International Journal for Environment& Global ClimateChange

ISSN 2310-6743

Utilization of Stone Cutting Waste in Production of Calcium Stearate

Shadi Sawalha*and RenadShanaa.
Chemical Engineering Department, An-Najah National University, Nablus, Palestine
*Corresponding Author: Shadi Sawalha

ABSTRACT
Stone cutting waste (SCW) which contains large amounts of calcium carbonates (CaCO3) was
converted to calcium stearate (C36H70CaO4) by two methods; First: converting SCW into
calcium chloride (CaCl2) by reacting it with excess hydrochloric acid (HCl) then the produced
CaCl2 was reacted with sodium soap (sodium stearate; C18H35NaO2) prepared from used
cooking oil, the soap was dissolved in water at 60 ºC, while in the second method the
produced CaCl2 was reacted with sodium hydroxide (NaOH) to produce calcium hydroxide
Ca(OH)2 which then reacted with oil to produce calcium stearate, the former reaction took
place at 150 ºC.
Some tests were carried out; PH, solubility, ash and DSC test to examine the properties of the
produced calcium stearate, it was found that the sample prepared from reacting 250g of SCW
with 333 ml HCl (15 wt.%) and reacted with 0.5 Kg of sodium soap dissolved in 1 liter water
at 60 ºC had the following properties; it is a hard powder, insoluble in water, with melting
temp 129.87 ºC and softening temp 73.92 ºC, the ash content was 21% and with a PH equal
6.5. The aforementioned sample costs about 0.53 $/kg compared with 1.2 $/kg for imported
calcium stearate. Produced calcium stearate could be used in different applications; wire
drawing lubricant or as thickening agent in preparation of lubricant calcium greases in
addition to other industrial applications such as paper, PVC, cement and in personal care and
pharmaceutical industry include tablet mold release, anti-tack agent, and gelling agent.

INTRODUCTION
Calcium stearate is a metallic soap which is prepared from fatty acid and calcium. [1]
Calcium-stearate is commercially used as a lubricant [2], stabilizer, catalyst, coating material,
cement additive, and animals feed additive [3]. Also it found its way in another specific
applications such as a green corrosion inhibitor for steel in concrete environment [4] in
addition to its positive effect on biodegradation rate of polyethylene spent silane vials and
improving the wear resistance of UHMW polyethylene [5,6]. Calcium stearate has been
recently used in preparation of composite Nano filtration membranes [7]. The main raw
material used for preparation of this important product is calcium [3] which could be obtained
from calcium carbonate, CaCO3 could be found in high percentage in some wastes such as
stone cutting waste (SCW).

In Palestine, stone cutting industry is largest industrial sector leads to large amounts of SCW
which is mainly disposed in near lands or collected inside the plant causing severe
environmental problems [8-10]. Several studies and researches were carried out to utilize this
waste, it was compounded with polyethylene to be used as an additive in plastic industry [11].
Others recycled SCW and used it in floor tiles production [12] in addition to its use in
concrete mixes [13] and in formulation of bricks and terrazzo tiles [14], also it was found that
SCW effect the compressive strength and slump characteristics of concrete [10].

___________________________________________________________________________
Page82 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

In this work SCW was used as a main raw material to produce calcium stearate by two
methods; by converting SCW into calcium chloride with then reacted with sodium soap
prepared from used cooking oil, another method was by converting SCW into calcium
hydroxide which then reacted with used oil to produce calcium stearate; the amount of
Hydrochloric acid in preparation of calcium chloride was varied to study its effect on final
properties of Calcium stearate such as ash content, pH, appearance and water solubility
compared to properties of standard sample and imported powder used for wire drawing
greasing. Finally the cost of produced calcium stearate and economic analysis of project to
produce the required amount of powder grease was carried out.

