WO2017144593A1 - Procédé et appareil pour le traitement thermique de solides contaminés - Google Patents

Procédé et appareil pour le traitement thermique de solides contaminés Download PDF

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Publication number
WO2017144593A1
WO2017144593A1 PCT/EP2017/054183 EP2017054183W WO2017144593A1 WO 2017144593 A1 WO2017144593 A1 WO 2017144593A1 EP 2017054183 W EP2017054183 W EP 2017054183W WO 2017144593 A1 WO2017144593 A1 WO 2017144593A1
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WO
WIPO (PCT)
Prior art keywords
solids
reactor
gas
temperature
heat
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/EP2017/054183
Other languages
English (en)
Inventor
Bertold Stegemann
Ludwig Herrmann
Tanja SCHAAF
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.)
Outotec Finland Oy
Original Assignee
Outotec Finland Oy
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 Outotec Finland Oy filed Critical Outotec Finland Oy
Priority to CN201780010201.1A priority Critical patent/CN110214049A/zh
Priority to EP17710831.3A priority patent/EP3419747A1/fr
Publication of WO2017144593A1 publication Critical patent/WO2017144593A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • B01J6/004—Calcining using hot gas streams in which the material is moved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/34—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
    • C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00513—Controlling the temperature using inert heat absorbing solids in the bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst

