GB1574452A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1574452A – Process for the production of sulphur from so2-containing gases
– Google Patents

GB1574452A – Process for the production of sulphur from so2-containing gases
– Google Patents
Process for the production of sulphur from so2-containing gases

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Publication number
GB1574452A

GB1574452A
GB13012/77A
GB1301277A
GB1574452A
GB 1574452 A
GB1574452 A
GB 1574452A
GB 13012/77 A
GB13012/77 A
GB 13012/77A
GB 1301277 A
GB1301277 A
GB 1301277A
GB 1574452 A
GB1574452 A
GB 1574452A
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GB
United Kingdom
Prior art keywords
gas
process according
sulfur
containing gas
sulfur dioxide
Prior art date
1976-03-29
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.)

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Application number
GB13012/77A
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Davy International AG

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Davy International AG
Priority date (The priority date 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 date listed.)
1976-03-29
Filing date
1977-03-28
Publication date
1980-09-10

1977-03-28
Application filed by Davy International AG
filed
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Davy International AG

1980-09-10
Publication of GB1574452A
publication
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patent/GB1574452A/en

Status
Expired
legal-status
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Classifications

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C

C01B17/00—Sulfur; Compounds thereof

C01B17/02—Preparation of sulfur; Purification

C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides

C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide

C01B17/0478—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrocarbons or mixtures containing them

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation

Y02E60/30—Hydrogen technology

Y02E60/32—Hydrogen storage

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P20/00—Technologies relating to chemical industry

