GLASS BATCH COMPOSITIONS COMPRISING CULLET AND METHODS OF FORMING GLASS WITH CULLET

Abstract

The present disclosure relates to glass batch compositions. The present disclosure also relates to methods of forming glass with cullet.

Claims

1. A glass batch composition, comprising: from 1 weight % to 50 weight % a first plurality of glass cullet particles, wherein the first plurality of glass cullet particles have a maximum dimension of 5mm or less and the glass cullet particles are organically contaminated; from 50 weight % to 99 weight % other components of the glass batch; and unavoidable impurities; wherein the organic contamination of the first plurality of glass cullet particles: a. measured by loss on ignition (“LOI”) is from 0.5 weight % to 20 weight % of the first plurality of glass cullet particles; and/or, b. measured by chemical oxygen demand (“COD”) is from 4,000 mg O.sub.2/L to 75,000 mg O.sub.2/L; and/or, c. measured by combustion analysis provides a carbon content of from 0.30 weight % to 15 weight %.

2. The glass batch composition according to claim 1, wherein the organic contamination of the first plurality of glass cullet particles: a. measured by loss on ignition (“LOI”) is from 0.5 weight % to 20 weight % of the first plurality of glass cullet particles; and b. measured by chemical oxygen demand (“COD”) is from 4,000 mg O.sub.2/L to 75,000 mg O.sub.2/L; and c. measured by combustion analysis provides a carbon content of from 0.30 weight % to 15 weight %.

3. The glass batch composition according to claim 1, wherein the organic contamination of the first plurality of glass cullet particles measured by loss on ignition (“LOI”) is: from 1.2 weight % to 20 weight % of the first plurality of glass cullet particles; or, from 2.5 weight % to 17.0 weight % of the first plurality of glass cullet particles.

4. The glass batch composition according to claim 1, wherein the organic contamination of the first plurality of glass cullet particles measured by chemical oxygen demand (“COD”) is: from 16,000 mg O.sub.2/L to 75,000 mg O.sub.2/L; or, from 15,000 mg O.sub.2/L to 63,000 mg O.sub.2/L.

5. The glass batch composition according to claim 1, wherein the organic contamination of the first plurality of glass cullet particles measured by combustion analysis provides: a carbon content of from 0.45 weight % to 11 weight %; or, a carbon content of from 1.5 weight % to 10 weight %.

6. The glass batch composition according to claim 1, wherein the first plurality of glass cullet particles: have a maximum dimension of: 2 mm or less; 1.5 mm or less; or, 1 mm or less; or, have a maximum dimension of: from 5 μm to 500 μm; or, from 5 μm to 300 μm.

7. The glass batch composition according to claim 1, wherein the glass batch composition comprises from 1 weight % to 50 weight % (or from 1 weight % to 25 weight %) a first plurality of glass cullet particles, wherein the glass cullet particles have a maximum dimension of 2 mm or less and the glass cullet particles are organically contaminated.

8. The glass batch composition according to claim 1, wherein the other components comprise a second plurality of glass cullet particles (optionally having a maximum dimension of greater than 5 mm), wherein the second plurality of glass cullet particles all have a maximum dimension greater than the first plurality of glass cullet particles.

9. The glass batch composition according to claim 1, wherein the first plurality of glass cullet particles, and optionally the second plurality of glass cullet particles, are organically contaminated with: one, two, three, four, five, six or seven of: cellulose, lignin, proteins, lipids, carbohydrates, polymers and/or plastics; and/or, one, two, three, four, five, six, seven or eight of: paper, glue, sugar, oil, fat, plastics, wood and/or cork.

10. The glass batch composition according to claim 1, wherein: the glass batch composition is a loose glass batch composition; optionally, wherein the loose glass batch is not agglomerated in pellet or briquette form; and/or, the first plurality of glass cullet particles, and optionally the second plurality of glass cullet particles, is free of metals and/or ceramics.

