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Procedia Environmental Sciences 31 (2016) 887 – 896

The Tenth International Conference on Waste Management and Technology (ICWMT)

An overall solution to cathode-ray tube (CRT) glass recycling

(Una solución general al reciclaje de vidrio con tubos de rayos catódicos (CRT))

Miao Yua, Lili Liua,b, Jinhui Lia,b *

a
School of Environment, Tsinghua University, Beijing 100084, China;
b
Basel Convention Regional Centre for Asia and the Pacific, Beijing 100084, China

Abstract

Cathode-ray tube (CRT) display has entered the peak period of elimination, therefore, the disposal of waste CRT glass is
becoming an urgent problem to be solved. At present, there are already many scholars having done a lot of researches on this
problem, but most of them are constrained in some details of the disposal process, lack of research and development on the
complete technical route of waste CRT glass. This paper highly summarized the overall solution of waste CRT glass, divided into
three main procedures: the first step is CRT glass separation technology and equipment, including thermal-shock method with
strong technical adaptation, simple operation and widely-used nowadays; diamond-cutting method, efficiency and with high
cutting speed; or ultrasonic-chemical separation method, using ultrasonic wave to promote the dissolution of low melting glass
and reduce the concentration of acid solution. The second step is water-ball milling cleaning technology and equipment, high
cleaning efficiency, reducing dust and saving water, combined the traditional wet and dry cleaning technology. The third step is
resource re-utilization, in which the direct use of CRT glass containing the leaded glass produces crystal glass and low lead
fluorescent tube, and lead-free panel glass manufactures foam glass and glass beads; and the indirect use, comprising lead fire-
extraction divided into collaborative smelting and electric furnace smelting, and lead mechanical-activation hydrometallurgy
extraction, reducing the concentration of acid and improving the recovery rate. According to the existing technologies and
equipment from your factory, the selection of appropriate technologies to deal with CRT glass achieves effective resource
recycling and environmentally sound management goals.
© 2016 The Authors. Published by Elsevier B.V This is an open access article under the CC BY-NC-ND
license
© 2015 The Authors. Published by Elsevier B.V.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-reviewunder
Peer-review underresponsibility
responsibilityofofTsinghua
TsinghuaUniversity/
University/ Basel
Basel Convention
Convention Regional
Regional Centre
Centre for for
AsiaAsia
and and
the the Pacific.
Pacific

Keywords: waste CRT glass overall solution; separation; cleaning; re-utilization

* Corresponding author. Tel.: +8601062794143; fax: +8601062772048.

E-mail address: jinhui@tsinghua.edu.cn

1878-0296 © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Tsinghua University/ Basel Convention Regional Centre for Asia and the
Pacific doi:10.1016/j.proenv.2016.02.106
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Introduction

As a result of rapid advances in television manufacturing technologies, more and more conventional televisions
such as CRTs have been replaced by new products such as Liquid Crystal Displays and Plasma Display Panel (Xu,
Li, He, Huang, & Shi, 2012). Therefore, the amount of waste CRT screens is increasing year by year, at the same
time entering the peak period of elimination (Song, Wang, Li, & Zeng, 2012; Yuan, Li, Zhang, & Saito, 2012). The
disposal of waste CRT glass is becoming an urgent problem to be solved (Yuan, Li, Zhang, Saito, & Yang, 2013a).
CRT displays consist of 85% glass, in which 65% panel, 30% funnel and 5% neck glass. Glass is so important part
of the screen that more than 90% of the glass was recycled by the waste recycling facility (Matsuto, Jung, & Tanaka,
2004). The chemical composition varies between the panel and funnel glass, which need to be treated as lead -free
glass and leaded glass respectively (Méar, Yot, Cambon, & Ribes, 2006). The lead content of the funnel glass is 22-
28%, and the lead amount in each display is about 0.68~2.72kg (Nnorom & Osibanjo, 2008; Song, Zeng, Li, Duan,
& Yuan, 2015). Accordingly, lead extraction technology is also quite significant in waste CRT glass recycling
process.
At present, many scholars have done quite amount of researches on CRT glass recycling. In the separation
procedure, the CRT glass was separated by electric-wire heating device (C.-H. Lee, Chang, Fan, & Chang, 2004) or
by thermal shock method (Herat, 2008). In the cleaning procedure, funnel glass containing Pb was washed into a
drum mixer with water for 25 min (Zeng et al., 2015), or by wet scrubbing and ultrasonic cleaning methods (Erzat &
Zhang, 2014a). In the last procedure of reutilization, lead-free glass can be used as fluxing agent in the porcelain
stoneware tile production (Andreola, Barbieri, Karamanova, Lancellotti, & Pelino, 2008), as ceramic productions (E
Bernardo, Andreola, Barbieri, & Lancellotti, 2005; Hreglich, Falcone, & Vallotto, 2001), or as glass foams (Enrico
Bernardo & Albertini, 2006); leaded glass can be used in cement mortar by using recycled beverage and CRT funnel
glass as fine aggregate (J.-S. Lee et al., 2012; Ling & Poon, 2012a; Sikora, Horszczaruk, & Rucinska, 2015), or in
dry-mixed concrete paving blocks (Ling & Poon, 2014); extraction researches include removing most of lead from
crushed funnel glass by 3% to 5% nitric acid (Ling & Poon, 2012b), extraction of lead by thermal reduction with
metallic iron (Lu, Shih, Liu, & Wang, 2013), or lead recovery by chlorinating volatilization process (Erzat & Zhang,
2014b). Most of them are constrained in one step of the procedures of the disposal process, lack of complete
technical route of waste CRT glass and the technologies are non-automated and poor efficiency. In this paper, there
is an overall solution of waste CRT glass summarized, divided into three main procedures: separation, cleaning and
resource re-utilization. According to their own industry characteristics, processing enterprises can integrate all kinds
of advanced technologies into a complete set of treatment scheme, providing an important technical support for
solving CRT leaded and lead-free glass.

