# US 11,440,829 B2 · Utilization of sulfate in the fining of submerged combustion melted glass > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,440,829 B2 - Document ID: US11440829B2 - Status: Granted - Kind: B2 - Application number: 16/590,079 - Filed: 2019-10-01 - Published: 2021-04-01 - Granted: 2022-09-13 - Earliest claimed: 2019-10-01 - Assignees: Owens-Brockway Glass Container Inc. - Applicants: Owens-Brockway Glass Container Inc. - Inventors: William Pinc; Udaya Vempati - Web page: https://patentgrep.com/patent/US11440829B2 ## CPC - C03B 5/225: Refining (C03B5/18 takes precedence {; Refining agents C03C1/004}) - C03B 5/2353: {by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances} - C03B 5/2356: {Submerged heating, e.g. by using heat pipes, hot gas or submerged combustion burners (bubblers C03B5/193)} - C03B 5/24: Automatically regulating the melting process - C03B 7/005: {Controlling, regulating or measuring} - C03C 1/004: {Refining agents (refining C03B5/225)} - C03C 3/078: containing an oxide of a divalent metal, e.g. an oxide of zinc - C03B 2211/22: by direct combustion in the melt - C03B 2211/23: using oxygen, i.e. pure oxygen or oxygen-enriched air - Y02P 40/50: Glass production, e.g. reusing waste heat during processing or shaping - C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES - 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 - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A method of producing and fining glass includes monitoring a temperature of a molten glass bath contained within a fining chamber of a fining vessel and, based on the monitored temperature, controlling an amount of a sulfate chemical fining agent added into a glass melt contained within an interior reaction chamber of an upstream submerged combustion melter that feeds the fining vessel. The temperature of the molten glass bath may be determined within a temperature indication zone that encompasses a subsurface portion of the molten glass bath that lies adjacent to a floor of a housing of the fining vessel. By monitoring the temperature of the molten glass bath and controlling the amount of the sulfate chemical fining agent added to the glass melt of the submerged combustion melter, the wasteful use of the sulfate chemical fining agent can be minimized and the fining process rendered more efficient. ## Claims ### Claim 1 A method of producing and fining glass, the method comprising: introducing a vitrifiable feedstock material into a glass melt contained within an interior reaction chamber of a submerged combustion melter, the vitrifiable feedstock material comprising glass-forming materials that melt-react into the glass melt, wherein the glass melt comprises unrefined molten glass; delivering an inflow of unrefined molten glass, which originates from the interior reaction chamber of the submerged combustion melter, into a fining chamber of a fining vessel, the inflow of unrefined molten glass merging with a molten glass bath contained within the fining chamber; monitoring a temperature of the molten glass bath within the fining chamber in a temperature indication zone of the molten glass bath that encompasses a subsurface portion of the molten glass bath; comparing the temperature of the molten glass bath in the temperature indication zone against a minimum glass fining temperature; and controlling an amount of a sulfate chemical fining agent added to the glass melt in the interior reaction chamber of the submerged combustion melter based on the comparison of the temperature of the molten glass bath in the temperature indication zone against the minimum glass fining temperature. ### Claim 2 (depends on 1) The method set forth in claim 1, further comprising: discharging combustion products from one or more submerged burners directly into the glass melt contained within the interior reaction chamber of the submerged combustion melter, the combustion products discharged from the one or more submerged burners agitating the glass melt. ### Claim 3 (depends on 1) The method set forth in claim 1, wherein the temperature indication zone lies adjacent to a floor of a housing of the fining vessel such that the temperature indication zone extends upwards from the floor of the housing. ### Claim 4 (depends on 3) The method set forth in claim 3, wherein the temperature indication zone rises upwards from the floor of the housing to a distance ranging from 10% to 60% of a depth of the molten glass bath while extending an entire width of the fining chamber and being spaced away from each of an inlet end wall of the housing and an outlet end wall of the housing by a distance ranging from 40% to 60% of a length of the fining chamber. ### Claim 5 (depends on 1) The method set forth in claim 1, wherein the unrefined molten glass in the glass melt has a soda-lime-silica glass chemical composition, and wherein the minimum glass fining temperature is between 1220° C. and 1260° C. ### Claim 6 (depends on 5) The method set forth in claim 5, wherein the inflow of unrefined molten glass delivered into the fining chamber of the fining vessel comprises between 30 vol % and 60 vol % of entrained gas bubbles and further has a density ranging from 0.75 gm/cm3 to 1.5 gm/cm3, and wherein an outflow of refined molten glass discharged from the fining chamber of the fining vessel has a density ranging from 2.3 gm/cm3 to 2.5 gm/cm3. ### Claim 7 (depends on 5) The method set forth in claim 5, wherein controlling the amount of the sulfate chemical fining agent added to the glass melt comprises: controlling the amount of the sulfate chemical fining