theGlassResearcher iS
`BULLETIN OF GLASS SCIENCE AND ENGINEERING ^fggpl
`
`New York State College of Ceramics
`
`I
`
`at Alfred University
`
`Volume 4 Number 1
`'ij Summer 1994
`Energy & Environment II: Innovative Glass Technology
`Glass manufacturers have responded to
`Batching and Melting Silicate Glass
`Containment of hazardous and nuclear
`waste in glass holds promise for envi-
`government environmental regulations
`by Linda E. Jones, Alexis G. Clare and
`and restrictions imposed on the indus-
`David Gerling, page 4.
`ronmentally sound solutions for one of
`society’s major problems. Availability
`try by developing innovative technolo-
`gies and processes that often stress,
`of this process is now becoming reality
`Environmental Considerations
`in
`often challenge to the fullest. This issue
`as explained in Hazardous Waste
`Glass Furnace Selection by Geoffrey
`B. Tuson. page 6. compares the energy
`of the GlassResearcher , the second on
`Vitrification Technology Matures by
`James C. Marra. Dennis F. Bickford,
`efficiency and environmental advan-
`the theme of energy and environment,
`explores some of
`those technologies
`Jantzen and M.
`Carol M.
`John
`tages of various types of glass melting
`Plodinec. page 10.
`that demonstrate the potential of the
`furnaces.
`glass industry to respond with unprece-
`dented creativity and ingenuity.
`An overview of a European approach to
`As dialogue on the uncomfortable
`recycling with major percentage of cul-
`issues of energy and environment
`let is described in Recycling of Glass
`Solutions to the problem of rising elec-
`develop between the glass industry and
`in Europe by R.G.C. Beerkens, A. J.
`trical energy costs are suggested in
`government agencies, more and more
`Faber, and J.G.J. Peelen. page 8.
`Cost Reduction Developed
`for
`resources arc becoming available and
`Electrical Energy by E. J. Williams,
`increased understanding is developing
`CGR to Meet in Europe
`page 3.
`technology.
`effective
`into more
`The Industry-University Center for
`Department of Energy Focuses on
`the Industry-
`Research carried out at
`U.S. Glass
`Industry’s Needs by
`Glass Research will hold a meeting for
`European affiliated members in Paris.
`University Center for Glass Research,
`Charles A. Sorrell, page 13. introduces
`which identifies emissions that evolve
`France, on Monday, Oct. 10, at
`a DOE project that could impact glass
`the
`from glass manufacturing, is reported
`manufacturers in a major way.
`headquarters of Air Liquide Inc. from
`in Part 2: Emissions Produced by
`9:30 a.m. to 5:30 p.m.
`Forum Scheduled for New York State Glass Industry
`regulatory officials. The conference
`issues of concern to representative sec-
`Glass industry executives and New
`will provide a forum in which to dis-
`tors of
`the glass industry-container
`York State government officials will
`cuss issues that concern the glass indus-
`glass, thin films, lighting, and glass as
`review the current status of the industry
`an environmental tool for vitrification
`try within New York State, where the
`and envision directions for the New
`York State glass industry at a one-day
`of hazardous waste.
`pulse of
`the national glass industry
`beats especially strong. By identifying
`forum to be held Monday, September
`the problems as well as the resources,
`19, in Corning, NY.
`industry and government can develop
`Emerging Priorities: The Scope. Needs
`understanding important to future oper-
`ation.
`and Future of the New York State Glass
`Industry w ill convene at 8:30a.m. at the
`James R. Houghton. Chief Executive
`Radisson Hotel with an overview of the
`Officer and Chairman of Corning
`Newr York State industry compiled
`from results of a survey conducted by
`Incorporated, will deliver the keynote
`address to envision future directions for
`Conference Chair Dr. L. David Pye and
`the glass industry.
`Dr. Innocent Joseph, assistant director
`Industry-
`technology
`for
`the
`at
`University Center for Glass Research.
`The goal of the conference is to devel-
`op constructive dialogue between glass
`industry executives and government
`
`Government 's perspective on energy,
`environment, and technology funding
`will be presented by state and federal
`government officials, who will explore
`issues that face glass as an energy-
`intensive industry in Session II.
`
`Emerging technologies and issues will
`be presented by a panel of industry per-
`sonnel from a broad area of glass pro-
`ducers. users, and fabricators
`i n
`Session II. Moderated by Dr. Richard
`Houghton 's address will be followed
`M. Spriggs, CACT director, this panel
`by Session I on the corporate perspec-
`will showcase innovative technologies
`tive on energy and environmental
`the glass industry.
