SYSTEM AND A METHOD FOR PRODUCING AQUEOUS SULPHURIC ACID
20190177914 ยท 2019-06-13
Inventors
- Asta Humalajoki (Ruutana, FI)
- Antti VAELJAE (Yloejaervi, FI)
- Heikki Airikkala (Tampere, FI)
- Seppo Tuominiemi (Pirkkala, FI)
- Peter Bjoerklund (Umea, SE)
Cpc classification
D21C11/06
TEXTILES; PAPER
D21C11/0064
TEXTILES; PAPER
B01D5/0054
PERFORMING OPERATIONS; TRANSPORTING
International classification
D21C11/06
TEXTILES; PAPER
D21C11/00
TEXTILES; PAPER
Abstract
A system (100) for producing aqueous sulphuric acid. The system (100) comprises a first heat exchanger (410) configured to cool water and/or aqueous sulphuric for producing cooled water and/or cooled aqueous sulphuric acid; a pre-cooling unit (200) configured to pre-cool some gas containing sulphur trioxide, the pre-cooling unit (200) comprising an inlet or inlets (212, 214) for receiving [i] the gas containing sulphur trioxide and [ii] the cooled water and/or the cooled aqueous sulphuric acid, an outlet (216) for letting out aqueous sulphuric acid and the gas containing sulphur trioxide, and a first nozzle (220) for spraying the cooled water and/or the cooled aqueous sulphuric acid onto the gas containing sulphur trioxide to cool the gas containing sulphur trioxide. The system further comprises a condensation tower (300) comprising a first inlet (302) for receiving the cooled gas containing sulphur trioxide and aqueous sulphuric acid from the pre-cooling unit (200) and means (320) for circulating the aqueous sulphuric acid within the
Claims
1-16. (canceled)
17. A system (100) for producing aqueous sulphuric acid from a sulphur dioxide containing gas of a liquor circulation of a pulp mill (600), the system (100) comprising: the pulp mill (600), configured to produce at least some gas containing sulphur dioxide; a pipeline (602) configured to convey at least some of the gas containing sulphur dioxide to a converter (500), the converter (500) comprising: an inlet arrangement (502) for receiving some gas containing at least some sulphur dioxide and some oxygen or some gas containing at least some sulphur dioxide and some other gas comprising oxygen, and catalyst (510) for converting at least some of the sulphur dioxide and the oxygen to sulphur trioxide, a pipeline (440) configured to convey gas containing sulphur trioxide from the converter (500) to an inlet (212) of a pre-cooling unit (200); and a first heat exchanger (410) configured to cool water and/or aqueous sulphuric acid for producing cooled water and/or cooled aqueous sulphuric acid, wherein: the pre-cooling unit (200) is configured to pre-cool some gas containing sulphur trioxide, the pre-cooling unit (200) comprising: the inlet or inlets (212, 214) for receiving [i] the gas containing sulphur trioxide and [ii] the cooled water and/or the cooled aqueous sulphuric acid, an outlet (216) for letting out aqueous sulphuric acid and the gas containing sulphur trioxide, and a first nozzle (220) for spraying the cooled water and/or the cooled aqueous sulphuric acid onto the gas containing sulphur trioxide to cool the gas containing sulphur trioxide and to react some of the sulphur trioxide with some of the cooled water and/or aqueous sulphuric acid, thereby strengthening or producing some aqueous sulphuric acid; the system further comprises: a pipeline (450) configured to convey the cooled aqueous sulphuric acid and/or the cooled water from the first heat exchanger (410) to the pre-cooling unit (200), a condensation tower (300) comprising: a first inlet (302) for receiving the cooled gas containing sulphur trioxide and aqueous sulphuric acid from the pre-cooling unit (200), and means (320) for circulating the aqueous sulphuric acid within the condensation tower (300) by spraying in order to strengthen the aqueous sulphuric acid, and a channel (290) configured to convey the aqueous sulphuric acid and the gas comprising sulphur trioxide from the outlet (216) of the pre-cooling unit (200) to the condensation tower (300).
18. The system (100) of claim 17, wherein at least one of: the condensation tower (300) comprises a wall (310) or walls (310) limiting a reaction chamber (312) and the wall (310) or the walls (310) of the condensation tower (300) comprise plastic material; or the wall (310) or the walls (310) of the condensation tower (300) further comprise fibrous reinforcing material.
19. The system (100) of claim 17, wherein the means (320) for circulating the aqueous sulphuric acid within the condensation tower (300) by spraying in order to strengthen the aqueous sulphuric acid comprises: a second heat exchanger (420) configured to cool the circulated aqueous sulphuric acid, a pump (322) configured to pump aqueous sulphuric acid through the second heat exchanger (410), a second nozzle (326) for spraying cooled aqueous sulphuric acid onto the cooled gas containing sulphur trioxide within the condensation tower (300), and a pipeline (324) configured to convey cooled aqueous sulphuric acid from the second heat exchanger (420) to the second nozzle (326).
20. The system (100) of claim 17, wherein the pulp mill (600) is a Kraft pulp mill (600).
21. The system (100) of claim 17, further comprising: a scrubber (700) configured to scrub at least some sulphur dioxide from flue gas entering the scrubber (700) to produce clean gas; and a pipeline (340) configured to convey flue gas from the condensation tower (300) to the scrubber (700).
22. The system (100) of claim 17, wherein the pre-cooling unit (200) is connected with first openable fastening means (233) to either: the condensation tower (300); or a pipeline (290) that is connected to the condensation tower (300).
