GB2062486A - Catalytic gauze packs - Google Patents

Catalytic gauze packs Download PDF

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Publication number
GB2062486A
GB2062486A GB8035343A GB8035343A GB2062486A GB 2062486 A GB2062486 A GB 2062486A GB 8035343 A GB8035343 A GB 8035343A GB 8035343 A GB8035343 A GB 8035343A GB 2062486 A GB2062486 A GB 2062486A
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Prior art keywords
wire
gauzes
pack
catalyst unit
unit according
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GB8035343A
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GB2062486B (en
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to GB8035343A priority Critical patent/GB2062486B/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58Fabrics or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/20Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24Nitric oxide (NO)
    • C01B21/26Preparation by catalytic or non-catalytic oxidation of ammonia
    • C01B21/265Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/20Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24Nitric oxide (NO)
    • C01B21/26Preparation by catalytic or non-catalytic oxidation of ammonia
    • C01B21/28Apparatus

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Catalyst units embodying or consisting of catalytic material in wire or strip (herein referred to simply as "wire") form, e.g. for use in the manufacture of nitric acid involving oxidation of ammonia to nitric oxide, comprises a pack of woven metallic gauzes wherein at least some of the gauzes disposed at or towards the front (considered in the direction of reactants passing through the unit) of the pack are made from wire having a cross-sectional area greater than at least some of the gauzes disposed at or towards the rear of the pack.