agent added to the glass melt contained in the interior reaction chamber of the submerged combustion melter to provide the unrefined molten glass, upon being discharged from the submerged combustion melter, with a retained sulfate content of at least 0.04 wt %, as expressed as SO3, when the temperature of the molten glass bath within the temperature indication zone is less than the minimum glass fining temperature. ### Claim 8 (depends on 5) The method set forth in claim 5, wherein controlling the amount of the sulfate chemical fining agent added to the glass melt comprises: controlling the amount of the sulfate chemical fining agent added to the glass melt contained in the interior reaction chamber of the submerged combustion melter to provide the unrefined molten glass, upon being discharged from the submerged combustion melter, with a retained sulfate content of between 0 wt % and less than 0.04 wt %, as expressed as SO3, when the temperature of the molten glass bath within the temperature indication zone is equal to or greater than the minimum glass fining temperature. ### Claim 9 (depends on 8) The method set forth in claim 8, wherein controlling the amount of the sulfate chemical fining agent added to the glass melt comprises suspending the addition of the sulfate chemical fining agent into the glass melt contained in the interior reaction chamber of the submerged combustion melter. ### Claim 10 (depends on 1) The method set forth in claim 1, wherein, relative to a flow direction through the fining chamber, the fining vessel includes a front skimmer, a rear skimmer, and an intermediate skimmer disposed between the front skimmer and the rear skimmer, the front skimmer and the rear skimmer dividing the fining chamber into a receiving section that receives the inflow of unrefined molten glass into the fining chamber, a delivery section from which an outflow of refined molten glass is drawn out of the fining chamber, and a conditioning section situated between the receiving section and the delivery section, and wherein the temperature indication zone is located in the conditioning section of the fining chamber. ### Claim 11 (depends on 1) The method set forth in claim 1, wherein the temperature of the molten glass bath within the temperature indication zone is determined by a temperature sensor. ### Claim 12 (depends on 11) The method set forth in claim 11, wherein the temperature sensor is a thermocouple that is in direct contact with the subsurface portion of the molten glass bath encompassed by the temperature indication zone. ### Claim 13 (depends on 1) The method set forth in claim 1, wherein the minimum glass fining temperature is determined based on the chemical fining activity of the sulfate chemical fining agent in relation to the temperature of the molten glass bath within the temperature indication zone. ### Claim 14 (depends on 1) The method set forth in claim 1, wherein the minimum glass fining temperature is based on a relationship between chemical fining activity associated with the sulfate chemical fining agent and thermal fining activity associated with the viscosity of the molten glass bath within the temperature indication zone. ### Claim 15 (depends on 1) The method set forth in claim 1, wherein at least some of the amount of the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber through an auxiliary inlet that is separate from a feed material inlet through which the vitrifiable feedstock material is introduced into the interior reaction chamber. ### Claim 16 (depends on 1) The method set forth in claim 1, wherein delivering the inflow of unrefined molten glass into the fining chamber of the fining vessel comprises delivering the inflow of unrefined molten glass directly from a molten glass outlet of the submerged combustion melter into an inlet of the fining vessel. ### Claim 17 A method of producing and fining glass, the method comprising: providing a glass melt that is contained within an interior reaction chamber of a submerged combustion melter, the glass melt comprising unrefined molten glass having a soda-lime-silica glass chemical composition that includes 60 wt % to 80 wt % SiO2, 8 wt % to 18 wt % Na2O, and 5 wt % to 15 wt % CaO; discharging combustion products from one or more submerged burners directly into the glass melt contained within the interior reaction chamber of the submerged combustion melter, the combustion products discharged from the one or more submerged burners agitating the glass melt; delivering an inflow of unrefined molten glass into a fining chamber of a fining vessel, the fining chamber being defined by a housing, and the inflow of unrefined molten glass, which is drawn from the glass melt in the interior reaction chamber of the submerged combustion melter, merging with a molten glass bath contained within the fining chamber; monitoring a temperature of the molten glass bath within the fining chamber, wherein the temperature of the molten glass bath is determined within a temperature indication zone that encompasses a subsurface portion of the molten glass bath that lies beneath a surface of the molten glass bath; controlling an amount of a sulfate chemical fining agent added to the glass melt within the interior reaction chamber of the submerged combustion melter based on a comparison of the temperature of the molten glass bath within the fining chamber against a minimum glass fining temperature; and discharging an outflow of refined molten glass from the fining chamber of the fining vessel, the outflow of refined molten glass having a glass density that is greater