WO2017068403A1 - A process for the manufacture of sulfur dioxide, sulfur trioxide, sulfuric acid, and sulfonated compounds - Google Patents
A process for the manufacture of sulfur dioxide, sulfur trioxide, sulfuric acid, and sulfonated compounds Download PDFInfo
- Publication number
- WO2017068403A1 WO2017068403A1 PCT/IB2015/059430 IB2015059430W WO2017068403A1 WO 2017068403 A1 WO2017068403 A1 WO 2017068403A1 IB 2015059430 W IB2015059430 W IB 2015059430W WO 2017068403 A1 WO2017068403 A1 WO 2017068403A1
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- WIPO (PCT)
- Prior art keywords
- manufacture
- liquid
- sulfur
- processes
- concentrated
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/502—Preparation of sulfur dioxide by reduction of sulfur compounds of sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
- C01B17/79—Preparation by contact processes characterised by the catalyst used containing vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/096—Amidosulfonic acid; Salts thereof
Definitions
- the invention relates to the manufacture of Sulfur Dioxide, Sulfur Trioxide, Sulfuric Acid, and Sulfonated compounds like, and not limited to, Methane Sulfonic Acid (MSA), Para Toluene Sulfonic Acid (PTSA), Sulfamic Acid.
- MSA Methane Sulfonic Acid
- PTSA Para Toluene Sulfonic Acid
- Sulfamic Acid Sulfamic Acid.
- the invention particularly relates to a process for the manufacture of S0 3 using a 'Cold Process' utilising unique properties of liquid SO? and liquid SO 3 , which leads to a higher quality and economic efficiency in the production of SO 3 than conventional processes, which further leads to higher quality and efficiency in the manufacture of the aforementioned derivative compounds.
- the invention is directed to reduced capital investment and utility cost, less plant area/size, and zero emission of sulfur dioxide.
- Sulfur Dioxide is a basic intermediate step in the manufacture of high-grade Sulfur Trioxide (SO 3 ) and Sulfuric Acid (H 2 S0 4 ). It is also an intermediate step in the manufacture of sulfonated compounds like, and not limited to, Methane Sulfonic Acid (MSA), Para Toluene Sulfonic Acid (PTSA), Sulfamic Acid.
- MSA Methane Sulfonic Acid
- PTSA Para Toluene Sulfonic Acid
- S0 2 is based on burning Sulfur in a high-temperature furnace based on the reaction S + C1 ⁇ 2 -> SO?. This reaction is highly exothermic and must be performed in a furnace able to withstand very high temperatures. A higher-temperature in the furnace due to a higher concentration of
- the SO 3 is further purified to obtain SO 3 as an end- product, or is used in the manufacture of H 2 SO , or is used for sulfonation to produce the aforementioned sulfonation compounds.
- the sulfur burning furnace is operated at 1050-1100°C. At this temperature, only 9.5-11% concentration by volume of S0 2 in the output-gas mixture is achieved.
- the SO 2 output from the furnace is at about 1 100°C and must be cooled to a temperature appropriate for the catalyst in the SO 3 converter.
- Vanadium Pentoxide is a commonly used catalyst that requires cooling to about 410- 430°C.
- the need to cool the gas mixture by almost 700°C requires an elaborate arrangement requiring additional capital expenditure and operating costs.
- the high incoming temperature precludes the use of a Cesium- activated catalyst that is more effective than the conventional Vanadium Pentoxide catalyst, but requires a lower operating temperature of 360-380 u C. 3.
- the high operating temperature of the furnace reduces the furnace's lifetime causing faster depreciation in the furnace's economic value and additional capital expenditures to replace the furnace frequently.
- the present invention has the following objectives:
- Figure 1 shows a block diagram for a typical conventional plant for manufacture of H2SO4 acid/oleum/SOj
- Figure 2 shows a flow diagram for part C of the process of invention as applied to existing plants for manufacturing S0 3 and H 2 S0 4
- Figure 3 shows a block diagram for parts A and B of the process of invention as applied to existing plants for manufacturing SO 3 and H 2 S0 4
- Figure 4 shows a block diagram for the process of invention as applied to new plants for manufacturing S0 3 and H 2 S0 4
- the invention proposes a method or a process to produce SO 2 by passing S0 3 through liquid sulfur.
- the S0 2 thus produced is then used as the sole source of SO 2 for downstream processes.
- the SO 2 thus produced is used to augment the S0 2 produced using conventional processes of S0 2 manufacture.
- the invention is applicable to a number of conventional processes for the manufacture of H 2 S0 4 and liquid SO 3 in particular as well as the aforementioned sulfonation compounds. Description of the invention:
- the invention discloses a process to manufacture SO 3 and H 2 S0 4 using SO 2 , wherein the S0 2 is manufactured in an innovative manner, as applied to existing plants for manufacturing SO 3 and H 2 S0 4 as well as new plants. Additional embodiments of the present invention disclose methods using SC1 ⁇ 2 that is manufactured in an innovative manner to manufacture the aforementioned sulfonation compounds.
