CA1300852C - Claus reaction furnace - Google Patents

Claus reaction furnace

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Publication number
CA1300852C
CA1300852C CA000559513A CA559513A CA1300852C CA 1300852 C CA1300852 C CA 1300852C CA 000559513 A CA000559513 A CA 000559513A CA 559513 A CA559513 A CA 559513A CA 1300852 C CA1300852 C CA 1300852C
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Canada
Prior art keywords
mol
reaction furnace
claus reaction
gas
catalyst structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA000559513A
Other languages
French (fr)
Inventor
Edward Adrian Luinstra
Charles Terrel Adams
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Shell Canada Ltd
Original Assignee
Shell Canada Ltd
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Filing date
Publication date
Application filed by Shell Canada Ltd filed Critical Shell Canada Ltd
Priority to CA000559513A priority Critical patent/CA1300852C/en
Priority to GB8903916A priority patent/GB2221853A/en
Application granted granted Critical
Publication of CA1300852C publication Critical patent/CA1300852C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04Alumina
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C01B17/0434Catalyst compositions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

A B S T R A C T

CLAUS REACTION FURNACE

Claus reaction furnace comprising a housing (1), a burner (3) with gas inlets (5 and 9), a gas outlet (7), and a rigid permeable catalyst structure (13) arranged between the burner (3) and the gas outlet (7), which rigid permeable catalyst structure (13) includes a support and a catalytically active substance comprising at least 0.80 kg of alumina/kg and being provided with pores having a specific surface area between 0.5 and 100 m2/g.

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Description

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Hsb CLAUS REACTION E~RNACE

The present invention relates to a Claus reaction furnace comprising a housing, a burner with gas inlets, and a gas outlet.
The gas outlet is normally in fluid communication with a waste heat boiler, condenser, and the first of a series of one or more interconnected catalytic reactors and other equipment.
During normal operation a feed gas, referred to as acidic feed gas, con-tai~ing hydrogen sulphide, carbon dioxide and varying amounts of other components, including water ? methane, ethane, other hydrocarbons and nitrogen, and air are supplied to the gas inlets of the Claus reaction furnace. The Claus reaction furnace is operated in such a way that part of the hydrogen sulphide is oxidised to sulphur dioxide which reacts with the remaining hydrogen s~lphide to form elemental sulphur To complete the reaction the gas mixture from the Claus reaction furnace is cooled, sulphur is condensed and removed thereProm, and the remaining gas mixture is passed to the first catalytic reactor in which elemental sulphur is produced. From the first catalytic reactor a gas mixture including hydrogen sulphide, sulphur dioxide and elemsntal sulphur is passed via a condenser, where elemental sulphur is removed from the gas stream, to the second catalytic reactor. From the second catalytic reactor a gas mixture including hydrogen sulphide, sulphur dioxide and elemental sulphur is passed via a condenser, where elemental sulphur is removed from the gas stream, to the third catalytic reactor. In a last condenser elemental sulphur is removed from the gas mixture leaving the third catalytic reactor.
The abo~e described Claus sulphur recovery unit contains three ; catalytic reactors, Claus sulphur recovery units can have between two to four catalytic reactors.

