A 95 octane calibration gasoline for testing high intake valve deposits and a method of making the same

Abstract

The present application belongs to the technical field of petroleum chemical industry, and discloses a 95 calibration gasoline for testing high intake valve deposits and a preparation method thereof, which is mainly prepared from the following raw materials in parts by mass: alkylated gasoline 20-25 parts, hydrogenated gasoline 30-45 parts, reforming gasoline 20-30 parts, aromatized gasoline 4-10 parts, and dicyclopentadiene 0.6-1.2 parts. After the above raw materials are mixed, hard pitch is added in a dosage of 10-15 mg / L and uniformly mixed to obtain the 95 calibration gasoline for testing high intake valve deposits, which meets the requirements of a detection agency on the weight of deposits 230±70 mg / 300 ml and the GB 17930-2016 national standard for 95 gasoline of the VI B standard.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology, specifically relating to a 95-octane calibrating gasoline for testing high intake valve deposits and its preparation method. Background Technology

[0002] With increasingly stringent environmental standards, the quality standards for automotive gasoline are becoming more and more stringent. In addition to strict control over the content of aromatics, olefins, benzene, sulfur, and oxygen, gasoline detergents that can effectively inhibit and remove carbon deposits from the engine's fuel intake system must also be added. To address this trend, the "Standard for the Control of Hazardous Substances in Automotive Gasoline" explicitly requires the addition of detergents with highly efficient carbon deposit removal capabilities to gasoline.

[0003] GB / T 19230.6, the gasoline detergent evaluation standard, stipulates that after adding detergent to calibrated gasoline, the changes in intake valve deposits before and after the addition are tested to evaluate the detergent performance; this is also known in the industry as the M111 bench test. Third-party testing agencies have found that it is difficult to establish a correlation between the physicochemical properties of calibrated gasoline and the required deposits. Experience is needed to repeatedly adjust the raw material ratios, and the results of the M111 test are required to confirm whether the calibrated gasoline meets the standards. Furthermore, there are batch-to-batch variations, making it difficult to stabilize the formula. All of these factors pose significant challenges to the production of calibrated gasoline and, in severe cases, can affect the normal testing schedule of testing agencies.

[0004] In view of this, there is an urgent need in the field to provide a dedicated calibration gasoline that meets the actual needs of testing institutions. Summary of the Invention

[0005] The primary technical problem to be solved by this invention is to provide a 95-octane calibration gasoline for testing high intake valve deposits, which can meet both the GB17930-2016 national standard for automotive gasoline and the simulated intake valve deposit results and the M111 engine bench intake valve deposit index requirement of 230±70mg / 300ml, thereby better meeting the testing needs of fuel while meeting gasoline standards.

[0006] The calibration gasoline provided by this invention is mainly made from alkylated gasoline, hydrogenated gasoline, reformed gasoline, aromatic gasoline, dicyclopentadiene, and hard asphalt. By using a specific dosage of dicyclopentadiene, hard asphalt, and other controllable coking amounts, a strong correlation between the physicochemical properties of the benchmark gasoline and the weight of the deposits is achieved, making the product properties controllable and easier to produce.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] According to a first aspect of the present invention, a 95-octane calibration gasoline for testing high intake valve deposits is provided, which is mainly composed of the following raw materials in parts by weight: 20-25 parts alkylated gasoline, 30-45 parts hydrogenated gasoline, 20-30 parts reformed gasoline, 4-10 parts aromatic gasoline, 0.6-1.2 parts dicyclopentadiene, and 10-15 mg / L hard asphalt.

[0009] Preferably, the alkylated gasoline has a distillation range of 29-200°C, a recovery volume of 20-40% (volume fraction) at 70°C, a recovery volume of 60-80% (volume fraction) at 100°C, a recovery volume of greater than 92% (volume fraction) at 125°C, a saturated vapor pressure of 55-65 kPa, a research octane number of 93.5-95.5, and a density of 685-698 kg / m³. 3 More preferably, the alkylated gasoline is isooctane alkylated gasoline.

[0010] Preferably, the aromatic gasoline has a distillation range of 30-190℃, a saturated vapor pressure of 75-90 kPa, a research octane number of 95.0-97.5, and a density of 675-690 kg / m³. 3 It contains no oxygen, no aromatics, and ≥80% (volume fraction) olefins.