`that have been developed and put into
`impact
`issues that
`practice in response to energy and envi-
`Corporate CEO's and presidents of
`ronmental concerns.
`major glass corporations will address
`SPONSORED BY THE NSF INDUSTRY-UNIVERSITY CENTER FOR GLASS RESEARCH
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 001
`
`

`

`the GlassResearclier: Bulletin of Glass
`Science and Engineering is published by
`the Industry-University Center for Glass
`Research, a National Science Foundation
`Industry-University Cooperative Research
`Center. Information contained herein may
`be reprinted only by written consent of
`the publisher. Circulation: 6.000 glass
`industrialists, scientists, engineers and
`educators and the engineering and science
`alumni of the NYS College of Ceramics
`at Alfred University. Published: biannual-
`ly; 134 Binns-Merrill Hall. NYSCC.
`Alfred University. Alfred. NY 14802: (607 )
`871-2495: FAX (607) 871-2812.
`Editor: Margaret Adams Rasmussen
`Guest Editor:
`Ronald Schroeder
`Praxair Inc.
`Editorial Advisory Board:
`Edward Boulos Ford Motor Co.
`Paul Danielson Corning Incorporated
`Wilfrid Gaboury Viracon Inc.
`Emery Homyak Lihhev Inc.
`Jorge Loredo Murphy Vitro
`Jan G. J. Peelen Philips Glass
`Jeffrey Sacks CertainTeed Corp.
`Ronald W. Schroeder Praxair Inc.
`Robert A. Smith U.S. Borax Inc.
`E. Lowell Svvarts. PPG Industries Inc.
`L. David Pye ex officio
`Corporate Members:
`ALCOA Technical Center
`Air Liquide Inc.
`Asahi Glass Co. Inc.
`Cardinal IG
`CertainTeed Corp.
`Corning Incorporated
`Ford Motor Co.
`Gas Research Institute
`Libbey Inc.
`Nippon Electric Glass Co.. Ltd.
`OSRAM-SYLVANIA Inc.
`Owens-Coming Fiberglas Corp.
`Owens-Illinois Inc.
`PPG Industries Inc.
`Philips Glass
`Pilkington pic
`Praxair Inc.
`Schott Corporation
`Schuller International
`Thomson Consumer Electronics Inc.
`Trans-Resources Inc.
`US Borax Inc.
`Viracon Inc.
`Vitro
`Westinghouse Savannah River Co.
`Affiliate Organizations
`National Science Foundation
`U.S. Department of Energy
`Huettentechnische Vereinigung
`der Deutschen Glasindustrie
`Institute of Silicate Chemistry
`Howard University
`Virginia Military Institute
`
`2
`
`Mission Statement of the Industry-University Center for Glass Research:
`To advance the field of glass science and engineering through research , educa-
`tion. and technology exchange driven by the cooperative efforts of academe,
`industry and government.
`Director’s Message
`Leading MIT economist Lester Thurow
`depicts the world as one giant game
`board. The players of the game are the
`world 's industrial leaders, and the rules
`keep changing. The winners will be
`those industrial nations that can accept
`the changing rules and w ho know how
`to play as teams. In his book. Head to
`Head: The Coming Economic Battle
`Among Japan. Europe and America."
`try needs to play—and win—in the
`Thurow identifies the elements a coun-
`
`(cid:127)Train a high technology work force:
`Although the U.S. educational system
`reportedly fails to train students in sci-
`ence and math , the brightest and best
`science students are attracted to the
`NYS College of Ceramics. The Center's
`research program then fine tunes Alfred
`University 's graduates to enter
`the
`international glass industry. Students
`supervised by faculty glass scientists
`have published over 30 theses and dis-
`sertations. numerous journal articles
`and other publications in the nine years
`of the Center 's existence. When under-
`graduate and graduate students have the
`opportunity to work on research pro-
`jects of the Center, they become aware
`industrv 's research needs and are
`of
`sensitized to the operation of industry.
`When industry w as questioned by a key
`appropriations subcommittee that con-
`trols funds to NASA and NSF about the
`to transfer academic
`best means
`research to the private sector, an indus-
`trv spokesperson said , “the best vehicle
`for transferring academic research to
`the private sector is the moving van that
`carries new PhD 's to their first jobs in
`the industry.*' Glass science PhD s
`from Alfred are coached to serve any
`one of the 25 Center members from the
`day they complete their dissertations.