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During normal operation of the Claus reaction furnace, varying amounts of organic sulphur compounds such as carbon disulphide and carbonyl suLphide are formed in addition to sulphur dioxide and sulphur. It has been postulated that carbon disulphide is formed by a reaction of hydrogen sulphide or sulphur with hydrocarbon impurities in regions of the furnace where unburned hydrocarbon exists. Carbonyl sulphide is probably formed by reaction of sulphur and carbon ~onoxide obtained from the reduction of carbon dioxide.
Some of the organic sulphur compounds initially formed will decompose as the gas mixture passes through the reaction furnace and the associated equipment.
However, in some situations, in particular when the acidic feed gas has a relatively low hydrogen sulphide content, or a relatively high hydrocarbon content, or where the reaction furnace provides a relatively low gas residence time, the gas mixture leaving the Claus reaction furnace can contain relatively large amounts of organic sulphur compounds. It is not uncomman that 10%
by weight or more of the sulphur in the gas mixture leaving the Claus react~on furnace of a susceptible Claus sulphur recovery unit is in the form of carbon disulphide and carbonyl sulphide.
If not converted to sulphur, these compounds will find their way to the tail gas, thereby either severely burdening any tail gas treating unit downstream of the sulphur recovery unit, or releasing unacceptable amounts of polluting sulphur-containing effluent to the atmosphere.
To reduce the amounts of carbon disulphide and carbonyl sulphide to required levels, the first catalytic reactor can be operated at a ~elatively high temperature, often as high as 380 to 400 ~C at the outlet. This practice is very effective, but causes a loss of efficiency in the Claus reaction, in which hydrogen sulphide and sulphur dioxide react to form sulphur and water, since the equilibrium point for this reaction is favoured by low tempera-tures. In addition, catalysts used in the catalytic reactors suffer : a loss of surface area when kept at high temperatures, especially in the presence of water vapour. For thiF reason, operators of ~L3(~ S2 Claus sulphur recovery units normally try to limit the increase in temperature in the catalytic reactors, consistent with satisfactory conversion of carbon disulphide and carbonyl sulphide.
Much research effort has been expended over the years to improve the conversion of carbon disulphide and carbonyl sulphide, and many improved catalysts for this purpose have been developed.
However, a further increase in temperature was avoided, because of the stated effects on the Claus reaction equilibrium, and catalyst stability.
; 10 It is an object of the present invention to provide a Claus reaction furnace which produces during normal operation a gas mixture which has a reduced amount of organic sulphur compounds.
To this end the Claus reaction furnace according to the invention comprises a housing, a burner with gas inlets, a gas outlet, and a rigid permeable catalyst structure arranged between the burner and the gas outlet, which rigid permeable catalyst structure includes a support and a catalytically active substance comprising at least 0.80 kg of alumina/kg and being provided with pores havi~g a specific surface area between O.S and lO0 m2/g.
The invention will now be described by way of example in more detail with reference to the accompanying drawing showing sche-matically a cross-section of the Claus reaction furnace according to the invention.
The Claus reaction furnace comprises a housing l, a burner 3 with gas inlets in the form of feed inlet 5 and air inlet 9, and a gas outlet 7.
The burner 3 is further provided with a fuel supply conduit 11 .
In the housing l is arranged rigid permeable catalyst structure 13 located between the burner 3 and the gas outlet 7.
~ The rigid permeable catalyst structure 13 includes a support and a catalytically active substance comprising at least 0.80 kg of alwnina/kg and being provided with pores having a specific surface area b~tween 0.5 and 100 m /g.

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The support of the rigid permeable catalyst structure com-prises a refractory material having a working temperature of at least ll00 C which supports the catalytically active substance.
During normal operation an acidic feed gas including hydrogen sulphide is supplied to the gas inlet 5 and oxidant is supplied to air inlet 9. Only during start-up, fuel is additionally supplied to the fuel supply conduit ll.
The Claus reaction furnace is operated in such a way that part of the hydrogen sulphide is oxidised to sulphur dioxide which reacts with the remaining hydrogen sulphide to form elemental sulphur.
The gas mixture passes through the longitudinal passages of the rigid permeable catalyst structure 13 where the organic sulphur compounds are converted into hydrogen sulphide. By arranging the rigid permeable catalyst structure in the housing the hot gas mixture is contacted with the catalytically active rigid permeable catalyst structure, which facilitates the conversion of organic sulphur compounds.
For a~ acidic feed gas containing about 0.50 mol hydrogen sulphide/mol, 0.42 mol carbon dioxide/mol, 0.04 mol methane/mol and 0.04 mol water, the gas mixture leaving the Claus reaction furnace comprises 0.02 mol hydrogen/moll 0.48 mol nitrogen/mol, 0.02 mol carbon monoxide/mol, 0.l4 mol carbon dioxide/mol, 0.03 mol hydrogen sulphide/mol, 0.05 mol sulphur dioxide/mol, 0.0l mol carbonyl sulphide/mol, 0.0l mol carbon disulphide and 0.04 mol sulphur (S2)/mol, the balance being water. The average molecular weight is about 32.
In the Claus reaction furnace, the space velocity of the gas is between 360 and 7200 l gas/hour/l space, wherein the gas volume is given at O C and at atmospheric pressure, and the temperature in the Claus reaction furnace is about l000 C.
If required the inner wall of the housing l can be lined with sultable refractory mater]al.

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' , ~;~V0852 In a suitable embodiment the catalytically active substance of the rigid permeable catalyst structure 13 includes at least 0.90 kg alumina/kg.
The support of the rigid permeable catalyst structure comprises a honeycomb of cordierite or mullite, the cell width is between 3 and 5 mm, and wherein the thickness of the walls between adjacent cells is between 0.1 and 5 mm. The honeycomb is so arranged that the gas passes through the cells.
In an alternative embodiment, the support of the rigid per-meable catalyst structure is provided with longitudinal passages,extending in the direc~ion of the gas flow, having a cross-sectional area between 0.2 and 78 mm . The support ca~
comprise a layer of alumina-containing bricks.
The rigid permeable catalyst structure may entirely consist of the catalytically active substance.
In a further embodiment of the invention the rigid permeable catalyst structure comprises a layer of particles arranged between vertical screens.
Alternatively, the rigid permeable catalyst structure comprises fibres having a thickness between 0.1 and 5 mm.
The thickness of the rigid permeable catalyst structure is between 0.3 and 2 m. During normal operation the pressure drop over the rigid permeable catalyst structure should be less than about 3.5 kPa.
The rigid permeable structure can be placed anywhere in the furnace, but is suitably placed near the outlet of the reaction furnace, where the temperature is expected to be lower. The life of the catalyst will likely be longer at the lower temperature.
The following experiments were carried out to simulate the 3~ conversion of organic sulphur compounds using a permeable catalyst structure arranged in a Claus reaction ~urnace. The gas fed to the experimental unit contained no elemental sulphur, but contained increased amounts of hydrogen sulphide and sulphur dioxide, and a reduced amount of water, so that after reaction of these compo-nents, their concentrations closely simulated the gas composition ~:

