KR102111500B1 - Special additives for lubricating oil to improve extreme pressure and improve soot - Google Patents

Abstract

The present invention relates to a special lubricant additive to enhance extreme pressure and reduce smoke. More specifically, the present invention relates to a special lubricant additive to enhance extreme pressure and reduce smoke. By providing special additives added to various engine oils and transmission oils, it is possible to maintain excellent extreme pressure and wear resistance, and also to further improve the performance of the lubricant by forming a strong coating film on an inner wall of a cylinder. In addition, the special lubricant additive can contribute to lifespan extension and smooth operation of a device and reduce exhaust gas because no harmful substances such as particulate metal and heavy metal are included.

Description

Special additives for lubricating oil to improve extreme pressure and improve soot}

The present invention relates to a lubricant additive for improving extreme pressure and soot. More specifically, by providing a special additive to be added to various engine oils or transmission oils, etc., a strong coating film is formed on the inner wall of the cylinder to maintain excellent extreme pressure and abrasion resistance, and the performance of the lubricant can be further improved. It relates to a special additive for lubricating oil to improve extreme pressure and to improve soot so as to contribute to maintaining operation and extending the service life, and to reduce emissions by not containing harmful substances such as particulate metal and heavy metal.

The engine, which is one of the core parts of automobiles, is exposed to the harshest environment due to high temperature, high pressure, and high friction among numerous automotive parts. Engine oil is used to protect the engine against these adverse conditions.

The engine oil is accommodated inside the engine and circulates the entire engine by a pump to perform various roles.

In particular, automotive engine oil performs functions such as lubrication, cooling, sealing, stress dispersing, clean dispersing, and purifying, but in addition, basic performance as the engine oil itself is required.

This performance ultimately has the important function of protecting the engine and reducing the cost of extending the life of the oil.

Meanwhile, in recent years, fine dust has emerged as a social issue. Fine dust is a particulate matter that floats in the atmosphere. It is generated from fossil fuels such as coal and oil, or from exhaust gas from factories and automobiles. Most of the fine dust contains chemicals containing heavy metals, which are formed by reaction in water vapor and air. When these particles enter the body, they act as chemicals and have a harmful effect on the human body.

Accordingly, the government and local governments have issued various post-measures to reduce fine dust, but since there are fundamental limitations, management of emission sources that generate actual pollutants is most important.

Accordingly, there is a need to develop additives capable of reducing the exhaust gas, which is the main cause of fine dust, as well as maintaining the smooth operation of the device and extending the life of the device by adding to various engine oils or transmission oils of automobiles.

Prior Art Literature: KR Registered Patent Publication No. 1261880 (2013.5.8.

The present invention was devised to solve the above problems, in particular to provide excellent extreme pressure and abrasion resistance, and to provide a lubricant additive for improving extreme pressure and soot improvement to further improve the performance of the lubricant. It has its purpose.

To achieve the above object, the lubricant additive for improving extreme pressure and soot improvement according to the present invention devised is a special reaction by adding 10% by weight of sulfur to 90% by weight of fatty acid ester product esterified by reacting donji and methanol. In the additive, the special additive may be characterized in that 3.5% by weight based on 100% by weight of the lubricant.

In addition, special additives are prepared by mixing raw paper and methanol in a molar ratio of 1: 2 to 1: 3 and subjecting the catalyst to esterification reaction at a constant temperature and stirring speed to prepare raw materials, and introducing the prepared fatty acid ester into the reactor to 120 ° C. It is dehydrated by heating, and when it reaches 120 ℃, sulfur is added to 10% by weight or less based on the total composition content, and then heated. After the second heating step, the temperature is continuously raised to gradually increase when it reaches 130 ℃, and when it reaches 150 ℃, 5 The temperature may be increased by 1 ° C in minute intervals, and when it reaches 170 ° C, it may be characterized in that it is manufactured through a process of terminating the reaction.

In addition, the catalyst may be characterized in that at least one selected from the group consisting of phosphoric acid, titanium, and PTSA (Para-Toluenesulfonic acid).

According to the present invention, by adding various engine oils or transmission oils, etc., a strong coating film is formed on the inner wall of the cylinder to maintain excellent extreme pressure and abrasion resistance, to further improve the performance of the engine oil, and to maintain smooth operation and life of the device. It is effective in making contributions to extensions.

In addition, according to the present invention, by adding various engine oils or transmission oils, etc., it provides an eco-friendly special additive that does not contain harmful substances such as particulate metals and heavy metals, so that it can reduce the exhaust gas that is the main cause of fine dust. There is.

