Sulfonation Of Petroleum Base Oils With Development Of The Emulsifiers
Sulfonation of Aromatic hydrocarbons, crude oil oil and vegetable oil has great importance in industry, in which utile wetting agents stuff could be produced. Such wetting agents could be used as detergent, emulsifying agent, softening agents, de emulsifying agents etc. The sulfonation of aromatic hydrocarbons is used to bring on the sulfonyl group ( SO & A ; shy ; 3H ) while the sulfation of aliphatic organic molecules such as intoxicants and alkenes produce sulphuric acid esters. This work concerns chiefly with sulfonation of crude oil base oil by change overing its aromatic hydrocarbons into crude oil sulfonate and so survey of the extraction procedure of these sulfonates, its development and utilizations. The Na sulfonate of the mean molecular weight ( 450- 500 glmol ) are widely used in composing of coolant fluids to work as a mulsifier in metal working applications.1,2,13-20 The sulfonates are synthesized specifically as additives for metal working fluids by sulfonating and neutralizing the sulfonic acid intermediates and eventually the extraction of produced sulfonate from the oil sulfonates.
The formation of sulfonic acid intermediates can be carried out by the sulfonation of crude oil base oil by utilizing gaseous sulfur trioxide ( SO3 ) diluted in air or Nitrogen3, 6 or by utilizing S dioxide which is dissolve in dichloroethane7 or by utilizing the Oleum.8
Consequences And Discussion
Extraction of Na sulfonate and its application in coolant fluid
Extraction of Na sulfonate from oil solutions
The preliminary experiments of extraction of crude oil sulfonate from oil solutions by aqueous solution of isopropyl intoxicant showed clearly the benefit of utilizing the hexane a dissolver in the extraction. However, the extraction procedure was more dependable and efficient when hexane acidic oil per centum was [ 1: 1 ] and three beds were observed during 10 – 15 proceedingss whereas, in the absence of hexane as so wert it takes about 60 proceedingss or more.
The relation between the deepness sulfonation ( sum of SO3 ) and the merchandises of extraction procedure is given in the tabular array ( 1 ) .
The consequences in table ( 1 ) show that the addition of the sum of sulfur trioxide ( more than 8 % tungsten ) do n’t take to increase in output of sulfonic acids, and the extra sum of sulfur trioxide may take to formation of bisulfonate.
The mean molecular weight of the aromatic hydrocarbons of this type of base oil was calculated to be 497 g / mal.
The value of weight was calculated as followers.
Molecular weight of sulfonic acid =
The mean molecular weight of aromatic hydrocarbons = 577 – 80 = 497g/mol ( whereas: 80 is the Mwt of SO3 ) and the output of SO3 ( % )
= = 0.062
Where ( 31 ) is per centum of the aromatic hydrocarbons in oil ( % tungsten ) that is the theoretical sum ( weight ) of sulfur trioxide required to reassign the whole sum of aromatic hydrocarbons to mono sulfonic acid become
= 0.062 ten 80 = 4.96. Therefore, the deepness of sulfonation towards the sweetening of sulfur trioxide obove the theoretical sum ( 5 % ) will take extra formation of bisulfonic acids. this observation is compatible to our consequences and decisions.
The survey consequences of the isopropyl intoxicant consequence of the emulsifier on the merchandise of the oil after extraction, the merchandise of the concentrated sulfonate and the content of the concentrated sulfonate ( % tungsten ) are given in tabular array ( 3 ) .
The values given in tabular array ( 2 ) are those obtained from the usage of the sulfonate oil ( % of SO3 = 4 % ) which is less the theoretical value required for the sulfonation of aromatic hydrocarbons in oil. However, these values indicate that the content of sulfonate in concentration is compatible with needed use of these sulfonates in coolant fluids2, and in the absence of a hydrocarbon dissolver in the extraction process.1 However another extraction survey of Na sulfonate from sulfonated base oil ( SO3 = 8 % tungsten ) which is greater than the theoretical value of the sulfonated aromatic hydrocarbon in oil and the consequences are given in tabular array ( 3 ) .
From the consequences in the tabular array ( 3 ) , the output factor of sulfonate was calculated by -this method.
The content of sulfonate % tungsten =
When, X = the content of the aromatic hydrocarbon of base oil ( = 31 % tungsten )
M2 = the molecular weight of Na sulfonate =
497 + 80 + 23 = 5509 g / mol
M1 = The molecular weight of aromatic hydrocarbon ( = 497 g /mol )
The output of pure sulfonate ( 100 % sulfonate )
( % tungsten ) = output of sulfonate concentration x content of sulfonate in concentration.
