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Effect of Non Anionic

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Effect of Non Anionic

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mohamadelnoby1
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Iranian Journal of Food Sciences and Industries, No.

138, Volume 20, August 2023


Journal of Food Science and Technology (Iran)

Homepage:www.fsct.modares.ir

Scientific Research

The effect nonionic surface-active components on cold crystallization in sugar industry

Mehdi Rajaee1, Vahid Hakimzadeh*, Akram Arianfar1, Mostafa Shahidi2

1-Department of Food Science and Technology, Quchan Branch, Islamic Azad University, Quchan, Iran

2- Department of Food Chemistry, Food Science and Technology Research Institute, Mashhad, Iran

ABSTRACT ARTICLE INFO


Many studies have been performed on the effect of viscosity on the qualitative
Article History:
characteristics of hot crystallization in the cooking stage of beet factories. In this
study, we tried to investigate the effect of newer viscosity reducing agents based Received:2022/1/2
Accepted:2022/2/5
on sucrose esters on the quality of cold crystallization. For this purpose, a
Keywords:
substance called Sisterna® which is a sucrose ester as a viscosity reducing agent
Crystallization efficiency,
in four levels 0 , 33, 66 and 100 ppm were used in weak effluent from centrifuge
cooking of a beet factory at 55 ° C and its effect on viscosity, crystallization Sugar soluble color,

efficiency, color of extracted sugar solution and purity percentage was Surfactants,
investigated. The results showed that the addition of this substance reduced the Viscosity
viscosity. Crystallization efficiency increased to 66 ppm and then decreased at
higher concentrations. The color of the extracted sugar solution and the purity DOI: 10.22034/FSCT.20.138.54
DOR:20.1001.1.20088787.1402.20.138.5.7
percentage of the effluent produced by centrifugation and separation of the solid
phase from the liquid decreased to this concentration of surfactant and at higher
*Corresponding Author E-Mail:
concentrations these parameters increased. In general, the use of these materials
v.hakimzadeh@yahoo.com
in cold crystallization of sugar factories can increase the efficiency and reduce
the waste of beet factories.

54
Iranian Journal of Food Sciences and Industries No. 138, Volume 20, August 2023

1- Introduction constant and increasing temperature


In sugar factories, crystallization is divided increases it.
into two stages, cold and hot, and increasing A large number of researchers have been
the efficiency of each can improve the looking for a way to reduce the viscosity of
factory's performance significantly.1The sugar solutions during the crystallization
process of crystallization and the growth of stages since 1875, and one of these methods
crystals becomes slower. For this reason, is the use of compounds and surface active
cold crystallization method is used to substances [2]. It has been almost 70 years
improve and complete the crystallization. that the use of surfactants as materials to
Crystallization by cold method is based on reduce viscosity has been investigated [3].
reducing the temperature and bringing the Surfactant is a substance that acts on the
baking to a supersaturated state. In this case, surface and when it is spread on the surface
due to the lowering of the temperature, the of a liquid, it reduces the surface tension to a
baking viscosity increases significantly. The great extent. This material is made of two
viscosity also acts as a resisting force in the components soluble in water (hydrophilic)
crystallization, with the increase in the and insoluble in water (hydrophobic).
viscosity, the amount of molasses produced Hydrophobic sources typically include
and the amount of sugar added to it is natural fats and oils. Hydrophilic groups
increased. increases, which reduces the usually define the primary classification of
quality and amount of sugar produced and surfactants, which can be anionic, cationic,
reduces the efficiency and performance of or nonionic compounds.
sugar extraction, and as a result, the income Chow3 The effect of several viscosity-
of the factories decreases [1]. reducing substances under the brand name
In general, the process of extraction and Flo4 and Hadak5 (9CB) investigated the hot
crystallization is according to the general crystallization process in beet sugar factories
laws of diffusion, which is a result of and obtained favorable results from the
random thermal conduction of sugar and effect of these substances [4]. Size et al., the
water molecules. These molecules normally effect of intrasol surfactants6FK and Hadak
diffuse from an area of higher concentration CB9 with slovapan material7 investigated
to an area of lower concentration. The and evaluated the effect of these materials
diffusion tendency increases with increasing on the viscosity of the final firings as very
concentration difference. According to the low [5]. Kolinchenko8 et al investigated the
first law of fic2 Diffusion speed is directly effect of several surfactants on improving
proportional to the constant diffusion the quality of extracted white sugar and
coefficient, concentration gradient and increasing the speed of hot crystallization
particle surface and inversely proportional to and emphasized the effect of these
the distance of particles from each other. In substances on improving the quality
1905, according to the equation he
presented, Einstein showed that viscosity 3
- Chou
has a reducing effect on the diffusion 4
- flo
5
- Hodak
6
- Intrasol
1 7
- Matrix - The slop
2 8
- Got - Kulinchenko

