WO2024251570A1 - Processus de fusion du verre avec une émission de co2 très faible à nulle - Google Patents

Processus de fusion du verre avec une émission de co2 très faible à nulle Download PDF

Info

Publication number
WO2024251570A1
WO2024251570A1 PCT/EP2024/064668 EP2024064668W WO2024251570A1 WO 2024251570 A1 WO2024251570 A1 WO 2024251570A1 EP 2024064668 W EP2024064668 W EP 2024064668W WO 2024251570 A1 WO2024251570 A1 WO 2024251570A1
Authority
WO
WIPO (PCT)
Prior art keywords
tank
melting
cullet
fining
melting tank
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/EP2024/064668
Other languages
English (en)
Inventor
François Bioul
Nicolas Bourgeois
Michel Bogaerts
Zakaria HABIBI
Fabrice FASILOW
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.)
AGC Glass Europe SA
Original Assignee
AGC Glass Europe SA
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 AGC Glass Europe SA filed Critical AGC Glass Europe SA
Priority to CN202480037894.3A priority Critical patent/CN121263384A/zh
Priority to KR1020257042266A priority patent/KR20260020397A/ko
Priority to EP24729835.9A priority patent/EP4688673A1/fr
Publication of WO2024251570A1 publication Critical patent/WO2024251570A1/fr
Priority to MX2025014634A priority patent/MX2025014634A/es
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting furnaces
    • C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
    • C03B3/023—Preheating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
    • C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
    • C03B5/03—Tank furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/225—Refining
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C03B5/2353—Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D99/00—Subject matter not provided for in other groups of this subclass
    • F23D99/002—Burners specially adapted for specific applications
    • F23D99/004—Burners specially adapted for specific applications for use in particular heating operations
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2211/00—Heating processes for glass melting in glass melting furnaces
    • C03B2211/40—Heating processes for glass melting in glass melting furnaces using oxy-fuel burners
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
    • F23C2900/9901—Combustion process using hydrogen, hydrogen peroxide water or brown gas as fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/50—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
    • F23L2900/07005—Injecting pure oxygen or oxygen enriched air
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping

Definitions

  • the present invention relates to a glass melting process aimed at continuously supplying molten glass to flat glass forming installations such as float or rolling installations.
  • the present invention relates to a glass melting process that provides a lot of advantages, especially in terms of CO2, especially its emissions and capture.
  • the invention is more particularly related, but not limited, to melting process for flat glass involving large production capacities, i.e. up to 1000 tons/day or more.
  • the glass sector has already identified a number of solutions/technologies to approach that ambitious goal, as, for example, use of electricity as energy source, use of alternative and greener sources of energy like H2 or biogas, use of alternative raw materials, increase use of cullet as raw materials, heat recovery, CO2 capture utilization and storage (or CCUS),...
  • Waste heat recovery from flue gas is already extensively applied in the glass industry to preheat the combustion air entering the furnace at temperatures higher than 1000°C, or gas and oxygen ("Hotox") at temperatures higher than 400 and 500°C respectively.
  • Hotox gas and oxygen
  • waste heat from flue gas can also be used to preheat the vitrifiable materials, especially cullet. Nevertheless, it is known that pre-heating raw materials/cullet cannot be coupled with electrical melting as the temperature of flue gas released by raw materials in this case is too low.
  • a CO? capture process in industrial processes/plants consists of two steps: (i) separation of CO? from an effluent gas mixture through a selective reaction with a separation material ("absorption" of CO?) and (ii) regeneration of the material used by a reverse reaction ("desorption" of CO?).
  • the separation material can be re-used for CO? capture by sequentially repeating steps (i) and (ii).
  • Amines, in the form of solvents or membranes or porous sorbents, are the most widely used material in CO? capture process in industry so far, as the technology is mature and an effective separation of amine and CO? via a reversible reaction is possible.
  • the amine-COj capture process requires a lot of energy in order to regenerate the amine sorbent (desorption process), thereby affecting the total energy consumption (and potentially the CO2 emission depending of the energy source used, which is obviously counter-productive in present context).
  • the present invention relates to a process for melting vitrifiable materials to produce flat glass, comprising the steps of : providing a furnace comprising (i) at least one main melting tank comprising electrical heating means, (ii) at least one auxiliary melting tank, (iii) a fining tank provided with oxycombustion heating means, (iv) at least one neck separating the at least one main melting tank and the fining tank, (v) inlet mean(s) located at the at least one main melting tank, (vi) outlet mean(s) located downstream of the fining tank; charging the vitrifiable materials comprising raw materials and cullet in the at least one main melting tank with the inlet mean(s) and/or in the at least one auxiliary melting tank, the amount of cullet being at least 10% in weight of the total amount of vitrifiable materials; melting the vitrifiable materials in the at least one main melting tank by heating with the electrical heating means and flowing the melt to the fining tank through the neck melting at least a part of the cullet
  • the invention is based on a novel and inventive approach.
  • the inventors have found that by combining, in a glass melting process to produce flat glass: the use of a furnace with a specific segmented design (separating an electrically-heated main melting zone and a combustion-heated fining zone), the use of oxygen as comburant, the use of gas and/or hydrogen as combustible, the use of a minimum amount of cullet in the vitrifiable materials, the use of a step of melting cullet, at least partially, in an auxiliary melter that flows downstream of the melting tank (esp.
  • the process of the invention shows a very low CO2 fingerprint and is economically viable.
  • upstream and downstream refer to the flow direction of the glass and are to be understood with their common sense, namely as meaning along the averaged moving direction of the vitrifiable materials/the glass melt, from the inlet mean(s) to the outlet mean(s).
  • upstream part is understood to mean the first upstream third of the length, said length being located along the horizontal and longitudinal axis of the furnace.
  • downstream part is understood to mean the last downstream third of said length.
  • FIG. 1 is a flowchart of an embodiment of the process of the invention.
  • the process for melting vitrifiable materials to produce flat glass comprises a step of providing a furnace comprising (i) at least one main melting tank comprising electrical heating means, (ii) at least one auxiliary melting tank, (iii) a fining tank provided with oxy-combustion heating means, (iv) at least one neck separating the at least one main melting tank and the fining tank, (v) inlet mean(s) located at the at least one main melting tank, (vi) outlet mean(s) located downstream of the fining tank (for the melted glass to flow to a working zone).
  • melting tank it is meant a tank defining a zone where the vitrifiable materials (raw materials and/or cullet) are charged and melt by heating, and comprising, when the furnace is in process, a melt and a "blanket” of unmelted vitrifiable materials that floats on the melt and is progressively melted.
  • fining tank it is meant a tank defining a zone where there is no more “blanket” of unmelted vitrifiable materials that floats on the melt and where the glass melt is heated at temperatures higher than melting tank temperatures (generally above 1400°C or even above 1450°C), in order to refine the glass (mainly by eliminating major part of bubbles).
