Professional Documents
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Ares(2016)2051960 - 29/04/2016
Deliverable 2.1
D 2.1
Project Funded by the European Commission under the Horizon 2020 Framework Programme. Grant Agreement No 641998
PROGRAMME H2020 – Water
GRANT AGREEMENT NUMBER 641998
PROJECT ACRONYM REMEB
DOCUMENT WP 2 INTERNAL DOCUMENT
TYPE (DISTRIBUTION LEVEL) ☒ Public
☐ Confidential
☐ Restricted
DUE DELIVERY DATE 30/04/2016
DATE OF DELIVERY 29/04/2016
STATUS AND VERSION Final version
NUMBER OF PAGES 35
WP / TASK RELATED 2.1
WP / TASK RESPONSIBLE FACSA / ITC-UJI
AUTHOR (S) ITC-UJI
PARTNER(S) CONTRIBUTING SAM, FACSA and CENTRO CERAMICO
FILE NAME Technical document with the study of the
ceramic process
DOCUMENT HISTORY
5. BIBLIOGRAPHY ......................................................................................................... 30
6. ANNEXES.................................................................................................................. 34
Figure 4. Scheme of an industrial pug mill with deairing chamber and extrusion auger. 8
Figure 11. Evolution of bulk density and water absorption with temperature of the
spray-dried powder. ....................................................................................................... 16
Figure 13. Fired tile scrap collected in a ceramic company located in Castellón area
(Spain). ............................................................................................................................ 20
Figure 14. Particle size distribution of fired tile scrap after milling, compared with
commercial chamotte, by dry sieving. ........................................................................... 21
Figure 15. FEG-ESEM micrographs of fired tile scarp after milling (500µm).
Magnification: a) 1000x, b)5000x. .................................................................................. 21
Figure 20. Facilities where olive bones and wet pomace were separated. ................... 25
Figure 23. Cumulate weight of milled olive bones, compared with olive bones as
collected ......................................................................................................................... 27
Note: most of the pictures used in this document belong to the ITC’s repository.
In this task, the extruded tile’s fabrication process has been analysed, assessing the
whole process, from the materials reception and characteristics to the final packaging.
Next, the sections that should be modified have been determined and the necessary
changes have been analysed, so that it has been proposed the use of waste materials
for membranes manufacture. This represents a big challenge for this project, since this
assessment includes the route to incorporate the waste materials in the manufacturing
process.
Wastes from different sources have been characterised, in order to analyse their
differences and the influence in the membrane’s properties. A first attempt to
introduce them in the membrane’s composition has been done, although the complete
study will be done in Task 3.4.
Finally, all the parameters necessary to carry off the Life Cycle Assesment (Task 3.5)
have been analysed and listed, to collect them in the next WPs.
Extrusion is a common plastic forming technique for the production of solid and hollow
products with a uniform cross section. Extrusion is shaping by forcing a cohesive plastic
material through the orifice of a rigid die. A lineated extrudate with a controlled cross
section is formed which is then cut to length to form the product. Extrusion is a very
productive forming technique that is used for the mass production of both large and
small products. Traditional construction materials such as bricks and tiles are produced
by extrusion, being the plastic consistency obtained by the use of a clay binder.
The traditional manufacturing extrusion process usually involves dry grinding of the
raw materials, plastic shaping by extrusion, following by drying and firing in continuous
or periodic kilns, a manufacturing process which usually takes longer than 24 h. In the
ceramic company contacted, raw materials are milled by the provider, so it is
unnecessary the stage of grinding, being the production process as follows:
Extruded
product
Raw materials Dosage and
storage mixing Kneading Extrusion Drying Sintering
Raw materials normally used by the ceramic company are placed in storage silos or big
bags. Thanks to the dosage and weighing system, raw materials are introduced in the
desired amount in the compositions. The ceramic company has the possibility to add 4
raw materials to the composition; nevertheless, since the conveyor belt is not closed,
other minority raw materials can be added manually to the composition.
After dosage, raw materials are directly carried to the mixer. Plastic feed material for
extrusion is prepared by directly batching and mixing the raw materials, additives and
water in a high-shear mixer. Further dispersion and mixing occur in a pug mill in which
an auger with broken flight mixes the feed material and forces it through a shredder
into a vacuum chamber (Figure 4). Shredded material that is small in cross section is
more uniformly deaired without surface drying. An auger is then used to consolidate
the material and extrude it through the die. The die alters the differential flow,
reduces the cross section, and produces a particular cross-sectional geometry.
Figure 4. Scheme of an industrial pug mill with deairing chamber and extrusion auger.