1 is a flow chart of a method for manufacturing a lubricant additive for improving extreme pressure and improving soot according to a preferred embodiment of the present invention.
2 to 5 is a test report showing the results of exhaust gas analysis before and after the addition of a special lubricant additive for improving extreme pressure and soot improvement according to a preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, when adding reference numerals to the components of each drawing, it should be noted that the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known structures or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted. In addition, although preferred embodiments of the present invention will be described below, the technical spirit of the present invention is not limited to or limited thereto, and can be variously implemented by a person skilled in the art.

1 is a flow chart of a method for manufacturing a lubricant additive for improving extreme pressure and soot according to a preferred embodiment of the present invention, and FIGS. 2 to 5 are for improving extreme pressure and improved soot according to a preferred embodiment of the present invention. This is a test report showing the results of exhaust gas analysis before and after the addition of a special lubricant additive.

Lubrication refers to the action of reducing friction that occurs inevitably on two relatively moving surfaces when transferring or redirecting force by a mechanical mechanism, and the functions of lubricant used for this purpose are largely divided into cooling, friction and wear functions. , It can be classified into fusion suppression function, sealing function, anti-rusting function. Among them, the friction and abrasion functions are very important functions in lubricants. As additives to prevent friction and abrasion, an oil film is maintained between the two friction surfaces with abrasion and extreme pressure additives to prevent the two friction surfaces from directly rubbing or being worn. It serves to keep the film formed on the rough friction surface. However, when the load increases and the temperature rises on the friction surface, the oil film becomes thin and, in severe cases, the oil film is destroyed and comes into direct contact with the two friction surfaces. Under such lubricating conditions, abrasion occurs severely, and in severe cases, two friction surfaces are fused. In this case, the extreme pressure additive forms an inorganic coating film on the friction surface, thereby stopping the progress of wear and preventing fusion.

Lubricant special additive for improving extreme pressure and improving soot according to a preferred embodiment of the present invention is prepared by mixing sulfuric acid with fatty acid ester (Neopentyl polyol ester), and has excellent extreme pressure and lubricity compared to general mineral oil. .

Generally, lubricating oils such as automobile engine oils and industrial lubricating oils mostly use mineral oil-based lubricating base oils except for special cases. This is because mineral oil is very cheaper than synthetic oil. Nevertheless, there is a case where synthetic oils are necessarily used because it is possible to supplement the disadvantages of the mineral oil system with synthetic oils.

A lubricant additive for improving extreme pressure and improving soot according to a preferred embodiment of the present invention provides a sulfur-based extreme pressure additive reacted by adding 10% by weight of sulfur to 90% by weight of fatty acid ester product esterified by reacting pork and methanol. do.

Because of its excellent wear resistance and lubricity among animal and vegetable oils, it has an excellent function as an oil-based improver, so it is intended to maximize the function of the oil-based improver using pig paper.

In addition, sulfur reacts with iron, a metal system, to form an iron sulfide film, which is a metal salt, to form a coating film on a metal surface (for example, the inner wall of a cylinder), thereby reducing friction and wear that occurs when metal and metal come into contact, making it an ideal lubricant type Phosphorus fluid lubrication is formed.

The content of sulfur is preferably added 10% by weight relative to the total composition. If the sulfur content is less than 10% by weight, the extreme pressure decreases, and even if the sulfur content exceeds 10% by weight, there is no significant change in extreme pressure, so the sulfur content is preferably 10% by weight.

* Formulation of automobile engine oil

1. Lubrizol 5W30 (API SN) manufacturing prescription

The manufacturing prescription of automobile engine oil is somewhat different for each manufacturer, but the results of testing according to the manufacturing prescription recommended by Lubrizol, a multinational company that is generally used, are shown in Tables 1 to 2 below.

 Prescription for manufacturing Lubrizol 5W30 (API SN) Raw material name purpose of use Mixing rate GS Caltex GroupⅢ Base 1 Base Oil 4cSt 16.6 Vol% GS Caltex GroupⅢ Base 2 Base Oil 6cSt 66.41 Vol% Lubrizol PV600 Friction Modifier 0.25 wt% Lubrizol PV611 Friction Modifier 0.16 wt% Lubrizol 7075K Viscocity Index 8.06 wt% Lubrizol PV1127K Package Additive 8.52 wt% system - 100 Vol%

Test result of Lubrizol's 5W30 (API SN) according to the manufacturing prescription Test Items Standard (KS M2121) Test result  Flash point (℃) More than 170 204
Kinematic viscosity (㎟ / s) 40 ℃ - 66.9 100 ℃ 3.8 or more 11.0  Viscosity index 85 or more 155  Viscosity index Low-temperature viscosity characteristics (-30 ℃, Pa.s) 6.60 or less 6.26  Pour point (℃) -30 or less -39  Total alkalinity (mgKOH / g) - 7.7  Computational value (mgKOH / g) - 2.1  Sulfuric acid ash (%) - 0.9 Oxidation stability
(165.5 ℃ / 24h) Viscosity ratio 1.2 or less 1.05 Increase in computational value (mgKOH / g) 2.0 or less 0.24 Lacquer No attachment No attachment

※ The standard and method of the test are in accordance with the Korean Industrial Standard (KS M 2121: Lubricant for internal combustion engines).