Y02P20/10—Process efficiency

Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Description

PATENT SPECIFICATION
( 11) ( 21) Application No 13012/77 ( 22) Filed 28 March 1977 ( 31) Convention Application No.
2 613 343 ( 32) Filed 29 March 1976 in ( 33) Fed Rep of Germany (DE) ( 44) Complete Specification published 10 Sept 1980 ( 51) INT CL 3 COIB 17/04 ( 52) Index at acceptance CIA K 9 B 3 B K 9 B 4 F K 9 B 5 A K 9 B ( 72) Inventors LARS HELLMER GERALD KOLLER GHAZI RASHID AL-MUDDARRIS KULDIP SUD ( 54) PROCESS FOR THE PRODUCTION OF SULFUR FROM SO 2-CONTAINING GASES ( 71) We, DAVY INTERNATIONAL AKTIENGESELLSCHAFT, a German Company of Borsigallee 1, 6000 Frankfurt 60, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed to be particularly described in and by the following statement:This invention relates to a process for the production of sulfur from SO-containing gases SQ-containing gases are formed in a number of technical processes, e g with the roasting of sulfide ores or with the burning of sulfur-containing fuels The SO, content of the roaster gases is sufficient for processing them to sulfuric acid and a waste gas which is poor in SO is produced with modern processes However, in the case of flue gases which are formed by combustion of sulfur-containing fuel oils or coal, the SO 2 content of the resulting flue gases is too low for a direct utilization but too high for being emitted into the atmosphere A great number of processes for the desulfurization of flue gases is known, including processes which are cyclic, with regeneration of the absorbent or adsorbent, and supply a gas with a higher SO 2 percentage from the regeneration Typically waste gases containing more than 10 vol -% SOQ are produced from the regeneration of absorbents or adsorbents of gas desulfurization plants In general, there is no demand for the sulfuric acid which can be produced from this regeneration gas so that the necessity arises of reducing the SQ to elemental sulfur which can be stored and transported at lower costs than sulfuric acid.
Several processes are known for the reduction of SO-containing gases to elemental sulfur In the case of one process, the SOcontaining gas is reduced by means of methane in the presence of sulfur and a reducing catalyst at about 760 to 1000 C The formed elemental sulfur is separated from the gas and the gas is subsequently processed to form further elemental sulfur in Claus contact plants Since the catalytic reduction is performed at relatively high temperatures, 50 the catalyst can easily be damaged and catalyst losses can occur Furthermore, it is necessary to maintain the exact temperature (DT-OS 2 327 616; VGB-Kraftwerkstechnik (VGB-power plant technique) 53 ( 1973) 55 pages 521-525).
It is also known how to reduce sulfur dioxide in regeneration waste gases with a hydrogen-rich gas above 650 WC without using a catalyst whereby a gas mixture com 60 prising sulfur, hydrogen sulfide, sulfur dioxide and carbon-sulfur-compounds is formed.
The use of a hydrogen-rich reduction gas, which should contain only small amounts 65 of methane, is comparatively expensive since the hydrogen must be produced in an associated plant, e g by means of catalytic reforming of natural gas In accordance with this process, hydrogen is preferred to hydro 70 carbons since the latter are supposed to be inclined to form soot whereby dark-coloured elemental sulfur is produced (DT-OS 2 365 116).
It is already known to reduce partially the 75 SO content of the waste gases of copper converters to sulfur with natural gas, without using a catalyst However, this process requires temperatures above 12500 C in order to assure that the carbon of the methane is 80 also oxidised and no dark-coloured sulfur is produced (Ind Eng Chem 42 ( 1950) 22492253).
According to the present invention a process for producing sulfur from a sulfur di 85 oxide-containing gas comprises burning a fuel with an oxygen-containing gas, mixing resultant hot combustion gases in a thermal reduction zone with sulfur dioxide-containing gas and with a reducing agent selected 90 N tn It 1574452 1 574452 from hydrogen, carbon monoxide, Cl to Q hydrocarbons, and mixtures thereof, the mol ratio of hydrogen equivalent (as herein defined) of said reducing agent to sulfur dioxide being within the range of from 1 8 to 2.2, so that a substantial proportion of the sulfur dioxide present in the sulfur dioxidecontaining gas is thermally reduced in the thermal reduction zone, and subsequently cooling the resulting reduction mixture.
Thus, in accordance with the invention, a gaseous or liquid fuel is burned with the 02-containing gas, the hot combustion gases are mixed with the SO-containing gas and with a CQ-CQ-hydrocarbon (e g methane), hydrogen and/or carbon monoxide serving for the reduction, and, after a partial reduction of the SQ, the mixture is cooled down.
The temperature in the thermal reduction zone preferably lies in the range of from 9500 C to 12500 C Resulting reduction mixture from the thermal reduction zone is preferably cooled to a temperature in the range of from 200 C to 460 TC A conventional fuel is methane The fuel and the reducing agent can be the same or different Suitable reducing agents include also gas mixture, as e.g coke oven gas, waste from refineries obtained by catalytic reforming, suitable natural gas and other suitable industrial gases.
Air, air enriched with oxygen, or an oxygencontaining industrial waste gas can be used, for instance, as 02-containing gas Of these, air is usually the most convenient Q 2-containing gas for use Preferably, a combustible gas is used as fuel, but fuel oil can also be used for this purpose Preferably, the fuel is burned with a stoichiometric amount of oxygen so that the combustion gases contain no, or only a small ( 0 2 % by volume), excess of oxygen The SO-containing gas can comprise, from case to case, very different concentrations of SO and may be, for example, a waste gas produced from regeneration of an absorbent or adsorbent of a gas desulfurization plant containing more than 10 vol -% 502 Thus the regeneration gas from adsorbents substantially consisting of carbon has, in general an SO 2 content of between 15 and 40 % by volume, whereas, the 502 content of the gases from the regeneration of alkali bisulfite solutions is considerably higher, e g within the range of from 50 to % by volume 502 After mixing the reducing agent and the 502-containing gas with the hot combustion gases, the temperature of the mixture is sufficiently high so that the SQ is reduced to elemental sulfur and partially to hydrogen sulfide The process of the invention is conducted so that a substantial proportion, preferably at least 30 % of the 502 present in the SO 2-containing gas is reduced to sulfur in the thermal reduction zone Generally speaking, it is preferable that at least 40 % of the SOQ present, typically 45 % or more, and most preferably at least 50 % of the SQ, present in the SQOcontaining gas is reduced to sulfur in the thermal reduction zone.