EXPERIMENTAL WORK:
Materials:
The following materials were used in this work to prepare calcium stearate:
1. Sodium soap which was prepared by cold saponification of used cooking oil.
2. 33 wt.%Commercial Hydrochloric acid (HCl).
3. Stone cutting waste (SCW) was collected from stone cutting plants with water content
of 40% by weight, SCW was used as a source of calcium carbonate (CaCO3)
Sample Preparations:
Calcium stearate was prepared by two methods: direct reaction of lime with fatty acid, or
indirect by converting sodium stearate into calcium stearate.
1. Indirect Method (ID):
500 g soap were dissolved in 2 liters of water and heated to 60°C, on another hand SCW (as a
source of CaCO3) was reacted with hydrochloric acid to produce calcium chloride. When the
desired temperature reached, the solution of CaCl2 added slowly to dissolved soap with
continuous stirring until a white product appeared.
Calcium Carbonate and Hydrochloric Acid, Soap and calcium chloride were reacted
according to these equations:
CaCO3(s) + 2HCl (L) CaCl2(L) + CO2(g) + H2O (1)

Soap(L) + CaCl2(L) Calcium Stearate(S) (2)

In this method the quantity of each of the hydrochloric acid, soap, and calcium carbonate has
been fixed, and the variable parameter was acid concentration.
Samples prepared by indirect method are summarized in Table (1):

Table (1): Samplesprepared by indirectmethod

(SCW) HCl HCl Soap
Sample
(g) (w/w%) (ml) (g)
ID(1) 166.5 6% 333.5 500
ID(2) 166.5 15% 333.5 500
ID(3) 166.5 25% 333.5 500
ID(4) 166.5 33% 333.5 500

___________________________________________________________________________
Page82 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

Some samples were prepared by indirect method with excess amount of (SCW) as an
additives, these sample are listed in Table (2) below:
Table (2): Samplesprepared by indirect method with excess SCW
(SCW) Excess (SCW) HCl HCl Soap
Sample
(g) (g) (w/w%) (ml) (g)
ID(5) 166.5 83.5 15% 333.5 500
ID(6) 166.5 166.5 15% 333.5 500

2. Direct Method (D):

In this method oil and calcium hydroxide was reacted directly,calcium hydroxidewas prepared
by the reaction between CaCO3 (from SCW), HCl and NaOH according to these equations:
CaCO3(s) + 2HCl (L) CaCl2(L) + CO2(g) + H2O (3)

CaCl2(L) + 2NaOH(L) 2NaCl + Ca(OH)2 (4)

In direct method; 200g of used oil was heated to 60ºC, then Ca(OH)2 added to the oil, the
resulting mixture heated to 150ºC until a white powder formed on the surface of mixture
which then collected and dried
Oil (L) + Ca(OH)2(s) Calcium Stearate(S) (5)

In this method, the amount of oil has been fixed, and the variable parameter was the amount
of calcium hydroxide, as shown in table (3):
Table (3): Samplesprepared by direct method
Used cooking oil Ca(OH)2
Sample
(g) (g)
D(1) 200 166.5
D(2) 200 233
D(3) 200 333

Testing:
The following tests were carried out to find the properties of produced calcium stearate and
compared with a sample imported from Italy; the sample is as a powder grease.
• DSC test: Differential Scanning Calorimetry is a thermal analysis used to test the
behavior of the product under heating and cooling in addition to find melting and
softening temperatures.
• Solubility in water.
• Physical properties such as: PH, Appearance and Density.
• Ash content: this test wasdone to determine the amount of residuethat does not burn
out, it was carried out by weighing 2 g of calcium stearate in a crucible burned by an
oven at 750ºC for half-hour

___________________________________________________________________________
Page03 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

RESULTS:
Previously prepared samples were tested according to the PH, ash content, water
solubility, and the appearance to decide if their properties match with those of
imported sample (termed accepted A or unaccepted UA).
Tables (4) and (5) show the results of samples prepared by indirect and direct
methods respectively:

