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WO2003037790A2 - Procede et appareil de production d'acide sulfurique - Google Patents

Procede et appareil de production d'acide sulfurique Download PDF

Info

Publication number
WO2003037790A2
WO2003037790A2 PCT/EP2002/011231 EP0211231W WO03037790A2 WO 2003037790 A2 WO2003037790 A2 WO 2003037790A2 EP 0211231 W EP0211231 W EP 0211231W WO 03037790 A2 WO03037790 A2 WO 03037790A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
gas
absorber
packed absorber
sulfuric acid
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.)
Ceased
Application number
PCT/EP2002/011231
Other languages
English (en)
Other versions
WO2003037790A3 (fr
Inventor
Karl-Heinz Daum
Wolfram Schalk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Outokumpu Oyj
Original Assignee
Outokumpu Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Outokumpu Oyj filed Critical Outokumpu Oyj
Priority to AU2002346966A priority Critical patent/AU2002346966A1/en
Publication of WO2003037790A2 publication Critical patent/WO2003037790A2/fr
Publication of WO2003037790A3 publication Critical patent/WO2003037790A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C01B17/80—Apparatus
    • C01B17/806—Absorbers; Heat exchangers
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1418—Recovery of products
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • 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
    • B01D53/14—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 by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • This invention relates to a process and an apparatus for producing concentrated sulfuric acid by means of an absorption tower.
  • Drying and absorption towers in plants for producing sulfuric acid are traditionally designed as countercurrent packed columns, wherein the gas is generally introduced into the packed bed from below and the sulfuric acid is guided countercurrently, i.e. is charged onto the bed from above.
  • various commercially available packings mostly as random packing, but also as structured packing.
  • ceramic materials In general, there are used ceramic materials.
  • the absorption towers are made both of steel with an inner lining, such as e.g. a plastic film plus acid-resistant brick lining, and also of pure stainless steel.
  • gases of a higher concentration e.g.
  • H 2 S0 4 Heat Recovery System
  • the wall of the absorption tower is made of stainless steel, which leads to a very narrow restriction of the admissible H 2 S0 4 concentration to e.g. 99.0 % to 99.6 % H 2 S0 4 .
  • the water for forming the sulfuric acid corresponding to the amount of S0 3 absorbed must be added in a suitable apparatus outside the tower under controlled conditions. The required sulfuric acid concentration is adjusted thereby.
  • the high acid concentration leads to an increased formation of acid fumes and an additional effort for the filtration and separation thereof. Deviations from the admissible acid concentration lead to extremely high corrosion rates and an immediate destruction of the apparatus involved.
  • DE-C-19800800 describes a two-stage process, in which the first stage is a Venturi absorber and the second stage is a packed tower.
  • the process employs separate circuits and conventional acid concentrations of e.g. 95 % to 100 % H 2 S0 4 . Due to the higher corrosion rate at this acid concentration, the apparatus must, however, partly be made of stainless steels of a very high quality, e.g. 1.4575. These materials can be used in a larger application range of the acid concentration, but they have the disadvantage of the extremely high costs and the restricted processability, such as e.g. welding. In plants of this type, the addition of the water for forming sulfuric acid is usually effected inside the Venturi absorber, either at the bottom or directly in the gas phase.
  • the latter can lead to the formation of extreme amounts of acid fumes and an additional effort for the filtration and separation thereof.
  • the process is suitable for recovering the absorption heat in the form of steam for about 90 %. Both processes are very sensitive as regards malfunctions and have very high investment costs due to the materials used.
