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D OI: http://dx.doi.org/10.20534/AJT-17-1.2-89-92
Nabiyev Akramjon Botijonovich, Abdurahimov S. A., Namangan State University, Tashkent Institute of Chemical Technology E-mail: akramnabiyev@umail.uz
Preparation of surfactants reducing the viscosity of heavy oil from raw fatty acid of cotton soap stock
Abstract: This paper studied the effective viscosity of the local oil at a constant voltage shifts evaluate the effectiveness of synthetic surfactant to reduce the viscosity of the local oil. Studies for obtaining surfactants reducing the viscosity of the oil from the raw fatty acid of cotton soapstock (CS) show that a rational scheme was selected for gaining of surfactants from raw fatty acid of cotton soap stock in the form of higher fatty alcohols and their modification methods sorbitan or sulfation.
Keywords: oil, viscosity, sulfate, paraffin, gossypol, lecithin, cephalin.
Specific feature of oil from the Jarkurgan (Sur- Today, promising is the use of depressant i. e. surface-
khandarya region) and Mingbulak (Namangan region) fields in Uzbekistan is the high content ofparaffin, resins, asphaltenes of mineral salts and other related hydrocarbon components that significantly increase their viscosity and reduce their flow through the pipeline.
It is known that the high viscosity of the oil, not only complicates the process of its production from the wells, but also its industrial processing, which has a negative impact on their technical and economic indicators. To address these shortcomings in practice (especially in autumn and winter) the pipelines should be heated with steam where oil transport distance exceeds 10-15 km. The use of solvents for diluting high-viscosity oil is not desirable because it is related to fire safety oil explosion [1].
With in-plant transport of high-viscosity oil for less (less than 5 km.) distance it is effectively to use their electromagnetic processing (including microwaves), which, along with a decrease in viscosity of the oil increases its turnover and significantly reduces the deposition of waxes, resins and mineral salts in the pipes [2]. In this case, the problem of explosion, fire of oil pipelines requires their own individual solutions tailored to their construction.
It was offered the methods of application of ultrasonic cavitation and mechanical-chemical activation (MCA) on lowering the viscosity of oils of different composition [3].
Unfortunately, the influence of mechanical stress on the decrease in viscosity of the oil is not a long time and should therefore be used repeatedly, which significantly overstates their energy costs for transportation by pipeline.
active agents (surfactants), and reduce the oil viscosity increase their fluidity in a pipeline.
It is known that the surfactants have the ability to lower surface tension in the interphase layer, as they dissolve selectively in one of the phases, the dispersion medium to be concentrated at the interface and there form an adsorption layer as a film. Reduced surface tension increases with the fineness of the disperse phase [4].
Mainly characterized by the oil viscosity, density, dispersion, electrical properties and stability of aggregate. Their viscosity usually varies within wide limits and depends on the intrinsic viscosity of the oil, the temperature and so on. They being dispersed systems have abnormal properties that under certain conditions are non-Newtonian fluids and characterized by an apparent (effective) viscosity [5].
We investigated on viscometer VPN-01 at a constant shear stress the effective viscosity of the local oil. This shear stress of test oil sample was calculated by the following formula [5]:
T = ass ^ (1)
where: k — the coefficient, which is equal to 0.63 Pa/V to 100 mm. gauge and 43 Pa/V to 20 mm. gauge;
U — stress in volts.
The shear rate was determined by the formula:
Y=A/T, (2)
where: A — a constant measuring unit; T — Period of rotation, determined by the frequency indication.
Hence, the effective viscosity of the oil is determined by the formula [5]:
n = T .a/!. (3)
Evaluation of the effectiveness of synthetic surfactant to reduce the viscosity of crude oils was produced using local viscometer VPN-01 and the above-mentioned formulas.
Analysis of the literature has shown that to reduce the viscosity of oils it is suggested many surfactants with ionic and nonionic nature. Moreover, the latter showed positive results in reducing the viscosity of crude oils of varying composition. For example, for the synthesis of ethoxylated fatty acids having more than 20 carbon atoms used bottoms fatty acid tar mixture. It found that the activity and physical properties of the surfactant depends on the number of oxyethylated groups with a carbon number of C - C 25 fatty acids per molecule. Thus a more active surfactant synthesized based on fatty acids with C25 ethylene oxide content of at least 70 % [6].