Table (4): Result of Indirect Method

Produced
Ash Water
Sample Appearance calcium PH Decision
content% Solubility
stearate (g)
The sample was
sticky and 80% of
ID(1) 88 8.6 37 Insoluble UA
its weight still in
Mixer
ID(2) Hard powder 379.24 7.6 23 Insoluble A
Hard powder but
ID(3) 393.55 6.6 10.5 Insoluble A
sticky on hand
One solid piece
ID(4) 467.5 7 9.5 Insoluble A
but sticky to hand
ID(5) Hard powder 515 6.5 21 Insoluble A
Soft and moist
ID(6) 756 6 25.5 Insoluble UA
powder

Table (5): Result of direct Method

Produced
calcium Ash Water Decision
Sample Appearance PH
stearate content% Solubility
(g)
D(1) Creamy ------ ------ ------ ------ UA
liquid
D(2) Hard 250 12.5 42% Insoluble A
powder
D(3) Hard 200 11 42.5% Insoluble A
powder
*A = Accepted
*UA = Unaccepted

DISCUSSION
According to our procedure we have 2 methods of preparing calcium stearate, direct and
indirect.
Six samples were prepared by Indirect method (ID1 to ID6); these samples were tested and
compared with the reference (a powder grease supplied by an Italian company) [15] regarding

___________________________________________________________________________
Page03 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

some physical properties such as; appearance, melting point, ash content, pH and solubility in
water. Therefore, four samples were accepted (ID2, ID3, ID4, ID5).
The accepted samples have values of ash content ranging from 9.5 to 23.8%, while the ash
contents for standard calcium stearate and reference sample (imported from Italy) are 9.5-
12.5% and 48% respectively. That means the produced calcium stearate needs other additives
to meet the required ash content which could be achieved by adding CaCO3 or other suitable
high ashcontent constituents which may serve also as cost reducers.
The difference in ash content is related to both the concentration of HCl and the initial amount
of cutting stone waste. In this project the concentration of HCl was varied from 6 to 33 wt%
for SCW and its effect on ash content was observed, Figure (1) shows the effect of acid
concentration on the ash content.
40

35

30

25
Ash content

20

15

10

0
0 5 10 15 20 25 30 35
concentration HCl wt %
Figure (1): Effect HCl concentration on ash content
It is obvious from Figure (1) that ash content decreases with increasing concentration of
hydrochloric acid. This behavior can be related to the amount of excess HCl needed to
complete the reaction.
Sample ID (5) was tested by DSC to find softening and melting temperatures; they were73.92
o
C and 129.87 oC, respectively. At the softening temperature grease (calcium stearate)
transferred from solid hard state into leathery state where it is helpful in lubricating action.
Cost analysis was carried out to find the cheapest accepted calcium stearate; it was found that
ID (5) is the optimum one (details shown in next section)
By direct method 3 samples were prepared (D1 toD3), only two samples were accepted
because they have nearly similar properties of the standard sample. But unfortunately their
costs are very high compared to ID samples

COST ANALYSIS
Market Analysis:
Calcium stearate as a powder grease is not produced in Palestine and mainly imported from
Italy to be used in wire drawing for producing of pins, electrodes and other drawn metals.
Several Palestinian factories use this product in their activity and their annual consumption is
nearly about 100,000 Kg, on another hand this product is not produced in middle east
markets, therefore a plan for increasing the sales could be built to reach these markets by
assuming 5% growth for proceeding 3years, the selling price of the current competitor (Italian
___________________________________________________________________________
Page08 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

source) is about 1,300 $/tonIn this study it will be assumed that one ton will be sold with
about 1,100 $.
Equipment’s:-
The main equipment’s used to prepare calcium stearate are listed in Table (6), equipment’s
cost, maintenance and depreciation costs based on the following assumptions are shown in the
table.
1. Maintenance equals 2% of equipment price.
2. Depreciation equals 10% of equipment price.

