CA2147195C - Processing sulfur-containing streams - Google Patents
Processing sulfur-containing streams Download PDFInfo
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- CA2147195C CA2147195C CA002147195A CA2147195A CA2147195C CA 2147195 C CA2147195 C CA 2147195C CA 002147195 A CA002147195 A CA 002147195A CA 2147195 A CA2147195 A CA 2147195A CA 2147195 C CA2147195 C CA 2147195C
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- Prior art keywords
- sulfur
- containing gas
- claus
- dioxide
- thermal reactor
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 183
- 239000007789 gas Substances 0.000 claims abstract description 168
- 238000000034 method Methods 0.000 claims abstract description 88
- 229940044609 sulfur dioxide Drugs 0.000 claims abstract description 65
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000001301 oxygen Substances 0.000 claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 111
- 229940032330 sulfuric acid Drugs 0.000 claims description 54
- 230000008929 regeneration Effects 0.000 claims description 44
- 238000011069 regeneration method Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910001868 water Inorganic materials 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 239000012717 electrostatic precipitator Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000010808 liquid waste Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000010977 unit operation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 3
- 239000001117 sulphuric acid Substances 0.000 claims 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 34
- 230000008901 benefit Effects 0.000 description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005804 alkylation reaction Methods 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000003842 industrial chemical process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- -1 sulfuric acid Chemical class 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
- B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
- Y10S423/02—Sulfuric acid
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
A process is disclosed for the recovery of sulfur from sulfur-containing fluid mixtures. The process in one sense comprises the steps of generating a sulfur-dioxide-containing gas in a sulfuric waste treatment unit; feeding an H2S-containing gas to a thermal reactor of a Claus plant; reacting at least a portion of the SO2-containing gas with an oxygen-enriched gas mixture in the Claus thermal reactor; and, recovering a sulfur product from the Claus plant.
Description
. 214'~19~
PATENT
PROCESSING SULFUR-CONTAINING STREAMS
BACKGROUND OF THE INVENTION
The present invention relates to an industrial chemical process. More specifically, it relates to an integrated process for the processing of sulfur-containing streams using improved combustion techniques and apparatus.
Sulfur-containing streams are common among the chemical process industries, particularly in petroleum refineries. Also, in the chemical area, sulfur-containing streams are produced, for example, in large quantities during the manufacture of methyl methacrylate in the Acetone Cyanohydrin or "ACH" process, acrylonitrile in the ammoxidation process, acrylic esters, caprolactame, toluene diisocyanate, titanium dioxide and as a result of sulfonation and nitration reactions.
As used herein, the term "sulfur-containing fluid"
includes any of the sulfur-containing fluids coming from any of many industries or processes which generates SO2 when combusted. Another source of sulfur-containing streams is in the production and processing of natural gas, wherein HZS is present in various amounts and typically must be treated in a sulfur recovery plant.
' 214719 PATENT
In addition to sulfur-containing fluids which are produced by industrial processes such as hydrogen sulfide in natural gas and petroleum refinery gases, refinery processes themselves may utilize sulfur-containing compounds, such as sulfuric acid, to carry out various conversion processes. Due in part to changes in environmental regulations, some petroleum refineries are presently dealing with increasing quantities of sulfuric acid used in hydrocarbon conversion processes.
Along with the need to treat hydrogen-sulfide containing gases, refiners are also now severely restricted on the amount of butanes allowed in product gasoline, and therefore are faced with an increasing need to convert the C3 and C4 range hydrocarbons to higher hydrocarbons. Refiners use alkylation processes to produce valuable gasoline components from such lower hydrocarbons. In the refinery context, an alkylation unit combines an isoparaffin with an olefin. The result of the alkylation processes is consumption of lower weight hydrocarbons to produce a high octane "alkylate" which is blended into the product gasoline.
Although the refinery alkylation process can take place at high temperatures and pressures without a catalyst, modern refineries employ either a hydrofluoric _ 214'~~9~
PATENT
or sulfuric acid catalyst to react isoparaffins such as isobutane or isopentane with olefins. During the refinery alkylation process, the liquid sulfuric acid catalyst becomes contaminated with various compounds, such as higher hydrocarbons, tars and water, causing the acid catalyst strength to decrease and alkylation reaction rate to drop.
When the acid concentration drops below a predetermined level, a portion of the acid must be removed and replaced with fresh sulfuric acid. Modern refineries produce from about 22 pounds of spent sulfuric acid per barrel of alkylate produced. The spent sulfuric acid removed is typically regenerated in an acid regeneration unit on the refinery site or off-site.
Typically, a Sulfuric Acid Regeneration ("SAR") plant comprises a furnace, a gas cleaning section, a converter, and an absorption unit. In the furnace, sulfuric acid is decomposed into sulfur dioxide, carbon dioxide and water in the presence of a fueled combustion flame. This is referred to as the regeneration or "regen furnace".
The gas cleaning section of the typical SAR plant eliminates particulates, residual 503, metal contaminants, and most of the water from the regen furnace effluent.
The converter is typically provided to react sulfur 214'~1~~
PATENT
dioxide with oxygen from air to produce sulfur trioxide, 503. Finally, an absorption tower contactor unit produces "regenerated" sulfuric acid and optionally oleum from the 503.
Sulfuric Acid Regeneration plant performance has been improved by providing an oxygen-enriched air to the regen furnace. U.S. Patent No. 4,490,347 discloses a SAR
process using oxygen-enriched air. U.S. Patent No.
5,022,332 discloses a recirculation scheme to dilute the feed to the regen furnace and reduce the flame temperature.
WO 92/02330, published July 8, 1993, discloses a process for effecting oxidation in a regen furnace using O2 enriched air or pure oxygen. The process described in WO 92/02330 is licensed by L'Air Liquide S.A., and is in commercial operation.
Claus process plants react hydrogen sulfide with sulfur dioxide to form sulfur vapor and water according to the net equation:
;~Oz + HzS - iz~S2 + H20 Claus-type plants are in use in refineries to treat gases containing hydrogen sulfide. The typical Claus plant comprises at least one furnace, or "thermal reactor", and multiple converters to produce an elemental _2~4~~~~
PATENT
sulfur product and result in a "tail gas" comprising residual unconverted hydrogen sulfide, other minor sulfur compounds, sulfur dioxide and inert gases. Some Claus plants may also comprise more than a single thermal reactor. Claus plant performance and capacity have been increased by the utilization of an oxygen-enriched air in the furnace. EP 0237 216 A1 published September 16, 1987, discloses one such modified Claus process using oxygen-enriched air.
While faced with need to expand capacity, refineries are often limited by both physical space and environmental restraints from expanding capacity of these process units, for example, by the addition of furnaces or converters.
In an article by Schendel, "SOZ-generation process can double refinery Claus unit capacity", Oil and Gas Journal, September 27, 1993, page 63, it is suggested to install a sulfur dioxide generation unit by releasing a stream of oxygen beneath the surface of a pool of boiling sulfur. The Schendel article discloses mixing the produced sulfur dioxide gas with hydrogen sulfide gases in a feed to a Claus unit.
In view of a continuing and increasing need for economic processing of sulfur containing waste streams, an improved process is much desired.
PATENT
PROCESSING SULFUR-CONTAINING STREAMS
BACKGROUND OF THE INVENTION
The present invention relates to an industrial chemical process. More specifically, it relates to an integrated process for the processing of sulfur-containing streams using improved combustion techniques and apparatus.
Sulfur-containing streams are common among the chemical process industries, particularly in petroleum refineries. Also, in the chemical area, sulfur-containing streams are produced, for example, in large quantities during the manufacture of methyl methacrylate in the Acetone Cyanohydrin or "ACH" process, acrylonitrile in the ammoxidation process, acrylic esters, caprolactame, toluene diisocyanate, titanium dioxide and as a result of sulfonation and nitration reactions.
As used herein, the term "sulfur-containing fluid"
includes any of the sulfur-containing fluids coming from any of many industries or processes which generates SO2 when combusted. Another source of sulfur-containing streams is in the production and processing of natural gas, wherein HZS is present in various amounts and typically must be treated in a sulfur recovery plant.
' 214719 PATENT
In addition to sulfur-containing fluids which are produced by industrial processes such as hydrogen sulfide in natural gas and petroleum refinery gases, refinery processes themselves may utilize sulfur-containing compounds, such as sulfuric acid, to carry out various conversion processes. Due in part to changes in environmental regulations, some petroleum refineries are presently dealing with increasing quantities of sulfuric acid used in hydrocarbon conversion processes.
Along with the need to treat hydrogen-sulfide containing gases, refiners are also now severely restricted on the amount of butanes allowed in product gasoline, and therefore are faced with an increasing need to convert the C3 and C4 range hydrocarbons to higher hydrocarbons. Refiners use alkylation processes to produce valuable gasoline components from such lower hydrocarbons. In the refinery context, an alkylation unit combines an isoparaffin with an olefin. The result of the alkylation processes is consumption of lower weight hydrocarbons to produce a high octane "alkylate" which is blended into the product gasoline.
Although the refinery alkylation process can take place at high temperatures and pressures without a catalyst, modern refineries employ either a hydrofluoric _ 214'~~9~
PATENT
or sulfuric acid catalyst to react isoparaffins such as isobutane or isopentane with olefins. During the refinery alkylation process, the liquid sulfuric acid catalyst becomes contaminated with various compounds, such as higher hydrocarbons, tars and water, causing the acid catalyst strength to decrease and alkylation reaction rate to drop.
