JP6126377B2 - Method for improving flash point of oil or oil composition and oil-based composition with improved flash point - Google Patents

Description

  The present invention relates to a method for improving the flash point of oils or oil compositions, and an oily composition having an improved flash point, and more particularly, to a flammable fluid of Class 4 flammable fluids and designated combustibles specified in the Fire Service Act. The present invention relates to a method for improving the flash point for flammable liquids, and more specifically, a third petroleum having a flash point of 150 ° C. or higher and a flash point of 200 to 250 ° C. The present invention relates to a method for improving the flash point of four petroleums or flammable liquids having a flash point of 250 ° C. or higher, and an oily composition having an improved flash point.

  The flammable fluids stipulated by the Fire Service Act as Class 4 hazardous materials and the flammable liquids stipulated by designated combustibles mainly contain oils such as petroleum and animal and vegetable oils. Since these are flammable, they are designated as dangerous goods by the Fire Service Act. However, the lower the flash point, the higher the risk of fire, so depending on the flash point, the handling and storage amount is legal. Regulations are in place.

  An increase in the flash point increases safety in handling the fire and facilitates handling such as storage and management, so that facilities and management costs required for storage can be reduced. In this way, the higher the flash point, the higher the safety, and the easier it is to handle storage and management easily and economically, so various methods have been adopted to improve the flash point of petroleum. Conventionally, it has been carried out mainly by reforming petroleum to low vapor pressure components or removing high vapor pressure components by distillation.

  However, the conventional methods described above require changes in the molecular structure and constituents of petroleum, so that it is necessary to perform physical and chemical operations in the petroleum production stage, which results in high costs for production and refining equipment. Was necessary. In addition, changes in the molecular structure and constituents of petroleum may cause changes in physical and chemical properties other than the flash point, and the treatment operation is difficult.

  In addition, as for the use of additives, an arc inhibitor when a short circuit occurs in an electrical device by adding an ignition suppression agent such as perfluoroalkylpromide which is an organic fluorine compound to transformer oil or insulating oil is a mineral oil. Some have been known to suppress the occurrence of explosions and fires. (Patent Document 1)

JP-A-3-157499

  As described above, in order to increase the flash point of oils or oil compositions, it is necessary to respond from the production and refining stages of oils, and the flash points of oils or oil compositions that have already been produced and refined. There was no effective means for raising the point, but this is intended to be done by simple means.

In order to increase the flash point of oils or oil compositions, the present inventors have made various studies and researches, but added a small amount of certain silicone compounds to oils or oil compositions. However, the present inventors have found that the flash point is increased and completed the present invention based on such knowledge.
Generally, silicone compounds are widely used as additives for industrial products such as composition materials for various lubricating oils such as insulating oil, damper oil, heat medium oil, resin and liquid lubricity imparting agents and antifoaming agents. In the present invention, at least one dialkylpolysiloxane is used as an active ingredient, and a small amount is added to oils or oil compositions to improve their flash points.

As the dialkylpolysiloxane, those having a kinematic viscosity at 25 ° C. of more than 50 mm ² / s and 1000 mm ² / s or less are used.
As such a dialkylpolysiloxane, one of dimethylpolysiloxane and diethylpolysiloxane or a combination of several kinds as required is appropriately added, and a small amount of about 1 to 100 ppm by mass is added to oils or oil compositions. To raise the flash point.

  According to the present invention, by adding the above-mentioned flash point improver to flammable oils or oil compositions, the flash point can be easily increased without causing a large change in both physical and chemical properties. Can be raised. Thereby, by the simple method of adding this flash point improving agent, the safety | security of oil or oil composition can be improved, a storage and management are also easy and can be handled economically.

  In the present invention, the flammable oil or oil composition mainly includes third oils having a flash point of 70 ° C. or higher as defined by the Fire Service Act, fourth oils and animals and plants having a flash point of 200 to 250 ° C. There are oils or flammable liquids having a flash point of 250 ° C. or higher. Moreover, as this oil or oil composition, it is effective especially with respect to what is not provided to food and drink.

The third petroleums, fourth petroleums, animal and vegetable oils, or flammable liquids have a relatively high flash point, and there is little risk of igniting unless heated. Are very flammable liquids that can be difficult to extinguish.
Third petroleums are flammable liquids that are liquid at 1 atm and temperature of 20 ° C. and have a flash point of 70 ° C. or higher and lower than 200 ° C., for example, ISO viscosity grade 10-22 mineral oil or synthetic hydrocarbon And fatty acid ester-based lubricating base oils, and lubricating oils using these as base oil compositions. In the present invention, oils that increase the flash point include oils having a flash point of 150 ° C. or higher and lower than 200 ° C. among the third petroleums.