  • melting tank temperatures generally above 1400°C or even above 1450°C
  • This fining tank is also commonly called “clarification tank” in the art.
  • a neck separating the at least one main melting tank and the fining tank, it is meant :
  • the crown of the neck according to the invention may be at a lower height than the crown of the main melting tank or essentially at the same height.
  • the neck also allows a wider opening and therefore lower glass velocities leading to lower refractory corrosion and wear. This point can advantageously improve furnace lifetime. Moreover, it provides a free surface that can be used to control glass temperature flowing out of the neck (important to control convection loops in the fining tank), and to possibly introduce skimbar/barriers introduced from the sides of the neck (can be used to control convection in the neck, and possibly avoid backward flow from fining to melting zone).
  • this furnace design with a segmentation of the main melting tank(s) and fining tank, brings a lot of advantages in favour of energy consumption/COj emissions and in favour of mechanical stability/ lifetime of the furnace.
  • this furnace with its specific segmented design allows to deal with flue gas from main melting tank(s) and flue gas from fining tank independently, if desired.
  • the furnace of the invention is defined by the following :
  • Wli being the width of the at least one main melting tank
  • W2 being the width of the fining tank
  • W3i being the width of the at least one neck.
  • the neck(s) between the melting zone(s) and the fining zone should be ideally as narrow as possible in order to (1) decrease the opening between melting and fining superstructures/crowns and (2) generate an obstacle to global glass melt convection strength in the main melting tank(s), and, from the other side, the neck should be ideally as wide as possible in order to limit glass velocity inside the neck(s), to limit neck refractory wall wear/corrosion.
  • the furnace may comprise one main melting tank and one neck; or two main melting tanks and two necks; or even three main melting tanks and three necks.
  • Embodiments of these specific designs are extensively described in European patent application EP21200998.9 herein incorporated by reference.
  • the furnace may comprise :
  • the furnace may be advantageously defined by the following :
  • Wli being the width of first main melting tank
  • Wlii being the width of second main melting tank
  • W2 being the width of the fining tank
  • W3i being the width of neck Ni
  • W3ii being the width of neck Nii.
  • the total surface area of the main melting tank(s) ranges from 25 to 400 m 2 .
  • the surface area of the fining tank ranges from 25 to 400 m 2 .
  • said inlet mean(s) is/are either located upstream of the at least one melting tank (either in the width of said tank or laterally in its length) or located at the top of the at least one melting tank ("top batch charger").
  • the furnace comprises at least one melting tank enlarged laterally and equipped with at least two inlet means, located on both sides of the melting tank based on the location of the neck, either at the lateral sides or as top batch chargers.
  • the process for melting vitrifiable materials to produce flat glass comprises a step of charging the vitrifiable materials comprising raw materials and cullet in the at least one main melting tank with the inlet mean(s) and/or in the at least one auxiliary melting tank.
  • the process for melting vitrifiable materials to produce flat glass comprises a step of melting at least a part of the cullet in the at least one auxiliary melting tank and flowing the melt (namely, the melted cullet) to the neck or to the fining tank.
  • the at least one auxiliary melting tank according to the invention is connected (or, in other words, flows) to the neck or to the fining tank.
  • the process of the invention comprises a step of melting at least a part of the cullet in the at least one auxiliary melting tank and flowing the melt to the neck. This allows to introduce the molten cullet in a symmetrical way, regarding the complete furnace, leading to better glass homogeneity in the fining tank and in the final glass product.
  • the at least one auxiliary melting tank flows (or is connected) to the fining tank
  • the at least one auxiliary melting tank is preferably connected at the upstream part of the fining tank, and more preferably, as upstream as possible of the fining tank.
  • the at least one auxiliary melting tank flows (or is connected) to the fining tank, this can be done through a connection commonly known in the art, preferably a throat or a neck.
  • the at least one auxiliary melting tank flows (or is connected) to the neck, this is preferably done through a connection commonly known in the art, like a throat.
  • the flowing can be done from a height higher than the top of the neck, the melt coming from the auxiliary melting tank flowing by gravity on the upper surface of the melt already present in the neck (and coming from the main melting tank). This reduces the required space around the neck at the ground level, and make easier operations inside the neck (for equipment introduction for instance). This could also advantageously be combined with a purification process that could be gravity-flow process.
  • the furnace of the invention may comprise more than one auxiliary melting tank, for example, two or three auxiliary melting tanks.
  • each auxiliary melting tank may flow/be connected independently to the neck or to fining tank.
  • the furnace comprises two auxiliary melting tanks
  • one auxiliary melting tank flows to the neck and the other flows to the fining tank, or both flow to the neck, or both flow to the fining tank.
