EP3472097A1 - Integrated process for the production of concentrated sulphuric acid - Google Patents
Integrated process for the production of concentrated sulphuric acidInfo
- Publication number
- EP3472097A1 EP3472097A1 EP17732408.4A EP17732408A EP3472097A1 EP 3472097 A1 EP3472097 A1 EP 3472097A1 EP 17732408 A EP17732408 A EP 17732408A EP 3472097 A1 EP3472097 A1 EP 3472097A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulphuric acid
- sulphur
- section
- sulphur dioxide
- production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/765—Multi-stage SO3-conversion
- C01B17/7655—Multi-stage SO3-conversion with intermediate absorption
-
- 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
- C01B17/54—Preparation of sulfur dioxide by burning elemental sulfur
-
- 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
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the present invention finds application in the field of filtration of gases produced by boilers in thermal power plants . Such thermal power plants are particularly integrated into refinery plants . Alternatively, the present invention is applied to the filtration of off- gases from various combustion processes .
- a refinery plant is a very complex structure, within which heavy crude processing systems for the production of hydrocarbons and important by-products for the petrochemical industry are located, and several facilities providing auxiliary services .
- the SNOX/WSA system is used for the removal of sulphur dioxide contained in the flue gas from boilers or from off gas from the combustion of hydrogen sulphide, from FCC (Fluid Catalytic Cracking) , exhausted hydrogen sulphide incineration, etc .
- the system essentially comprises a reaction section, a gas cooling section and a condensation section, as schematically shown in figure 1.
- the sulphur dioxide reacts catalytically with oxygen to give sulphur trioxide .
- the reaction conducted at about 400 °C, is as follows :
- the reactor may optionally be associated with a reactor for NOx removal .
- the off gas from the catalytic reaction section is cooled down to a temperature of about 260 °C .
- a part of sulphur trioxide is combined with water vapour, yielding sulphuric acid vapours , as shown hereinafter :
- Sulphuric acid stripping techniques with hot gases at about 400 °C are a possible alternative, but they suffer ma or problems of flexibility and the operating temperatures limit the use of materials .
- a sulphuric acid production system generally comprises three sections : combustion, reaction, absorption .
- elemental sulphur is sent at the liquid state to a burner where it is burnt with air to give :
- the liquefied sulphur at a temperature of about 140-150 °C is sprayed through an atomizer to generate very fine droplets, characterized by a high contact surface to promote combustion with air.
- the reaction reaches temperatures of about 1000 ⁇ -1600°C and a significant amount of heat is recovered in a steam generator, such as WHB with fume tubes .
- sulphur dioxide is made reacting catalytically with the oxygen contained in the gas to give sulphur trioxide :
- reaction is hindered by temperatures higher than 430 °C and, therefore, multiple catalytic beds must be used, from 2 to 3 , with an intercooler therebetween .
- gases containing sulphur trioxide are suitably cooled to about 250 °C .
- sulphur trioxide is absorbed by the water contained in a recirculating solution of sulphuric acid :
- Concentrated sulphuric acid (about 98% by weight ) is obtained in this way, in an azeotropic solution and gases which, after being properly treated, are released to the atmosphere .
- off gases containing unreacted SO2 are obtained from the absorption section, normally also released to the atmosphere.
- the concentration of acid is maintained around 98% by adding water.
- Figure 3 shows a diagram of such a system, in which the gas is treated passing through two catalytic beds and then treated in a first absorption column, where sulphur trioxide is converted to sulphuric acid .
- the gases containing the residual sulphur dioxide are again heated up to 420 °C and sent to the third bed, where part of the SO2 is converted to SO3.
- the gases leaving the third bed are cooled and sent to the second absorption tower, where sulphur trioxide is converted to sulphuric acid .
- This process is able to recover 99.7% of sulphur dioxide (the residual SO2 is ⁇ 2 Kg per ton of sulphuric acid produced) .
- EP 844211 it is disclosed sulphuric acid obtained from the condensation tower, which is sent to a stripping column at a temperature of 400-600 °C; in the column, part of the water is evaporated .
- an integrated system for the production of sulphuric acid is described .
- a solution of non-concentrated sulphuric acid is described, obtained from a SNOX/WSA process for the production of concentrated sulphuric acid in the absorption section of a system for the production of sulphuric acid from sulphur .
- the present invention describes the use of off gases rich in sulphur dioxide from the absorption section of a system for the production of sulphuric acid from sulphur, in the reaction section of a SNOX/WSA system.
