)

1. A monolithic catalytic structure that is a catalytic Active base metal oxide that is homogeneously scattered throughout a carrier structure of ceramic composition is, includes. 2. A catalytic structure according to claim 1, wherein the metal of the active base metal oxide is selected from the group of Ni, Ce, Cr, Zr, Fe, Co and La. 3. A catalytic structure according to claim 2, wherein the ceramic of the carrier is selected from the group of a mixed metal oxide with a spinel crystal structure or a mixed metal oxide with a corundum crystal structure. 4. A catalytic structure according to claim 1, which is a additional, catalytically active base metal oxide that is homogeneously interspersed throughout the support structure, includes. 5. A catalytic structure according to claim 4, wherein the additional metal oxide comprises yttria stabilized zirconia. 6. A method of formulating a catalyst system which includes the steps of making a catalytically active Base metal oxide with average particle size in the order of 10-20 μm, deformation of the oxide to a monolith structure and calcining the molded structure at a temperature of at least 1000 C to form comprises a homogeneous scattering of the metal oxide. 7. A combustion process to burn off reactants in the presence of a monolithic catalytic structure, which is a catalytically active base metal oxide that is homogeneous is interspersed throughout a carrier structure of ceramic composition includes. 8. Combustion process according to claim 7, wherein the metal of the active base metal oxide from the group of Ni, Ce, Cr, Zr, Fe, Co and La is selected. 9. A combustion process according to claim 8, wherein the ceramic of the carrier is selected from the group of a mixed metal oxide with a spinel crystal structure and a mixed metal oxide with a corundum crystal structure is selected. 10. A combustion process according to claim 7, wherein a additional, catalytically active base metal oxide is homogeneously scattered throughout the support structure. 11. A combustion process according to claim 10, wherein the additional metal oxide is yttria-stabilized zirconia includes.