11. The glass batch composition according to claim 1, wherein the glass batch composition is a soda lime glass batch composition; optionally, wherein the from 50 weight % to 99 weight % other components of the glass batch composition comprise, or consist of: silica sand, soda ash and limestone.

12. The glass batch composition according to claim 1, wherein the glass batch composition is a flint glass batch composition; optionally, comprising silica sand, soda ash, limestone and dolomite; optionally, further comprising sodium sulfate.

13. The glass batch composition of according to claim 1, wherein the: from 1 weight % to 50 weight % a first plurality of glass cullet particles component of the glass batch composition provides a contributing redox factor of from 0 to −1.5 to the glass batch composition; and/or, wherein the glass batch composition has a batch redox number of: from −40 to +20; or, from −20 to +20.

14. The glass batch composition according to claim 1, wherein the first plurality of cullet particles, and/or the second plurality of cullet particles, absent organic contamination (the glass fraction) have a chemical composition comprising: Fe.sub.2O.sub.3 in an amount ranging from 0.3 to 0.8 weight %; Al.sub.2O.sub.3 in an amount ranging from 1.5 to 2.2 weight %; K.sub.2O in an amount less than 1 weight %; CaO in an amount ranging from 11 to 12 weight %; MgO in an amount ranging from 1.3 to 1.6 weight %; Na.sub.2O in an amount ranging from 12 to 13 weight %; SiO.sub.2 in an amount ranging from 70.31 to 73.84 weight %; and Cr.sub.2O.sub.3 in an amount ranging from 0.06 to 0.09 weight %.

15. The glass batch composition according to claim 1, consisting of: from 1 weight % to 50 weight % the first plurality of glass cullet particles, wherein the first plurality of glass cullet particles have a maximum dimension of 5 mm or less and the glass cullet particles are organically contaminated; from 50 weight % to 99 weight % the other components of the glass batch; and unavoidable impurities.

16. A method of forming glass, the method comprising: introducing the glass batch composition according to claim 1 into a glass furnace; heating the glass batch composition to produce a glass solution; and cooling the glass solution to make a glass.

17. A method of controlling the redox number of a glass batch composition, comprising introducing a plurality of glass cullet particles into a glass melt furnace, wherein the glass cullet particles have a maximum dimension of 5 mm or less and the glass cullet particles are organically contaminated.

18. The method according to claim 17, wherein the glass cullet particles have a maximum dimension of 2 mm or less.

19. The method according to claim 17, wherein the glass cullet particles have a maximum dimension of 1 mm or less.

20. The method according to claim 17, wherein: the glass cullet particles contribute a redox factor of from 0 to −1.5 to the glass batch composition; and/or, wherein the glass batch composition has a batch redox number of: from −40 to +20; or, from −20 to +20.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0094] Embodiments of the disclosure are described below with reference to the accompanying drawings. The accompanying drawings illustrate various embodiments of systems, methods, and embodiments of various other aspects of the disclosure. Any person with ordinary skills in the art will appreciate that the illustrated element boundaries (e.g., boxes, groups of boxes, or other shapes) in the figures represent one example of the boundaries. It may be that in some examples one element may be designed as multiple elements or that multiple elements may be designed as one element. In some examples, an element shown as an internal component of one element may be implemented as an external component in another and vice versa. Furthermore, elements may not be drawn to scale. Non-limiting and non-exhaustive descriptions are described with reference to the following drawings. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating principles.

[0095] FIG. 1 shows the formation of green glass with targeted iron redox.

[0096] FIG. 2 shows the weight fraction of cullet particles of different sizes in certain example cullet fines.

DETAILED DESCRIPTION

[0097] Some embodiments of this disclosure, illustrating all its features, will now be discussed in detail. The words “comprising,” “having,” “containing,” and “including,” and other forms thereof, are intended to be equivalent in meaning and be open ended in that an item or items following any one of these words is not meant to be an exhaustive listing of such item or items, or meant to be limited to only the listed item or items.

