Materials Today: Proceedings 33 (2020) 4608–4616

Contents lists available at ScienceDirect

Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

A novel experimental study & design study on systematic designed

sea water purifier machine using activated carbon
R. Balaji a,⇑, S. Gowtham b, Kelam Meghana c, G. Manojkumar d, S. Akilan d
a
Department of Mechanical Engineering, Hindustan Institute of Technology & Science, Chennai, Padur 603103, India
b
Department of Mechatronics Engineering, Hindustan Institute of Technology & Science, Chennai, Padur 603103, India
c
Department of Computer Science Engineering, Hindustan Institute of Technology & Science, Chennai, Padur 60310, India
d
Department of Chemical Engineering, Arunai Engineering College Tiruvannamalai, India

a r t i c l e i n f o a b s t r a c t

Article history: Nowadays many emerging countries have seen a substantial increase in supply for fresh water. In present
Received 31 July 2020 scenario water comes into a drought. This paper represents converting of sea water into Drinking water
Accepted 7 August 2020 processing machine. To reach the demands of the basic needs filtration and purification of water has been
Available online 1 October 2020
investigated. This paper presents on the effects of purifying water in behavior of activation carbon in
comparison to conventional method. Activated carbon is used to investigate the efficiency in the water
Keywords: filtration mechanism Activated Carbon frequently used to extract water contaminants from tap water
Sea Water
and salt water in water treatment. In domestic water filters, activated carbon is used because of its excel-
Purifier
Activated Carbon (AC)
lent ability of adsorption. In this research, the grades A of Activated Coal are used to analyze their effi-
Ultra-Violet Radiation ciency in the filters. Ultraviolet radiation is used for the purification of water without abandoning
Machine hazardous chemicals. Prototype is produced through the use of a water treatment with activated carbon
and ultraviolet radiation. Two activated carbons perform surface region and porosity observation. The
magnified image of Granulized Activated Carbon is used for the contrast between ground structures by
Scanning Electron Microscopy (SEM). Before and after water treatment, two forms of water tests inves-
tigated, the ground water and the bore-well water are evaluated. The pH test, total suspended solid par-
ticle test, biochemical oxygen requirement check, and Chemical Oxygen Demand (COD) experiment were
used to evaluate the water samples. The assessment conducted is an initial effort to deal with such an
issue. The maximum intensity of the radiation is 256 nm which is the most effective wavelength in inac-
tivating bacteria. The UV-C portion is totally blocked out with prevalent bottles. A fraction of UV-C radi-
ation exits. However, the purified water layer that implemented in larger containers. Thus, paper
examines an effectiveness of technology and economics in future studies.
Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Nanotechnology: Ideas, Innovation and Industries.

1. Introduction: This development happens where there is a frequent and endemic

shortage of water resources. The disposal of marine water there-
In recent years the demand for fresh water in numerous emerg- fore appears to be one of the feasible alternatives to the water
ing countries in the warm regions of the world has increased shortage. Water is vital for all the living organisms; it comprises
remarkably. This is primarily due to improved welfare, industrial approximately 60 percent of human weight and loses must be bal-
growth and agricultural development. The scenario exists compa- anced by a sufficient consumption through a variety of metabolic
rable in nations facing the South Mediterranean Sea, where certain and excretion procedures. Water may comprise pollutants that
regions are susceptible to a desiccation system leading to climatic can influence wellness and life quality. Water for individual con-
changes which eventually determine the need for fresh water [2]. sumption should be safe of bacteria and should constitute levels
of chemical components which could be harmful to safety. There
are two different types of potable water, pure water and safe
⇑ Corresponding author. water. The difference between these two kinds of drinking water
E-mail address: sridharabalaa@gmail.com (R. Balaji). is relevant. In practical terms, however, even today’s advanced

https://doi.org/10.1016/j.matpr.2020.08.197
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Nanotechnology: Ideas, Innovation and Industries.
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