Continuous tunnel kilns are commonly used for firing high-volume production items. In
a single-layer roller kilns (or roller hearth kiln), large flat products (such as ceramic
tiles) are conveyed on refractory roller through the heated tunnel. Roller kilns are
commonly used when the firing cycle is as short as 30 minutes.
The contacted ceramic industry possesses both intermittent and single-layer roller
kilns. The intermittent kilns have capacities between 3 and 5 m3. The heating power of
both kilns is between 500,000 and 700,000 kcal/h.
The ceramic company also possesses the facilities to carry off the glazing and
decoration processes. Nevertheless, since these processes will not be adapted to the
membrane’s manufacturing process, they are not explained in detail in this document.
In order to analyse the tile’s fabrication process of the contacted ceramic company,
raw materials most commonly used have been characterize. These raw materials are
Spanish spray-dried powder for porcelain stoneware, Spanish clay and a commercial
chamotte; feldspars are also used, but they will not be analysed, since they do not take
part in the membrane’s composition. Clayey materials (spray-dried powders and clays)
give the plasticity necessary to conduct the extrusion process. The non-plastics
(chamotte and feldspars) facilitate drying and the breakdown reactions that take place
during firing (removal of residual moisture, breakdown of the clay materials, oxidation
of organic matter, etc.) and provide the finished product’s targeted quality. Moreover,
to avoid defects (such as cracks or breaking, etc.) in the fired tiles, the tile body needs
to be sufficiently permeable. The permeability of a ceramic material depends on its
microstructural characteristics (porosity, mean pore diameter and tortuosity), which
are defined by the body’s composition and particle-size distribution.
Consequently, raw materials were analysed to determine their properties, being the
characterization as follows:
- Chemical and mineralogical composition of all raw materials.
- Fusion test of the clayey raw materials (clay and spray-dried powder).
- Carbonates content and the reject on a 63-µm sieve of the clayey raw
materials.
- Firing behaviour and water permeability of spray-dried powder.
The mineralogical and chemical compositions of raw materials were supplied by the
different providers. Tables 1 and 2 show the chemical and mineralogical composition
of all raw materials.
Table 2. Mineral composition of the raw materials used by the ceramic company.
Illite Illite
Albite Montmorillonite
Potassic feldspar
30
shrinkage (%)
25
20
15
10
0
1000 1100 1200 1300 1400 1500 1600
temperature (ºC)
The behavior of spray-dried powder during sintering step has been analyzed by means
of the evolution of bulk density and water uptake with the sintering temperature. Discs
were formed by dry pressing with a laboratory unidirectional press (Model Mignon,
Nannetti, S.r.l., Italy). After drying, samples were sintered in a laboratory electric kiln
(Model Rapido, Pirometrol, S.L., Spain) at different temperatures. The sintered bulk
density was determined by the Archimedes displacement technique using mercury as
non-wetting liquid and the water uptake in sintered bodies was measured by the
boiling water immersion method [1]. Figure 11 shows the obtained results.
2.35
12
2.30
10
2.25
2.20 8
2.15 6
2.10
4
2.05
2
2.00
1.95 0
1050 1060 1070 1080 1090 1100 1110 1120 1130 1140 1150
temperature (ºC)
Figure 11. Evolution of bulk density and water absorption with temperature of the
spray-dried powder.
Finally, the permeability coefficient for water was obtained with a liquid permeameter
(LEP101-A, PMI, USA); the table 4 presents the results for all temperatures, showing all
of them very low permeabilities.
The particle size distribution of the commercial chamotte was done by the dry sieving
method, using a vibrating sieve, with different mesh sieves: 75 µm, 125 µm, 200 µm,
300 µm y 500 µm. The obtained results are showed in the Figure 12.
90
70
60
50
40
30
20
10
0.0
<0.075 0.1 0.2 0.3 0.4 0.5
The ceramic industry, especially brick and tile industry, is a major purchaser and user
of waste material from other industrial processes. Many porosifiers are commonly
used in the production of clay blocks, which are waste materials: sawdust and wood
bark, plant residues (chopped straw, etc.), paper, expanded polystyrene, as a residue
or in bead form, organic waste (slurry from papermaking, brewing, tanning, or waste
treatment plants, or residues from the food or textile industry, etc.), waste from
foundry moulds, coal powder, coal shale, ashes and residues from incomplete
combustion, etc. These wastes are difficult to recycle completely in other processes
and sometimes they should be placed in disposals. They are organic compounds that
decompose during the sintering step and are differentiated by their properties
(particle size, moisture content, morphology, etc.). García-Ten et al. showed in their
work [14] that the properties of the fired product, as well as the process’ parameters,
varied depending on the amount and nature of the used porosifiers (agricultural
residues, paper industry residues, sawdust and coke) when they were added to a
composition normally used in the manufacture of Termoarcilla® blocks (lightweight
perforated bricks).