`We 're training the players right here at
`the CGR.
`Almost 10 years ago. 10 U.S. glass cor-
`I n c ..
`porations-AFG Industries
`Corp..Corning
`C e r t a i n T e e d
`Incorporated. Ford Motor Co.. Schuller
`I n t e r n a t i o n a l , O w e n s-C o m i n g
`Fiberglas, Owens-Illinois. Inc., PPG
`Industries Inc.. Specialty Products Co.,
`W e s t i n g h o u s e S a v a n n a h R i v e r
`Co.-watched the play on the giant
`world game board and committed their
`first membership fees. Today the CGR
`team has almost tripled in membership
`and our members understand the
`changing rules.
`L. David Pye
`Director
`
`international economic game of
`the
`21st century. Those representatives of
`the U.S. glass industry who were deter-
`mined to form an industry-university
`research collaboration did a lot of
`things right , according to Thurow s
`theory.J
`In many ways, the Center for Glass
`Research represents a microcosm of
`what an industrial nation must do to
`play in the world 's industrial game.
`Two points are especially clear to
`for Glass
`the Center
`members of
`Research.
`(cid:127)Form a consortia to develop needed
`technology: Our 25 members work as a
`team to select glass research projects
`the
`from faculty proposals that meet
`needs of our collective membership.
`Under the CGR subcommittee system
`established over the past two years, we
`have identified the broad agenda of
`reflects our members '
`research that
`research needs.
`
`According to the new world rules,
`members of industry must cooperate
`with each other, putting aside any fierce
`competition that will cause all players
`to lose. We must team up w i t h other
`players in the world since optical fibers
`have shrink wrapped the world. At pre-
`sent. over half of our Center members
`are linked w i t h international corpora-
`tions from Europe to Asia. In October,
`the CGR will visit Europe for a meet-
`ing. hosted in Paris by Air Liquide. for
`the benefit of our international compa-
`nies. We play on the world field.
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 002
`
`

`

`I
`
`Cost Reduction Developed for Electrical Energy
`E. J. Williams
`Corning Incorporated
`Rising electrical energy costs are a
`major concern for the glass manufac-
`turing community, particularly within
`New York State. Over the past several
`years, a multi-thrust program has been
`pursued aggressively to reduce the cost
`of electrical energy to several of
`Corning Incorporated 's manufacturing
`facilities.
`Coming has developed a win-win-win
`that substantially reduces
`agreement
`the cost of electrical energy to
`Coming's largest electric melting oper-
`ation. The
`benefits
`arrangement
`Corning, its electrical energy supplier,
`and the community. Working with New
`York State Gas&Electric. Coming has
`negotiated an electrical energy rate
`schedule. SC13. w hich is very compet-
`itive with alternative energy cost reduc-
`tion approaches.
`A team of purchasing, engineering and
`manufacturing personnel formulated a
`plan that w ould reduce the cost of elec-
`trical energy. Empowered to pursue
`promising options,
`the team held
`reviews at all levels to keep customers,
`associates, and suppliers informed of
`plans and progress. The objective was
`simple:
`reduce the cost of electrical
`energy. Success was enjoyed, along
`with a favorable return on Coming's
`investment for a 20MW plus facility.
`In late 1991. Coming's electrical ener-
`gy supplier requested substantial rate
`increases of 157c for two successive
`from the
`years
`Public Service
`Commission. Energy price increases
`were old news. See Figure 1 for aver-
`age cost of Southwestern New York
`electrical energy against
`that of
`the
`average of some other east coast utili-
`ties. Personnel aware of the price pres-
`sures at Coming 's local manufacturing
`facilities banded together informally
`and bootlegged a project to avoid the
`proposed increases.
`A six-person team began to explore
`solutions to the problem. As the project
`became more complex, it was neces-
`sary to expand the information network
`to include the community, management
`and more suppliers.
`The team discussed the situation with
`the electrical energy supplier to explore
`potential paths around the increases.
`The energy supplier agreed that
`the
`
`Unit Cost Of Electricity
`New York
`Figure 1 Average cost of electrical energy comparison
`All Others
`increases were large but had no altema-
`lines to the end user. Wheeling is a
`tive, due to New York State utility reg-
`common practice between public utili-
`sations. With legal counsel and inter-
`can only be done in special
`ties but
`vention from other industries at
`cases with private industries. Successful
`the
`Public Service Commission, increases wheeling involves two key factors: 1 )
`an agreement between the utility, sup-
`were held to eight percent.
