CC BY
12
48
AZERBAIJAN CHEMICAL JOURNAL № 4 2023
ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
UDC 665.7.038.2.665.765
SULFONATE ADDITIVES TO LUBRICATING OILS
11 2 1 P.Sh.Mammadova , I.D. Kulaliyev , K.A.Salmanova , I.A.Sadirzadeh
Academician A.Guliyev Institute of Chemistry of Additives, Ministry of Science and Education of
the Republic of Azerbaijan 2Azerbaijan State Pedagogical University
aki05@mail.ru
Received 18.01.2023 Accepted 04.04.2023
To expand the resource base and increase the efficiency of sulfonate additives, the possibility of obtaining them based on mixed raw materials - petroleum oil M-8 and alkylbenzene synthesized using propylene fraction C18-C30 oligomers was studied. It is shown that during sulfonation of mixed raw materials, the yield of sulfonic acids is 89-93%, the content of hard-to-recycle waste - acid tar is lower than during sulfonation of petroleum oil by 30-35%. The influence of the ratio of ingredients in the initial mixture on the indicators of neutral sulfonate was studied and the conditions for obtaining additives of the required quality were found. The properties of the developed additives in M-11 oil at a concentration of 5% were studied by standard methods. The composition and structure of sulfonates were studied by elemental analysis and IR spectroscopy. The resulting additives have a micellar structure. The results of laboratory tests have shown that neutral, medium - and highly alkaline semi-synthetic calcium sul-fonates have high physico-chemical and functional properties. The neutral sulfonate is superior in yield, active substance content, and dispersing properties to NCK petroleum sulfonate and OLOA 246B additive. Medium- and high-alkaline additives in terms of physicochemical and detergent properties are at the level of commercial petroleum sulfonates C-150, C-300 and Hightech 6060M additives, and surpass them in dispersing, anti-corrosion properties and stability against oxidation. Alkaline semi-synthetic calcium sulfonates have a high stability of the colloidal dispersion to the action of water and have better performance compared to analogues. With an increase in the alkalinity of the obtained additives, the physicochemical properties improve, which is associated with the features of their colloidal structure. Using the developed neutral and high-alkaline additives as detergent-dispersant components, experimental motor oils M-10DM and M-10G2, were prepared, which meet the requirements in terms of quality. The high efficiency of semi-synthetic sulfonates allows them to be used in modern motor oils.
Keywords: petroleum oil, alkylbenzene, semi-synthetic sulfonates, detergent-dispersant additives, motor oils, functional properties.
doi.org/10.32737/0005-2531-2023-4-48-54 Introduction
When creating high-quality motor oils that meet the stringent requirements of modern technology, effective additives of various functional effects are widely used to provide the necessary detergent, dispersant, antioxidant, anti-corrosive, antiwear, and other properties [1-5]. Currently, almost the entire world production of lubricating oil additives is provided by a number of specialized manufacturers - Lubrizol, Infineum, Afton, as well as large transnational, oil and gas and chemical corporations such as British Petroleum, Shell, Chevron Oronite, Basf, Chemtura and etc.
Among these additives, a significant proportion are detergent-dispersant additives of the alkyl salicylate, sulfonate, alkyl phenolate type,
which is due to their high service properties [611]. Almost all additive packages for modern motor oils contain these additives.
The most common detergent-dispersant additives are sulfonate additives produced on the basis of petroleum oils and synthetic al-kylaromatic hydrocarbons [11-14]. The main indicator of the quality of additives of this type is the content of the active substance - metal sulfonate, which should be more than 30%. The production of sulfonate additives from petroleum oils with the specified content of the active substance is a multi-stage and complex process, including two-fold extraction of sulfosalts, an exchange decomposition reaction, solvent distillation, etc. In this case, along with the target product, a significant amount of hard-to-recycle
waste is formed - acid tar. In the production of synthetic sulfonate additives, the final product is diluted with oil, which leads to some deterioration in quality indicators.
