A method for producing light white oil and industrial white oil

Abstract

The present invention relates to a method for producing light white oil and industrial white oil, the method comprising: S1, in the presence of hydrogen, contacting the raw oil with a hydroprocessing catalyst for hydroprocessing to obtain a hydroprocessing product; S2, in the presence of hydrogen, contacting the hydroprocessing product with a hydrodecondensation catalyst for hydrodecondensation treatment to obtain a hydrodecondensation treatment product; S3, in the presence of hydrogen, contacting the hydrodecondensation treatment product with a hydrorefining catalyst for hydrorefining treatment to obtain a hydrorefined oil; S4, separating the hydrorefined oil; wherein the hydroprocessing catalyst contains an alumina carrier and a first hydrogenation active component, the alumina carrier contains fluorine, and the ratio of B acid to L acid of pyridine infrared measured by the alumina carrier at 200°C is 0.15-1.45. The method of the present invention broadens the scope of application of the raw oil, the prepared product has a low aromatic content, and can meet the requirements of light white oil and industrial white oil for pour point.

Description

Technical Field

[0001] The invention relates to a method for producing light white oil and industrial white oil. Background Art

[0002] White oil is a kind of ultra-deeply refined mineral oil, mainly composed of paraffins and cycloalkanes, and almost no aromatics. Because it is colorless, tasteless, odorless and chemically inert, and exhibits excellent light and thermal stability, it is widely used in the fields of chemical industry, food, medicine, daily chemicals, etc. Traditionally speaking, white oil belongs to the lubricating oil fraction >350℃, but with the emergence of new industries using white oil, the distillation range of white oil has been greatly expanded, and the fractions above 120℃ can produce white oil products.

[0003] In addition to meeting the functional indicators of white oil, impurities such as S and N in the raw materials must be deeply removed during its production process, and aromatics must be highly saturated, so that the product meets the safety indicators for use. In recent years, hydrogenation technology has been widely used in the field of white oil production. In the presence of hydrogen and catalysts, aromatics in the raw materials can be deeply hydrogenated and saturated, and non-ideal components can be converted into qualified products, with the characteristics of good product quality, stable production process, and high product yield.

[0004] Patent CN107937024A discloses a method for producing high-quality light white oil from base oil. In this method, the raw base oil is heated to a reaction temperature and fully mixed with hydrogen, and then enters a hydrogenation reactor carrying a catalyst I. Under the action of the hydrogenation refining catalyst I, a hydrogenation refining reaction is carried out to remove most of the S, N, and aromatic impurities in the raw base oil; the product after the reaction enters two reactors in series carrying catalysts II and III, respectively, and contacts with catalysts II and III to carry out S removal and aromatic saturation reaction; the obtained reactants are separated into gas and liquid by high and low pressure separators and then enter the fractionation system for fine cutting to obtain a variety of high-quality light white oil products with different registration numbers. However, the acidity of catalysts II and III used in this method is relatively strong. In the process of further desulfurization and aromatic saturation reaction of the refined raw materials, a relatively obvious cracking reaction occurred, resulting in some light oil and "1# light white oil" with a final boiling point of <120°C, which does not meet the technical standard of NB / SH / T 0913-2015 "Light White Oil" (hereinafter referred to as "Light White Oil Standard"). Moreover, the three reactors in series make the process too long and the investment high.

[0005] Patent CN 103059974B discloses a hydrogenation process for producing food-grade solvent oil; Patent CN103059975B discloses a hydrogenation process for producing solvent oil flexibly; Patent CN 103666554B discloses a hydrogenation process for producing high-quality solvent oil. The above methods can produce high-quality solvent products with a sulfur content of <0.5μg / g and an aromatic content of <100μg / g from kerosene or light diesel fractions. However, both methods use a two-stage dearomatization process using a non-precious metal catalyst and a precious metal catalyst, and require a separation device to be set between the reactors or a countercurrent contact reaction to be performed in the precious metal catalyst reaction zone, which has the problems of high catalyst cost, long process, and complicated operation.