`plier. regulatory body, and end-user to
`An investigation into four alternatives
`establish cost and conditions; 2 ) a cost
`to reduce the cost of electrical energy
`of purchasing power and transmitting
`was started. (See Table 1 ) The team
`power
`lower than the current utility
`divided into four subgroups, based on
`rate. Wheeling electrical energy could
`individual strengths and expertise , to
`become a reality within the next five to
`address options w ith the electrical ener-
`10 years.
`gy supplier. All options were consid-
`(cid:127) Bulk Power, under many utility rate
`ered possible, but each had advantages
`structures, provides a lower cost
`for
`and disadvantages. Relative attributes
`purchasing electrical energy at a higher
`of each approach are summarized in
`voltage. A higher voltage transformer
`Table 1.
`and associated hardware
`can
`be
`installed to secure a lower rate. This
`Four approaches w ere explored closely:
`rate is independent of the amount of
`(cid:127) Cogeneration is the simultaneous
`energy purchased.1
`creation of two forms of energy, elec-
`tricity and steam, or hot water, in this
`(cid:127) Negotiated Energy Cost, working
`case. The system would generate elec-
`closely with the electrical energy sup-
`tricity for use in the manufacturing
`plier may open new avenues within the
`facility and excess thermal energy for
`public utility structure to secure lower
`use in HVAC functions. Working with
`rates. A plan that clearly identifies the
`outside engineering firms, the Corning
`need and alternatives helps in this situ-
`group discovered that it could generate
`ation. Corning reached an agreement
`its own power economically. A plan
`through the introduction of a new elec-
`trical energy rate schedule that benefit-
`was devised to contract a firm to
`design, build, own, and operate a facil-
`ed all parties involved.
`ity to provide electrical energy to
`Corning as a sole customer.
`The Corning team has sharpened its
`(cid:127) W heeling Power, the retail sale of
`pencils and continues to learn. The
`electrical energy,
`involves purchase
`next step will be to apply the team 's
`findings to other Corning facilities.
`from one supplier, in this case the New
`York Power Authority, and transmis-
`The utility may require a minimum num-
`1
`sion of the power via the local utility
`ber of KWH's.
`Electrical Energy Cost
`Reduction Opportunities
`Cogeneration Wheeling Bulk Negotiated
`10-20%
`10-15% 5-8% 0-20%
`Opportunity
`10-20 yr.
`3-5 yr.
`Commitment
`5 yr.
`n/a
`2-3 yrs.
`< 1 yr.
`1-3 yrs.
`Implementation time
`1 yr.
`Table 1 Attributes of each approach
`
`3
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 003
`
`

`

`I
`
`Release of all oxides during glass man-
`ufacturing is an important process as
`in fining of the melt, the
`they assist
`physical and chemical process of
`removing gas bubbles from the molten
`glass melt. A wide variety of gases is
`clearly evolved, as is well known, dur-
`ing the first stages of melting because
`of the decomposition of the constituents,
`carbonates, sulfates, and nitrates; air
`trapped between the grains of the fine-
`grained batch materials; water evolved
`from the hvdrated batch materials: and
`o'
`the changes in oxidation state of some
`of the batch materials.
`to which gas evolution
`The extent
`occurs is not well understood. Major
`emissions from soda-lime glasses have
`been identified as consisting of COT
`NOX. SOT and volatile hydrocarbons.
`It is of interest to identify the tempera-
`ture ranges of specific species that
`evolve and to critically identify the
`*
`evolved gases.
`
`Part 2: Emissions Produced by Batching and Melting of Silicate Glass
`trometer analysis equipment used.) The
`Linda E. Jones
`Batch
`Raw
`glass composition was introduced into
`Assistant Professor
`Composition wt%
`Material
`the batching furnace in a pelletized
`Alexis G. Clare
`form. (See Table I.) When a mixed
`51.7
`SiOi
`Associate Professor
`CaCP3
`15.0
`batch is charged into the hot isothermal
`David Gerling
`furnace, a series of melting, dissolu-
`K2CO3
`1
`Graduate Research Assistant
`tion. volatilization and redox reactions
`' 2
`MgCQ3
`ATS College of Ceramics
`take place. The issue of species
`24.1
`NaN03
`1.7
`Na2SQ4
`volatilization and the influence of these
`5.9
`concurrent processes on volatilization
`Soda Feldspar
`is critical to the release of emissions. A
`SrCP3
`1.4
`secondary series of questions requires
`Tablel Soda-lime-silicate glass compo-
`an understanding of reaction chemistry
`sition introduced into batching furnace.