When a C, CJ hydrocarbon is used as 70 the reducing agent, or as part of the reducing agent, with the high temperatures of 1000 C and more, the C,-Cs-hydrocarbon is at least partially cracked with formation of hydrogen so that also in this case the re 75 duction is at least partially effected by means of hydrogen The SQ,-containing gas can contain a lot of other components, particularly inert gases as CO 2, N 2, CO and, especially, water vapor Furthermore, they can 80 also contain other sulfur compounds, as e g.
COS, C 52, H S, and mercaptans If the adsorbent used for the desulfurization was regenerated by using reducing conditions, the SQ 0-containing gas can also contain excess 85 reducing agents, particularly hydrogen and/ or hydrocarbon Furthermore, the 50-containing gas can carry along dust if the dust is not previously separated In the thermal reduction stage, the 502 is reduced partially 90 to elemental sulfur and partially to hydrogen sulfide That portion of the SO 2 which was not reduced, is converted with hydrogen sulfide formed in the reduction stage to additional elemental sulfur in the subse 95 quent contact stages.
In accordance with a preferred process according to the invention, a temperature within the range from 1050 to 1250 C, preferably from 1050 to 1120 C, is maintained in l( O the reduction zone Whereas the reduction rate is too low below 950 C and practically no formation of elemental sulfur is observed, the rate increases slowly within the range from 950 to 1050 C, and above 1050 C a 1 MS very rapid increase of the reduction rate is observed Reduction temperatures above 1250 C are uneconomical because an unnecessarily great amount of fuel must be burned to maintain these high temperatures 110 in the reduction zone.
The optimum temperature range, i e the temperature range in which a high SO 2 reduction is effected with a minimum consumption of fuel and reducing agent, depends on 1 5 the type of reducing agent and on the composition of the SQ-containing gas With a given reducing agent and a given composition of the SQ 2-containing gas, the optimum temperature range for the thermal reduc 120 tion is that which provides a sufficient SO 2 reduction with minimum consumption of reducing agent.
The reduction conditions can be controlled by the amount of fuel and the ratio reduc 125 ing agent/SQ-containing gas The temperature in the reduction zone can substantially be controlled by the amount of fuel, whereas the reduction potential is determined by the ratio reducing agent/502 130 1 574 452 In accordance with the invention the reducing agent and the SO, are supplied to the hot combustion gases in a mole ratio of hydrogen equivalent to SQ, within the range from 1 8 to 2 2 «Hydrogen equivalent» is defined as the number of moles of reducing agent which has the same reducing effect as one mole hydrogen (i e in general, 0 25 mole CH,, 0 14 mole CMH 6) If this mole ratio remains below 1 8, the mole ratio of hydrogen sulfide to sulfur dioxide in the gas leaving the thermal reduction zone is still unsuitable for the subsequent Claus reaction, so that a readjustment may be necessary.
If the mole ratio of hydrogen equivalents to sulfur dioxide is higher than 2 2, the discharged gas from the thermal reduction zone still contains unused reducing agent In the case of an after-burning of the waste gas from the Claus plant, the excessive reducing agent is burned at this point By maintaining the mole ratio of hydrogen equivalents to SQ 2 within the indicated range a maximum yield of elemental sulfur and a good adjustment of the mole ratio l S/SO 2 in the gas is obtained.
The hot combustion gases have, in general, a temperature of 1100 to 2000 WC, preferably of 1200 to 1600 C, before the SO 2containing gases and the reducing agent are added After mixing these hot combustion gases with the considerably colder reducing agent and 502-containing gas, the temperature prevailing in the reduction zone is produced which is preferably within the range of 1050 to 1150 WC Suitably, the reducing agent and/or the 502-containing gas are preheated to a temperature within the range of to 600 C By means of this preheating, the fuel consumption is reduced or, depending on the kind of the used reducing agent, it becomes entirely superfluous The preheating of the SO-containing gas and/or of the reducing agent can be effected by means of heat exchange with the hot gas of the process Reducing agent and SO 2 gas can be preheated separately or together after having been mixed with each other.
Preferably, an 502-containing gas with a water vapor content of 5 to 90 vol -%, preferably with 20 to 70 vol -% is reduced.
The SQ 2 content of the gas can vary very much, for instance it may be 80 to 95 vol -% with a gas from the regeneration of alkali bisulfite solutions or about 20 to 30 vol -% with a gas from the regeneration of adsorbents based on carbon If adsorbents based on carbon or A 1,03 are regenerated with superheated steam, the regeneration gas naturally has a high steam content which, however, does not need to be condensed before subjecting the gas to the process according to the invention This is an essential advantage since the condensation of great amounts of steam from an S Of/H 2 O-mixture produces an 502-containing water which cannot be simply purged The steam content in the reduction zone promotes the conversion of carbon formed by incomplete combustion, according to the water gas reaction 70 C + H 20 H 2 + CO and prevents thus a dark color of the sulfur condensed after the thermal reduction stage.
Furthermore, suitably the gas velocity is to be maintained in the reduction zone with 75 in the range of 1 to 25 m/s, preferably within the range of 3 to 15 m/s The residence time of the gas mixture in the reduction zone is, in general, in the range from 0 1 to 4 s, preferably in the range from 0 5 to 2 0 s In 80 this time, in general, 50 to 80 % of the SQ are reduced to S and 12 S Longer residence times are not needed since a further SO 2 reduction is not possible due to the given ratio hydrogen equivalents/SO, and is not 85 even intended in view of the subsequent Claus stages.