equipment makes pure water complicated to generate. Safe water, an significant part in water adsorption of contaminants [7]. These
on the other hand, is water which will probably not have adverse features of activated carbon perform an significant part. These con-
or undesirable effects [2]. Safe waters may comprise some contam- taminants are responsible for poor smells and tastes and can also
inants but they will not present any human health hazards or be a cause of infection. Total suspended solids (TSS) may be
impacts. There must be an appropriate variety of contaminants. removed by activated carbon. The effectiveness in exceeding the
Chlorination, for instance, is used for water disinfection. However, biological oxygen is 9% to 1 mg/l and improves the bathing water’s
Tri-Halo-Methane’s (THM) are included in the completed com- smells and tastes [8]. This is reason that the Activated Carbon is
modity. The prospective safety hazards associated with THM [3]. used in most house water filtration systems as the main filter
According to research released in the journal of the National Can- material (Fig. 1).
cer Institute (St. Paul Dispatch & Pioneer Press, 1987), long-term
consumption of chlorinated water seems to be increased up to 2. Experimental set-up
80% of the danger of emerging breast cancer. In the year of 2006,
18,956 the occurrence of water pollution sources, mainly compris- 2.1. Methods & methodology
ing water treatment systems (9,060: 47.79% including 601 service-
pump-stations), manufacturing (8,543: 45,07%), animal farms 2.1.1. New design proposed
(869, 80%) and agri-based industries (484: 2,55%) were registered A Design is a simplified representation of reality that serves a
with the Department of Environment in the United State (DOE) Well-defined purpose. In Sea-Water Purifier the design of a
[5]. Indirect pollution from these causes has an impact on individ- machine with each part is investigated and modeled by utilizing
ual beverages. As the world’s population rises and demand for safe innovative techniques for using renewable sources and discover a
water rises more than ever, water treatment systems will become manner to achieve a technological and energy sustainable decision
more efficient in the close future. Household water resources still with proper standard as been followed.
have contaminants such as chemicals and microorganisms endan- Activated carbons are recognised for their capacity to remove
gered. The world’s health issues have also risen with drinking- multiple pollutants from drinking Water. The economic viability
water contaminants. Contaminants in drinking water are rarely of traditional desalination technologies provided with solar con-
large enough to produce instant safety consequences. The acute centrate energy was evaluated by Olwing et al. [6]. El-Ghonemy
impacts of drinking air contaminants are more probable. Chronic et al. had suggested using solar energy the purification of sea water
wellness impacts usually occur when a person being repeatedly can be processed to produce desalinated water, adding renewable
exposes himself in drinking water to tiny quantities of chemicals. to untraditional techniques by removing moisture from the atmo-
E.g. cancer, liver, and renal damages are permanent wellness sphere the purification can be achieved.
impacts. Drinking water contaminants that can cause environmen-
tal impacts in five types, including micro-organisms, disinfectants,
and the sub-product of disinfection. Activated carbon has been uti- 3. Methods & methodology
lized for many decades as a drinking water filtration technique.
Due to their elevated ability for adsorption of such compounds, 3.1. Activated carbon filtration
which result from their wide region and porosity, it is commonly
used for removing contaminants from water. Activated carbon By treating with sea water with activated carbon will remove
has different ground features and pore distribution, which take the chlorine content from the water. Which we used the activated
carbon as basic filtration in the process. Unlike other filtration is
good for health and hygienic and have high purity of water. It also
used to remove some heavy metals like lead in the water. If the car-
bon pores are large the adsorption is high so carbon pores make
major role here. There are two types of activated carbon are used
namely Powdered Activated Carbon (PAC) and Granular Activated
Carbon (GAC) here we are using Granular Activated Carbon. Gran-
ular Activated Carbon is made up of coal, lignite and wood. We are
using activated carbon at first stage is because the first container is
easy to clean and most of the dust and heavy metal will remain in
first container. It is quiet efficient than any other filter.

3.1.1. Desalination process by novelty techniques using distillation unit

Desalination is the process which removes the salt from the sal-
ine water. Which have high efficiency in removing salt from any
other process. We choose Desalination because sea water will high
amount of salt content. The water made into water vapor and then
cooled down in different chamber. The salt which remains back it
the container that can be taken out and cleaned. Heat is generated
by solar power and 2nd backup power is electric power. Solar
power can be used in day time to save power consumption. The
water is boiled till it get vaporized. By this process we can get
60% purified water but taste of the water will differ because of
boiling.