Description

SPECIFICATION Improvements in and relating to catalyst units This invention relates to catalyst units embodying or consisting of catalytic material in wire or strip (herein referred to simply as "wire") form and especially to such units for catalytic oxidation of gases.
One weil known form of catalyst unit comprises a closely packed sequential array, "pack" or "pad" of gauzes woven from wire made from precious metal such as a platinum-rhodium alloy.
Such a unit used for the catalytic oxidation of ammonia gas to nitric oxide and water during the manufacture of nitric acid where ammonia gas is oxidised in the unit according to the equation: 4NH3 + 502 - 4NO + 6H2O (AH = -894 KJ) The resulting nitric oxide is further oxidised to nitrogen dioxide which is subsequently absorbed in water or an aqueous medium to form nitric acid.
in the manufacture of nitric acid ammonia gas and air are usually passed downwards through the gauzes of the catalyst unit at high speed and under pressure. The gases generally enter the pack at temperatures of up to about 2500C and, because the oxidation of ammonia is a highly exothermic reaction, the reaction products and any unreacted gases leave it at a temperature in the region of 8500C or more.
It is the desire of the nitric acid producer to operate a plant continuously under conditions giving the highest yield of nitric oxide but this does not necessarily mean operation of the plant under the most economical conditions. In many instances the most economical operating conditions may dictate that the plant is operated below maximum yield. Operating below maximum yield can be unsatisfactory to the producer who also has to consider the return on capital for the plant.
For the producer it is essential that the ammonia oxidation process satisfies the following criteria: (i) maximum conversion is obtained with (ii) minimum precious metal content and therefore also minimum metal loss from the catalyst.
Attempts have been made to reduce the amount of platinum metal used in the catalyst units by reducing the diameter of the wire from which gauzes are made. This has not been successful because the durability of such gauzes has been found to be inferior. We have not found that the poor durability stems from the fact that the bulk of the oxidation reaction occurs on certain gauzes positioned towards the front of the unit (considered in the direction of gases passing through the unit). The accompanying Figure is a graph of weight loss against gauze position and shows a typical weight loss profile through a 40gauze catalyst unit having a loading of 100 metric tons of ammonia per square metre of gauze per day. Catalyst units according to the present invention are designed on the basis of weight loss curves of the kind shown in the accompanying Figure.
The present invention therefore provides means for obtaining the same conversion efficiency as previously obtained but with the use of less precious metal or alternatively of obtaining greater conversion efficiency with the same or approximately the same quantity of precious metal. It is a further object of the invention to maintain activity of the catalyst unit for longer periods than hitherto and also reduce the effects of contamination thereof whilst using less metal than such an increase would require in a conventional plant.
According to the present invention a catalyst unit for use for example in the oxidation of ammonia comprises a pack of woven metallic gauzes wherein at least some of the gauzes disposed at or towards the front of the pack are made from wire (as hereindefined) having a crosssectional area greater than at least some of the gauzes disposed at or towards the rear of the pack. By "front" of the pack we mean that portion of the pack through which gas first enters the pack.
The invention also includes a catalyst unit comprising a pack of woven metallic gauzes wherein the pack is divided into a plurality of stages, each individual stage including at least one gauze with the gauze thereof made from wire (as herein defined) of the same cross-sectional area and wherein the cross-sectional area of the wire of the gauze or gauzes in any one stage is greater than the cross-sectional area of the wire of the gauze or gauzes in the next succeeding stage considered in the direction of flow of reactants through the unit. The number of gauzes in each stage is conveniently determined with reference to the graph of the accompanying figure which can be readily changed into a step-wise graph.In such a graph, the horizontal extent of each step represents the number of gauzes used in each stage which number if commensurate with the weight loss which is represented by the vertical position of the step.
Thus those gauzes having the thickest wire are positioned where most of the reaction occurs and, therefore, where greatest weight loss occurs.
Preferably, the wire forming the gauzes is composed of a platinum group metal, an alloy of platinum group metals or an alloy of one or more platinum groups metal with one or more nonplatinum group metals wherein the platinum group metal component is at least 90% by weight of the total metal content. Preferred platinum group metal alloys are a 10% rhodium platinum, alloy or a 5% rhodium 5% palladium platinum alloy.
One embodiment of the invention will now be described and compared with a catalyst knit comprising a pack of gauzes. A specified number of gauzes at the front of the pack remain unchanged but the succeeding gauzes are replaced by a number of gauzes made from a wire of smaller diameter. Either all of the replacement gauzes may be made of wire of the same reduced diameter or groups of them may be made of wire of the same diameter but the wire for each group being progressively less in diameter than the previous group. In an alternative embodiment all the replacement gauzes are made of wire having a diameter which is less than that of the wire of the gauzes preceding them.
The operational life of a gauze pack is also limited by contamination of the leading gauzes.
According to the present invention this problem may be overcome without increasing the platinum group metal inventory by increasing the total number of gauzes involving the substitution of a greater number of thin wire gauzes for some of the existing thick wire gauzes. This increases the life of the pack without a reduction in efficiency but with the use of less catalytic metal than would otherwise be the case.
It is not feasible to indiscriminately reduce the diameter of the wire in all the gauzes since during the catalytic process there is loss of metal from the gauzes and to make them of too thin wire would result in a shorter operating life and consequently in more frequent shut-downs of the plant.
Catalyst gauzes conventionally used in ammonia oxidation plants are generally 76, in diameter. Sometimes thinner 60,u wire is used but this is usually in atmospheric pressure oxidation plants in which in any case the number of gauzes used is relatively small i.e. about 4.
The heavier gauge wire 76,u is used for gauzes in medium and high pressure oxidation plants, another feature of which is that more gauzes are used, about 6-10 in medium pressure plants and up to 50 in high pressure plants.
According to a further aspect of the present invention, a pack of catalytic metal gauzes for use in plants for catalytic air oxidation of ammonia operating at medium or high pressure contains at least 10 gauzes, the gauzes towards one face of the pack (which in use will be the back of the pack) being made of thinner wire or wire of smaller cross-sectional area than the wire in gauzes towards the other face of the pack (which in use will be the front of the pack.
Conveniently 25 to 60% of the gauzes, and preferably 30 to 50%, are made of wire of the thicker type or of wire having greater crosssectional area.
Using the presently manufactured gauzes in the present invention the thicker gauzes will be of 76,u gauge wire and the thinner gauzes of 60,u gauge wire.
Where a specified number of gauzes are unchanged their number in a high pressure plant will generally be about 20 to 25. In medium Pressure plants the number of gauzes which rein unchanged will preferably be about 3.
In a further embodiment of the present invention, gauzes normally made from thinner wire and positioned at or towards the rear of the catalyst may also contain wire of the greater thickness normally present in gauzes at or towards the front of the pack. In other words, some components at least of either the warp or the weft of the gauze may be made of thin wire and some of thick wire. Alternatively the entire warp or the entire weft may be made of thin wire and the entire weft and the entire warp respectively made of thick wire.
The present invention also includes a process for the manufacture of nitric acid by the oxidation of ammonia present in a mixture of gases, the process comprising passing said mixture of gases at elevated temperature through a catalyst unit as described above and nitric acid when manufactured by such a process.
EXAMPLE 1 In a plant of a commercial nitric acid producer approximately 95.5% conversion efficiency is obtained using 9 gauzes made from 0.076 mm diameter 10% Rh-Pt wire having a mesh size of 1024 cam~2. The total weight of catalytic metal used is 38.285 kg. When the final 7 of these 9 gauzes were replaced by 9 gauzes of the same mesh size woven from 10% Rh-Pt wire of 0.060 mm diameter the conversion efficiency and life of the pack remain unchanged. The total quantity of metal used, however, was reduced from 38.285 to 33.5 kg, a saving of 123%.
EXAMPLES 2 4 A plant currently running at 1 5.7 tonnes NH3 per square meter per day has nine 0.076 mm diameter wire gauzes made from a 10% Rh/Pt alloy. The conversion efficiency is usually 95.0% and 38.285 kg of precious metal is used Three experiments were carried out in which one third of the large wire diameter gauzes were retained, namely 3, and differing numbers of a thinner gauge wire gauzes were substituted.
EXAMPLE 2 In this example, the pack of woven metallic gauzes consisted of 3 gauzes of 0.076 mm diameter and 9 gauzes of 0.060 mm diameter.
This pack used 37.744 kg of precious metal, that is, a saving of 1.4% and the conversion efficiency obtained was 95.2%. Further, the life of pack showed a slight increase.
EXAMPLE 3 In this example, the pack consisted of 3 gauzes of 0.076 mm diameter and 10 gauzes of 0.060 mm diameter. This pack used 40.52 kg of precious metal, that is, an increase of 5.84%. The conversion efficiency increased to 95.7% and the life of the pack was definitely prolonged.
EXAMPLE 4 In this example, the pack consisted of 3 gauzes of 0.076 mm diameter and 7 gauzes of 0.060 mm diameter. This pack used 32.193 kg metal, that is, a saving of 1 5.9% by weight. The conversion efficiency obtained was 95.0% and no increase in pack life was experienced.
Thus, using 10 thin wire gauzes, 5.8% by weight more metal was used but produced a substantial increase in the yield of nitric acid and pack life. The use of 9 thin wire gauzes actually saved precious metal (1.4% by weight) but still gave a slight increase in acid production and life of pack. The use of 7 thin wire gauzes gave a very substantial saving in precious metal (15.9% by weight) for about the same conversion and life.
EXAMPLE 5 A nitric acid plant containing twenty-one 76y gauzes weighing 31.471 kg operates at 93.0% conversion efficiency. 3% of the 21 thick wire gauzes were retained (i.e. 7) and the remainder were replaced by 23 gauzes having 601u gauze wire. The total precious metal weight was then 32.982 kg, an increase in 4.8%. The conversion efficiency however increased to 94.5% and the life of the pack was substantially increased. This provided a substantial saving to the operation for only a minimal increase in metal content.