When the acid concentration drops below a predetermined level, a portion of the acid must be removed and replaced with fresh sulfuric acid. Modern refineries produce from about 22 pounds of spent sulfuric acid per barrel of alkylate produced. The spent sulfuric acid removed is typically regenerated in an acid regeneration unit on the refinery site or off-site.
Typically, a Sulfuric Acid Regeneration ("SAR") plant comprises a furnace, a gas cleaning section, a converter, and an absorption unit. In the furnace, sulfuric acid is decomposed into sulfur dioxide, carbon dioxide and water in the presence of a fueled combustion flame. This is referred to as the regeneration or "regen furnace".
The gas cleaning section of the typical SAR plant eliminates particulates, residual 503, metal contaminants, and most of the water from the regen furnace effluent.
The converter is typically provided to react sulfur 214'~1~~
PATENT
dioxide with oxygen from air to produce sulfur trioxide, 503. Finally, an absorption tower contactor unit produces "regenerated" sulfuric acid and optionally oleum from the 503.
Sulfuric Acid Regeneration plant performance has been improved by providing an oxygen-enriched air to the regen furnace. U.S. Patent No. 4,490,347 discloses a SAR
process using oxygen-enriched air. U.S. Patent No.
5,022,332 discloses a recirculation scheme to dilute the feed to the regen furnace and reduce the flame temperature.
WO 92/02330, published July 8, 1993, discloses a process for effecting oxidation in a regen furnace using O2 enriched air or pure oxygen. The process described in WO 92/02330 is licensed by L'Air Liquide S.A., and is in commercial operation.
Claus process plants react hydrogen sulfide with sulfur dioxide to form sulfur vapor and water according to the net equation:
;~Oz + HzS - iz~S2 + H20 Claus-type plants are in use in refineries to treat gases containing hydrogen sulfide. The typical Claus plant comprises at least one furnace, or "thermal reactor", and multiple converters to produce an elemental _2~4~~~~
PATENT
sulfur product and result in a "tail gas" comprising residual unconverted hydrogen sulfide, other minor sulfur compounds, sulfur dioxide and inert gases. Some Claus plants may also comprise more than a single thermal reactor. Claus plant performance and capacity have been increased by the utilization of an oxygen-enriched air in the furnace. EP 0237 216 A1 published September 16, 1987, discloses one such modified Claus process using oxygen-enriched air.
While faced with need to expand capacity, refineries are often limited by both physical space and environmental restraints from expanding capacity of these process units, for example, by the addition of furnaces or converters.
In an article by Schendel, "SOZ-generation process can double refinery Claus unit capacity", Oil and Gas Journal, September 27, 1993, page 63, it is suggested to install a sulfur dioxide generation unit by releasing a stream of oxygen beneath the surface of a pool of boiling sulfur. The Schendel article discloses mixing the produced sulfur dioxide gas with hydrogen sulfide gases in a feed to a Claus unit.
In view of a continuing and increasing need for economic processing of sulfur containing waste streams, an improved process is much desired.
214' ~. 9 PATENT
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, a process for treating sulfur-containing streams comprises the steps of recovering a SOZ-containing gas from a sulfuric acid treatment plant; feeding a hydrogen-sulfide containing gas to a thermal reactor of a Claus plant; reacting at least a portion of the SO2-containing gas in the thermal reactor; and, recovering a sulfur product from the Claus plant.
In other words, the invention provides a process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of:
a) recovering a sulfur-dioxide-containing gas from a sulfuric waste treatment unit;
b) feeding a H2S-containing gas to a thermal reactor of a Claus unit;
c) reacting at least a portion of said S02-containing gas in said Claus unit thermal reactor; and, d) recovering a sulfur product from said Claus unit.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, a process for treating sulfur-containing streams comprises the steps of recovering a SOZ-containing gas from a sulfuric acid treatment plant; feeding a hydrogen-sulfide containing gas to a thermal reactor of a Claus plant; reacting at least a portion of the SO2-containing gas in the thermal reactor; and, recovering a sulfur product from the Claus plant.
In other words, the invention provides a process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of:
a) recovering a sulfur-dioxide-containing gas from a sulfuric waste treatment unit;
b) feeding a H2S-containing gas to a thermal reactor of a Claus unit;
c) reacting at least a portion of said S02-containing gas in said Claus unit thermal reactor; and, d) recovering a sulfur product from said Claus unit.
r CA 02147195 2004-04-27 In a presently preferred embodiment, the sulfur-dioxide-containing gas is recovered from a sulfuric acid regeneration plant, which comprises dissociating the sulfuric acid to form a gas mixture comprising the sulfur-dioxide-containing gas. Preferably, the sulfuric acid is dissociated in the presence of a mixture of fuel and oxygen-enriched gas. The oxygen-enriched gas can comprise greater than 210 oxygen by volume, or preferably greater than 400 oxygen by volume, or even greater than 950 oxygen by volume.
In presently preferred embodiments, the thermal reactor average temperature is less than about 3250°F, and preferably between about 1650°F and about 3200°F, provided thermal sulfur is produced.
The step of dissociating is carried out in a process comprising controlling the flow of a portion of said oxygen-enriched gas to a first stage of an acid regeneration process, to result in incomplete combustion of the fuel mixture in the first stage. The sulfuric acid can be fed to the sulfuric acid regeneration plant in a liquid waste comprising at least 5% by weight sulfuric acid, and at least 100 of sulfur by weight. Alternatively, at least a portion of the sulfur-dioxide-containing gas can be bypassed around the thermal reactor to the Claus converter zone.
The process can further comprise drying at least a portion of the sulfur-dioxide-containing gas in a dryer prior to the combusting step. This maintains a water concentration in the sulfur-dioxide-containing gas to a predetermined range.
6a The process can further comprise adjusting the effective SOZ concentration in the sulfur-dioxide-containing gas by treating at least a portion of the sulfur-dioxide-containing gas in at least one unit operation selected from the group consisting of a spray tower, a cooling tower, an electrostatic precipitator, a dryer and a C02 removal system prior to reacting at least a portion of the sulfur-dioxide-containing gas in the Claus thermal reactor. The process can also comprise a step of mixing a quantity of oxygen-enriched air with the sulfur-dioxide-containing gas to form a mixture prior to reacting the mixture in the Claus unit. The oxygen concentration of this mixture is preferably less than about 20s. The mixing of a quantity of oxygen-enriched error with the sulfur-dioxide-containing gas prior to reacting the mixture and the Claus unit can further comprise adjusting the flow of the oxygen-enriched air based upon the flow rate of the sulfur-dioxide-containing gas to maintain the oxygen concentration of the mixture to within a predetermined range.
The sulfur-dioxide-containing gas is preferably delivered to the sulfur recovery surface at a pressure of between about 10 psig and about 30 psig. This may be accompanied by pressurization of the SAR regen furnace, and/or compressing the sulfur-dioxide-containing gas recovered from the effluent of the sulfuric acid regeneration unit furnace.
The preferred embodiment of the present invention comprises injecting the SOZ-rich gas effluent from the regen furnace of a sulfuric acid treatment plant into the thermal reactor and/or the catalytic reactor of a 6b ' CA 02147195 2004-04-27 Claus-type plant in order to increase the Claus plant capacity and/or to control the temperature of the furnace. Preferably, at least a portion of the SOZ-containing gas is generated from a SAR regen furnace, which furnace is also fed with enriched air or preferably pure oxygen. The present invention thus provides an advantageous method for treating spent sulfuric acid, and furthermore allows the increased capacity or "debottlenecking" of a Claus unit.
In preferred embodiments, oxygen or oxygen-enriched air is also injected at the inlet of the Claus unit in quantities which are a function of sulfur dioxide flowrate.
In a further aspect, the present invention provides a process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of (a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
(b) feeding a HZS-containing gas to a thermal reactor of a Claus plant; and (c) reacting at least a portion of the sulfur-dioxide-containing gas in the thermal reactor.
Preferably, the process further comprises the steps of:
(d) determining the volume ratio of H2S-S02 at the inlet in the Claus thermal reactor; and (e) adjusting the volume ratio to a volume ratio greater than 2.
In a presently preferred embodiment, the adjusting of the volume ratio comprises diverting at least a portion of the S02 in the SO2-containg gas to another 6c _ CA 02147195 2004-04-27 piece of equipment other than the thermal and catalytic reactors of the Claus units. Alternatively, the step of adjusting can comprise converting at least a portion of the H2S in the H2S-containing gas to S02 in a furnace prior to the Claus thermal reactor.
The process of the second aspect of the invention can further comprise a step of reacting the H2S-containing gas with at least a portion of the sulfur-dioxide-containing gas derived from a sulfuric acid regeneration unit, to reduce the temperature in the Claus unit. At least a portion of the H2S-containing gas can be derived from a sour water stripper column.
In a further aspect, the present invention provides a process for treating sulfur-containing waste streams, comprising steps of:
(a) recovering a quantity of sulfur-dioxide-containing gas from a sulfuric acid regeneration unit;
(b) feeding a first portion of said sulfuric-dioxide-containing gas to a Claus thermal reactor;
(c) flowing a second portion of the sulfuric-dioxide-containing gas to a converter without reacting the SOz in the thermal reactor, the second portion being selected to maintain a predetermined temperature range in the Claus thermal reactor.