55
Hakimzadeh et al Investigation of the effect of non-ionic surfactant reducing...

parameters [6]. Palanius9 The effect of purpose of this research is to investigate the
surfactants GMS-S, Varin-310 and effect of this surfactant on the efficiency of
investigated Intrasol on final firings and cold crystallization in the cooking 2 of beet
found that GMS-S surfactant is more sugar factories.
effective in reducing viscosity in hot
crystallization [7]. Hojjat al-Islami et al. on 2- Materials and methods
the use of isopropyl myristate surfactants11 2-1- Raw materials
2-1-1- Sugar solution
and 9CB found that the use of these
In general, white sugar is extracted from
surfactants improves the efficiency of hot
cooking 1 and the effluent produced in the
crystallization, reduces the color of
process of centrifugation and separation of
chlorinated sugar and improves sugar
white sugar crystals is called weak effluent
extraction from molasses [8 and 9].
of cooking 1, and because this effluent is
Hakimzadeh et al. using Tween 20 non-ionic
used as feed for subsequent cooking, and in
surfactants12 found that the use of these
the process of crystallization of this effluent,
surfactants in the enhanced ultra-refining
it is sent to cooking 2 and so on. It is
(MEUF) process reduces raw sugar
transferred as cooking base 3, the
impurities, turbidity, soluble color and total
importance and necessity of increasing the
dissolved matter (TDS) [10].
efficiency of extraction from it is much
Reducing the percentage of purity of sugar
higher than other effluents and syrups [11].
effluents from the centrifuge and separating
sugar crystals in the last stages of the 2-1-2 - Surfactant
process can improve the overall efficiency in Stressors14SP50 as a surfactant was prepared
sugar factories and improve the extraction from Sisterna (Netherlands) and its chemical
coefficients in this industry. In addition, by structure is presented in Figure 1. Its side
increasing the speed of crystallization, we chain is the alkyl group of the fatty acid.
will see more utilization of the production Fatty acids react with one or more (primary)
capacity. hydroxyl groups of sucrose to form mono-,
di-, or tri-esters. SP represents stearate esters
According to the studies conducted and and 50 represents the percentage of
considering that cold crystallization, like hot
monoesters. This saccharoster has15 HLB It
crystallization, has a significant role in was equal to 11 and part of it is soluble in
reducing the waste of beet sugar factories, in water between 25 and 80 degrees Celsius.
this research, different concentrations of
non-ionic surfactants were used.13 Cisterna,
which is a sucrose ester, has been used on
the weak effluent syrup obtained from the
cooking centrifuge 1 at a constant
temperature of 55 degrees Celsius, and the

Figure 1: Chemical structure of sucrose ester [12].


9
- Palanius
10
- verin3
11
- Isopropyl myristate
12 14
- Tween 20 - Sucrose Stearate patrician (%Mono Ester 50)
13 15
- Non-ionic surfactant - Hydrophilic-Lipophilic Balance