[0011] More preferably, the aromatic gasoline is prone to coking, with a simulated intake valve deposit result of 9.4 mg / 100 ml.

[0012] Preferably, the hydrogenated gasoline has an aromatic content (volume fraction) of 28%-32%, an olefin content (volume fraction) of 18%-25%, and a simulated intake valve deposit result of 6.0-7.8 mg / 100 ml.

[0013] Preferably, the reformed gasoline has an aromatic content (volume fraction) of 60%-70% and an unwashed gum content of 3.5-7.0 mg / 100ml.

[0014] Preferably, the dicyclopentadiene is 0.8-1.0 parts. As a coking agent, dicyclopentadiene can accelerate the coking speed of gasoline. Existing commonly used coking agents are generally tert-butyl peroxide and iron naphthenate. However, tert-butyl peroxide is water-based and contains a lot of water, which is not compatible with the system. Iron naphthenate contains metal elements, and the national standard for finished gasoline prohibits the addition of metal elements. Therefore, the inventors prefer to use dicyclopentadiene as a coking agent.

[0015] Preferably, the 95-octane calibration gasoline used for testing high intake valve deposits further includes 10-15 mg / L of hard asphalt, wherein the hard asphalt component is composed of the following four components by mass: 35-50 parts asphaltenes, 25-30 parts gums, 5 parts saturated components, and 26-32 parts aromatic components.

[0016] Hard asphalt, as a coking accelerator, synergistically with dicyclopentadiene, successfully solved the problem of low deposit detection results in the intake valve of calibrated gasoline of National VI B 95 standard. The method is simple, reliable, and low in cost.

[0017] The additive in this solution is hard asphalt, which contains a high amount of asphaltenes and trace amounts of metal elements, thus promoting the coking of gasoline. Adding ordinary asphalt will cause the oil to turn black and fail to meet national standards, while adding hard asphalt ensures that the oil meets national standards for gasoline.

[0018] Compared to regular commercially available gasoline, the gasoline used in this test has a higher amount of gum, both before and after washing. In addition, the simulated intake valve deposits and the weight of the intake valve deposits are significantly greater than those of regular gasoline, which can meet the requirements for testing high intake valve deposits.

[0019] Preferably, the 95-octane calibrated gasoline used for testing high intake valve deposits contains unwashed gum content:

[0020] 3.0-7.0mg / 100ml, solvent-washed gum content 1.5-3.0mg / 100ml; ordinary commercially available 95-octane gasoline unwashed gum 1.0-2.5mg / 100ml (without gasoline detergent), solvent-washed gum 0.5-1.0mg / 100ml;

[0021] Preferably, the 95-octane calibrated gasoline used for testing high intake valve deposits simulates intake valve deposits with a weight of 10.0-17.0 mg / 300 ml; while commercially available 95-octane gasoline simulates intake valve deposits with a weight of 5-8 mg / 300 ml.

[0022] Preferably, the 95-octane calibration gasoline used for testing high intake valve deposits has a gasoline engine intake valve deposit (M111 method) weight of 230±70mg / 300ml.

[0023] The 95-octane calibrated gasoline used for testing high intake valve deposits meets the technical requirements of GB 17930-2016 Gasoline VIB.

[0024] This invention also provides a method for preparing 95-octane calibration gasoline for testing high intake valve deposits, comprising the following steps:

[0025] (1) Raw material ratio: by weight, alkylated gasoline 20-25 parts, hydrogenated gasoline 30-45 parts, reformed gasoline 20-30 parts, aromatic gasoline 4-10 parts, dicyclopentadiene 0.6-1.2 parts, and also includes hard asphalt 10-15 mg / L;

[0026] (2) Add the raw materials to the mixing tank according to the above proportions and mix evenly.

[0027] This invention provides a 95-octane calibrating gasoline for testing high intake valve deposits and its preparation method. The method utilizes aromatization with the addition of gum-producing components, and further optimizes the product formulation with dicyclopentadiene and hard asphalt. These components, while meeting relevant requirements, offer significant advantages in both storage ease and price, thus reducing the cost of the finished calibrating gasoline. The final product exhibits an unwashed gum content of 4.5-7.5 mg / 100ml, simulated intake valve deposits of 10-17 mg / 300ml, and gasoline engine intake valve deposits (M111 method) weighing 230±70 mg / 300ml. This meets national gasoline standards and testing requirements, successfully solving the problem of low intake valve deposit detection results for National VI B 95-octane calibrating gasoline. The method is simple, reliable, and cost-effective.