[0098] It must also be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Although any systems and methods similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present disclosure, the preferred systems and methods are now described.

[0099] Embodiments of the present disclosure will be described more fully hereinafter with reference to the accompanying drawings in which like numerals represent like elements throughout the several figures, and in which example embodiments are shown.

[0100] Embodiments of the claims may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. The examples set forth herein are non-limiting examples and are merely examples among other possible examples.

[0101] Some of the terms used to describe aspects of the present disclosure are set out below:

[0102] “Carbon content” refers to the total amount of carbon present in a sample. Carbon content can be measured by combustion analysis. In some examples, the carbon content can be measured by combustion analysis with a LECO™ CS230.

[0103] “Chemical oxygen demand” or “COD” refers to a measure of the amount of oxygen that can be consumed by reactions in a measured solution. COD is expressed in mass of oxygen consumed over volume of solution. A measure of COD quantifies the amount of organic material present in water. In some examples, the chemical oxygen demand can be measured according to a COD procedure using a HACHTM LCK 514.

[0104] “Cullet” refers to broken and/or ground waste glass. Cullet can be separated into different waste streams, depending on particle size and/or contamination. Cullet can be contaminated with organic material, metals and/or ceramic pieces.

[0105] “Cullet fines” refers to cullet in which the cullet particles have a maximum dimension of 5 mm or less. Cullet fines can be separated into different streams in which the cullet particles have the following maximum dimensions: [0106] 1. Finest cullet fines: Less than 0.5 mm [0107] 2. Finer cullet fines: From 0.5 mm to less than 2 mm [0108] 3. Fine cullet fines: From 2 mm to 5 mm.

[0109] “Glass” is an amorphous, non-crystalline, solid material. Glasses are typically brittle and often optically transparent. A glass is defined as an inorganic product of fusion which has been cooled through its glass transition to the solid state without crystallising. The main component of most glasses, in general use, is silica (SiO.sub.2). Common glass is generally produced in a two step process, and then shaped to make it suitable for a variety of applications. The first step is batch mixing. The mixture of ingredients to make up the glass (typically at least, silica, sodium carbonate, calcium carbonate and recycled glass (in the form of cullet), together with small quantities of various other trace ingredients) are mixed, to ensure an even mix of ingredients, and fed into the furnace. In the second step, the mixture is heated to around 1,500° C., where the ingredients melt, various chemical reactions take place and CO.sub.2 and SO.sub.2 are evolved. These chemical reactions form molten glass (or, “glass solution”) which can be moulded and cooled.

[0110] “Glass batch” or “Glass batch composition” refers to a mixture of ingredients intended to form a glass melt. A glass batch for forming a soda lime glass comprises silica sand, soda ash and limestone (along with other, optional, components). These components of a glass batch can be combined from separate raw materials or can be supplied pre-mixed.

[0111] “LOI” refers to loss on ignition. This measurement is obtained by strongly heating a sample (optionally a dried sample) at a specified temperature and allowing any volatile substances to escape. This continues until the mass of the sample stops changing. The value of LOI represents the mass of volatile material present in a sample. In some examples, the LOI can be measured from the decrease in mass after heat treatment in an oven.

[0112] “Maximum dimension” refers to the longest cross-sectional dimension of any particular particle.

[0113] “Redox number” refers in glass technology to a measure of the oxidation/reduction potential of glass batch components. One technique for quantifying the redox number of glass batch components is described in Simpson and Myers, “The Redox Number Concept and Its Use by the Glass Technologist,” Glass Technology, Vol. 19, No. 4, Aug. 4, 1978, pages 82-85 (the disclosure of which is incorporated herein by reference). A glass batch (as a whole) has a “batch redox number”. In general, a glass batch having a batch redox number of zero and above is considered “oxidized,” and a glass batch having a negative batch redox number is considered “reduced.”

[0114] “Redox factor” refers in glass technology to the amount one specific component of a glass batch contributes to the overall redox number of a glass batch, i.e. it is a weighing factor.