  • the furnace of the invention comprises more than one auxiliary melting tank, for example, two or three auxiliary melting tanks, they may be arranged in series (one after the other).
  • the furnace comprises three auxiliary melting tanks arranged in series, the first one (the most upstream from the neck or fining tank) flows to the second one that flows to the last one that finally flows to the neck or to the fining tank.
  • the total amount of cullet charged in the furnace of the invention is either fully and only charged in the at least one auxiliary melting tank (meaning that only raw materials from the vitrifiable materials of the invention are charged in the at least one main melting tank) or, alternatively, the total amount of cullet is split between the at least main melting tank and the at least one auxiliary tank (this means that only a part of the cullet is melted in the at least one auxiliary melting tank, the remaining part of the cullet being melted in the at least one main melting tank).
  • the part of the cullet that is considered as "polluted” or not sufficiently clean is melted in the at least one auxiliary melting tank and the remaining "clean" part of the cullet is charged, together with raw materials, and melted in the at least one main melting tank.
  • At least a part of the cullet (namely a part of the total amount of cullet charged in the furnace of the invention) is charged in the at least one auxiliary melting tank, meaning that essentially cullet is charged in the at least one auxiliary melting tank.
  • essentially cullet it means that cullet is charged alone in the at least one auxiliary melting tank or together with small amounts of compounds (for example, up to 5 or 10 wt% of charged materials), i.e. helping to adjust properties of the melt in the auxiliary melting tank.
  • some soda and/or calcium oxide may be added together with the cullet in order to adjust the viscosity of the melt/melted cullet, without departing from the invention.
  • the cullet is charged in the at least one main melting tank together with the raw materials, i.e. through same inlet mean(s) or, alternatively, independently of the raw materials through different inlet mean(s).
  • the step of melting at least a part of the cullet in the at least one auxiliary melting tank may include one or several steps of purifying said cullet.
  • metallic compounds present in the cullet can be eliminated in this auxiliary melting tank, by using reductants (like coke or anthracite) to produce molten metal that will separate from the glass melt by decanting at the bottom of the auxiliary melting tank, while the obtained "purified" glass melt could flow from the top towards the neck or the fining tank.
  • the at least a part of the cullet that is melted in the at least one auxiliary melting tank represents at least 2% in weight of the total amount of cullet and preferably, at least 5% in weight, or even at least 10% in weight, and more preferably, at least 20% in weight.
  • the step of melting at least a part of the cullet in the at least one auxiliary melting tank may be carried out with electrical heating means like, for example, immersed electrodes and/or with combustion means like, for example, aerial burners or immersed combustion means.
  • the amount of cullet is at least 10% in weight of the total amount of vitrifiable materials.
  • the amount of cullet is at least 20% in weight of the total amount of vitrifiable materials. More preferably, the amount of cullet is at least 30% in weight of the total amount of vitrifiable materials, or even, very preferred, at least 40% in weight. This is advantageous as it allows to reduce the CO2 production/emission of the process of the invention (due to a reducing of the emission occurring from the decarbonization of the carbonate raw materials).
  • the amount of cullet is at maximum 90% in weight of the total amount of vitrifiable materials, or even at maximum 80% in weight.
  • the process for melting vitrifiable materials to produce flat glass comprises a step of melting the vitrifiable materials in the at least one main melting tank by heating with the electrical heating means.
  • Electrical heating means according to the invention are possibly located at the bottom of the at least one main melting tank and preferably, in such a case, composed of immersed electrodes.
  • the "bottom electrodes” are advantageously arranged in grid pattern (checkerboard) multiple of 3 or 2, in order to facilitate connection to transformers and electric current balance.
  • the electrical heating means according to the invention extends from the top of the at least one main melting tank (for example, maintained commonly by a water-cooled holder) and are immersed.
  • These "top electrodes” are advantageously located along the edge of the melting tank and/or at the corner(s).
  • the number of electrodes in the invention is for example designed in order to limit maximum power for each electrode to 400kW, by respecting a maximum current density of 1.5A/cm 2 at the electrode surface.
  • height is between 0.3 and 0.8 times glass melt height.
  • the electrical input fraction ranges from 50% to 85%.
  • electrical input fraction it is meant the part of electricity in the total energy input of the process/furnace for the melting/fining, namely electricity/(fuel+electricity), the total energy input being that of the process/furnace in standard/normal production mode, i.e. at its standard pull range (excluding periods of start-up, maintenance, hot repair, culleting,).
  • the process for melting vitrifiable materials to produce flat glass comprises a step of fining the melt in the fining tank by heating with the oxy-combustion heating means announced with gas and/or hydrogen.
  • gas herein includes, but not only, natural gas, synthetic gas and biogas. Natural gas is the most widely used presently for practical, economical and availability reasons.