These studies show the increasing tendency to valorize wastes of different sources in
ceramic products, since they are usually inertized during the sintering step.
Nevertheless, many considerations should be taken into account, as the influence of
such residues in the final properties of the ceramics or the environmental effects of
using these ceramic products (leachability and toxicity).
In the recent years, some studies of low-cost ceramic membranes whose compositions
include wastes have been published. Most of the studies attempt to valorize residues
as fly ash [8, 12, 21], coal gangue [27] or phosphates industry sub-products [22] in
membrane’s support compositions, although this residue do not create porosity in the
support, and other poreformers should usually be introduced to this purpose. Related
to wastes used to create porosity in low-cost ceramic membranes compositions, the
few works found are based on the use of wood wastes (mainly sawdust) as
poreformers [6, 7] or rice bran [20]. Finally, all these works are at laboratory scale.
In this task, wastes were collected, characterized and conditioned to be used as raw
materials in the membrane’s composition. Wastes collected were: fired tile scrap,
marble dust and olive bones.
Olive oil solid wastes (known in the trade as orujillo) have been used to create porosity
in membrane supports at laboratory and pilot scale in previous studies, showing good
results of permeability and porosity. Moreover, the support should present stable
calcium phases, which are formed by addition of marble working wastes and mainly
consist of calcium carbonate particles. Finally, chamotte from fired scrap (a sub-
product generated by the ceramic tile industry) is added in the support as filler. Since
the ceramic industry where the membrane will be manufactured is located in the area
of Castellón (Spain), wastes have been supplied by nearby sectors.
The glazed ceramic tile manufacturing branch is an important sector in Spain. During
glazed tile manufacture, 30-40 mass% of produced wastes is fired tile scrap. This scrap
consists of tiles with dimensional or aesthetic defects which have been transformed
into inert waste through firing (Figure 13). Total fired tile scrap in the ceramic tile
branch amounts to 2-3 mass% of tile production [28, 29, 30]. As a result, the generated
amount of fired tile scrap (or chamotte) in Spain was approximately 184,000 t in 2015
[36]. This product is the most difficult ceramic waste to recycle: about 60-70% is
dumped at disposal sites, since it is only used as filler in some ceramic extrusion
products.
After collecting the fired tile scarp from several companies located in the area of
Castellón (Spain), it was crushed and dry milled in a laboratory hammer mill with an
output sieve of 500 µm. The obtained powder was characterized by the following tests:
specific surface area determination (BET method: Tristar 3000 Micromeritics
Instruments Co, USA), particle size distribution by laser diffraction (Mastersizer 2000,
Malvern Instruments Ltd., UK) and particle size distribution by dry sieving. Results are
summarized in Table 5 and Figure 14.
90
70
60
50
40
30
20 Commercial chamotte
Fired tile scrap
10
0.0
<0.075 0.1 0.2 0.3 0.4 0.5
Figure 14. Particle size distribution of fired tile scrap after milling, compared with
commercial chamotte, by dry sieving.
Finally, the microstructure of the fired tile scrap was examined by electron microscopy
(FEG-ESEM Quanta 200F, FEI, USA) and the some of the micrographs obtained are
shown in Figure 15.
a) b)
Figure 15. FEG-ESEM micrographs of fired tile scarp after milling (500µm).
Magnification: a) 1000x, b)5000x.
Marble working waste comes from the area of Alicante and Murcia (Spain), the major
producer and exporter of Spanish marble (Spain is the second world marble producer).
These wastes are generated in a process that involves a series of operations which
transform the quarried blocks into slabs and pieces with the shape, size and finish
required by the market. In some of these operations, such as cutting, sawing and
grinding/polishing, waste is produced and consist of carbonate particle (calcite and
dolomite), together with minor amounts of other minerals present in the processed
rocks, and small quantities of products stemming from the marble working process
(resins, grinding tools, etc.). During the year 2014 around 350,000 t of such waste were
produced in Spain [37]. Nowadays, there are few uses for marble working waste, for
instance, as filler for paints or in concrete and paving materials, and they are currently
dumped at disposal sites near the marble working companies [15,16]. In addition, by
2020, the European Union has set a goal for member countries to recycle 70% of their
waste from non-hazardous construction sites, such us marble.