2. Preparation of 5W30 (API SN) using additives prepared according to the present invention

  A certain amount of the sulfur-based extreme pressure additive according to the present invention was added to the preparation of Lubrizol 5W30 (API SN). Table 3 and Table 4 show the manufacturing specifications and test results.

Prescription for manufacturing 5W30 (API SN) using extreme pressure additive Raw material name purpose of use Mixing rate GS Caltex Kixxlubo 4cSt GroupⅢ Base Base Oil 15.1 Vol% GS Caltex Kixxlubo 6cSt GroupⅢ Base Base Oil 64.41 Vol% Lubrizol PV600 Friction Modifier 0.25 wt% Lubrizol PV611 Friction Modifier 0.16 wt% Lubrizol 7075K Viscocity Modifier 8.06 wt% Lubrizol PV1127K Package Additive 8.52 wt% ★ Additive according to the invention For extreme pressure improvement and soot improvement 3.5 wt% system - 100 Vol%

Referring to Table 3, the special additive according to the present invention is characterized in that it is added with respect to 100% by weight of lubricant, 3.5% by weight.

When the excess amount is added, there is a possibility of causing corrosion due to sulfur, and when the lower content is added, it is difficult to expect the effect of reducing fuel efficiency or reducing smoke due to extreme pressure or abrasion resistance. It is preferable to add 3.5 weight% with respect to the weight%.

Test result according to the manufacturing prescription of 5W30 (API SN) added with extreme pressure additive Test Items Standard (KS M2121) Test result  Flash point (℃) More than 170 206
Kinematic viscosity (㎟ / s) 40 ℃ - 69.0 100 ℃ 3.8 or more 11.2  Viscosity index 85 or more 155  Viscosity index Low-temperature viscosity characteristics (-30 ℃, Pa.s) 6.60 or less 6.20  Pour point (℃) -30 or less -39  Total alkalinity (mgKOH / g) - 7.6  Computational value (mgKOH / g) - 2.2  Sulfuric acid ash (%) - 1.1 Oxidation stability
(165.5 ℃ / 24h) Viscosity ratio 1.2 or less 1.06 Increase in computational value (mgKOH / g) 2.0 or less 0.27 Lacquer No attachment No attachment

※ The standard and method of the test are in accordance with the Korean Industrial Standards (KS M 2125).

3. Analysis of test results with and without the addition of extreme pressure additives

  In the above test, the test result of adding or not adding the special additive of the present invention to the preparation of Lubrizol 5W30 (API SN) was only slightly increased in the amount of sulfuric acid ash in the added product. The test results before and after addition were not significantly different. Accordingly, it was found that when the special additive according to the present invention was added to the product of Lubrizol 5W30 (API SN) by about 3.5%, the specifications specified in KS M 2121 (lubricant oil for internal combustion engines) and general physical properties tests were not significantly affected. Could.

4. Ingredients and properties of raw materials

Raw material name Ingredients and functions General constellation GS Caltex
Kixxlubo 4cSt Hydrocarbon mixture of paraffins
(20 to 45 carbon atoms)

GroupⅢ Base oil Specific gravity (15/4 ℃) 0.842
Kinematic viscosity (40 ℃) 19.7 cSt
Flash point 227 ℃
Pour point -18 ℃ GS Caltex
Kixxlubo 6cSt Specific gravity (15/4 ℃) 0.850
Kinematic viscosity (40 ℃) 36.0cSt
Flash point 238 ℃
Pour point -18 ℃ Lubrizol PV600 Metal-based mixture
Friction Modifier Specific gravity (15/4 ℃) 0.934
Kinematic viscosity (40 ℃) 50.0cSt
Flash point 197 ℃
Pour point -6 ℃ Lubrizol PV611 Metal-based mixture
Friction Modifier Specific gravity (15/4 ℃) 0.934
Kinematic viscosity (40 ℃) 43.0cSt
Flash point 206 ℃
Pour point 0 ℃ Lubrizol 7075K Non-dispersant
olefin copolymer Specific gravity (15/4 ℃) 0.850
Kinematic viscosity (40 ℃) 5000cSt
Flash point 229 ℃
Pour point -12 ℃ Lubrizol PV1127K Metal-based mixture
Package Additive Specific gravity (15/4 ℃) 0.976
Kinematic viscosity (40 ℃) 2900cSt
Flash point 148 ℃
Pour point -12 ℃ Special additives according to the invention Sulfurized fatty acid
+ High-grade fatty acid ester Specific gravity (15/4 ℃) 1.3
Kinematic viscosity (40 ℃) 260cSt
Flash point 204 ℃
Pour point -20.0 ℃

Hereinafter, a method for preparing a fatty acid ester as a raw material for a sulfur-based extreme pressure additive according to a preferred embodiment of the present invention will be described.