23. The system (100) of claim 17, wherein the system is free from such a strengthening device that is configured to strengthen the aqueous sulphuric acid to sulphuric acid having a strength of more than 80 w-%.
24. The system (100) of claim 17, wherein at least one of: the pre-cooling unit (200) comprises a sacrificial lid (240) and the sacrificial lid (240) is connected to a frame (260) of the pre-cooling unit (200) with second openable fastening means (243); the sacrificial lid (240) comprises metal (241) that is coated with a second lining (244) that comprises plastic and is heat resistant to at least 240 C.; the system further comprises a cooling channel (248) that is arranged in contact with the sacrificial lid (240); at least a part of the cooling channel (248) and at least some of the second lining (244) are arranged on a same straight line (L) that is parallel to a surface normal (N) of the sacrificial lid (240); or the pre-cooling unit (200) comprises: a first inner wall (252) made of acid proof material and surrounding a reaction chamber (202) of the pre-cooling unit (200), and a thermally insulating inner wall (256) surrounding the first inner wall (252), arranged in such a way that at least a part of the cooling channel (248), at least some of the second lining (244), and at least part of the thermally insulating inner wall (256) are arranged on a same straight line (L) that is parallel to a surface normal (N) of the sacrificial lid (240).
25. A method for producing aqueous sulphuric acid from a sulphur dioxide containing gas of a liquor circulation of a pulp mill (600), the method comprising the steps of: separating some gas containing sulphur dioxide from a liquor circulation of the pulp mill (600), conveying the gas containing sulphur dioxide to a converter (500), in the converter (500), catalytically oxidizing at least some of the sulphur dioxide to sulphur trioxide, thereby producing the gas comprising sulphur trioxide, conveying the gas comprising sulphur trioxide to a pre-cooling unit (200) such that such that at a an inlet (212) of the pre-cooling unit, the temperature of the gas containing sulphur trioxide is at least 300 C., in a first heat exchanger (410), cooling water and/or aqueous sulphuric acid thereby producing cooled water and/or cooled aqueous sulphuric acid, in the pre-cooling unit (200), cooling the gas containing sulphur trioxide to a temperature of at most 120 C. by spraying the cooled water and/or the cooled aqueous sulphuric acid onto the gas containing sulphur trioxide using a first nozzle (220), whereby at least some of the sulphur trioxide forms aqueous sulphuric acid with the water and/or the aqueous sulphuric acid, conveying the cooled gas containing sulphur trioxide and aqueous sulphuric acid from the pre-cooling unit (200) to a condensation tower (300), and in the condensation tower (300), strengthening the aqueous sulphuric acid by circulating the aqueous sulphuric acid in the condensation tower (300) and by spraying the aqueous sulphuric acid onto the gas containing sulphur trioxide using a second nozzle (326).
26. The method of claim 25, wherein at least one of: gas or gases, in particular the gas comprising sulphur trioxide, are only conveyed into the condensation tower (300) in such a way that at an inlet of the condensation tower (300) the temperature of the gas or gases is at most 120 C.; or the wall (310) or the walls of the condensation tower (300) that limit a reaction chamber (312) for strengthening the aqueous sulphuric acid comprise plastic material.
27. The method of claim 25, further comprising: conveying some aqueous sulphuric acid from the condensation tower (300) to a second heat exchanger (420), cooling the aqueous sulphuric acid in the second heat exchanger (420) to produce cooled aqueous sulphuric acid, and conveying at least some of the cooled aqueous sulphuric acid from the second heat exchanger (420) to the second nozzle (326) in the condensation tower (300) to spray at less some of the cooled aqueous sulphuric acid onto the gas containing sulphur trioxide.
28. The method of claim 25, wherein: The temperature of the gas containing sulphur dioxide at an inlet arrangement (502) of the converter (500) is from 350 C. to 450 C., and the temperature of the gas containing sulphur trioxide at an outlet (504) of the converter (500) is from 460 C. to 480 C.
29. The method of claim 25, further comprising: conveying flue gas from the condensation tower (300) to a scrubber (700); and removing some sulphur dioxide from the flue gas by scrubbing the flue gas in the scrubber (700).
30. The method of claim 25, wherein the aqueous sulphuric acid is produced in such a way that at least one of: the sulphuric acid concentration of the aqueous sulphuric acid does not exceed 80 w-% in the condensation tower (300); or only such aqueous is produced, of which strength is less than 80 w-%.
31. A pre-cooling unit (200) suitable for cooling gas comprising sulphur trioxide from a temperature of at least 400 C. to a temperature of at most 150 C., the pre-cooling unit comprising: an outer wall (260) limiting a reaction chamber (202) of the pre-cooling unit (200), an inlet or inlets (212, 214) for receiving [i] the gas containing sulphur trioxide and [ii] cooled water and/or cooled aqueous sulphuric acid into the reaction chamber (202), a first nozzle (220) for spraying the cooled water and/or the cooled aqueous sulphuric acid onto the gas containing sulphur trioxide to cool the gas containing sulphur trioxide and to react some of the sulphur trioxide with some of the cooled water and/or cooled aqueous sulphuric acid, thereby strengthening or producing some aqueous sulphuric acid, a thermally insulating inner wall (256) surrounded by the outer wall (260) and surrounding the reaction chamber (202), a first inner wall (252) made of acid proof material, surrounded by the outer wall (260) and surrounding the reaction chamber (202), a sacrificial lid (240) that comprises metal (241) that is coated with a lining (244) that comprises plastic material, the plastic material being heat resistant to at least 230 C. and facing the interior of the pre-cooling unit (200), and the sacrificial lid (240) being connected to the outer wall (260) with second openable fastening means (243), a cooling channel (248) that is arranged in contact with the sacrificial lid (240), an inlet (248a) for feeding coolant to the cooling channel (248), and an outlet (248b) for removing coolant from the cooling channel (248), wherein at least a part of the cooling channel (248) and at least some of the lining (244) are arranged on a same straight line (L) that is parallel to a surface normal (N) of the sacrificial lid (240).