Table (6): Installation, Maintenance and Depreciation Costs

Numbe Power(hp Equipment's Depreciation Maintenance
Equipment's
r ) Cost($) ($) ($)
Oil storage tank 1 0 260 26.00 5.200
Jacketed reactor 1 3 2597 259.7 51.94
Water tanks 1 0 260 26.00 5.200
Mixers 2 1 5195 519.5 103.9
Pumps 3 1 1169 116.9 23.38
Reactor 1 1 1948 194.8 38.96
Filter conveyer 1 0.5 1818 181.8 36.36
Cars and
1 0 25974 2597.4 519.5
vehicles
Dryer 1 0.5 2078 207.8 41.56
Total 7 41299 4129.9 825.98
Total Capital Investment = 41299 $
Revenue:
The selling price of one ton of calcium stearate was assumed 1100 $
Price of 1 Kg of calcium stearate = 1.1 $
Revenue = production rate × selling price =114285.7 $
Raw Materials:-
The following raw materials are needed to produce calcium stearate by indirect preparing
method: used corn oil, Caustic soda, Hydrochloric acid and Calcium carbonate (as SCW).
Table (7) shows amounts of raw materials and their prices required to produce 100 tons
annually.

Table (7): Raw Materials, Prices and Amounts kg/year

Cost of Raw Material Cost of Raw Material
Raw Material
$/Kg $/100 ton
HCl 0.12 12127
CaCO3 0.038* 1948
Soap 0.38 38610
Total cost 0.53 53000
 Cost of transportation from stone plant to project site
Total cost of raw material = 53000 $/year
Utilities:-
Assume that:
The plant operates 200 days/year, with 8 hours per day. The Electricity cost = 0.16$/kW

___________________________________________________________________________
Page00 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

Electricity cost / year = 1322 $/year

Labor:
Assume daily production 500Kg, these needs 3 labors with 8 hours working
Salaries of workers= * 8hr * 2.6$ * 3 labor= 12467 $/year

Maintenance:
Maintenance = 825.98 $/year see Table (6) for maintenance
Depreciation:
Depreciation= 4129.9 $/year see Table (6) for maintenance

General and Administration cost (G&A):

General and administration cost assumed to be 8% from revenue.
G&A = 114285.7 * 8% = 9142.86 $/year
Plant site Rent:
The area of this plant was assumed to be 500 m2, and the rent rate of 1m2 is 21 $/yr, so the
total expense for the land will be 10389.6 $/yr.
Income statement:
The following table shows the income statement for the supposed plant, with 100 ton
production for the first year and growth percent 5% for the next 3 years (2018-2020).
Table (8): Income and Expenses statement
Income and Expenses 2017 2018 2019 2020
Revenue 114285.7 120000.0 126000.0 132300.0
Raw Material 52685.71 53274.55 55938.18 58735.06
Electricity 1321.818 1388.052 1457.403 1530.390
Labor 12467.53 13090.91 13745.45 14432.73
Depreciation 4129.900 4129.900 4129.900 4129.900
Maintenance 825.9800 825.9800 825.9800 825.9800
Gross Margin 33290.91 37726.75 40339.22 43082.08
G&A 9142.857 9600.000 10080.00 10583.90
EBIT 24148.05 28126.75 30259.22 32498.18
Taxes 11428.57 12000.00 12600.00 13229.87
Net Profit 12719.48 16126.75 17659.22 19268.05
Cash flow 16849.35 36280.00 57243.12 79815.32
Payback period About 2.5 years

CONCLUSION:
It is concluded that calcium stearate could be successfully produced from abundant waste
which was stone cutting waste (SCW), two methods were used; it was found that sample ID
(5) is the optimum regarding properties and total cost of production.

___________________________________________________________________________
Page03 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

This sample was prepared by using HCl with concentration 15% and 50% SCW as additives
(total amount reaches 250 g). It’s a hard powder, insoluble in water, its Melting Temp
129.87ºC, Softening Temp 73.92ºC, Ash content 21% and PH for 10% suspension is 6.5
It was obvious that investing in this project will lead to an annual net profit of about 16849 $
in the first year and a payback period of 2.5 years.