Claims (13)

1. A catalyst unit comprising a pack of woven metallic gauzes wherein at least some of the gauzes disposed at or towards the front (considered in the direction of reactants passing through the unit) of the pack are made from wire (as herein defined) having a cross-sectional area greater than at least some of the gauzes disposed at or towards the rear of the pack.
2. A catalyst unit according to claim 1 comprising a pack of woven metallic gauzes wherein the pack is divided into a plurality of stages, each individual stage including at least one gauze with the gauze(s) made from wire (as herein defined) of the same cross-sectional area and wherein the cross-sectional area of the wire of the gauze(s) in any one stage is greater than the cross-sectional area of the wire of the gauze(s) in the next succeeding stage considered in the direction of flow of reactants through the unit.
3. A catalyst unit according to claim 1 or claim 2 wherein the wire forming the gauze(s) is composed of a platinum group metal, an alloy of platinum group metals or an alloy of at least one platinum group metal with at least one nonplatinum group metal wherein the platinum group metal component is at least 90% by weight of the total metal content.
4. A catalyst unit according to claim 3 wherein the platinum group metal is platinum.
5. A catalyst unit according to claim 3 wherein the alloy of platinum group metals if a 10% rhodium platinum alloy.
6. A catalyst unit according to claim 3 wherein the alloy of platinum group metals is a 5% rhodium 5% palladium platinum alloy.
7. A catalyst unit according to any preceding claim wherein between 25 and 60% of the total number of gauzes are made of thicker wire or of wire of greater cross-sectional area.
8. A catalyst unit according to claim 7 wherein between 30 and 50% of the total number of gauzes are made of thicker wire or wire of greater cross-sectional area.
9. A catalyst unit according to any preceding claim containing wire of 76,u gauge.
10. A catalyst unit according to any one of claims 1 to 9 containing wire of 60y gauge.
11. A pack of catalytic metal gauzes for use in apparatus for the catalytic/air oxidation of ammonia operating at medium or high pressure and containing at least 10 gauzes, the gauzes towards the rear face of the pack being made of thinner wire or wire of smaller cross-sectional area than the wire in gauzes towards the front face of the pack.
12. A process for the manufacture of nitric acid by the oxidation of ammonia present in a mixture of gases comprising passing said mixture of gases at elevated temperature through a catalyst unit or pack according to any preceding claim and absorbing the resulting gases in water or an aqueous medium.
13. Nitric acid when manufactured by a process according to claim 12.
GB8035343A 1979-11-08 1980-11-04 Catalytic gauze packs Expired GB2062486B (en)