After collecting the marble wastes from Centro Tecnológico del Mármol (Murcia,
Spain), it was dried, homogenized and dry milled in a laboratory hammer mill with an
output sieve of 500 µm. The obtained powder was characterized by the following tests:
carbonates content, thermogravimetric analysis and differential thermal analysis
(TGA/STDA851e/LF/1600ºC, Thermogravimetric Analyzer, Mettler-Toledo GMBH,
Switzerland) and particle size distribution by laser diffraction (Mastersizer 2000,
Malvern Instruments Ltd., UK). Results are summarized in Table 6.
The thermogravimetric analysis shows a weight loss of 44%wt between 840ºC and
900ºC, which corresponds to an endothermic peak in the differential thermal analysis.
These results confirm that the marble dust consists wholly in calcite.
-10 -1
∂m/∂t (%/min)
-20 -2
∆m(%)
-30 -3
TG
-40 -4
DTG
-50 -5
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
Temperature (ºC)
-2
∆T(ºC)
-4
-6
-8
0 200 400 600 800 1000 1200
Temperature (ºC)
Olive wastes
Olive wastes are residual by-products of the olive oil production industry. Nearly a half
of the world’s olive oil production takes place in Spain. In the production of olive oil,
around 80% of the processed olives become residue, which may reach approximately 4
millions tons of olive wastes by year [9]. In Spain, after milling and pressing, olive
wastes are separated in-situ in olive bones and wet pomace. Olive bones (also called
orujillo) have a residue after calcination of 4-6% and 8–10% of moisture. Nevertheless,
this waste is only used as fuel (owed to its elevated heating value), as pore former in
some ceramic bricks [26] or, in recently experimental studies, as biomass fuel. On the
other hand, wet pomace (also called alperujo), which has high moisture content,
slightly acidic pH values and a very high content of organic matter, mainly composed
by lignin, hemicellulose and cellulose, can be treated by composting or gasification
[1,9].
To collect diverse samples, different oil mills of the Castellon province were visited. In
all of them, olive wastes are treated to separate olive bones from wet pomace (a
mixture of water, bones and pulp residue).
Figure 20. Facilities where olive bones and wet pomace were separated.
Olive residues were collected and characterized, by means of water content (dry basis)
and particle size distribution by dry sieving. Results are summarized in Table 7 and
Figure 21.
90
80
70
Cumulate weight (%)
60
50
OH-1
40
OH-2
30
OH-3
20
OH-4
10
OH-5
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Mesh sieve (mm)
Olive bones’ particle size is higher than 0.5 mm, so it should be reduced by milling. In
order to establish the best milling method, different equipments were used: laboratory
hammer mill and pilot pendular mill.
After milling, particle size was determined again by dry sieving (Figure 23) and laser
diffraction (Mastersizer 2000, Malvern Instruments Ltd., UK), being the mean particle
size around 90-120 µm.
90
80
Cumulate weight (%)
70
60
50
40
30
Olive bones as collected
20
Hammer mill
10
Pendular mill
0
<0.125
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Figure 23. Cumulate weight of milled olive bones, compared with olive bones as
collected
Since wet pomace has a level of oil content too high, after dying (110ºC) it remains in
the sample, which makes difficult its deagglomeration and milling, as was establish not
to use it in the membrane’s manufacture at real scale (Task 3.6). Nevertheless, its use
as pore former could be analyzed in Task 3.4, as an alternative waste.
Since the process to manufacture low-cost membranes is similar to the one used to
produce ceramic tiles by extrusion, it has been possible to find a company where
membranes will be manufactured. This company is located in the surroundings of
Castellón (Spain), where the ceramic cluster is located, and is a SME, since, at the
beginning, the membrane production will be limited. For the sake of simplifying the
consortium, the membrane manufacturer will be subcontracted instead of being part
of the consortium.
Cutting and drying will be done with the procedure detailed in section 2.1. To reduce
cracks appearance, it is advisable that the supports would be dried at least 24 hours at
room temperature.
Related to the sintering process, low cost recycled ceramic membranes must be done
with slow thermal cycles, to avoid cracks during sintering owed to the organic
material’s combustion. For this kind of thermal cycles periodic kilns should be used.
Life Cycle Assessment (LCA) is a standardized method widely used for identifying
opportunities to improve the environmental performance of products at various points
in their life cycle and analyzing the environmental interactions of a technological
system with the environment [19,33,25].
LCA is defined as “compilation and evaluation of the inputs, outputs of material and
energy and the potential environmental impacts of a product system throughout its
life cycle” [38]. This methodology enables to analyze complicated product in a
systematic way. The overall assessment throughout the life cycle considering all
environmental aspects is to avoid possible hidden environmental aspects or burden
shifting between stages of the life cycle for instance, geographical region or
environmental impacts. Particular improvements targeted at a specific life-cycle stage
can adversely affect environmental impacts at other stages of the product [39].