One of the promising directions in the development of sulfonate additives for motor oils is the use of a mixture of petroleum oils with alkylaromatic hydrocarbons as a raw material. In this case, the technology for the produc-
tion of additives is simplified, the content of the active substance in them increases, and their functional and servise properties improve [15, 16]. Considering the urgency of the problem, in order to expand the raw material base of sul-fonates and improve their quality, in this work, they were synthesized based on a mixture of petroleum oil and alkylbenzene according to the following scheme:
R'
RArH +
+ SO3-*-RArSO3H +
R
R
+ Ca(OH),-^(RArSO3)Ca +
2 3 2
+ CO2+Ca(OH)2
SO3H
(RArSO3)Ca-CaCO3 +
R
Ca +
SO3 / 2
SO3/2
Ca . CaCO
where RArH - alkylaromatic hydrocarbon oils; R- C18-C30
Experimental part
M-8 oil obtained from mixed Baku oils, containing 17% of light and medium alkylaromatic hydrocarbons, was used as petroleum raw material. Synthetic raw material is alkylbenzene obtained by alkylation of benzene with olefins of the Ci8-C30 fraction in the presence of zeolite-containing catalyst according to the method [17]. Alkylbenzene has the following physical and chemical parameters: density at 200C - 865
3 20
kg/m ; refractive index nD - 1.4860; molecular weight - 425; boiling point - >4300C.
The mixture of petroleum oil and al-kylbenzene was sulfonated with gaseous sulfur trioxide at a temperature of 40-450C for 2 hours. The content of sulfonic acids in the sul-fonation product is 89-93%, and the yield of acid tar is 30-35% lower than in the sulfonation of petroleum oil.
Neutralization of the mixture of formed sulfonic acids was carried out with 20% aqueous solution of calcium hydroxide at a tempera-
ture of 70-75 C for 3 hours until alkalescent reaction. Then the temperature was raised to 125-1300C to evaporate the reaction water and kept at this temperature for 3 hours. The resulting product was dissolved in octane, mechanical impurities were separated by centrifugation, and the solvent was distilled off. The yield of neutral sulfonate made 87-90%, which is significantly higher than the corresponding petroleum sulfonate (35%).
The influence of the ratio of ingredients in the initial mixture on the content of the active substance and other indicators of the neutral sulfonate was studied. It has been established that in order to obtain an additive of the required quality, the optimal addition of alkylben-zene to petroleum oil is in the range of 30-40% mass and a further increase in its amount leads to an increase in viscosity and the content of mechanical impurities in the sulfonate.
By carbonation of the neutral sulfonate with carbon dioxide in the presence of an ex-
50
P.SH.MAMMADOVA et al.
cess of calcium hydroxide, methanol promoter, diluent oil, and toluene solvent medium-alkaline (C-150 type) and high-alkaline (C-300 type) additives were produced.
Composition and structure of the sul-fonates were confirmed by elemental analysis and IR spectroscopy. The content of the active substance in the additives was determined by liquid adsorption microchromatography, which makes it possible to isolate the sulfonate and oil parts of the additives using polar solvents. The calcium content was determined on a metal analyzer MP-4200 AES, IR spectra were taken from on a spectrometer NICOLET IS-10.
The absorption bands are present in the IR spectra of sulfonates at 1160-1250 and 10501070 cm-1, arising from symmetric and asymmetric vibrations of the S = O bonds of the SO3 group. The most characteristic of the spectra of alkaline sulfonates is the presence of bands in the region of 850-880 and 1400-1500 cm-1, related to vibrations of the carbonate ion CO32-.