[0028] This invention creatively uses hard asphalt combined with dicyclopentadiene to solve the current problem of gasoline not easily producing coke, and achieves a strong correlation between the physicochemical properties of benchmark gasoline and the weight of deposits, making product indicators controllable and easier to produce. Detailed Implementation

[0029] The present invention will now be described in more detail with reference to specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any modifications and / or alterations made to the present invention will fall within the protection scope of the present invention.

[0030] In this invention, unless otherwise specified, all parts and percentages are by weight. All equipment and raw materials are available from the market or commonly used in this industry. The component oil used is produced by Shandong Jingbo Petrochemical Co., Ltd. or purchased from the market. Dicyclopentadiene CAS: 77-73-6, purity 97%, is produced by Shandong Keyuan Biochemical Co., Ltd.

[0031] Unless otherwise specified, the methods described in the following embodiments are conventional methods in the art.

[0032] This invention discloses a 95-octane calibration gasoline for testing high intake valve deposits. It is mainly composed of the following raw materials in parts by weight: 20-25 parts alkylated gasoline, 35-55 parts hydrogenated gasoline, 20-30 parts reformed gasoline, 4-10 parts aromatic gasoline (aromaticated into a high C5 olefin component oil with an olefin volume fraction of 90%), 0.6-1.2 parts dicyclopentadiene, and also includes 10-15 mg / L of hard asphalt.

[0033] The 95-octane calibration gasoline used in this test has a high unwashed gum content, simulated intake valve deposits of 10-17 mg / 300 ml, and gasoline engine intake valve deposits (M111 method) of 230±70 mg / 300 ml. Furthermore, other indicators of this 95-octane calibration gasoline meet the technical requirements of GB 17930-2016 Automotive Gasoline VIB. Alkylated gasoline and hydrotreated gasoline are used as base oils, and aromatic gasoline, reformed gasoline, dicyclopentadiene, and 10-15 ppm hard asphalt are used as components prone to gum formation, meeting the product's high requirements for simulated intake valve deposits and gasoline engine intake valve deposits (M111 method).

[0034] The hard asphalt components are as follows, according to the four-component method: 35-50 parts asphaltene, 25-30 parts resin, 5 parts saturated components, and 26-32 parts aromatic components by mass.

[0035] The following description, in conjunction with comparative and example examples, further illustrates the use of 95-octane calibration gasoline for testing high intake valve deposits. The formulations for the comparative and example examples are shown in Table 1 below.

[0036] Table 1. Formulations (parts by weight) for Comparative Examples / Examples 1-6

[0037]

[0038]

[0039] 850 liters of 95-octane calibrated gasoline were blended according to the mass ratio scheme described in Table 1 for testing high intake valve deposits. The macroscopic physical properties of each batch of gasoline are shown in Table 2 (the macroscopic physical property analysis method for the 95-octane calibrated gasoline in Table 2 adopts the method in GB17930-2016 for automotive gasoline; the simulated intake valve deposits adopt the simulation test method for gasoline engine intake valve deposits in GB / T37322-2019 for evaluating gasoline detergent performance; the intake valve deposits adopt the test method in GB / T19230.6-2003, Test Method for Evaluating the Effect of Gasoline Detergents Part 6: Engine Bench Test Method (M111 Method) for the Influence of Gasoline Detergents on the Tendency of Deposit Formation in Gasoline Engine Intake Valves and Combustion Chambers). The carbon number distribution of each batch of 95-octane calibrated gasoline is shown in Table 3 (Cnr: number of carbon atoms, Naph.: n-alkanes, Paraf.: isoalkanes, Cycl...). Ol.: cyclic olefins, Arom.: aromatic hydrocarbons, Oxyg.: oxygen-containing compounds), the volume fractions are shown in Table 3.

[0040] Table 2

[0041]

[0042]

[0043] Table 3

[0044]

[0045]

[0046]

[0047] As can be seen from Tables 1 and 2, in Comparative Examples 6, 7, and 8, only dicyclopentadiene was used as a coking agent, and no hard asphalt was used to increase the macromolecular substances in the oil. The test results for both simulated intake valve deposits and intake valve deposits (M111 method) were relatively small and failed to meet the test requirements.