Definitions

  • This invention relates to a process and an apparatus for the thermal treatment of contaminated solids, comprising a step (i) for preheating the solids in at least one preheating stage to a temperature between 100 and 600 °C with a heat- transfer medium, a step (ii) for heating the solids in a first reactor to a temperature between 600 and 1300 °C, whereby the impurities contained in the solids are partly expelled in gaseous form and a waste gas is obtained, a step (iii) directed to a thermal treatment of the solids in a second reactor at a temperature between 600 and 1300 °C, whereby impurities contained in the solids are at least partly driven out in gaseous form and a step (iv) routing of the off-gas into the at least one preheating stage as heat-transfer medium.
  • the thermal treatment of solids to remove impurities is known from a plurality of processes, such as e.g. the thermal decontamination of contaminated soils or the high-temperature degasification of coals and petroleum coke.
  • the heating of solids in the usual temperature range between 600 and 1300 °C however is very energy-intensive. An optimum energy recovery from the waste gases involved in these processes therefore is essential for the economy of such processes.
  • the contaminated solids initially are preheated in a process step (i) in at least one preheating stage in direct contact with the waste gas to a temperature between 100 and 600 °C, preferably however to a temperature which allows a largely technically expedient utilization of the sensible heat of the combustion gas released.
  • a process step (i) in at least one preheating stage in direct contact with the waste gas to a temperature between 100 and 600 °C, preferably however to a temperature which allows a largely technically expedient utilization of the sensible heat of the combustion gas released.
  • the solids preheated in this way are preheated in a first reactor to a temperature between 600 and 1300 °C, preferably 600 to 1200 °C, even more preferred 750 to 1000 °C, and the gaseous impurities contained therein are partly driven out, whereby an off-gas is obtained.
  • the so operated first process stage allows for the recovery of the bulk of the sensible heat contained in the combustion off-gas.
  • the off-gas is supplied as heat-transfer medium to a preheating stage, where it gets in direct contact with the solids by counter- current-flow with the same.
  • the so preheated solids are further increased in temperature in the first reactor by means of the combustion of a gaseous or liquid fuel.
  • the solids preheated in the first reactor are discharged to the second reactor where, the hot solids subsequently - depending on the solids tempera- ture achieved in the first process step - are either kept at that particular temperature or further heated (in a second reactor) to a temperature between 600 and 1300 °C, whereby impurities still contained are driven out in gaseous form. Due to the fact that the off-gas stream of the second reactor - is of a comparatively small quantity - may no longer be thermally utilized and the pollutants contained therein are not resorbed again on the solids now purified.
  • preheating consists of at least two preheating stages. It is particularly favorable when the off-gas from the first reactor is guided in counter- flow to the solids to be heated, as thus a high energy transfer is achieved with low investment costs at the same time.
  • step (ii) takes place in oxidizing atmosphere while step (iii) is performed with reducing atmosphere.
  • a further advantageous aspect of the invention provides that the material to be purified is cooled after passing the second reactor, wherein a gas, preferably air, likewise is used for cooling.
  • a gas preferably air
  • the gas heated by cooling subsequently can be introduced into the preheating stage and/or the first and/or the second reactor, whereby this energy is utilized as well. The energy efficiency of the process thereby can be increased further.
  • the described process can easily be utilized for phosphate-containing solids, in which impurities typically are driven out by a thermal treatment.
  • sedimentary raw phosphates are impaired with regard to the further processing to and the utilization as fertilizer both by carbonate compounds and by comparatively high cadmium contents, which can be removed by the process described here.
  • the process also is suitable for phosphate-containing secondary raw materials whose impurities can be reduced or even be eliminated with the described process steps.
  • the described process can be used particularly well in solids having a cadmium content between 1 and 500 ppm, preferably 5-300 ppm, as cad- mium (Cd) safely can be removed from the solids by a thermal treatment.
  • the effect of the process on ores is not only limited to cadmium, but includes all substances which can be volatilized or decomposed by action of high temperatures and defined atmospheres, such as e.g. arsenic, to name only one impurity out of many.
  • first and/or the second reactor is operated as fluidized-bed reactor with a stationary or a circulating fluidized bed, wherein here any combination is conceivable.
  • a fluidized-bed reactor offers the advantage of a particularly good mass and heat transfer.
  • the process according to the invention in particular is expedient in a fluidized bed, as due to the fluidizing gases an intensive intermixing of the gas and solids phases is ensured with the result of a very uniform temperature distribution.
  • the invention also comprises an apparatus with the features of claim 1 1 .
  • Such apparatus includes at least one preheating stage for preheating the solids to a temperature between 100 and 600 °C, preferably by counter-current-flow, with a heat-transfer medium.
