WO2008003297A2 - Verfahren und anlage zum konzentrieren metallsulfathaltiger schwefelsäure - Google Patents
Verfahren und anlage zum konzentrieren metallsulfathaltiger schwefelsäure Download PDFInfo
- Publication number
- WO2008003297A2 WO2008003297A2 PCT/DE2007/001169 DE2007001169W WO2008003297A2 WO 2008003297 A2 WO2008003297 A2 WO 2008003297A2 DE 2007001169 W DE2007001169 W DE 2007001169W WO 2008003297 A2 WO2008003297 A2 WO 2008003297A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- evaporator
- stage
- acid
- heat exchangers
- circulation
- Prior art date
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
- C01B17/88—Concentration of sulfuric acid
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
Definitions
- the invention relates to a method for concentrating metal sulfate-containing sulfuric acid in an evaporator system with at least two forced circulation evaporator stages connected in series, consisting of evaporator, circulation pump, heat exchanger and connecting pipelines.
- water is evaporated from this sulfuric acid in a first steam-heated evaporator stage at 100 to 160 0 C and a pressure of 0.05 to 0.3 MPa.
- the water vapor generated in the first stage is used in the second evaporator stage as a heating medium in which at 70 to 125 ° C and a pressure of 0.003 to 0.02 MPa further water is evaporated.
- a third evaporator stage heated with live steam at 80 to 150 ° C. and from 0.003 to 0.02 MPa, further water is evaporated until the desired sulfuric acid concentration is reached.
- the invention also relates to a system for carrying out this method.
- Tube heat exchangers with graphite tubes are used as heat exchangers (EP 0 418 544 A1, EP 0 425 000 A1 (page 3, line 3), EP 0 476 744 A1, EP 1 098 844 B1) 5 as centrifugal pumps made of silicon iron castings.
- a general problem of these methods is the encrustation of the heat exchange surfaces, but also of all other acid-contacting surfaces, the deposits may consist either of water-insoluble compounds such as calcium sulfate, silica and titanium dioxide or mixtures of these compounds with soluble metal sulfates.
- Problems arise in particular the first case because the mechanical cleaning with pressurized water are limited by the limited strength of graphite. At least partial dissolution and softening by the action of chemicals such as hydrofluoric acid causes problems because of the relatively large volumes. Therefore, z. B. proposed to avoid the deposition of calcium sulfate by adhering to certain acid concentrations (EP 1 098 844 Bl).
- EP 0 476 744 A1 it is proposed in EP 0 476 744 A1 to divide the acid streams so that mixtures of iron sulfate and insoluble compounds are deposited in all evaporator stages.
- a disadvantage of this method is that due to the increased acid concentration in the first evaporator stage, the dew point of the vaporized Water (vapors) is lowered and thus in the second evaporator stage, in which these vapors are used as a heating medium, less water evaporates.
- axial circulation pumps require higher engine power at a reduced volumetric flow rate due to the increased pressure drop.
- a general problem of concentrating dilute acid in forced circulation evaporators with shell and tube heat exchangers and axial circulation pumps is the occasional chipping of deposits from the walls of the evaporators and piping. These are promoted as a result of the gentle promotion by the axial pumps up to the tubes of the heat exchanger and block them. The dissolution of metal sulfates from blocked pipes by means of hot water is very time consuming.
- the object of the present invention is to provide a method and a system suitable for this purpose, with which the abovementioned disadvantages are largely avoided.
- This object is achieved in that are used as heat exchangers plate heat exchangers made of graphite and as circulation pumps radial pumps, which allow lower circulation currents associated with greater temperature increase.
- the pressure in the heat exchangers is adjusted by androssehi of the exiting acid stream so that the boiling of the acid in the heat exchangers is safely avoided. This is preferably effected by a throttle or nozzle in the region of the introduction into the evaporator.
- Radial pumps and plate heat exchangers are preferably used when the circulated acid contains at most 10% by weight of solids. Therefore, a combination of the system according to the invention with radial pump and plate heat exchanger in the first evaporator stage and with traditional axial pump and tube bundle heat exchanger in the second and optionally third evaporator stage is advantageous.