[0115] “Unavoidable impurities” refers to components present in a composition which do not affect the properties of the composition. Unavoidable impurities are present in a composition at: less than 5 weight %; or, less than 4 weight %; or, less than 3 weight %; or, less than 2 weight %; or, less than 1 weight %; or less than 0.5 weight %; or less than 0.1 weight %.

[0116] “Weight %” refers to the percentage weight in grams of a component of a composition in every 100 grams of a composition. For example, if a glass batch composition contains cullet at 10 weight %, then there is 10 g of cullet for every 100 g of the glass batch composition.

EXAMPLES

[0117] The following are non-limiting examples that discuss, with reference to tables and figures, the advantages of using organically contaminated cullet according to the present disclosure. Prior to the present disclosure such organically contaminated cullet was sent to landfill because organic contamination was seen as an unacceptable waste component.

[0118] Formation of Green Glass

[0119] The following non-limiting examples discuss the preparation and use of glass batches according to the presently claimed invention.

[0120] A glass batch (GB1) was made from quartz sand (58 wt %), soda ash (18 wt %), limestone (13 wt %), dolomite (5.6 wt %), nepheline syenite (4.8 wt %), sodium sulfate (0.2 wt %), iron oxide (0.2 wt %), iron chromite (0.2 wt %). To this mixture (GB1) varying additions of cullet fines were made. Table 1 shows the varying amounts and types of cullet fines. Each column of Table 1 shows the following: [0121] The “Type” column shows the internal nomenclature used to refer to each type of cullet fines used. [0122] The “Amount of cullet fines” column shows the amount of the type of cullet fines included in the glass batch (i.e. added to GB1). FIG. 2 shows the distributions of the maximum dimensions in the tested cullets. FIG. 2 shows the weight fraction of the cullet maximum dimensions (y axis) resting on particular sieve sizes (the x axis), for each type of cullet fine (i.e. designated A, B, C and D in Table 1). [0123] The “GB1” column shows the amount of GB1 included in the particular example glass batch. [0124] The “Batch redox number” column shows the batch redox number for each glass batch. [0125] The “Cullet fines LOI” column shows the measured value of LOI for the cullet fines of the particular types. [0126] The “Cullet fines COD” column shows the measured value of COD for the cullet fines of the particular types. [0127] The “Cullet fines carbon content” column shows the measured value of carbon content for the cullet fines of the particular types. [0128] The “Characteristics of resulting glass (iron redox)” column shows the iron redox of the resulting glass, as determined with UV-Vis spectroscopy.

TABLE-US-00002 TABLE 1 Cullet fines Characteristics Amount of GB1 (identical Batch Cullet fines Cullet fines carbon of resulting cullet fines/ proportions)/ redox LOI/ COD/ content/ glass (iron Type weight % weight % number weight % mg O.sub.2/L weight % redox) A 3.85% 96.15% −4.6 5.89 25500 3.36 0.2356 A 13.79% 86.21% −16.8 5.89 25500 3.36 0.6358 B 1.96% 98.04% −4.6 12.62 47000 7.57 0.2563 B 6.98% 93.02% −16.8 12.62 47000 7.57 0.6324 C 5.35% 94.65% −4.6 2.84 16000 1.55 0.3064 C 24.53% 75.47% −16.8 2.84 16000 1.55 0.6504 D 1.47% 98.53% −4.6 16.29 62000 9.89 0.2491 D 5.39% 94.61% −16.8 16.29 62000 9.89 0.5836

[0129] Acceptable levels for the iron redox values depend on the glass type that is to be made. The whole range from oxidised (batch redox number of zero and above) to reduced (negative batch redox number) can be chosen, depending on the type of glass produced. After this choice is made, typically a glass manufacturer will not change the desired batch redox number because this will affect the production method and the product quality. The fact that organic contamination of cullet affects the redox number of glass batches leads to the problem of uncontrolled variations in the iron redox of glass produced from glass batches containing organically contaminated cullet. The present inventors surprisingly discovered that with measurement and control over the characteristics of the organically contaminated cullet, the organically contaminated cullet can be used as an effective reductant without uncontrolled disturbances to the glass melting process.