56
Iranian Journal of Food Sciences and Industries No. 138, Volume 20, August 2023

andrpm 27 was tested at the desired


temperature.
In this research, its effect on the weak
effluent sample obtained from the cooking 2-3-5-Efficiency and content of crystals
centrifuge of a sugar beet factory "Shirvan- To determine the efficiency and crystal
Qochan-Bojnoord" was investigated. content, a certain amount of the weak
effluent of baking one was removed and the
2-3- Tests amount of dry matter, polarimetry and its
2-3-1- amount of sugar (polarity)
purity percentage were determined. Then
The basis of sugar percentage measurement
surfactant was added to the sample in
is the deviation of polarized light or
different concentrations and the
polarization. Asymmetric carbon deflects
crystallization process was performed by
polarized light. Due to having asymmetric
cooling it non-continuously.
carbon, sugars deflect polarized light to the 18
Muscovites (Mixture of solid and liquid
left or right according to their chemical
phase) the result of the analysis and dry
structure, and the amount of this deviation is
matter, percentage of sugar and percentage
proportional to the concentration. The
of its purity were determined. After that, a
amount of dissolved sugar by a polarimeter
specific amount of muscoite was weighed
device (modelSchmidt, Germany) according
and then centrifuged, and during this
to instructionsCUMSUAwas determined.]13[.
process, sucrose crystals (solid phase) were
2-3-2-percent puritypurity) separated from the background or mother
It indicates the percentage of sucrose in the effluent (liquid phase). Next, the amount of
dry matter of the sample, which is obtained dry matter, percentage of sugar and
from equation 1 [11]. percentage of purity of the resulting effluent
(liquid phase) were determined. The content
Equation 1
𝑆 of sucrose crystals was calculated based on
𝑝𝑢𝑟𝑖𝑡𝑦(%) = 𝐷𝑆 the change of refractometric dry matter and
purity according to equation 2 [3].
2-3-3-breaks16 or dry matter17(DS)
In sugary industrial syrups, the
refractometric method is used to determine
the amount of dry matter (brix) based on the
deflection of a ray of radiation when it hits
the surface of a solution. Brix of the sample
by refractometerSchmidt's, DUR-S. Germany)
was determined [11].
2-3-4-viscosity
Viscosity of samples by
viscometerBROOKFIELD LV ,DV-III ULTRA).
Made in America) with spindle number
418SC at shear speed at shear speed s/1 35

16
-Brix
17 18
- Dry substant - Massecuite

57
Hakimzadeh et al Investigation of the effect of non-ionic surfactant reducing...

Brix values, degree of polarization and


𝐷𝑆𝑚(𝑃𝑚−𝑃𝑚𝑙) 𝑆𝑚−𝑆𝑚𝑙
degree of purity of waste 1 used are listed in
𝐶𝐶 = = ∗ 100
100−𝑃𝑚𝑙 100−𝑆𝑚 Table No. 1, as it can be seen, the values are
Relationship 2 in the acceptable range for weak waste of
In this regard DSm19 Muscovites dry matter, cooking 1 [11 and 15].
Pm20: Purity percentage of muscoite, Table 1- Results of chemical tests of weak effluent
Pml21Purity percentage of mother syrup, Sm22 used
The amount of sucrose muscovit and SmlL23 Brix Pol° Purity %
The amount of sucrose in mother syrup is in Acceptible
78-80 66-68 85-88
percentage. range
Sample 78.60±0.34 66.90±0.31 85.4±0.59
2-3-6-color of sugar solution
The color of a sugar solution is determined
based on the decrease in the intensity of 3-1- The effect of different surfactant
monochromatic light that passes through the concentrations on viscosity
solution. This reduction is due to the The results of the analysis of variance and
absorption of the rays emitted by the colored the comparison of the average value of
substances in the solution. The color of the viscosity at different concentrations of
extracted sugar solution, after the surfactant at 55 °C presented in (Figure 2)
centrifugation process, sampling of the showed that the effects of different
resulting sugar and the color of its solution concentrations of surfactant on the viscosity
with a colorimeterINSTRUMENTS,INDEX . parameter were significant at the 5%
Made in England) by spectrophotometric probability level (p<0.05)..
method at a wavelength of 420 nm using a
quartz cell with a diameter of 1 cm [9, 14].
2-4-Statistical analysis
All tests were performed in 3 repetitions and
to compare the averages, Duncan's statistical
scheme was used24 It was used based on a
completely random design at a confidence
level of 95% (p>0.05). The software used
for analysis of variance and comparison of
averagesSPSS It was version 16.