  The fourth petroleum is a liquid at 1 atm and a temperature of 20 ° C., and has a flash point of 200 ° C. or higher and lower than 250 ° C., for example, SAE viscosity grade is 30, 5W-30, 10W-30, 15W- Engine oils such as 40, mineral oils or synthetic hydrocarbons having an ISO viscosity grade of 32-68, fatty acid ester-based lubricating base oils, and lubricating oils using these as base oil compositions.

  The above-mentioned animal and vegetable oils are extracted from animal fat or the like or plant seeds or pulp, are liquid at 1 atm / 20 ° C., and have a flash point of less than 250 ° C., for example, Examples include coconut oil and linseed oil.

  The flammable liquids described above are liquids at a temperature of 20 ° C at 1 atm as defined in Japan's “Decree on the Regulation of Dangerous Goods” (Appendix Table 4). Is.

  As said 3rd petroleum, 4th petroleum, animal and vegetable oils, or flammable liquids, mineral oil or synthetic oil can be mentioned. Examples of mineral oils or synthetic oils include base oils belonging to Group 1, Group 2, Group 3, Group 4, etc. in the API (American Petroleum Institute, American Petroleum Institute) base oil category, or mixtures thereof.

As Group 1 base oil, for example, paraffin obtained by applying a suitable combination of solvent refining, hydrotreating, dewaxing, etc., to a lubricating oil fraction obtained by atmospheric distillation of crude oil Listed are mineral oils.
Group 2 base oils include, for example, paraffinic mineral oils obtained by appropriately combining refining means such as hydrocracking and dewaxing for lubricating oil fractions obtained by atmospheric distillation of crude oil Can be mentioned.

Group 3 base oils include, for example, paraffinic mineral oil produced by advanced hydrorefining of lubricating oil fractions obtained by atmospheric distillation of crude oil, and Fischer Tropu, a natural gas liquid fuel technology. GTL (gas-to-liquid) synthesized by the method, wax and base oil refined by ISODEWAX process that converts and dewaxes wax produced by dewaxing process to isoparaffin, and refined by mobile WAX isomerization process Mention may be made of base oils.
Group 4 base oils include polyolefins.

  Synthetic oils include, for example, alkylbenzene, alkylnaphthalene, ester, polyoxyalkylene glycol, in addition to the above-mentioned polyolefin, GTL (gas-tuly liquid) oil synthesized by the Fischer-Tropsch method of natural gas liquid fuel technology, Examples thereof include polyphenyl ether, dialkyl diphenyl ether, fluorine-containing compounds (perfluoropolyether, fluorinated polyolefin, etc.) and mixtures thereof.

  The third petroleum, fourth petroleum, animal and vegetable oils, or flammable liquids can be used for various applications. These applications are not particularly limited, but hydraulic oil, turbine oil, compressor oil, bearing oil (oil film bearing oil), sliding surface oil, gear oil, vacuum pump oil, refrigerator oil, heat medium oil Examples include industrial lubricating oils such as electrical insulating oils, internal combustion engine lubricating oils, vehicle drive system lubricating oils, vehicle powertrain lubricating oils, and the like.

  In order to improve the performance of the third petroleums, fourth petroleums, animal and vegetable oils, or flammable liquids, various additives may be added as necessary. These additives include antioxidants, metal deactivators, extreme pressure agents, oiliness improvers, non-silicone alcohol defoamers and polyethyl acrylate defoamers, viscosity index improvers, pour point depressants. Agents, cleaning dispersants, rust inhibitors, demulsifiers, and other known additives.

A dialkylpolysiloxane is added to the oils or oil compositions. The dialkylpolysiloxane has a kinematic viscosity at 25 ° C. of more than 50 mm ² / s and 1000 mm ² / s or less, and preferably less than 1000 mm ² / s.
The kinematic viscosity of this dialkylpolysiloxane at 25 ° C. is preferably 70 mm ² / s or more and 1000 mm ² / s or less (or less than 1000 mm ² / s), more preferably 200 mm ² / s or more and 1000 mm ² / s or less. (Or less than 1000 mm ² / s).