Example  1. Fatty acid ester production method

After mixing the donji and methanol at a constant molar ratio, and performing an esterification reaction under a reaction temperature of 80 ° C at a stirring speed of 600 rpm under the catalyst (S110), when the first reaction is completed, cool to 30 ° C or lower and wash with water. Measuring the acid value, if the acid value does not reach the target value, performing a secondary reaction (S120), when the secondary reaction is completed, cooling and washing with water to measure the acid value (S130), the acid value is the target value When it is confirmed that it has dropped to 0.5 to 1.5, it is then neutralized by adding a small amount of acid value to less than 0.5 with KOH (S140), and when the neutralization is completed, it is stored through a dehydration process (S150).

S110 is characterized in that the molar ratio of donji and methanol is 1: 2 ~ 1: 3. More preferably, the molar ratio of donji and methanol is 1: 2.5.

In S110, the catalyst is injected with any one selected from the group containing phosphoric acid, titanium, and PTSA (Para-Toluenesulfonic acid). More preferably, it is preferable to add a phosphoric acid catalyst.

The amount of catalyst to be injected in S110 is preferably 0.5% by weight of the fatty acid pig.

In S140, KOH performs a neutralizing function for the catalyst, and the input amount of KOH is diluted with water and added according to the amount of the catalyst, but it is preferable to input a small amount over a plurality of times. If a large amount is excessively added from the beginning of the reaction, the fatty acid and KOH of the raw material may cause saponification reaction, and the viscosity of the final product may increase, resulting in stiffness. More preferably, the content of KOH is preferably added 0.2 times by weight multiple times.

S150 is preferably stored in an environment that can block oxygen in the atmosphere to prevent oxidation.

In Example 1, the first reaction time is 8-10 hours, the second reaction time is 6-8 hours, and the third reaction time is maintained at 4-6 hours.

Example  2. Yellow Extreme pressure additive  Manufacturing method

Referring to FIG. 1, a method of manufacturing a sulfur-based extreme pressure additive according to a preferred embodiment of the present invention includes a raw material preparation step (S100), a first temperature raising and dehydration step (S200), a second temperature raising step (S300), and a third temperature raising step ( S400), a fourth temperature raising step (S500), and a reaction termination step (S600).

The raw material preparation step (S100) prepares a raw material prepared by the method of Example 1 of the present invention. The raw material used to prepare the sulfur-based extreme pressure additive of the present invention is a fatty acid ester prepared through a reaction by mixing pork and methanol.

The primary heating and dehydration step (S200) is a step in which the fatty acid ester prepared in S100 (1000 ml) is introduced into a reactor and heated to 120 ° C. to dehydrate.

The second heating step (S300) is a step in which a predetermined amount of sulfur is taken into the reactor and heated up when it reaches 120 ° C.

 S300 provides excellent extreme pressure by introducing sulfuric acid, and at the same time reduces soot.

In the second heating step (S300), the content of sulfur is preferably added at least 2% to 10% by weight based on the total reactant weight. When the sulfur is reacted with the fatty acid ester in a range exceeding the above-mentioned range, even after a long reaction, a part of the sulfur is not completely dissolved, and some unreacted sulfur remains, and unreacted sulfur may cause a peculiar smell of sulfur. Not only the color of the reactants may be slightly darkened due to the deterioration caused by the long-term reaction, but also a result of severe corrosion on the copper plate in the copper plate corrosion test, which may cause corrosion due to free sulfur in other metals.

In addition, it can be seen that as the content of sulfur gradually increases from 2% by weight, the extreme pressure gradually increases, and the extreme pressure in this experiment is measured by a simple type Timken tester, and the sulfur content exceeds 10% by weight. It was also found that the extreme pressure was no longer increased due to the effect of unreacted free sulfur.

When the content of sulfur is 10% by weight based on the total reactant weight, it shows the best results in color, odor, activity, and extreme pressure, so it is most preferable to add the content.

The third heating step (S400) is a step of gradually raising the temperature after the second heating step (S300) and gradually raising the temperature when reaching 130 ° C.

The fourth heating step (S500) is a step of raising the temperature by 1 ° C at 5 minute intervals when reaching 150 ° C.

Reacting several times, such as S200 to S500, results in less water generated during the esterification process when the reaction is not sufficiently performed, and in this case, it also affects the acid value. In order to carry out the reaction.

The reaction termination step (S600) is a step of terminating the reaction when 170 ° C is reached.