3. Results and Discussion

19
- Dray substance of massecuite (%)
20
- Purity of massecuite (%)
21
- Purity of mother liquor (%)
22
- Sucrose content ofmassecuite (%)
23
- Sucrose content ofmassecuite (%)
24
- Duncan

58
Iranian Journal of Food Sciences and Industries No. 138, Volume 20, August 2023

between the tail (tail) groups of the


surfactant reduces the surface tension
between sucrose and non-sugar compounds
[16]. It is necessary to explain that if the
amount of surfactant used in the sample is
not enough, the surface tension will not
decrease and the necessary coating will not
Vis
be created to create electrostatic repulsion
cosi and compensate van der Waals attraction
ty [17].
mP 2-3- The effect of different concentrations
a.s of surfactant on the content of crystals
According to the results and listed in Table
No. 2, by adding surfactant to a
concentration of 66 ppm, the purity of the
solid phase increased and, accordingly, the
Surfactant concentration
purity of the liquid phase decreased due to
the diffusion phenomenon, which ultimately
increased the amount of crystal content.
Figure2: Investigation of the effect of adding
which indicates the increase of
surfactant in different concentrations at 55 ° C on
crystallization efficiency in this
viscosity concentration of surfactant. As shown by
*The lower-case letters indicate a statistically Scheibler et al. in 1875, viscosity can have
significant difference in the 95% confidence level an inhibitory effect on crystal growth.
Considering that the surfactant used is a According to the results obtained in graph
non-ionic saccharose, the mechanism of number 1, it can be seen that adding the
action of this surfactant in the sample is such amount of surfactant has significantly
that the sucrose molecule in the head reduced the viscosity of the sample.
(hydrophilic) part of the surfactant joins According to Fick's law, it is expected to
with the sucrose molecules dissolved in the have a significant effect on the crystal
non-sugar compounds of the sample, and the growth rate. Similar results have been
tail part of the surfactant, which is made of reported by Hojat al-Islami et al. [8] and
acids Stearic (hydrophobic) fat is formed Palanius et al. regarding the use of
and connected with other non-sugar surfactants and their effect on the growth
compounds, considering that the basis of rate of crystals on matrix viscosity [18].
surfactant action is basically the reduction of Contrary to what was expected based on
surface tension on the basis of the reduction Fick's law, adding surfactant at a higher
of repulsive forces between the solvent concentration decreased the crystal content.
molecule and the hydrophobic solvent which corresponds to Figure 3 and the
group, in fact, the electrostatic repulsion obtained results agree with the results
force between the solvent-loving groups and reported by Hojjat
the van der Waals force of attraction.

59
Hakimzadeh et al Investigation of the effect of non-ionic surfactant reducing...

Al-Islami et al. [1 and 9] and Siz et al. [5]. micelles.27are absorbed by the micelles and
The reason for this can be based on the cause a decrease in the solubility of sucrose
theory of Silin et al., 1955, that the presence in these compounds, as can be seen in Table
of any non-sugar substance, even water, No. 2, the use of surfactant up to a
prevents crystallization during the concentration of 66 ppm reduces the color of
crystallization of sucrose. Therefore, the the produced sugar solution, and as a result,
positive effect of reducing the viscosity can the impurities are reduced and the purity
have a positive effect on the growth of percentage of the liquid phase (wastewater)
crystals to some extent, and more than that, maternal) has decreased. It should be noted
the molasses effect of these materials will that the increase in the difference in the
decrease the growth and decrease the degree of purity between wastewater and
crystallization efficiency [1]. muscoite indicates the greater success of the
crystallization process [10, 19, 20, 21].
3-3- The effect of different concentrations
of surfactant on the color of sugar
solution
According to the results of Table No. 2, it
can be seen that adding viscosity reducers
up to a concentration of 66 ppm reduces the
color of the sugar crystals solution, and at
higher concentrations, it is probably because
Silin et al. have mentioned that by
increasing the effect of non-sugar
substances, the color of the solution
increases compared to 66 ppm. become] 3[.
melanoid 25The most common are colorants
that have a major effect on the color of sugar
through the Maillard reaction26 (non-
enzymatic browning) which are formed
between reducing sugars and amine-
containing compounds, some of which have
gone through the syrup purification stage in
the condensation and crystallization stage in
the vicinity of heat. In fact, colored
substances are among the non-sugar
compounds in the sample, which are formed
by electrostatic forces between them and
surfactant monomers, which play the role of
joining and forming spherical masses called