REFERENCES

1- Hyang-Bok L.,Jin-Soo K.,Young-Bum K.&Eun-Ki K., Production of Calcium-

Stearate by Lipase Using Hydrogenated Beef Tallow, Appl.Biochem.Biotechno.l 157
(2), 2009, 278–284

2- Dhaher S., Preparation of Dry Solid Lubricant for Drawing of Welding Steel Wires
from Local Iraqi Materials, Al- Mustansiriya J. Sci, 20 (5), 2009, 28-34

3- Perez Alba L. M., De Souza Cavalcanti S., Perez Hernandez M., Martinez Marin A.,
& Marin, G. F, Calcium soaps of olive fatty acids in the diets of Manchega dairy
ewes: effects on digestibility and production, Journal of Dairy Science, 80 (12), 1997,
3316–3324

4- Quraishi M.A., Kumar V., Abhilash P.P., Singh B.N., Calcium Stearate: A Green
Corrosion Inhibitor for Steel in Concrete Environment, J. Mater. Environ. Sci. 2 (4),
2011, 365-372

5- Carol D, Karpagam S, Kingsley S J, Vincent S, Synergistic effect of calcium stearate

and photo treatment on the rate of bidegradation of low density polyethylene spent
saline vials, Indian J. of Experimental Biology, 50 (7) 2012, 497-501

6- Panin C.V., Kornienko L.A., Nguyen Suan T., Ivanova L.R., Poltaranin M.A, The
effect of adding calcium stearate on wear resistance of ultra high molecular weight
polyethylene, Procedia engineering, ELSEVIER, 113, 2015, 490 – 498

7- Ekambaram K, Doraisamy M, Study on the fabrication, characterization and

performance of PVDF/calcium stearate composite nanofiltration membranes,
Desalination 385, 2016, 24–38

8- Aljabari M., Sawalha H., Treating stone cutting waste by flocculation-sedimentation,

28th Conference Sustainable Environmental sanitation & water Services, Kolkata
(Calcutta) India, 2002, 18 – 22

9- Al-Joulani N., Soil Contamination in Hebron District Due to stone Cutting Industry,
Jordan J. of applied Science, 10 (1), 2008, 37- 50

10-Alzboon K., Mahasneh, K. Effect of Using Stone Cutting Waste on the Compression
Strength and Slump Characteristics of Concrete. International Journal of
___________________________________________________________________________
Page03 Vol 5, Issue 2, 2017
 International Journal for Environment& Global ClimateChange
ISSN 2310-6743

Environmental, Chemical, Ecological, Geological and Geophysical Engineering, 3 (3),

2009, 83-88

11- Sawalha H, Sawalha Sh, Yousef T, AbuSaa W, AlSheikh H, Utilization of Stone cutting
waste powder as a compounding filler for polyethylene, International Journal of
EnvironmentandWater,4(4),2015, 122-131

12- Al Zboon K, Tahat M, Recycling of Stone Cutting Waste in Floor Tiles Production,
International Journal of Theoretical & Applied Sciences, 1(1),2009, 64-71

13- Al-Zboon K, Al-Zou’by J, Recycling of stone cutting slurry in concrete mixes,

J.Cycles Waste Manag, 17 (2), 2015 324-335

14- Al-Zboon K, Tahat M, Abu-Hamatteh ZS, Al-Harahsheh MS., Recycling of stone

cutting sludge in formulations of bricks and terrazzo tiles, Waste Management &
Research , 28(6), 2010, 568–574

15- PAN Chemical S.p.A, Calcium lubricants with low fat content, Via Leopardi, 24-
24060 Rogno BG Italy, info@panchemical.com

___________________________________________________________________________
Page03 Vol 5, Issue 2, 2017