Preferably, the predetermined temperature range is between about 1650°F and about 3200°F. The process can further comprise steps of:
(a) feeding a portion of sour water stripper gas to the Claus thermal reactor;
dd (b) feeding a second portion of sour water stripper gas to the SAR regen furnace of the sulfuric acid regeneration unit;
(c) adjusting the relaLiYe flow of the sour water stripper feeds of steps (a) and (b) to mazntain the temperature of the Claus thermal reactor to within a predetermined temperature range. The process can further comprise ad~ust~.ng the sulfur-dioxide content of the sulfur-dioxide-containing gas from the sAR rcgen furnace by delivering and controlling a quantity of oxygen-enxiched air to the burner of the SAR regen furnace.
The preferred en~badiment of the present invention comprises zn~ecting the SO~-rich gas effluent from the regen furnace of a sulfuric acid treatment plant into the thermal reactor and/or the eatalyt~.c reactor of a Claus-type plant in order to incrzase the Claus plant capacity and/or co control the ternperature of the furnace. Preferably, at least a portion of the S0~-containing gas is generated from a SAR regen furnace, which furnace Zs also fed with enriched air or preferably pure oxygen. The present invention thus provides an advantageous method for treating spent sulfuric acid, and furthermore allows the increased capacity or "debottlenecking° of a Claus unit.
In preferred embodiments, oxygen or oxygen-enriched air is also injected at the inlet of the Claus unit in quantities which are a function of sulfur dioxide flowrate 6e 214~19~
PATENT
to the thermal reactor to control the conversion of H2S
and limit the temperature of the thermal reactor.
Moreover, with the embodiments which include feeding the SAR regen furnace with oxygen-enriched air or pure oxygen, the cost of the regen furnace is minimized.
Furthermore, with oxygen-enriched air or pure oxygen feed to the SAR regen furnace, the quantity of inerts present in the flow of SOZ-rich gas to the Claus thermal reactor and therefore, downstream Claus converters is minimized, thus adding to the advantages of the process of the present invention.
Major savings in investment are possible from practice of the present invention if, among other factors, the facility operator does not have to invest in gas cleaning, converter and absorber sections downstream of the SAR regen furnace of an acid regeneration plant.
Furthermore, minimal capital investment in new plant equipment is required to implement the present process in a commercial facility. The investment in many cases is limited to a minimum number of new or modified flowlines and burners and perhaps a new or modified process control system.
Monitoring or otherwise determining stream constituents during the operation of the thermal reactor PATENT
in the Claus plant may be carried out in several embodiments, to then adjust the operation of the SAR
plant, or sulfuric-containing stream source operation, based upon the monitored or determined Claus plant variables.
Sulfur-containing gas, acid gas and Sour Water Stripper (SWS) gas which are treated in the Claus unit are themselves typically saturated with water vapor. Although the Claus unit usually operates with some water and some other impurities in the process gas, in alternative embodiments of the present invention, several other pieces of equipment such as a spray tower, a cooling tower, Electrostatic Precipitator, dryer or C02 removal system may be located downstream of the SAR regen furnace. The effect of the dryer is to reduce the water content and thus increase the relative concentration of sulfur dioxide in the feed to the Claus unit. The effect of the scrubber is to reduce or eliminate the residual particles. The effect of the cooler is to adjust the temperature of the SOz-rich gas or adjusted to achieve integration with the sulfur recovery unit. The effect of COZ removal is to achieve an increased effective SOZ concentration in the SOZ-containing gas.
_ g -PATENT
Further benefits and advantages of the process of the present invention as claimed in the appended claims will become evident through the benefit of the following description and reference to the appended Figure.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 represents schematically an installation for the practice of preferred embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to Figure 1 wherein the preferred embodiments of the process of the present invention are depicted; the process of the present invention is conceptually divisible into a sulfuric acid treatment area and an acid gas treatment area. In the acid gas treatment area 1, a thermal reactor 40 comprises a burner end and a waste heat boiler 42 at the opposing end. Typically, a Claus unit thermal reactor and boiler total heat input is between about 2MW-80MW.
By the term "Claus", it is meant the widely used industrial method of obtaining a sulfur product by the partial oxidation of gaseous hydrogen sulfide in the presence of an oxygen-containing gas to give a water and sulfur product. The thermal reactor 40 is fed a gaseous stream comprising hydrogen sulfide depicted in Figure 1 as stream 10. The hydrogen sulfide containing gas may be from a number of sources, for example, an amine unit or a sour water stripper column typical in a chemical process plant or petroleum refinery. Natural gas production and processing operations also are a major source of sulfur containing streams. Depending upon the source and the content of the hydrogen-sulfide-containing gas, air or an oxygen-containing gas is also fed to thermal reactor 40 at the burner end to maintain partial oxidation at a predetermined level.
In accordance with preferred embodiments of the present invention, an oxygen-enriched air is fed to the thermal reactor 40 of the Claus unit. Oxygen-enriched air via line 11 is employed to increase the capacity of the thermal reactor 40 to oxidize increased quantities of hydrogen-sulfide-containing gas.
In another preferred embodiment, a portion of the oxygen or the oxygen-enriched air is mixed with a portion of the sulfur dioxide-containing gas prior to entering the Claus thermal reactor. A typical oxygen content of the resulting mixture is less than about 20%
by volume. Oxygen content in the mixture can be controlled by adjusting the flow of that portion of oxygen-enriched air based upon the flow rate of that portion of sulfur-dioxide-containing gas.
Following partial oxidation in thermal reactor 40, hot gases are flowed from the burner end to the waste heat recovery section 42 of the Claus furnace. Steam is typically produced from feedwater by convection using well known heat recovery methods. Exhaust gases from the Claus furnace flow to separator 45, wherein an elemental sulfur-containing product may be separated and flowed via line 44 to a sulfur pit.
The catalytic conversion of sulfur dioxide to elemental sulfur is well known in the Claus method. The gaseous phase flows overhead from separator 45 via line 41 to be heated in heater 49 and converted to a sulfur product in at least one catalytic converter 46.
Typically, following a plurality of catalytic conversion and sulfur separations steps, the "tail gas"
is hydrogenated to substantially convert the remaining sulfur dioxide to hydrogen sulfide, prior to incineration of the hydrogen sulfide.
In accordance with the present invention, thermal reactor 40 is further supplied a sulfur-dioxide-containing gas; which gas is preferably recovered from a sulfuric acid regeneration ("SAR") process. Referring still to Figure 1, a preferred sulfuric acid regeneration process 2 is depicted wherein a regeneration furnace 20 is supplied a sulfuric-acid-containing stream via line 15 and optionally fuel via line 16 and oxygen-containing gas via line 18 which together in the regen furnace dissociate the sulfuric acid to produce a sulfur-dioxide-containing gas which flows from the regeneration furnace 20 via line 24.
A typical concentration of the liquid waste sulfuric-acid-containing stream is at least 5% by weight sulfuric acid and 10% by weight sulfur. A
typical oxygen content of oxygen-containing gas supplied to the regeneration furnace of a SAR plant is greater than 21% by volume, or preferably greater than 40o by volume, or even greater than 95o by volume.
The flow of at least a portion of oxygen-containing gas into a first stage of SAR process is controlled to yield incomplete combustion of the fuel mixture supplied to this first stage.
11~
21:'7195 PATENT
A typical temperature of the gaseous combustion products at the regen furnace outlet is about 2000°F.
A typical composition of the SOz-rich gas leaving a SAR
regen furnace utilizing pure oxygen, prior to any drying operation, is shown below:
component o by volume SOz 2 2 Hz0 4 5 0 Oz 2 A typical SOZ content of the S02-rich gas leaving a SAR regen furnace using air is about 8 to 12o by volume.
Such S02 content is far below the 21% of OZ content in air, even if water is removed, and therefore cannot provide any debottlenecking effect on the Claus unit.
By contrast, the SOz content of a regen furnace utilizing OZ-enriched air or pure oxygen produces a stream having a SOZ content of between about 22% and up to about 40% if the stream is dried. This aspect is very advantageous in the practice and achieving the benefits of the present invention.
Among other factors, the practice of the present invention enables several operational advantages with respect to the effluent from the SAR regen furnace. The SAR regen furnace is preferably operated to maximize the S02 content of the SOZ-rich gas . This is preferred because the rate of debottlenecking of the Claus unit is a function to the S02 content of the gas. Depending on the amount of S02 generated from the SAR regen furnace, a portion may selectively be flowed to and injected in the Claus thermal reactor, and the second portion of the effluent flowed directly to one of the catalytic converters of the Claus unit, to be directly converted to sulfur .
Water in the acid regeneration plant furnace effluent cumulates with the water already typically present in the acid gas feed to the Claus thermal reactor and would, in most cases, further enhance the quenching effect of SO2.
However, a large water content in the feed to the Claus thermal reactor may have an adverse effect on the hydrogen sulfide conversion and more importantly could have an impact on the pressure drop of the entire Claus unit. Accordingly, a dryer may be provided in alternate embodiments, as depicted in Figure 1 as included in element 36.
Preferably, if a dryer is provided, a water content of 2 ~. 4'~ 19 ~
PATENT
between about 0.5 to 5.0 percent by volume is desired at the dryer outlet.