In accordance with a preferred process according to the invention, the SO 2-containing gas and the reducing agent are supplied 90 a suitable distance downstream of the fuel supply SO 2 and reducing agent are mixed with the combustion gas which is burned out completely or to a large extent With this mixing (intermediate mixing zone) the 95 reduction gas and the SO 2 reach the reducing temperature, oxygen being no longer present or only in small amounts (less than 0.2 vol -%) In the subsequent final mixing zone, the gases are completely mixed, the 100 sulfur dioxide is reduced, and the temperature differences possibly still existing in the gas flow are equalized The separation of the combustion zone from tite reduction zone permits, furthermore, a decrease of 105 the entire reaction volume and a simpler and more exact control of the temperature in the reduction zone.
Suitably the SQ-containing gas and the reducing agent are mixed together (premix 110 ing zone) before being combined with the combustion gases In the most simple case, this premixing can be effected by joining together the two pipelines supplying these two gases, a sufficient mixing length being 115 provided between the joining point of the two pipelines and the inlet into the furnace.
A plurality of inlet points for the reducing agent/SO 2 gas mixture can, of course, be provided with large plants 120 The reducing agent can be supplied separately from the 502-containing gas and/ or mixed with it and/or the reducing agent can be produced by partial burning of the fuel If, for instance, the adsorbent used for 125 the flue gas desulfurization is regenerated using reducing conditions, the SO-rich regeneration gas contains often an excess of reducing agent, e g hydrogen, which then covers at least part of the reducing agent 130 4 1 574452 4 required for the 503 reduction The partial burning of the fuel, i e the forming of the reducing agent from the fuel, can only be used to a limited extent and, in general, can only supply a part of the required reducing agent because there exists the risk of forming carbon which would give the separated sulfur a dark color In accordance with the preferred embodiment of the invention, the reducing agent is not produced by partial burning of the fuel but is supplied separately in its totality.
Preferably, solid impurities are separated from the SO 0-containing gas prior to its reduction The decrease of the dust content to an acceptable value is effected in the customary manner, e g by means of filters or other separators In order to avoid breakdowns of the blower, the dust is separated from the SOQ gas flow before it enters the blower.
Suitably, the hot SO,-containing gas from the regeneration of the absorption or adsorption agents of the gas desulfurization plants is cooled to a temperature still sufficiently high to prevent corrosion and corresponding to the mechanical blower design; it is compressed by means of a blower to the necessary processing pressure and is afterwards heated again Since the SQ-containing gas contains frequently also small amounts of SQ, it is supplied in hot condition to avoid corrosion, but, before passing through the blower, it is cooled down to the maximum admissible temperature for this purpose so as to avoid exceeding the limits of stress Subsequently, the gas can be heated again Any sulfuric acid condensation in the pipelines up to the inlet into the furnace as well as in the blower is to be avoided In the reduction furnace itself, the 503 as well as the SOQ are reduced to sulfur and hydrogen sulfide so that corrosive action is therewith eliminated.
In accordance with a preferred process according to the invention, the steam-containing reaction gas product, after having been cooled down in a waste heat boiler is led at 240 to 400 C, preferably 250 to 3500 C, over a CS, and/or COS hydrolyzing catalyst, preferably a Co Mo catalyst (in general a cobalt sulfide/molybdenum sulfide catalyst).
In this way CS_ and COS contained in the gas is hydrolyzed and additional SOQ is reduced to H 2 S, formed sulphur is condensed by cooling the gas to a temperature within the range of 118 to 1700 C, and the sulfur is separated from the gas and then the reaction gas is led through, preferably at least two, Claus contact stages following which each time the formed sulfur is condensed and separated by means of cooling the gas to a temperature within the mentioned range.
In the first stage operating with a Co Mo catalyst, besides the hydrolysis of COS and C 52 favored by the content of water vapor in the reaction gas, also additional SO, still contained in the gas is hydrogenated to H 2 S as well as a Claus reaction with formation of elemental sulphur takes place Suit 70 ably, the reaction gas is, after each of the contact stages, cooled down to temperatures decreasing from stage to stage In this way, it is taken into account that the partial pressure of sulphur in the gas stream de 75 creases behind the contact stages one stage to the next so that the gas stream must be cooled down as far as possible for a continued separation of sulphur The lowest temperature is at about 118 C below which 80 the risk of separating solid sulphur arises whereby trouble would arise in the plant.
In general, the condensation takes place within the range from 118 to 125 C, and the aim is to reach a temperature as close 85 to 118 C as possible.
In one particular preferred process, the mole ratio of hydrogen equivalents to SQ, in the gas from the thermal reduction, after the cooling in the waste heat boiler and the 90 sulphur separation, is adjusted again to a value within the range from 1 8 to 2 2 by addipg reduction gas and then the gas is heated to the reaction temperature of the first contact stage By means of the adjust 95 ment of the H 2 S/SO 2 ratio, an improved control of the Claus reaction is obtained in the subsequent contact stages as well as an improved conversion The reheating can be effected by means of heat exchange, or by 100 means of adding hot gas directly from the thermal reduction, or by in line burning fuel A possible excess of fuel is not lost if the catalytic stages are followed by an afterburner which requires fuel anyway 105 In normal operation of the process of the invention it will be necessary from time to time to regenerate the catalytic charges in the contact stages, since the catalyst activity decreases with time Regeneration can be 110 carried out upon the contact stages either one at a time or several at a time Such regeneration can be effected using a gas having an increased reduction potential, for instance by temporarily operating the ther 115 mal reduction stage with the excess of reducing gas Hence regeneration can be achieved, for example, by interrupting the normal operating conditions used in the process of the invention and increasing the flow 120 of reducing gas and/or reducing the flow of the SQ-containing gases so as to bring the hydrogen equivalents/SO, ratio to a value within the range of from 2 0 3 0 during the regeneration, whilst maintaining the con 125 tact stage or stages being regenerated at a temperature within the range of from 350 C to 5000 C for a period of 8 to 36 hours In order to reach the regeneration temperature, a part of the reducing gas by-passes the 130 1 574 452 1 574452 waste heat boiler and is combined with the gas flowing to the contact stage or stages.