The physicochemical and functional properties of the obtained additives were studied by standard laboratory methods [18]. Detergent properties were determined using PZV method according to GOST 5726-2013, dispersant properties at 2500C were determined according to the described method [19], anticorrosion properties were evaluated on DK-NAMI device at 140°C for 25 hours, stability against oxidation -
o
on DK-NAMI unit at 200 C for 30 hours according to GOST 11063-77. The colloidal dispersion stability of alkaline sulfonates was evaluated by the method [20], consisting of the decomposition of the additive in the presence of 15% of water at 1100C for 4 hours. The colloidal dispersion stability was determined by reducing the alkalinity of the additive, expressed in % of the initial one.
Results and discussion
The obtained additives NSKab (neutral), PS-150ab (medium-alkaline) and PS-300ab (high alkaline) are viscous liquids of dark brown color, the characteristics of which are shown in Table 1 and 2. In the same place for comparison there are presented similar indicators of commercial petroleum sulfonates C-150 and C-300, as well as foreign analogues - OLOA 246B and Hightech 6060M additives.
The synthesized additives have a micellar structure characteristic of sulfonates. The resulting alkalini sulfonates are colloidal dispersions of calcium carbonate stabilized in oil by an ad-sorption-solvate layer of alkylarylsulfonate. They are characterized by high physicochemical and functional properties. With the introduction of the developed additives in M-11 oil at a concentration of 5%, its detergent, dispersant, neutralizing, anticorrosive properties and antioxida-tive stability are significantly improved.
Table 1. Characteristics of neutral sulfonate additives
Indicators Neutral sulfonates
PSKab NSK OLOA 246B
Yield, mass % for feedstock 93 39 -
Alkaline number, mg KOH/g 24.3 22 23
Mass fraction, %
calcium sulfonate 45.1 41.5 41.1
calcium 3.5 2.1 -
mechanical impurities 0.05 0.08 0,1
Sulfate ash, % mass 8.8 8.3 8.6
Detergent properties on PZV installation, points* 0.5 0.5 0.5
Dispersant ability at 250°C, %* 47 40 40
*M-11 oil with 5% additive
Table 2. Characteristics of medium- and high-alkaline sulfonate additives
Indicators Medium- and high-alkaline sulfonate additives
PS-150ab ^150 PS-300ab ^300 Hightech 6060M.
Alkalinity number, mg KOH/g 152 150 304 303 142
Mass fraction, % calcium sulfonate calcium calcium carbonate mechanical impurities 32.1 6.2 13.5 0,05 31.5 0,08 30.5 13.7 26.8 0,05 30.0 0.09 32.0 0,05
Sulfate ash, % mass 23.2 23.0 43.2 42.9 23,1
Temperature flashes in open crucible, ^ 190 180 210 200 185
Detergent properties on PZV installation, points, no more than 0 0 0 0 0,5
Dispersant ability at 250 °C, % * 67 60 80 75 60
Corrosion of lead plates, g/m2 * 64 85 58 90 85
Stability over the induction period of pre* cipitation: sludge, % increase in viscosity, % 0.5 66 0.7 71 0.7 55 0.8 77 0.9 78
Colloidal dispersion stability, % 82 75 94 90 76
*M-11 oil with 5% additive
The neutral sulfonate PSKab has a higher content of the active substance, a lower content of mechanical impurities and better dispersant properties compared to the NSK additive obtained on the basis of M-8 oil according to a complex technology.
The developed semisynthetic calcium sulfonates PS-150ab and PS-300ab are at the level of C-150 and C-300 additives in detergent properties, and surpass them in dispersant, anticorrosion properties and oxidation stability. Thus, the dispersant properties of PS-150ab and PS-300ab additives are 67 and 80%, while for ^ 150 and ^300 additives these figures are 60 and 75%. In addition, experimental additives have a higher colloidal stability to the action of water compared to analogues.
Alkaline semisynthetic additives are superior to foreign analogues in a number of indicators. Thus, the increase in viscosity after oxidation of oil with PS-150ab, PS-300ab and Hig-tech 6060M additives is 66, 53 and 78%, respectively.