25
- Melanoidins
26 27
- Maillard - Micelle

60
Iranian Journal of Food Sciences and Industries No. 138, Volume 20, August 2023

Table 2: The effect of surfactant addition at 55 °C on pan boiling process and color of obtained sugar

Dry substance of Purity Purity of Crystal Color


Massecuite (%) of Mother liquor content (%) Of
massecuite (%) (%) sugar solution
Control 78.6±0.13c 86±0.21c 85±0.21c 4.68±0.67c 1315±9.07a

33ppm 79.48±0.22b 89.29±0.35b 85.33±0.15b 21.45±1.34b 1200±22.27b

66 ppm 79.8±0.19a 91.0±0.36a 85.36±0.26a 30.73±2.07a 989±41.98c

100ppm 79.63±0.22b 89.3±0.24b 84.61±0.14b 23.27±1.77b 1218±12.09b

*a, b,c…. indicatd significant difference in p<0.05

As can be seen in Figure 3, adding viscosity- and content of sugar crystals. It also reduced
reducing substances to the sample, in the colored compounds in the produced
addition to increasing the crystallization sugar and caused the amount of impurities in
efficiency, has increased the amount of the produced product to decrease. As a
crystals per unit weight. These results result, it causes a significant increase
confirm the results of Hojjat al-Islami and between the purity percentage of muscoite
colleagues [2]. and effluent obtained in the cold
crystallization. At the concentration of 66
ppm of the surfactant used and the
temperature of 55 degrees Celsius, the
efficiency of the cold crystallization has
increased, so that the amount and content of
the crystals are at their maximum value, i.e.
30.73% and the color of the sugar solution
has decreased to 989 icomsa. At higher
a b c d concentrations, as expected, the growth rate
and crystallization efficiency have
decreased, which is due to the molasses-
forming properties of non-sugar compounds
in sugar solutions.
a: 0 ppm, b: 33ppm, c:66ppm,d:100ppm
5- Thank
Figure 3: Images of sugar Solid phase
The authors of the article appreciate and
4 - Conclusion thank the respected management of the
Shirvan-Qochan-Bojnoord sugar production
The results of this research showed that the
company for providing all the facilities for
reduction of viscosity in the sample with the
the investigation and research in this article.
help of Cisterna non-ionic surfactant (SP50)
was quite evident and increased the amount 6- Resources
changes on the efficiency of surface-active
chemicals in sugar processing industry.J.
[1] Hojjatoleslamy, M., Mesbahi,G., Agric.Sci.Natur.Resour., Vol 9(3):161-170
Shokrani , R. and Karbasi , A., 2002 . Effect [2] Marrinova, N., and L. Bozhkov, 1988.
of Sugar beet quality and composition Application of the surface-active substace

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GMS-S on crystallization of the sugar. [11] Vander Poel, p., Schiweak , H. and
KhranitclnaPromyshlcnnost (1) :97-102 Schwartz , T . 1998 Sugar Technology
[3] Hojjatoleslamy , M. , Shokrani , R. , BartenPub.
Karbassi , A. , Jamalian , J. and Mesbahi , [12] Sisterna .Co.2016.Codex Alimentarius
Gh. 2004. The effect of viscosity reducing Sucrise esters INS 473 . Roosendaal The
agents on c massecuite and molasses in beet Nethelands.
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Science and Nutrition (2): 13-21. Bartens Pub. Berlin.
[4] Chou, J.C.1974. Reduction of molasses [14] The Official Method ICUMSA GS
viscosity surface-active chemicals. Int. 9/1/2/3-8.2011. The determination of sugar
Sugar J. (76) : 195-198 solution color at pH 7.0 by MOPS buffer
[5] Ciz , K., J. Gelber , and V . Hoblicva, method.
1975. Boiling low grade product with [15] Asadi, M.2007. Beet-Sugar Handbook,
addition of Intrasol FK wetting agent. Published by John Wiley & Sons, Inc.,
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Karbasi , A. , 2008 . Effect of viscosity on C micellar solution for the recovery of
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62
‫مجله علوم و صنایع غذایی ایران‪ ،‬شماره ‪ ،138‬دوره ‪ ،20‬مرداد ‪1402‬‬