3.2. Copper tube

Copper tubes have water cooling policy and most processes are
Fig. 1. Innovative Design on Sea Water Purifier. using copper vessel due to its medical plus point. When water
4609
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

Fig. 2. Steps involved in the methodology.

vapor from desalination process enters into copper tube it will the water. We use copper tube to cool down the vapor and water
become liquid again. The water that is passed through copper tube is stored in copper vessel. Copper tube should be cleaned because
will make digestion easy. Mostly water stored in copper will help vapor will leave a salt waste in the tube.
to reduce weight. Mostly it acts against bacteria and germs in
3.3. Ultraviolet treatment

Ultraviolet purification is the most effective germ and bacteria

killing method. Ultraviolet treatment is better than chemical
purification method. Ultraviolet rays will directly affect the genetic
core of the bacteria and germs. UV method will destroy 99.9%
harmful things. This is the final stage of our purification process.
After this process water is goes under normal filtration and it will
give you the purified drinking water.

4. Results & discussion

4.1. Preparation of granulized activated carbon from banana dried

leaves extracted activated carbon

Fig. 2 shows the methods that involved in the methodology

clearly. The dried banana leaf samples were collected from a local
banana and vegetable marketing OMR, Chennai, TamilNadu, India.
These were crushed into small pieces of about 3 to 4 mm diameter
for providing wider surface area. Then these particles are sieved to
Fig. 3. Activated Carbon processing method. get rid of dust particles and other impurities. These crushed pieces

Fig. 4. Activated Carbon synthesis method.

4610
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

Fig. 5. Distillation set-up.

were put in an oven and the temperature was maintained at 105oC of 600 °C using a furnace followed by physical activation using CO2
and soaked for 24 h. The dried samples were taken in airtight plas- gas at a temperature of 850 °C which produces porous activated
tic bags to avoid re-absorption of moisture from the atmospheric carbon. Thus both Solid and Porous activated carbon particles are
air. About 103 g of samples were taken in a crucible with tightly obtained. These different forms of activated carbon were compared
closed tightened lid for ensuring airtight environment. The crucible later for gas adsorption performances (Figs. 3 and 4).
is placed in the furnace carefully. The furnace was switched on,
heated to a temperature of 470 °C and held constant for 40 min. 4.1.1. Characterization of the activated carbon
The charcoal obtained from pyrolysis process was kept in an air- The activated carbon produced was characterized for its mois-
tight bag in the activation unit and the furnace was heated to a ture content, ash content, bulk density, yield of charcoal, fixed car-
temperature of 750 °C. Steam was allowed to flow to it for bon, hardness and gas adsorption capability.
40 min by keeping the temperature constant. Activated carbon
thus obtained has very less porosity which is ignorable and thus 4.1.2. Moisture content (MC)
considered Solid activated carbon particles. In order to produce Moisture content of activated carbon was calculated by finding
porous structured activated carbon [2], chemical activation was the difference in weight of sample before and after drying. The
performed using KOH at various concentrations like 0.0 M, 0.5 M weight of the empty crucible was noted down first. Then total
preferably at 0.5 M. All samples were carbonized at a temperature weight of sample and crucible was noted as Ws. The sample was
4611
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

4.1.5. Yield of charcoal (YC)

The yield of charcoal [1] that is available in the activated carbon
was estimated as,
ðWS
AC þ MC Þ  100=WS
where, WS is the original weight of dry sample, AC is the ash con-
tent, MC is the moisture content.