[0006] Patent CN 1190474C discloses a method for producing kerosene-type solvent oil and its catalyst. The method uses 130-300°C straight-run kerosene or hydrocracking kerosene fraction as raw material, and uses W-Ni / TiO2-Al2O3 or W-Mo-Ni / TiO2-Al2O3 as catalyst to produce high-quality kerosene-type solvent oil. Patent CN 100513530C discloses a method for hydrogenation and reforming of solvent oil. The method uses a petroleum fraction containing one or more fractions of gasoline, kerosene and diesel as raw material, and reacts with a hydrogenation and reforming catalyst containing β zeolite in the presence of hydrogen and under suitable conditions to produce solvent oil with excellent performance. However, the aromatic content of the product obtained by the above method cannot meet the requirements for aromatic content of "Light White Oil II" in the light white oil standard. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of the existing methods for producing light white oil and industrial white oil, such as long process, high cost, complicated operation, low yield, high aromatic content in the white oil product, and failure to meet the pour point requirement, and to provide a method for producing light white oil and industrial white oil.

[0008] In order to achieve the above object, the present invention provides a method for producing light white oil and industrial white oil, the method comprising:

[0009] S1. In the presence of hydrogen, the feedstock oil is contacted with a hydroprocessing catalyst for hydroprocessing to obtain a hydroprocessing product; the feedstock oil contains a straight-run kerosene fraction and / or a straight-run diesel fraction;

[0010] S2. In the presence of hydrogen, contacting the hydroprocessing product with a hydrodecondensation catalyst to perform hydrodecondensation treatment to obtain a hydrodecondensation treated product;

[0011] S3, in the presence of hydrogen, contacting the hydrodecondensation product with a hydrorefining catalyst for hydrorefining treatment to obtain a hydrorefined oil;

[0012] S4, separating the hydrorefined oil;

[0013] The hydroprocessing catalyst contains an alumina carrier and a first hydrogenation active component, the alumina carrier contains fluorine, and the ratio of B acid to L acid of pyridine infrared measured at 200° C. of the alumina carrier is 0.15-1.45.

[0014] Optionally, the ratio of B acid to L acid of pyridine infrared measured at 200° C. of the alumina carrier is 0.16-1.35.

[0015] Optionally, the hydroprocessing catalyst is a non-precious metal catalyst; the first hydrogenation active component is a VIB group metal and / or a VIII group metal; preferably, the first hydrogenation active component is selected from one or more of Co, Ni, Mo and W;

[0016] Based on the dry weight of the hydroprocessing catalyst, the content of the first hydrogenation active component is 1-35% by weight in terms of oxide.

[0017] Optionally, the fluorine content is 0.01-6 wt % based on the dry weight of the hydroprocessing catalyst.

[0018] Optionally, in step S1, the conditions of the hydrotreatment include: hydrogen partial pressure of 1-20 MPa, temperature of 260-400°C, volume space velocity of 0.3-10 h -1 , the volume ratio of hydrogen to oil is (100-3000):1.

[0019] Preferably, the hydrogen partial pressure is 6-18 MPa, the temperature is 280-360°C, and the volume space velocity is 0.5-8 h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0020] Optionally, in step S2, the conditions of the hydrodecondensation treatment include: hydrogen partial pressure of 1-20 MPa, temperature of 260-400°C, volume space velocity of 0.3-10 h -1 , the volume ratio of hydrogen to oil is (100-3000):1.

[0021] Preferably, the hydrogen partial pressure is 6-18 MPa, the temperature is 280-380°C, and the volume space velocity is 0.5-5h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0022] Optionally, in step S3, the conditions of the hydrofining treatment include: hydrogen partial pressure of 1-20 MPa, temperature of 240-400°C, volume space velocity of 0.3-10 h -1 , the volume ratio of hydrogen to oil is (100-3000):1.

[0023] Preferably, the hydrogen partial pressure is 6-18 MPa, the temperature is 260-320°C, and the volume space velocity is 0.5-8 h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0024] Optionally, the distillation range of the feedstock oil is 120-400°C and the pour point is -27°C to 50°C.

[0025] Optionally, the method comprises: contacting the feedstock oil with the hydroprocessing catalyst in a hydroprocessing reaction zone to carry out the hydroprocessing; then contacting the obtained hydroprocessing product with the hydrodegrading catalyst in a hydrodegrading reaction zone to carry out the hydrodegrading treatment; and then contacting the hydrodegrading product with the hydrorefining catalyst in a hydrorefining reaction zone to carry out the hydrorefining treatment.

[0026] Optionally, the feedstock oil contains a straight-run kerosene fraction and a straight-run diesel fraction, and the straight-run kerosene fraction and the straight-run diesel fraction are alternately fed into the hydroprocessing reaction zone in a switching feed manner.

[0027] Optionally, in step S4, the separation includes: distilling the hydrorefined oil to obtain light white oil and industrial white oil.