- Figure 1 shows the diagram of a typical SNOX/WSA system
- Figure 2 shows a schematization of a single contact sulphuric acid production system
- Figure 3 shows a schematization of a double contact sulphuric acid production system
- Figure 4 shows a typical SNOX/WSA system (A) and for the production of sulphuric acid from sulphur (B) ;
- Figure 5 is a block diagram of a system according to the present invention, with a three-phase catalytic section;
- Figure 6 is a block diagram of a system according to the present invention, with a two-phase catalytic section;
- Figure 7 is a schematization of a system according to the present invention.
- concentrated sulphuric acid refers to sulphuric acid at the concentration of about 98% by weight, corresponding to the azeotropic concentration .
- sulphur dioxide or “sulphur trioxide” are to be construed as equivalent to "a gas rich in ... " or "a gas comprising ... "
- a process is described for the preparation of concentrated sulphuric acid from a gas containing sulphur dioxide .
- such a process comprises the steps of a) sub ecting a gas containing sulphur dioxide to a catalytic oxidation step in the presence of oxygen so as to obtain a gas comprising sulphuric anhydride ; b) sub ecting the gas comprising sulphuric anhydride to a cooling step in the presence of water so as to obtain an aqueous solution of non-concentrated sulphuric acid; c) sub ecting the solution obtained from step b) to an absorption step in the presence of sulphuric anhydride, wherein the sulphuric anhydride of step c) comprises sulphuric anhydride obtained from an oxidation step of the sulphur dioxide obtained in a process for preparing concentrated sulphuric acid from sulphur .
- such a process comprises the steps of :
- step d ' subject the sulphur dioxide obtained from step c ' ) to a catalytic oxidation in the presence of oxygen, thus obtaining sulphur trioxide ;
- steps c') r d ' ) and e ' ) are carried out separately from steps a') and b ' ) , but in integration therewith .
- steps a') and b ' ) are steps of a SNOX/ SA process for the production of sulphuric acid from sulphur dioxide .
- steps c ' ) , d ' ) and e ' ) are carried out in a process for the production of sulphuric acid from sulphur .
- the sulphuric acid obtained in a SNOX/WSA process is sent to the absorption step of a process for the production of sulphuric acid from sulphur .
- such a process comprises the steps of :
- sulphur dioxide of step f) comprises sulphur dioxide from the absorption step in a process for the production of concentrated sulphuric acid from sulphur.
- such a process comprises the steps of :
- step h' subjecting the sulphur trioxide of step g ' ) to an absorption step, thus obtaining concentrated sulphuric acid and an off gas rich in sulphur dioxide ;
- step j ' subjecting sulphuric anhydride obtained from step i ' ) to a cooling and condensation step in the presence of water so as to obtain a solution of non TM concentrated sulphuric acid
- gas containing sulphur dioxide of step i ' comprises the off gas of step h' ) .
- steps f ' ) , g ' ) and h ' ) are carried out in (are part of) a process for the production of concentrated sulphuric acid from sulphur, while steps i ' ) and j ' ) (as well as the above steps f) and g) ) are carried out in (are part of) a SNOX/WSA process .
- steps f ' ) , g ' ) and h ' ) are carried out separately from steps i ' ) and j') f but in integration therewith .
- the off gas rich in sulphur dioxide obtained from the absorption step of a process for the production of sulphuric acid from sulphur is sent to the reaction step of a SNOX/WSA process .
- Suitable catalysts known to the man skilled in the art are used in the catalytic oxidation steps .
- the embodiment of the invention above described therefore allows to eliminate the treatment step of off gases resulting from a process for the production of sulphuric acid from sulphur and from the structural point of view, it allows to eliminate a gas emission point to the atmosphere from the system.
- a process for the production of concentrated sulphuric acid comprising the steps of :
- step 11 sub ecting the sulphur dioxide of step I ) to catalytic oxidation, thus obtaining sulphur trioxide ;
- step V) subjecting the sulphuric anhydride of step IV) to a cooling and condensation step in the presence of water so as to obtain a solution of non-concentrated sulphuric acid
- step III) is carried out in the presence of non- concentrated sulphuric acid obtained from step V) , and wherein
- step IV) is carried out in the presence of the sulphur dioxide of the off gas produced in step III.
- steps I), I I ) and III) are carried out in (are part of) a process for the production of sulphuric acid from sulphur .
- steps IV) and V) are carried out in (are part of) a SNOX/WSA process .
- an integrated system for the production of concentrated sulphuric acid is described .
- such a system comprises:
- condensation section is functionally connected to the absorption section (ASS2 ) of a system for the production of concentrated sulphuric acid from sulphur .
- the oxidation (0X1), cooling (RAFF1 ) and condensation (CONDI ) sections are parts of a SNOX/WSA system.
- such a system comprises:
- absorption section (ASS2 ) is operatively connected to the catalytic oxidation section (0X1 ) of a system for the production of non-concentrated sulphuric acid from sulphur dioxide .
- such a catalytic oxidation section (0X1 ) is part of a SNOX/WSA system.