  • the apparatus comprises a first reactor for heating the solids to a temperature between 600 and 1300 °C, whereby impurities contained in the solids are partly driven out in gaseous form and an off-gas is obtained.
  • the apparatus includes a return conduit from the first reactor, through which the off-gas is introduced into the preheating stage as heat-transfer medium, and a second reactor, in order to further thermally treat the solids at a temperature between 600 and 1300 °C, so as to expel impurities in gaseous form.
  • the first and/or the second reactor are designed as rotary kiln.
  • an advantageous aspect of the invention provides that the at least one preheating stage is designed as cyclone.
  • the solids residence times required for the various chemico-physical processes taking place in the two reactors depending on the intended use can optimally be adjusted both by the chosen geometry (construction) and by bed heights or bed densities variable in operation.
  • a two separate reactor design for different atmosphere especially a first reactor with oxidizing atmosphere and a second rector with reducing atmosphere, are preferred.
  • the first reactor typically hands over the solids to the second reactor preferably with that temperature with which the second reactor is to be operated. In the normal case, this results in minimum of energy to be expended. Since the temperatures in the two reactors can be chosen freely within wide ranges by corresponding fuel supply, it also is possible to employ different temperatures in the two reactors - if expedient in other applications.
  • Fig. 1 shows a schematic representation of the process according to the invention.
  • conduits 1 and 2 the solids are introduced into the first preheating stage 10 in the form of particles or pellets.
  • conduit 2 a mixture of fresh solids and hot off-gases from conduit 23 is obtained already.
  • the fresh solids from conduit 1 then are heated by the gas from conduit 23 and the off-gas is discharged via conduit 1 1 .
  • conduit 12 the heated solids are supplied to a second preheating stage 13.
  • conduit 22 opens and introduces hot gas into the second preheating stage 13 for preheating, wherein the gas then is withdrawn via conduit 23 and is again used as heat-transfer medium in the first preheating stage 10 in slightly cooled form.
  • the solids preheated further are withdrawn via conduit 14 and supplied to a third preheating stage 15.
  • the same is fed with the heat-transfer medium from con- duit 21 , which subsequently is again discharged from the cyclone 15 via conduit 22.
  • This interconnection in general leads to the fact that the individual preheating stages are flown through counter-currently, i.e. the solids are more and more heated via the individual preheating stages and off-gas cools down more and more. This results in a maximum heat transfer.
  • the preheating stag- es are designed as cyclones.
  • Said first reactor advantageously is designed as fluidized-bed reactor, particularly preferably as circulating fluidized bed.
  • fuel preferably in liquid or gaseous form, particularly preferably as methane-containing or hydrogen-containing gas
  • conduit 25 the heated solids are withdrawn and supplied to a further solids conveyor 26, from where they are supplied to the second reactor 30 via conduits 27, 28.
  • Said second reactor may be of a stationary fluidized type or likewise preferably s be designed as circulating fluidized-bed reactor.
  • Via conduit 31 it can also be supplied with fuel or hot gas. The gas is withdrawn via conduit 32 and supplied to a cyclone 33 or another gas-solids separator.
  • a contaminated off-gas is withdrawn via conduit 34, while via conduit 35 the product is supplied to a solids conveyor 36.
  • a solids conveyor 36 From the solids conveyor 36 parts of the solids are recirculated into the reactor via conduit 37 and conduit 28, in order to further improve the product quality.
  • the other part of the product gets into the cooler 40.
  • the product is cooled by means of air which is introduced into the cooler 40 and conduit 43 via conduit 41 and the condenser 42.
  • the cooled product is discharged via conduit 47.
  • the air heated as a result of cooling can be introduced into the first reactor 20 via conduits 44 and 45 and preferably be used there as fluidizing gas. It likewise is conceivable to introduce this air instead or also proportionately via conduit 46 into the second reactor 30.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Environmental & Geological Engineering (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un traitement thermique de solides contaminés. Dans une première étape (i), les solides contaminés sont préchauffés dans au moins un étage de préchauffage à une température entre 100 et 600 °C par un écoulement à contre-courant avec un milieu de transfert de chaleur. Dans une deuxième étape (ii), les solides contaminés sont ensuite chauffés dans un premier réacteur à une température entre 600 et 1300 °C, les impuretés contenues dans les solides étant partiellement éliminées sous forme gazeuse et un dégagement gazeux étant obtenu. Par une troisième étape (iii), les solides sont traités thermiquement dans un second réacteur à une température entre 600 et 1300 °C, des impuretés contenues dans les solides étant éliminées sous forme gazeuse et, dans la quatrième étape (iv), les dégagements gazeux sont mis en recirculation sous forme de milieu de transfert de chaleur et/ou d'air de combustion dans l'au moins un étage de préchauffage.
PCT/EP2017/054183 2016-02-25 2017-02-23 Procédé et appareil pour le traitement thermique de solides contaminés Ceased WO2017144593A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780010201.1A CN110214049A (zh) 2016-02-25 2017-02-23 用于受污染固体的热处理的方法和装置
EP17710831.3A EP3419747A1 (fr) 2016-02-25 2017-02-23 Procédé et appareil pour le traitement thermique de solides contaminés