The COz typically present in the gaseous effluent from the regen furnace is commensurate with that usually present in refinery acid gas at the level of between about 2 percent and about 25 percent. If the COz content of the SOz-containing gas from the regen furnace is too high to allow an adequate integration with the Claus unit, one of several methods may be used to reduce it; for example, a caustic wash column. Other unit operations such as an electrostatic precipitator (ESP), or cooling tower, may be employed in the gas cleaning section to adjust the conditions of the SAR regen effluent. The gas treatment operations are collectively depicted in Figure 1 as gas treatment element 36.
Residual oxygen present in the regen furnace effluent which, according to the present invention, is injected in the thermal reactor of the Claus unit as a part of this SOz-rich gas will normally react with and be consumed by the compounds contained in the acid gas, such as H2S. The advantageous result of the residual oxygen in the regen furnace effluent is a reduction in the quantity of oxygen (if any) required for the combustion of the acid gas in the Claus unit. If any amount of the sulfur-dioxide-21~'~~.~5 PATENT
containing gas is bypassed around the thermal reactor, as described above with reference to line 71, this amount should be adjusted so that the resulting Oz content of the total process gas at the inlet of the catalytic converter will be very small, i.e. preferably preferably less than .O1 percent (or less than 100 ppm), and will not significantly affect the life of the catalyst in the catalytic reactor.
Due to the dilution with the gas coming from the thermal reactor, the OZ content of the above described total process gas at the converter section inlet will typically be less than the OZ content of the S02-containing gas coming from the SAR regen furnace. In practice, it is therefore highly preferred to operate the regen furnace so as to minimize the OZ content of the S02-rich gas in the regen furnace effluent.
Nitrogen present in the SAR plant gaseous effluent 14 normally will pass through the sulfur recovery plant section 1 unaffected. However, the presence of nitrogen dilutes the concentration of sulfur dioxide. As with water vapor, it is, therefore, preferable to maximize the SOZ content of the SOZ-rich gas by minimizing the presence of nitrogen, by, for example, replacing air fed via line 2~4~1~~
PATENT
18 to the regen furnace with oxygen-enriched air via oxygen source 8, or preferably pure oxygen.
None of the components typically present in the SOZ-rich gas stream 24 prevents this gas from being used in the Claus process. Preferably, the SOz-rich gas should be injected in the Claus unit at about 15-20 prig. To obtain this pressure, either the SAR regen furnace may be pressurized or the effluent SOz-rich gas itself could be compressed in conventional compression means.
The practice of the present invention is best accomplished with careful regard to the ratio of sulfur dioxide to hydrogen sulfide in the Claus thermal reactor.
The maximum volume of SOz that can be fed to the Claus sulfur recovery section is normally equivalent to 500 of the total volume of HzS to be treated in the sulfur recovery section. We define the HZS/SOZ ratio as the quantity of H2S present in the acid gas 10 to be treated in the sulfur recovery unit divided by the quantity of SOz present in the SOz-rich gas from the SAR regen furnace, at the inlet of the Claus thermal reactor.
If the HzS/SOZ ratio is very close to 2.0, no HZS
which is feeding the sulfur recovery unit needs to be converted to SO2, and no oxygen needs to be added to the thermal reactor. The mixed HzS-S02 stream along with the 214'~19~
PATENT
impurities present in each of the individual streams can be fed directly to the first catalytic reactor provided that the temperature of the mixed stream falls in or is adjusted to the appropriate temperature range of about 400-700°F, and that there is no ammonia present in the stream. In this case, no thermal sulfur is produced.
Such bypass can only be made if the converter capacity is available, however. If the HZS/S02 ratio is significantly above 2.0, the entire SOz-rich gas stream can be injected in the thermal reactor and additional 02 is preferably added in order to sustain the combustion and to convert a portion of HZS to SO2, the downstream part of the sulfur recovery section being operated in the manner typical with Claus plants.
Lastly, if the HZS/SOZ ratio is only marginally above 2.0, only a small amount of H2S has to be burned with OZ
to reduce the ratio close to 2Ø This amount may be too small to sustain a stable combustion which means that there is a small range of HzS/SOZ ratio which is undesirable in the practice of the process, and thus the ratio should be adjusted.
In accordance with the present invention, by sending some of the excess HzS to the SAR regen furnace to be converted to S02 thereby driving back the H2S/S02 ratio ~:
down to nearer 2.0, the overall process is improved. The most preferable control conditions for this process are for H2S/SOZ ratios significantly above 2.0, but the above described undesirable range can be reduced to a minimum by selecting burners which have extensive turndown capabilities. In practice, a minimum H2S/SO2 ratio should be calculated in each case to ensure the temperature is sufficiently great enough to trigger and sustain the thermal reaction. For example, at 1800°C (3270°F), a 50°s conversion is achieved, and at 2200°C (3990°F), a 700 conversion is possible.
As shown in the above two paragraphs, there may be certain conditions in which the SOZ-rich gas will be preferably injected downstream of the thermal reactor and upstream of the catalytic converter of the sulfur recovery section, depicted in Figure 1 by stream 71. The exact injection location, however, will be variable and a matter of choice according to the temperature of the process gas feeding the particular catalytic reactor.
It is preferred to install a HZS/SOz control means 80 upstream of the inlet of the thermal reactor to ensure that the H2S/S02 ratio is maintained above 2Ø If the H2SjS02 ratio is below 2, excess S02-rich gas could be sent either to the sulfuric acid plant (if present) or to the 214?i95 PATENT
tail gas treatment unit of the Claus unit, if the Claus unit has sufficient capacity.
The process of the present invention is advantageously flexible, and can be implemented for a wide range of feed conditions present for either the acid gas or the sulfuric stream to the SAR regen furnace provided, however, that the total flow rates do not exceed hydraulic limits of, for example, piping and fluid transfer equipment.
In sulfuric acid regeneration processes, prior to the present invention, the effluent gases from the regeneration furnace were typically then sent to a gas cleaning section to remove substantially the water contained therein and then through a catalytic conversion section wherein the sulfur dioxide is converted in the presence of oxygen to produce sulfur trioxide. The sulfur-trioxide-containing product was then passed to an absorption tower in which the sulfur trioxide is reacted in the presence of water to produce sulfuric acid and/or oleum by contacting in the absorption tower.
In accordance with preferred embodiments of the present invention, at least a portion of the sulfur-dioxide-containing gas recovered from the SAR regeneration furnace 20 of a sulfuric acid regeneration process is PATENT
flowed to the thermal reactor 40 of a Claus process. The sulfur-dioxide-containing gas acts to limit the temperature rise in thermal reactor 40, which is typically the constraining factor in limiting the capacity of thermal reactor 40 to convert hydrogen-sulfide-containing gas to sulfur dioxide. Moreover, by diverting a portion, or the entire sulfur-dioxide-containing stream from the regeneration furnace 20, part of the downstream gas cleaning and absorption tower section may be reduced in capacity, idled or even eliminated.
Among other factors, the combined advantages of increasing capacity of hydrogen-sulfide-containing gas treatment plant, and eliminating equipment and operational expense of a sulfuric acid regeneration process, the process of the present invention affords a chemical plant or petroleum refinery operator a significant advantage over prior available processes.
Preferred embodiments of the process of the present invention afford further advantages and operational benefits. In one such preferred embodiment, oxygen-enriched air is supplied to the SAR regeneration furnace 20.
In accordance with the present invention, the oxygen-enriched air may be supplied to increase the sulfur PATENT
dioxide content of the sulfur-dioxide-containing gas which is flowed to thermal reactor 40 of the Claus unit. The oxygen-containing air, or pure oxygen, is supplied to the regeneration furnace 20 according to operational requirement, such as measured average temperature of thermal reactor 40, to achieve an increased capacity to treat hydrogen-sulfide-containing gas supplied by the line to thermal reactor 40.
In another embodiment, control means 80 monitors a 10 temperature in thermal reactor 40, flow rate of sulfur-dioxide-containing gas in line 14 to thermal reactor 40, and the flow rate of hydrogen-sulfide-containing gas in line 10. Injection of oxygen-enriched air is thereby controlled by the control means 80 to maintain and advantageously increase the capacity of the Claus unit.
In another embodiment, a treatment section 36 which may comprise in any combination an ESP, cooling tower, dryer, COZ removal system, or adsorption tower may be provided to adjust the composition and temperature of the SOZ-containing gas exiting regeneration furnace 20 to achieve a higher net effective SOZ concentration and thus further improve performance of the Claus unit.
It is a somewhat common practice for refiners to inject Sour Water Stripper ("SWS") gas into the Claus 3..
unit due to its HZS content. It is also a common practice for those refiners who have a sulfuric acid regeneration ("SAR") plant to inject the SWS gas into the SAR regeneration furnace due to its H2S04 content. In accordance with the present invention, additional advantages such as increased flexibility or additional tuning may be realized by injecting a predetermined portion of the SWS gas into the thermal reactor, or by splitting the SWS gas between the SAR
regen furnace and the Claus thermal reactor depending on the quantity of S02 available from the SAR regen furnace, the H2S
quantity to be treated in the Claus unit and the ammonia destruction required.
As a result, the integrated process of the present invention affords an operator much flexibility because, among other factors, there are many ways to adjust the key operating parameters of the Claus unit, most importantly including the Claus unit capacity.