  • this object is solved in that inside a packed absorber an empty tube is integrated, wherein the gas and the acid are introduced at the head of the empty tube and are cocurrently passed into the lower portion of the succeeding packed absorber, subsequently the gas is passed upwards through the packings, further acid is introduced into the packed absorber above the packings and countercurrently mixes with the gas in the packing region, the gas being withdrawn from the head of the packed absorber and the acid being discharged from the bottom of the packed absorber.
  • the absorption means may be made of a steel jacket with inner brick lining, completely of stainless steel or as a combination of a brick-lined design with stainless steel and can be operated for a very wide temperature range of 50 to 250°C. Therefore, an application in a conventional design can be used unchanged both for acid temperatures around 70-120°C (with heat dissipation via cooling water) and for heat recovery with temperatures of 160-230°C. A retrofitting or conversion of a plant of conventional technology to heat recovery is thus easily possible, namely exclusively by changing external equipment parts.
  • the apparatus can be operated with conventional acid concentrations, which considerably reduces the formation of acid fumes.
  • a special water mixing means is not required, as industrially successful means are employed.
  • the reduced formation of acid fumes provides for the use of coalescers/demisters for the separation thereof, and the expensive candle-type filters can be omitted.
  • the absorber (1 ) comprises a packed absorber (2) with an integrated empty tube (3).
  • the empty tube usually is made of high-alloy stainless steel and, to improve the mixing of the gas with the sulfuric acid, can have a Venturi nozzle (4) in the upper portion.
  • the empty tube (3) is centrically held in the packed absorber (2) by means of two gas-permeable reinforcements (5).
  • the upper portion of the packed absorber is made of steel or stainless steel, whereas the bottom wall (6) of the packed absorber (2) is made of steel in combination with a brick lining or of stainless steel with or without brick lining.
  • the packing (7) may consist of loose material or of a structured packing. As feed materials, in particular ceramic materials can be used.
  • this gas consists of the S0 3 to be absorbed in a concentration of 0.1 to 20 vol-% (the rest are inert gases) and has a temperature of 120-250°C.
  • sulfuric acid is introduced into the empty tube (3) with a concentration of 98- 99 % and a temperature of 60-130°C. Due to the Venturi nozzle (4), an acceleration of the flow takes place and thus a cocurrent mixing between gas and acid.
  • the acid At the bottom end of the empty tube (3), the acid has a concentration which is increased corresponding to the absorption and a corresponding temperature of 80-150°C.
  • the gas consists of an inert component and the residual non-absorbed S0 3 and has a temperature which at this point is approximately equal to the acid temperature.
  • the sulfuric acid flows to the bottom of the absorber and is discharged through the outlet (10) for further processing.
  • the gas rises and flows through the packing (7) from the bottom to the top.
  • further sulfuric acid with 98-99 % H 2 S0 4 and a temperature of 60-130°C is introduced into the absorber through the connections (11 ) and distributed rather uniformly over the diameter of the packing (7) by means of a system of distributors (12).
  • gas and acid are mixed countercurrently.
  • the acid Upon flowing through the packing (7), the acid has a temperature of 60-130°C and a concentration which is increased corresponding to the absorption.
  • the gas exclusively consists of the inert component and has a temperature which is approximately equal to that of the acid added.
  • the gas flows through the reinforcements (5) in the middle portion of the absorber and leaves the absorber (1) through the outlet (13) for further processing.
  • the required process water is supplied in the interior of the means, and the concentration is thereby reduced to 98-99 % H 2 S0 .
  • a gas from a sulfuric acid plant on the basis of the combustion of elementary sulfur is supplied to the absorption means as follows:
  • a gas from a metallurgical sulfuric acid plant on the basis of the use of oxygen- enriched melting is supplied to the absorption means as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Industrial Gases (AREA)