Later surfactants synthesized from fatty acids, containing sulfonate group — SO2OH or a sulfite group OSO2OH. For such purposes were different macromo-lecular sulfonated unsaturated fatty acids, hydroxy acids, their derivatives, alkylated amides or esters and glycer-ides of natural acids [7].
It is known that surfactant activity not only depends on its structure, but also on the location of the functional groups and on the value of hydrophilic-lipophilic balance (HLB) [8].
Currently, Uzbekistan has successfully operated more than 25 oil and fat enterprises, which produce about 500 thousand tons of refined cottonseed oil per year. Waste alkali refining cottonseed oil is soapstock, which contains up to 45 % C , sodium salts of fatty acids
C_, Clon, C100, C10, and others up to 30 % of neutral
16:0 ' 18:0 ' 18:2 ' 18:1 ^
fat (oil) and 5 % gossypol, chlorophyll and derivatives thereof, up to 3 % phospholipids, and others. The current
technology this soapstock will be saponifies the remaining with alkaline reagent (NaOH), decomposed with sulfuric acid (H2SO3) and gain raw fatty acids (RFA), which was distilled to improve the color and removing their low-boiling component [9].
RFA are a mixture of saturated and unsaturated fatty acids and therefore is considered the results of their tests averaged.
Table 1 presents the physical and chemical indicators of the RFA, which we have obtained from cottonseed soapstock. These tests are performed according to the approved standard [10].
From table 1 it is seen that raw fatty acids derived from cotton soapstock have substantial amounts of unsaturated fatty acids (110-112 g y. ch. = J2/100 g), which gives them at room temperature liquid and low melting point. RFA relatively more reactive because It contains substantial amount of ethylene bonds which are necessary for the interaction with the other reagents in the preparation of surfactants.
Table 1. - Physical and chemical parameters RFA cotton soapstock
RFA Indices The values of the indicator
Appearance at 20 °C The liquid mass of dark brown color
Acid number , mg KOH/g 201 * 203
Iodine number, gJ2/100 g 110 * 112
Melting temperature, °C 19 * 30
Mass fraction of unsaponifiables, % 2.1 * 3.9
Water content, % 0.2 * 0.6
Preparation of the surfactant in the form of higher fatty alcohols modified by various additives was carried our as follows:
We performed esterification process by reaction RFA cotton soapstock with methanol (CH3OH) in the presence of 70 % sulfuric acid (ca talyst) at 115-120 °C. The chemical reaction proceeds according to the formula:
RCOOH + CH2OH = RCOOCH3 + H2O. In this case, the remaining sulfuric acid and fatty acid was removed by neutralization with a 5 % caustic solution at 80 °C.
The results of analysis of the main indicators of methyl RFA cholesterol are shown in Table 2.
Table 2. - Physical and chemical indicators of cholesterol and free fatty acids methyl ester
Table 3. - The organoleptic and physico-chemical characteristics of fatty alcohols derived from RFA CS
The name of indicators CS RFA Methyl RFA cholesterol
Acid number, mg KOH/g 201.5 1.4
Essential numbers, mg KOH/g 0.7 187
Iodine number, % J 2/100 117.2 115.8
Table 2 shows that the two parameters in the process and the acid number of the esterification essential basically changed, which is 14 and 187 mg KOH/g, respectively. In the course of the ether synthesis, we sought to increase its output as during removal of the formed esterification water which was azeotropically escaping to condense in the reflux condenser, and gradually accumulates in the trap, the reaction equilibrium shifts toward increasing the yield of ester. In this way we were able to increase the yield of methyl RFA CS up to 93 %, against 56 %. The ester is a liquid and odor, readily soluble in many hydrocarbons.
Analysis showed that the resulting methyl ester RFA CS has a boiling point lower than the boiling temperature of the acids themselves.