Consequently, the gas used for the regeneration is rich in H 2 S The preferred regeneration period amounts to 12 to 24 hours After the regeneration has been effected the mole ratio of hydrogen equivalents/SO, in the gas is again reduced to a value within the range of from 1 8 to 2 2 The regeneration can also be effected with a gas enriched with hydrogen from the thermal reduction or with hydrogen alone Hydrogen can be used if the thermal reduction is shut down.
According to a modification of the process according to the invention, one part of the contact stages can be regenerated and, at the same time, reduction gas can be fed to the other part of the contact stages to carry out the Claus reaction By alternate switching of the contact stages from Claus reaction to regeneration and vice versa, continuous operation of the pant is assured For the regeneration, the mole ratio of hydrogen equivalents to SO, of the gas before entering the contact stages to be regenerated is increased to a value within the range from 2 0 to 3 0 by adding reduction gas Special attention is to be paid to keep warm the contact stages when interrupting the thermal reduction due to the lack of the sulfur dioxide supply; It is important that the contact stages are kept, in this case, at at least 150 WC so that blocking the catalyst beds is avoided This temperature can be maintained by means of a hot gas stream led through the catalyst beds from outside, by means of a steam flow or by means of indirect heating of the catalyst beds This measure is particularly important in the case of flue gas desulfurization plants operated after peak-load power stations which are also only periodically in operation.
Suitably, the waste gas of the last contact stage is afterburned after having been cooled down and the condensed sulfur having been separated In this way, sulfur, H 25, COS, C 52 and CO contained in the gas stream are completely oxidized The exhaust gas could possibly be mixed with the nondesulfurized flue gas.
In the process of the invention the steps of burning the fuel with the oxygen-containing gas and of mixing resultant hot combustion gases with sulphur dioxide-containing gas and with the reducing agent are preferably performed in a substantially cylindrically shaped, fireproof-lined furnace chamber having a combustion muffle attached at one end thereof, said muffle being provided with supply sockets for fuel, oxygencontaining gas, reducing agent and the sulfur dioxide-containing gas, the supply socket or sockets for the reducing agent and the sulfur dioxide-containing gas being arranged downstream in the direction of gas flow from the supply sockets for fuel and oxygen-containing gas By this design of furnace, a certain separation between combustion zone and reduction zone is achieved.
The temperature in the reduction zone can 70 be precisely controlled and this control is simple compared with a construction in which the fuel, oxygen, reducing agent and sulfur dioxide gas are all supplied to the furnace at about the same place 75 In the reduction furnace, a mixing wall with openings is preferably arranged transversely to the direction of the gas flow, by means of which the mixing of the gases in the final mixing zone is favoured The pres 80 sure drop of the gas stream at the mixing wall amounts, in general, to 25 to 250 mm water column, preferably to 50 to 150 mm water column In addition, the combustion muffle can be provided with installations 85 to promote the mixing of the gas, particularly the mixing of the fuel with the oxygen-containing gas.
The invention is described hereinbelow in greater detail with reference to the drawing 90 Fig 1 shows a flow sheet of a plant to carry out the process in accordance with the invention, for the sulfur recovery from an SO-containing gas and Fig 2 shows a diagrammatic representa 95 tion of a furnace used for the thermal reduction stage of the process according to the invention.
The 502-containing regeneration gas is supplied to a thermal reduction furnace 5 100 via line 1 Before entering the reduction chamber 5, the regeneration gas is mixed with a gaseous reducing agent which is supplied via line 2 Simultaneously, methane is supplied as fuel via line 3 and air is sup 105 plied via line 4 to a burner the combuston gases of which flow through the reduction furnace 5 In the furnace 5, the sulfur dioxide is mostly reduced to elemental sulfur and hydrogen sulfide The gas mixture leav l 10 ing the furnace 5 is first cooled down in the waste heat boiler 6 and then cooled in the heat exchanger 7 to such a degree that already a part of the formed sulfur is condensed and withdrawn at 8 115 In order to adjust the mole ratio H 25/ SO to a value of about 2, reduction gas, particularly hydrogen, is added to the gas stream at 9 Subsequently, the gas stream is heated in the small chamber 10 to the 120 temperature of the contact stage 13 by means of a burner In this burner, methane, natural gas or another heating gas is burned which is supplied via line 11 The burner can also be arranged directly in the gas line The 125 carbonyl sulfide and the carbon disulfide formed in the reduction furnace 5 are hydrolysed over a Co Mo catalyst to form hydrogen sulfide and carbon dioxide Simultaneously, an additional part of the SO 2 contained in 130 Is S 1 574452 the gas is hydrogenated to HRS and/or converted with H 1 S to elemental sulfur Subsequently, the gas is cooled down in the heat exchangers 16 and 17 to the condensing temperature of the sulfur, i e about 1350 C.
The condensed sulfur is collected in the separator 18.
For further conversion of the SO 2 and HS still contained in the gas mixture, the gas mixture is then heated to the temperature of the Claus contact stage 14 in the heat exchanger 16, converted at this contact, and, subsequently, the formed sulfur is separated in the separator 18 after having been cooled down again (not shown).