than a glass density of the inflow of unrefined molten glass received in the fining chamber of the fining vessel. ### Claim 18 (depends on 17) The method set forth in claim 17, wherein the temperature indication zone rises upwards from a floor of the housing to a distance ranging from 10% to 60% of a depth of the molten glass bath while extending an entire width of the fining chamber and being spaced away from each of an inlet end wall of the housing and an outlet end wall of the housing by a distance ranging from 40% to 60% of a length of the fining chamber. ### Claim 19 (depends on 18) The method set forth in claim 18, wherein, relative to a flow direction through the fining chamber, the fining vessel includes a front skimmer, a rear skimmer, and an intermediate skimmer disposed between the front skimmer and the rear skimmer, the front skimmer and the rear skimmer dividing the fining chamber into a receiving section that receives the inflow of unrefined molten glass into the fining chamber through an inlet defined in the housing, a delivery section from which the outflow of refined molten glass is drawn out of the fining chamber through an outlet defined in the housing, and a conditioning section situated between the receiving section and the delivery section, and wherein the temperature indication zone is located in the conditioning section of the fining chamber. ### Claim 20 (depends on 17) The method set forth in claim 17, wherein the minimum glass fining temperature is between 1220° C. and 1260° C. ### Claim 21 (depends on 17) The method set forth in claim 17, wherein controlling the amount of the sulfate chemical fining agent added to the glass melt comprises: controlling the amount of the sulfate chemical fining agent added to the glass melt contained in the interior reaction chamber of the submerged combustion melter to provide the unrefined molten glass, upon being discharged from the submerged combustion melter, with a retained sulfate content of at least 0.04 wt %, as expressed as SO3, when the temperature of the molten glass bath in the temperature indication zone is less than the minimum glass fining temperature. ### Claim 22 (depends on 17) The method set forth in claim 17, wherein controlling the amount of the sulfate chemical fining agent added to the glass melt comprises: controlling the amount of the sulfate chemical fining agent added to the glass melt contained in the interior reaction chamber of the submerged combustion melter to provide the unrefined molten glass, upon being discharged from the submerged combustion melter, with a retained sulfate content of between 0 wt % and less than 0.04 wt %, as expressed as SO3, when the temperature of the molten glass bath in the temperature indication zone is equal to or greater than the minimum glass fining temperature. ### Claim 23 (depends on 17) The method set forth in claim 17, further comprising: introducing a vitrifiable feedstock material into the glass melt contained within the interior reaction chamber of the submerged combustion melter through a feed material inlet, the vitrifiable feedstock material comprising glass-forming materials that melt-react into the glass melt, and wherein at least some of the amount of the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber through an auxiliary inlet that is separate from the feed material inlet. ### Claim 24 (depends on 17) The method set forth in claim 17, wherein delivering the inflow of unrefined molten glass into the fining chamber of the fining vessel comprises delivering the inflow of unrefined molten glass directly from a molten glass outlet of the submerged combustion melter into an inlet of the fining vessel. ### Claim 25 A method of producing and fining glass, the method comprising: producing a glass melt in an interior reaction chamber of a submerged combustion melter, the glass melt comprising unrefined molten glass having a soda-lime-silica glass chemical composition; discharging combustion products from one or more submerged burners directly into the glass melt contained within the interior reaction chamber of the submerged combustion melter; delivering an inflow of unrefined molten glass from the glass melt and into a fining chamber of a fining vessel, the inflow of unrefined molten glass merging with a molten glass bath contained within the fining chamber; monitoring a temperature of the molten glass bath within the fining chamber in a temperature indication zone of the molten glass bath that encompasses a subsurface portion of the molten glass bath; comparing the temperature of the molten glass bath in the temperature indication zone against a minimum glass fining temperature, wherein the minimum glass fining temperature is between 1220° C. and 1260° C.; and controlling an amount of a sulfate chemical fining agent added to the glass melt in the interior reaction chamber of the submerged combustion melter based on the comparison of the temperature of the molten glass bath in the temperature indication zone against the minimum glass fining temperature such that the unrefined molten glass of the glass melt, upon being discharged from the interior reaction chamber of the submerged combustion melter, is provided with a retained sulfate content, as expressed as SO3, of (i) between 0 wt % and less than 0.04 wt % when the temperature of the molten glass bath in the temperature indication zone is equal to or greater than the minimum glass fining temperature and (ii) at least 0.04 wt % when the temperature of the molten glass bath in the temperature indication zone is less than the minimum