Environment-friendly agricultural mineral oil base oil and continuous production method and device thereof

Abstract

The present application relates to the technical field of agricultural mineral oil base oil, and particularly relates to an environment-friendly agricultural mineral oil base oil and a continuous production method and device thereof.The environment-friendly agricultural mineral oil base oil is medium-quality lubricating oil.The environment-friendly agricultural mineral oil base oil meets the requirements of 20 DEG C density ≤0.8330 kg / m 3 , 40 DEG C kinematic viscosity 9.0-13.0 mm 2 / s, open flash point higher than 180 DEG C, viscosity index higher than 93, relative normal alkane carbon number difference ≤7, relative normal alkane average carbon number 21-24, and non-sulfonated substance content ≥98%, and can be applied to mineral oil pesticides.

Description

Technical Field

[0001] This invention relates to the field of agricultural mineral oil base oil technology, and in particular to an environmentally friendly agricultural mineral oil base oil and its continuous production method and apparatus. Background Technology

[0002] Mineral oil pesticides, as the name suggests, are pesticides made using mineral oil as the base oil; they are one of the three types of natural product pesticides (microbial pesticides, mineral-derived pesticides, and plant-derived pesticides).

[0003] Mineral oil pesticides have been used as crop protectants for over 100 years abroad. The advent of synthetic organic pesticides in the 1940s initially limited their large-scale application; however, in recent years, concerns about the environmental and health problems associated with synthetic organic pesticides have led to renewed interest in mineral oil pesticides recommended by the Integrated Pest Management Program (IPDM). Mineral oil pesticides are less harmful to natural enemies of pests and are generally safer than synthetic pesticides from both an environmental and human health perspective. Since 1960, when the petroleum processing industry was able to produce high-quality horticultural or agricultural mineral oils, the application of biorationally sound mineral oil pesticides in pest control has greatly increased. In agriculturally developed countries such as the United States, Australia, and New Zealand, guidelines for the use of mineral oil pesticides to control insects, mites, and diseases on specific crops have been issued. Mineral oil pesticides are ideal products for the Integrated Pest Management Program (IPDM) and have a bright future.

[0004] Internationally, this product is developed by large oil companies. Currently, leading companies include Sunoco (USA), Caltex (USA), SK (South Korea), Australian Petroleum Corporation, Shell (Netherlands), Total (France), and BP (UK). Many of their mineral oil products are registered and sold in my country, such as SunSpray (USA), DC-Tron (a joint venture between Caltex and Australian Petroleum Corporation), Enspray (South Korea's SK), "Lingmei" (a joint venture between Shell and China National Chemical Corporation), and BANOLE (France's Total).

[0005] Currently, there is no unified national standard for base oils used by China's three major oil companies, let alone for mineral oil pesticide base oils. In the past, a wide variety of base oils were used for mineral oil pesticides, including transformer oil, lubricating oil, hydraulic oil, and even waste engine oil. However, due to the high degree of unsaturation of these base oils, their use easily scorched leaves, resulting in oily, pesticide-damaged symptoms.

[0006] Starting in 2005, international oil prices suddenly surged, and the price of mineral oil base oil increased exponentially. Some mineral oil pesticide companies began to use large quantities of inferior base oil, leading to frequent pesticide damage and agricultural product quality problems.

[0007] On December 25, 2008, in order to improve the quality of mineral oil pesticide products and ensure the safety of agricultural products and the environment, the Ministry of Agriculture of China (now the Ministry of Agriculture and Rural Affairs) issued Announcement No. 1133 on the Registration Management of Mineral Oil Pesticides after review by the National Pesticide Registration Review Committee. The announcement stipulated that manufacturers should use refined mineral oil to produce mineral oil pesticide products and were prohibited from using ordinary petrochemical products. The physicochemical properties of refined mineral oil should meet the following requirements: the difference in carbon number between relative n-alkanes should not exceed 8, the average carbon number of relative n-alkanes should be between 21 and 24, and the non-sulfonate content should not be less than 92%. (Note: "Refined mineral oil" refers to highly refined petroleum products.)

[0008] Currently, there are no national or industry standards for refined mineral oil used in pesticides.