32. The pre-cooling unit of claim 31, wherein: at least a part of the cooling channel (248), at least some of the lining (244), and at least part of the thermally insulating inner wall (256) are arranged on a same straight line (L) that is parallel to a surface normal (N) of the sacrificial lid (240).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0007]
[0008]
[0009]
[0010]
[0011]
[0012]
DETAILED DESCRIPTION
[0013]
[0014] In this description, the term aqueous sulphuric acid refers to an aqueous solution of sulphuric acid, in which the content of sulphuric acid is at most 80 w-%. As discussed below, in a typical process, the strength of the aqueous sulphuric acid is at most 70 w-%. At a given temperature, the strength of aqueous sulphuric acid correlates with its density and pH, which can be used as evidence on the strength of the aqueous sulphuric acid. In alternative terms, the term aqueous sulphuric acid refers to a liquid that can be made by mixing only water H.sub.2O and sulphuric acid H.sub.2SO.sub.4, wherein the weight percentage of H.sub.2SO.sub.4 is at most 80 or at most 70. As known to a skilled person the aqueous solution of H.sub.2SO.sub.4 will result in the following reactions:
H.sub.2SO.sub.4+H.sub.2OH.sub.3O.sup.++HSO.sub.4.sup.
and
HSO.sub.4.sup.+H.sub.2OH.sub.3O.sup.++SO.sub.4.sup.2
[0015] In both these reactions, the balance is strongly to the right side. Throughout this description, the terms aqueous sulphuric acid and aqueous H.sub.2SO.sub.4 refer to an aqueous solution comprising at least H.sub.2O, H.sub.3O.sup.+, and HSO.sub.4.sup. or SO.sub.4.sup.2. The aqueous sulphuric acid may be free from H.sub.2SO.sub.4 or HSO.sub.4.sup. or SO.sub.4.sup.2 as indicated by the reactions above.
[0016] Purposes of producing only aqueous sulphuric acid are twofold. First, when sulphuric acid is only needed in a process that only needs aqueous sulphuric acid, the aqueous sulphuric acid can be produced in a resource efficient manner compared to producing substantially pure H.sub.2SO.sub.4 and diluting it in the process. Second, when strong sulphuric acid is not needed, also a strengthening tower is not needed. This helps to keep the investment costs low.
[0017] In the method and system, sulphuric acid is produced in an exothermic reaction of SO.sub.3 with water. The water may be contained in aqueous sulphuric acid. The reaction can be formally written as
SO.sub.3+H.sub.2OH.sub.2SO.sub.4+heat.
[0018] With reference to
[0019] With reference to
[0020] If needed, the processed gas (i.e. flue) can be further washed in a scrubber 700 e.g. with scrubbing solution including alkali, such as NaOH, to remove essentially all sulphur from the flue (
[0021] In the pre-cooling unit 200, the gas containing sulphur trioxide is cooled to a temperature of at most 120 C., preferably at most 100 C., by spraying cooled liquid (e.g. the aqueous sulphuric acid and/or water) onto the gas containing sulphur trioxide. The temperature refers to the temperature of the gas at the outlet 216 of the pre-cooling unit 200. As indicated above, least some of the sulphur trioxide forms sulphuric acid by reacting with water, optionally the water of the aqueous sulphuric acid, thereby producing aqueous sulphuric acid or stronger aqueous sulphuric acid.
[0022] The system 100 further comprises a first heat exchanger 410. The first heat exchanger 410 comprises a first inlet 412 for hot aqueous sulphuric acid and/or water, a first outlet 414 for cooled aqueous sulphuric acid and/or cooled water, a second inlet 416 for coolant (i.e. cooling medium) and an second outlet 418 for the coolant. The system further comprises a pipeline 450 configured to convey the cooled aqueous sulphuric acid and/or the cooled water from the first outlet 414 of the first heat exchanger 410 to the second inlet 214 of the pre-cooling unit 200. As evident, from the second inlet 214 of the pre-cooling unit 200 the aqueous sulphuric acid and/or water is conveyed to the first nozzle 220 in a pipeline.
[0023] When the process starts, and optionally also later on, water H.sub.2O is fed into the process for making the aqueous sulphuric acid. In
[0024] Correspondingly, the method comprises cooling water and/or aqueous sulphuric acid thereby producing cooled water and/or cooled aqueous sulphuric acid. The cooling is done in the first heat exchanger 410 as indicated above. Preferably the water and/or aqueous sulphuric acid is cooled in such a way that the temperature of the water and/or aqueous sulphuric acid at the first outlet 414 of the heat exchanger 410 is at most 80 C.