- SO 2 is generated by passing SO 3 through liquid Sulfur (S + 2S0 3 -> 3S0 2 - ⁇ ).
- This reaction is referred to as the "New Reaction" in the remainder of the present disclosure.
- the S0 2 produced by means of the New Reaction is used as the sole source of S0 2 or as an augmentation of the conventional steps of S0 2 production outlined above.
- the new reaction is only mildly exothermic (in other words, generates less heat) compared to the burning of Sulfur.
- this component is called the "Cold SO 2 Generator” or CSG.
- the S0 2 so generated is used in the process of manufacturing SO 3 or Sulfuric acid or the aforementioned sulfonation compounds.
- the New Reaction produces the S0 2 at a lower temperature and at a higher concentration and pressure as described herein.
- the liquid sulfur in the New Reaction is nominally maintained at 140°C, which is also about the temperature at which S0 2 is generated in the aforementioned CSG.
- the generated S0 2 is used in the following manner: t is mixed with the S0 2 from the furnace to increase the S0 2 concentration that is input to the SO 3 converter (the next stage). It is possible to increase the concentration to 20-25%, which is ideal for the catalyst in the SO 3 converter unit.
- the S0 2 generated in this manner is at about 140°C, its mixture with the SO 2 from the furnace is used to cool the gas mixture. It is feasible to cool the gas mixture that is at a temperature in the range of about 950 °C to 1100 °C when coming out of the furnace to about 600-800 °C by mixing it with the SO 2 from the aforementioned CSG.
- the lower S0 2 mixture temperature is beneficial because it requires a less elaborate cooling system, and importantly, allows a Cesium-activated Vanadium Pentoxide catalyst to be used in the S0 3 converter.
- the Cesium-activated Vanadium Pentoxide catalyst lowers the operating temperature requirement to about 360-380°C as against the typical Potassium-activated Vanadium Pentoxide catalyst that requires a temperature of 410-430°C.
- the Cesium-activated Vanadium Pentoxide catalyst is desirable since it improves the efficiency of the S0 3 converter. Using this process, higher steam generation is achieved than the existing Double Contact Double Absorption (DCDA) processes. In effect, the combination of the higher SO? concentration and the use of the Cesium activated catalyst enabled by the CSG unit enhances the overall efficiency of the Sulfur-to-S0 3 subsystem.
- a significant benefit of this scheme is that it can be retrofitted into an existing chemical plant for the manufacture of SO 3 and H 2 SO 4 .
- the CSG unit is envisaged as an add-on into the existing system and the S0 3 converter catalyst can be reloaded for the new parameters. In effect, the efficiency of an existing chemical plant can be improved at very low capital and operational cost.
- the SO 3 converter When the SO 3 converter is a part of an H 2 S0 4 manufacturing chemical plant, the SO 3 is nominally input into an Oleum Tower at 1 10-130°C. As a consequence of the lower converter temperature enabled by the aforementioned CSG unit, it becomes easier to achieve the required 1 10-130°C.
- the aforementioned CSG-based system for producing SO 2 and SO 3 is used to efficiently produce liquid SO 3 with liquid S0 2 as a solvent with further application in the manufacture of high-grade H 2 S0 4 .
- This process of manufacturing SO 3 or H 2 S0 4 according to the invention is divided into three parts:
- Part A Manufacturing liquid S0 2 without compression or refrigeration
- FIG. 3 shows a block diagram for application of the present invention for producing liquid SO 3 (parts A and B described above) from an existing Sulfuric acid plant. The figure shows liquid SO 3 and liquid sulfur plants that produce liquid S0 2 , which is then converted using a catalyst and dry air from the drying tower into SO 3 , which is passed through an Oleum tower after which it is dissolved into liquid phase producing H 2 S0 4 and SO3 and H2S2O7.
- the process of manufacturing SO 3 according to the invention yields greater quantities of SO 3 than existing plants. This is because in the process of the present invention, SO 3 is first absorbed in H 2 S0 4 and then condensed to yield gaseous SO 3 at a higher yield.
- the S0 2 and S0 3 produced therein is used in the augmentation of the manufacture of the aforementioned sulfonation compounds.
- a typical example of such process augmentation is to produce the sulfonation compound called Sulfamic Acid (NH 2 S0 2 OH) by reaction of Ammonia (NH ) & S0 .
- the reaction carried out is ⁇ ]
- the S0 3 produced by the CSG and the S0 3 converter is used with S0 2 as a solvent for S0 3 .
- the heat of reaction is removed by evaporation of liquid S0 2 , which is injected in the reactor by a metering system after calculating the quantity based on the latent heat for the given temperature and pressure at which the reaction takes place.
- additional liquid SO? is provided to form a slurry, the amount of which will vary from case to case.