4.1.6. Fixed carbon (Fc)

The fixed carbon content in each activated carbon sample was
estimated [1] using:
ðYC
AC
MC Þ  100=YC
where; YC is the yield of charcoal, AC is the ash content and MC is
the moisture content.
Fig. 6. Copper Fin-Tube.
4.1.7. Hardness (H)
The method of Hardness involves the following steps. Primarily
dried in an oven at 105 °C for a time period of 24 h and then it was 2 g of activated carbon sample was measured in a standard sieve of
allowed to cool down. The sample along with crucible was weighed size 40. The sieve was made to shake along with particles for a time
again Wf and the value of ((Ws-Wf*100))/(Ws-We) gives the per- period of 1 h using mechanical shaker at 160 rpm with four steel
cent of moisture content [1]. balls of 6.00 mm diameter inside the sieve [1]. Finally the quantity
of activated carbon retained inside the sieve after 1 h was
expressed in percentage as hardness.
4.1.3. Ash content (AC)
Dried sample of activated carbon was weighed and recorded as 4.1.8. Impurity adsorption
Wd, These were placed in a higher temperature and the total To obtain the impurity level of adsorption characteristics of
weight of crucible plus dry sample was noted and recorded as activated carbon, batch adsorption experiments were conducted
Ws. Finally it was placed in a furnace at 500 °C for a time period [4]. This involves taking into account the effects of the following
of 6 h [1]. It was removed and its content reweighed and recorded parameters like; initial concentration, contact time, volume and
Wf. These steps were repeated twice for all the activated carbon weight of adsorbent. The adsorbed amounts of the solution is given
samples, and the estimated value of the ash content was calculated by the equation [4] as
as; ((Ws-Wf*100))/(Wd). Q ¼ ðCO
CT Þ  V=W
where CO – the initial concentration of solution is, CT – is the final
4.1.4. Bulk density concentration of solution at time T, V – is the volume of solution
For calculating this, the activated carbon sample was trans- and W – is the weight of adsorbent used.
ferred into a cylinder of 10 mL capacity and the weight of the sam-
ple along with cylinder was recorded as Ws [2]. The estimated 4.1.9. Scanning electron microscopy
value of the bulk density was calculated as; The surface morphology was obtained using scanning electron
Weight of Sample (Ws)/Weight of equal Volume of Water (Ww) microscopy (SEM).

Fig. 7. Solid works designed-Innovative Design for Sea-Water conversion Machine.

4612
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

Fig. 8. Distillation & AC processed unit.

inventory solution for each metallus metallic ion concentration

(CdCl2.H2 O, CuCl2.2H2 O, HgCl2), MnCl24 H2 O and PbCl2 was
developed with an equivalent amount dissolved by the dissolution
into a stock solution of 1000 mg/L. Heavy metal removal is a major
step towards safe drinking water. Drinking water heavy metal
studies focus on As, Cd, Cr, Cu, Fe, Hg, Ni, Pb and Zn, mainly. In
the past, several hundred studies reported several experiments in
waste water and drinking water removal and/or sequestration of
heavy metals, some of them for removing heavy metals from
drinking water. The adsorption process was defined as being
usable for this reason with specific adsorbents. The following tech-
niques also included chemical precipitation, physical isolation, ion
substitution, filter filtration, distillation membrane and hybrid
phase.
Using a cluster adsorption method, all adsorption tests have
been performed three times. The stock solution of 1000 mg/L of
the metallic ion concentration was dissolved in 250 mL of de-
ionized water for each metal with the help of equivalent quantities
of analytical reagent grade metal salts. In each of the six flasks of
100 mL of metal-ion solutions and continuously shaken at room
temperature, approximately 0.1 g of activated carbon was added.
Following absorption, the aqueous stage was filtered through Acti-
vated Carbon and other screening methods.

Fig. 9. Activated Carbon.

5.1. Statistical analysis

5. Removal of metal ions from water Concentration determinations for three times and standard
errors for all results were calculated. SPSS (part 16.1) has analysed
The removing of metal ions in saline water for the extraction of data acquired for the extraction of ion oxide (Student T-test) in
carbon particles–Cd (II), Cu (II), Hg (II), Mn (II) and Pb (II) – from order to assess distinctions between alternatives of single and
the water. All adsorption studies with batch adsorption techniques multi-element metal ions in the extraction of metal ions. P < 0.05
were performed threefold. In 250 mL of water de-ionized, the was regarded as significant.
4613
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

Fig. 10. SEM image on Activated Carbon.

Fig. 11. Proposed whole-System Flow-Chart.