- waste acid metal sulfate-containing sulfuric acid (hereinafter referred to as waste acid) (absolute) evaporated in a first evaporator stage at 100 to 160 0 C and a pressure of 0.05 to 0.3 MPa water
- the temperature of the means of radial pump in the circulation promoted acid in heated with steam steam plate heat exchangers by 5 to 25 K, preferably increased by 8 to 20 K, more preferably by 10 to 15 K.
- the ratio of the circulating volume flow to the injected dilute acid volume flow is set in the range from 10: 1 to 50: 1, preferably in the range from 12: 1 to 30: 1.
- the vapors leaving the evaporator are fed to the second evaporator stage as heating steam.
- the second stage of the evaporation is operated at 70 to 125 ° C and at a pressure in the range of 0.003 to 0.02 MPa (absolute).
- both Radial pumps and plate heat exchangers are installed as well as axial and shell and tube heat exchangers.
- the plate heat exchangers offer particular advantages when the salt content of the circulated acid is so low that only water-insoluble compounds are precipitated as deposits on the heat transfer surfaces. Due to the high turbulence less deposition occurs in the heat exchangers than in shell and tube heat exchangers. When the deposit has taken place, however, the plates can be exchanged for clean plates with little expenditure of time. The occupied boards can be cleaned mechanically, advantageously after prolonged exposure to chemicals such as hydrofluoric acid, without impairing plant operation.
- the process according to the invention for concentrating dilute acid in a two-stage evaporator plant can be carried out particularly advantageously.
- the second evaporator stage consists of an evaporator, an axial circulation pump and a shell-and-tube heat exchanger, into which the vapors from the first stage are introduced as heating medium.
- the first evaporator stage consists of an evaporator, one or more Radial Vietnamese spastic pump and one or more plate heat exchangers.
- the temperature in the second evaporator stage is kept constant in the range of 90 to 120 ° C., the pressure in the range of 0.003 to 0.015 MPa, in order to ensure a constant acid concentration in the range from 60 to 70% by weight (in the liquid phase).
- the temperature is increased in the range of 110 to 160 0 C during operation so that the reduced by deposits in the tube bundle heat exchanger of the second stage heat transfer is compensated.
- the proposed system offers the advantages of significantly lower investment costs and lower steam consumption compared to the prior art because the entire water evaporation takes place in two stages.
- dilute acid (24% H 2 SO 4 , 12.2% metal sulfates) is concentrated.
- metal sulfates By evaporation of 15 t / h of water, 13 t / h of a suspension containing 51% H 2 SO 4 and 25.3% metal sulfates are produced from 28 t / h of dilute acid.
- the evaporator stage 1 consists of a steel evaporator, which is internally leaded and lined with carbon stones.
- a circulation pump a radial pump made of silicon cast iron with a capacity of 560 m 3 / h and a head of 26 m is installed.
- 4 graphite plate heat exchangers SGL CARBON GROUP
- the steel pipes are lined with polytetrafluoroethylene (PTFE) Vaporizers and pipelines of the evaporator stage 2 are made of steel, lined with fluorine-containing polymer (PTFE) and bricked.
- PTFE polytetrafluoroethylene
- an axial pump with a capacity of 1800 m 3 / h and a head of 4.5 m is installed.
- the heated with the vapors from the first evaporator stage heat exchanger is a Graphitrohrbündel Anlagenmaster.
- the preheated to about 9O 0 C dilute acid is fed into the intake of the radial pump.
- the with 135 0 C leaving evaporator 1 circulating acid is heated in the plate heat exchangers to 146 ° C.
- the pressure in the evaporator is O 5 IlMPa (abs.).
- the feed of the circulating acid into the evaporator takes place through 4 nozzles, through which a pressure of 0.18 MPa (abs.) Is established in the lines in front of the nozzles.
- the casing side adjusts a temperature of 101 0 C.
- the temperature of the exiting from the heat exchanger circulating acid is 94 0 C.
- the pressure in the evaporator 2 is 0,005MPa (abs.).
- the temperature of the exiting recycle acid is increased according to the invention in the heat exchanger of stage 1 to 155 0 C, whereby the jacket temperature in Heat exchanger 2 is increased to 112 ° C.