glass fining temperature. ### Claim 26 (depends on 25) The method set forth in claim 25, wherein delivering the inflow of unrefined molten glass from the glass melt and into the fining chamber of the fining vessel comprises delivering the inflow of unrefined molten glass directly from a molten glass outlet of the submerged combustion melter into an inlet of the fining vessel. ### Claim 27 (depends on 25) The method set forth in claim 25, wherein, relative to a flow direction through the fining chamber, the fining vessel includes a front skimmer, a rear skimmer, and an intermediate skimmer disposed between the front skimmer and the rear skimmer, each of the front skimmer, the rear skimmer, and the intermediate skimmer extending downwards from a roof of a housing of the fining vessel towards a floor of the housing of the fining vessel, the front skimmer and the rear skimmer dividing the fining chamber into a receiving section that receives the inflow of unrefined molten glass into the fining chamber through an inlet, a delivery section from which an outflow of refined molten glass is drawn out of the fining chamber through an outlet, and a conditioning section situated between the receiving section and the delivery section, and wherein the temperature indication zone is located in the conditioning section of the fining chamber. ### Claim 28 (depends on 27) The method set forth in claim 27, wherein the temperature indication zone extends upwards from the floor of the housing of the fining vessel to a distance ranging from 10% to 60% of a depth of the molten glass bath while extending an entire width of the fining chamber. ### Claim 29 (depends on 25) The method set forth in claim 25, further comprising: introducing a vitrifiable feedstock material into the glass melt contained within the interior reaction chamber of the submerged combustion melter through a feed material inlet, the vitrifiable feedstock material comprising glass-forming materials that melt-react into the glass melt. ### Claim 30 (depends on 29) The method set forth in claim 29, wherein the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber as part of the vitrifiable feedstock material. ### Claim 31 (depends on 29) The method set forth in claim 29, wherein at least some of the amount of the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber through an auxiliary inlet that is separate from a feed material inlet through which the vitrifiable feedstock material is introduced into the interior reaction chamber. ### Claim 32 A method of producing and fining glass, the method comprising: producing a glass melt in an interior reaction chamber of a submerged combustion melter, the glass melt comprising unrefined molten glass; adding a sulfate chemical fining agent to the glass melt in the interior reaction chamber of the submerged combustion melter; discharging combustion products from one or more submerged burners directly into the glass melt contained within the interior reaction chamber of the submerged combustion melter; delivering an inflow of unrefined molten glass from the glass melt and into a fining chamber of a fining vessel, the inflow of unrefined molten glass merging with a molten glass bath contained within the fining chamber; monitoring a temperature of the molten glass bath within the fining chamber in a temperature indication zone of the molten glass bath that encompasses a subsurface portion of the molten glass bath; comparing the temperature of the molten glass bath in the temperature indication zone against a minimum glass fining temperature; and limiting or suspending an amount of the sulfate chemical fining agent added to the glass melt when the temperature of the molten glass bath in the temperature indication zone is equal to or greater than the minimum glass fining temperature. ### Claim 33 (depends on 32) The method set forth in claim 32, further comprising: introducing a vitrifiable feedstock material into the glass melt contained within the interior reaction chamber of the submerged combustion melter through a feed material inlet, the vitrifiable feedstock material comprising glass-forming materials that melt-react into the glass melt. ### Claim 34 (depends on 33) The method set forth in claim 33, wherein the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber as part of the vitrifiable feedstock material. ### Claim 35 (depends on 33) The method set forth in claim 33, wherein at least some of the amount of the sulfate chemical fining agent added to the glass melt is introduced into the interior reaction chamber through an auxiliary inlet that is separate from the feed material inlet through which the vitrifiable feedstock material is introduced into the interior reaction chamber. ### Claim 36 (depends on 32) The method set forth in claim 32, wherein delivering the inflow of unrefined molten glass from the glass melt and into the fining chamber of the fining vessel comprises delivering the inflow of unrefined molten glass directly from a molten glass outlet of the submerged combustion melter into an inlet of the fining vessel. ### Claim 37 (depends on 32) The method set forth in claim 32, wherein the minimum glass fining temperature is determined based on the chemical fining activity of the sulfate chemical fining agent in relation to the temperature of the molten glass bath within the temperature indication zone. ### Claim 38 (depends on 32) The method set forth in claim 32, wherein, relative to a flow direction through the fining chamber, the fining vessel includes a front skimmer, a rear skimmer, and an intermediate skimmer