  • combustion means supplied with gaseous oxygen (O2) as comburant.
  • O2 gas comburant supplied to glass melting furnaces is at least 90% purity, or even at least 95% purity.
  • An advantage of using gaseous oxygen as comburant, compared to using air, is the drastic decrease of the so-called « NOx » pollutants appearing during the combustion. Even if they could still be present in the flue gas (depending on the O2 purity and amount of parasitic air), it will be in very low amounts.
  • Oxy-combustion heating means may be composed of burners, advantageously arranged along the side walls of said tank on each side thereof to spread the flames over practically the entire width of the tank.
  • the burners may be spaced from one another in order to distribute the energy supply over a portion (i.e. ⁇ 50% of the length) of the fining tank. They are also commonly arranged in rows on either side of the tank.
  • the oxy-combustion heating means are maintainedd with gas and/or hydrogen.
  • the oxy-combustion heating means are maintained with at least 50% hydrogen and preferably, at least 80% hydrogen. More preferably, the oxy-combustion heating means areentred with 100% hydrogen. This is advantageous as it allows to decrease drastically to global CO2 emission of the process.
  • the oxy-combustion heating means are maintained with more than 50% gas and preferably, at least 80% gas, or even at least 100% gas. This is advantageous as it allows to reach a higher concentration of CO2 in the flue gas, thereby facilitating and improving the CO2 capture step, but also to limit impact on the chemistry of glass and on furnace refractory materials.
  • the oxy-combustion heating means areotted with 50% gas and 50% hydrogen.
  • the process for melting vitrifiable materials to produce flat glass comprises a step of flowing the melt from the fining tank to a working zone trough the outlet mean(s).
  • the outlet mean(s) is/are located downstream of the fining tank, for the melted glass to reach a working zone.
  • the outlet mean(s) is/are composed usually of a neck, in order to lead the melt towards a working zone commonly called "working end".
  • the outlet mean(s) is/are composed of a throat, in order to lead the melt towards a working zone including, for example, forehearth(s).
  • the working zone according to the invention may comprise, for example, a conditioning zone in which thermal conditioning by controlled cooling is carried out prior to glass melt leaving said zone through an outlet to a forming zone.
  • a forming zone may comprise, for example, a float installation and/or a rolling installation.
  • the furnace of the invention may comprise a removable wall located at the neck (e.g. a skimbar coming from the side wall of the neck), in order to (i) possibly stop unmelted vitrifiable materials that could arrive at the end of the melting tank and thereby avoid their passing through the neck towards the fining tank and (ii) control the intensity of or annihilate the backward flow of the melt from the fining towards the melting tank.
  • a removable wall located at the neck (e.g. a skimbar coming from the side wall of the neck), in order to (i) possibly stop unmelted vitrifiable materials that could arrive at the end of the melting tank and thereby avoid their passing through the neck towards the fining tank and (ii) control the intensity of or annihilate the backward flow of the melt from the fining towards the melting tank.
  • the furnace may comprise a removable wall located at the neck (e.g. a shadow wall passing through the crown of the neck) in order to increase segmentation of melting and fining tanks in terms of atmosphere and heat radiations.
  • a removable wall located at the neck (e.g. a shadow wall passing through the crown of the neck) in order to increase segmentation of melting and fining tanks in terms of atmosphere and heat radiations.
  • the process for melting vitrifiable materials to produce flat glass comprises further a step of capturing CO2 from flue gas.
  • said flue gas (namely the flue gas which undergoes the step of CO2 capture) has a CO2 concentration of at least 35%.
  • the CO2 concentration according to the invention is the concentration defined for the dry flue gas, namely the flue gas with all its components except the water (H2O).
  • the flue gas in the invention has a CO2 concentration of at least 40%, and more preferably, of at least 50%, or even more of at least 60%. This is advantageous as the higher the concentration in CO2 of the flue gas, the easier and effective the CO2 capture applied on this flue gas.
  • the step of capturing CO2 from flue gas comprises step(s) of compression and/or dehydration.
  • the step of dehydration corresponds to a step of water condensation and/or drying of the flue gas.
  • the step of compression corresponds to increasing the pressure of CO2, commonly by using a compressor.
  • the step of dehydration may be prior to the step of compression, and/or the step of dehydration may be concomitant to the step of compression.
  • the step of capturing CO2 from flue gas according to the invention may carried out, in a known manner, using a CO2 compression and purification unit (or CPU).
  • a CO2 compression and purification unit or CPU
  • the flue gas according to this invention may be recovered for CO2 capture either from (i) the at least one main melting tank, (ii) from the at least one main melting tank and the at least one auxiliary melting tank, (iii) from the fining tank or (iv) from the whole furnace.
  • the flue gas are advantageously recovered only from the at least one melting tank (the flue gas evolving from the fining tank does not include CO2) or from the at least one main melting tank and the at least one auxiliary melting tank.