A comparison of the functional properties of sulfonates obtained on the basis of mixed raw materials shows that with an increase in alkalinity, the content of calcium carbonate in additives increases and their effectiveness increases.
Using the developed PSKab neutral sulfonate, M-10DM low-ash motor oil was prepared, and the PS-300ab high-alkaline additive was studied in the composition of M-10G2 motor oil for automotive diesel engines.
The results of preliminary laboratory tests (Tables 3 and 4) showed that semisynthetic sulfonates provided experimental oils with high physicochemical and functional (detergent-dispersant, anticorrosion, antioxidant) properties and met the requirements for these oils. A comparison of the functional properties of sul-fonates obtained on the basis of mixed raw materials shows that with an increase in alkalinity, the content of calcium carbonate in additives increases and their effectiveness increases.
52 P.SH.MAMMADOVA et al. Table 3. Characteristics of M-10DM experimental motor oil_
Indicators M-10DM motor oil
norm for M-10DM oil experimental
Kinematic viscosity at 100 0C, mm2/s, not less than 11.4 11.4
Viscosity index, not less than 90 91
Sulfate ash, %, no more than 1.5 1.45
Alkaline number, mg KOH/g oil no less than 8.2 8.9
Mass fraction of mechanical impurities,%, no more than 0,025 0,008
Mass fraction of water, %, no more than traces none
Temperature, 0C flashes in open crucible, no less than hardening, no higher than 220 - 18 220 - 18
Corrosion of lead plates, g/m2, no more than none none
Detergent properties on PZV installation, points, no more than - 0
Stability over the induction period of precipitation, h, no less than 60 60
Density at 200C, kg/m3, no more than 905 903
Table 4. Characteristics of M-10G2 experimental motor oil
Indicators M-10G2 motor oil
norm for M-10G2 oil experimental
Kinematic viscosity at 100 0C, mm2/s 11 ± 0.5 11.2
Viscosity index, not less than 85 90
Sulfate ash, %, no more than 1.65 1.56
Alkaline number, mg KOH/g oil, no less than 6.0 8.0
Mass fraction of mechanical impurities,%, no more than 0.015 0.007
Mass fraction of water, %, no more than traces none
Temperature, 0C flashes in open crucible, no less than hardening, no higher than 205 - 15 205 - 15
Detergent properties on PZV installation, points, no more than 1.0 0
Corrosion of lead plates, g/m2, no more than 20 none
Density at 200C, kg/m3, no more than 905 903
The observed high efficiency of semisyn-thetic sulfonates is apparently due to the presence in their structure of an alkylbenzene fragment with a long alkyl radical, a sulfo group in combination with a colloidal dispersion of calcium carbonate and their synergism.
Conclusions
Based on a mixture of petroleum oil and alkylbenzene, effective sulfonate additives having improved physicochemical and functional properties compared to petroleum analogues were obtained with high yield.
High efficiency of the developed additives makes it possible to use them as a part of additive compositions when creating modern motor oils.
References
1. Fialko V.M. Importozameshchenie v oblasti prisa-dok k maslam. Mir nefteproduktov. 2013. № 2. S. 40-43.
2. Danilov A.M., Bartko R.V., Antonov S.A. Sovre-mennye dostizheniya v oblasti primeneniya i raz-rabotki prisadok k smazochnym maslam. Neftekhimiya. 2021. T. 61. №1. S.43-51.
3. Suhoverhov V.D., Vasilkevich I.M. Sovremennye aspekty proizvodstva i primeneniya masel i prisadok k nim. Mir nefteproduktov. 2008. № 6. S. 31-34.
4. Patent RF 2732123. Kompoziciya smazochnogo masla dlya dizel'nogo dvigatelya. Mao Ueda, Kiesi Han'yuda. 0p.11.09.20.
5. Yunisov I.K. Sovershenstvovanie ekspluatacion-nyh svojstv masla dlya vysokoforsirovannyh benzinovyh dvigatelej. Diss...kand.tekh.nauk. M.: RGU Nefti i Gaza im I.M.Gubkina. 2020. 146 s.