[0009] The difference in carbon number between relative to n-alkanes should not exceed 8 --- this specifies the distillation range difference of the refined mineral oil;

[0010] The average carbon number of relative n-alkanes should be between 21 and 24 --- this specifies the carbon number distribution of the distilled mineral oil;

[0011] The non-sulfonate content should be no less than 92% --- this specifies the degree of refining (or saturation) of the refined mineral oil;

[0012] Based on the above analysis of the Ministry of Agriculture and Rural Affairs Announcement No. 1133 and the applicant's understanding of oil products, it can be concluded that the national requirements for the physicochemical properties of mineral oil for pesticide refining are primarily based on the degree of oil refining; only after meeting the degree of refining requirements should appropriate fractions be selected. For crude oil processing enterprises, the former mainly involves chemical reactions, while the latter mainly involves physical reactions. In terms of current refining processes, refined mineral oil for pesticide applications should be fully hydrogenated base oil.

[0013] Hydrogenated base oils are composed of (n- and isomer) alkanes, cycloalkanes, and aromatics with different carbon numbers (as shown in the following structures).

[0014]

[0015] Application trials of mineral oil pesticides have shown that hydrogenated base oils with high alkane content have better insecticidal effects than naphthenic base oils. The relationship between the carbon number of the base oil and its insecticidal efficacy is as follows: Figure 3 As shown.

[0016] As shown above, consistent with the Ministry of Agriculture and Rural Affairs' Announcement No. 1133, the carbon numbers of mineral oil pesticides such as Sunspray from U.S. Sun Oil Company, DC-Tron from Australia Caltex Company, and Enspray from South Korea SK Company are mainly concentrated around carbon 21, carbon 23, and carbon 24, respectively.

[0017] The upgrading of industrial and agricultural sectors in recent years has led to a surge in demand for higher quality mineral oil base oils from oil consumers. Narrow distillation ranges and high levels of refining (such as ultra-low aromatics and high viscosity index) are the development trends for mineral oil base oils.

[0018] The same applies to mineral oil-based pesticide base oils. Ideally, a mineral oil-based pesticide base oil should be a fully hydrogenated oil with a narrow distillation range and a high viscosity index, between HVI-2 and HVI-3. Currently, the viscosity index of HVI-2 to HVI-3 base oils from China's three major oil companies is generally low, mostly between 80 and 105. Therefore, how to produce environmentally friendly agricultural mineral oil base oils that meet user needs is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0019] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide an environmentally friendly agricultural mineral oil base oil and its continuous production method and apparatus. Specifically, the environmentally friendly agricultural mineral oil base oil that meets user needs is produced in the base oil fractionation tower of the lubricating oil hydrogenation unit, and a continuous production preparation method is provided to solve the problems in the prior art.

[0020] To achieve the above and other related objectives, the present invention provides an environmentally friendly agricultural mineral oil base oil, wherein the physicochemical properties of the environmentally friendly agricultural mineral oil base oil include: a1) density at 20℃ ≤ 0.8330 kg / m³ 3 a2) Kinematic viscosity at 40℃ is 9-13 mm. 2 / s; a3) Open flash point higher than 180℃; a4) Viscosity index higher than 93; a5) Carbon number difference of relative n-alkanes ≤7; a6) Average carbon number of relative n-alkanes is 21-24; a7) Non-sulfonate content ≥98%.

[0021] The second aspect of the present invention provides the application of the environmentally friendly agricultural mineral oil base oil described in the first aspect of the present invention in mineral oil pesticides.

[0022] This invention provides a third aspect: a continuous production method for environmentally friendly agricultural mineral oil base oil, the continuous production method comprising the following steps:

[0023] 1) Hydrogenating vacuum distillate oil to obtain hydrogenated oil products;

[0024] 2) The hydrogenated oil obtained in step 1) is fractionated to obtain naphtha, kerosene and lubricating oil fractions respectively;

[0025] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil and reduced-base lubricating oil respectively. The medium lubricating oil is an environmentally friendly agricultural mineral oil base oil. The extraction temperature of the medium lubricating oil is 225℃~245℃ and the extraction rate is 1~8 tons / hour.

[0026] A fourth aspect of the present invention provides a continuous production apparatus for environmentally friendly agricultural mineral oil base oil, comprising a hydrogenation reactor, a first fractionation tower, and a second fractionation tower connected in sequence. The hydrogenation reactor includes a vacuum distillate inlet and a hydrogenated oil outlet. The first fractionation tower includes a first inlet and a naphtha outlet, a kerosene outlet, and a lubricating oil fraction outlet. The hydrogenated oil outlet is connected to the first inlet. The second fractionation tower includes a second inlet and a vacuum top gas outlet, a diesel outlet, a light lubricating oil outlet, a medium lubricating oil outlet, a heavy lubricating oil outlet, and a vacuum bottom lubricating oil outlet. The second inlet is connected to the lubricating oil fraction outlet.

