Low-ash-content fixed gas engine oil composition based on coal CTL base oil and preparation method of low-ash-content fixed gas engine oil composition

Abstract

The invention discloses a low-ash fixed gas engine oil composition based on coal CTL base oil and a preparation method of the low-ash fixed gas engine oil composition in the field of fine chemical engineering, and the low-ash fixed gas engine oil composition comprises the following components in percentage by weight: 40-90% of coal CTL base oil, 0-40% of mineral base oil, 7-10% of a composite additive, 0.1-0.3% of a pour point depressant, 0.1-0.4% of a purification dispersant and 1-5% of a viscosity index improver, the gasoline engine oil composition is simple in preparation method, has good compatibility with coal CTL base oil, can improve the containment to natural gas fuel, has excellent low-temperature fluidity, high-temperature volatility resistance and oxidation resistance, is suitable for ash content, remarkably reduces the friction coefficient, reduces abrasion, effectively prevents the preignition phenomenon, prolongs the service life of an engine, and is suitable for industrial production. And the engine oil consumption is reduced, and the raw material cost is greatly reduced on the basis of ensuring better performance.

Description

Technical Field

[0001] The present invention relates to the field of fine chemicals, and in particular to a low-ash fixed gas engine oil composition based on coal-to-CTL base oil and a preparation method thereof. Background Art

[0002] Gas engine oils can be divided into mobile gas engine oils and fixed gas engine oils according to the equipment operation mode. Fixed engine oils are applicable to fixed high-output power, turbocharged two-stroke and four-stroke natural gas engines, dual-fuel engines and integral natural gas compressors fueled by natural gas.

[0003] Fixed gas engine oils are divided into ashless, low-ash and medium-ash types.

[0004] Ashless products can meet the use requirements of fixed, high-output power, turbocharged two-stroke natural gas engine equipment fueled by sulfur-free and low-sulfur natural gas; low-ash products can meet the use requirements of fixed high-output power, turbocharged two-stroke and four-stroke natural gas engine equipment fueled by low-sulfur natural gas; medium-ash products can meet the use requirements of fixed high-output power, high-turbocharged four-stroke engine equipment fueled by high-sulfur natural gas or dual-fuel engines.

[0005] Ash refers to the non-combustible substances remaining after burning and the inorganic substances obtained by combustion under specified conditions. The composition of ash is generally considered to be some metal elements and their salts. The ash referred to in the lubricating oil industry, also called sulfate ash, is the result obtained by accurately weighing and calculating after adding a small amount of concentrated sulfuric acid before burning and ashing the oil sample to convert the metal elements of the additive into sulfates.

[0006] For the lubrication of engines fueled by natural gas, ash is particularly important. As a fuel, natural gas has different combustion characteristics from gasoline and diesel. Gas combustion belongs to complete combustion and is relatively clean. The friction between metals and the wear of valves and valve seats caused by high-temperature corrosion rely on ash control. Therefore, it is required that the ash of the lubricating oil cannot be too low. If the ash is too low, it will lead to wear, embedding and sinking of valves and valve seats.

[0007] However, if the ash content is too high, ash will be deposited after a period of use. Ash deposition is formed by carbon particles formed by poor combustion and metal salts in the oil additives. High temperature will cause ash deposition before the spark plug ignites, causing pre-ignition and knocking, which will increase the burden on the engine, especially the bearings and crankshaft. This will lead to uncontrolled combustion, overheating, power loss, and increased vibration and noise. The ash aggregates on the piston are likely to spontaneously ignite due to changes in the pressure in the cylinder, that is, knocking will occur, which is very unfavorable to the engine. In addition, the accumulation of a large amount of deposits will lead to valve melting, wear of the combustion chamber and piston deposit lining, dirty spark plugs, and blockage of the intake port of the two-stroke engine.

[0008] Therefore, gas engine lubricating oil has strict requirements on ash content and needs to have an appropriate ash content.

[0009] The prior art includes CN105567387A and CN105567387B, which provide a fixed gas engine oil composition, comprising the following components: polyisobutylene, accounting for 3-10% of the total mass of the composition; a compounding agent, which at least includes the following components: one or more detergents, one or more dispersants, one or more antioxidants, an organic molybdenum salt anti-wear agent, and an anti-foaming agent, wherein the compounding agent accounts for 6-16% of the total mass of the composition; a pour point depressant, accounting for 0.1-0.3% of the total mass of the composition; and a deeply refined base oil, the remainder. No requirements are made for ash content.