EXAMPLE
A typical capacity for a sulfuric acid catalyzed alkylation unit in a refinery is 10,000 bbl/day of alkylate. The spent alkylation acid quantity generated from such a unit is about 110 tons per day. 'this liquid typically would in turn be decomposed in the regen furnace PATENT
of a separate acid regeneration plant and generate about 70 t/d of SOz from which about 35 tons per day of sulfur could be recovered in the Claus unit.
A typical refinery also has one or several Claus units totalling more than 70 tons per day capacity.
Therefore, the overall HZS/S02 ratio will normally be greater than 2. This means that additional equipment to treat excess SOz-rich gas will not be required. The SO2 available from the SAR regen furnace could be used to debottleneck the Claus unit and/or to control the temperature of the Claus thermal reactor. If it is used to debottleneck the Claus unit, the extent of the debottlenecking will depend on the SOZ concentration of the SOZ-rich gas and the nominal capacity of the Claus unit. The extent of debottlenecking can be further increased if 02 is added in conjunction with SOz. The extent of debottlenecking is reduced if SOZ is not pure.
For example 70 t/d of pure SOz may be used in accord with the invention to double the capacity of a 70 t/d air-based Claus unit, or alternatively to debottleneck by 70 t/d a larger capacity Claus unit.
Should the Claus unit be able to accommodate the resulting process gas flow, in practice the air flow may have to be reduced, and the reduced OZ content in the 214'19 PATENT
resulting air flow may be at least partially replaced by pure oxygen, to achieve a proper minimum residence time.
In presently preferred embodiments, the thermal reactor average temperature is less than about 3250°F, and preferably between about 1650°F and about 3200°F, provided thermal sulfur is produced.
The step of dissociating is carried out in a process comprising controlling the flow of a portion of said oxygen-enriched gas to a first stage of an acid regeneration process, to result in incomplete combustion of the fuel mixture in the first stage. The sulfuric acid can be fed to the sulfuric acid regeneration plant in a liquid waste comprising at least 5% by weight sulfuric acid, and at least 100 of sulfur by weight. Alternatively, at least a portion of the sulfur-dioxide-containing gas can be bypassed around the thermal reactor to the Claus converter zone.
The process can further comprise drying at least a portion of the sulfur-dioxide-containing gas in a dryer prior to the combusting step. This maintains a water concentration in the sulfur-dioxide-containing gas to a predetermined range.
6a The process can further comprise adjusting the effective SOZ concentration in the sulfur-dioxide-containing gas by treating at least a portion of the sulfur-dioxide-containing gas in at least one unit operation selected from the group consisting of a spray tower, a cooling tower, an electrostatic precipitator, a dryer and a C02 removal system prior to reacting at least a portion of the sulfur-dioxide-containing gas in the Claus thermal reactor. The process can also comprise a step of mixing a quantity of oxygen-enriched air with the sulfur-dioxide-containing gas to form a mixture prior to reacting the mixture in the Claus unit. The oxygen concentration of this mixture is preferably less than about 20s. The mixing of a quantity of oxygen-enriched error with the sulfur-dioxide-containing gas prior to reacting the mixture and the Claus unit can further comprise adjusting the flow of the oxygen-enriched air based upon the flow rate of the sulfur-dioxide-containing gas to maintain the oxygen concentration of the mixture to within a predetermined range.
The sulfur-dioxide-containing gas is preferably delivered to the sulfur recovery surface at a pressure of between about 10 psig and about 30 psig. This may be accompanied by pressurization of the SAR regen furnace, and/or compressing the sulfur-dioxide-containing gas recovered from the effluent of the sulfuric acid regeneration unit furnace.
The preferred embodiment of the present invention comprises injecting the SOZ-rich gas effluent from the regen furnace of a sulfuric acid treatment plant into the thermal reactor and/or the catalytic reactor of a 6b ' CA 02147195 2004-04-27 Claus-type plant in order to increase the Claus plant capacity and/or to control the temperature of the furnace. Preferably, at least a portion of the SOZ-containing gas is generated from a SAR regen furnace, which furnace is also fed with enriched air or preferably pure oxygen. The present invention thus provides an advantageous method for treating spent sulfuric acid, and furthermore allows the increased capacity or "debottlenecking" of a Claus unit.
In preferred embodiments, oxygen or oxygen-enriched air is also injected at the inlet of the Claus unit in quantities which are a function of sulfur dioxide flowrate.
In a further aspect, the present invention provides a process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of (a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
(b) feeding a HZS-containing gas to a thermal reactor of a Claus plant; and (c) reacting at least a portion of the sulfur-dioxide-containing gas in the thermal reactor.
Preferably, the process further comprises the steps of:
(d) determining the volume ratio of H2S-S02 at the inlet in the Claus thermal reactor; and (e) adjusting the volume ratio to a volume ratio greater than 2.
In a presently preferred embodiment, the adjusting of the volume ratio comprises diverting at least a portion of the S02 in the SO2-containg gas to another 6c _ CA 02147195 2004-04-27 piece of equipment other than the thermal and catalytic reactors of the Claus units. Alternatively, the step of adjusting can comprise converting at least a portion of the H2S in the H2S-containing gas to S02 in a furnace prior to the Claus thermal reactor.
The process of the second aspect of the invention can further comprise a step of reacting the H2S-containing gas with at least a portion of the sulfur-dioxide-containing gas derived from a sulfuric acid regeneration unit, to reduce the temperature in the Claus unit. At least a portion of the H2S-containing gas can be derived from a sour water stripper column.
In a further aspect, the present invention provides a process for treating sulfur-containing waste streams, comprising steps of:
(a) recovering a quantity of sulfur-dioxide-containing gas from a sulfuric acid regeneration unit;
(b) feeding a first portion of said sulfuric-dioxide-containing gas to a Claus thermal reactor;
(c) flowing a second portion of the sulfuric-dioxide-containing gas to a converter without reacting the SOz in the thermal reactor, the second portion being selected to maintain a predetermined temperature range in the Claus thermal reactor.
Preferably, the predetermined temperature range is between about 1650°F and about 3200°F. The process can further comprise steps of:
(a) feeding a portion of sour water stripper gas to the Claus thermal reactor;
dd (b) feeding a second portion of sour water stripper gas to the SAR regen furnace of the sulfuric acid regeneration unit;
(c) adjusting the relaLiYe flow of the sour water stripper feeds of steps (a) and (b) to mazntain the temperature of the Claus thermal reactor to within a predetermined temperature range. The process can further comprise ad~ust~.ng the sulfur-dioxide content of the sulfur-dioxide-containing gas from the sAR rcgen furnace by delivering and controlling a quantity of oxygen-enxiched air to the burner of the SAR regen furnace.
The preferred en~badiment of the present invention comprises zn~ecting the SO~-rich gas effluent from the regen furnace of a sulfuric acid treatment plant into the thermal reactor and/or the eatalyt~.c reactor of a Claus-type plant in order to incrzase the Claus plant capacity and/or co control the ternperature of the furnace. Preferably, at least a portion of the S0~-containing gas is generated from a SAR regen furnace, which furnace Zs also fed with enriched air or preferably pure oxygen. The present invention thus provides an advantageous method for treating spent sulfuric acid, and furthermore allows the increased capacity or "debottlenecking° of a Claus unit.
In preferred embodiments, oxygen or oxygen-enriched air is also injected at the inlet of the Claus unit in quantities which are a function of sulfur dioxide flowrate 6e 214~19~
PATENT
to the thermal reactor to control the conversion of H2S
and limit the temperature of the thermal reactor.
Moreover, with the embodiments which include feeding the SAR regen furnace with oxygen-enriched air or pure oxygen, the cost of the regen furnace is minimized.
Furthermore, with oxygen-enriched air or pure oxygen feed to the SAR regen furnace, the quantity of inerts present in the flow of SOZ-rich gas to the Claus thermal reactor and therefore, downstream Claus converters is minimized, thus adding to the advantages of the process of the present invention.
Major savings in investment are possible from practice of the present invention if, among other factors, the facility operator does not have to invest in gas cleaning, converter and absorber sections downstream of the SAR regen furnace of an acid regeneration plant.
Furthermore, minimal capital investment in new plant equipment is required to implement the present process in a commercial facility. The investment in many cases is limited to a minimum number of new or modified flowlines and burners and perhaps a new or modified process control system.
Monitoring or otherwise determining stream constituents during the operation of the thermal reactor PATENT
in the Claus plant may be carried out in several embodiments, to then adjust the operation of the SAR
plant, or sulfuric-containing stream source operation, based upon the monitored or determined Claus plant variables.
Sulfur-containing gas, acid gas and Sour Water Stripper (SWS) gas which are treated in the Claus unit are themselves typically saturated with water vapor. Although the Claus unit usually operates with some water and some other impurities in the process gas, in alternative embodiments of the present invention, several other pieces of equipment such as a spray tower, a cooling tower, Electrostatic Precipitator, dryer or C02 removal system may be located downstream of the SAR regen furnace. The effect of the dryer is to reduce the water content and thus increase the relative concentration of sulfur dioxide in the feed to the Claus unit. The effect of the scrubber is to reduce or eliminate the residual particles. The effect of the cooler is to adjust the temperature of the SOz-rich gas or adjusted to achieve integration with the sulfur recovery unit. The effect of COZ removal is to achieve an increased effective SOZ concentration in the SOZ-containing gas.