`and recombination reactions on the
`evolution of gases from the melt. To
`SETRAM.TAG 24. Decomposition
`to isolate emissions released
`data were obtained in ultra-high purity
`attempt
`(UHP ) oxygen flowing at 20 cc/min.
`from the melt, isothermal gas analysis
`was conducted using a batch furnace.
`loss data obtained as a
`The weight
`function of the increasing temperature
`However, issues associated with the
`enabled the identification of tempera-
`reactions between volatiles and release
`ture ranges over which significant gas
`of volatiles as a function of the chem-
`evolution occurred.
`istry of the melt also clearly need to be
`addressed. Evolved gas species identi-
`2 ) Gases evolved from the batch under
`fication was conducted using a Dycor
`isothermal conditions were measured in
`mass spectrometer and capillary sam-
`an isothermal batching furnace fabri-
`this purpose.
`pling system. Mass spectrometry is a
`cated specifically for
`technique which uses an electron beam
`for
`(Fart 1: Emissions Concerns
`to bombard the evolved gas and create
`the
`Manufacturing
`Glass
`in
`GlassResearcher, Vol. 3. No. 2.
`a spectrum of identifiable positive ion
`fragments. Fragments are then separat-
`Winter 1994. p. 5, for a schematic of
`ed on the basis of a mass to charge
`the furnace and capillary mass spec-
`ratio. Mass to charge ratios have been
`identified as possible evolved gas
`Percent
`G;is Species or M;iss to Charge Ratio
`\bundnnce
`fragment Species
`aittu (cid:127) electron 1
`species ( see Table 2 ) along with their
`relative abundances. The sampling sys-
`co
`co.
`tem makes use of a 2-meter length of
`capillary tubing to develop a pressure
`NO
`NO.
`from 1 atm ( 760 torr )
`gradient
`to
`’-SO
`1O *6 torr at the ionizer head. The end
`wSO
`(cid:127)«SO,
`introduced directly
`the capillary,
`of
`’JSO,
`above the class undergoing thermal
`’-SO,
`processing, can “sniff * gases evolved
`’4SP,
`above the melt surface.
`Na.
`Nil
`*>Ca
`The detection limit for this instrument
`“Ca
`is 10'12 torr (~0.3ppm). The nitrogen
`-’Wig
`content in air (78%) serves as the inter-
`«Mg
`“Mg
`nal standard by which concentrations
`are calculated. The N2 pressure for a
`typical run is 3 x 10”6 torr.
`N
`K>.
`i*0'*0
`The soda-lime-silicate ( SLS ) glass
`O
`H O
`composition used in the study does not
`OH
`directly mirror any composition cur-
`jHAr
`rently in use. However, constituents in
`40 \r
`this model enable the measurement of
`both evolved oxides of nitrogen and
`sulfur to be made from the same batch
`composition.
`decomposition
`The
`
`*
`
`the NSF
`In a study undertaken at
`Industry-University Center
`for Glass
`Research on soda-lime-silica (SLS )
`glasses, batch compositions were-
`batched and melted, and the resultant
`emissions were identified and quanti-
`fied. These data were then compared to
`those predicted by thermodynamic
`modeling of the phase equilibria pro-
`duced upon batching and melting. The
`predicted concentrations of products
`formed at temperature were based upon
`minimum Gibbs free energy considera-
`tions.
`While this routine does not provide
`reac-
`information on ’ the kinetics of
`tions.
`tendencies
`for
`indicates
`it
`volatilization through vapor pressure
`data and predicted emissions through
`temperature-dependent phase equilibria
`calculations.
`The experimental study involved two
`approaches:
`1 ) A decomposition analysis of
`the
`glass batch required a high-temperature
`analyzer,
`gravimetric
`a
`thermal
`4
`
`28
`44
`30
`46
`48
`50
`64
`66
`80
`82
`23
`46
`40
`44
`24
`25
`26
`28
`14
`32
`34
`16
`18
`17
`38
`40
`
`98.66
`98.84
`99.39
`99.16
`94.79
`4.200
`94.57
`4.190
`94.34
`4.180
`100.00
`100.00
`96.76
`2.086
`78.99
`10.00
`11.01
`99.26
`99.63
`99.52
`0.200
`99.762
`99.60
`99.75
`0.63
`99.6
`
`[CRC B109-3291
`Table 2 Mass to charge ratios of gas
`fragments expected in
`species or
`detectable concentrations at quadru-
`pole from melting a sulfate fined SLS
`at furnace temperatures above 625°C.