And the said dialkyl polysiloxane can be used combining the 1 type or multiple types of thing suitably. If the kinematic viscosity of the added dialkylpolysiloxane is too low (for example, 50 mm ² / s or less), there is a possibility that the effect of improving the flash point cannot be expected, which is considered because the molecular weight of the dialkylpolysiloxane is small.

The value of the specific gravity at 25 ° C. of the dialkylpolysiloxane is not particularly limited, but may exceed 0.960, preferably 0.965 or more, and more preferably 0.970 or more.
The value of the viscosity temperature coefficient VTC of the dialkylpolysiloxane is not particularly limited, but may exceed 0.59, preferably 0.60 or more.
Further, the value of the 25 ° C. refractive index of the dialkylpolysiloxane is not particularly limited, but may exceed 1.402, and may preferably be 1.403 or more.

The viscosity temperature coefficient VTC (Viscosity Temperature Coefficient) is calculated by the following formula, and indicates that the smaller the viscosity temperature coefficient VTC, the smaller the viscosity change due to temperature.
VTC = 1- [Kinematic viscosity at 210 ° F. (98.9 ° C.) / Kinematic viscosity at 100 ° F. (37.8 ° C.)]

  As the dialkylpolysiloxane, dimethylpolysiloxane having an alkyl group of methyl and diethylpolysiloxane having an alkyl group of ethyl are preferably used, and dimethylpolysiloxane is particularly preferable.

Such a dialkylpolysiloxane can be added by directly adding to an oil or oil composition using a homogenizer or the like and dissolving or dispersing it.
If necessary, a dilute solution can be prepared in advance with a solvent capable of dissolving the dialkylpolysiloxane, and this can be added to the oil or oil composition, diluted and dispersed.

As a solvent used for preparing the dilute solution of dimethylpolysiloxane, kerosene, toluene, cyclohexanone, methyl isobutyl ketone (MIBK) and the like can be used. Especially, any solvent that can easily dissolve or disperse a desired dialkylpolysiloxane. It is not limited and various things can be used.
In addition, when a solvent having a low flash point is used as this solvent, the flash point is lowered if the amount of the diluted solvent is excessively increased. Therefore, it is desirable to reduce the amount of the solvent as much as possible. It is preferably used in an amount of about 0.5% by mass or less based on the total amount of the composition.

The above-mentioned dialkylpolysiloxane can be used in the range of 1 to 100 ppm by mass, preferably in the range of 1 to 70 ppm by mass, based on the total amount of oil or oil composition to be improved in flash point. More preferably, it is good to use in the range of 1-30 mass ppm, More preferably, it is 1-10 mass ppm.
If the dialkylpolysiloxane concentration is too low, the effect of improving the flash point may not be expected. If it is too high, it will be difficult to maintain a good dissolved and dispersed state, causing separation / sedimentation and improving the flash point. The effect may not be sustained.

The oily composition with improved flash point according to the method of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
The following were prepared in order to produce Examples and Comparative Examples.

(Oil and oil composition)
Oils 1: Hydrorefined base oil with high viscosity index corresponding to Group 3 of the American Petroleum Institute (API) lubricant base oil category [Properties, etc .: density is 0.84 g / ml (15 ° C), flash point (COC) ) 230 ° C., 40 ° C. kinematic viscosity 36 mm ² / s, viscosity index 130, pour point −15 ° C., sulfur content 1 mass ppm, nitrogen content 1 mass ppm]
Oil composition 1: A product obtained by adding an industrial additive package (IRGALUBE 2030A, manufactured by BASF) to the oil 1 described above. In the examples and comparative examples, 0.43% by mass of the additive package is added to 99.57% by mass of the oils 1 described above. This industrial additive package includes N-1-naphthylaniline, N, N-bis (2-ethylhexyl)-(4 or 5) -methyl-1H-benzotriazol-1-methylamine, (4-nonylphenoxy) ) Acetic acid, alkylated diphenylamine, sterically hindered hindered phenol, acyl sarcosine acid.