1. Technical route

Based on the research of waste CRT glass harmless processing and resource reuse, through CRT glass separation
technique, cleaning technology and reutilization technology, a total solution of CRT glass was proposed, and
specific technology roadmap is shown in Fig. 1.
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Fig.1 An Overall Solution to CRT Glass Recycling

2. An overall solution to waste CRT glass recycling

2.1 The separation technology

The chemical compositions of panel and funnel glass are quite different, the panel glass almost no lead, while the
funnel glass containing high level of lead. As you all known, lead has great harm to human body and environment,
and it has a large resource utilization risk. To increase the utilization rate of CRT glass, it has to separate the panel
and funnel glass before disposing the waste CRT glass. The panel glass was recycled to make new glass products,
while the funnel glass was made into products after harmless treatment. It plays great function to recycle panel and
funnel glass by different treatment.
The following technical schemes can be used for the separation of CRT glass:
x The thermal shock method
This separation method is used by electric wire heating and quench, widely used in China at present. Based on the
traditional electric heating wire method, we developed an automatic, multifunction and efficiency method, using
reticle and heating with heat burst separation method, with the characteristics of pneumatic rotary groove, automatic
winding, nichrome heating flat with constant current, operation table blowing and other core technology features,
shown in Fig.2. It is suitable for different sizes of waste CRT glass, more applicable and operation easily (Li & Li,
2008).
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1.Graver˗2. Funnel glass˗3. Vacuum chuck˗4. Turntable˗5. Panel glass

Fig.2 Electric wire cutting operation platform

x The diamond cutting method

This method is used by diamond wheel, diamond belt or high-pressure water with abrasive. On the basis of the
traditional mechanical cutting method, it improved the equipment and technology, with the characteristics of
automatic edge searching, laser positioning, dual blade pneumatic cutting, vacuum adsorption and closed dust
recovery. Compared with the traditional mechanical method cutting 20 units per hour, the cutting rate is so fast and
efficiency that it can cut 118 units per hour, and at the same time reducing the dust pollution.
x The ultrasonic-chemical separation method
This method is used by nitric and organic acid to dissolve the low melting point glass in the way of soaking or
washing and separate the CRT display glass by cold and hot shock process. Based on the traditional chemical
separation method, combining ultrasonic assisted acid with thermal shock method (shown in Fig.3), it promotes the
dissolution of low melting glass and reduces the concentration of acid solution, better effect on the separation of
waste CRT glass (Li & Wu, 2004).
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1. Panel glass 2. Funnel glass 3. Neck glass 4. Top vent 5. Melting glass 6. Ultrasonic vibration plate 7. External tank 8. Bracket 9. Internal
tank
10. Heating plate 11. Through-hole 12. Waterproof pad 13. CRT tube 14. Cleaning liquid level 15. Water level 16. The height of
ultrasonic vibration plate 17. Heating switch button 18. Temperature instrument
Fig. 3 Ultrasonic-acid leaching separation apparatus

2.2 The cleaning technology of funnel glass

In the waste CRT glass, the inner and outer layer of the glass surface is coated with a fluorescent powder coating
and graphite coating, which need to be removed to ensure the smooth progress of the recycling of waste CRT glass.
At present, there are two cleaning methods in the electronic waste treatment enterprises and waste CRT glass
recycling enterprises, divided into wet cleaning method and dry cleaning method. Wet cleaning uses the special
potion, and the medicinal liquid contains a certain amount of hydrofluoric acid, using the principle of hydrofluoric
acid dissolution of glass, but this method will produce lead containing wastewater. Dry cleaning method means dry
grinding with a roller mill, removing the surface coating from the waste CRT glass, but this method is nois y, easy to
cause dust pollution, and a certain amount of glass dust into the coating dust, easy to enter the air, causing a certain
environmental hazards.
Combined with the wet and dry cleaning method, using water as the cleaning agent, the glass completel y soaked
in the water, the funnel glass dust suspended in the water after grinding, eliminating the step of cleaning with the
individual water in dry grinding, the cleaning effect of the dust on the surface of the glass is better, the cleaning
parameters shown in Tab.1 (Yuan et al., 2013a).