5.2. Experimental procedure After that water is purified by triple action processing and going
to next chamber, the water is stopped for certain period of time
In the Sea Water Purifier, The proposed Purifier Machine works because of desalination process. Water is boiled at 100°Celsius so
on the process. it becomes vapor and it get droplet on the cone shaped top and
Primarily Sea water is poured into the 1st chamber of Basic Fil- made as droplets. In 3rd Chamber the two powers input solar
ter Paper and the Brine water goes to the 2nd process of Activated energy and electric energy inputted to save electricity during day
Carbon filter Chamber in that the Activated carbon will absorb time. Vapor or droplets are sent to chamber-3 the design fabrica-
heavy metals like lead. It also removes chlorine from the water. tion has insulated with a copper tube that helps water to cool
4614
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

 This 4 chambers processing is highly hygienic and healthy tech-

niques due to very low chemical enact and zero toxicity of haz-
ardous chemical.
 In conventional methods there is a drawback of toxicity (exam-
ple. Chlorine) is mixed to purify the water.
 The machine that proposed above Fig. 5 sea water purifier
comes through the 4 chamber of filtration which gives germs
and bacteria free water (Figs. 6 and 7).
 It filters not only sea water it also meant to filter nearly all kind
of water dirt and unclean water thus, this machine has the abil-
ity to remove heavy metals.
 By treating with Ultraviolet purification method, it kills 99.9%
germs so it’s safe to drink.
 Activated carbon will reduce the heavy metal pass through.
 By processing Desalination, it will remove saline nature from
the water. This process is most effective than any other conven-
tional processing techniques (Figs. 9–12).

7. Conclusion

 The paper examined the current state of research in drinking

water with regard to Sea water and heavy metals through
design and experimental validation. The report focuses mainly
on the prevalence and variation of heavy metals, impurities, sal-
ine quality from sea water to the conversion in the distribution
of clean drinking water and on their origins, toxicity, health
effects, treatment and essential holes from sea water and other
impurity water.
 From this Research, the evidence of the experiment has shown
that exposure to heavy metals from drinking water is almost
unavoidable. Significant risk for human health is an important
Fig. 12. Chamber design on New Design. factor for exposure to few heavy metals (e.g. As, cd and pb).
Co-exposure to several heavy metals can have synergistic and
down and alters the taste. The structural design is fixed with cop- anti-human effects, and during co-exposure to several metals
per tubes due to the cooling capacity and health factor. After the that can be greatly affected.
cooling treatment water goes to the 4th Chamber that is the signif-  Significantly, Water Scarcity has become a global issue in irriga-
icant stage of all of the process. UV tubes are fixed to kill 99% germs tion, particularly in India, Cape Town and many other Countries
in the water. It is scientifically proved the germs kill and produce facing water scarcity. To avoid these struggles this research
best results in purification and anti-germ. The last chamber is com- pays a way to all the people in the world. In many instances,
pletely covered from the environment to avoid toxicity and pollu- As, Mn and/or Sb have been co-present for drinking water. As
tion from outer region of atmosphere. Finally these all stages with other heavy metals (sb and mn for example), co-
process had purified drinking water which is completely drinkable exposure should be best described as having effects on human
and germs free. wellness. Regulatory agencies may correlate total metal levels
in the drinking water with the possibilities of co-exposure as
6. Theoretical background & discussion well as other considerations, such as epidemiology and toxicol-
ogy, treatability, etc. Point of Use of this device processes the
 The effectiveness of dried banana leaves in providing activated treatments of impure water that could be an alternative to
carbon was analyzed in this work by means of comparing the ensuring safe drinking water for small/rural communities and
performance observation made for different activated carbon individuals. The concentration of low-cost adsorbents, are lower
samples prepared at different activation temperatures, that than the WHO recommended a level of 10 lg/L when filling into
the gas adsorption was better filtration and also at a higher acti- columns at the bed volume of 6000. It was calculated that the
vation temperature. price was affordable by all the people.
 The sample showed promising performance in other properties  The proposed Purifier House-hold Machine can be utilized by
like hardness, fixed carbon, and bulk density also whereas the every individual. Moreover, in the rural areas of South and East
moisture removal and ash removal had been better correspond- Asian countries few low-cost technology locally available have
ing to the oven temperature of 20 h soaking time duration. been applied in this proposed research. This proposed machine
 Dried banana leaves had shown better ability to be a best puri- is best and 1st home-application based Sea-Water purifier
fying resource for activated carbon synthesis. The porosity pro- machine in the world incorporated with natural banana acti-
viding effect of potassium hydroxide solution was also very vated carbon.
clear from the results.
 The design proposed in this paper for the purification of Brine
water and converts the salt tasty and impure water to ‘‘Drinking Declaration of Competing Interest
water”. As mentioned in Fig. 8 the purification technique is
mainly concentrated to make sea water to highly Purified drink- The authors declare that they have no known competing finan-
ing water. This type of filtration is needed due to present scar- cial interests or personal relationships that could have appeared
city state not only in India but also across the world. to influence the work reported in this paper.
4615
R. Balaji et al. Materials Today: Proceedings 33 (2020) 4608–4616