The use of industrial wastes in ceramic membranes has a double impact in terms of
materials sustainability:
• It allows for a more rational use of assets, saving natural resources such as
calcium carbonate, clay or starch (used for producing not recycled low cost
membranes) and saving energy spent in extraction/transformation raw
materials;
The composition of the membranes that are currently used in MBRs is based on
chlorinated polyethylene and ABS resin and membranes are thrown out after their use.
Replacing polymeric membranes with ceramic membranes has environmental
advantages:
Nevertheless, in order to verify that the new ceramic membranes will have a better
environmental profile than the conventional ones (chlorinated polyethylene
membranes), a comparison from the life cycle approach has to be develop. For this, a
study of life cycle assessment (LCA) of the new solution based on the results of the
actions of WP3 will be done in Task 3.5. Furthermore, a literature review is being
carried out to obtain information about the environmental impacts of the
manufacturing of polymeric membranes. This review includes scientific papers, PhD
thesis and databases of LCA and will be use to establish a comparison with the existing
solutions.
In order to compile all the inputs and outputs of material and energy from the very
beginning of the design and development process of the ceramic membranes, a
questionnaire has been developed (see annex 1 and 2). The required information to fill
in this questionnaire will be provided by partners that cooperate in this WP.
5. BIBLIOGRAPHY
1. Alburquerque, J. A. et al. Agrochemical characterization of “alperujo”, a solid
by-product of the two-phase centrifugation method for olive oil extraction.
Bioresour. Technol., 91(2), 195–200, 2004.
4. Beltran, V. et al. Extruded rustic floor tile I. Impact of the composition on the
body’s behaviour in the prefiring process stages. Tile & Brick Int., 11(3), 169-
176, 1995.
5. Beltran, V. et al. Extruded rustic floor tile II. Impact of the composition on the
body’s behaviour during firing and fired product characteristics. Tile & Brick
Int., 12(4), 320-326, 1996.
8. Cao, J. et al. Recycling of waste fly ash for production of porous mullite ceramic
membrane supports with increased porosity. J. European Ceramic Society,
34(13), 3181-3194, 2014.
9. Cotes Palomino, M.T. et al. Study of the wet pomace as an additive in ceramic
material. Desalination and Water Treatment, 57(6), 2712-2718, 2016.
10. Cusidó, J.A. et al. Incorporation of paper sludge in clay brick formulation: Ten
years of industrial experience. Applied Clay Science, 108, 191-198, 2015.
12. Dong, Y. et al. Recycling of fly ash for preparing porous mullite membrane
supports with titania addition. J. Hazardous Materials, 180, 173-180, 2010.
17. Garcia-Ibañez, P. et al. Gasification of leached orujillo (olive oil waste) in a pilot
plant circulating fluidised bed reactor. Preliminary results. Biomass and
Bioenergy, 27, 183 – 194, 2004.
19. Guinée, J. B. Handbook on life cycle assessment operational guide to the ISO
standards. The international journal of life cycle assessment, 7(5), 311-313,
2002.
21. Jedidi, I. et al. Elaboration and characterization of fly ash based mineral
supports for microfiltration and ultrafiltration membranes. Ceramics
International, 32, 2749-2753, 2009.
23. Kingery, W.D. et al. Introduction to ceramics. 2nd Edition. New York: John Wiley,
1975. ISBN: 0-471-47860-1.
24. Koch, G. Recycling: a challenge for the brick and tile industry. ZI Int., 7-8, 14-19,
2013.
25. Klöpffer, W. et al. Ökobilanz (lca): Ein leitfaden für ausbildung und beruf. John
Wiley & Sons, 2009.
26. Kornmann, M. Clay bricks and rooftiles: manufacturing and properties. Paris:
Société de l'industrie minérale, 2007. ISBN: 2-9517765-6-X.
30. Montfort, E. et al. Recycling red-fired tile scrap in red-firing floor and wall tile
compositions. Tile Brick Int., 16(6), 420-427, 2000.
32. Reed, J.S. Principles of ceramics processing. 2nd Edition. New York: John Wiley,
1995. ISBN: 0-471-59721-X.
33. Tan, R. R. et al. Environmental life-cycle assessment: a tool for public and
corporate policy development. Manila: De La Salle University, 2002.
34. www.igme.es
36. www.ascer.es
37. http://clusterpiedra.com/
39. ISO guide 64:2008, Guide for addressing environmental issues in product
standards, 2008.
3. Address/es where the preparation of the raw materials will take place.
Layer:
5. Immersions
Electric consumption (kwh/kg)