Finally, the gas mixture is once more heated in the heat exchanger 17 and converted in the last Claus contact stage 15 and, after having been cooled down again (not shown), it is again subjected to a sulfur separation.
The off-gas flows then through an afterburning furnace 21 in which fuel supplied via line 20 is burned with 0-containing gas fed via line 19 Combustible sulfur values, such as H 2 S and elemental sulfur, are simultaneously burned so that the exhaust gas of the afterburning stage contains only a little SO 2 Suitably, this exhaust gas is fed to the associated gas desulfurization plant.
The heating of the gas, after sulfur separation in separator 18, to the temperatures of the contact stages 14 and 15 can, in principle, also be effected by means of burners installed in the gas line instead of using the heat exchangers 16 and 17 Methane, natural gas or another heating gas is burned by these burners into the gas stream The catalyst stages 13 to 15 are charged with a reducing gas having a temperature of more than 3500 C in order to regenerate the catalyst.
For this purpose, gas supplied to the contact stages 13 to 15 directly from the reduction furnace 5 via the line 12 (shown in broken lines) is mixed with reduction gas to which hydrogen was added via line 9 The desired temperature of the gas stream used for the regeneration can be controlled by means of the mixing ratio Of course, more than two Claus contact stages can be used, one part of which is in operation while the other part is being regenerated The regeneration can also be effected with complete shutdown of the thermal reduction stage by using a correspondingly heated hydrogen-containing gas. In Fig 2, the furnace 5 for the thermal
reduction is shown on a larger scale The furnace has a cylindrical cross section and is equipped at its front end with a combustion muffle 5 a to which the fuel and air are supplied through lines 4 and 3, respectively Downstream of these two lines, the SO-containing gas, which is to be reduced, -’65 is introduced via line 1 Before being introduced, the 502-containing gas is mixed with the gaseous reducing agent, as for instance, methane and/or hydrogen which is fed via line 2 The oxidation zone 50 in which substantially only the fuel burns, is formed in the 70 combustion muffle The oxidation zone 55 is followed by the reduction zone 5 d in which the 502-containing gas, which had already been mixed in line 1 with the reducing agent, is mixed with the hot com 75 bustion gases from the oxidation zone 50 whereby the 502-containing gas and the reduction gas are heated to the reduction temperature and simultaneously the reduction of SO 2 to sulfur and hydrogen sulfide 80 starts In the subsequent final mixing zone e the mixing of the gases is continued and is supported by the perforated mixing wall ‘, and the gases are converted to elemental sulfur and hydrogen sulfide The pressure 85 drop in the reduction zone is essentially determined by the mixing wall and amounts, in general, to 25 to 250 mm water column pressure, preferably to 50 to 150 mm water column pressure The concentration of ele 90 mental oxygen in the reduction zone 5 d is extremely low and amounts to 0 2 vol -0, as a maximum The consumption of reducing agent by combustion with oxygen is, therefore, negligible In order to intensify the 95 combustion in the combustion zone 50, the combustion muffle St can be provided with appropriate installations which, however, are not shown The gas which has reacted almost completely, flows then through the 100 waste heat boiler 6 in which its temperature is lowered from about 1100 to, for instance, 350 C.
The reducing gas and the SO, containing gas can be mixed in a premixing device (not 105 shown) separate from the furnace 5 For this purpose, customary gas mixing units can be used such as injectors, jet mixers or mixing chambers The exit of this mixing unit is connected to the supply socket 5 h 110 of the furnace 5.
EXAMPLE
In a flue gas desulfurization plant, a flue gas from a combustion of a carbonaceous sulfur-containing fuel is contacted with coke 115 which is activated to adsorb sulfur dioxide and water vapor with formation of sulfuric acid at the coke surface The coke having the adsorbed sulfuric acid is then heated to form again sulfur dioxide from the adsorbed 120 acid, and to regenerate the coke for further contact with flue gas The sulfur dioxide-containing gas liberated in the regeneration stage contains about 21 volume percent sulfur dioxide and about 20 volume 12 b percent water vapor.
The sulfur-dioxide-containing gas is fed via line 1 into the thermal reduction chamber 5 at a rate of 2920 Nm 3/h with 754 Nm 3/h of coke-oven gas via line 2 con 130 1 574 452 taining 57 0 vol -% hydrogen, 22 0 vol -% methane, 7 6 vol -% carbon monoxide, 2 6 vol -% ethane and higher hydrocarbons, the balance being carbon dioxide and nitrogen.
The mole ratio of hydrogen equivalents to sulfur dioxide is 2 1 The temperature in the reduction chamber is maintained at about 1070 to 1110 ‘C through combustion of additional coke-oven gas with air supplied via lines 3 and 4 respectively The sulfur dioxide in the sulfur dioxide-containing gas is largely reduced, thereby providing effluent gases containing primarily elemental sulfur, sulfur dioxide and hydrogen sulfide The gas leaving the thermal reduction chamber is cooled to about 3000 C whereby 437 kg/h elemental sulfur are condensed and drawn off corresponding to a yield of 50 % The remaining gas is further converted in a threestage Claus unit with sulfur separation after each stage The yield is 810 kg/h sulfur having a bright color The sulfur product is analyzed to be about 99 95 percent pure.
The overall yield of sulfur is 92 5 %.
In order to regenerate the Claus contact stages the rate of coke-oven gas through line 2 (Figure 1) is increased to 1042 Nm&/h with the same rate of sulfur containing gas, corresponding to a mole ratio of hydrogen equivalents to sulfur dioxide of 2 9 22 5 volume percent of the hot reaction gas bypasses waste heat boiler 6, heat exchanger 7 and combustion chamber 10, is conducted through line 12 and recombined with the main gas stream before the contact stages 13, 14 and 15 The recombined gas has a temperature of 4800 C and performs the regeneration of the catalyst After a regeneration time of 24 hours the rate of coke-oven gas through line 2 is again decreased to 754 Nm /h.