[0027] The beneficial effects of this invention are as follows:

[0028] The environmentally friendly agricultural mineral oil base oil of this invention meets the requirement of density ≤ 0.8330 kg / m³ at 20℃. 3 The kinematic viscosity at 40℃ is 9–13 mm. 2 With a flash point above 180℃, viscosity index above 93, relative n-alkanes carbon number difference ≤7, relative n-alkanes average carbon number of 21-24, and non-sulfonate content ≥98%, it can be used in mineral oil pesticides.

[0029] Furthermore, this invention produces environmentally friendly agricultural mineral oil base oil through a specific continuous production method for agricultural mineral oil base oil. Attached Figure Description

[0030] Figure 1 The diagram shown is a structural schematic of the continuous production apparatus for the environmentally friendly agricultural mineral oil base oil of the present invention.

[0031] Figure 2 The diagram shows a flow chart of the continuous production method of the environmentally friendly agricultural mineral oil base oil of the present invention.

[0032] Figure 3 This is a graph showing the relationship between the carbon number of base oil and insecticidal efficacy in the prior art.

[0033] 1. Hydrogenation reactor

[0034] 11. Vacuum Distillate Oil Inlet

[0035] 12. Export of hydrotreated petroleum products

[0036] 2 First Fractionating Column

[0037] 21 First feed inlet

[0038] 22 Naphtha Exports

[0039] 23. Kerosene exports

[0040] 24 Lubricating oil fraction outlet

[0041] 3 Second Fractionating Column

[0042] 31 Second feed inlet

[0043] 32. Reduced-top gas outlet

[0044] 33 Diesel fuel exports

[0045] 34 Light Lubricating Oil Export

[0046] 35 Medium-quality lubricating oil exports

[0047] 36 Heavy Lubricating Oil Export

[0048] 37. Reduced lubricating oil outlet

[0049] 4 First pump body

[0050] 5 Feeding heating furnace

[0051] 6 Second pump body Detailed Implementation

[0052] The following detailed description discloses an embodiment of an environmentally friendly agricultural mineral oil base oil and its continuous production method and apparatus. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0053] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0054] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0055] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0056] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0057] Environmentally friendly agricultural mineral oil base oil

[0058] This invention also provides an environmentally friendly agricultural mineral oil base oil, obtained using the continuous production method described in the first aspect of this invention. The environmentally friendly agricultural mineral oil base oil is a medium-strength lubricating oil.

[0059] The key physicochemical properties of the environmentally friendly agricultural mineral oil base oil provided by this invention are as follows: density at 20℃ ≤ 0.8330 kg / m³. 3 The kinematic viscosity at 40℃ is 9–13 mm. 2 / s, open flash point above 180℃, viscosity index above 93, relative n-alkanes carbon number difference ≤7; relative n-alkanes average carbon number 21~24; non-sulfonate content ≥98%.

[0060] Optionally, the density at 20℃ is 0.8210~0.8315kg / m³. 3 The open flash point is 186℃~200℃; the viscosity index is 100~110; and the carbon number difference relative to n-alkanes is 3~5.

[0061] Table 1. Mineral Oil, Pesticide, and Base Oil Indicators

[0062]

[0063]

application

[0064] The present invention also provides the application of the aforementioned environmentally friendly agricultural mineral oil base oil in mineral oil pesticides.

[0065] Continuous Production Method of Environmentally Friendly Agricultural Mineral Oil Base Oil

[0066] This invention provides a continuous production method for environmentally friendly agricultural mineral oil base oil, the continuous production method comprising the following steps:

[0067] 1) Hydrogenating vacuum distillate oil to obtain hydrogenated oil products;

[0068] 2) The hydrogenated oil obtained in step 1) is fractionated to obtain naphtha, kerosene and lubricating oil fractions respectively;

[0069] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil and reduced-base lubricating oil, wherein the medium lubricating oil is an environmentally friendly agricultural mineral oil base oil.

[0070] In the continuous production method of environmentally friendly agricultural mineral oil base oil provided in this embodiment of the invention, step 1) involves hydrogenating vacuum distillate oil to obtain hydrogenated oil. Specifically:

[0071] In step 1) of this invention, the kinematic viscosity of the vacuum distillate oil at 100°C is 3.864–5.771 mm. 2 / s; nitrogen content is 295mg / kg~470mg / kg, chlorine content is <0.5mg / kg, and sulfur content is 0.0718%wt~0.164%wt.