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cited previously. The feed gas entered a quartz reactor having an inside diameter of 1 cm, which contained the catalyst samp?e heated to 1000 C. Elemental sulphur and water were removed from the gas leaving the reactor, before the composition of the gas leaving the reactor was analysed using gas chromatography.
Experiment 1, not according to the invention. In this experi-ment the reactor was empty. The composition of the gas as supplied to the reactor was 0.0205 mol H2/mol, 0.4857 mol N2/mol, 0.0203 mol CO/mol, 0.1412 mol CO2/mol, 0.0103 mol COS/mol, 0.0872 mol H2S/mol, 0.0103 mol CS2/mol, 0.0794 mol S02/mol and the balance being water.
The molar flow rate of the gas was 0.84 mol/hour and the linear velocity was 0.31 m/s. The composition of the gas leaving the reactor was 0.4857 mol N2/mol of feed, 0.1455 mol CO2/mol of feed, 0.0074 mol COS/mol of feed, 0.0124 mol H2S/mol of feed, 0.00887 mol CS2/mol of feed, 0.0467 mol SO2/mol of fsed. The COS conversion was 29% and the CS2 conversion 13.8%.
Experiment 2, according to the invention. In this experiment the reactor was provided with a rigid permeable catalyst structure in the form~of 0.79 g of refractory particles having diameters in the range of from 1.2 to 1.7 mm, a surface area of 0.92 m2/~. The composition of the particles was 0.94 kg A12O3/kg, 0.002 kg SiO2/kg, 0.053 kg CaO/kg, 0.002 kg Fe2O3/kg, 0.001 kg MgO/kg and the balance being alkali oxides. The composition of the gas as supplied to the reactor was 0.0197 mol H2/mol, 0.4651 mol N2/mol, 0.0195 mol CO/mol, 0.1310 mol CO2/mol, 0.0113 mol COS/mol, 0.1055 mol H2S/mol, 0.0126 mol CS2/mol, 0.0903 mol SO2/mol and the balance ; be:Lng water. The molar flow rate of the gas was 0.84 mol/hour, the linear velocity in the reactor was 0.31 m/s, and the space velocity in the reactor was 28822 1 gas~lour/l space, wherein the gas volume is given at 0 C and at atmospheric pressure. The composition of the gas leaving the reactor was 0.4651 mol N2/mol of feed, 0.1484 mol CO2/mol of feed, 0.0063 mol COS/mol of feed, 0.0500 mol H2S/mol of feed, 0.0061 mol CS2/mol of feed, 0.0570 mol SO2/mol of feed.
Ihe COS conversion was 44~ and the C52 conversion 99.5~.

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Experiment 3, according to the invention. In this experiment the reactor was provided with a rigid permeable catalyst structure in the form of a one-cell specimen cut from a honeycomb coated ~ith a catalytically active substance containing 0,9 kg A1203/kg. The length of the specimen was 5 cm, its mass was 1.71 g, the width of the square longitudinal hole was 4 mm and the thickness of the wall surrounding the hole was 1 mm. The surface area of the catalyti-cally active substance was between 10-15 m /g. The composition of the gas as supplied to the reactor was 0.0205 mol H2/mol, 0.4857 mol N2/mol, 0.0203 mol CO/mol, 0.1412 mol C02/mol, 0.0103 mol COS/mol, 0.0872 mol H2S/mol, 0.0103 mol CS2/mol, 0.0794 mol S02/mol and the balance being water. The molar flow rate of the gas was 0.84 mol/hour, the linear velocity in the reactor was 0.31 m/s, and the space velocity in the reactor was 4814 1 gas/hour/l space wherein the gas volume is given at O C and at atmospheric pressure. The composition of the gas leaving the reactor was 0.4857 mol N2/mol of feed, 0.1580 mol C02/mol of feed, 0.0036 mol COS/mol of feed, 0.0260 mol H2S/mol of feed, 0.00018 mol CS2/mol of feed, 0.0344 mol~S02/mol of feed. The COS conversion was 65% and the CS2 conversion 98.3~.
In conclusion, catalytically active substance comprising at least 0.80 kg of alumina/kg and being provided with pores having a specific surface area between 0.5 and 100 m /g were found to have very high activity for carbon disulphide conversion even though surface areas were much lower than those of normal first converter catalyst, By operating these catalysts at or close to the tempera-ture of the reaction furnace, little or no deterioration of the Claus equilibrium wi].l take place. The first catalytic stage, con~aining conventional Claus catalyst, can now be oparated at lower temperatures, improving the yield of sulphur.