[0048] In Comparative Example 1 and Examples 2-5, when a suitable amount of hard asphalt was added to the blended fuel while meeting the China VI B standard for 95 gasoline, the results of both simulated intake valve deposits and intake valve deposits (M111 method) were significantly improved. In particular, the intake valve deposit weight (M111 method) in Comparative Example 1 increased by up to 420 mg / 300 ml. Analysis suggests that the large molecules in hard asphalt are prone to coking, and certain substances in it promote or improve the coking of olefins in gasoline, ultimately enabling the simulated intake valve deposits and intake valve deposits to meet the requirements of the test fuel.

[0049] As can be seen from Tables 2 and 3, in Comparative Examples 6, 7, and 8, increasing the proportion of C9+ aromatics (Category VI B aromatics volume fraction ≤35%) in the oil can also improve the results of simulated intake valve deposits and intake valve deposits (M111 method). However, the improvement effect is not significant and still does not meet the requirements of the test oil index. Therefore, it is believed that increasing the C9+ aromatics content in the oil is unlikely to solve the problem of the simulated intake valve and intake valve deposits (M111 method) results not meeting the standards. Therefore, this application adopts the method of adding an appropriate amount of hard asphalt on the premise of adding dicyclopentadiene to improve the simulated intake valve deposit and intake valve deposit (M111 method) results, and adjusts the ratio of dicyclopentadiene and hard asphalt in the oil to make the intake valve deposit (M111 method) result distribution at 230±70mg / 300ml. The intake valve deposit (M111 method) results of Examples 2 and 3 are 247mg / 300ml and 197mg / 300ml, respectively. The final compounded oil fully meets the requirements of the test oil index, while the intake valve deposit weight (M111 method) of Comparative Example 1 reaches 420mg / 300ml, which is too large. Therefore, the hard asphalt addition amount is finally determined to be 10-15mg / L.

[0050] This invention provides a 95-octane calibration gasoline for testing high intake valve deposits and its preparation method, overcoming the production technology difficulties in this field. By adding dicyclopentadiene and hard asphalt to the National VI B 95-octane calibration gasoline, the simulated intake valve deposit and intake valve deposit (M111 method) results are improved, successfully solving the problem of low intake valve deposit results for National VI B 95-octane calibration gasoline. The use of dicyclopentadiene as a coking agent and hard asphalt as a coking accelerator creatively solves the technical problem of test oil production. This method is simple, reliable, and low-cost.

[0051] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. The above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A 95-octane calibration gasoline for testing high intake valve deposits, characterized in that: It is prepared by mixing the following raw materials in parts by weight: 20-25 parts alkylated gasoline, 30-45 parts hydrogenated gasoline, 20-30 parts reformed gasoline, 4-10 parts aromatic gasoline, 0.6-1.2 parts dicyclopentadiene, and 10-15 mg / L hard asphalt; the unwashed gum content of the 95-octane calibration gasoline used for testing high intake valve deposits is 3.0-7.0 mg / 100ml, and the solvent-washed gum content is 1.5-3.0 mg / 100ml.

2. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 1, characterized in that: The hard asphalt component is composed of the following four components by mass: 35-50 parts asphaltene, 25-30 parts resin, 5 parts saturated components, and 26-32 parts aromatic components.

3. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 1, characterized in that: By volume fraction, alkylated gasoline has a distillation range of 29-200℃, a recovery volume of 20-40% at 70℃, 60-80% at 100℃, and greater than 92% at 125℃. It has a saturated vapor pressure of 55-65 kPa, a research octane number of 93.5-95.5, and a density of 685-698 kg / m³. 3 .

4. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 3, characterized in that: The alkylated gasoline is isooctane alkylated gasoline.

5. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 1, characterized in that: The aromatic gasoline has a distillation range of 30-190℃, a saturated vapor pressure of 75-90 kPa, a research octane number of 95.0-97.5, and a density of 675-690 kg / m³. 3 The olefin content is ≥80% by volume fraction.

6. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 1, characterized in that: The hydrogenated gasoline has an aromatic content of 22%-28% and an olefin content of 18%-25% by volume, and the simulated intake valve deposits result is 6.0-7.8 mg / 100ml.

7. The 95-octane calibration gasoline for testing high intake valve deposits as described in claim 1, characterized in that: The reformed gasoline has an aromatic content of 60%-70% and an unwashed gum content of 3.5-7.0 mg / 100ml by volume fraction.

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