[0130] Formation of Flint Glass

[0131] A glass batch (GB2) was made from quartz sand (61.2 wt %), soda ash (18.36 wt %), limestone (13.77 wt %), dolomite (6.12 wt %), and sodium sulfate (0.55 wt %). To this mixture (GB2) cullet fines were added. Table 2 shows the amount of cullet fines. Each column of Table 2 shows the following: [0132] The “Type” column shows the internal nomenclature used to refer to the type of cullet fines used. [0133] The “Amount of cullet fines” column shows the amount of the type of cullet fines included in the glass batch (i.e. added to GB2). FIG. 2 shows the distributions of the maximum dimensions in the tested cullets. FIG. 2 shows the weight fraction of the cullet maximum dimensions (y axis) falling through particular sieve sizes (the x axis), for each type of cullet fine (i.e. designated E in Table 2). [0134] The “GB2” column shows the amount of GB2 included in the particular example glass batch. [0135] The “Cullet fines LOI” column shows the measured value of LOI for the cullet fines of the particular types. [0136] The “Cullet fines COD” column shows the measured value of COD for the cullet fines of the particular types. [0137] The “Cullet fines carbon content” column shows the measured value of carbon content for the cullet fines of the particular types. [0138] The “Characteristics of resulting glass (iron redox)” column shows the iron redox of the resulting glass, as determined with UV-Vis spectroscopy.

TABLE-US-00003 TABLE 2 GB2 Cullet Amount (identical Cullet Cullet fines of cullet propor- fines fines carbon Characteristics fines/ tions)/ LOI/ COD/ content/ of resulting weight weight weight mg weight glass (iron Type % % % O.sub.2/L % redox) E 3.85% 96.15% 5.64 25000 3.11 Not measured The batch redox number for the batch shown in Table 2 was +5.4.

[0139] The methods of obtaining the information in Tables 1 and 2 are set out below.

[0140] Cullet Fines Characteristics

[0141] The carbon content of the cullet fines was measured by combustion analysis with a LECO™ CS230.

[0142] The loss-on-ignition of the cullet fines was determined from the decrease in mass after heat treatment. The cullet fines were first dried for 1 hour at 105° C. in a drying chamber (Memmert GmbH UFB500). An alumina crucible with the dried material was inserted in a laboratory furnace (Nabertherm GmbH) and subjected to a temperature of 550° C. for 3.5 hours or of 1100° C. for 1 hour. The decrease in mass of the material (i.e. the dried material), which had been subjected to the heat treatment, was measured and determined the loss-on-ignition.

[0143] The chemical oxygen demand (COD) of the cullet fines was measured by inserting 50 g of the cullet fines in a glass beaker with 2 L of water, preheated to 65° C. The temperature of the water was maintained at 65° C. with a recirculation bath. Every 30 minutes the mixture was agitated with a glass rod. After 60 minutes, the glass beaker was removed from the bath, covered with a lid and left to cool to room temperature. The contaminated water was then analysed according to the COD procedure (Hach LCK 514). The value is normalised to mg O.sub.2/kg or equivalently mg O.sub.2/L to enable a direct comparison with COD measurements on cullet, where conventionally 10 kg is inserted into 10 L of water.

[0144] The particle size distribution of the cullet fines was determined with a vibration sieve shaker using sieve sizes of 1000, 710, 500, 355, 250, 180, 125, 90 and 63 μm.

[0145] The composition ranges of the organically contaminated cullet used in these experiments was as shown in Table 3.