`
`continued on p. 5
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 004
`
`

`

`temperature studied
`
`7 :
`
`-
`
`5 e
`
`4
`DTG
`
`-i
`—
`->
`
`:
`r
`
`-
`
`T
`
`IEJ ?
`
`5
`
`0 ! ICl [ HIM \ i r i l l i M
`4
`
`C
`
`TGA
`
`0)
`CL
`E
`GO
`</)
`O)
`E
`
`D1I~ -10-
`
`<D
`O
`o
`
`CO5 -15H
`|-20
`
`JO
`U)
`
`-25
`
`c<
`
`DO£
`
`-30-
`0
`
`200
`
`400
`
`Emissions
`continued from p. 4
`behavior of this SLS batch in dry ultra
`high purity (UHP) oxygen is given in
`Figure 1. Weight loss of the soda lime
`silicate composition was recorded as a
`function of temperature through 1600°C.
`These data were used to identify the
`temperature ranges during which sig-
`nificant volatilization had occurred.
`The decomposition curve for this SLS
`glass was divided into three distinct
`temperature regimes of steady-state
`volatile release. These three regimes
`were defined between 600 and 700° C.
`700 and 1350°C and >1350°C. The
`rates for volatile release differed great-
`ly from regime to regime, indicating a
`change in the mechanism for release.
`Differences in the rates of volatile
`release could be explained by differ-
`ences in the species evolved, changes
`in the diffusion processes, or chemistry
`involved in the release of a given
`species.
`Concentrations of
`the most stable
`species formed from NaNOj and
`Na2S04 as a function of temperature
`are predicted and given in Figures 2
`and 3. The concentrations of gases
`evolved are based upon the concentra-
`tions of NaNO} and Na2S04 in the
`batch. These concentrations can then
`be compared directly. On a molar
`basis, the initial species concentrations
`for this thermodynamic prediction indi-
`cate that, at temperatures in excess of
`1300°C. volatile sodium would exist at
`significantly higher concentrations
`than all other volatile oxides, except
`CO-,.
`
`at
`
`1000 1200 1400 1600
`800
`600
`Degrees Centigrade
`Figure 1 Decomposition of SLS glass in dry UHP Op at 20cc/min heated at rate
`of 10°C/min.
`Species predicted to form from NaNO^
`temperatures in excess of 1400°C
`are. in the order of intensity, Na, NO.
`NaO. Na20. and NO2. Species predict-
`ed to form from Na2S04 at
`tempera-
`tures in excess of 1400°C are Na. S02,
`NaO. SO3. and SO. respectively.
`Oxides of sulfur would not be expected
`in detectable concentrations
`to exist
`until approximately 1300°C. At
`the
`highest temperature the batch furnace is
`capable of achieving (1500°C), equi-
`librium concentration for elemental
`sodium should surpass the concentra-
`tion for any other volatile species. All
`thermodynamic calculations were made
`assuming an atmosphere of dry oxygen.
`An isothermal batch furnace was then
`used in conjunction with the capillary
`mass spectrometer to study gas evolu-
`tion from the batch.
`
`The batch furnace was operated
`isothermally. heated electrically, and
`opened to the environment. Once the
`selected temperature was achieved in
`the furnace, the batch was introduced in
`pelletized form, and the emissions pro-
`duced via melting were analyzed using
`the capillary mass spectrometer. ( See
`Figures 4 and 5.) Mass spectroscopy
`records the intensity of various mass to
`charge ratios (m/e ) as a function of
`time. These m/e ratios were assigned to
`specific species.
`the highest
`At
`(1400°C). emissions were recorded
`
`approximately 30 seconds after the pel-
`let was dropped into the batch tube, and
`continued on p. 1 2
`
`Na
`
`Na
`
`/
`
`rr
`
`0.1
`
`0.001
`
`to *5
`
`to 7
`10 *
`10‘"
`r
`10 u r
`10 *,s
`
`10‘17
`
`400
`
`600
`
`=
`
`c a
`
`.f
`
`uU
`
`Temperature ( C )
`Figure 2 Decomposition equilibrium for 0.00113 mol NaNO0 Figure 3 Decomposition equilibrium for 0.00096 mol Na2So4
`in .005 mol dry O2 determined by SOLGASMIX.
