EP4146373A1 - Procédé de piégeage d'alcali à partir de gaz de fumée - Google Patents

Procédé de piégeage d'alcali à partir de gaz de fumée

Info

Publication number
EP4146373A1
EP4146373A1 EP21732997.8A EP21732997A EP4146373A1 EP 4146373 A1 EP4146373 A1 EP 4146373A1 EP 21732997 A EP21732997 A EP 21732997A EP 4146373 A1 EP4146373 A1 EP 4146373A1
Authority
EP
European Patent Office
Prior art keywords
additive
kaolin
less
preferably less
flue gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21732997.8A
Other languages
German (de)
English (en)
Inventor
Joseph Jan Peter Biermann
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.)
MinPlus BV
Original Assignee
MinPlus BV
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 MinPlus BV filed Critical MinPlus BV
Publication of EP4146373A1 publication Critical patent/EP4146373A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/10—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of field or garden waste or biomasses
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B01D2258/0291—Flue gases from waste incineration plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/26—Biowaste

Definitions

  • the present invention relates to a method of scavenging alkali from flue gas; the method comprising the steps of
  • W02013093097 discloses a method for scavenging alkali wherein a mineral additive blend comprising a clay and a functional mineral is used.
  • the clay is for example, kaolin, andalusite, kyanite, sillimanite, hydro-topaz, mullite, pyrophyllite, or dombassite, montmorillonite, meta-kaolin (dehydrated kaolin), beidellite, bentonite, with hydrated clays, such as kaolin, particularly preferred.
  • the functional mineral is for example magnesium salt or calcium salt, for example, talc, dolomite, brucite and magnesium carbonate, magnesium carbonate, hydro-magnesite, vermiculite, smectite, phlogopite, clinochlore, sepiolite, attapulgite, palygorskite, calcium carbonate, calcium hydroxide, limestone, marble, chalk, dolomite, aragonitic sand, sea shells, coral, cement kiln dust, marl.
  • the additive is introduced into a furnace, a fuel is introduced into the furnace and the two components are heated with the fuel being incinerated.
  • water strongly enhances the capture of volatile alkali.
  • W02013093097 discloses adding the additive as a mixture comprising at least 1% water by weight or as a slurry, and as the clay kaolin.
  • the object of the present invention is to reduce the operational costs of the method according to the preamble.
  • a method according to the preamble is characterized in that the additive is added as a powder, said additive comprising based on the weight of the additive
  • an additive powder particle is an aggregate of micro-particles and a micro-particle of the additive powder particle is a micro-aggregate comprising both the meta-kaolin and the calcium oxide.
  • an operational cost saving is achieved based on the active material in the additive.
  • a typical incinerator needs 1-2 lorries with additive every week, so over 50 per year.
  • the specific activity of the additive according to the present invention by weight is higher, which means that less material has to be transported, saving operational cost.
  • the combustion chamber into which the fuel is introduced is for example a fluidized bed or the chamber of a grate incinerator.
  • the size of the fuel particles may be relatively small (e.g. in the order of millimeters or smaller) or relatively large (e.g. in the order of centimeters or larger).
  • the biomass is, for example, straw, refuse from industrial processes or households or mixtures thereof.
  • powder or powdery material indicates material having a particle size of less than 100 pm. Between the particles there is gas (air), and the additive material can be dispersed by air.
  • the additive material will be introduced in the flue gas where the flue gas has a temperature of at least 750°C and less than 1150°C, which conditions are typically higher than those where the condensation of alkali compounds starts to occur. In case of an incineration process involving flames, it is preferred that the additive material is injected downstream of the flames.
  • the flue gas contains non-gaseous material.
  • non-gaseous material in the flue gas typically comprises solid or at least partially molten particles originating from the fuel.
  • concentration of non-gaseous material is more than 0.02% by wt. relative to the weight of the flue gas.
  • the method according to the invention is very suitable for the incineration of particulate waste material.
  • the particulate fuel will typically consist for more than 50%, preferably more than 75%, and even more preferably more than 90% of such material (including mixtures of household and industrial waste materials).
  • the oxygen-comprising gas is typically air.
  • Obtaining the desired additive composition including the amount of meta-kaolin will typically involve the dehydratation of hydroxyl groups present in the clay used as starting material by means of a controlled heat treatment of the additive prior to its application in the incineration process, as is further detailed below.
  • Dehydrated additive as can be obtained by such a pre-heat-dehydratation step, was found to result in an increased efficiency of the additive when applied in the incineration process for the scavenging of alkali components. This finding is surprisingly opposite to the teachings of M.P. Glazer and of W02013093097, where the presence of water and hydroxyl groups in the additives described were indicated to substantially increase the alkali scavenging efficiency.
  • the additive comprises based on the weight of the additive material preferably at least 20% by weight meta-kaolin as the clay, and more preferably at least 30% by weight.
  • the additive comprises based on the weight of the additive material at least 20% by weight calcium oxide as the calcium compound, and more preferably at least 30% by weight.
  • the weight ratio between CaO and meta-kaolin will typically be in the range from 1:10 to 3:1.
  • meta-kaolin is made mention of in W02013093097, but not in a composition according to the present invention, wherein each additive particle is an agglomerate of smaller particles, and a smaller particle in itself is yet another agglomerate of calcium oxide and meta-kaolin.
  • the additive particle is referred to as an aggregate particle and the smaller particle as a micro-aggregate.
  • the additive in accordance with the present invention allows for a cycle of water (generated by the combustion of biomass) within the additive particle, which is made possible by the minute distances that the water has to travel in a micro-aggregate particle.
  • the calcium oxide is in very close proximity to the meta-kaolin.
  • Water is recycled within the micro-aggregate particle between the calcium and meta-kaolin compounds present in such micro-aggregate particle, allowing the additive to be effective despite a low water or hydroxyl group content of the additive introduced.
  • Water in the flue gas is derived from the biomass and/or the combustion thereof.
  • the amount of biomass in the fuel is for example at least 5 wt.%, typically at least 10 wt.% and preferably at least 15 wt.% of the total amount of fuel.
  • the additive powder to be introduced is an additive obtained by heat-treatment at a temperature of at least 750°C.
  • Such an additive has a reduced amount of bound water, having very suitable characteristics for scavenging alkali.
  • the heat treatment is performed at a temperature of less than 900 °C, preferably less than 850 °C, and most preferably less than 800 °C, for a time period of less than 5 minutes, preferably less than 2 minutes, and most preferably less than 1 minute.
  • the additive obtained in such a manner is very suitable for the method of scavenging alkali from flue gas.
  • a shorter time period is preferred.