[0010] Stationary gas engine oil is composed of base oil and additives, but the proportion of base oil accounts for more than 80-90%, and the antioxidant performance of different types of base oils is in descending order: base oil Class I (HVI150) > Class II (HVIP6) > Class III (Yubase6) ≈ Class IV (PAO6). Coal-to-liquid (CTL) base oil, as a newly developed lubricant base oil, has excellent air release performance, thermal oxidation stability, oil-water separation performance and rust prevention performance compared to mineral base oils; at the same time, the performance is close to that of Class IV PAO base oils, with excellent low-temperature flow performance, viscosity-temperature performance, antioxidant performance and low evaporation loss, and is an ideal raw material for preparing low-loss gasoline engine oil; and coal-based III + CTL base oil has greater cost advantages, which can greatly reduce the production cost of cost oil. (Currently, the price of CTL base oil is 9,000-13,000 yuan / ton, and the price of PAO and ester base oil is more than 24,000 yuan / ton).

[0011] The low-ash fixed gas engine oil composition of the present invention is developed by using coal-based CTL base oil as the main component, supplemented with synthetic compound additives and friction improvers, and adding pour point depressants, viscosity index improvers, and foam inhibitors. It has excellent low-temperature fluidity, good piston detergency performance, effectively reduces pre-ignition caused by ash deposition before spark plug ignition, reduces knocking, and alleviates the burden on the engine, especially the bearings and crankshaft. In addition, it reduces valve melting loss, wear of the combustion chamber and piston deposit lining, and blockage of the intake port of two-stroke engines. It has a smaller internal friction resistance, reduces fuel consumption; has excellent antioxidant performance, significantly reduces oil consumption; effectively inhibits and controls the formation of deposits, reduces sludge generation, and extends the engine life.

[0012] In summary, there is no low-ash fixed gas engine oil product developed based on coal-based CTL base oil. The present invention provides an engine oil composition based on coal-based CTL base oil, which has good stability, improves the lubrication effect of gas engines and reduces the failure rate. Summary of the Invention

[0013] The purpose of this part is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Simplifications or omissions may be made in this part, as well as in the abstract and title of the present invention, to avoid obscuring the purpose of this part, the abstract, and the title, and such simplifications or omissions shall not be used to limit the scope of the present invention.

[0014] Therefore, the object of the present invention is to provide a low-ash fixed gas engine oil composition based on coal-based CTL base oil and its preparation method, which can provide an engine oil composition based on coal-based CTL base oil, having good stability, improving the lubrication effect of gas engines and reducing the failure rate.

[0015] To solve the above technical problems, the present invention provides a low-ash fixed gas engine oil composition based on coal-based CTL base oil and its preparation method, adopting the following technical scheme: by weight percentage, it contains 40 - 90% of coal-based CTL base oil, 0 - 40% of mineral base oil, 7 - 10% of compound additives, 0.1 - 0.3% of pour point depressant, 0.1 - 0.4% of detergent-dispersant, and 1 - 5% of viscosity index improver.

[0016] Optionally, the base oil is coal-based CTL base oil, and its physical and chemical properties are: the viscosity at 100 °C is 3 - 10 / S, the total saturated hydrocarbon content ≥ 99.8%, the total aromatic hydrocarbon content < 0.2%, the sulfur content < 1 mg / kg, the air release value (50 °C) ≤ 0.9 min, the initial oxidation temperature > 200 °C, and the oxidation induction period (150 °C) is 27 - 28 min.

[0017] Optionally, the ester oil is one or more of 500N, 600N, and 150BS.

[0018] Optionally, the pour point depressant is one of the polymethacrylate types.

[0019] Optionally, the detergent-dispersant is one of alkyl salicylates and metal salts.

[0020] Optionally, the viscosity index improver is one of hydrogenated styrene-diene copolymers (HSD).

[0021] Optionally, after adding the above compositions to the blending kettle in sequence according to the proportion, heat to 55 ± 5 °C, stir for 60 - 90 minutes, and after cooling and filtering, a low-ash stationary gas engine oil composition is obtained.