References [2] P. Payment, M. Waite, A. Dufour, Introducing Parameter for the Assessment of
Drinking Water Quality, World Health Organization (WHO), 1997.
[3] Joseph C. Akan, Fanna I. Abdulrahman, Rmmanuel Yusuf, Physical and chemical
[1] World Health Organization (WHO). (1971). International Standards for
parameters in abattoir wastewater sample, Maiduguri Metropolis, Nigeria,
Drinking-Water, 3 rd Edition. Geneva, Switzerland. pp. 9.
Pacific J. Sci. Technol. 11 (2010).
[2] G.C. Whipple, The Value of Pure Water, John Wiley and Sons, New York, 1907, p.
[4] Metcalf and Eddy. (2004). Wastewater Engineering, Treatment and Reuse. 4 th
58.
edition. The McGraw-Hill Companies. Singapore. Pp 293-294, 1138.
[3] R.J. Bull, F.C. Kopfler, Health Effects of Disinfectants and Disinfection By-
[5] Z. Hájek, Z. Jegla, Recent situation and actual possibilities in development of sea
products, AWWA Research Foundation, Denver, CO, 1991.
water desalination equipment, ChemEng Trans. 29 (2012) 1381–1386.
[4] Muhammad B. Mat Junor @ Yunus (2008). Development of Activated Carbon for
[6] Tsiourtis NX. Desalination and the environment. Desalination 2001;141:223–
Textile Wastewater Bioremediation System. UniversitiTeknologi Malaysia:
36. [7] Hájek Z, Jegla Z. Recent situation and actual possibilities in development
Thesis Master.
of sea water desalination equipment. ChemEng Trans 2012;29:1381–1386.
[5] Department Of Environment Malaysia. River Water Pollution Sources. http://
[7] M. Darwish, R. Mohtar, Y. Elgendy, M. Chmeissani, Desalting seawater in Qatar
www.doe.gov.my.
by renewable energy: a feasibility study, Desalination Water Treatment 47
[6] David G. Stevenson (1997). Water Treatment Unit Processes. Imperial College
(2012) 279–294.
Press. Singapore. pp 20-22, 35-36
[8] R. Olwig, T. Hirsch, C. Sattler, H. Glade, L. Schmeken, S. Will, et al.,
[7] S. Ismadji, S.K. Bhatia, Characterization of activated carbon using liquid phase
Technoeconomic analysis of combined concentrating solar power and
adsorption, Carbon 39 (2001) 1237–1250.
desalination plant configurations in Israel and Jordan, Desalination Water
[8] Harry March, Francisco Rodriguez-Reinoso, Activated Carbon, Elsevier Ltd.,
Treatment 41 (2012) 9–25.
Great Britain, 2006, pp. 425–428.
[9] A.M.K. El-Ghonemy, Fresh water production from/by atmospheric air for arid
regions, using solar energy: review, Renew. Sustain. Energy Rev. 16 (2012)
Further Reading 6384–6422.
[10] G. Zaragoza, A. Ruiz-Aguirre, E. Guillén-Burrieza, Efficiency in the use of solar
[1] Frank R. Spellman, Joanne Drinan, The Drinking Water Handbook, Technomic thermal energy of small membrane desalination systems for decentralized
Publishing Co, Inc., United States of America, 1999, pp. 151–152. water production, Appl. Energy 130 (2014) 491–499.

4616