- This section describes the innovative application of the aforementioned CSG in the production of liquid (condensed) S0 2 , and pure liquid (condensed) S0 3 with SO?, as a solvent. It has been described previously in the disclosure how the CSG can be used to augment SO? production by injecting the CSG-produced S0 2 into the SO 2 stream generated by the Sulfur burning furnace. In a different pure-S0 2 process, the S0 2 produced by the CSG can be fed directly into the next stage (nominally the SO 3 converter).
- the pure-S0 2 process would have S0 2 at 6-8 Atmospheres (6-8 Kg/cm2) and 360 °C. Under such high pressure, it becomes possible to condense S0 2 while leaving the residual S0 2 in the gaseous state. As a result, the process enables the production of pure SO 3 in liquid form. Note that this process is enabled by the production of pure S0 2 at high pressure by the CSG unit. Given that this process produces pure SO 3 , its use in the manufacture of high-grade H 2 S0 4 can lead to significant process simplifications. For example, it would become possible to avoid having to use an Oleum Tower altogether in such a process.
- Figure 4 shows the process to manufacture SO 3 and I hSO . using a new plant. As shown in the figure it requires:
- the liquefied S0 2 produced using the process of the present invention and pure oxygen are supplied to a condensation reaction chamber containing a catalytic converter which is kept at a pressure of 6-8 kg/cm2.
- the remnants of the mixture of SO?, and 0 2 with traces of S0 3 are recycled into the reaction chamber carrying catalyst.
- the catalyst is preferably Cesium-activated vanadium pentoxide.
- a process for the manufacture of SO 2 in higher concentrations in chemical plants producing SO 3 , H 2 S0 4 , or sulfonation compounds comprising the step of passing gaseous SO 3 through liquid sulfur.
- a process for the manufacture of H 2 S0 4 wherein the SO3 generated from said isothermal catalytic converter as disclosed in embodiments 7 or 8 is introduced into an oleum tower to produce liquid SO3 as an intermediate step.
- a process for the manufacture of H 2 SO 4 as disclosed in embodiment 9 wherein said liquid SO3 is introduced to a glass-lined reactor where it is reacted with demineralized water to produce liquid H 2 S0 4 .
- a process specifically for the manufacture of Sulfamic Acid wherein the SO 3 produced using the processes as disclosed in embodiments 1 through 13 is reacted with Ntk.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU2015412464A AU2015412464B2 (en) | 2015-10-20 | 2015-12-08 | A process for the manufacture of sulfur dioxide, sulfur trioxide, sulfuric acid, and sulfonated compounds |
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IN3963MU2015 | 2015-10-20 | ||
IN3963/MUM/2015 | 2015-10-20 |
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WO2017068403A1 true WO2017068403A1 (en) | 2017-04-27 |
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PCT/IB2015/059430 WO2017068403A1 (en) | 2015-10-20 | 2015-12-08 | A process for the manufacture of sulfur dioxide, sulfur trioxide, sulfuric acid, and sulfonated compounds |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2813006A (en) * | 1953-08-12 | 1957-11-12 | Allied Chem & Dye Corp | Production of sulfur dioxide from sulfur and sulfur trioxide |
DE1667621A1 (en) * | 1967-08-25 | 1971-07-01 | Metallgesellschaft Ag | Process for the production of liquid sulfur trioxide and sulfuric acid |
US3671194A (en) * | 1970-05-01 | 1972-06-20 | Treadwell Corp | Sulfur dioxide conversion |
DE2827553A1 (en) * | 1977-06-28 | 1979-01-04 | Ugine Kuhlmann | METHOD FOR PRODUCING SULPHAMIC ACID |
US20150191425A1 (en) * | 2012-08-20 | 2015-07-09 | Solvay Specialty Polymers Usa, Llc. | Process for sulfonating halobenzene derivatives with sulfur trioxide |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH477364A (en) * | 1967-06-16 | 1969-08-31 | Schweizerhall Saeurefab | Process and device for the continuous production of high-purity sulfur dioxide |
-
2015
- 2015-12-08 WO PCT/IB2015/059430 patent/WO2017068403A1/en active Application Filing
- 2015-12-08 AU AU2015412464A patent/AU2015412464B2/en not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2813006A (en) * | 1953-08-12 | 1957-11-12 | Allied Chem & Dye Corp | Production of sulfur dioxide from sulfur and sulfur trioxide |
DE1667621A1 (en) * | 1967-08-25 | 1971-07-01 | Metallgesellschaft Ag | Process for the production of liquid sulfur trioxide and sulfuric acid |
US3671194A (en) * | 1970-05-01 | 1972-06-20 | Treadwell Corp | Sulfur dioxide conversion |
DE2827553A1 (en) * | 1977-06-28 | 1979-01-04 | Ugine Kuhlmann | METHOD FOR PRODUCING SULPHAMIC ACID |
US20150191425A1 (en) * | 2012-08-20 | 2015-07-09 | Solvay Specialty Polymers Usa, Llc. | Process for sulfonating halobenzene derivatives with sulfur trioxide |
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AU2015412464B2 (en) | 2021-05-20 |
AU2015412464A1 (en) | 2018-05-17 |
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