[0072] In step 1) of this invention, the hydrogenation is carried out in hydrogenation reactor 1. Hydrogenation reactor 1 is a lubricating oil hydrogenation device; this device was initially built using patented technology, process packages, and catalysts from Chevron Corporation, USA.

[0073] The hydrogenation reactor 1 comprises three hydrogenation reactors connected in series: a hydrocracking reactor, an isomerization dewaxing reactor, and a hydrorefining reactor. Hydrogenation consists of these three hydrogenation reactors connected in series.

[0074] The hydrocracking conditions are a reaction temperature of 368℃~373℃ and a reaction pressure of 14.1Mpa~15.0Mpa.

[0075] The conditions for isomerization dewaxing are: reaction temperature 330℃~350℃; reaction pressure 14.0MPa~14.2MPa.

[0076] The conditions for the hydrorefining reaction are: reaction temperature 235℃~240℃; reaction pressure 14.0Mpa~14.2MPa.

[0077] In addition, the liquid phase from the hydrocracking reaction enters a fractionation tower for atmospheric distillation. Light hydrocarbon gas and naphtha are obtained at the top of the fractionation tower. Part of the naphtha is cooled and sent out of the unit; the other part is returned to the top of the fractionation tower as reflux. The qualified isomerization dewaxing feed obtained from the bottom of the fractionation tower is sequentially exchanged with a kerosene reboiler. After heat exchange, the feed oil enters the isomerization dewaxing / post-refining section.

[0078] In the continuous production method of environmentally friendly agricultural mineral oil base oil provided in this embodiment of the invention, step 2) involves fractionating the hydrogenated oil obtained in step 1) to obtain naphtha, kerosene, and lubricating oil fractions, respectively. Specifically:

[0079] In step 2) of this invention, the feed temperature for fractionation of the hydrotreated oil is 305℃~310℃. It can be selected as 305℃~308℃ or 308℃~310℃.

[0080] In step 2) of this invention, the extraction temperature of the lubricating oil fraction is 287℃~297℃. It can be selected as 287℃~290℃, 290℃~293℃, or 293℃~297℃.

[0081] In step 2) of this invention, the lubricating oil fraction extraction rate is 30-45 tons / hour. It can be selected as 30-35 tons / hour, 35-40 tons / hour, or 40-45 tons / hour.

[0082] In step 2) of this invention, the fractionation is carried out in the first fractionation tower 2. The fractionation performed in the first fractionation tower 2 is atmospheric pressure fractionation.

[0083] In the continuous production method of environmentally friendly agricultural mineral oil base oil provided in this embodiment of the invention, step 3) is to fractionate the lubricating oil fraction obtained in step 2) to obtain diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil and reduced lubricating oil respectively.

[0084] In step 3) of this invention, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320℃~325℃, which can be selected as 320~323℃ or 323~325℃. The feed temperature for fractionation is 308℃~316℃; which can be selected as 308℃~310℃, 310℃~313℃ or 313℃~316℃.

[0085] In step 3) of the present invention, the extraction temperature of the medium-quality lubricating oil is 225℃~245℃; it can be selected as 225℃~230℃, 230℃~235℃, 235℃~240℃, 240℃~245℃, 225℃~235℃, or 235℃~245℃.

[0086] In step 3) of the present invention, the extraction rate of the medium-quality lubricating oil is 1 to 8 tons / hour; it can be selected as 1 to 4 tons / hour or 4 to 8 tons / hour.

[0087] In step 3) of this invention, the top temperature of the distillation column is 91℃~94℃. It can be selected as 91℃~93℃ or 93℃~94℃.

[0088] In step 3) of this invention, the vacuum degree at the top of the distillation column is -93 to -100 kPa. It can be selected as -93 to -96 kPa or -96 to -100 kPa.

[0089] In step 3) of this invention, the fractionation is carried out in the second fractionation tower 3. The fractionation in the second fractionation tower 3 is vacuum fractionation.

[0090] In summary, this invention consists of three processes: hydrocracking, isomerization dewaxing / hydrorefining, and fractionation. The feedstock oil undergoes hydrocracking, hydroisomerization, and post-hydrorefining reactions, followed by fractionation to obtain high-quality lubricating oil base oil, while also producing byproducts such as diesel, kerosene, naphtha, and dry gas.

[0091] Continuous production unit for environmentally friendly agricultural mineral oil base oils

[0092] The present invention also provides a continuous production apparatus for environmentally friendly agricultural mineral oil base oil, comprising a hydrogenation reactor 1, a first fractionation tower 2, and a second fractionation tower 3 connected in sequence.