Hydrogenation of the methyl ester RFA CS to obtain high-molecular (higher) fatty alcohols was carried out in the presence of a copper-chromium-barium catalyst at a temperature of about 300 °C and a pressure of 30 MPa, where the chemical reaction takes place according to the equation [11]:
RCOOCH 3 + 2H 2 ■ R-CH 2 OH + CH 3 OH.
The resulting alcohol is separated from the soap (reaction product of unreacted methyl ester RFA CS with sodium hydroxide) by distillation.
Physical and chemical parameters resulting higher fatty alcohol are presented in table 3.
Table 3 shows that the higher fatty alcohol obtained from the RFA CS has indicators, relevant non-ionic surfactant.
The name of indicators The values of the indicator
Appearance and color Liquid light yellow
Smell With a slight characteristic odor
Temperature, °C 45.5
congeal 350
ignition -kipeniya 155
hydroxyl number, mg KOH 230
The content of hydrocarbons, % 0.85
Modification i. e. ethoxylation of higher fatty alcohols it will be modified the properties of the resulting surfactant. This process we conducted at 135-145 °C and pressures of ethylene oxide equal to 1.8-2.0 atm., Within 1.5-2.0 hours and in the presence of potassium (as a catalyst) in an amount of1 % alcohol. Herewith the reaction proceeds as follows [12]:
RH + n (C2H4O) R ■ (C2H4O)H, where: n — is the number of ethylene oxide.
Study obtained by ethoxylation of higher alcohol from RFA CS showed that the surfactant containing 10-12 moles of ethylene oxide per mole of alcohol is a water soluble liquid which with increasing chain length ofthe ethoxylated surface tension ofthe latter increases. We conditionally to name a surfactant-1 and the resulting liquid were examined by lowering the viscosity of the local oil.
Next, we sulfited higher fatty alcohol, free fatty acids derived from cholesterol sulfuric acid solution at a temperature of 50 °C to a depth of 86 %. In the process of sulfonation of higher alcohols, a large amount of heat, so we surfactant cooled to room temperature. And, humidity higher alcohol should not exceed 0.2 %.
Table 4 presents the colloid-chemical parameters ethoxylated (surfactant 1) sulfited (surfactant -2) and the higher fatty alcohol derived from RFA CS.
Table 4. - Basic colloidal-chemical characteristics of surfactant 1, surfactant 2 and higher fatty alcohol obtained from the RFA CS
Naimeno-SURFACTANT tion Viscosity, east pH surface tension of, dyne/cm Blowing capacity at 25 °C, see 3 Wetting-ability
Higher fatty alcohols of the RFA CS (control) 0.85 8.7 65 355 eleven'
SURFACTANT 1 0.53 9.8 35 230 19''
SURFACTANT 2 0.47 6.9 22 335 17''
From table 4 it is seen that obtained surfactant 1, surfactant 2 and higher fatty alcohol of RFA CS differ among themselves; despite the identity of the feedstock SURFACTANT-1 is more soluble in water than the SURFACTANT-2, which has a lower foaming capacity.
We have studied the reduction of the effective viscosity Mingbulak oil fields of administration depending on the surfactant1 and surfactant 2.
The results of analyzes are presented in table 5.
From table 5 it is seen that the addition of 0.05 % surfactant 2 in oil composition containing high paraffin from Mingbulak deposits compared with SURFACTANT-1 in
the same amount effective to reduce its viscosity to about 10-13 times, while the SURFACTANT-1 decreases 6-9 times (depending on the composition of researched oil).
Thus studies for obtaining surfactants reducing the viscosity of the oil from the RFA CS show that a rational scheme of the selected surfactants of RFA CS in the form of higher fatty alcohols and their modification methods sorbitan or sulfation.
It is found that the use of the resulting surfactant 2 in an amount of 0.05 % by weight of oil to reduce its effective viscosity 10-13 times (depending on the composition containing high paraffin from Mingbulak oil deposits).