(Additive)
Additive A: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-1000CS) [Properties, etc .: 25 ° C. kinematic viscosity 1000 mm ² / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive B: Dimethylpolysiloxane (KF96-500CS, manufactured by Shin-Etsu Chemical Co., Ltd.) [Properties, etc .: 25 ° C. kinematic viscosity 500 mm ² / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive C: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-200CS) [Properties, etc .: 25 ° C. kinematic viscosity 200 mm ² / s, 25 ° C. specific gravity 0.970, viscosity temperature coefficient VTC 0.60, The refractive index at 25 ° C. is 1.403]
Additive D: Dimethylpolysiloxane (KF96-50CS manufactured by Shin-Etsu Chemical Co., Ltd.) [Properties, etc .: 25 ° C. kinematic viscosity 50 mm ² / s, 25 ° C. specific gravity 0.960, viscosity temperature coefficient VTC 0.59, The refractive index at 25 ° C. is 1.402]
Additive E: Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. KF96-30CS) [Properties, etc .: 25 ° C. kinematic viscosity 30 mm ² / s, 25 ° C. specific gravity 0.955, viscosity temperature coefficient VTC 0.58, Refractive index at 25 ° C. is 1.401]

(Examples 1-3)
With respect to the additives A to C, a 1000-fold dilution was prepared using kerosene as a solvent, and the additives A to C were added to the oils 1 based on the formulation shown in Table 1 (the numerical values in the table indicate mass%). Diluent was added and stirred well so that the additives A to C finally had a concentration of 5 ppm by mass, whereby the oil compositions of Examples 1 to 3 were obtained.

(Comparative Example 1)
Based on the formulation shown in Table 1, kerosene as a solvent is added to the oils 1 and stirred well to obtain an oily composition.
(Comparative Examples 2 and 3)
With respect to the additives D and E, a 1000-fold dilution was prepared using kerosene as a solvent, and the additives D and E were added to the oils 1 based on the formulation shown in Table 1 (the values in the table indicate mass%). Diluents were added and stirred well so that the additives D and E finally had a concentration of 5 ppm by mass.

(Examples 4 to 6)
A 1000-fold dilution is prepared for the additives A to C using kerosene as a solvent, and the additive is added to the oil composition 1 based on the formulation shown in Table 2 (the numerical values in the table indicate mass%). The diluents A to C were added and stirred well so that the additives A to C finally had a concentration of 5 ppm by mass, whereby oil compositions of Examples 4 to 6 were obtained.

(Comparative Example 4)
Based on the formulation shown in Table 2, kerosene as a solvent is added to the oil composition 1 and stirred well to obtain an oily composition.
(Comparative Examples 5 and 6)
With respect to the additives D and E, a 1000-fold dilution was prepared using kerosene as a solvent, and this was added to the oil composition 1 based on the formulation shown in Table 2 (the values in the table indicate mass%). Comparative Examples 5 and 6 were prepared by adding E diluent and stirring well so that the additives D and E finally had a concentration of 5 ppm by mass.

(Measure flash point)
The flash point was measured for each sample of the example and the comparative example with a Cleveland open type automatic flash point measuring device according to JIS K2265-4, and obtained by rounding off to one decimal place.

(Measurement result of flash point)
Tables 1 and 2 show the results of flash point measurement.

(Evaluation of flash point)
As shown in Table 1, it can be seen that in Examples 1 to 3, the flash point can be improved by 8 to 16 ° C. relative to those in which the additive of Comparative Example 1 is not added. In addition, it can be seen that in Comparative Example 2, the flash point cannot be increased even if the additive D is added, and that in which the additive E of Comparative Example 3 is added, the flash point is rather lowered by 8 ° C.
Moreover, as shown in Table 2, in Examples 4-6, it turns out that a flash point can be improved 6-13 degreeC with respect to what does not add the additive of Comparative Example 4. FIG. In addition, it can be seen that in Comparative Example 5, the flash point cannot be raised even when the additive D is added, and the flash point is lowered by 10 ° C. rather than the additive E of Comparative Example 6.

Claims (2)

A base oil belonging to Group 3 in the API (American Petroleum Institute, American Petroleum Institute) base oil category has a flash point (COC) of 230 to 250 ° C., and a kinematic viscosity at 25 ° C. of 200 mm ² / s or more and 1000 mm ² / s. A method for improving the flash point of oils or oil compositions, comprising adding 1 to 100 ppm by mass of the following dimethylpolysiloxane to raise the flash point. The base oil belonging to Group 3 in the API base oil category has a flash point (COC) of 230 to 250 ° C., and dimethylpolysiloxane having a kinematic viscosity of 25 ° C. of 200 mm ² / s to 1000 mm ² / s to 1 to 100 An oily composition having an increased flash point by adding ppm by mass.