• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    Highly basic Calcium Sulphonate with improved solubility in heavy paraffinic oils and improved filterability is prepared by carbonating a mixture of sulphonic acid, calcium hydroxide, water, alcohol and solvent at a temperature from 20 DEG C to 35 DEG C and using a stoichiometric excess of calcium hydroxide and a specified amount of water.
    公开号:SU919592A3
    申请号:SU782632855
    申请日:1978-07-03
    公开日:1982-04-07
    发明作者:Луи Пиерр Ленэк Элен；Тиртио Робер
    申请人:Эксон Рисерч Энд Инджиниринг Компани (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD OF OBTAINING HIGH-BASIC CALCIUM SULPHIATES

    This invention relates to the method of halogen1 and highly basic calcium sulfonates, which are used as additives to lubricating oils.
    A known method for producing highly basic calcium sulfonates, according to which a mixture of calcium sulfonate, calcium hydroxide, hydrocarbon oil and alcohol with 1-5 carbon atoms) is reacted with carbon dioxide to convert 50-83% calcium hydroxide to carbonate at C 93 ° C, followed by by filtering the mixture fl.
    Closest to NredlagaAomu is a method for the preparation of highly basic calcium sulfonates, according to which a mixture containing 5-30 parts by weight. oil-soluble calcium sulfonate, 20 10-50 weight.h. hydrocarbons with so kip. not less than 150 ° C, weight.h. methanol, about 0.25 hours of non-volatile oil with so Kip. above, 1-25 parts of calcium oxide, calcium hydroxide, processing
    carbon dioxide in the calculation of 0.75, 0.95 mol per 1 mol of hydroxide or calcium oxide at a temperature not higher than 35 ° C, 20-85 parts by weight are added. non-volatile oil per 100 parts of the mixture, heat to remove most of the volatile substances, and then carbon dioxide is passed through the mixture to convert all hydroxide or calcium oxide to carbonate, followed by filtration 12.
    However, this method is characterized by a relatively low solubility of the target product in the oil, which degrades the quality of the product, as well as a low filtration rate of the resulting dispersions.
    The purpose of the invention is to intensify the process and improve the quality of the target product.
    The goal is achieved by the fact that according to the method of obtaining highly basic calcium sulfonates a mixture containing calcium sulfonate or calcium sulfonate, calcium hydroxide in 5 to 50% by weight excess, hydrocarbon solvent, alcohol with 1-3 carbon atoms and water in the amount of 4-35 from the weight of calcium hydroxide, is treated with carbon dioxide at 20-35 ° C, then the volatiles are removed and filtered, the carbon is treated with acid gas in the presence of water, taken in amount from the weight of calcium hydroxide, and using 5-50% excess hydroxide Calcium, and preferably using methyl alcohol. In order to increase the filtration rate, the reaction mixture is kept at 20-35 ° C after the completion of the addition of carbon dioxide and calcium hydroxide. The sulfonic acids used in this process include oil-soluble sulfonic acids of natural or synthetic origin, for example, petroleum alkylsulfonic acids or alkarylsulfonic acids. The alkylsulfonic acid should preferably contain at least 25 carbon atoms per molecule, and the alkarylsulfonic acid (for example alkyl benzene sulfonic acids) should have at least 18 carbon atoms in the alkyl chain. The most preferred are sulfonic acids with a molecular weight of from 300 to 700, for example 400-500. Preferably, the sulfonic acid or sulfonate is applied as a solution in mineral oil with a content of 50-30%. The hydrocarbon solvent may be an aromatic or aliphatic hydrocarbon. Preferred are aromatic hydrocarbons, for example toluene, xylene, ethylbenzene. Suitable aliphatic hydrocarbons include steam (| new as n-hexane, n-heptane, n-decane, n-dodecane, white alcohol, petroleum or iso-paraffins, and cyclic paraffins, such as cyclohexane. Used C-Cj- The alcohol is preferably methanol, since in the case of using other alcohols during carbonization, a tendency to gel formation is observed. According to the present invention, products soluble in paraffinic oils with a viscosity at 37 ° C or above 500 cP are obtained or equal to this value. These products also have improved filterability. The exact amount of water required for this reaction depends on the amount of excess calcium hydroxide used and its purity.The use of a stoichiometric excess of calcium hydroxide leads to a product with increased solubility in oil, in particular paraffinic mineral oils. The expression stoichiometric excess is higher and below indicates an excess relative to the amount required to react with the sulfonic acid and carbon