[0093] In the continuous production apparatus for environmentally friendly agricultural mineral oil base oil provided by the present invention, the hydrogenation reactor 1 includes a vacuum distillate oil inlet 11 and a hydrogenated oil outlet 12, and the first fractionation tower 2 includes a first inlet 21 and a naphtha outlet 22, a kerosene outlet 23, and a lubricating oil fraction outlet 24, and the hydrogenated oil outlet 12 is connected to the first inlet 21.

[0094] In the continuous production apparatus for environmentally friendly agricultural mineral oil base oil provided by the present invention, the second fractionation tower 3 includes a second feed inlet 31 and a top gas outlet 32, a diesel oil outlet 33, a light lubricating oil outlet 34, a medium lubricating oil outlet 35, a heavy lubricating oil outlet 36, and a bottom lubricating oil outlet 37. The second feed inlet 31 is connected to the lubricating oil fraction outlet 24.

[0095] In the continuous production device for environmentally friendly agricultural mineral oil base oil provided, a first pump body 4 is provided on the pipeline connecting the second feed inlet 31 and the lubricating oil fraction outlet 24.

[0096] In the continuous production device for environmentally friendly agricultural mineral oil base oil provided, a feed heating furnace 5 is provided on the pipeline connecting the second feed inlet 31 and the lubricating oil fraction outlet 24.

[0097] In the continuous production device for environmentally friendly agricultural mineral oil base oil provided, a second pump body 6 is provided at the bottom-reducing lubricating oil outlet 37.

[0098] In the continuous production apparatus for environmentally friendly agricultural mineral oil base oil provided, the hydrogenation reactor 1 of this invention comprises three hydrogenation reactors connected in series: hydrocracking, isomerization dewaxing, and hydrorefining.

[0099] The working process of the continuous production device for environmentally friendly agricultural mineral oil base oil of this invention:

[0100] The hydrocracking reactor primarily saturates the olefin and aromatic components and removes impurities such as sulfur, nitrogen, and oxygen. The cracking reaction then proceeds, and the reaction products enter a separator. The gaseous phase serves as circulating hydrogen, entering a circulating hydrogen desulfurization tower for desulfurization. The liquid phase enters a fractionation system. Light hydrocarbon gas and naphtha are obtained from the top of the fractionation tower. Part of the naphtha is cooled and sent out of the unit; the other part is returned to the top of the fractionation tower as reflux. The qualified isomerization dewaxing feed from the bottom of the fractionation tower is sequentially exchanged with the kerosene reboiler and feedstock oil before entering the isomerization dewaxing reactor for isomerization dewaxing. The isomerization dewaxing reaction products are exchanged with waxy mixed hydrogen feedstock oil and then enter a post-refining reactor for deep hydrodearomatization. The post-refining reaction products are cooled by heat exchange and then separated in a separator. The gaseous phase serves as circulating hydrogen, and the liquid phase enters an atmospheric feed heater 5 for heating before entering the first fractionation tower 2 for atmospheric fractionation. The atmospheric fractionation section consists of a 26-layer main fractionation tower and a kerosene side-stream stripping tower. Light hydrocarbons and crude naphtha are separated from the top of the main fractionation tower. A portion of the naphtha is cooled and sent out of the unit; the other portion is returned to the top of the fractionation tower as reflux. The light hydrocarbon gas is compressed by K401 and sent to the hydrogen production unit as feedstock. The kerosene fraction is stripped in a side-stream tower, and the resulting kerosene product is cooled and sent out of the unit. The bottom oil of the fractionation tower exchanges heat with the bottom oil of the second fractionation tower 3, and then enters the second fractionation tower 3 (vacuum-reducing tower) after being heated by the feed heater 5 of the second fractionation tower 3. The vacuum fractionation section consists of a 7-layer packed vacuum tower and side-stream stripping towers for top gas, diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil, and bottom lubricating oil. The top gas, diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil, and bottom lubricating oil are obtained through the top gas outlet 32, diesel outlet 33, light lubricating oil outlet 34, medium lubricating oil outlet 35, heavy lubricating oil outlet 36, and bottom lubricating oil outlet 37, respectively.

[0101] The technical solution of this application will be clearly and completely described below with reference to embodiments of the present invention. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention still fall within the scope of protection of the present invention.

[0102] Table 2. Statistical values ​​of the actual mass of medium-quality lubricating oil distillate (January 2023 to March 2024)

[0103]

[0104]

[0105] From Table 2, we know that:

[0106] 1) During the statistical period, the average physical quality of medium-quality lubricating oil distillate outlet met the mineral oil pesticide base oil index; however, the real-time quality fluctuated greatly.