[0022] In summary, the present invention includes at least one of the following beneficial effects: The preparation method of the gasoline engine oil composition is simple, has good compatibility with coal-based CTL base oil, can improve the inclusiveness of natural gas fuel, has excellent low-temperature fluidity, high-temperature anti-volatility and antioxidant properties, an appropriate ash content significantly reduces the friction coefficient and wear, effectively prevents the occurrence of pre-ignition, extends the engine service life, and reduces oil consumption, and significantly reduces the raw material cost on the basis of ensuring better performance. Description of the Drawings

[0023] Figure 1 It is a comparison data chart of the physical and chemical properties of the stationary gas engine oil prepared for Example 1 and Control Group 1; Figure 2 It is a comparison data chart of the thermal oxidation stability (SH / T 0300) of the stationary gas engine oil prepared for Example 1 and Control Group 1; Figure 3 It is a comparison data chart of the detergency (SH / T0645) of the stationary gas engine oil prepared for Example 1 and Control Group 1; Figure 4 It is a comparison data chart of the physical and chemical properties of the stationary gas engine oil prepared for Example 2 and Control Group 2; Figure 5 It is a comparison data chart of the thermal oxidation stability (SH / T 0300) of the stationary gas engine oil prepared for Example 2 and Control Group 2; Figure 6 It is a comparison of the detergency (SH / T0645) of the stationary gas engine oil prepared for Example 2 and Control Group 2. Detailed Embodiments

[0024] Combined with the attached Figures 1-6, the objective of the invention is to provide a low-ash fixed gas engine oil composition based on coal-to-CTL base oil and its preparation method, which can provide an engine oil composition based on coal-to-CTL base oil with good stability, improved lubrication effect of gas engines and reduced failure rate.

[0025] It contains 40 - 90% of coal-to-CTL base oil, 0 - 40% of mineral base oil, 7 - 10% of compound additive, 0.1 - 0.3% of pour point depressant, 0.1 - 0.4% of detergent-dispersant, and 1 - 5% of viscosity index improver by weight percentage.

[0026] The base oil is coal-to-CTL base oil, and its physical and chemical properties are: the viscosity at 100 °C is 3 - 10 / S, the total saturated hydrocarbon content ≥ 99.8%, the total aromatic hydrocarbon content < 0.2%, the sulfur content < 1 mg / kg, the air release value (50 °C) ≤ 0.9 min, the initial oxidation temperature > 200 °C, the oxidation induction period (150 °C) is 27 - 28 min. The commercial example of this coal-based base oil is Lu'an ICCSYN (registered trademark), and the combination method is: trademark + viscosity (100 °C), for example: ICCSYN 3, ICCSYN 4, ICCSYN 6, ICCSYN10. The coal-based base oil described in the present invention is selected from one or more of ICCSYN 3, ICCSYN 4, ICCSYN 6, and ICCSYN 10.

[0027] The ester oil is one or more of 500N, 600N, and 150BS.

[0028] The compound additive is the commercially available Oronite OLOA44507 compound.

[0029] The pour point depressant is one type in the polymethacrylate (PMA) type.

[0030] The detergent-dispersant is one type in the alkyl salicylate, metal salt type.

[0031] The viscosity index improver is one type in the hydrogenated styrene diene copolymer (HSD).

[0032] The present invention also provides the application of the above fixed gas engine oil composition. It is applied in fixed gas engine oil, and the application method is: add the above composition to the blending kettle in proportion, heat it to 55 ± 5 °C, stir for 60 - 90 minutes, and obtain the product after cooling and filtration.

[0033] Example 1 is compared with Control Group 1 (compared with competing products).

[0034] Example 1: 90.00% of coal-based CTL base oil ICCSYN 10, 8.67% of Oronite OLOA44507 compound additive, 0.1% of pour point depressant, 0.1% of detergent-dispersant, and 1.13% of viscosity index improver were successively added into a blending kettle under stirring. The temperature was raised to 60 °C and stirred for 80 minutes, then cooled and filtered to obtain the low-ash fixed gas engine oil product of Example 1 (coal-based base oil).

[0035] Control Group 1: The commercially available conventional oil SAE40 for fixed gas engines was evaluated.

[0036] Figures 1-3 For the performance comparison between Example 1 and Control Group 1. It can be seen that compared with the oil of Control Group 1, the low-ash fixed gas engine oil blended in Example 1 has more excellent viscosity-temperature performance (viscosity index and pour point), better high-temperature resistance and antioxidant performance (open flash point, hot tube oxidation, coking plate experiment).