- an integrated system for the production of concentrated sulphuric acid comprising a SNOX/WSA system and a system for the production of sulphuric acid from sulphur, wherein both systems are structurally modified with respect to traditional ones .
- the modifications comprise the functional connection of the cooling (RAFF1) and the condensation (CONDI ) section of the SNOX/WSA system, so that it is functionally connected to the absorption section (ASS2 ) a system for the production of sulphuric acid from sulphur and the functional connection of the absorption section (ASS2 ) of a system for the production of sulphuric acid from sulphur with the catalytic oxidation section (0X1 ) of a SNOX/WSA system.
- RAFF1 cooling
- CONDI condensation
- such a system comprises:
- a plant for the production of non-concentrated sulphuric acid from sulphur dioxide comprising:
- RAFF1 a section for cooling the gases obtained from the non-concentrated sulphuric acid oxidation section in the form of steam;
- a plant for the production of concentrated sulphuric acid from sulphur comprising:
- condensation section 3 (CONDI ) is functionally connected to the absorption section 6) (ASS2 ) in a system for the production of sulphuric acid from sulphur; and in that
- said absorption section 6) (ASS2 ) is operatively connected to the catalytic oxidation section 1 ) (0X1 ) .
- sulphuric acid produced by the SNOX/WSA system is sent directly to the section of a system for the production of sulphuric acid from sulphur, and that the off gases from the absorption section of a system for the production of sulphuric acid from sulphur are sent directly to the catalytic oxidation section of the SNOX/WSA system.
- a solution of non-concentrated sulphuric acid is described, obtained by a SNOX/WSA process in the absorption section of a system for the production of sulphuric acid from sulphur to obtain concentrated sulphuric acid .
- the invention describes the use of off gases rich in sulphur dioxide from the absorption section of a system for the production of sulphuric acid from sulphur, in the catalytic reaction section of a SNOX/ SA system.
- this ratio increases as the dilution of sulphuric acid from SNOX/WSA increases .
- ⁇ 1 ⁇ 2 ⁇ 0.3 corresponding to a concentration of sulphuric acid of about 93% (by weight) .
- the process of the present invention operates in conditions in which R > 0.1, i.e. corresponding to a concentration of about 98% by weight of sulphuric acid.
- a sulphuric acid system of about 100 MTPD must be associated to it .
- construction of a system for sulphuric acid associated with another system according to the present invention has a lower cost than a standard sulphuric acid system with the same capacity .
- the impact on the CAPEX for the construction of the system for sulphuric acid is estimated in the order of about 5-10% of the SNOX system.
- the integrated process described allows to use a low efficiency system for sulphuric acid, such as represented by a single contact process , thus resulting in a reduction in the manufacturing costs (CAPEX) .
- the integrated system of the present invention does not increase the emission points , indeed, it eliminates at least one emission point .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITUA2016A004559A ITUA20164559A1 (en) | 2016-06-21 | 2016-06-21 | Integrated process for the production of concentrated sulfuric acid |
PCT/EP2017/065246 WO2017220656A1 (en) | 2016-06-21 | 2017-06-21 | Integrated process for the production of concentrated sulphuric acid |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3472097A1 true EP3472097A1 (en) | 2019-04-24 |
Family
ID=57209744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17732408.4A Pending EP3472097A1 (en) | 2016-06-21 | 2017-06-21 | Integrated process for the production of concentrated sulphuric acid |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3472097A1 (en) |
IT (1) | ITUA20164559A1 (en) |
WO (1) | WO2017220656A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112299380A (en) * | 2019-08-02 | 2021-02-02 | 托普索公司 | Method and apparatus for producing oleum via integrated WSA technology |
CN113666342A (en) * | 2021-07-13 | 2021-11-19 | 南通醋酸化工股份有限公司 | Waste acid treatment method and system for producing acesulfame potassium |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0844211B1 (en) * | 1996-11-26 | 2001-04-11 | Haldor Topsoe A/S | Process for concentration of sulphuric acid |
EP2760566B1 (en) * | 2011-09-29 | 2016-03-02 | Haldor Topsøe A/S | Sulphuric acid production with recycle of desulphurized gas |
-
2016
- 2016-06-21 IT ITUA2016A004559A patent/ITUA20164559A1/en unknown
-
2017
- 2017-06-21 WO PCT/EP2017/065246 patent/WO2017220656A1/en unknown
- 2017-06-21 EP EP17732408.4A patent/EP3472097A1/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
Also Published As
Publication number | Publication date |
---|---|
WO2017220656A1 (en) | 2017-12-28 |
ITUA20164559A1 (en) | 2017-12-21 |
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RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SAIPEM S.P.A. |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BRUNO, LORENZO |
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Effective date: 20230728 |