disposed between the front skimmer and the rear skimmer, each of the front skimmer, the rear skimmer, and the intermediate skimmer extending downwards from a roof of a housing of the fining vessel towards a floor of the housing of the fining vessel, the front skimmer and the rear skimmer dividing the fining chamber into a receiving section that receives the inflow of unrefined molten glass into the fining chamber through an inlet, a delivery section from which an outflow of refined molten glass is drawn out of the fining chamber through an outlet, and a conditioning section situated between the receiving section and the delivery section, and wherein the temperature indication zone is located in the conditioning section of the fining chamber. ### Claim 39 (depends on 38) The method set forth in claim 38, wherein the temperature indication zone extends upwards from the floor of the housing of the fining vessel to a distance ranging from 10% to 60% of a depth of the molten glass bath while extending an entire width of the fining chamber. ### Claim 40 A method of producing and fining glass, the method comprising: producing a glass melt in an interior reaction chamber of a submerged combustion melter, the glass melt comprising unrefined molten glass; discharging combustion products from one or more submerged burners directly into the glass melt contained within the interior reaction chamber of the submerged combustion melter; delivering an inflow of unrefined molten glass, which is drawn and originates from the glass melt contained the interior reaction chamber of the submerged combustion melter, into a fining chamber of a fining vessel, the inflow of unrefined molten glass merging with a molten glass bath contained within the fining chamber; monitoring a temperature of the molten glass bath within the fining chamber in a temperature indication zone of the molten glass bath that encompasses a subsurface portion of the molten glass bath, the temperature indication zone extending upwards from a floor of a housing of the fining vessel to a distance ranging from 10% to 60% of a depth of the molten glass bath while extending an entire width of the fining chamber and being spaced away from each of an inlet end wall of the housing and an outlet end wall of the housing by a distance ranging from 40% to 60% of a length of the fining chamber; comparing the temperature of the molten glass bath in the temperature indication zone against a minimum glass fining temperature, the minimum glass fining temperature being determined based on the chemical fining activity of the sulfate chemical fining agent in relation to the temperature of the molten glass bath within the temperature indication zone; and controlling an amount of a sulfate chemical fining agent added to the glass melt in the interior reaction chamber of the submerged combustion melter based on the comparison of the temperature of the molten glass bath in the temperature indication zone against the minimum glass fining temperature. ### Claim 41 (depends on 40) The method set forth in claim 40, wherein the minimum glass fining temperature is between 1220° C. and 1260° C. ### Claim 42 (depends on 41) The method set forth in claim 41, wherein delivering the inflow of unrefined molten glass into the fining chamber of the fining vessel comprises delivering the inflow of unrefined molten glass directly from a molten glass outlet of the submerged combustion melter into an inlet of the fining vessel. ### Claim 43 (depends on 40) The method set forth in claim 40, wherein, relative to a flow direction through the fining chamber, the fining vessel includes a front skimmer, a rear skimmer, and an intermediate skimmer disposed between the front skimmer and the rear skimmer, each of the front skimmer, the rear skimmer, and the intermediate skimmer extending downwards from a roof of the housing of the fining vessel towards the floor of the housing of the fining vessel, the front skimmer and the rear skimmer dividing the fining chamber into a receiving section that receives the inflow of unrefined molten glass into the fining chamber through an inlet, a delivery section from which an outflow of refined molten glass is drawn out of the fining chamber through an outlet, and a conditioning section situated between the receiving section and the delivery section, and wherein the temperature indication zone is located in the conditioning section of the fining chamber. ### Claim 44 (depends on 40) The method set forth in claim 40, wherein controlling the amount of a sulfate chemical fining agent added to the glass melt comprises: adding the sulfate chemical fining agent to the glass melt in the interior reaction chamber of the submerged combustion melter when the temperature of the molten glass bath in the temperature indication zone is less than the minimum glass fining temperature such that the unrefined molten glass of the glass melt, upon being discharged from the interior reaction chamber of the submerged combustion melter, is provided with a retained sulfate content, as expressed as SO3, of at least 0.04 wt %; and limiting or suspending the amount of the sulfate chemical fining agent added to the glass melt when the temperature of the molten glass bath in the temperature indication zone is equal to or greater than the minimum glass fining temperature such that the unrefined molten glass of the glass melt, upon being discharged from the interior reaction chamber of the submerged combustion melter, is provided with a retained sulfate content, as expressed as SO3, of between 0 wt % and less than 0.04 wt %.