[0037] Comparison between Example 2 and Control Group 2: Comparison of different additives.

[0038] Example 2: 40.00% of coal-based CTL base oil ICCSYN 10, 41.13% of 500N mineral base oil, 9.00% of 150BS mineral base oil, 8.67% of Oronite OLOA44507 compound additive, 0.1% of pour point depressant, 0.1% of detergent-dispersant, and 1.00% of viscosity index improver were successively added into a blending kettle under stirring. The temperature was raised to 60 °C and stirred for 80 minutes, then cooled and filtered to obtain the low-ash fixed gas engine oil product of Example 2 (coal-based base oil).

[0039] Control Group 2: 40.00% of coal-based CTL base oil ICCSYN 10, 40.8% of 500N mineral base oil, 9.00% of 150BS mineral base oil, 9.00% of Xinxiang Ruifeng RF6206S compound additive, 0.1% of pour point depressant, 0.1% of detergent-dispersant, and 1.00% of viscosity index improver were successively added into a blending kettle under stirring. The temperature was raised to 60 °C and stirred for 80 minutes, then cooled and filtered to obtain the fixed gas engine oil product of Control Group 2 (coal-based base oil).

[0040] Figures 4-6 For the performance comparison of the low-ash fixed gas engine oil prepared in Example 2 and Control Group 2. It can be seen that compared with different additives, the low-ash fixed gas engine oil blended in Example 2 also has lower ash content, more excellent low-temperature fluidity (pour point), better antioxidant performance (open flash point, coking plate experiment), and better detergent-dispersancy.

[0041] Verification of the on-road experiment of the oil product: The low-ash fixed gas engine oil blended with OLOA44507 completed a 3000-hour application test on the Caterpillar G3520C gas generator set of Shanxi Jinju Coal Chemical Co., Ltd., and the lubrication performance of the oil product was good.

[0042] A low-ash fixed gas engine oil composition based on coal-based CTL base oil and its preparation method. The test results show that the prepared gasoline engine oil composition has good compatibility with coal-based CTL base oil: (1) Compared with mineral oil, the gasoline engine oil blended with coal-based base oil has excellent low-temperature fluidity, high-temperature anti-volatility and antioxidant properties, significantly reduces the friction coefficient and wear, effectively improves the fuel efficiency of the engine, and reduces the oil consumption. (2) Compared with the gasoline engine oil products formulated with PAO base oil, the present invention greatly reduces the raw material cost on the basis of ensuring better performance.

[0043] The good performance of the present invention mainly stems from the reasonable selection and compounding of various base oils and additives compatible with coal-based CTL base oil. Base oils with excellent antioxidant performance are selected to make the oil product have a low ash value and take into account good high-temperature antioxidant performance; at the same time, by introducing a detergent-dispersant, the deposition of ash on the spark plug is reduced, and the knocking phenomenon caused by low-speed pre-ignition is achieved.

[0044] The above are all the preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby. Therefore, all equivalent changes made according to the structure, shape and principle of the present invention shall be covered by the protection scope of the present invention.

Claims

1. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil, characterized in that: The invention comprises, by weight percentage, 40-90% of coal-based CTL base oil, 0-40% of mineral base oil, 7-10% of composite additives, 0.1-0.3% of pour point depressant, 0.1-0.4% of detergent dispersant, and 1-5% of viscosity index improver.

2. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The physical and chemical properties of the coal-based CTL base oil are as follows: the viscosity at 100°C is 3-10 / S, total saturated hydrocarbon content ≥99.8%, total aromatic hydrocarbon content <0.2%, sulfur content <1mg / kg, air release value (50℃) ≤0.9min, initial oxidation temperature >200℃, oxidation induction period (150℃) 27-28min.

3. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The ester oil is one or more of 500N, 600N and 150BS.

4. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The pour point depressant is one of the polymethacrylate type.

5. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The detergent dispersant is an alkyl salicylate, a type of metal salt.

6. A low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The viscosity index improver is one of hydrogenated styrene diene copolymers.

7. The method for preparing a low-ash stationary gas engine oil composition based on coal-derived CTL base oil according to claim 1, characterized in that: The above compositions are sequentially added into a blending kettle according to a certain proportion, heated to 55±5° C., stirred for 60-90 minutes, cooled and filtered to obtain a low-ash stationary gas engine oil composition.

Images