  • the CO2 product has, for example, a pressure of about 35 bar at temperature 5°C-40°C, in a gaseous form, appropriate for transport through pipelines, or of about 100 bar in the liquid form, appropriate for transport through pipelines but also truck or rail transport. For transport by truck, a value of 15 bar at -35°C is also known as appropriate.
  • the step of capturing CO2 from flue gas consists essentially in step(s) of compression and/or dehydration.
  • the process of the invention comprises further a step of eliminating acidic components from flue gas.
  • This step of eliminating acidic components is carried out prior or concurrent to the step of capturing CO2 (for example prior to or concurrent to/together with the step(s) of compression and/or dehydration).
  • the step of eliminating acidic components may include a step of desulphurization (or removing of the so-called « SOx » compounds) of the flue gas. It may also include a step of removing the so-called « NOx » compounds, that could still be present even if in very low amounts due to the use of oxygen as comburant. This is advantageous as this allows removing the corrosive compounds (SOx, NOx) before the transportation, storage and/or utilization.
  • the CO2 product (for example, in a liquid form) may be transported to its final destination through pipelines, then either stored/sequestrated (for example, deep undersea or in a geological formation such as a saline aquifer) or, alternatively, utilized (for example, for enhanced oil recovery, or for food/beverage applications or for fire protection applications).
  • stored/sequestrated for example, deep undersea or in a geological formation such as a saline aquifer
  • the CO2 product obtained after the step of capturing CO2 may be used locally, to limit transportation. This can be considered if the amount of CO2 captured is not too high so that it can be absorbed by local market(s).
  • the process comprises further a step of cullet pre-heating, at least partially by recovering heat from the furnace, before charging said cullet in the at least one main melting tank and/or in the at least one auxiliary melting tank.
  • recovering heat from the furnace may be carried out from flue gas coming from (i) the melting tank(s), or (ii) the fining tank or (iii) from the whole furnace (thereby including flue gas from the melting, auxiliary and/or main one(s), and fining tanks).
  • the CO2 capturing step may be carried out from the flue gas that is used at the step of cullet pre-heating.
  • the raw materials are charged in the at least one main melting tank either together with the pre-heated cullet through same inlet mean(s) (this implies therefore that both type of vitrifiable materials are mixed before charging) or independently of the pre-heated cullet, through different inlet mean(s).
  • the maximum temperature of the cullet at the step of cullet pre-heating is 450°C. This allows to avoid clogging issues.
  • the step of cullet pre-heating may be carried out in at least one cullet pre-heater, for example, of the type of one of those described in US5526580 or DE3716687.
  • the at least one cullet pre-heater may be located at upstream part of the at least one main melting tank or of the at least one auxiliary melting tank, either in the width of said tank or laterally in its length.
  • the step of cullet pre-heating may be carried out in at least two cullet pre-heaters located, for example, at upstream part of the main melting tank, in its width or laterally in its length on both sides.
  • the step of cullet pre-heating may be carried out in four cullet pre-heaters located at upstream part of the main melting tank, distributed in its width or laterally in its length (for example, two on each side).
  • the step of cullet pre-heating may be carried out in six cullet preheaters located at upstream part of the main melting tank, in its width or laterally in its length (for example, three on each side), or also in eight cullet pre-heaters located at upstream part of the main melting tank, in its width or laterally in its length (for example, four on each side).
  • the raw materials comprise less than 25% in weight of carbonate compounds.
  • carbonate compounds it is meant for example alkali carbonates and alkaline earth carbonates.
  • the raw materials comprise less than 20% in weight of carbonate compounds, and more preferably less than 10%, and even less than 5%.
  • the raw materials may be advantageously free of any carbonate compound.
  • This embodiment is advantageous as it allows to reduce the part of CO 2 emission occurring from the decarbonization of raw materials, compared to classical glass meting process where sodium carbonate Na 2 CO3, limestone CaCOs and dolomite CaMg COsh are generally essentially used as sources of sodium and calcium.
  • the alkali and alkaline earth sources may advantageously be present, at least partially, in the form of oxides or hydroxides such as CaO, CaO.MgO (dolime), Ca(OH) 2 , Mg(OH) 2 , NaOH, KOH.
  • the process for melting vitrifiable materials to produce flat glass comprises the steps of : providing a furnace comprising (i) at least one main melting tank comprising electrical heating means, (ii) at least one auxiliary melting tank, (iii) a fining tank provided with oxycombustion heating means, (iv) at least one neck separating the at least one main melting tank and the fining tank, (v) inlet mean(s) located at the at least one main melting tank, (vi) outlet mean(s) located downstream of the fining tank; charging the vitrifiable materials in the at least one main melting tank with the inlet mean(s) and/or in the at least one auxiliary melting tank, said vitrifiable materials comprising (i) raw materials with less than 25% in weight of carbonate compounds and (ii) cullet in an amount of at least 10% in weight of the total amount of vitrifiable materials, cullet pre-heating, at least partially by recovering heat from the furnace, before charging said cul