  • the weight ratio between calcium carbonate and calcium oxide is less than 1, preferably less than 0.5 and most preferably less than 0.1.
  • the free water content of the additive material is less than 0.9 wt./wt. %, preferably less than 0.45 wt./wt. %.
  • Such an additive material can be introduced with little risk of clogging a nozzle or conduit towards the nozzle used for introducing the additive material.
  • the free water content of the additive material as it is to be understood in the present application may be measured by a before and after measurement, wherein the additive material is kept at 400°C until a constant weight is reached.
  • the bound water content of the clay of the additive material is less than 0.9 wt./wt. %, preferably less than 0.45 wt./wt. %.
  • the loss of hydroxyl groups from kaolin that is the loss of bound water as it is to be understood in the present application, may be determined using a before and after measurement, wherein the additive material is kept at a temperature of 600°C until a constant weight is reached.
  • the powdery additive is injected pneumatically.
  • the additive material is obtained by combusting paper waste material.
  • the freeboard of the combustion apparatus is controlled to a temperature of less than 1150°C to avoid breakdown of the meta-kaolin.
  • the freeboard temperature is not necessarily restricted to less than 850°C as is necessary to obtain a hydraulic material; wherein lifting that restriction lowers the complexity of producing of the additive material.
  • the weight ratio between CaO and meta-kaolin in the additive material is in a range of 1:4 to
  • Such a powdery additive has improved reactivity, allowing less additive material to be transported.
  • the distance between the calcium and meta-kaolin compounds in the additive is minute. This is achieved by producing the additive from a dispersed phase wherein kaolin is present and a dissolved phase wherein a calcium oxide precursor, typically calcium hydroxide, is present.
  • the kaolin is finely dispersed with a typical particulate size of less than 50 pm, preferably less than 20 pm, even more preferred less than 10 pm.
  • the calcium precursor typically is dissolved in the liquid of the dispersed phase containing the kaolin. If this is not the case, the dispersed and dissolved phases are mixed together prior to the further treatment described below.
  • the dissolved calcium is made to precipitate onto the kaolin, which can be done by leading C0 2 gas through the suspension, causing calcium carbonate to precipitate.
  • the thus obtained suspension contains an intimate mixture of kaolin, and calcium carbonate.
  • the suspension is then filtered to obtain a starting material for a heat treatment to obtain the additive material as will be described below. After the filtration, the starting material contains micro-aggregates of particles, wherein each particle contains both the kaolin and the calcium oxide precursor.
  • a similar starting material to obtain the additive through heat treatment, containing a similarly intimate mixture of kaolin and calcium carbonate can be obtained from waste paper and/or residues that stem from the recycling of waste paper.
  • the multitude of paper recycling and paper production processes involving repeated dissolving, dispersion, and drying, has provided for a similar intimacy between the kaolin and calcium precursor as obtained from the precipitation method described in the previous section.
  • the heat treatment of the starting material (which is carried out prior to and separate from the actual application of the resulting additive in the incineration process according to the present invention), sees on steps of i) evaporation of excess physical water (thermal drying), ii) conversion of kaolin into meta-kaolin under the release of bound water from the dehydratation (elimination of OH groups) present in the kaolin, seriously reducing the number of OH groups present in the kaolin (dehydration); and iii) conversion of at least part of the calcium carbonate into calcium oxide under the release of carbon dioxide (calcination).
  • care is taken to prevent unwanted temperatures and residence times wherein meta-kaolin is converted into less wanted minerals like mullite, and to prevent reaction between (meta)kaolin and calcium into less wanted minerals like gehlenite - which processes occur at temperatures of more than 800°C, and residence times at such temperature of several minutes.
  • the heat treatment is carried out by exposure of the starting material to a controlled temperature of less than 900 °C, preferably less than 850 °C, most preferred less than 800 °C, for a limited time period of less than 5 minutes, preferably less than 2 minutes, most preferred less than 1 minute.
  • the controlled heat pre-treatment adds an additional step in producing the additive material prior to its application in the incineration process, the obtained increased reactivity more than offsets this apparent disadvantage.
  • the method results in a more stable and predictable composition of the additive as compared to efforts wherein the heat treatment is incorporated in the incineration process.
  • the heat treatment thus furthermore does not place additional demands on operations of the incineration process.
  • Thermogravimetric characterization can be applied, wherein the weight reduction due to the dehydratation of the kaolin-hydroxyl groups is measured.
  • TGA Thermogravimetric characterization
  • the container was filled with a mixture of 1 gram of pure sodium chloride and/or 0.4 gram of additive material.
  • the solid materials placed in the container were fine powders with a typical particulate size of 5-20 micrometers.
  • the container was then carefully wiped, rinsed with water, and dried to the ambient atmosphere, The material that was collected from the container after its exposure to 600 degrees centigrade and the simulated flue gas was washed with water to remove dissolvable salts like the non-scavenged sodium chloride.
  • EDX Energy Dispersive X-Ray characterisation
  • the ratio of non-dissolvable Na: A1 was used to evaluate the alkali scavenging capacity of the applied additives. After being used in the above experiment, each container was weighed. The weight was then compared to the initial weight of the container prior to the experiment.
  • the measured weight loss of the container is used to indicate the degree of sodium chloride induced corrosion.
  • the observed weight loss was normalized to the maximum weight loss measured, which occurred as expected in the experiment wherein pure sodium chloride was applied without the application of alkali scavenging additives.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Un procédé de piégeage d'alcali à partir de gaz de fumée comprend les étapes consistant à introduire un gaz contenant de l'oxygène et un combustible solide comprenant de la biomasse dans une chambre de combustion pour incinérer ledit combustible solide, ce qui permet d'obtenir un gaz de fumée comprenant un alcali, et introduire un matériau additif comprenant i) une argile et ii) un composé de calcium dans le gaz de fumée. Pour réduire les coûts de fonctionnement, l'additif est ajouté sous la forme d'une poudre qui comprend à la fois du métakaolin en tant qu'argile et de l'oxyde de calcium en tant que composé de calcium. Une particule de poudre d'additif est un agrégat de microparticules et une microparticule de la particule de poudre d'additif est un micro-agrégat comprenant à la fois le métakaolin et l'oxyde de calcium.
EP21732997.8A 2020-05-08 2021-05-04 Procédé de piégeage d'alcali à partir de gaz de fumée Pending EP4146373A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2025539A NL2025539B1 (en) 2020-05-08 2020-05-08 A method of scavenging alkali from flue gas.
PCT/NL2021/050289 WO2021225436A1 (fr) 2020-05-08 2021-05-04 Procédé de piégeage d'alcali à partir de gaz de fumée