[0025] The system 100 comprises a condensation tower 300. The condensation tower 300 comprises a wall 310 or walls 310 limiting a reaction chamber 312 for strengthening the aqueous sulphuric acid. The wall 310 may be an outer wall of the condensation tower 300. The condensation tower 300 comprises an inlet 302 for receiving the aqueous sulphuric acid and the gas comprising sulphur trioxide from the outlet 216 of the pre-cooling unit 200. As shown in the
[0026] The system 100 comprises a pump arrangement (322, 402) configured [i] to pump aqueous sulphuric acid from the condensation tower 300 to the first nozzles 220 via the first heat exchanger 410 and [ii] to pump aqueous sulphuric acid from the condensation tower 300 to the second nozzles 326. In
[0027] Correspondingly, the method comprises conveying [i] the cooled gas containing sulphur trioxide and [ii] the cooled water and/or aqueous sulphuric acid from the pre-cooling unit 200 to the condensation tower 300. The method further comprises strengthening, in the condensation tower 300, the aqueous sulphuric acid by circulating the aqueous sulphuric acid in the condensation tower 300 and by spraying the aqueous sulphuric acid onto the gas containing sulphur trioxide. In this way, sulphuric acid is produced into the aqueous sulphuric acid. In particular, by selecting the flow velocities within the pre-cooling device 200 and the condensation tower 300 properly, e.g. by selecting the cross-sectional areas of the pre-cooling device 200 and the condensation tower 300 properly, a large part of the reactions of SO.sub.3 with H.sub.2O may occur in the condensation tower 300.
[0028] The method has the beneficial effect, that since the temperature of the gas containing sulphur trioxide is cooled before the condensation tower 300, the material of the condensation tower 300 need not be very heat resistant. In particular some plastics may be suitable for the material of the wall(s) 310 of the condensation tower 300. In an embodiment of the system, the wall 310 or the walls 310 of the condensation tower 300 comprise plastic material. Preferably the wall 310 comprises a part that extends through the wall 310 in the direction of thickness thereof, and that part consists of plastic material and optionally fibrous reinforcing material. Correspondingly, in an embodiment of the method, gas or gases are only conveyed into the condensation tower 300 in such a way that the temperature of the gas or gases is at most 120 C. at an inlet of the condensation tower 300.
[0029] Throughout this description, the term plastic refers to a synthetic or semi-synthetic organic compounds that are malleable and can be molded into solid objects. The term may refer to a material comprising an organic polymer (or comprising organic polymers), which may comprise also other substances. The term may refer to a synthetic material comprising an organic polymer.
[0030] As for the plastic material, preferably the wall 310 comprises weldable plastic material. Weldable materials can be easily joined to other weldable materials by welding. Thus, with such materials, manufacturing the condensation tower 300 becomes easier. However, the plastic material should be reasonably resistant to heat and corrosion. The plastic material may be heat resistant to at least 130 C. Therefore, preferably the plastic material comprises fluorinated plastic material, even if some other plastic materials are also heat resistant to a sufficient degree. In an embodiment, the wall 310 or the walls 310 of the condensation tower 300 comprises plastic material. In an embodiment, the wall 310 or the walls 310 of the condensation tower 300 comprises fluorinated plastic material. In an embodiment, the wall 310 or the walls 310 of the condensation tower 300 further comprise reinforcing material. In an embodiment, the reinforcing material is a synthetic fibrous reinforcing material. Examples of synthetic fibrous reinforcing material include glass fibres, carbon fibres, para-aramid synthetic fibres (Kevlar), and/or aramid fibres. Preferably, the synthetic fibrous material is heat resistant to at least 130 C. In an embodiment, the wall 310 or the walls 310 of the condensation tower 300 comprise at least 10 w-% weldable plastic material in addition to fibrous reinforcing material. The weldable plastic material may be heat resistant to at least 130 C. The plastic material may be a fluorinated plastic material.
[0031] As indicated in
[0032] Regarding the temperature of the gas comprising SO.sub.3 entering the condensation tower 300, it is pointed out that typically the gas comprising SO.sub.3 further comprises steam. Therefore, when the temperature of the gas comprising SO.sub.3 is as low as discussed above, strong sulphuric acid cannot be produced, since the steam of the gas comprising SO.sub.3 becomes condensed. If stronger acid would be needed, a pre-cooling device could not be used, and the material requirements for a strengthening tower would be significantly stricter, since a strengthening tower needs to receive SO.sub.3 at a high temperature, in order to avoid condensation of water and/or dilute H.sub.2SO.sub.4.
[0033] In an embodiment of the method, aqueous sulphuric acid is produced in such a way that the sulphuric acid concentration of the aqueous sulphuric acid does not exceed 80 w-%. This allows for selection of simple materials for the condensation tower 300. As indicated below, the production of stronger H.sub.2SO.sub.4 from SO.sub.3 typically requires a higher temperature than indicated above.
[0034] Correspondingly, a system is free from such a strengthening tower that would be configured to strengthen the aqueous sulphuric acid to a strength of more than 80 w-%. As indicated above, since the present invention solves problems related to corrosion, there is typically no need for a strengthening tower. Omitting such a tower decreases the investment costs, because, as indicated above, plastic materials cannot be used in a strengthening tower because of the high temperatures involved with strengthening.