`in 0.0005 mol dry O2 determined by SOLGASMIX.
`5
`
`1200
`800
`1000
`Temperature (C )
`
`1400
`
`1600
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 005
`
`

`

`Environmental Considerations in Glass Furnace Selection
`Geoffrey B. Tuson
`tion furnaces and operate essentially
`Only limited success has been achieved
`free of problem emissions. However,
`Praxair Inc.
`in reducing these emissions with flue
`deNOx
`systems.
`except for a few specialized melting
`Selective
`gas
`Glass manufacturers must consider
`these advantages are out-
`Noncatalytic Reduction (ammonia or
`sectors,
`many factors in selecting the type of
`weighed by the high cost of electricity
`urea injection) operates effectively only
`furnace to use for glass melting.
`for heating and generally shorter fur-
`in a fairly narrow temperature window
`Compliance with stringent environ-
`( 1600 to 2000°F). and so is difficult to
`nace life.
`required
`regulations
`mental
`has
`apply in regenerators where tempera-
`increased attention in recent years.
`Emissions of nitrogen oxides (NOx )
`ture zones shift during the course of an
`Regulations in effect at the time of fur-
`exhaust cycle. Selective Catalytic
`and particulates from glass melters are
`nace construction or rebuild , as well as
`often subject to strict regulations. High
`Reduction, applied to glass furnaces,
`regulations that could impact opera-
`operating temperatures and.
`in some
`faces the difficult problem of catalyst
`tions later in the furnace campaign ,
`“poisoning" by alkali dusts and causes
`cases, high air preheat temperatures of
`lowered NOx reduction efficiency.-
`must be considered. Alternatives that
`furnaces
`combustion heated glass
`meet environmental regulations must
`enhance the formation of flame gener-
`be evaluated in terms of their effect on
`ated NOx. Particulate emissions result
`Particulate emission rates vary with
`glass quality and cost. Two primary
`primarily from volatilization of glass
`glass type, glass surface temperature,
`forming compounds, and physical carry-
`factors, energy and capital investment,
`and gas velocity across the glass and
`affect cost.
`batch surface. Typical particulate emis-
`over of batch materials into the flue.1
`sions rates from regenerative container
`Glass furnaces can be divided by heat
`glass melters without pollution control
`source into those heated electrically
`to 3 lbs per ton of
`equipment are 1
`and those heated primarily by combus-
`glass, increasing as glass pull per unit
`tion. Combustion of liquid or gaseous
`of melter area increases. Electrostatic
`fuel is the predominant source of heat
`precipitators can typically capture
`in most glass furnaces. These fuel-fired
`about 80% of glass furnace particulate
`furnaces can be differentiated further
`emissions. 1
`by their design for recovery of heat
`Oxy-fuel glass melting has been com-
`from furnace exhaust gases and by
`whether fuel is burned with air or with
`mercially demonstrated to reduce NOx
`commercially pure oxygen (90% -
`emissions by 90% or more, and partic-
`100%).
`ulate emissions by 25 to 70% , relative
`to regenerative melting. The level of
`Heat recovery practice ranges from that
`NOx emissions from an oxy-fuel melter
`of day tanks and unit melters. in which
`is influenced greatly by the type of oxy-
`recovery at all. to
`there is no heat
`fuel burner used, by the concentration
`regenerative furnaces, in which energy
`of nitrogen in the furnace atmosphere
`is extracted from the furnace exhaust,
`from air infiltration and other sources,
`to heat combustion air to within 500 to
`600°F of furnace temperature. In terms
`continued on p. 7
`of amount of heat recovered, recupera-
`in between. They
`tive furnaces fall
`NOx EMISSIONS
`require less capital
`than
`investment
`regenerative furnaces yet are less ener-
`gy efficient.
`Oxy-fuel
`fired glass furnaces,
`in
`which air for combustion is replaced
`with commercially pure oxygen, have
`gained grow ing acceptance by the glass
`industry in recent years. To date, these
`furnaces are operated with no heat
`recovery but. because losses related to
`sensible heating of nitrogen in air is
`eliminated, they have fuel efficiencies
`better than air-fuel fired regenerative
`melters.