Experimental Example  One. In moby  Follow Esterification  Experiment

Table 6 below is a table showing the results of measuring the acid value by performing an esterification reaction according to the method of Example 1 by setting different molar ratios in the process of mixing oleic acid, pork and palm oil with methanol, respectively.

Raw material name Test result (acid value after the 3rd reaction) Oleic acid Money palm oil Oleic acid Money palm oil 1: 2.0 1: 2.0 1: 2.0 2.7 2.0 2.4 1: 2.5 1: 2.5 1: 2.5 1.0 0.8 0.9 1: 3.0 1: 3.0 1: 3.0 1.0 0.8 0.9

Referring to Table 6, oleic acid, pork, palm oil, respectively, was mixed with methanol to carry out an esterification reaction according to Example 1 of the present invention, and as a result of measuring the acid value, it was confirmed that the most stable acid value was the donji. .

In addition, referring to Table 6, as a result of reacting oleic acid, pork and palm oil with methanol in a molar ratio of 1: 2.0, 1: 2.5, and 1: 3.0, respectively, the molar ratio is a stable acid value at 1: 2.5 to 1: 3.0. It was found that indicates.

Experimental Example  2. Depending on the reaction time Esterification  Experiment

Table 7 below is a table showing the result of measuring the acid value after performing an esterification reaction of oleic acid, pork, and palm oil with methanol, respectively, according to each reaction time according to Example 1 of the present invention. The reaction time was set differently for each of the 1st, 2nd, and 3rd phases, and the esterification reaction was performed.

Raw material name Test result (acid value after the 3rd reaction) Oleic acid Money palm oil Oleic acid Money palm oil 1st: 8, 2nd: 6, 3rd: 4 hours 1.2 0.8 1.0 1st: 10, 2nd: 8, 3rd: 6 hours 1.1 0.9 1.0

Referring to Table 7, as a result of measuring the acid value according to the reaction time, there was no significant change for the 8th, 6th, 4th and 10th, 8th and 6th hours of the 1st, 2nd and 3rd order, respectively.

Therefore, the first reaction time is 8 to 10 hours, the second reaction time is 6 to 8 hours, and the third reaction time is to be maintained at 4 to 6 hours. In particular, in the reaction between donji and methanol, the first reaction time is It was confirmed that the 8 hour, 2nd reaction time was 6 hours, and the 3rd reaction time was 4 hours.

3) Ester test results by catalyst

Raw material name Test result (acid value after the 3rd reaction) Oleic acid Money palm oil Oleic acid Money palm oil Phosphoric acid catalyst 1.1 0.7 0.8 Titanium catalyst 1.2 0.8 1.0 PTSA catalyst 1.2 0.8 1.1

Referring to Table 8, when the acid value after the reaction according to the catalyst was measured, almost the same result was obtained for the titanium and PTSA catalysts, and when the phosphoric acid catalyst was used, the acid value after the third reaction represents the most stable value. Was confirmed.

According to the above test results, the catalyst may be any one selected from phosphoric acid, titanium, and PTSA, but more preferably, it was found that the use of phosphoric acid shows the most stable acid value.

Experimental Example  3. According to the content of sulfur Reaction  And test results

In Example 2 of the present invention, in order to confirm whether or not the reaction was performed according to the content of sulfur, the reaction was performed according to the content of sulfur, and the test results are shown in Tables 9 to 10 below.

1) Whether to react according to the content of sulfur

Sulfur content (%) Reaction temperature (℃) Total reaction time Reaction result 2


130 ~ 170

4-5 hours Sulfur is completely dissolved 5 4-5 hours Sulfur is completely dissolved 7 5-6 hours Sulfur is completely dissolved 10 6-7 hours Sulfur is completely dissolved 12 10 hours or more A small amount of sulfur remains 15 10 hours or more A small amount of sulfur remains

2) Test result for the above reaction

Sulfur content (%) smell
(smell) Color (ASTM)
(KS M2106) Copper plate corrosion test
(KS M2018) Friction and wear extreme pressure test
(Simple Transplant Timken Tester) 2 Good Light yellow 1a 0.5 M pa 5 Good Light yellow 1a 0.9 M pa 7 Good Light yellow 1b 1.2 M pa 10 Good Light yellow 1b 1.5 M pa 12 A weak odor Dark brown 2a 1.6 M pa 15 A weak odor Dark brown 3c 1.7 M pa

* Copper plate corrosion test: As specified in KS M ISO2160, this method is to test the discoloration by comparing the copper plate corrosion comparison plate by placing the specified copper plate in a sample and standing at 100 ° C for 3 hours.