_ g -PATENT
Further benefits and advantages of the process of the present invention as claimed in the appended claims will become evident through the benefit of the following description and reference to the appended Figure.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 represents schematically an installation for the practice of preferred embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to Figure 1 wherein the preferred embodiments of the process of the present invention are depicted; the process of the present invention is conceptually divisible into a sulfuric acid treatment area and an acid gas treatment area. In the acid gas treatment area 1, a thermal reactor 40 comprises a burner end and a waste heat boiler 42 at the opposing end. Typically, a Claus unit thermal reactor and boiler total heat input is between about 2MW-80MW.
By the term "Claus", it is meant the widely used industrial method of obtaining a sulfur product by the partial oxidation of gaseous hydrogen sulfide in the presence of an oxygen-containing gas to give a water and sulfur product. The thermal reactor 40 is fed a gaseous stream comprising hydrogen sulfide depicted in Figure 1 as stream 10. The hydrogen sulfide containing gas may be from a number of sources, for example, an amine unit or a sour water stripper column typical in a chemical process plant or petroleum refinery. Natural gas production and processing operations also are a major source of sulfur containing streams. Depending upon the source and the content of the hydrogen-sulfide-containing gas, air or an oxygen-containing gas is also fed to thermal reactor 40 at the burner end to maintain partial oxidation at a predetermined level.
In accordance with preferred embodiments of the present invention, an oxygen-enriched air is fed to the thermal reactor 40 of the Claus unit. Oxygen-enriched air via line 11 is employed to increase the capacity of the thermal reactor 40 to oxidize increased quantities of hydrogen-sulfide-containing gas.
In another preferred embodiment, a portion of the oxygen or the oxygen-enriched air is mixed with a portion of the sulfur dioxide-containing gas prior to entering the Claus thermal reactor. A typical oxygen content of the resulting mixture is less than about 20%
by volume. Oxygen content in the mixture can be controlled by adjusting the flow of that portion of oxygen-enriched air based upon the flow rate of that portion of sulfur-dioxide-containing gas.
Following partial oxidation in thermal reactor 40, hot gases are flowed from the burner end to the waste heat recovery section 42 of the Claus furnace. Steam is typically produced from feedwater by convection using well known heat recovery methods. Exhaust gases from the Claus furnace flow to separator 45, wherein an elemental sulfur-containing product may be separated and flowed via line 44 to a sulfur pit.
The catalytic conversion of sulfur dioxide to elemental sulfur is well known in the Claus method. The gaseous phase flows overhead from separator 45 via line 41 to be heated in heater 49 and converted to a sulfur product in at least one catalytic converter 46.
Typically, following a plurality of catalytic conversion and sulfur separations steps, the "tail gas"
is hydrogenated to substantially convert the remaining sulfur dioxide to hydrogen sulfide, prior to incineration of the hydrogen sulfide.
In accordance with the present invention, thermal reactor 40 is further supplied a sulfur-dioxide-containing gas; which gas is preferably recovered from a sulfuric acid regeneration ("SAR") process. Referring still to Figure 1, a preferred sulfuric acid regeneration process 2 is depicted wherein a regeneration furnace 20 is supplied a sulfuric-acid-containing stream via line 15 and optionally fuel via line 16 and oxygen-containing gas via line 18 which together in the regen furnace dissociate the sulfuric acid to produce a sulfur-dioxide-containing gas which flows from the regeneration furnace 20 via line 24.
A typical concentration of the liquid waste sulfuric-acid-containing stream is at least 5% by weight sulfuric acid and 10% by weight sulfur. A
typical oxygen content of oxygen-containing gas supplied to the regeneration furnace of a SAR plant is greater than 21% by volume, or preferably greater than 40o by volume, or even greater than 95o by volume.
The flow of at least a portion of oxygen-containing gas into a first stage of SAR process is controlled to yield incomplete combustion of the fuel mixture supplied to this first stage.
11~
21:'7195 PATENT
A typical temperature of the gaseous combustion products at the regen furnace outlet is about 2000°F.
A typical composition of the SOz-rich gas leaving a SAR
regen furnace utilizing pure oxygen, prior to any drying operation, is shown below:
component o by volume SOz 2 2 Hz0 4 5 0 Oz 2 A typical SOZ content of the S02-rich gas leaving a SAR regen furnace using air is about 8 to 12o by volume.
Such S02 content is far below the 21% of OZ content in air, even if water is removed, and therefore cannot provide any debottlenecking effect on the Claus unit.
By contrast, the SOz content of a regen furnace utilizing OZ-enriched air or pure oxygen produces a stream having a SOZ content of between about 22% and up to about 40% if the stream is dried. This aspect is very advantageous in the practice and achieving the benefits of the present invention.
Among other factors, the practice of the present invention enables several operational advantages with respect to the effluent from the SAR regen furnace. The SAR regen furnace is preferably operated to maximize the S02 content of the SOZ-rich gas . This is preferred because the rate of debottlenecking of the Claus unit is a function to the S02 content of the gas. Depending on the amount of S02 generated from the SAR regen furnace, a portion may selectively be flowed to and injected in the Claus thermal reactor, and the second portion of the effluent flowed directly to one of the catalytic converters of the Claus unit, to be directly converted to sulfur .
Water in the acid regeneration plant furnace effluent cumulates with the water already typically present in the acid gas feed to the Claus thermal reactor and would, in most cases, further enhance the quenching effect of SO2.
However, a large water content in the feed to the Claus thermal reactor may have an adverse effect on the hydrogen sulfide conversion and more importantly could have an impact on the pressure drop of the entire Claus unit. Accordingly, a dryer may be provided in alternate embodiments, as depicted in Figure 1 as included in element 36.
Preferably, if a dryer is provided, a water content of 2 ~. 4'~ 19 ~
PATENT
between about 0.5 to 5.0 percent by volume is desired at the dryer outlet.
The COz typically present in the gaseous effluent from the regen furnace is commensurate with that usually present in refinery acid gas at the level of between about 2 percent and about 25 percent. If the COz content of the SOz-containing gas from the regen furnace is too high to allow an adequate integration with the Claus unit, one of several methods may be used to reduce it; for example, a caustic wash column. Other unit operations such as an electrostatic precipitator (ESP), or cooling tower, may be employed in the gas cleaning section to adjust the conditions of the SAR regen effluent. The gas treatment operations are collectively depicted in Figure 1 as gas treatment element 36.
Residual oxygen present in the regen furnace effluent which, according to the present invention, is injected in the thermal reactor of the Claus unit as a part of this SOz-rich gas will normally react with and be consumed by the compounds contained in the acid gas, such as H2S. The advantageous result of the residual oxygen in the regen furnace effluent is a reduction in the quantity of oxygen (if any) required for the combustion of the acid gas in the Claus unit. If any amount of the sulfur-dioxide-21~'~~.~5 PATENT
containing gas is bypassed around the thermal reactor, as described above with reference to line 71, this amount should be adjusted so that the resulting Oz content of the total process gas at the inlet of the catalytic converter will be very small, i.e. preferably preferably less than .O1 percent (or less than 100 ppm), and will not significantly affect the life of the catalyst in the catalytic reactor.
Due to the dilution with the gas coming from the thermal reactor, the OZ content of the above described total process gas at the converter section inlet will typically be less than the OZ content of the S02-containing gas coming from the SAR regen furnace. In practice, it is therefore highly preferred to operate the regen furnace so as to minimize the OZ content of the S02-rich gas in the regen furnace effluent.
Nitrogen present in the SAR plant gaseous effluent 14 normally will pass through the sulfur recovery plant section 1 unaffected. However, the presence of nitrogen dilutes the concentration of sulfur dioxide. As with water vapor, it is, therefore, preferable to maximize the SOZ content of the SOZ-rich gas by minimizing the presence of nitrogen, by, for example, replacing air fed via line 2~4~1~~
PATENT
18 to the regen furnace with oxygen-enriched air via oxygen source 8, or preferably pure oxygen.
None of the components typically present in the SOZ-rich gas stream 24 prevents this gas from being used in the Claus process. Preferably, the SOz-rich gas should be injected in the Claus unit at about 15-20 prig. To obtain this pressure, either the SAR regen furnace may be pressurized or the effluent SOz-rich gas itself could be compressed in conventional compression means.
The practice of the present invention is best accomplished with careful regard to the ratio of sulfur dioxide to hydrogen sulfide in the Claus thermal reactor.
The maximum volume of SOz that can be fed to the Claus sulfur recovery section is normally equivalent to 500 of the total volume of HzS to be treated in the sulfur recovery section. We define the HZS/SOZ ratio as the quantity of H2S present in the acid gas 10 to be treated in the sulfur recovery unit divided by the quantity of SOz present in the SOz-rich gas from the SAR regen furnace, at the inlet of the Claus thermal reactor.
If the HzS/SOZ ratio is very close to 2.0, no HZS
which is feeding the sulfur recovery unit needs to be converted to SO2, and no oxygen needs to be added to the thermal reactor. The mixed HzS-S02 stream along with the 214'~19~
PATENT
impurities present in each of the individual streams can be fed directly to the first catalytic reactor provided that the temperature of the mixed stream falls in or is adjusted to the appropriate temperature range of about 400-700°F, and that there is no ammonia present in the stream. In this case, no thermal sulfur is produced.