`Electric melters also play a significant
`role in glass melting. They require less
`initial capital investment than combus-
`
`Electric glass furnaces produce the
`lowest emissions of nitrogen oxides
`and particulates. The “cold top" of
`floating batch materials in these fur-
`naces suppresses the escape of volatiles
`from the melt: the absence of flames
`and combustion exhaust gases elimi-
`nates the emissions of NOx and other
`gaseous pollutants.
`In air-fuel fired glass melters. the drive
`to achieve high air-preheat
`tempera-
`tures to maximize energy efficiency
`works counter to the goal of minimiz-
`ing NOx emissions. NOx emissions
`from regenerative melters are typically
`not less than 4 to 5 pounds per ton of
`glass, and NOx emissions of 10 to 20
`ton are not uncommon.
`pounds per
`
`CONVENTIONAL BURNER
`Figure 1 NOx Emissions vs. Melter N2 Content 100% Oxy-Gas Fired Melters
`
`(cid:127)ULTRA-LOW NOx BURNER
`
`6
`
`(kg/tonne)
`
`1.2
`
`1 -
`
`0.8
`
`0.6
`
`0.4
`
`0.2
`
`0
`
`0
`
`5
`
`(NITER IN BATCH) #
`
`(Ib/ton)
`
`2.4
`
`2
`
`1.6
`
`1.2
`
`0.8
`
`0.4
`
`0
`40
`
`35
`
`20
`10
`30
`25
`15
`N2 IN MELTER ATMOSPHERE (% wet)
`
`O-I Glass, Inc.
`Exhibit 1023
`Page 006
`
`

`

`Environmental
`continued from p. 6
`and by the use of batch nitrates. Praxair
`Inc. has developed low flame tempera-
`ture ultra-low NOx oxy-fuel burners
`that result in much lower NOx emis-
`sions than conventional , higher flame
`temperature oxy-fuel burners. Figure 1 ,
`which plots data taken from several
`commercial oxygen-natural gas fired
`melters, shows the influence of burner
`design , combustion space nitrogen con-
`centration , and batch nitrates on NOx
`emissions.
`Energy Performance
`Electric melters typically operate at 150
`to 850 kWh per ton of glass produced,
`with 70 to 80% of electrical energy
`transferred to the molten glass.
`input
`Melters heated by combustion are less
`energy efficient, with efficiencies rang-
`ing from about 15 to 20% for unit
`melters, up to 50 to 55% for oxy-fuel
`fired melters.
`Typical energy requirements of differ-
`ent furnace options for a 300 tpd con-
`tainer glass melting operation at 25%
`cullet ratio are listed in Table I. Utility
`inputs to the melter itself , as well as a
`“global analysis'* of energy usage that
`considers the fuel required for electric
`power generation, is listed in Table I .
`This data shows the apparently efficient
`electric melter to be the most energy
`intensive option.
`For oxy-fuel melting,
`the energy
`requirement for oxygen production can
`be offset
`largely by fuel savings and
`reduction of electric boosting in the
`melter. Electric boost reductions are
`made possible by the increased flexibil-
`ity of burner location achieved with
`oxy-fuel firing. Also, new oxygen pro-
`duction technology continues to reduce
`the energy requirements and overall
`cost of oxygen. New technologies for
`adsorbent and process improvements
`have made substantial energy reduction
`possible.
`A hypothetical case where heat from
`the exhaust gases of an oxy-fuel melter
`is used to preheat
`incoming batch
`materials is shown in the last column of
`Table I . This represents the lowest
`energy use option , both at
`the melter
`and “globally." Batch/cullet preheating
`has not yet been demonstrated on an
`oxy-fuel fired glass melter.
`To determine the most economic fur-
`nace option , operating costs and
`required investments are analyzed for
`the furnace itself , as well as for any
`
`FURNACE TYPE:
`
`REGEN ELECTRIC OXY-FUEL OXY-FUEL OXY-FUEL */
`3-6
`0.6-i
`0.6-1
`
`YES
`300
`
`NO
`300
`
`N /A
`300
`0
`
`BATCH/CULLET
`PREHEAT
`NO
`)00
`0.5-0.8
`
`YES
`300
`
`3.70
`0.50
`
`446
`
`ELECTRIC BOOST?
`GLASS PULL ( TPDI
`NOX EMISSIONS
`( LB/TOW GLASS I
`MELTER F.NERGY
`( KMHTU/TON I
`FUEL
`ELECTRIC
`OXYGEN ( TPDI
`(cid:127)GLOBA1” ENERGY ANALYSIS
`ELECTRICITY ( KKM /DAY >
`4