1a: No discoloration (good)

1b: No discoloration, but copper plate corrosion is very weak

2a: Moderate discoloration occurred

3c: Severe discoloration occurred

(a means relatively discolored, b means discolored to medium, and c means discolored is the strongest)

Referring to Table 10, when the sulfur is reacted with fatty acid ester in excess of 12% by weight, some unreacted sulfur remains because some of the sulfur is not completely dissolved even after a long reaction, and the sulfur has a characteristic odor due to the residual sulfur. Was generated, and it was confirmed that the color of the reactant was slightly darkened due to the deterioration caused by the long-time reaction.

In addition, in the copper plate corrosion test, when sulfur is reacted with fatty acid ester in excess of 12% by weight, it appears as 2a, 3c, causing excessive corrosion to the copper plate, and thus it is highly likely to cause corrosion due to free sulfur in other metals. appear.

In addition, it can be seen that as the content of sulfur increases, the extreme pressure gradually increases. In Experimental Example 3, the extreme pressure was determined by a simple-type Timken tester, but the sulfur content was increased even if the sulfur content exceeded 10% by weight. It was found that the extreme pressure was not increased due to the influence of the reacted free sulfur.

Therefore, it was found that when the content of sulfur is 10% by weight or less, it shows the best results in color, odor, dynamic activity, and extreme pressure.

Experimental Example  4. Dynamic activity  exam

Oleic acid, pork, and palm oil were reacted with methanol, respectively, to perform an esterification reaction, and after adding sulfur, copper activity was measured according to the copper plate corrosion test method of KS M2018 to confirm the activity. It is shown in Table 11 below.

No Sulfur content (%) Reaction conditions Dynamic activity according to raw materials used Mole ratio Reaction time catalyst Oleic acid Money palm oil One 15 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 4a 3c 3c 2 12 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 3b 2a 3b 3 10 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 3a 1b 3a 4 9 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2b 1b 2c 5 8 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2b 1b 2b 6 7 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2b 1b 2b 7 6 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2b 1b 2a 8 5 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2a 1a 2a 9 4 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2a 1a 2a 10 3 1: 2.5 1,2,3rd 18h PTSA or phosphoric acid 2a 1a 1c

Referring to Table 11, as a result of the test, the fatty acid ester synthesized with pork belly showed that the copper activity did not change significantly even when the sulfur content increased, but after 12% by weight of sulfur was added, corrosion was observed in the copper plate.

In addition, fatty acid esters synthesized with oleic acid and palm oil showed relatively poor copper activity as the sulfur content increased, and it was found that the copper activity was not significantly improved despite the low sulfur content.

Therefore, as shown in the above test, it was confirmed that the addition of sulfur to the fatty acid ester synthesized with pork fat in an amount of 10% by weight or less was the most stable in the activity.

Experimental Example  5. (Test method: Extreme pressure  Wear and friction characteristics evaluation)

1. Test method

Hereinafter, a test method for wear resistance and extreme pressure, which are the main elements of the performance as a high-functional special additive, will be described.

The friction test for examining the frictional wear characteristics of general lubricants was a four-ball test machin manufactured by Cameron plint, UK. The test ball was manufactured by SKF, and is a standard test bearing (steel ball) of AISI 52100 series with 1/2 inch diameter. Was used.

Cleaning of the tester and bearings was performed before and after each test with n-hexane to remove residues or external contamination of the entire test oil. Three test steel balls (hereinafter referred to as 'fixing balls') are fixed to the sample container, and one test steel ball (hereinafter referred to as 'rotating balls') is rotated to 1760 under load. The oil temperature of the sample is set to 18 ~ 35 ℃, and the test is continued until the fusion occurs while increasing the load at 10 second intervals. (The test is repeated repeatedly by applying a higher load, but the measured flaw is recorded once. Discard the used test sphere and repeat until fusion finally occurs). No further fusion test is performed at 10 loads, or when there is no evidence of wear at that load within 5% of the calibration line. After the friction test is over, the diameter of the wear on the bearing is accurately measured to ㎜ with an optical microscope, and the long and short diameters of all three bearings are measured, and the average value is measured as the wear diameter of the test lubricant (WSD: Wear Scar diameter). Compared.

2. Test conditions

The above test method is the method specified in KS M 2026, but in this test, a comparative test using Lubrizol's 5W30 (API SN) engine oil as follows to evaluate the wear resistance of the additive produced according to the preferred embodiment of the present invention. Did.