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Claims (10)

1. Claus reaction furnace comprising a housing, a burner with gas inlets, a gas outlet, and a rigid permeable catalyst structure arranged between the burner and the gas outlet, which rigid permeable catalyst structure includes a support and a catalytically active substance comprising at least 0.80 kg of alumina/kg and being provided with pores having a specific surface area between 0.5 and 100 m2/g.
2. Claus reaction furnace as claimed in claim 1, wherein the support comprises a refractory material having a working temperature of at least 1100°C.
3. Claus reaction furnace as claimed in claim 1 or 2, wherein the catalytically active substance includes at least 0.90 kg alumina/kg.
4. Claus reaction furnace as claimed in claim 1, wherein the thickness of the rigid permeable catalyst structure is between 0.3 and 2 m.
5. Claus reaction furnace as claimed in claim 1, wherein the support of the rigid permeable catalyst structure comprises a honeycomb of cordierite or mullite arranged perpendicular to the fluid flow.
6. Claus reaction furnace as claimed in claim 5, wherein the cell width of the honeycomb is between 3 and 5 mm, and wherein the thickness of the walls between adjacent cells is between 0.1 and 5 mm.
7. Claus reaction furnace as claimed in claim 1, wherein the support is provided with longitudinal passages having a cross-sectional area between 0.2 and 78 mm2.
8. Claus reaction furnace as claimed in claim 7, wherein the support comprises a layer of alumina-containing bricks.
9. Claus reaction furnace as claimed in claim 1, wherein the rigid permeable catalyst structure comprises a layer of particles arranged between vertical screens.
10. Claus reaction furnace as claimed in claim 1, wherein the rigid permeable catalyst structure comprises flbres having a thickness between 0.1 and 5 mm.
CA000559513A 1988-02-23 1988-02-23 Claus reaction furnace Expired - Fee Related CA1300852C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA000559513A CA1300852C (en) 1988-02-23 1988-02-23 Claus reaction furnace
GB8903916A GB2221853A (en) 1988-02-23 1989-02-21 Claus reaction furnace

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA000559513A CA1300852C (en) 1988-02-23 1988-02-23 Claus reaction furnace

Publications (1)

Publication Number Publication Date
CA1300852C true CA1300852C (en) 1992-05-19

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Family Applications (1)

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CA000559513A Expired - Fee Related CA1300852C (en) 1988-02-23 1988-02-23 Claus reaction furnace

Country Status (2)

Country Link
CA (1) CA1300852C (en)
GB (1) GB2221853A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10233819A1 (en) * 2002-07-25 2004-02-12 Thyssenkrupp Encoke Gmbh Claus processing of hydrogen sulfide in coke oven gas achieves high removal efficiency operating with a single furnace and at lower temperatures than is usual practice
DE10233820A1 (en) * 2002-07-25 2004-02-12 Thyssenkrupp Encoke Gmbh Cracking reactor, for a Claus reactor to convert hydrogen sulfide into pure sulfur, has a horizontal cylindrical boiler, to take the hot gas into a combustion chamber and through a catalyst zone giving a hot process gas

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1317168A (en) * 1970-07-13 1973-05-16 Shell Int Research Porous media burner
GB1473943A (en) * 1974-04-17 1977-05-18 Uop Inc Recuperative form of thermal-catalytic incinerator
GB1536866A (en) * 1976-10-15 1978-12-20 Horstmann Gear Co Ltd Thread and worm grinding and milling machines
FR2481145A1 (en) * 1980-04-23 1981-10-30 Rhone Poulenc Ind PROCESS FOR PRODUCING CATALYSTS OR TITANIUM OXIDE-BASED CATALYST SURFACE SUPPORTS AND THEIR CATALYSIS CLAUS APPLICATIONS
DE3535815A1 (en) * 1985-10-08 1987-04-09 Metallgesellschaft Ag METHOD FOR PURIFYING HYDROGEN SULFUR AND EXHAUST GAS SULFUR DIOXIDE

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GB8903916D0 (en) 1989-04-05
GB2221853A (en) 1990-02-21

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