Yield Factor % = output of pure ssulfonate
The Content Of Sulfonate
The values of output factor harmonizing to isopropyl intoxicant concentration in extraction factor is given in tabular array ( 4 ) .
All consequences of extraction procedure given in tabular arraies ( 3 ) and ( 4 ) are shown in figures 1, 2 and 3.
The diminution in the output of sulfonate and the addition of the oil output after the extraction ( figure 1 ) is compatible with literature1 after heightening the concentration of isopropyl intoxicant in extraction factor. However, the highest value of the output factor reached ( 90.3 % ) .When the concentration of isopropyl intoxicant was 65 % which is twice the sulfonated oil. On the other manus, it was found that the more addition in the concentration of isopropyl intoxicant, the more yield factor was obtained ( figure 3 ) .This decision was in contrary way with the antecedently found relation.1 This is may be due to the alteration in chemical construction of formed sulfonic acids, that is during addition in the deepness of sulfonation some glandular fever sulfonic acids transportation to bisulfonic acid which causes in an sweetening in the output factor for the sulfonic acids.
The standard concentration of isopropyl intoxicant required to obtain the sulfonate non less than 50 % for the intent of coolant fluids formation.
Experimentally, two instances were recognized. foremost, during the partial sulfonation of aromatic hydrocarbon ( table 2 ) , the concentration of isopropyl intoxicant 30 % was used in the extraction procedure, whereas in the instance of the deepness sulfonation, the concentration of isopropyl intoxicant should non be less than 45 % to guarantee obtaining the needed sulfonate concentration harmonizing to tabular array ( 3 ) . However, the concentration of isopropyl intoxicant was 55 % .
The application of crude oil Na sulfonate in fiction of coolant fluids.
The rating consequences of the stableness of coolant fluids – lubrication of the emulsifier type which introduced in its composing crude oil Na sulfonate ( table 5 ) .
The consequences given in tabular array ( 5 ) are having considerable world-wide scientific and applied importance.
As shown in tabular array ( 5 ) .
The content of sulfonate in Na concentrated sulfonate which was extracted from oil solutions was really considerable and prevarication between 55 – 70 % . The alteration in the method of sulfonation caused a really clear alteration in the emulsion stableness of the coolant fluids – lubrication, which contains one unit construction of composing and its per centum but they differ in the type of Na sulfonate in it.
The sulfonation of base oil type 500 NS by sulfor trioxide lead to the production of extremely efficient sulfonate to stabilise the emulsion of coolant fluids – lubrication as compared by the method of with oleum.
this difference in the efficiency of sulfonate may be due to the alteration in the chemical construction of produced sulfonic acids, that is the produced sulphuric acid from the sulfonation with sulfor trioxide consist fundamentally of acids that are soluble in oil, whereas by utilizing oleum in the sulfonation some produced sulfonic acid are solube in H2O besides to oil.9,22
The presence of sulfonic acids that are soluble in H2O in the composing of Na sulfonate introduced into the formation of the emulsified coolant fluids – lubrication led to a diminution of the emulsion stableness. This decision was approved by utilizing heavy base oils ( BSS ) , these contain usually hydrocarbons of high aromatically.
The sulfonation of these hydrocarbons produce H2O – soluble sulfonic acids,9 and as shown in tabular array ( 5 ) , the sulfonation of this type of oil by oleum lead to a diminution in the emulsion stableness.
The crude oil base oil of the type NS 500 and the dynamic poise = p= 10-1 Pa.S viscousness II centistokes at 100 C & A ; # 9702 ; was used for this work. The chemical construction of this oil was identified by absorbent chromatography method on silica – gel. This oil was eluted by different solutions such as hexan, benzine and ethyl alcohol respectively.7 The hydrocarbon groups were separated harmonizing to the fraction as following [ no 20 ] .
Parrafins – Naphthenes from 1.74 to 1.49
Monocylic aromatic hydrocarbons from 1.49 to 1.51
Bicyclic aromatic hydrocarbon from 1.51 to 1.53
Polycyclic aromatic hydrocarbons was greater than 1.53.