Claims (1)

WHAT WE CLAIM IS:-
1 A process for producing sulfur from a sulfur dioxide-containing gas comprising burning a fuel with an oxygen-containing gas, mixing resultant hot combustion gases in a thermal reduction zone with sulfur-dioxidecontaining gas and with a reducing agent selected from hydrogen, carbon monoxide, C, to C 5 hydrocarbons, and mixtures thereof, the mol ratio of hydrogen equivalent (as herein defined) of said reducing agent to sulfur dioxide being within the range of from 1 8 to 2 2, so that a substantial proportion of the sulfur dioxide present in the sulfur-dioxide-containing gas is thermally reduced in the thermal reduction zone, and subsequently cooling the resulting reduction mixture.
2 A process according to claim 1, in which at least 50 % of the sulfur dioxide present in the sulfur dioxide-containing gas is thermally reduced to sulfur in the thermal reduction zone.
3 A process according to claim 1 or claim 2, in which the sulfur dioxide containing gas comprises a waste gas containing more than 10 % by volume of sulfur dioxide.
4 A process according to any one of 70 claims 1 to 3, in which the sulfur dioxide containing gas is derived from the regeneration of an absorbent or adsorbent used in a gas desulfurization plant.
A process according to any one of 75 claims 1 to 4, in which the temperature in the thermal reduction zone lies within the range of from 950 ‘C to 12500 C.
6 A process according to any one of claims 1 to 5, in which the resulting reduc 80 tion mixture is cooled to a temperature of from 200 C to 460 ‘C.
7 A process according to any one of claims 1 to 6, in which the temperature in the reduction zone lies within the range 85 of from 1050 ‘C to 1250 C.
8 A process according to claim 7, in which the temperature in the reduction zone lies within the range of from 1050 ‘C to 1120 WC 90 9 A process according to any one of claims 1-8, in which the reduction conditions in the thermal reduction zone are controlled by the quantity of fuel and the ratio of reducing agent to sulfur dioxide-containing 5 gas.
A process according to any one of claims 1 to 9, in which at least one of the reducing agent and/or the SQ-containing gas is preheated to a temperature within 100 the range from 50 to 6000 C before being mixed with the hot combustion gases.
11 A process according to any one of claims 1 to 10, in which the hot combustion gases have a temperature of from 105 1100 C to 2000 ‘C, before being mixed with the sulfur dioxide-containing gas and the reducing agent.
12 A process according to claim 11, in which the hot combustion gases have a 110 temperature of from 12000 C to 1600 ‘C before being mixed with the sulfur dioxide containing gas and the reducing agent.
13 A process according to any one of claims 1 to 12, in which the sulfur dioxide 115 containing gas has a water vapor content of from 5 to 90 % by volume.
14 A process according to claim 13, in which the sulfur dioxide-containing gas has a water vapor content of from 20 to 70 % 120 by volume.
A process according to any one of claims 1 to 14, in which a gas velocity of from 1 to 25 m/s, is maintained in the thermal reduction zone 125 16 A process according to claim 15, in which a gas velocity of from 3 to 15 m/s is maintained in the thermal reduction zone.
17 A process according to any one of claims 1 to 16, in which a residence time 130 1 574 452 of from 0 1 to 4 0 S is maintained in the thermal reduction zone.
18 A process according to claim 17, in which a residence time of from 0 5 to 2 0 S is maintained in the thermal reduction zone.
19 A process according to any one of claims 1 to 18, in which the sulfur dioxidecontaining gas and the reducing agent are supplied at a suitable distance downstream from the fuel supply.
A process according to any one of claims 1 to 19, in which the sulfur dioxidecontaining gas and the reducing agent are 1 S mixed with each other before being combined with the combustion gases.
21 A process according to any one of claims 1 to 19, in which the reducing agent is supplied to the thermal reduction zone separately from the sulfur dioxide-containing gas.
22 A process according to any one of claims 1 to 21, in which the reducing agent is produced by partial combustion of the fuel.
23 A process according to any one of claims 1 to 22, in which the sulfur dioxidecontaining gas is freed from solid impurities before admission to the thermal reduction zone.
24 A process according to any one of claims 1 to 23, in which the sulfur dioxidecontaining gas comprises a hot sulfur dioxide-containing gas which is derived from the regeneration of the absorbent or adsorbent of a gas desulfurization plant and which, prior to admission to the thermal reduction zone, is cooled down to a temperature which is still sufficiently high to prevent corrosion and corresponds to the mechanical blower design, compressed to the required process pressure by means of a blower, and subsequently heated up again.
A process according to any one of claims 1 to 24, in which sulfur dioxide in resulting reduction mixture is submitted in one or more stages to catalytic conversion to elemental sulfur and to subsequent condensation and separation of sulfur produced.
26 A process according to claim 25, in which resulting reduction mixture is cooled in a waste heat boiler and led at a temperature in the range of from 240 WC to 400 C over a catalyst effective for hydrolyzing carbon disulfide and/or carbon oxysulfide so that CS, and COS contained in the gas is hydrolyzed and further sulfur dioxide is reduced to hydrogen sulfide, in which the elemental sulfur formed is condensed by cooling the gas to a temperature within the range from 118 ‘C to 170 TC and separated and in which the thus-treated reaction gas is then conducted through at least one Claus contact stage after which the newly formed sulfur is removed by condensation and separated by cooling the sulfur-containing gas to a temperature in the range from 18 C to 170 C.
27 A process according to claim 26, in which resulting reduction mixture is cooled 70 in the waste heat boiler and led at a temperature in the range of from 250 C to 350 C over the catalyst effective for hydrolyzing carbon disulfide and/or carbon oxysulfide.
28 A process according to claim 26 or 75 claim 27, in which the catalyst effective for hydrolyzing carbon disulfide and/or carbon oxysulfide is a Co Mo catalyst.
29 A process according to any one of claims 26 to 28, in which the cooled reduc 80 tion mixture is led through at least two Claus contact stages and is cooled after each Claus contact stage to an inlet temperature to the next stage lower than the inlet temperature to the Claus contact stage 85 A process according to any one of claims 26 to 29, in which the mole ratio of the hydrogen equivalents (as herein defined) to sulfur dioxide in resulting reaction mixture from the thermal reduction zone, after o cooling in the waste heat boiler and sulfur Se Daration, is readjusted to a value within the range from 1 8 to 2 2 by adding reduction gas, and the gas is reheated to the reaction temperature of the first contact stage 95 31 A process according to any one of claims 26 to 30, in which the catalyst of the catalytic stages is regenerated with a reducing gas having a mole ratio of hydrogen equivalents (as herein defined) to sulfur di 100 oxide within the range from 2 0 to 3 0 at a temperature of from 350 C to 500 C for a period of 8 to 36 hours.
32 A process according to claim 31, in which the reducing gas is an effluent from 105 the thermal reduction zone which is enriched with hydrogen.
33 A process according to claim 31 or claim 32, in which at least two Claus contact stages are provided and at least one 110 of the Claus stages is regenerated while at least one of the Claus stages is used to convert hydrogen sulfide and sulfur dioxide to elemental sulfur.
34 A process according to any one of 115 claims 26 to 33, in which the waste gas of the last stage, after it has been cooled and the condensed sulfur has been separated, is afterburned.
A process according to any one of 120 claims 1 to 34, in which the steps of burning the fuel with the oxygen-containing gas and of mixing resultant hot combustion gases with sulphur dioxide-containing gas and with the reducing agent are performed in a sub 125 stantially cylindrically shaped, fireprooflined furnace chamber having a combustion muffle attached at one end thereof, said muffle being provided with supply sockets for fuel, oxygen-containing gas, reducing 130 1 574 452 agent and the sulfur dioxide-containing gas, the supply socket or sockets for the reducing agent and the sulfur dioxide-containing gas being arranged downstream in the direction of flow of gas from the supply sockets for fuel and oxygen-containing gas.
36 A process according to claim 35, in which mixing of the gases within the furnace is assisted by means of a mixing wall provided with openings which are arranged transversely to the overall direction of gas flow in the furnace.
37 A process according to claim 35 or claim 36, in which gas mixing in the combustion zone is promoted by means of installations provided in the combustion muffle.
38 A process according to any one of claims 35 to 37 in which the reducing agent and the sulfur dioxide-containing gas are supplied through the same supply socket and are premixed by means of a premixing device for these two components connected upstream from that supply socket.
39 A process for producing sulfur from 25 a sulfur dioxide-containing gas conducted substantially as herein described with particular reference to the accompanying drawings.
A process for producing sulfur from 30 a sulfur dioxide-containing gas conducted substantially as herein described and exemplified.
41 Sulfur in solid or liquid form produced by a process according to any one 35 of claims 1 to 40.
BATCHELLOR, KIRK & EYLES, Chartered Patent Agents, 2 Pear Tree Court, Farringdon Road, London, EC 1 R ODS.
For the Applicants.
Printed for Her Majesty’s Stationery Office by The Tweeddale Press Ltd, Berwick-upon-Tweed, 1980.
Published at the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