[0028] Optionally, the hydrotreating catalyst is a non-precious metal catalyst;

[0029] The hydrotreating catalyst contains a second hydrogenation active component and an inert carrier;

[0030] The inert carrier includes one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the second hydrogenation active component is selected from one or more of nickel, molybdenum, tungsten and cobalt.

[0031] Optionally, the hydrodecondensation catalyst is a non-precious metal catalyst;

[0032] The hydrofining catalyst contains a molecular sieve, a third hydrogenation active component and an inert carrier;

[0033] The inert carrier comprises one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the third hydrogenation active component is selected from the metal component of Group VIB and / or the metal component of Group VIII; the molecular sieve is selected from ZSM-3, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-37, MCM-37, MCM-68, β molecular sieve, USY or mordenite.

[0034] Compared with the prior art, the method provided by the present invention for producing light white oil and industrial white oil has the following obvious advantages:

[0035] (1) The method of the present invention uses a hydroprocessing catalyst containing a fluorine-containing alumina carrier with suitable acidity, which can achieve deep desulfurization and denitrification of the feedstock oil while moderately opening and saturating the polycyclic aromatic hydrocarbons, and can significantly reduce the sulfur, nitrogen, and aromatic hydrocarbon (especially polycyclic aromatic hydrocarbon) contents of the hydroprocessed oil, ensuring that the final product can meet the requirements of "light white oil II" in the light white oil standard for aromatic hydrocarbon content;

[0036] (2) The method of the present invention can process raw materials with higher pour points, thus broadening the scope of application of the raw materials, and the products can meet the requirements of light white oil and industrial white oil for pour points;

[0037] (3) The hydrotreating catalyst, hydrodegassing catalyst and hydrofining catalyst used in the method of the present invention are all non-precious metal catalysts, and there is no need to set up a gas stripping tower between different reaction zones. The method has the characteristics of small investment, simple process and easy operation.

[0038] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0040] Figure 1 It is a process flow diagram of a specific implementation mode of the present invention. DETAILED DESCRIPTION

[0041] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0042] The present invention provides a method for producing light white oil and industrial white oil, the method comprising:

[0043] S1. In the presence of hydrogen, the feedstock oil is contacted with a hydroprocessing catalyst for hydroprocessing to obtain a hydroprocessing product; the feedstock oil contains a straight-run kerosene fraction and / or a straight-run diesel fraction;

[0044] S2. In the presence of hydrogen, contacting the hydroprocessing product with a hydrodecondensation catalyst to perform hydrodecondensation treatment to obtain a hydrodecondensation treated product;

[0045] S3, in the presence of hydrogen, contacting the hydrodecondensation product with a hydrorefining catalyst for hydrorefining treatment to obtain a hydrorefined oil;

[0046] S4, separating the hydrorefined oil;

[0047] The hydroprocessing catalyst contains an alumina carrier and a first hydrogenation active component, the alumina carrier contains fluorine, and the ratio of B acid to L acid of pyridine infrared measured at 200° C. of the alumina carrier is 0.15-1.45.

[0048] The scope of the raw oil applicable to the method of the present invention is broadened, and the hydroprocessing catalyst used is a chlorine-containing non-precious metal catalyst with suitable acidity, which can effectively remove sulfur and nitrogen in the raw oil, and make the polycyclic aromatic hydrocarbons moderately ring-opened and saturated, and the obtained hydroprocessing product is subjected to hydrodecondensation treatment and hydrofining treatment, so that the final product can meet the requirements of light white oil and industrial white oil for pour point and the requirements of "light white oil II" in the light white oil standard for aromatic content, and the yield of light white oil and industrial white oil is high. At the same time, the hydrofining catalyst and the hydrodecondensation catalyst are also non-precious metal catalysts, which realizes that the reaction does not use a precious metal catalyst, thereby avoiding the setting of a gas stripping tower between different reaction zones, and simplifying the process flow and operation.

[0049] In a preferred embodiment of the present invention, the ratio of B acid to L acid of pyridine infrared measured at 200° C. on the alumina carrier is 0.16-1.35, which can further improve the yield of white oil and reduce the content of aromatics in white oil.

[0050] According to the present invention, the hydroprocessing catalyst can be purchased commercially or prepared by the method of the prior art, and the present invention does not impose specific restrictions on this. In a specific embodiment, the hydroprocessing catalyst is a non-precious metal catalyst; the first hydrogenation active component is a metal of Group VIB and / or a metal of Group VIII; preferably, the first hydrogenation active component is selected from one or more of Co, Ni, Mo and W; based on the dry weight of the hydroprocessing catalyst, the content of the first hydrogenation active component in terms of oxide can vary in a large range, for example, 1-35% by weight, preferably 5-25% by weight. The present application does not limit the preparation method of the hydroprocessing catalyst, which can be a method conventionally adopted by technicians in the field.