  1) Test method: 4-ball wear test of KS M 2026

  2) Test load: 80㎏

  3) Test temperature: 25 ℃

  4) Test speed: 1760rpm

  5) Test sample: Lubrizol 5W30 (API SN) engine oil

3. Test contents

Shell-type 4-ball test results with and without the addition of additives prepared according to the invention  Test Items / Sample Classification Not added Added Abrasion test (㎜) 0.78 0.55 Extreme pressure test (kg) 80 200

4. Test results

This test is abrasion resistance through a shell type 4-ball test for two samples of a certain amount of sulfur-based extreme pressure additive prepared according to a preferred embodiment of the present invention in a 5W30 (API SN) engine oil of Lubrizol and none at all. As a result of testing the extreme pressure resistance, as shown in Table 12, it was confirmed that the added engine oil than the engine oil to which the sulfur-based extreme pressure additive prepared according to the present invention was not added has excellent wear resistance and extreme pressure resistance.

As a sample of this test, Lubrizol's 5W30 (API SN) engine oil was used, but when the results of this test were added, the addition of the sulfur-based extreme pressure additive prepared according to the embodiment of the present invention was further observed as in the results of this test. By showing superior wear resistance and extreme pressure, it is confirmed that the load of various parts in the device is reduced, friction is reduced, and a smooth lubrication operation is achieved, thereby establishing a complete fluid lubrication system, ultimately reducing fuel consumption and exhaust gas. .

Experimental Example  6. Characteristics of exhaust gas

1. Emissions investigation

In the above test, when a certain amount of the sulfur-based extreme pressure additive prepared according to the preferred embodiment of the present invention is added to the engine oil and used, friction and abrasion characteristics are remarkably good, improving fuel efficiency and exhaust gas. You could see through.

In addition, a certain amount (300 ml: 3.5% for 4 liter) of sulfur-based extreme pressure additive prepared according to a preferred embodiment of the present invention is added to a gasoline vehicle and a diesel vehicle as follows. The exhaust gas before and after the sulfur-based extreme pressure additive was added was investigated. And the test results are shown below.

2. Exhaust gas analysis result

Vehicle model No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention



A
(Gasoline vehicle) ITEMS MEAS UNIT ITEMS MEAS UNIT HC 91 ppm HC 0 ppm CO 0.14 % CO 0.06 % CO2 13.50 % CO2 12.97 % O2 0.33 % O2 0.31 % NO 107 ppm NO 0 ppm SO - ppm SO - ppm LAM 1.01 % LAM 1.02 % AFR 14.69 - AFR 14.73 - RPH 0 rpm RPH 0 rpm OIL 0.0 deg 0.0 deg

Vehicle model No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention




B
(Gasoline vehicle) ITEMS MEAS UNIT ITEMS MEAS UNIT HC 115 ppm HC 6 ppm CO 0.54 % CO 0.07 % CO2 13.17 % CO2 13.17 % O2 0.21 % O2 0.16 % NO 49 ppm NO 5 ppm SO - ppm SO - ppm LAM 0.99 % LAM 1.00 % AFR 14.42 - AFR 14.62 - RPH 0 rpm RPH 0 rpm OIL 0.0 deg 0.0 deg

Vehicle model  No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention



C
(Gasoline vehicle) ITEMS MEAS UNIT ITEMS MEAS UNIT HC 166 ppm HC 30 ppm CO 0.72 % CO 0.07 % CO2 10.26 % CO2 11.95 % O2 3.02 % O2 1.25 % NO 62 ppm NO 65 ppm SO - ppm SO - ppm LAM 1.23 % LAM 1.09 % AFR 16.83 - AFR 15.52 - RPH 0 rpm RPH 0 rpm OIL 0.0 deg 0.0 deg

3. Results of Free Acceleration Test)

vehicle  No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention

Diesel vehicle No Opacity
(%) Rpm Oil No Opacity
(%) Rpm Oil One 20.0 0 0.0 One 13.8 0 0.0 2 37.7 0 0.0 2 12.3 0 0.0 3 27.7 0 0.0 3 5.7 0 0.0

4. Exhaust gas (soot) inspection result

Tables 17 to 19 below show exhaust gas (fume) test results depending on whether or not the sulfur-based pressure additive is added according to the present invention.

Vehicle model No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention
D
(Vehicle) inspection
Item Measure permit
standard Judgment inspection
Item Measure permit
standard Judgment smoke 69.00
% 25.00
% incongruity smoke 13.00
% 25.00
% fitness

Vehicle model No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention
E
(Vehicle) inspection
Item Measure permit
standard Judgment inspection
Item Measure permit
standard Judgment smoke 34.0
% 25.00
% incongruity smoke 5.0
% 25.00
% fitness

Vehicle model No additives 3.5% addition of sulfur-based extreme pressure additive prepared according to the present invention
F
(Via vehicle) inspection
Item Measure permit
standard Judgment inspection
Item Measure permit
standard Judgment smoke 34.0
% 25.00
% incongruity smoke 10.0
% 25.00
% fitness

Looking at Table 17 to Table 19, the exhaust gas (fume) test according to the addition of the sulfur-based extreme pressure additive prepared according to the present invention, as a result, compared to the case where the sulfur-based extreme pressure additive is not added, the measured value of the exhaust gas It was found that decreases.