Tab. 1 Cleaning parameters of funnel glass

Number Milling time/min Rotation speed/r/min Charging ratio Material size ratio Solid liquid ratio

1 30 60 30% 6:1 3: 1

2 50 100 40% 5:1 2: 1

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3 70 140 50% 4:1 1.5˖1

4 90 180 60% 3:1 1: 1

5 110 220 70% 2:1 1: 1.5

Fig.4 Before cleaning Fig.5 After cleaning

The optimal scheme for the orthogonal analysis of the experimental results is (by the order of the infl uence
factors to the order from large to small): rotation speed: 180 r / min, milling time: 110mins; material size ratio: 6:1;
solid liquid ratio: 3:1; charging ratio (charging rate for tank volume ratio): 40%. To verify the optimal scheme, the
cleaning efficiency is as high as 99%, the obtain rate is 98.7% (shown in Fig.4 and 5).

2.3 The resource reuse of CRT glass

At present, due to the differences in the world industrial structure, the level of development and concrete national
conditions, and abandoned the particularity of CRT glass, the national recycling waste CRT mainly concentrated in
dismantling, cleaning, panel and funnel glass separation and recycling of CRT glass to manufacture new CRT
cement or ceramic, the further applied research and industrialization of lead containing glass is less. With the CRT
display elimination, the recycled CRT dosage used in the manufacture of new CRT electronic glass will continue to
decrease, at the same time CRT has started a new way of application of electronic glass or disposal methods
domestic and international.
The resource reuse of CRT glass can be divided into direct and indirect use, the details as follows:
x Direct use
The development of new type of glass based on waste CRT glass has been carried out long before, but the
reaction mechanism and the optimum reaction conditions of the preparation process are not yet clear, and the
comparison and analysis of physical and chemical properties and standards of new type glass material are still
deficient. Mature technologies include: crystal and low lead fluorescent tube which are made of lead glass; foam
glass and glass beads which are made of lead-free glass.
Leaded glass
Crystal can be made of waste CRT funnel glass. The lead quantity in waste CRT glass and in lead crystal glass
(PbO ≥ 24%) are almost the same, therefore, the way to use of waste CRT funnel glass as the raw material of crystal
products is more suitable for resource utilization. In the process of producing crystal, addition of lead oxide in order
to increase the product material properties, gloss and heavy metal sense, translating the production of one ton of
crystal glass products can reduce the use of about 0.2 tons of lead oxide by using funnel glass.
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Fig. 6 Waste CRT funnel glass products - crystal

Low lead fluorescent tube also can be made of waste CRT funnel glass. After cleaning, the funnel glass can be
used for the manufacture of low lead fluorescent lamp. CRT funnel glass added potassium and barium glass, and
there is no need to add red lead or lead silicate, saving a lot of lead resource. Compared with adding red lead or lead
silicate directly, it decreased lead dust and improved working conditions. The fluorescent lamp made of CRT funnel
glass is in accordance with the product standards, the company standards shown in Tab.2.

Tab.2 Tianjin Renxin glass materials Co., Ltd. enterprise product standards Q/12DG4686-2012
3DUDPHWHUV ,QGH[ UHTXLUHPHQWV