Harmonizing to the old mentioned method the chemical construction ( % tungsten ) for base oil was as followers:
Paraffin – naphthens ( 67.65 ) ; Monocyclic aromatic hydrocarbons ( 13.80 ) ; Bicyclic aromatic hydrocarbons ( 17.50 ) ; Polycyclic aromatic hydrocarbons ( 0.05 ) .
Two methods have been used for sulfation: in the first method. Oleum incorporating 30 % SO3 by weight was used. The oleum was added easy over 30 proceedingss with stirring at certain temperature. In the 2nd method, the SO3 diluted with N ( approximative 4 % by volume ) was used. The extra SO3 oof was librated by heating the oleum and go throughing current of N. The sulfating agent ( SO3 diluted with N ) was passed through the gas distributer placed in underside of reactor that contains oil. this was within + 2 C & A ; # 9702 ; . by heating the reactor, by utilizing sulfation in this manner, the unreacted residuary gas was expelled at the terminal of reaction of reaction by heating to 70 C & A ; # 9702 ; .
The reaction deepness was determined by mensurating the content of reacted SO3 gas and besides by mensurating the sourness of the resulted sulfated oil. The stableness of the emulsion versus, the clip was besides studied four hours, stand foring and the per centum of detached H2O was criterion of the emulsifier stableness.
Methods Of Characterization And Extraction
Sourness of sulfonated oil:
The sourness of sulfonated oil was determined by titration with standard solution of KOH.21 The sulfated oil ( 1 g ) was dissolved in mixture ( 100 cm3 ) of touluen and isopropyl intoxicant in ration of 2:1 V/ V at high temperature.
Acidity ( mg KOH / g ) =
Extraction Method Of Petroleum Sulfonate
Neutralization of sulfonated crude oil base oil was carried out by 10 % of Na hydrated oxide ( NaOH ) at 50 C & A ; # 9702 ; in the presence of isopropyl alcohol.1 After add-on of the hexane to the merchandise, three beds were formed the upper bed was the unreacted base oil with hexane, and the in-between bed was sodium sulfonate in isopropyl intoxicant, and the lower bed was sodium sulphate with H2O.
The merchandise of crude oil sulfonate was obtained from the extracted sulfonate bed vaporisation of isopropyl intoxicant.
Word picture Of Sulfonate
The extracted crude oil sulfonate was characterized by the above method and the per centum of pure Na sulfonate and its oil content was determined.
The method depends upon the rule of the adsorbent chromatography on silica – gel.21 The column was prepared from the slurry of silica – gel in trichloromethane. The trichloromethane was eluted through the column to make certain volume above silicon oxide gel degree. The Na sulfonate was dissolved in certain volume of trichloromethane and so added to silica gel column and left to spread through the separation column. both sulfonate and oil were eluted severally with trichloromethane and ethyl alcohol and finally, the merchandises were obtained after acquiring drive of dissolvers by evaporization.
Formation Of Coolant Fluids
The coolant fluids were obtained harmonizing to the method13 from the extracted sulfonate by blending 30 % of Na sulfonate 60 % base oil 5 % Oleic oil and 5 % triethylamine. The produced compound was dissolved in 3 % H2O to organize the coolant fluid as hydrate emulsion the stableness of this emulsion was examined by this technique. Certain volumes of the emulsion transferred to separatory funnel and left for 24 hr so the upper oil bed was separated and purified from the drosss by the fade outing it in methylene chloride and H2O. After agitating, two beds were formed, and so the ethene chloride bed was separated and eventually the coveted merchandise was isolated and the output which represents the emulsion stableness of the coolant fluid was calculated.
1- The sulfonation of crude oil base oil of high viscousness ( 11 cent is took at 100 & A ; # 1618 ; C ) was studied by both oleum and gaseous S trioxide and the crude oil Na sulfonate was extracted from the produced oil solutions.
2- The output of pure sulfonates and the oil lessening after extraction with the addition of the isopropyl intoxicant concentration in the produced extraction factor from the isopropyl intoxicant and H2O. However the output factor of sulfonate was found additions with addition of isopropyl intoxicant concentration in H2O.
3- The highest output factor of sulfonate was found 95.5 % when the concentration of isopropyl intoxicant was 65 % which is twice of sulfonated base – oil.
4- The stableness rating consequences of coolant fluids -lubrication of the emulsifier type where the prepared crude oil Na sulfonate was introduced in its composing by different methods showed the alteration in the method of sulfonated base oil lead to obvious alteration in the stableness of these fluids.
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