[0107] 2) The process operating parameters need to be adjusted to produce the mineral oil pesticide base oil of this invention. See the examples for details.

[0108] Example 1

[0109] 1) Hydrogenation was carried out on 31.4 tons / hour vacuum distillate oil. The hydrocracking conditions were: reaction temperature 371.4℃, reaction pressure 14.2 MPa; isomerization dewaxing reaction temperature 341.3℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 238.4℃, reaction pressure 14.0 MPa, to obtain hydrotreated oil. The kinematic viscosity of the vacuum distillate oil at 100℃ was 5.099 mm. 2 / s, nitrogen content is 402 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.110% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0110] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 308.2℃; the extraction temperature of the lubricating oil fraction is 294.0℃; and the extraction rate of the lubricating oil fraction is 35.5 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0111] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 321.3℃, the feed temperature for fractionation is 309.9℃, the extraction temperature of the medium lubricating oil is 241.2℃, the extraction rate of the medium lubricating oil is 1.9 tons / hour, the top temperature of the fractionation column is 92.2℃, and the top vacuum degree is -96.50 kPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0112] Table 3

[0113]

[0114]

[0115] Example 2

[0116] 1) Hydrogenation of 31.5 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 371.4℃, reaction pressure 14.2 MPa; isomerization dewaxing reaction temperature 341.2℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 238.3℃, reaction pressure 14.0 MPa, to obtain hydrogenated oil; wherein, the kinematic viscosity of the vacuum distillate oil at 100℃ was 5.263 mm. 2 / s, nitrogen content is 402 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.110% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0117] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 308.2℃; the extraction temperature of the lubricating oil fraction is 293.5℃; and the extraction rate of the lubricating oil fraction is 36.1 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0118] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320.1℃, the feed temperature for fractionation is 309.9℃, the extraction temperature of the medium lubricating oil is 241.3℃, the extraction rate of the medium lubricating oil is 3.89 tons / hour, the top temperature of the fractionation column is 92.2℃, and the top vacuum degree is -96.5KPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0119] Table 4

[0120]

[0121]

[0122] Example 3

[0123] 1) Hydrogenation of 30.8 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 371.7℃, reaction pressure 14.2 MPa; isomerization dewaxing reaction temperature 333.8℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 237.6℃, reaction pressure 14.0 MPa, to obtain hydrogenated oil; wherein, the kinematic viscosity of the vacuum distillate oil at 100℃ was 3.864 mm. 2 / s, nitrogen content is 295 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.0718% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0124] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 306.9℃; the extraction temperature of the lubricating oil fraction is 296.3℃; and the extraction rate of the lubricating oil fraction is 40.6 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0125] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 314.6℃, the feed temperature for fractionation is 314.6℃, the extraction temperature of the medium lubricating oil is 244.9℃, the extraction rate of the medium lubricating oil is 2.7 tons / hour, the top temperature of the fractionation column is 92.3℃, and the top vacuum degree is -97.31 kPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0126] Table 5

[0127]

[0128] Example 4

[0129] 1) Hydrogenation of 33.5 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 371.0℃, reaction pressure 14.18 MPa; isomerization dewaxing reaction temperature 348.7℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 239.4℃, reaction pressure 14.0 MPa, to obtain hydrogenated oil; wherein, the kinematic viscosity of the vacuum distillate oil at 100℃ was 5.771 mm. 2 / s, nitrogen content is 470 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.164% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0130] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 308.7℃; the extraction temperature of the lubricating oil fraction is 288.8℃; and the extraction rate of the lubricating oil fraction is 33.0 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0131] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320.0℃, the feed temperature for fractionation is 311.0℃, the extraction temperature of the medium lubricating oil is 242.3℃, the extraction rate of the medium lubricating oil is 2.1 tons / hour, the top temperature of the fractionation column is 93.4℃, and the top vacuum degree is -95.9 kPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0132] Table 6

[0133]

[0134] Example 5

[0135] 1) Hydrogenation of 31.7 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 368.9℃, reaction pressure 14.15 MPa; isomerization dewaxing reaction temperature 346.7℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 239.1℃, reaction pressure 14.0 MPa, to obtain hydrogenated oil; wherein, the kinematic viscosity of the vacuum distillate oil at 100℃ was 5.053 mm. 2 / s, nitrogen content is 453 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.128% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0136] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 309.8℃; the extraction temperature of the lubricating oil fraction is 293.6℃; and the extraction rate of the lubricating oil fraction is 42.4 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0137] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320.0℃, the feed temperature for fractionation is 312.7℃, the extraction temperature of the medium lubricating oil is 225.5℃, the extraction rate of the medium lubricating oil is 3.8 tons / hour, the top temperature of the fractionation column is 91.9℃, and the top vacuum degree is -94.7KPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0138] Table 7