Abstract

L'invention concerne un procédé et un appareil de production d'acide sulfurique concentré au moyen d'un absorbeur. Pour l'absorption de grandes quantités de SO3 (ou H2O) dans de l'acide sulfurique à concentration différente, un tube vide est intégré à l'intérieur dudit absorbeur garni, le gaz et l'acide étant introduits dans la partie supérieure du tube vide et passant de manière cocourante dans la partie inférieure dudit absorbeur garni suivant. Le gaz remonte ensuite à travers la garniture, de l'acide supplémentaire est introduit à l'intérieur de l'absorbeur garni au-dessus de la garniture et est mélangé à contre-courant avec le gaz dans la région de la garniture, le gaz provenant de la partie supérieure de l'absorbeur fixe étant retiré et l'acide étant évacué du fond de l'absorbeur garni.
PCT/EP2002/011231 2001-10-31 2002-10-08 Procede et appareil de production d'acide sulfurique Ceased WO2003037790A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002346966A AU2002346966A1 (en) 2001-10-31 2002-10-08 Process and apparatus for producing sulfuric acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10153692.5 2001-10-31
DE10153692A DE10153692A1 (de) 2001-10-31 2001-10-31 Verfahren und Vorrichtung zur Herstellung von Schwefelsäure

Publications (2)

Publication Number Publication Date
WO2003037790A2 true WO2003037790A2 (fr) 2003-05-08
WO2003037790A3 WO2003037790A3 (fr) 2003-10-16

Family

ID=7704303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/011231 Ceased WO2003037790A2 (fr) 2001-10-31 2002-10-08 Procede et appareil de production d'acide sulfurique

Country Status (5)

Country Link
AR (1) AR036964A1 (fr)
AU (1) AU2002346966A1 (fr)
DE (1) DE10153692A1 (fr)
PE (1) PE20030485A1 (fr)
WO (1) WO2003037790A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007076921A3 (fr) * 2006-01-02 2007-08-23 Outotec Oyj Systeme de refroidissement de gaz metallurgiques
WO2017192264A1 (fr) 2016-05-03 2017-11-09 Chemetics Inc. Système d'acide sulfurique à bon rendement énergétique pour environnements humides
CN119951280A (zh) * 2025-03-18 2025-05-09 湖北瑞力源环保科技有限公司 一种盐酸再生酸雾的气体排放处理装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1571772B2 (de) * 1966-03-10 1976-07-08 Metallgesellschaft Ag, 6000 Frankfurt Absorptionsvorrichtung
DE2510241A1 (de) * 1975-03-08 1976-09-23 Bayer Ag Verfahren zur absorption von gasfoermigen bestandteilen aus gasen
DE2755327A1 (de) * 1977-12-12 1979-06-13 Davy Powergas Gmbh Vorrichtung zur absorption von schwefeltrioxid oder wasserdampf aus einem gas
US4576813A (en) * 1983-07-05 1986-03-18 Monsanto Company Heat recovery from concentrated sulfuric acid

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007076921A3 (fr) * 2006-01-02 2007-08-23 Outotec Oyj Systeme de refroidissement de gaz metallurgiques
EA013961B1 (ru) * 2006-01-02 2010-08-30 Оутотек Ойй Охладительная система для металлургических газов
AU2006332210B2 (en) * 2006-01-02 2011-02-03 Metso Metals Oy Quench system for metallurgical gases
AP2591A (en) * 2006-01-02 2013-02-05 Outotec Oyj Quench system for metallurgical gases
KR101441143B1 (ko) * 2006-01-02 2014-09-17 오토텍 오와이제이 야금 가스용 퀀치 시스템
WO2017192264A1 (fr) 2016-05-03 2017-11-09 Chemetics Inc. Système d'acide sulfurique à bon rendement énergétique pour environnements humides
US10532929B2 (en) 2016-05-03 2020-01-14 Chemetics Inc. Energy efficient sulfuric acid system for humid environments
CN119951280A (zh) * 2025-03-18 2025-05-09 湖北瑞力源环保科技有限公司 一种盐酸再生酸雾的气体排放处理装置
CN119951280B (zh) * 2025-03-18 2026-01-06 湖北瑞力源环保科技有限公司 一种盐酸再生酸雾的气体排放处理装置

Also Published As

Publication number Publication date
DE10153692A1 (de) 2003-05-15
AR036964A1 (es) 2004-10-13
AU2002346966A1 (en) 2003-05-12
PE20030485A1 (es) 2003-06-30
WO2003037790A3 (fr) 2003-10-16

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