Table 5. - Changes the rheological properties of oil deposits Mingbulak depending on the type of surfactant used
Configu- Higher fatty alcohols RFA CS SURFACTANT 1 SURFACTANT 2
rable shear The shear rate Effective vis- The shear rate Effective vis- The shear rate Effective vis-
stress, Pa of oil, 1 cosity, Pa.s of oil, 1 cosity, Pa.s of oil, 1 cosity, Pa.s
6.30 1.902 3.341 11.614 0.547 25.425 0.251
9.45 2.921 3.283 17.388 0.552 37.531 0.255
12.60 3.935 3.209 22.815 0.561 51.292 0.259
15.75 4.974 3.172 29.104 0.569 62.814 0.267
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3. Rehbinder P. A. Physico-chemical mechanics of disperse structures//AT Sat. Physical - chemical Mechanics disperse structures - M.: Science, 1966. - P. 12-16.
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Studying technological tools that prepare materials with a combination of polyether and cotton fiber for finishing-touch process
D OI: http://dx.doi.org/10.20534/AJT-17-1.2-93-97
Nabieva Iroda Abdusamatovna, Doctor of science, the faculty of textile industry and technology, Tashkent institute of textile and light industry, Republic of Uzbekistan
Khasanova Makhfuza Shukhratovna, Assistant professor, the faculty of textile industry and technology
Artikboeva Ruza Maxsudjanovna, Student, the faculty of textile industry and technology
E-mail: niroda@bk.ru
Studying technological tools that prepare materials with a combination of polyether and cotton fiber for finishing-touch process
Abstract: Preparation thread and fabric containing polyether and cotton fiber in various ratios for polishing process are studied. The ways how to give strong capillarity by boiling process with flimsy alkaline condition are shown. Possibility of higher alkali fiber material than mixed fiber material is scientifically proved. Bleaching machine for fabrics containing synthetic fiber is introduced. Increase in hygroscopic and durability of fabrics during mercerization process is emphasized.
Keywords: polyether, cotton, yarn, fabric, mixed yarn, boiling, bleaching, mercerization process, capillarity, degree of whiteness.
Introduction
Solving science-technological problems associated with textile and light industry related to recycling local raw material profoundly, localizing the range of goods is essential. In this sphere expanding the usage of polyether fiber manufactured in the Republic, including the availability of manufacturing technologies thatproducenew types of products from the mixture of synthetic and natural fibers is considered as a crucial issue. Likewise, expanding the range of recycling of locally manufactured cotton fibers, developing assortment of readymade textile products is regarded as an import ant task.
The process of preparing materials that are made of synthetic fibers for dying and polishing includes cleaning from lubricate emulsion, the solution of antistatic substance and starch that is used to soak the thread before weaving material. To achieve this, the cloth is treated in the solution of surface active substances with the aid of soda and rinsed several times. It is obvious that the nature and structure of fibers contain variety of polymer, so the process of dying and polishing differs completely. To prepare fabrics produced from the mixture of those fibers special condition that is suitable for the features of both fibers which ensures qualified coloring is required. Certainly, the condition of process is also linked to the component of substances and features of fabric in textile process. In practice, the amount of starch that is used for fabrics with mixed fibers consists of 6-8 %. To clean
the fabrics from that it should become water-soluble in alkaline condition, afterwards it excludes from the fabrics through the rinsing process. The feature of textile materials obtained from the mixture of those fibers varies according to the nature of fiber.
Types and ratio of fiber components in the mixture that makes up textile material defines the range of usage and is regarded as a basic factor in organizing recycling technologies. As chemical polishing technologies of materials containing different fiber are available, manufacturing problem of products which can meet the demands of consumers is tackled. But, the condition ofproduction cannot be utilized on polishing of mixed fiber materials because not only the nature and structure of mixed fibers but also ratio of fibers should be taken into consideration by a machine. It is known that, the process of mercerizing cotton fiber is performed under the influence of highly concentrated corrode alkali. In this condition, to prevent polyether fiber from changing its traits technology through which the process of mercerizing with the aid of reducers is done has been studied. To bleach fabrics made of the mixture of cotton and polyether fibers, alkali concentration and process temperature are paid a special attention. Through the surveyschances ofbleach-ing the cotton with the presence of hydrogen peroxide in neutral environment is learned. In published works the possibility of getting positive results from the method of polishing through the combination of hypochlorite