[0035] As evidenced by
[0036] For controlling the strength of the aqueous sulphuric acid H.sub.2SO.sub.4, the system 100 may comprise a first regulator 460, such as a valve 460, configured to regulate the flow of aqueous sulphuric acid H.sub.2SO.sub.4 from the process. Referring to
[0037] For controlling the strength of the aqueous sulphuric acid H.sub.2SO.sub.4, the system 100 may comprise a second regulator 465, such as a valve 465, configured to regulate the flow of water into the process. Referring to
[0038] In addition, the system 100 may comprise a sensor 470 configured to give information indicative of the strength of the aqueous sulphuric acid. The sensor 470 may be configured to measure at least one of electrical conductivity, electrical resistivity, density (i.e. specific mass), and molarity (e.g. by titration), of the aqueous sulphuric acid. As known, the electrical resistivity (and conductivity) correlates with the pH. The system may comprise a processing unit 475 configured to receive the information indicative of the strength of the aqueous sulphuric acid from the sensor 470, and by using this information control at least one of the first regulator 460 and the second regulator 465.
[0039] In a typical process, the gas containing SO.sub.3 further contains steam to such an amount that water needs not to be added to process after the process has started. Moreover, in such a case the molar amount of aqueous sulphuric acid that is removed from the process is substantially the same as the molar amount of condensed steam. Typically, the steam to SO.sub.3 ratio of the gas containing SO.sub.3 is such that the final strength of the aqueous sulphuric acid is in the range of from 60 w-% to 75 w-%, when no additional water is fed to the process e.g. through the second valve 465 after the process has started. As indicated above, the strength may be controlled (i.e. decreased) by feeding some water or steam to the process.
[0040] In an embodiment, the system comprises a sensor configured to give information on the surface level of the aqueous sulphuric acid within the condensation tower 300. Provided that the surface level rises above a limit, aqueous sulphuric acid may be removed from the process. Aqueous sulphuric acid may be removed from the process to such an amount that the surface level of the aqueous sulphuric acid within the condensation tower 300 lowers below the limit or another limit. In a corresponding embodiment of the method, water is fed to the condensation tower 300 only initially, when the process is started.
[0041] Because the reaction of SO.sub.3 with H.sub.2O is exothermic, if no further cooling was done, the aqueous sulphuric acid within the condensation tower 300 would heat up. This could pose problems related to safety, when plastic materials are used in the condensation tower 300.
[0042] Therefore, an embodiment of the system 100 comprises a second heat exchanger 420. The second heat exchanger 420 comprises a first inlet 422 for hot aqueous sulphuric acid, a first outlet 424 for cooled aqueous sulphuric acid, a second inlet 426 for coolant (i.e. cooling medium) and an second outlet 428 for the coolant. In the embodiment, the pump 322 is pump configured to pump aqueous sulphuric acid to the first inlet 422 of the second heat exchanger 420. Moreover, the pipeline 324 is configured to convey cooled aqueous sulphuric acid from the first outlet 424 of the second heat exchanger 420 to the second nozzle 326; and a pipeline 430 is configured to convey aqueous sulphuric acid from the reaction chamber 312 of the condensation tower 300 to the first inlet 422 of the second heat exchanger 420. When present, the second heat exchanger 420 can be considered to be a part of the means 320 for circulating the aqueous sulphuric acid within the reaction chamber 312 by spraying in order to strengthen the aqueous sulphuric acid.
[0043] A corresponding embodiment of the method comprises cooling the aqueous sulphuric acid before spraying it onto the gas containing sulphur trioxide in the condensation tower 300. In particular, a corresponding embodiment of the method comprises cooling the aqueous sulphuric acid in between [i] taking the aqueous sulphuric acid out from the condensation tower 300 and [ii] spraying it onto the gas containing sulphur trioxide in the condensation tower 300. As indicated above, the aqueous sulphuric acid is cooled in the second heat exchanger 420 and conveyed through the pipelines 430 and 324 from the condensation tower 300 to the second nozzle 326.
[0044] To prevent droplets of aqueous sulphuric acid from escaping from the condensation tower 300, in an embodiment, the condensation tower 300 comprises a first droplet separator 330. The first droplet separator is arranged above the reaction chamber 312 or in the upper part of the reaction chamber 312 of the condensation tower 300. The droplet separator 330 is configured to arrest some droplets of the aqueous sulphuric acid sprayed through the second nozzles 326, in order to prevent these from flowing with the flue gas out of the condensation tower 300.
[0045] Referring to
SO.sub.2+O.sub.2SO.sub.3+heat
[0046] The oxidization reaction is preferably catalysed using a catalyst, such as vanadium pentoxide V.sub.2O.sub.5 and/or platinum Pt.
[0047] The converter 500 comprises an inlet arrangement 502 for receiving sulphur dioxide SO.sub.2 and oxygen O.sub.2. The inlet arrangement 502 may comprise a first inlet for receiving gas comprising SO.sub.2 but free from O.sub.2 and a second inlet for receiving other gas comprising O.sub.2. The inlet arrangement 502 may comprise only a first inlet for receiving gas comprising SO.sub.2 and O.sub.2. The inlet arrangement 502 may comprise a first inlet for receiving gas comprising SO.sub.2 (optionally comprising also O.sub.2) and a second inlet for receiving other gas comprising O.sub.2 (optionally free from SO.sub.2). The converter 500 comprises an outlet 504 for gas containing sulphur trioxide SO.sub.3. The converter 500 comprises catalyst 510, such as V.sub.2O.sub.5 and/or Pt, for converting at least some of the sulphur dioxide SO.sub.2 and the oxygen O.sub.2 to sulphur trioxide SO.sub.3. The system 100 comprises a pipeline 440 configured to convey gas containing sulphur trioxide SO.sub.3 from the outlet 504 of the converter 500 to first inlet 212 of the pre-cooling unit 200.