Publications (1)

Publication Number Publication Date
EP4146373A1 true EP4146373A1 (fr) 2023-03-15

Family

ID=76483334

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21732997.8A Pending EP4146373A1 (fr) 2020-05-08 2021-05-04 Procédé de piégeage d'alcali à partir de gaz de fumée

Country Status (3)

Country Link
EP (1) EP4146373A1 (fr)
NL (1) NL2025539B1 (fr)
WO (1) WO2021225436A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7561890B2 (ja) 2022-07-19 2024-10-04 株式会社ブルーオーシャン産業 バイオマス燃焼用添加剤組成物
JP7550918B2 (ja) 2022-07-19 2024-09-13 ジョン，クウォンホ ウッドペレット製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9401366A (nl) 1994-08-24 1996-04-01 Brp De Bilt Bv Werkwijze voor de bereiding van een puzzolaan materiaal uit papierresidu en werkwijze voor het daaruit vervaardigen van cement.
JP6227551B2 (ja) 2011-12-21 2017-11-08 ケンタッキー−テネシー クレイ カンパニー 凝集、沈着、腐食等の問題を回避し、及び放出物を減じるための、鉱物添加物ブレンド組成物及び燃焼器の運転方法
PL2891843T3 (pl) * 2014-01-07 2019-03-29 Imerys Ceramics France Sposób spalania odpadów z użyciem dodatku mineralnego
WO2018182406A1 (fr) * 2017-03-29 2018-10-04 Minplus B.V. Procédé de réduction de la corrosion d'un échangeur de chaleur d'un incinérateur comprenant ledit échangeur de chaleur
NL2020048B1 (en) * 2017-03-29 2019-02-18 Minplus B V A method of reducing corrosion of a heat exchanger of an incinerator comprising said heat exchanger

Also Published As

Publication number Publication date
WO2021225436A1 (fr) 2021-11-11
NL2025539B1 (en) 2021-11-23

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