Such bypass can only be made if the converter capacity is available, however. If the HZS/S02 ratio is significantly above 2.0, the entire SOz-rich gas stream can be injected in the thermal reactor and additional 02 is preferably added in order to sustain the combustion and to convert a portion of HZS to SO2, the downstream part of the sulfur recovery section being operated in the manner typical with Claus plants.
Lastly, if the HZS/SOZ ratio is only marginally above 2.0, only a small amount of H2S has to be burned with OZ
to reduce the ratio close to 2Ø This amount may be too small to sustain a stable combustion which means that there is a small range of HzS/SOZ ratio which is undesirable in the practice of the process, and thus the ratio should be adjusted.
In accordance with the present invention, by sending some of the excess HzS to the SAR regen furnace to be converted to S02 thereby driving back the H2S/S02 ratio ~:
down to nearer 2.0, the overall process is improved. The most preferable control conditions for this process are for H2S/SOZ ratios significantly above 2.0, but the above described undesirable range can be reduced to a minimum by selecting burners which have extensive turndown capabilities. In practice, a minimum H2S/SO2 ratio should be calculated in each case to ensure the temperature is sufficiently great enough to trigger and sustain the thermal reaction. For example, at 1800°C (3270°F), a 50°s conversion is achieved, and at 2200°C (3990°F), a 700 conversion is possible.
As shown in the above two paragraphs, there may be certain conditions in which the SOZ-rich gas will be preferably injected downstream of the thermal reactor and upstream of the catalytic converter of the sulfur recovery section, depicted in Figure 1 by stream 71. The exact injection location, however, will be variable and a matter of choice according to the temperature of the process gas feeding the particular catalytic reactor.
It is preferred to install a HZS/SOz control means 80 upstream of the inlet of the thermal reactor to ensure that the H2S/S02 ratio is maintained above 2Ø If the H2SjS02 ratio is below 2, excess S02-rich gas could be sent either to the sulfuric acid plant (if present) or to the 214?i95 PATENT
tail gas treatment unit of the Claus unit, if the Claus unit has sufficient capacity.
The process of the present invention is advantageously flexible, and can be implemented for a wide range of feed conditions present for either the acid gas or the sulfuric stream to the SAR regen furnace provided, however, that the total flow rates do not exceed hydraulic limits of, for example, piping and fluid transfer equipment.
In sulfuric acid regeneration processes, prior to the present invention, the effluent gases from the regeneration furnace were typically then sent to a gas cleaning section to remove substantially the water contained therein and then through a catalytic conversion section wherein the sulfur dioxide is converted in the presence of oxygen to produce sulfur trioxide. The sulfur-trioxide-containing product was then passed to an absorption tower in which the sulfur trioxide is reacted in the presence of water to produce sulfuric acid and/or oleum by contacting in the absorption tower.
In accordance with preferred embodiments of the present invention, at least a portion of the sulfur-dioxide-containing gas recovered from the SAR regeneration furnace 20 of a sulfuric acid regeneration process is PATENT
flowed to the thermal reactor 40 of a Claus process. The sulfur-dioxide-containing gas acts to limit the temperature rise in thermal reactor 40, which is typically the constraining factor in limiting the capacity of thermal reactor 40 to convert hydrogen-sulfide-containing gas to sulfur dioxide. Moreover, by diverting a portion, or the entire sulfur-dioxide-containing stream from the regeneration furnace 20, part of the downstream gas cleaning and absorption tower section may be reduced in capacity, idled or even eliminated.
Among other factors, the combined advantages of increasing capacity of hydrogen-sulfide-containing gas treatment plant, and eliminating equipment and operational expense of a sulfuric acid regeneration process, the process of the present invention affords a chemical plant or petroleum refinery operator a significant advantage over prior available processes.
Preferred embodiments of the process of the present invention afford further advantages and operational benefits. In one such preferred embodiment, oxygen-enriched air is supplied to the SAR regeneration furnace 20.
In accordance with the present invention, the oxygen-enriched air may be supplied to increase the sulfur PATENT
dioxide content of the sulfur-dioxide-containing gas which is flowed to thermal reactor 40 of the Claus unit. The oxygen-containing air, or pure oxygen, is supplied to the regeneration furnace 20 according to operational requirement, such as measured average temperature of thermal reactor 40, to achieve an increased capacity to treat hydrogen-sulfide-containing gas supplied by the line to thermal reactor 40.
In another embodiment, control means 80 monitors a 10 temperature in thermal reactor 40, flow rate of sulfur-dioxide-containing gas in line 14 to thermal reactor 40, and the flow rate of hydrogen-sulfide-containing gas in line 10. Injection of oxygen-enriched air is thereby controlled by the control means 80 to maintain and advantageously increase the capacity of the Claus unit.
In another embodiment, a treatment section 36 which may comprise in any combination an ESP, cooling tower, dryer, COZ removal system, or adsorption tower may be provided to adjust the composition and temperature of the SOZ-containing gas exiting regeneration furnace 20 to achieve a higher net effective SOZ concentration and thus further improve performance of the Claus unit.
It is a somewhat common practice for refiners to inject Sour Water Stripper ("SWS") gas into the Claus 3..
unit due to its HZS content. It is also a common practice for those refiners who have a sulfuric acid regeneration ("SAR") plant to inject the SWS gas into the SAR regeneration furnace due to its H2S04 content. In accordance with the present invention, additional advantages such as increased flexibility or additional tuning may be realized by injecting a predetermined portion of the SWS gas into the thermal reactor, or by splitting the SWS gas between the SAR
regen furnace and the Claus thermal reactor depending on the quantity of S02 available from the SAR regen furnace, the H2S
quantity to be treated in the Claus unit and the ammonia destruction required.
As a result, the integrated process of the present invention affords an operator much flexibility because, among other factors, there are many ways to adjust the key operating parameters of the Claus unit, most importantly including the Claus unit capacity.
EXAMPLE
A typical capacity for a sulfuric acid catalyzed alkylation unit in a refinery is 10,000 bbl/day of alkylate. The spent alkylation acid quantity generated from such a unit is about 110 tons per day. 'this liquid typically would in turn be decomposed in the regen furnace PATENT
of a separate acid regeneration plant and generate about 70 t/d of SOz from which about 35 tons per day of sulfur could be recovered in the Claus unit.
A typical refinery also has one or several Claus units totalling more than 70 tons per day capacity.
Therefore, the overall HZS/S02 ratio will normally be greater than 2. This means that additional equipment to treat excess SOz-rich gas will not be required. The SO2 available from the SAR regen furnace could be used to debottleneck the Claus unit and/or to control the temperature of the Claus thermal reactor. If it is used to debottleneck the Claus unit, the extent of the debottlenecking will depend on the SOZ concentration of the SOZ-rich gas and the nominal capacity of the Claus unit. The extent of debottlenecking can be further increased if 02 is added in conjunction with SOz. The extent of debottlenecking is reduced if SOZ is not pure.
For example 70 t/d of pure SOz may be used in accord with the invention to double the capacity of a 70 t/d air-based Claus unit, or alternatively to debottleneck by 70 t/d a larger capacity Claus unit.
Should the Claus unit be able to accommodate the resulting process gas flow, in practice the air flow may have to be reduced, and the reduced OZ content in the 214'19 PATENT
resulting air flow may be at least partially replaced by pure oxygen, to achieve a proper minimum residence time.
Claims (24)
1. A process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of:
a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
b) feeding a H2S-containing gas to a thermal reactor of a Claus unit;
c) reacting at least a portion of said SO2-containing gas in said Claus unit thermal reactor;
d) controlling the temperature in the Claus unit thermal reactor by diverting a portion of said portion in step c) of the SO2-containing gas to a downstream catalytic Claus convertor without reacting the diverted SO2 in the Claus thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor at less than 3250°F.; and e) recovering a sulfur product from said Claus unit.
a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
b) feeding a H2S-containing gas to a thermal reactor of a Claus unit;
c) reacting at least a portion of said SO2-containing gas in said Claus unit thermal reactor;
d) controlling the temperature in the Claus unit thermal reactor by diverting a portion of said portion in step c) of the SO2-containing gas to a downstream catalytic Claus convertor without reacting the diverted SO2 in the Claus thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor at less than 3250°F.; and e) recovering a sulfur product from said Claus unit.
2. The process as recited in claim 1, wherein said sulphuric acid treatment unit is a sulphuric acid regeneration plant, and said sulfur-dioxide-containing gas is recovered from said sulfuric acid regeneration plant which comprises dissociating said sulfuric acid to form a gas mixture comprising said sulfur-dioxide-containing gas.
3. The process as recited in claim 2, wherein said sulfuric acid is dissociated in the presence of a mixture of fuel and oxygen-enriched gas.
4. The process as recited in claim 3, wherein said oxygen-enriched gas comprises greater than 21 percent oxygen.
5. The process as recited in claim 3, wherein said oxygen-enriched gas comprises greater than about 40 percent oxygen.
6. The process as recited in claim 3, wherein said oxygen-enriched gas comprises greater than about 95 percent oxygen.
7. The process as recited in any one of claims 3 to 6, wherein said dissociating is carried out in a process comprising controlling the flow of a portion of said oxygen-enriched gas to a first stage of an acid regeneration process at said sulphuric acid regeneration plant to result in incomplete combustion of said fuel mixture in said first stage.
8. The process as recited in any one of claims 2 to 7, wherein said sulfuric-acid is fed to said sulfuric acid regeneration plant in a liquid waste comprising at least 5 percent by weight sulfuric acid and at least 10 percent of sulfur by weight.