[0048] The corresponding method comprises receiving sulphur dioxide SO.sub.2 and oxygen O.sub.2, both of them contained in some gas or gases. The method comprises catalytically oxidizing at least some of the sulphur dioxide SO.sub.2 to sulphur trioxide SO.sub.3 in the converter 500, thereby producing the gas containing sulphur trioxide SO.sub.3. The method comprises conveying the gas containing sulphur trioxide SO.sub.3 to the pre-cooling unit 200. An embodiment comprises using V.sub.2O.sub.5 and/or Pt to catalytically oxidize SO.sub.2 to SO.sub.3.
[0049] The oxidization reaction is somewhat sensitive to temperature. Typical catalysts perform well at temperature above 400 C. However, the reaction favours formation of SO.sub.3 at low temperatures. Therefore, in an embodiment of the method, a reaction temperature in the converter 500 is adjusted to be from 350 C. to 480 C., such as from 400 C. to 480 C. The reaction temperature refers to the temperature within the converter 500 at a point that is in the middle between the inlet arrangement 502 and the outlet 504 along the flow path of the gas within the converter 500. The temperature in the converter 500 or of the converter 500 may be adjusted by using steam H.sub.2O(g) from a boiler 610. Preferably, some steam from the boiler 610 is fed to the converter 500 for adjusting the temperature within the converter 500. As indicated in
[0050] The balance of the oxidization reaction depends also on the ratio of oxygen to sulphur dioxide. Typically the molar ratio of O.sub.2 to SO.sub.2 is more than 3, such as at least 5.
[0051] A corresponding system 100 comprises means for adjusting the temperature of the converter 500. Such means may comprise a heater configured to heat the gas containing SO.sub.2 and/or the converter 500. A corresponding system 100 may comprise a boiler 610 configured to produce steam and a pipeline 612 for conveying the steam and from bringing the steam in contact with the gas containing SO.sub.2. The system 100 may comprise a control unit 614 configured to control the amount of steam in such a way that the reaction temperature in the converter 500 is within the aforementioned limits.
[0052] Because the oxidization reaction is exothermic, the temperature of the gas rises in the converter 500. Typically, the temperature of the gas at the outlet 504 of the converter 500 is from 460 C. to 480 C.
[0053] Even if the catalyst, the process temperature, and the molar ratio are suitably selected, the conversion efficiency of the converter 500 is not necessarily 100%. Typically, the conversion efficiency is at least 90%, i.e. at least 90 v-% of SO.sub.2 is converted to SO.sub.3. Even more typically, the conversion efficiency is in the range of from 93% to 98%. Therefore, the gas indicated by Flue in
[0054] In an embodiment, circulation of the gas comprising SO.sub.3 is enhanced with a pump or pumps 480a, 480b (see
[0055] When the pump (480a or 480b) or the pumps (480a and 480b) is/are used, one does not need to use additional carrier gas for conveying the gas containing SO.sub.2 or SO.sub.3. Therefore, the obtainable strength of the aqueous sulphuric acid is reasonably high. For example, in case medium-pressure steam was used to carry the gas containing SO.sub.2 or SO.sub.3, the steam would dilute the aqueous sulphuric acid.
[0056] Examples of suitable pumps and pump configurations in such systems are disclosed e.g. in the patent WO2010/019079. The document discloses liquid ring pumps (1a and 1b therein), equivalent to the pumps 480a, 480b discussed above. Such pump solutions are incorporated by reference to the present embodiments.
[0057] In an embodiment, the system 100 further comprises a pulp mill 600. A pulp mill 600 refers to an arrangement that converts wood chips or other plant fibre source into fibre boards. The fibre boards can be shipped to a paper mill for further processing. The pulp mill 600 may be a Kraft mill (i.e. a sulphate mill) or a sulphite mill. In an embodiment, the pulp mill 600 is a sulphate pulp mill. The aforementioned boiler 610 may be a part of the pulp mill 600 such as the sulphate pulp mill 600.
[0058] As a side product, the pulp mill 600 is configured to produce at least some gas containing sulphur dioxide SO.sub.2. The system 100 comprises a pipeline 602 configured to convey the gas containing sulphur dioxide from the pulp mill 600 to the inlet arrangement 502 of the converter 500. In such a system, the benefits are three-fold. First the sulphur dioxide, which has a pungent odour, can be safely removed from the pulp mill 600, thus reducing environmental disadvantages. Second, by using SO.sub.2, aqueous sulphuric acid can be made. Third, since the pulp mill 600 requires some dilute sulphuric acid for operation, the produced aqueous sulphuric acid can be utilized in the pulp mill 600. To this end, an embodiment of the system 100 comprises a pipeline 604 for conveying the aqueous sulphuric acid from the condensation tower 300 to the pulp mill 600.
[0059] The corresponding method comprises separating some gas containing sulphur dioxide from a liquor circulation of a pulp mill 600 and conveying the gas containing sulphur dioxide to the converter 500. For the details of the liquor circulation of the sulphate pulp mill, see the patent SE 510 171. An embodiment comprises conveying at least some of the produced aqueous sulphuric acid to a pulp mill. An embodiment comprises conveying at least some of the produced aqueous sulphuric acid to the same pulp mill 600 from which the gas containing SO.sub.2, which is converted to SO.sub.3 in the converter 500 and to H.sub.2SO.sub.4 in the condensation tower 300, is received in to the converter 500.