GB13012/77A
1976-03-29
1977-03-28
Process for the production of sulphur from so2-containing gases

Expired

GB1574452A
(en)

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DE2613343C3
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1976-03-29
1976-03-29

Process for the production of sulfur from gases containing SO2

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1980-09-10

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1977-03-28
Process for the production of sulphur from so2-containing gases

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DE2613343C3
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FR
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FR2346288A1
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GB1574452A
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Families Citing this family (16)

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Publication number
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DE2923704A1
(en)

1979-06-12
1980-12-18
Bergwerksverband Gmbh

METHOD FOR REDUCING SO LOW 2 – GASES TO ELEMENTAL SULFUR

JPS6265909A
(en)

1985-09-13
1987-03-25
Mitsui Miike Kakoki Kk
Method and apparatus for treating gas containing sulfur dioxide

DE3735002A1
(en)

1987-10-16
1989-04-27
Metallgesellschaft Ag

PROCESS FOR REMOVING SULFUR HYDROGEN FROM EXHAUST GAS

US5498270A
(en)

1994-09-12
1996-03-12
Smith; Strom W.
Sulfur trap

FR2730721B1
(en)

1995-02-21
1997-03-21
Air Liquide

PROCESS FOR THE PARTIAL OXIDATION OF A GAS FLOW CONTAINING HYDROGEN SULPHIDE

US7074375B2
(en)

2002-12-03
2006-07-11
Engelhard Corporation
Method of desulfurizing a hydrocarbon gas by selective partial oxidation and adsorption

CA2413563C
(en)

2002-12-04
2011-07-19
Enflow Power Generation Inc.
Power generation from sulphur-containing fuels

US7112308B2
(en)

2003-07-15
2006-09-26
Smith Strom W
Sulfur trap sealing device

EA014246B1
(en)

2006-02-22
2010-10-29
Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
Method for disposal of di-sulphide compounds

US7722852B2
(en)

2007-07-05
2010-05-25
Worleyparsons Group, Inc.
Process for the thermal reduction of sulfur dioxide to sulfur

US8425874B2
(en)

2011-06-04
2013-04-23
Rameshni & Associates Technology & Engineering
Process for the production of sulfur from sulfur dioxide with tail gas recycle

US9522346B2
(en)

2012-03-22
2016-12-20
Controls Southeast, Inc.
Sulfur seal device

US10106410B2
(en)

2017-03-10
2018-10-23
Saudi Arabian Oil Company
Enhancement of Claus tail gas treatment by sulfur dioxide-selective membrane technology

US10106411B2
(en)

2017-03-13
2018-10-23
Saudi Arabian Oil Company
Enhancement of claus tail gas treatment by sulfur dioxide-selective membrane technology and sulfur dioxide-selective absorption technology

US9943802B1
(en)

2017-03-13
2018-04-17
Saudi Arabian Oil Company
Enhancement of claus tail gas treatment with membrane and reducing step

WO2019166905A1
(en)

2018-02-28
2019-09-06
Zohal Safaei Mahmoudabadi
Oxidative desulfurization of liquid fuels using metal sulfide quantum dots/graphen oxid hybrid nanocatalyst

Family Cites Families (10)

* Cited by examiner, † Cited by third party

Publication number
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AU223904B
(en)

1904-12-31
1906-01-23
Joseph Keali John
An improved cooler for cream andother liquids

US1917685A
(en)

1930-07-29
1933-07-11
Bacon
Recovery of sulphur

BE398255A
(en)

1932-08-24

US3199955A
(en)

1962-08-20
1965-08-10
Texas Gulf Sulphur Co
Process of reducing sulphur dioxide to elemental sulphur

US3752877A
(en)

1969-08-27
1973-08-14
Parsons Co Ralph M
Recovery of sulfur compounds from tail gases

CA905083A
(en)

1970-02-11
1972-07-18
O. Archambault Jacques
Process for recovery of sulphur from sulphur dioxide

CA1004441A
(en)

1970-10-27
1977-02-01
Thomas Nicklin
Recovery of sulphur from gases containing h2s and so2

JPS4998395A
(en)

1973-01-02
1974-09-18

US4039621A
(en)

1974-03-25
1977-08-02
Ralph M. Parsons Company
Power generation wherein sulfur and nitrogen oxides are removed

US3970744A
(en)

1974-11-07
1976-07-20
Ralph M. Parsons Company
Process for the production of sulfur from sulfur dioxide extracted from gas streams

1976

1976-03-29
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DE2613343A
patent/DE2613343C3/en
not_active
Expired

1977

1977-03-28
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SE7703537A
patent/SE7703537L/en
unknown

1977-03-28
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GB13012/77A
patent/GB1574452A/en
not_active
Expired

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US05/782,360
patent/US4117100A/en
not_active
Expired – Lifetime

1977-03-29
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NL7703393A
patent/NL7703393A/en
not_active
Application Discontinuation

1977-03-29
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FR7709416A
patent/FR2346288A1/en
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Withdrawn

1977-03-29
JP
JP3515777A
patent/JPS52120295A/en
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1977-09-30

JPS52120295A
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1977-10-03

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(en)

1980-08-28

FR2346288A1
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1977-10-28

US4117100A
(en)

1978-09-26

DE2613343A1
(en)

1977-10-06

DE2613343B2
(en)

1979-12-20

IT1115635B
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1986-02-03

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