[0146] Table 3: Composition ranges cullet fines (glass fraction; excluding unavoidable impurities)

TABLE-US-00004 Compound Weight % Fe.sub.2O.sub.3 From 0.3 to 0.8 Al.sub.2O.sub.3 From 1.5 to 2.2 K.sub.2O <1 CaO From 11 to 12 MgO From 1.3 to 1.6 Na.sub.2O From 12 to 13 SiO.sub.2 From 70.31 to 73.84 Cr.sub.2O.sub.3 From 0.06 to 0.09

[0147] The ranges of organic contamination for the cullet samples tested (not all shown in Table 1) had the following characteristics: [0148] L01: 1.2-20 wt % [0149] Carbon content: 0.45-11 wt % [0150] COD: 16,000-75,000 mg O.sub.2/L

[0151] Resulting Glass Characteristics

[0152] The glass batch mixture, in each case, was melted in a platinum crucible (XRF Scientific Ltd, 87Pt-10Rh-3Au) in a laboratory furnace (Nabertherm GmbH LHT08/17) at 1450° C. for 2 hours. The glass melt was quenched, ground, mixed and remelted at 1450° C. for 2 hours. The molten glass was then poured from the crucible onto a heating plate (LHG) and the resulting glass bead is transferred to an annealing furnace (Nabertherm GmbH N7/H) at 580° C. for annealing for two hours and slow cooling to room temperature, over at least six hours.

[0153] The annealed glass bead was ground in a grinder (Struers Inc. Tegramin 25) with resin-bonded diamond-surface plates (Struers Inc. MD-Piano) to approximately 4 mm (as maximum dimension) and then polished with a woven-acetate polishing cloth (Struers Inc. MD-Dac). The light transmission of the polished glass bead was measured with a spectrophotometer (PerkinElmer™ Lambda 950) in the wavelength range of from 250 to 1100 nm.

[0154] Remnant glass from the melting procedure was ground with a ball mill and used for composition analysis. The glass powder was mixed with lithium tetraborate and converted to a glass disc by fusion (XRF Scientific XRFuse 6). This glass disc was used to measure the glass composition with an X-ray fluorescence spectrometer (Malvern PANalytical B.V. Axios.sup.mAx).

[0155] The iron redox value of the glass was calculated from the total iron oxide concentration measured with XRF and the light transmission of the glass bead, according to the following formula:

[00001]$\frac{{\mathrm{Fe}}^{2+}}{{\mathrm{Fe}}_{\mathrm{tot}}}=-\frac{\log \left(T/0.92\right)}{\mathrm{dc}\alpha }$

[0156] The light transmission of the glass bead was measured in each instance using a PerkinElmer™ Lamda 950 spectrophotometer.

[0157] In this formula, T is the light transmission at 1050 nm (%), d is the thickness of the glass bead (cm), c is the total iron oxide concentration (wt %) and a is the linear extinction coefficient for ferrous iron with a value of 9.1.

[0158] Effect of Organic Contamination on Iron Redox in Resulting Glass

[0159] FIG. 1 shows that as the organic contamination increases (i.e. LOI-equivalent added) the iron redox figure increases. Therefore, adding relatively more organically contaminated cullet fines to a glass batch provides control over the glass batch reaction (the organically contaminated cullet acts as a reductant). High levels of organically contaminated cullet leads to more reduced glass (which is likely not the aim in most desired glass products). At extremely high levels of organically contaminated cullet (for example greater than 50 weight % in a glass batch), actual metal, e.g. metallic iron, can form during a glass batch melt method.

[0160] The present inventors surprisingly discovered that the use of cullet fines in glass batch compositions provide beneficial glass compositions. Prior to the present disclosure, such cullet fines were generally sent to landfill. The present inventors also discovered that by varying the organic contamination in cullet fines it is possible to control the iron redox of the produced glass.

[0161] When used in this specification and claims, the terms “comprises” and “comprising” and variations thereof mean that the specified features, steps or integers are included. The terms are not to be interpreted to exclude the presence of other features, steps or components.

[0162] The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the claimed invention in diverse forms thereof.