[0060] As indicated above, the temperature in the pre-cooling unit 200 is high. Moreover, both SO.sub.3 and H.sub.2SO.sub.4 are very corrosive. Therefore, the corrosion and heat resistance requirements of the materials of the pre-cooling unit 200 are high. Thus, the materials of the pre-cooling unit 200 are expensive. For this reason alone, the pre-cooling unit 200 should be relatively small, i.e. smaller than the condensation tower 300. Moreover, when the pre-cooling unit 200 is small in comparison to the condensation tower 300, the formation of H.sub.2SO.sub.4 can be shifted from the pre-cooling unit 200 mainly to the condensation tower 300. This helps the selection of the materials for the pre-cooling unit 200, as less H.sub.2SO.sub.4 will be produced therein.
[0061] For these reasons and with reference to
[0062] The condensation tower 300 has a second cross sectional area A.sub.300 on a plane having a surface normal that is parallel to the direction of flow of gases within the condensation tower 300. The second cross sectional area A.sub.300 refers to the area in the aforementioned plane limited by such wall(s) of the condensation tower 300 that limit the flow of the gas comprising SO.sub.3. Such wall may be the walls 310, or the flow may be further limit by additional walls limiting the reaction chamber 312. Correspondingly, the second cross sectional area A.sub.300 refers to the area of the flow channel of the condensation tower 300, in which the gas comprising SO.sub.3 is configured to flow. Within the condensation tower 300, the direction of flow of gases is parallel to the direction of the flow velocity v.sub.2 of the gas containing SO.sub.3 in the condensation tower 300. The velocity v.sub.2 shown in
[0063] To have a lot of H.sub.2SO.sub.4 being produced in the condensation tower 300, the flow velocity of the gas comprising sulphur trioxide should be larger in the pre-cooling unit 200 than in the condensation tower 300. Therefore, in an embodiment, the second cross sectional area A.sub.300 is greater than the first cross sectional area A.sub.200 (i.e. A.sub.300>A.sub.200). In an embodiment, the second cross sectional area A.sub.300 is at least two times or at least three times the first cross sectional A.sub.200 area (i.e. A.sub.3002A.sub.200 or A.sub.3003A.sub.200). As indicated in
[0064] When using such a system 100, i.e. in an embodiment of a method, the gas comprising sulphur trioxide has a first flow velocity v.sub.1 (see
[0065] Referring to
[0066] As an alternative or in addition to the solution of
[0067] However, it has been noticed that the most corrosive points within the pre-cooling unit 200 are the ones, where the aqueous sulphuric acid condensates on the walls of the pre-cooling unit 200, in the inner side thereof. It has been found that most of the interior of the pre-cooling unit can be made acid proof in such a way that only a small corrosive part of the pre-cooling unit 200 needs to be replaced for every now and then for maintenance. The part that is designed to corrode during use will be referred to as a sacrificial lid 240 (see
[0068] Referring to
[0069] For better acid proofness, in an embodiment, the pre-cooling unit 200 comprises a second inner wall 254 laterally surrounding the first inner wall 252. The second inner wall 254 is made of acid proof material, preferably from acid resistant bricks. The pre-cooling unit 200 may comprise mortar in between the first inner wall 252 and the second inner wall 254.
[0070] When the first inner wall 252 is made from acid free bricks, the thickness of the first inner wall 252 is preferably from 80 mm to 150 mm, such as from 90 mm to 110 mm, such as 100 mm. When the second inner wall 254 is made from acid free bricks, the thickness of the second inner wall 254 is preferably from 80 mm to 150 mm, such as from 90 mm to 110 mm, such as 100 mm. These thicknesses may be applicable also to other suitably acid proof materials.
[0071] To thermally insulate the inner wall(s) 252, 254 from the outer wall 260, and in this way helping to maintain the proper reaction temperature within the reaction chamber 202, the pre-cooling unit 200 comprises a thermally insulating inner wall 256 laterally surrounding the reaction chamber 202 of the pre-cooling unit 200 and laterally surrounded by an outer wall 260 of the pre-cooling unit 200. Preferably, the thermally insulating inner wall 256 laterally surrounds the first inner wall 252, and if present, also the second inner wall 254.
[0072] To have the thermally insulating inner wall 256 reasonably thermally insulating, the material of the thermally insulating inner wall 256 may have a thermal conductivity of at most 0.1 W/m.Math.K, preferably at most 0.05 W/m.Math.K at a temperature 10 C. The thermally insulating inner wall 256 may be made of foam glass. In an embodiment, the thermally insulating inner wall 256 is made of foam glass and the thickness t.sub.256 of the thermally insulating inner wall 256 is from 60 mm to 160 mm, such as from 70 mm to 100 mm, such as 80 mm; for it to have suitable thermal insulation properties. Preferably, the ratio (/t.sub.256) of the thermal conductivity and the thickness t.sub.256 is at most 5 W/m.sup.2.Math.K, more preferably at most 1 W/m.sup.2.Math.K, as calculated at the temperature 10 C. The pre-cooling unit 200 may comprise mortar in between the walls 252 and 256 and/or in between the walls 254 and 256.
[0073] To further protect the outer wall 260 from corrosion, the outer wall 260 may comprise, on the inner side thereof, a first lining 258. The first lining 258 may be e.g. a heat resistant polymer lining, such as a rubber lining. The heat resistance of the first lining 258 may be e.g. at least 100 C. It should be noted that because the outer wall 260 is in contact with the environment and may conduct heat reasonably well, the temperature of the second lining 258, in use, may be reasonably low. Moreover, the thermal insulation provided by the other walls (252, 254, 256) will help to keep the temperature of the first lining 258 reasonably low. The pre-cooling unit 200 may comprise mortar in between the first lining 258 and the thermally insulating inner wall 256.