- stage 1 After reaching this temperature in stage 1, the system is emptied and rinsed with water.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE112007002056T DE112007002056A5 (de) | 2006-07-03 | 2007-06-28 | Verfahren und Anlage zum Konzentrieren metallsulfathaltiger Schwefelsäure |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006030660 | 2006-07-03 | ||
DE102006030660.0 | 2006-07-03 | ||
DE102007005545.7 | 2007-02-05 | ||
DE102007005545A DE102007005545A1 (de) | 2006-07-03 | 2007-02-05 | Verfahren und Anlage zum Konzentrieren metallsulfathaltiger Schwefelsäure |
Publications (3)
Publication Number | Publication Date |
---|---|
WO2008003297A2 true WO2008003297A2 (de) | 2008-01-10 |
WO2008003297A3 WO2008003297A3 (de) | 2008-04-03 |
WO2008003297B1 WO2008003297B1 (de) | 2008-06-12 |
Family
ID=38724335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2007/001169 WO2008003297A2 (de) | 2006-07-03 | 2007-06-28 | Verfahren und anlage zum konzentrieren metallsulfathaltiger schwefelsäure |
Country Status (1)
Country | Link |
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WO (1) | WO2008003297A2 (de) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2004469A (en) * | 1977-09-21 | 1979-04-04 | Montedison Spa | Sulphuric acid concentration |
EP0022181A2 (de) * | 1979-06-13 | 1981-01-14 | Bayer Ag | Verfahren und Vorrichtung zum Regenerieren von Schwefelsäure |
EP0262510A2 (de) * | 1986-09-25 | 1988-04-06 | Bayer Ag | Verfahren zum Aufkonzentrieren von Schwefelsäure |
EP0297275A1 (de) * | 1987-06-04 | 1989-01-04 | Bayer Ag | Verfahren zur Herstellung von Titandioxid |
EP0425000A1 (de) * | 1989-10-27 | 1991-05-02 | METALLGESELLSCHAFT Aktiengesellschaft | Verfahren zum Konzentrieren einer Schwefelsäure und Wasser enthaltenden Flüssigkeit |
-
2007
- 2007-06-28 WO PCT/DE2007/001169 patent/WO2008003297A2/de active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2004469A (en) * | 1977-09-21 | 1979-04-04 | Montedison Spa | Sulphuric acid concentration |
EP0022181A2 (de) * | 1979-06-13 | 1981-01-14 | Bayer Ag | Verfahren und Vorrichtung zum Regenerieren von Schwefelsäure |
EP0262510A2 (de) * | 1986-09-25 | 1988-04-06 | Bayer Ag | Verfahren zum Aufkonzentrieren von Schwefelsäure |
EP0297275A1 (de) * | 1987-06-04 | 1989-01-04 | Bayer Ag | Verfahren zur Herstellung von Titandioxid |
EP0425000A1 (de) * | 1989-10-27 | 1991-05-02 | METALLGESELLSCHAFT Aktiengesellschaft | Verfahren zum Konzentrieren einer Schwefelsäure und Wasser enthaltenden Flüssigkeit |
Non-Patent Citations (2)
Title |
---|
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TANG, GUANGWEI ET AL: "Application of fluoroplastic- graphite plate heat exchanger in a smelter sulfuric acid system" XP002466933 gefunden im STN Database accession no. 2001:682802 & LIUSUAN GONGYE , (3), 32-34 CODEN: LIGOEH; ISSN: 1002-1507, 2001, * |
DATABASE COMPENDEX [Online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; KALASHNIKOV B G: "Dismountable plate heat exchangers for sulfuric acid production" XP002466932 Database accession no. EIX97483855090 & KHIM I NEFT MASHINOSTR; KHIMICHESKOE I NEFTYANOE MASHINOSTROENIE JULY-AUG 1997 MEZHDUNARODNAYA KNIGA, MOSCOW, RUSSIA, Nr. 4, Juli 1997 (1997-07), Seiten 23-24, * |
Also Published As
Publication number | Publication date |
---|---|
WO2008003297A3 (de) | 2008-04-03 |
WO2008003297B1 (de) | 2008-06-12 |
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