9. The process as recited in any one of claims 1 to 8, wherein said thermal reactor average temperature is between about 1650°F. and about 3200°F. provided thermal sulfur is produced.
10. The process as recited in any one of claims 1 to 9, further comprising drying at least a portion of said sulfur-dioxide-containing gas recovered from said sulfuric acid treatment unit in a gas dryer to reduce the water concentration in said sulfur-dioxide-containing gas, and increase the sulfur-dioxide concentration in said sulfur-dioxide-containing gas to at least twenty-two percent by volume.
11. The process as recited in any one of claims 1 to 10, further comprising adjusting the effective SO2 concentration in said sulfur-dioxide-containing gas recovered from said sulfuric acid treatment unit by treating at least a portion of said sulfur-dioxide-containing gas in at least one unit operation selected from the group consisting of a spray tower, a cooling tower, an electrostatic precipitator, a gas dryer and a CO2 removal system prior to reacting at least a portion of said sulfur-dioxide-containing gas in said Claus thermal reactor.
12. The process as recited in any of claims 1 to 11, further comprising mixing a quantity of oxygen-enriched air with said sulfur-dioxide-containing gas to form a mixture prior to reacting said mixture in said Claus unit thermal reactor.
13. The process as recited in claim 12, wherein the oxygen concentration of said mixture is less than about 20%.
14. The process as recited in claim 12 or 13, further comprising adjusting the flow of said oxygen-enriched air based upon the flow rate of said sulfur-dioxide-containing gas to control the oxygen concentration of said mixture.
15. The process as recited in any of claims 1 to 14, wherein said sulfuric acid treatment unit comprises a SAR
regeneration furnace and said sulfur-dioxide-containing gas is delivered to said Claus unit thermal reactor at a pressure of between about 15 psig and about 20 psig.
regeneration furnace and said sulfur-dioxide-containing gas is delivered to said Claus unit thermal reactor at a pressure of between about 15 psig and about 20 psig.
16. The process as recited in claim 15, further comprising pressurizing said SAR regeneration furnace.
17. The process as recited in claim 15 or 16, further comprising compressing said sulfur-dioxide-containing gas recovered from the effluent of said SAR regeneration furnace.
18. A process for the recovery of sulfur from sulfur-containing fluid mixtures, comprising the steps of:
a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
b) feeding a H2S-containing gas to a Claus thermal reactor;
c) reacting at least a portion of said sulfur-dioxide-containing gas in said Claus thermal reactor; and d) controlling the temperature in the Claus thermal reactor by diverting a portion of said portion in step c) of the SO2-containing gas to a downstream catalytic Claus convertor without reacting the diverted SO2 in the Claus thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor at less than 3250°F.
a) recovering a sulfur-dioxide-containing gas from a sulfuric acid treatment unit;
b) feeding a H2S-containing gas to a Claus thermal reactor;
c) reacting at least a portion of said sulfur-dioxide-containing gas in said Claus thermal reactor; and d) controlling the temperature in the Claus thermal reactor by diverting a portion of said portion in step c) of the SO2-containing gas to a downstream catalytic Claus convertor without reacting the diverted SO2 in the Claus thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor at less than 3250°F.
19. The process as recited in claim 18, further comprising the steps of:
e) determining the volume ratio of H2S/SO2 at the inlet in said Claus thermal reactor; and f) adjusting said volume ratio to a volume ratio greater than 2.
e) determining the volume ratio of H2S/SO2 at the inlet in said Claus thermal reactor; and f) adjusting said volume ratio to a volume ratio greater than 2.
20. The process as recited in claim 19, wherein said adjusting comprises converting at least a portion of H2S in said H2S-containing gas to SO2 in a furnace prior to said thermal reactor.
21. The process as recited in claim 18, 19 or 20, wherein at least a portion of said H2S-containing gas is derived from a sour water stripper column.
22. A process for treating sulfur-containing waste streams, comprising the steps of:
a) recovering a quantity of sulfur-dioxide-containing gas from a sulfuric acid regeneration unit comprising a SAR
regeneration furnace;
b) feeding a first portion of said sulfur-dioxide-containing gas to a Claus thermal reactor;
c) diverting a portion of said first portion of said sulfur-dioxide-containing gas to a downstream catalytic Claus converter without reacting diverted SO2 in said thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor between about 1650°F. and about 3200°F.
a) recovering a quantity of sulfur-dioxide-containing gas from a sulfuric acid regeneration unit comprising a SAR
regeneration furnace;
b) feeding a first portion of said sulfur-dioxide-containing gas to a Claus thermal reactor;
c) diverting a portion of said first portion of said sulfur-dioxide-containing gas to a downstream catalytic Claus converter without reacting diverted SO2 in said thermal reactor, in an amount effective to maintain the average temperature in the Claus thermal reactor between about 1650°F. and about 3200°F.
23. The process as recited in claim 22, further comprising the steps of:
d) feeding a portion of sour water stripper gas to said Claus thermal reactor;
e) feeding a second portion of sour water stripper gas to the SAR regeneration furnace of said sulfuric acid regeneration unit:
f) adjusting the relative flow of said portions of sour water stripper gas of steps a) and b) to control the temperature of said Claus thermal reactor.
d) feeding a portion of sour water stripper gas to said Claus thermal reactor;
e) feeding a second portion of sour water stripper gas to the SAR regeneration furnace of said sulfuric acid regeneration unit:
f) adjusting the relative flow of said portions of sour water stripper gas of steps a) and b) to control the temperature of said Claus thermal reactor.
24. The process as recited in claim 23, further comprising adjusting the sulfur-dioxide content of said sulfur-dioxide-containing gas from said SAR regeneration furnace by delivering and controlling a quantity of oxygen-enriched air to the burner of said SAR regeneration furnace.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22823894A | 1994-04-15 | 1994-04-15 | |
| US08/228,238 | 1994-04-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2147195A1 CA2147195A1 (en) | 1995-10-16 |
| CA2147195C true CA2147195C (en) | 2005-04-05 |
Family
ID=22856360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002147195A Expired - Fee Related CA2147195C (en) | 1994-04-15 | 1995-04-18 | Processing sulfur-containing streams |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5702678A (en) |
| CA (1) | CA2147195C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7695701B2 (en) * | 2008-03-07 | 2010-04-13 | Du Pont | Process for treating acid gas in staged furnaces with inter-stage heat recovery |
| US20090226364A1 (en) * | 2008-03-07 | 2009-09-10 | E. I. Du Pont De Nemours And Company | Process for treating acid gas in staged furnaces with inter-stage heat recovery and inter-stage sulfur production |
| JP5455528B2 (en) * | 2009-09-29 | 2014-03-26 | 三菱重工業株式会社 | Combustion control device |
| US11492306B2 (en) * | 2020-09-30 | 2022-11-08 | Honeywell International Inc. | Alkylation process with thermal oxidation system |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1199243B (en) * | 1963-07-10 | 1965-08-26 | Huels Chemische Werke Ag | Process for the production of gases containing sulfur dioxide from waste sulfuric acid containing ammonium salts |
| US4543245A (en) * | 1981-12-30 | 1985-09-24 | Atlantic Richfield Company | Process for controlling temperature of a Claus sulfur unit thermal reactor |
| US4490347A (en) * | 1983-02-07 | 1984-12-25 | E. I. Du Pont De Nemours And Company | Process for sulfuric acid regeneration |
| DE3311372C2 (en) * | 1983-03-29 | 1986-07-10 | Carl Still Gmbh & Co Kg, 4350 Recklinghausen | Process for the production of sulfur by the Claus process from coke oven gas |
| US4552747A (en) * | 1984-06-20 | 1985-11-12 | Gaa Engineered Systems, Inc. | Temperature moderation of an oxygen enriched Claus sulfur plant |
| US4826670A (en) * | 1985-03-20 | 1989-05-02 | Air Products And Chemicals, Inc. | Oxygen enriched claus system with sulfuric acid injection |
| US4684514A (en) * | 1985-07-22 | 1987-08-04 | Air Products And Chemicals, Inc. | High pressure process for sulfur recovery from a hydrogen sulfide containing gas stream |
| EP0237216B1 (en) * | 1986-03-07 | 1991-05-22 | The BOC Group plc | Treatment of gas streams |
| DE3777861D1 (en) * | 1986-03-07 | 1992-05-07 | Boc Group Plc | TREATMENT OF GASES. |
| DE3842599A1 (en) * | 1988-12-17 | 1990-06-21 | Linde Ag | METHOD FOR THE TREATMENT OF A WASTE SAUERAGE-CONTAINING WASTE |
| US5022332A (en) * | 1990-08-15 | 1991-06-11 | Union Carbide Industrial Gases Technology Corporation | Combustion method for improved endothermic dissociation |
| GB9127096D0 (en) * | 1991-12-20 | 1992-02-19 | Ici Plc | Treatment of liquid waste material |
| GB9205877D0 (en) * | 1992-03-18 | 1992-04-29 | Boc Group Plc | Treatment of waste or other material |
-
1995
- 1995-04-18 CA CA002147195A patent/CA2147195C/en not_active Expired - Fee Related
-
1996
- 1996-07-01 US US08/673,033 patent/US5702678A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2147195A1 (en) | 1995-10-16 |
| US5702678A (en) | 1997-12-30 |
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