[0074] In general, acid proof brick walls having an arbitrary shape are hard to manufacture. Therefore, the ceiling of the reaction chamber 202 of the pre-cooling unit 200 may be hard to insulate from the reaction chamber in an acid proof manner. To simplify the construction, in an embodiment, the pre-cooling unit 200 comprises a sacrificial lid 240. The sacrificial lid 240 is configured to corrode during use, and is thus arranged to be easily replaceable.
[0075] As indicated in
[0076] As indicated in
[0077] In addition, the sacrificial lid 240 comprises a second lining 244. The second lining 244 need not fully cover a side of the material 241. The purpose of the second lining is to protect at least a part of the layer 241 from liquid aqueous sulphuric acid. Therefore, the second lining 244 is arranged in between the interior of the pre-cooling unit 200 and the material 241. In other words, the second lining 244 faces towards the interior of the pre-cooling unit 200. The second lining 244 should be heat resistant to at least the boiling point of the aqueous sulphuric acid. In an embodiment, the second lining 244 is heat resistant to at least 230 C., preferably at least 300 C. In an embodiment, the second lining 244 comprises plastic material. In an embodiment, the second lining 244 comprises fluorinated plastic material. In an embodiment, the second lining 244 consists of plastic material. In an embodiment, the second lining 244 consists of fluorinated plastic material.
[0078] As indicated in
[0079] Furthermore, in an embodiment, the pre-cooling unit 200 comprises a cooling channel 248 that is arranged in contact with the sacrificial lid 240. The cooling channel 248 is arranged in contact with the sacrificial lid 240 in a thermally conductive manner. In use, some liquid coolant may flow in the cooling channel 248. The pre-cooling unit 200 comprises an inlet 248a for this coolant and an outlet 248b for this coolant (see
[0080] Preferably, the cooling channel 248 is arranged on an opposite side of the sacrificial lid 240 with respect to the second lining 244. Moreover, preferably the cooling channel 248 is arranged on the sacrificial lid 240 to such a location that a straight line L that is parallel to a surface normal N of the sacrificial lid 240 penetrates both the cooling channel 248 and the second lining 244. This has the technical effect, that as the coolant flowing in the cooling channel 248 cools the sacrificial lid 240 locally near the channel 248 itself, the aqueous sulphuric acid will condense at the point, where the cooling channel 248 is located; however, on the other side of the lid 240. Thus, the aqueous sulphuric acid will condense at a point comprising second lining 244, which protects the material 241 from corrosion at that point. As indicated in
[0081] However, as indicated in
[0082] As indicated in
[0083] Since the pre-cooling unit 200 may be replaceable, it is evident, that the pre-cooling unit 200 can be sold even without the rest of the system 100. In this way, a pre-cooling unit 200 may be seen as an embodiment independent of the other components of the system.
[0084] Referring to
[0085] In connection with a pulp mill, an extremely usable type of scrubber is a bisulphite scrubber. In a bisulphite scrubber, the sulphur dioxide is reacted with an aqueous solution of alkaline, thereby producing some bisulphite. As an example, an aqueous solution of NaOH may be used to scrub SO.sub.2, resulting in sodium sulphite Na.sub.2SO.sub.3 and/or sodium bisulphite NaHSO.sub.3, depending on the alkalinity of the scrubbing liquid. If the pH of the scrubbing liquid is about 10 or more, substantially only Na.sub.2SO.sub.3 and water will be produced by the reaction of SO.sub.2 with NaOH.
[0086] Other possible alkalis include potassium hydroxide KOH and ammonia water NH.sub.3(aq). Using them in the scrubber 700 produces corresponding sulphite and/or bisulphite.
[0087] As known to a skilled person, such sulphites and/or bisulphites are used in a pulp mill. More precisely, such sulphites and/or bisulphites are needed in both a sulphate pulp mill (i.e. a Kraft pulp mill) and a sulphite pulp mill; even if a sulphite mill uses sulphites in larger amounts. For example, in a sulphate mill, sulphites and/or bisulphites may be utilized is the process of scrubbing vent gases containing chlorine dioxide ClO.sub.2. In this way, the reaction products of the scrubber 700 are usable in the pulp mill 600 regardless of its type. A system comprises a channel 752 for conveying some reaction products from the scrubber 700 to the pulp mill 600. Such a means may comprise a pipeline 752 configured for the purpose. The reaction product may comprise at least one of a sulphite and a bisulphite. The reaction product may comprise at least one of sodium sulphite, sodium bisulphite, potassium sulphite, potassium bisulphite, ammonium sulphite (NH.sub.4).sub.2SO.sub.3, and ammonium bisulphite NH.sub.4HSO.sub.3.
[0088]
[0089] A corresponding method comprises removing at least some SO.sub.2 from the flue (i.e. the remaining gas) that is removed from the condensation tower 300. The SO.sub.2 may be removed in a scrubber 700. The SO.sub.2 may be removed in a wet scrubber 700. The SO.sub.2 may be removed in a bisulphite scrubber 700 using an alkaline scrubbing solution.
[0090] The scrubber 700 comprises an outlet 750 for letting out at least some of the liquid reaction products. An embodiment comprises a channel 752, such as a pipeline 752, configured to convey at least some of the solid and/or liquid reaction products from the outlet 750 to a pulp mill 600. Another channel 754 may be used to convey another part of the reaction products e.g. to a waste treatment plant, e.g. if the scrubber is a two stage scrubber.