As described above, in the exhaust gas analysis result, free acceleration test, and exhaust gas (soot) inspection results for each vehicle, the overall engine oil added was significantly improved compared to before adding the sulfur-based extreme pressure additive prepared according to the present invention. It was confirmed that the result of the numerical value was produced.

2 to 5 are the results of conducting a test for the analysis of exhaust gas before and after adding a special lubricant additive for improving extreme pressure and improving soot according to a preferred embodiment of the present invention in gasoline vehicles and diesel vehicles, gasoline vehicles 3 Tests were conducted on three vehicles and two diesel vehicles, each three times.

Referring to Figures 2 to 4, as a result of conducting a test on a gasoline vehicle, a contaminant gas containing CH, CO, CO ₂ , NO after addition compared to before adding the lubricant additive according to the present invention (in exhaust gas It was confirmed that the mixed air pollutants) were significantly reduced.

Referring to FIG. 5, as a result of conducting a test on a diesel vehicle, the opacity of the gas was measured by transmitting light through the flue gas after addition, compared to before adding the lubricant additive according to the present invention. It was confirmed that it decreased.

The sulfur-based extreme pressure additive prepared according to a preferred embodiment of the present invention is capable of maintaining abrasion resistance and friction characteristics directly related to driving performance, fuel efficiency, and exhaust gas of a vehicle.

In addition, the sulfur-based extreme pressure additive manufactured according to the present invention has excellent load-bearing performance so that smooth lubrication of various parts including pistons, cylinders, and valves in the engine device can be maintained.

In addition, the sulfur-based extreme pressure additive prepared in accordance with the present invention may be prevented from corrosion of bearings or rust in various parts due to mixing of oil oxidation products and moisture with long-term use by adding an antirust additive and a corrosion inhibitor additive. To make.

In addition, the sulfur-based extreme pressure additive prepared according to the present invention does not affect the swelling, shrinking, curing, etc. for the rubber seal used in each part of the part.

In addition, the sulfur-based extreme pressure additive prepared according to the present invention chemically reacts with the metal surface to form a stable film to protect and strengthen the metal surface.

In addition, the sulfur-based extreme pressure additive prepared in accordance with the present invention allows the components in the device to be kept clean and energy loss reduced by introducing a clean dispersant.

In addition, the sulfur-based extreme pressure additive prepared according to the present invention is harmless to the human body, and raw materials such as some esters can produce environmentally friendly products.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains may make various modifications, changes, and substitutions without departing from the essential characteristics of the present invention. will be. Therefore, the embodiments and the accompanying drawings disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain the scope of the technical spirit of the present invention. . The scope of protection of the present invention should be interpreted by the claims below, and all technical spirits within the equivalent range should be interpreted as being included in the scope of the present invention.

S100-Raw material preparation step S200-1st heating and dehydration step
S300-2nd heating stage S400-3rd heating stage
S500-4th heating step S600-Reaction termination step

Claims (3)

In the special additive reacted by adding 10% by weight of sulfur to 90% by weight of the fatty acid ester product esterified by reacting pork and methanol,
The special additive is characterized in that, based on 100% by weight of lubricant, 3.5% by weight is added,
The special additive is
After mixing the donji and methanol in a molar ratio of 1: 2 to 1: 3 and conducting an esterification reaction under a catalyst at a constant temperature and agitation rate, the prepared fatty acid ester is introduced into the reactor and heated to 120 ° C to dehydrate, and when it reaches 120 ° C Sulfur is added and heated up to 10% by weight or less compared to the total composition content, and after the second heating step, the temperature is continuously raised to gradually increase the temperature when it reaches 130 ° C, and when it reaches 150 ° C, the temperature is increased by 1 ° C every 5 minutes, 170 It is manufactured through the process of terminating the reaction when it reaches ℃.
Characterized by,
The catalyst is at least one selected from the group consisting of phosphoric acid, titanium, and PTSA (Para-Toluenesulfonic acid)
Characterized by,
The fatty acid ester
After mixing the donji and methanol in a molar ratio of 1: 2 to 1: 3, an esterification reaction was carried out under a catalyst at a stirring speed of 600 rpm under a reaction temperature of 80 ° C, and after the first reaction was completed, the mixture was cooled to 30 ° C or lower and washed with water. After measuring the acid value, when the acid value reaches a predetermined target value, after cooling and washing with water, the acid value is measured to confirm that the acid value has dropped to the target value of 0.5 to 1.5 mg KOH / g, and the acid value of 0.5 mgKOH / g or less by adding KOH After being neutralized so as to be manufactured through dehydration
Lubricant special additive for improving extreme pressure and soot.




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