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Application Number Priority Date Filing Date Title
GB8035343A GB2062486B (en) 1979-11-08 1980-11-04 Catalytic gauze packs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7938722 1979-11-08
GB8035343A GB2062486B (en) 1979-11-08 1980-11-04 Catalytic gauze packs

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GB2062486A true GB2062486A (en) 1981-05-28
GB2062486B GB2062486B (en) 1984-09-19

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364153A1 (en) * 1988-10-12 1990-04-18 Johnson Matthey Public Limited Company Metal fabrics
WO1992002301A1 (en) * 1990-07-31 1992-02-20 Alan Edward Heywood Improvements in or relating to catalysts and getter systems
EP0504723A1 (en) * 1991-03-16 1992-09-23 Degussa Aktiengesellschaft Preparation process of permeable precious metal nets for catalytic processes
EP0519699A1 (en) * 1991-06-17 1992-12-23 Johnson Matthey Public Limited Company Low pressure drop, high surface area oxidation catalyst and catalyst for production of hydrocyanic acid
US5268157A (en) * 1991-03-16 1993-12-07 Degussa Aktiengesellschaft Process for the production of catalytic gas permeable nets and process for oxidizing ammonia
US5278124A (en) * 1991-06-17 1994-01-11 Johnson Matthey, Inc. Low pressure drop, high surface area ammonia oxidation catalyst
US5356603A (en) * 1991-06-17 1994-10-18 Johnson Matthey Inc. Method for the production of hydrocyanic acid using a corrugated catalyst

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364153A1 (en) * 1988-10-12 1990-04-18 Johnson Matthey Public Limited Company Metal fabrics
US5188813A (en) * 1988-10-12 1993-02-23 Johnson Matthey Public Limited Company Metal fabrics
US5266293A (en) * 1988-10-12 1993-11-30 Johnson Matthey Public Limited Company Metal fabrics
WO1992002301A1 (en) * 1990-07-31 1992-02-20 Alan Edward Heywood Improvements in or relating to catalysts and getter systems
EP0504723A1 (en) * 1991-03-16 1992-09-23 Degussa Aktiengesellschaft Preparation process of permeable precious metal nets for catalytic processes
US5268157A (en) * 1991-03-16 1993-12-07 Degussa Aktiengesellschaft Process for the production of catalytic gas permeable nets and process for oxidizing ammonia
TR26402A (en) * 1991-03-16 1995-03-15 Degussa A PROCESS FOR THE PRODUCTION OF GAS GENERATIVE VALUABLE METAL NETWORKS FOR CATALYSTIC PROCEDURES
EP0519699A1 (en) * 1991-06-17 1992-12-23 Johnson Matthey Public Limited Company Low pressure drop, high surface area oxidation catalyst and catalyst for production of hydrocyanic acid
US5278124A (en) * 1991-06-17 1994-01-11 Johnson Matthey, Inc. Low pressure drop, high surface area ammonia oxidation catalyst
US5356603A (en) * 1991-06-17 1994-10-18 Johnson Matthey Inc. Method for the production of hydrocyanic acid using a corrugated catalyst
TR26289A (en) * 1991-06-17 1995-03-15 Johnson Matthey Inc LOW PRESSURE DROP, HIGH-SIDED AMMONIA OXIDATION CATALYST AND CATALYST FOR HYDROCYANIC ACID PRODUCTION

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Publication number Publication date
GB2062486B (en) 1984-09-19

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19961104