6. Kotov S.V., Zerceva I.M., Guseva I.A., Naumkin P.V., Timofeeva G.V., Baklan N.S. Sintez vyso-koshchelochnoj magnijsoderzhashchej alkilsali-cilatnoj prisadki. Neftekhimiya. 2019. T. 59. № 2. S.234-240.
7. Patent RF 2611431. Sposob polucheniya ma-lozol'noj alkilsalicilatnoj prisadki k maslam. Ko-tov S.V., Tarasov A.V., Timofeeva G.V., Kotova N.S., Naumkin P.V., Guseva I.A. Op. 22.02.2017.
8. Zibrova S.N. Razrabotka tekhnologii proizvodstva moyushchih fenatnyh prisadok k motornym maslam. Diss.kand.tekh.nauk. Moskva: RGU Nefti i Gaza im. I.M.Gubkina. 2018, 123 s.
9. Kyazim-zade A.K., Nagieva E.A., Mamed"yarova H.N., Gadirov A.A., Rzaeva I.A. Mnogofunkcio-
nal'nye alkilfenolyatnye prisadki k motornym maslam. Mir nefteproduktov. 2020. №6. S.52-56.
10. Mamedova A.H., Farzaliev V.M., Kyazim-zade A.K. Novye sero-,azot- i borsoderzhashchie mno-gofunkcional'nye alkilfenolyatnye prisadki k motornym maslam. Neftekhimiya. 2017. T.57. №4. S.457-461.
11. Sadyhov K.I. Neftyanye i sinteticheskie sul'fonat-nye prisadki k motornym maslam. Baku: Elm, 2006. 180 s.
12. Patent RF 2728713. Sposob polucheniya sin-teticheskih sul'fonatnyh prisadok k motornym maslam. Kotov S.V., Tyshchenko V.A., Timofeeva G.V., Guseva I.A., Baklan N.S., Lavrent'eva E.M., Zajnulina A.V., Horoshev Yu.N., Laryuhin M.V., Luksha S.V Op. 30.07.2020.
13. Mammadova P.Sh., Veliyeva S.M., Kulaliyev I.D. Synthetic sulfonate additives for lubricating oils. Azarbaycan Mühandislik Akademiyasinin Xabar-lari. 2021. C. 13. №3. S. 67-73.
14. .Mammadova P.Sh, Veliyeva S.M., Kulaliyev I.D., Sadirzadeh I.A., Salmanova K.A. Multifunctional sulfonat additive for lubricating oils. Ali Texniki maktablarin xabarlari. 2022. C. 24. Buraxili§ 1. S. 29-33.
15. Agaev A.N., Velieva S.M., Kulaliev I.D., Gasano-va S.A. Mnogofunkcional'naya moyushche-disper-giruyushchaya prisadka k smazochnym maslam. Materialy XXX Mezhdunarodnoj nauchno-tekhnicheskoj konf. «Himicheskie reaktivy, reagenty i processy malotonnazhnoj himii» posvyash. pamyati akademika AN Respubliki Bashkortostan Dilyusa Lutfullicha Rahmankulova. Ufa, 14-16 noyabrya 2016. S. 125-126.
16. Agaev A.N., Velieva S.M., Kulaliev I.D., Salmanova K.A., Gasanova.S.A., Askerova. H.A. Mnogofunkcional'nye polusinteticheskie prisadki sul'fonatnogo tipa k smazochnym maslam. Nef-tepererabotka i neftekhimiya, 2017. № 3. S. 38-40.
17. Magerramov A.M., Cadyhov K.I., Agaev A.N., Magerramov M.N. Ceolitsoderzhashchie kataliza-tory v ekologicheski chistom proizvodstve sul'fonatnyh prisadok k smazochnym maslam. Materialy azerbajdzhano-rossijskogo simpoziuma s mezhdunarodnym uchastiem «Kataliz v reshenii problem neftekhimii i neftepererabotki». Baku., 28-30 centyabrya 2010. S. 216-217.