dioxide gas. The increase in oil solubility is achieved by introducing an excess of calcium hydroxide into the reaction mixture and adjusting the amount of carbon dioxide so that some unreacted calcium hydroxide remains, or by carbonizing the reaction mixture until the absorption of carbon dioxide is complete, followed by adding additional calcium hydroxide before filtering. In order for a product to be distinguished by its increased solubility in oil, it must be alkalinity in phenolphthalein. The reaction mixture is a solution in the oil of the components, and suitable oils include hydrocarbon oils, in particular, of mineral origin. Oil with a viscosity of the order of cp should be considered very suitable at 37.78 s. Alternatively, lubricating oils are described below. The proportions of the components in the reaction mixture are not critical, but the values of the following order are preferred: for every 350 hours, by weight of the sulfonic acid, there are 150-350, preferably 250-300 hours of alcohol, together with 300-800, preferably 00600 h, hydrocarbon solvent and 180-210 parts by weight of calcium hydroxide. The reaction mixture is maintained during carbonization within the range of 20-35 ° C, preferably 20-30 ° C, because when using higher temperatures, for example, the product becomes viscous, while in the case of temperatures below 10 ° C, it becomes milky. In the case of carbonation up to the saturation point and the subsequent addition of an excess of calcium hydroxide for every 550 parts by weight of the sulphonic acid contained in the reaction mixture, 95-115 are absorbed and. by weight of carbon dioxide. Upon completion of carbonation and addition of excess calcium hydroxide, the reaction mixture, preferably to increase the filtration rate, is maintained at a temperature in the order of 20-35 ° C, more preferably 25-30 ° C for at least half an hour. Detergents based on superbasic calcium sulfonate, obtained by the proposed method, are suitable for use as additives and additives to lubricating oils of mineral and synthetic origin. Lubricating oil may be animal, vegetable or mineral, for example, oil fractions from naphtha to spindle oil and lubricating oils such as castor oil, fish oil or oxidized mineral oil. In particular, the products are used in paraffinic mineral oils, in which the previously known calcium sulfonates dissolve only to a limited extent. Suitable synthetic ester lubricants include diesters such as dioctyl adipate, dioctyl sebacate, didecylazate, tridecyl adipate, didecyl succinate, didecyl glutarate, and mixtures thereof. On the other hand, a synthetic ester can be a polyester, for example, obtained by the interaction of microfluoric ethanol, such as trimethylolpropane and pentaerythritol, with monocarboxylic acids, such as oil, caproic, caprylic, and pelargric, to produce the corresponding and tetraesters. Complex esters as basic oils and those obtained by esterification into esters by reacting dicarboxylic acid with alcohol or monocarboxylic acid can be used as well. Together with the additives obtained by the proposed method, other additives can be added to the lubricating oil. The choice of these additives depends on the value of the lubricant. Corresponding additives include alkylsuccinimide dispersants, copolymer viscosity enhancers and anti-wear additives based on dialkyldithiophosphate-zinc. In the examples, the filtration rate is measured in a Buchner funnel, either for 1 hour or additionally receiving 500 g of filtrate. A paper filter of 77 cm at 150 ° C and 7 g of auxiliary filtering agent are applied as a layer on the paper filter. Example 1. 52 parts by weight of alkylaryl sulphonic acid and 90 parts by weight of toluene are mixed in the reactor until the sulfoxe slots are completely dissolved. Then 1 part of methanol and 6.7 parts of water are added, the mixture is stirred, added 28, 5 hours calcium hydroxide (purity grade of 3% by weight calcium carbonate) and can withstand temperatures of about. Carbon dioxide is passed through the reaction mixture at a rate C, 2 hours, per hour, until its adsorption stops. For example, k 1 at 25-30 ° C. After carbonation is complete, another 6 parts of calcium hydroxide are added and the mixture is stirred for 1 hour at. Then 6 parts of paraffinic mineral oil are added, the mixture is heated to remove volatile substances, distilled off under toluene and water, and the residual toluene is removed by distillation and the light fractions in a stream of nitrogen at. At the end, 7.5 parts of this auxiliary filtering agent is added, the product is filtered by the method described above to obtain a total alkalinity filtrate (OC) in the order of 300-320 mgKOH / g. If carbonization is stopped until the absorption of carbon dioxide is completed, or the amount of calcium hydroxide added after carbonization and the amount of water introduced into the reaction mixture varies, the product has a concentration of about 300, and its filterability, appearance and solubility in heavy paraffin mineral oil . Bone 600 cp with memory. and with a content of 60% paraffin carbon atoms are given in Table. 