$SSHDUDQFH &DQDU\ \HOORZ

3DUWLFOH VL]H PP İ

0RLVWXUH FRQWHQW İ
/HDG R[LGH FRQWHQW ̚
'HQVLW\ J FP f

Lead-free glass
Foam glass can be made of waste CRT panel glass. Due to panel glass containing foaming agent Sb2O3, it can
reduce the additive amount of Sb2O3, so as to reduce the cost of foam glass. Foaming process does not need any
change, and can produce 17cm thick foam glass, its parameters and its performance in line with the national standard
of foam glass (Ling & Poon, 2012a).
Top-grade glass beads can be made of waste CRT panel glass, without any additives, and the production of glass
beads with high refractive index, reaching 1.537. They can be widely used in mechanical processing of surface
treatment (shot peening), road reflective tape and road marking.
x Indirect use
By some estimates, China generated 50 thousands to 80-thousand tons of waste CRT lead glass each year from
waste electrical and electronic products dismantling processing plant. At present, the annual capacity of the direct
use, such as crystal and energy-saving lamps, is unable to meet the needs of processing. Indirect utilization refers to
the extraction of lead from the glass network, and then used in other fields. At present, there are mainly two ways to
extract lead from the funnel glass, fire extraction and wet extraction, and the former one is more widely.
Fire extraction
Fire extraction can be divided into two ways: one is co-treatment of CRT leaded glass with existing lead smelting
facilities; the other one is lead glass melting furnace for CRT.
Co-melted
Waste CRT funnel glass is co-melting with the existed lead melting equipment, not only saving the raw material
of lead, reducing import of lead concentrate, but also solving the treatment of waste CRT funnel glass and
preventing environment pollution. In the process of lead melting, SiO 2 was added as the fluxing medium, promoting
the formation of silicon slag. While PbO amount in CRT funnel glass is 20%, and SiO2 is 50%, as lead raw materials
for smelting, it does not need add extra smelting flux.
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Waste CRT funnel glass is co-melted with waste lead acid battery paste melting furnace. Waste CRT funnel glass
can replace SiO2 as slagformer, having little effect on the technological parameters, improving the comprehensive
recovery of lead, and with the characteristics of continuous operation and low lead content.
Waste CRT funnel glass is co-melted with primary lead. CRT funnel glass can replace quarz as flux when lead
melting, suitable for primary lead melting company. At present, oxygen bottom blowing, blast furnace and flash
smelting technologies can add CRT funnel glass.
The effect of the proportion of adding lead glass and that of flux is the same, non-affecting the original process,
shown in Tab.3 (Li, Li, Xie, & Zhou, 2014).
Tab. 3 Test material formula parameter list (Kg/min)

Output
Water
Program Lead Funnel Ion Melting Water
number glass slag Limestone quenching Anthracite Regenerative
anthracite quenching
slag lead
slag
201300 185 0 8.5 2.4 26.3 6.6 10.6 142.4 37
201301 270 7 16.5 3.9 0 9.6 13.2 181.6 27
201302 349 18 39.7 14.5 0 15.9 22.9 232.2 72

Electric furnace smelting

In the process of electric furnace smelting, electrode is inserted into the furnace charge or liquid melt, relying on
the dual role of forming electrode and slag on the interface between the micro arc and melt resistance, converting the
electric energy into heat energy. After putting the funnel glass into the furnace, the temperature is raised to more
than 1000ć, and additive of a kind of chemical substance is sinking the lead and floating the glass. The extraction
of lead can be sold directly, and the use of pure glass is currently being explored, with the advantages of direct
treatment and getting pure glass, and the disadvantages of high cost and small treatment amount.
Mechanical-activation hydrometallurgy
With the development of wet metallurgy, the strengthening of mineral leaching process has gradually attracted the
attention of scholars. In the past, among the strengthening methods, high temperature, high concentration, high
fineness and strong stirring, etc. are common methods, but it has the defects of the material and energy consumption,
high cost and a large amount of three kinds of waste.
Mechanical-activation hydrometallurgy changes the surface and inner structures of CRT glass by pretreatment of
CRT lead funnel glass by mechanical activation method, so as to increase the internal energy of the material, the
reaction activity and the leaching rate (Yuan, Li, Zhang, Saito, & Yang, 2013b). This method can change the
chemical properties of CRT funnel glass, making it difficult to dip into a dip type. The CRT funnel glass after
mechanical-activation, combing the traditional wet acid leaching technology and curing technology, can be extracted
lead efficiently with mild reaction condition and easy process flow. It reduces the leaching time and improves the
lead recycling rate.

3 Conclusion

This paper highly summarized the overall solution of waste CRT glass. There are three main procedures: the first
step is CRT glass separation technology and equipment, including thermal-shock method with strong technical
adaptation, simple operation and widely-used nowadays; diamond-cutting method, efficiency and with high cutting
speed; or ultrasonic-chemical separation method, using ultrasonic wave to promote the dissolution of low melting
glass and reduce the concentration of acid solution. The second step is water-ball milling cleaning technology and
equipment, high cleaning efficiency, reducing dust and saving water, combined the traditional wet and dry cleaning
technology. The third step is resource re-utilization, in which the direct use of CRT glass containing the leaded glass
produces crystal glass and low lead fluorescent tube, and lead-free panel glass manufactures foam glass and glass
beads; and the indirect use, comprising lead fire-extraction divided into collaborative smelting and electric furnace
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smelting, and lead mechanical-activation hydrometallurgy extraction, reducing the concentration of acid and
improving the recovery rate. According to the existing technologies and equipment from your factory, the selection
of appropriate technologies to deal with CRT glass achieves effective resource recycling and environmentally sound
management goals.

Acknowledgements

The work was financially supported by the National Key Technology R&D Program (2014BAC03B04), and the
National Natural Science Foundation of China (71373141).

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