[0139]

[0140] Comparative Example 1

[0141] 1) Hydrogenation of 31.6 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 374.8℃, reaction pressure 14.2 MPa; isomerization dewaxing reaction temperature 341.1℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 238.0℃, reaction pressure 14.0 MPa, to obtain hydrogenated oil; wherein, the kinematic viscosity of the vacuum distillate oil at 100℃ was 6.811 mm. 2 / s, nitrogen content is 727 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.138% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0142] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 308.9℃; the extraction temperature of the lubricating oil fraction is 298.6℃; and the extraction rate of the lubricating oil fraction is 42.0 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0143] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 330.0℃, the feed temperature for fractionation is 320.0℃, the extraction temperature of the medium lubricating oil is 251.5℃, the extraction rate of the medium lubricating oil is 5.0 tons / hour, the top temperature of the fractionation column is 94.2℃, and the top vacuum degree is -97.4KPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0144] Table 8

[0145]

[0146]

[0147] Comparative Example 2

[0148] 1) Hydrogenation of 33.9 tons / hour vacuum distillate oil was carried out under the following conditions: reaction temperature 370.9℃, reaction pressure 14.07 MPa; isomerization dewaxing reaction temperature 348.7℃, reaction pressure 14.0 MPa; hydrorefining reaction temperature 238.8℃, yielding hydrotreated oil; the kinematic viscosity of the vacuum distillate oil at 100℃ was 6.899 mm. 2 / s, nitrogen content is 808 mg / kg, chlorine content is <0.5 mg / kg and sulfur content is 0.212% wt; such as Figure 1 As shown, hydrogenation is carried out in hydrogenation reactor 1;

[0149] 2) The hydrotreated oil obtained in step 1) is fractionated to obtain naphtha, kerosene, and lubricating oil fractions. The feed temperature for fractionation of the hydrotreated oil obtained in step 1) is 307.3℃; the extraction temperature of the lubricating oil fraction is 285.9℃; and the extraction rate of the lubricating oil fraction is 32.1 tons / hour. Figure 1 As shown, this fractionation takes place in the first fractionation column 2;

[0150] 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain the diesel oil, light lubricating oil, medium lubricating oil, heavy lubricating oil, and reduced-volume lubricating oil; wherein, the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320.6℃, the feed temperature for fractionation is 311.5℃, the extraction temperature of the medium lubricating oil is 232.1℃, the extraction rate of the medium lubricating oil is 2.1 tons / hour, the top temperature of the fractionation column is 92.4℃, and the top vacuum degree is -95.6KPa; Figure 1 As shown, this fractionation takes place in the second fractionation tower 3.

[0151] Table 9

[0152]

[0153]

[0154] Comparing Examples 1 to 5 with Comparative Examples 1 and 2, it can be seen that:

[0155] 1) The medium-quality lubricating oil obtained in Example 1 meets the mineral oil pesticide base oil index in Table 1, and is close to the physical quality data of medium-quality lubricating oil 2023.1 to 2024.3 in Table 2, indicating that Example 1 is relatively easy to implement;

[0156] 2) The medium-quality lubricating oil obtained in Example 4 meets the mineral oil pesticide base oil index in Table 1, and differs significantly from the physical quality data of medium-quality lubricating oil 2023.1 to 2024.3 in Table 2, indicating that Example 4 is difficult to implement.

[0157] 3) The medium-quality lubricating oils obtained in Examples 2, 3, 4, and 5 meet the relevant requirements in Table 1;

[0158] 4) The medium-run lubricating oil obtained in Comparative Example 1 has a higher kinematic viscosity at 40℃ and a higher average carbon number relative to n-alkanes, which does not meet the requirements of Table 1.

[0159] 5) The viscosity index and open flash point of the medium-lubricating oil obtained in Comparative Example 2 are too low and do not meet the requirements of Table 1.

[0160] 6) Among the five examples, the medium-run lubricating oil obtained in Example 4 has the best quality, followed by Example 3, Example 1, and Example 2, while the medium-run lubricating oil obtained in Example 5 has the worst quality.