1. In all cases of water addition, the product has an acceptable viscosity. Solubility is determined by adding 5 g of filtrate to 95 g of oil, followed by visual observation of the solubility at room temperature. Example 2. Under the conditions of Example 1, calcium hydroxide was used at a level of 98% purity and with a content of less than 1% by weight of calcium carbonate, while the entire amount of calcium hydroxide was added to the initial reaction mixture, and carbonization was stopped by absorption by the reaction mixture. B2% of the stoichiometric amount of carbon dioxide, then various amounts of water, half-products, whose properties are given in Table 2, are added. 2. In this example, 15 g of auxiliary filtering agent is added for every 500 g of sulfonate before filtration. Oil 1 is paraffin oil used in Example 1, oil 2 is a mixture of 70 parts of oil of example 1 and 30 parts of paraffin oil containing 60% of paraffinic atoms of 9 8 carbon and with a viscosity of 17. 2500 cP. Example 3. Under the conditions of Example 2, the calcium hydroxide used in Example 1 was used, including 7.5% by weight of water based on the weight of calcium hydroxide. Depending on the time during which the mixture is kept approximately before filtering, various results on the filtration rate are obtained (Table 3). Both products are transparent after filtration. In a similar experiment where the product is heated to 50 ° C for 1 hour, the filtration rate is only 48 kg / h / m. The filtration rate is the same regardless of the addition of the dilution oil before or after exposure. Table 1
    In terms of 8, calculated on the initial amount of calcium hydroxide, the total amount of calcium hydroxide.
    6.5
    权利要求:
    Claims (2)
    [1]
    52 Time at, hr I Speed of filtration, kg / h / m Claim 1. Gluteness of calcium sulfate, calcium hydroxide, hydrocarbon solution ({tel and alcohol, carbon dioxide) at a temperature of 20-35 ° C with the subsequent removal of volatile substances and (((for a short time) with this and that.
    919592TO
    Table 2
    Transparent Transparent Transparent improvements in the quality of the target product, treatment with carbon dioxide is carried out in the presence of water, taken in 4-4 Be of 35 calcium hydroxide, and calcium hydroxide is used in excess. 2. The method according to claim. T, o tl and which is based on the use of methyl alcohol. 3. The method according to claim 1, wherein and in order to increase the filtration rate, the reaction mixture is kept at a temperature of 20-35 ° C after the completion of the addition of carbon dioxide and calcium hydroxide. (Sources of information taken into account in the examination 1.US Patent Vf 3537996, class 252-33.4, 1972.
    [2]
    2. Patent СЮЙ Vf 3830739, cl. 252-33., 197.
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    同族专利:
    公开号 | 公开日
    BR7804263A|1979-02-28|
    EP0000264A1|1979-01-10|
    DE2861618D1|1982-03-18|
    JPH034599B2|1991-01-23|
    CA1139078A|1983-01-11|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3170880A|1959-02-20|1965-02-23|Bray Oil Co|Dispersions of calcium compounds in oils|
    US3429811A|1966-08-17|1969-02-25|Exxon Research Engineering Co|Preparation of overbased sulfonates|
    US3830739A|1970-07-17|1974-08-20|Witco Chemical Corp|Preparation of hyperbasic dispersions|
    JPS5040525A|1973-08-15|1975-04-14|US4165291A|1978-06-20|1979-08-21|Phillips Petroleum Company|Overbasing calcium petroleum sulfonates in lubricating oils employing monoalkylbenzene|
    GB2036781A|1978-12-13|1980-07-02|Exxon Research Engineering Co|Preparation of basic magnesium sulphonates|
    GB2058118A|1979-08-31|1981-04-08|Exxon Research Engineering Co|Overbased calcium sulphonate production|
    EP0121024B1|1982-12-08|1987-03-18|Exxon Research And Engineering Company|Preparation of overbased calcium sulphonates|
    DE3461791D1|1983-04-08|1987-02-05|Shell Int Research|Process for preparing an alkyl aryl sulphonate concentrate composition|
    JPH0735515B2|1990-03-30|1995-04-19|株式会社松村石油研究所|Method for producing basic calcium sulfonate|
    CA2067842A1|1991-05-23|1992-11-24|Peggy Jo Harris|Process for overbased calcium sulfonate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB2793277|1977-07-04|
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