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Glass Melting And Manufacturing (AREA)

Abstract

L'invention concerne un processus de fusion de matières vitrifiables pour produire du verre plat, comprenant les étapes consistant à : (i) fournir un four comprenant au moins une cuve de fusion principale pourvue de moyens de chauffage électrique, au moins une cuve de fusion auxiliaire, une cuve d'affinage pourvue de moyens de chauffage par oxy-combustion, une cuve de fusion principale à séparation de col et une cuve d'affinage ; (ii) charger les matières vitrifiables comprenant des matières premières et un calcin dans la cuve de fusion principale et/ou dans la cuve de fusion auxiliaire, la quantité totale de calcin étant d'au moins 10 % en poids de matières vitrifiables ; (iii) faire fondre les matériaux vitrifiables dans la cuve de fusion principale par chauffage avec les moyens de chauffage électrique et les faire s'écouler dans la cuve d'affinage à travers le col ; (iv) faire fondre au moins une partie du calcin dans la cuve de fusion auxiliaire et le faire s'écouler dans le col ou dans la cuve d'affinage, avec une fraction d'entrée électrique allant de 50 % à 85 %; (v) affiner la masse fondue dans la cuve d'affinage par chauffage avec les moyens de chauffage par oxy-combustion alimentés en gaz et/ou en hydrogène, (vi) faire s'écouler la masse fondue de la cuve d'affinage à une zone de travail (vii) capturant du CO2 d'un gaz de combustion comprenant une ou plusieurs étapes de compression et/ou de déshydratation, ledit gaz de combustion ayant une concentration en CO2 d'au moins 35 %.
PCT/EP2024/064668 2023-06-07 2024-05-28 Processus de fusion du verre avec une émission de co2 très faible à nulle Ceased WO2024251570A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202480037894.3A CN121263384A (zh) 2023-06-07 2024-05-28 具有非常低至零co2排放的玻璃熔融方法
KR1020257042266A KR20260020397A (ko) 2023-06-07 2024-05-28 Co₂ 배출이 매우 낮거나 제로인 유리 용융 프로세스
EP24729835.9A EP4688673A1 (fr) 2023-06-07 2024-05-28 Processus de fusion du verre avec une émission de co2 très faible à nulle
MX2025014634A MX2025014634A (es) 2023-06-07 2025-12-04 Proceso de fusion de vidrio con emisiones de co2 muy bajas o nulas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23177878.8 2023-06-07
EP23177878 2023-06-07

Publications (1)

Publication Number Publication Date
WO2024251570A1 true WO2024251570A1 (fr) 2024-12-12

Family

ID=86732012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/064668 Ceased WO2024251570A1 (fr) 2023-06-07 2024-05-28 Processus de fusion du verre avec une émission de co2 très faible à nulle

Country Status (5)