18. Nefteprodukty: Masla. Smazki. Prisadki. M.: Standarty, 1987. Ch. 3. S. 144-147.
19. Glavati O.L. Fiziko-himiya dispergiruyushchih prisa-dok k maslam. Kiev: Naukova dumka, 1989. 183 s.
20. Velieva S.M., Zejnalova N.N., Kulaliev I.D., A.N.Agaev. Issledovanie kolloidnoj stabil'nosti gidroksialkilbenzilsul'fonatnyh prisadok. Azerb. Neft. Hoz-vo. 2011. №2. S. 60-63.
54
P.SH.MAMMADOVA et al.
MOTOR YAGLARINA SULFONAT A§QARLARI
P.^.Mammadova, i.C.Güteliyev, K.A.Salmanova, LO.Sadirzada
Sulfonat ajqarlarinin gejidini genijlandirmak va tasir effektini artirmaq maqsadi ila onlarin M-8 neft yagi va Ci8-C30 fraksiyali oliqomer propilendan istifada etmakla sintez edilmij alkilbenzol qarijigi asasinda alinmasinin mümkünlüyü öyranilmiijdir Göstarilmiijdir ki, qariijiq xammalin sulfolajmasi prosesinda sulfoturjularin giximi 89-93%, emal edilmasi gatin olan tullanti - turj qudronun miqdari isa sulfolajmiij neft yaglarina nisbatan 30-35% ajagidir. Neytral sulfonatin göstaricilarina ilkin xammal qarijiginda inqrediyentlarin nisbatinin tasiri öyranilmiij va talab olunan ajqarin alinmasi ügün jarait müayyan edilmijdir. Yaradilmij ajqarlarin xassalari M-11 yaginda 5% qatiliqda standart üsullarla öyranilmiijdir Sulfonatlarin tarkibi va quruluju element analizi va iQ spektroskopiya üsullari ila öyranilmiijdir Alinmij sulfonatlar mitselyar quruluja malikdir. Laboratoriya sinaqlarin naticalari göstarmijdir ki, neytral, orta- va yüksak qalavili yarimsintetik kalsium sulfonatlari yüksak fiziki-kimyavi va funksional xassalara malikdir. Neytral sulfonat gixima, aktiv maddanin miqdarina, dispersedici xassalara göra neft manjali NSK sulfonatindan va OLOA 246B ajqarindan üstündür. Orta- va yüksak qalavili ajqarlar fiziki-kimyavi va yuyucu xassalarina göra neft manjali C-150, C-300 amtaa sulfonatlarla va Xaytek 6060M ajqarla eyni saviyyada oldugu halda, dispersedici, korroziyaya, oksidlajmaya qarji stabilliya göra analoqlardan üstündürlar. Qalavi yarimsintetik kalsium sulfonatlari suyun tasirina qarji yüksak kolloid stabilliyina malikdir va onlarin analoqlara nisbatan daha yaxji göstaricilari müayyan edilmijdir. Qalavi adadi artdiqca yaradilmij sulfonatlarin fiziki-kimyavi, funksional xassalari yüksalir, bu da onlarin kolloid qurulujlarinin xüsusiyyatlari ila izah edilir. Alinmij neytral va yüksak qalavili ajqarlann ijtiraki ila keyfiyyat göstaricilarina göra irali sürülan talablara cavab veran M-10DM va M-10r2 tipli tacrübi motor yaglari ijlanilmijdir. Yarimsintetik sulfonatlarin yüksak effektivliyi onlari müasir motor yaglarinda istifada etmaya imkan verir.
Agar sözlzr: neft yagi, alkilbenzol, yarimsintetik sulfonatlar, yuyucu-dispersedici a§qarlar, motor yaglari, funksional xassalar.