‫مجله علوم و صنایع غذایی ایران‬

‫مجله‪www.fsct.modares.ac.ir :‬‬ ‫سایت‬

‫مقاله علمی_پژوهشی‬
‫بررسی اثر ماده فعال سطحی غیر یونی کاهنده ویسکوزیته بر کارآیی کریستالیزاسیون سرد کارخانههای قند‬
‫‪2‬‬
‫مهدی رجائی‪ ،1‬وحید حکیمزاده‪ ،*1‬اکرم آریانفر‪ ،1‬مصطفی شهیدی‬

‫‪-1‬گروه علوم و صنایع غذایی‪ ،‬واحد قوچان‪ ،‬دانشگاه آزاد اسالمی‪ ،‬قوچان‪ ،‬ایران‪.‬‬

‫‪ -2‬گروه شیمی مواد غذایى ‪ ،‬موسسه پژوهشی علوم و صنایع غذایی‪ ،‬مشهد‪ ،‬ایران‪.‬‬
‫چکیده‬ ‫اطالعات مقاله‬

‫مطالعات بسیاری روی اثر ویسکوزیته بر ویژگیهای کیفی کریستالیزاسیون گرم در مرحله‬
‫تاریخ های مقاله ‪:‬‬
‫طباخی کارخانجات چغندری انجام شدده اسد ‪ .‬امدا در اید حقییدس سدعی شدد حدا اثدر‬
‫تاریخ دریافت‪1400/10/12 :‬‬
‫کریستالیزاسدیون‬ ‫موادکاهندهی ویسکوزیته جدیدحری همچون استرهای ساکارز بر کیفید‬
‫تاریخ پذیرش‪1400/11/16 :‬‬
‫سرد مورد حقییس قرار گیرد‪ .‬برای ای منظور از ماده فعال سطقی با نام حجداری سیسدترنا‬
‫که یک استر ساکارزی می باشد بعنوان ماده کاهنده ویسکوزیته در چهار سطح صدفر‪،33 ،‬‬ ‫کلمات کلیدی‪:‬‬

‫یک کارخانههای چغنددری‬ ‫‪ 66‬و ‪ ppm 100‬در پساب ضعیف حاصل از سانتریفوژ پخ‬ ‫راندمان کریستالیزاسیون‪،‬‬
‫مقلول شکر‪،‬‬ ‫رن‬
‫در دمای ‪ 55‬درجه سانتیگدراد اسدتفاده شدد و حداثیر آن بدر روی ویسدکوزیته ‪ ،‬رانددمان‬
‫مواد فعال سطقی‪،‬‬
‫مقلدول شدکر استقیدالی و درصدد خلدوپ پسداب حاصدل از‬ ‫کریستالیزاسیون ‪ ،‬رند‬ ‫ویسکوزیته‪.‬‬
‫سانتریفوژ مورد بررسی قرارگرف ‪ .‬نتایج نشدانداد کده افدزودن اید مداده باعدش کداه‬
‫‪66 ppm‬‬ ‫چشمگیری در ویسدکوزیته گردیدد‪ .‬رانددمان کریستالیزاسدیون نیدز حدا غلظد‬ ‫‪DOI: 10.22034/FSCT.20.138.54‬‬
‫‪DOR:20.1001.1.20088787.1402.20.138.5.7‬‬
‫مقلدول شدکر‬ ‫یافد ‪ .‬همچندی رند‬ ‫اما در غلظ های باالحر از آن کاه‬ ‫یاف‬ ‫افزای‬ ‫‪ ‬مسئول مکاحبات‪:‬‬

‫‪ v.hakimzadeh@yahoo.com‬استقیالی و درصد خلوپ پساب حولیدی حاصل از سانتریفوژ و جداسازی فاز جامدد از‬
‫یافته و در غلظ های باالحر از آن‪ ،‬ای پارامترهدا‬ ‫کاه‬ ‫از سورفکتان‬ ‫مایع حا ای غلظ‬
‫کریستالیزاسیون سرد مدیحواندد باعدش‬ ‫یافتند‪ .‬لذا استفاده از ای مواد در بخ‬ ‫نیز افزای‬
‫ضایعات کارخانههای چغندری شود‪.‬‬ ‫راندمان و کاه‬ ‫افزای‬

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