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016103349.9A DE102016103349A1 (de) 2016-02-25 2016-02-25 Verfahren und Vorrichtung zur thermischen Behandlung eines verunreinigten Feststoffes
DE102016103349.9 2016-02-25

Publications (1)

Publication Number Publication Date
WO2017144593A1 true WO2017144593A1 (fr) 2017-08-31

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/054183 Ceased WO2017144593A1 (fr) 2016-02-25 2017-02-23 Procédé et appareil pour le traitement thermique de solides contaminés

Country Status (5)

Country Link
EP (1) EP3419747A1 (fr)
CN (1) CN110214049A (fr)
DE (1) DE102016103349A1 (fr)
MA (1) MA43718A (fr)
WO (1) WO2017144593A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1557248A (en) * 1976-09-09 1979-12-05 Macaskill D Calcination of materials
US4592900A (en) * 1984-03-09 1986-06-03 F. L. Smidth & Co. A/S Method of removing cadmium from raw phosphate
US4670237A (en) * 1983-06-21 1987-06-02 Metallgesellschaft Ag Process of removing pollutants from exhaust gases
US5560762A (en) * 1994-03-24 1996-10-01 Metallgesellschaft Ag Process for the heat treatment of fine-grained iron ore and for the conversion of the heat treated iron ore to metallic iron
US20070079666A1 (en) * 2003-08-09 2007-04-12 Stuart Sneyd Process and plant for reducing solids containing iron oxide
US20070137435A1 (en) * 2002-12-23 2007-06-21 Andreas Orth Method and plant for the heat treatment of solids containing iron oxide using a fluidized bed reactor
US20090208402A1 (en) * 2008-02-20 2009-08-20 Rossi Robert A Process and system for producing commercial quality carbon dioxide from fine particle limestone
US20100074805A1 (en) * 2002-12-23 2010-03-25 Outotec Oyj Fluidized bed method for the heat treatment of solids containing titanium
US20100187161A1 (en) * 2007-07-13 2010-07-29 Outotec Oyj Process and plant for refining oil-containing solids
US20110034318A1 (en) * 2008-04-24 2011-02-10 Outotec Oyj Process and plant for the heat treatment of fine-grained mineral solids
WO2014177228A1 (fr) * 2013-05-03 2014-11-06 Outotec (Finland) Oy Procédé et installation de séparation de métaux lourds à partir d'une matière première phosphorique

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017585A (en) * 1974-10-29 1977-04-12 Dorr-Oliver Incorporated Fluid bed calcination process
DD237762A3 (de) * 1984-01-30 1986-07-30 Schwermasch Liebknecht Veb K Verfahren und vorrichtung zur mehrstufigen veredlung von organischen schuettguetern
EP1109940B1 (fr) * 1999-06-21 2003-08-13 POHANG IRON & STEEL CO., LTD. Appareil de reduction du fin minerai de fer a lits fluidises double etage et procede de reduction faisant appel a cet appareil
DE19945771C1 (de) * 1999-09-24 2001-02-22 Muehlen Gmbh & Co Kg Dr Verfahren zur Vergasung von organischen Stoffen und Stoffgemischen
DE10343662B4 (de) * 2003-09-18 2005-10-27 Outokumpu Oyj Verfahren und Anlage zur Wärmebehandlung titanhaltiger Feststoffe
DE102005012524A1 (de) * 2005-03-16 2006-09-21 Outokumpu Technology Oy Verfahren und Anlage zur Wärmebehandlung titanhaltiger Feststoffe

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1557248A (en) * 1976-09-09 1979-12-05 Macaskill D Calcination of materials
US4670237A (en) * 1983-06-21 1987-06-02 Metallgesellschaft Ag Process of removing pollutants from exhaust gases
US4592900A (en) * 1984-03-09 1986-06-03 F. L. Smidth & Co. A/S Method of removing cadmium from raw phosphate
US5560762A (en) * 1994-03-24 1996-10-01 Metallgesellschaft Ag Process for the heat treatment of fine-grained iron ore and for the conversion of the heat treated iron ore to metallic iron
US20070137435A1 (en) * 2002-12-23 2007-06-21 Andreas Orth Method and plant for the heat treatment of solids containing iron oxide using a fluidized bed reactor
US20100074805A1 (en) * 2002-12-23 2010-03-25 Outotec Oyj Fluidized bed method for the heat treatment of solids containing titanium
US20070079666A1 (en) * 2003-08-09 2007-04-12 Stuart Sneyd Process and plant for reducing solids containing iron oxide
US20100187161A1 (en) * 2007-07-13 2010-07-29 Outotec Oyj Process and plant for refining oil-containing solids
US20090208402A1 (en) * 2008-02-20 2009-08-20 Rossi Robert A Process and system for producing commercial quality carbon dioxide from fine particle limestone
US20110034318A1 (en) * 2008-04-24 2011-02-10 Outotec Oyj Process and plant for the heat treatment of fine-grained mineral solids
WO2014177228A1 (fr) * 2013-05-03 2014-11-06 Outotec (Finland) Oy Procédé et installation de séparation de métaux lourds à partir d'une matière première phosphorique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3419747A1 *

Also Published As

Publication number Publication date
CN110214049A (zh) 2019-09-06
MA43718A (fr) 2018-11-28
EP3419747A1 (fr) 2019-01-02
DE102016103349A1 (de) 2017-08-31

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