Country Link
EP (1) EP4688673A1 (fr)
KR (1) KR20260020397A (fr)
CN (1) CN121263384A (fr)
MX (1) MX2025014634A (fr)
WO (1) WO2024251570A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716687C1 (en) 1987-05-19 1988-11-24 Zippe Gmbh & Co Plate heat exchanger for preheating broken glass or similar bulk materials
US5526580A (en) 1992-04-24 1996-06-18 Zippe Gmbh & Co Method and heat-exchanger for preheating broken glass and glass-batching melt-goods or similar bulk goods using a heating gas
EP0761287A2 (fr) * 1995-08-23 1997-03-12 The Boc Group, Inc. Procédé pour la récupération de gaz de combustion d'un four de fusion de verre
US20040168474A1 (en) * 2003-02-27 2004-09-02 Saint-Gobain Glass France Process for producing a glass by mixing molten glasses
CN104418484A (zh) * 2013-09-06 2015-03-18 邢韫韬 燃气双预热高温富氧碳氢热量循环无氮单向辐射燃烧系统
WO2018039398A1 (fr) * 2016-08-26 2018-03-01 Corning Incorporated Appareil et procédé pour la mise en forme d'un article en verre
JP7153241B2 (ja) * 2017-09-05 2022-10-14 日本電気硝子株式会社 無アルカリガラス基板の製造方法及び無アルカリガラス基板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716687C1 (en) 1987-05-19 1988-11-24 Zippe Gmbh & Co Plate heat exchanger for preheating broken glass or similar bulk materials
US5526580A (en) 1992-04-24 1996-06-18 Zippe Gmbh & Co Method and heat-exchanger for preheating broken glass and glass-batching melt-goods or similar bulk goods using a heating gas
EP0761287A2 (fr) * 1995-08-23 1997-03-12 The Boc Group, Inc. Procédé pour la récupération de gaz de combustion d'un four de fusion de verre
US20040168474A1 (en) * 2003-02-27 2004-09-02 Saint-Gobain Glass France Process for producing a glass by mixing molten glasses
CN104418484A (zh) * 2013-09-06 2015-03-18 邢韫韬 燃气双预热高温富氧碳氢热量循环无氮单向辐射燃烧系统
WO2018039398A1 (fr) * 2016-08-26 2018-03-01 Corning Incorporated Appareil et procédé pour la mise en forme d'un article en verre
JP7153241B2 (ja) * 2017-09-05 2022-10-14 日本電気硝子株式会社 無アルカリガラス基板の製造方法及び無アルカリガラス基板

Also Published As

Publication number Publication date
KR20260020397A (ko) 2026-02-11
MX2025014634A (es) 2026-02-03
EP4688673A1 (fr) 2026-02-11
CN121263384A (zh) 2026-01-02

Similar Documents

Publication Publication Date Title
EP4441001B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
US20250011213A1 (en) Glass melting process with very low to zero-co2 emission
EP4441000B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
WO2024251570A1 (fr) Processus de fusion du verre avec une émission de co2 très faible à nulle
EP4440998B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
EP4504672B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
US20250353773A1 (en) Glass melting process with very low to zero-co2 emission
EP4504669B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
EP4504670B1 (fr) Procédé de fusion de verre avec des émissions de co2 très faibles à nulles
EA052625B1 (ru) Способ плавления стекла с уровнем выброса co2 от очень низкого до нулевого
EA052376B1 (ru) Способ плавления стекла с уровнем выброса co2 от очень низкого до нулевого

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24729835

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024729835

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

ENP Entry into the national phase

Ref document number: 2025569853

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025569853

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

WWE Wipo information: entry into national phase

Ref document number: 2501008220

Country of ref document: TH

WWE Wipo information: entry into national phase

Ref document number: 202517121205

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: MX/A/2025/014634

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112025026793

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

WWP Wipo information: published in national office

Ref document number: 202517121205

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

WWE Wipo information: entry into national phase

Ref document number: 202593527

Country of ref document: EA

ENP Entry into the national phase

Ref document number: 2024729835

Country of ref document: EP

Effective date: 20251105

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: MX/A/2025/014634

Country of ref document: MX

WWP Wipo information: published in national office

Ref document number: 2024729835

Country of ref document: EP