[0161] In summary, this invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0162] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. An environmentally friendly agricultural mineral oil base oil, characterized in that, The physicochemical properties of the environmentally friendly agricultural mineral oil base oil include: a1) Density at 20℃ ≤ 0.8330 kg / m³ 3 a2) Kinematic viscosity at 40℃ is 9-13 mm. 2 / s; a3) Open flash point higher than 180℃; a4) Viscosity index higher than 93; a5) Carbon number difference of relative n-alkanes ≤7; a6) Average carbon number of relative n-alkanes is 21-24; a7) Non-sulfonate content ≥98%.

2. The application of the environmentally friendly agricultural mineral oil base oil as described in claim 1 in mineral oil pesticides.

3. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 1, characterized in that, The continuous production method includes the following steps: 1) Hydrogenating vacuum distillate oil to obtain hydrogenated oil products; 2) The hydrogenated oil obtained in step 1) is fractionated to obtain naphtha, kerosene and lubricating oil fractions respectively; 3) The lubricating oil fraction obtained in step 2) is fractionated to obtain diesel, light lubricating oil, medium lubricating oil, heavy lubricating oil and reduced-base lubricating oil respectively. The medium lubricating oil is an environmentally friendly agricultural mineral oil base oil. The extraction temperature of the medium lubricating oil is 225℃~245℃ and the extraction rate is 1~8 tons / hour.

4. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 3, characterized in that, The hydrogenation is carried out in hydrogenation reactor (1); And / or, in step 1), the kinematic viscosity of the vacuum distillate oil at 100°C is 3.864–5.771 mm. 2 / s; nitrogen content is 295mg / kg~470mg / kg, chlorine content is <0.5mg / kg, and sulfur content is 0.0718%wt~0.164%wt.

5. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 4, characterized in that, The hydrogenation reactor (1) consists of three hydrogenation reactors connected in series: a hydrocracking reactor, an isomerization dewaxing reactor, and a hydrorefining reactor.

6. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 5, characterized in that, The conditions for hydrocracking are a reaction temperature of 368℃~373℃ and a reaction pressure of 14.1MPa~15.0MPa. And / or, the isomerization dewaxing reaction temperature is 330–350℃; the reaction pressure is 14.0–14.2 MPa; And / or, the hydrogenation refining reaction temperature is 235–240℃; the reaction pressure is 14.0–14.2 MPa.

7. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 3, characterized in that, In step 2), the feed temperature for fractionation of the hydrotreated oil is 305℃~310℃; And / or, in step 2), the fractionation is carried out in the first fractionation column (2); And / or, in step 2), the extraction temperature of the lubricating oil fraction is 287℃~297℃; And / or, in step 2), the lubricating oil fraction extraction rate is 30 to 45 tons / hour.

8. The continuous production method of environmentally friendly agricultural mineral oil base oil as described in claim 3, characterized in that, In step 3), the outlet temperature of the lubricating oil fraction obtained in step 2) after entering the heating furnace is 320-325℃, and the feed temperature for fractionation is 308℃-316℃. And / or, in step 3), the top temperature of the distillation column is 91°C to 94°C; And / or, in step 3), the vacuum degree at the top of the distillation column is -93 to -100 kPa; And / or, in step 3), the fractionation is carried out in the second fractionation tower (3).

9. A continuous production apparatus for environmentally friendly agricultural mineral oil base oil as described in claim 1, characterized in that, The system includes a hydrogenation reactor (1), a first fractionation tower (2), and a second fractionation tower (3) connected in sequence. The hydrogenation reactor (1) includes a vacuum distillate inlet (11) and a hydrogenated oil outlet (12). The first fractionation tower (2) includes a first inlet (21) and a naphtha outlet (22), a kerosene outlet (23), and a lubricating oil fraction outlet (24). The hydrogenated oil outlet (12) is connected to the first inlet (21). The second fractionation tower (3) includes a second inlet (31) and a vacuum top gas outlet (32), a diesel outlet (33), a light lubricating oil outlet (34), a medium lubricating oil outlet (35), a heavy lubricating oil outlet (36), and a vacuum bottom lubricating oil outlet (37). The second inlet (31) is connected to the lubricating oil fraction outlet (24).

10. The continuous production apparatus for environmentally friendly agricultural mineral oil base oil as described in claim 9, characterized in that, A first pump body (4) is provided on the pipeline connecting the second feed inlet (31) and the lubricating oil fraction outlet (24); And / or, a feed heating furnace (5) is provided on the pipeline connecting the second feed inlet (31) and the lubricating oil fraction outlet (24); And / or, a second pump body (6) is provided at the bottom-reducing lubricating oil outlet (37).

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