[0051] According to the present invention, the fluorine content can vary within a wide range, for example, 0.01-6 wt %, preferably 1-5 wt %, based on the dry weight of the hydroprocessing catalyst.

[0052] In a specific embodiment of the present invention, in step S1, the conditions of the hydrotreatment include: hydrogen partial pressure of 1-20 MPa, temperature of 260-400°C, volume space velocity of 0.3-10 h -1 , the hydrogen-oil volume ratio is (100-3000):1; preferably, the hydrogen partial pressure is 6-18MPa, the temperature is 280-360°C, and the volume space velocity is 0.5-8h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0053] In a specific embodiment of the present invention, in step S2, the conditions of the hydrodecondensation treatment include: hydrogen partial pressure of 1-20 MPa, temperature of 260-400°C, volume space velocity of 0.3-10 h -1 , the hydrogen-oil volume ratio is (100-3000):1; preferably, the hydrogen partial pressure is 6-18MPa, the temperature is 280-380°C, and the volume space velocity is 0.5-5h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0054] In a specific embodiment of the present invention, in step S3, the conditions of the hydrofining treatment include: hydrogen partial pressure of 1-20 MPa, temperature of 240-400°C, volume space velocity of 0.3-10 h -1 , the volume ratio of hydrogen to oil is (100-3000):1; preferably, the pressure is 6-18MPa, the temperature is 260-320℃, and the volume space velocity is 0.5-8h -1 , the volume ratio of hydrogen to oil is (300-1000):1.

[0055] In the present invention, the distillation range of the raw oil can be 120-400°C, and the pour point can be -27°C to 50°C; preferably, the distillation range is 155-350°C, and the pour point is -18°C to 32°C. The scope of raw oil applicable to the method of the present invention is broadened, and when the raw oil with the above characteristics is used to produce white oil, the quality and yield of the white oil product can be further improved.

[0056] In a specific embodiment of the present invention, the method comprises: contacting the feedstock oil with the hydroprocessing catalyst in a hydroprocessing reaction zone to perform the hydroprocessing; then contacting the obtained hydroprocessing product with the hydrodecompression catalyst in a hydrodecompression reaction zone to perform the hydrodecompression treatment, and then contacting the hydrodecompression treatment product with the hydrodecompression catalyst in a hydrorefining reaction zone to perform the hydrorefining treatment. In the above embodiment, the hydroprocessed product is directly subjected to the hydrodecompression treatment and the hydrorefining treatment in sequence, without the need to set a separation device between the reactors or to perform a countercurrent contact reaction in the noble metal catalyst reaction zone, and the process flow is short and the process operation is simple.

[0057] In a specific embodiment of the present invention, the raw oil contains a straight-run kerosene fraction and a straight-run diesel fraction. Preferably, the raw oil is pre-fractionated to obtain a straight-run kerosene fraction and a straight-run diesel fraction, and the straight-run kerosene fraction and the straight-run diesel fraction are alternately fed into the hydroprocessing reaction zone in a switching feed manner to adjust the operating conditions of the reaction according to different raw material properties, so that the hydroprocessing process is more sufficient, which is beneficial to further improve the yield and quality of the white oil product.

[0058] According to the present invention, in step S4, the separation includes: distilling the hydrorefined oil to obtain light white oil and industrial white oil. Distillation is an operation well known to those skilled in the art, such as flash distillation, precision distillation, atmospheric distillation, and vacuum distillation, as long as the light white oil and industrial white oil in the hydrorefined oil can be separated.

[0059] According to the present invention, the hydrorefining catalyst can be used to further remove sulfur and nitrogen, and deeply saturate aromatics, thereby improving the odor, color, thermal oxidation stability and other indicators of the oil product, so that the final products can meet the quality standards of "light white oil II" and industrial white oil in the light white oil standard. The hydrorefining catalyst can be selected from any catalyst that can achieve this function in the prior art, and can be a commercially available product or prepared by any existing method. For example, the hydrorefining catalyst of the present invention can be prepared by the method described in patent CN 1840618A, patent CN 1133723C, patent CN 1648214A and CN 1626279A. In a specific embodiment, the hydrorefining catalyst can be a non-precious metal catalyst; the hydrorefining catalyst contains a second hydrogenation active component and an inert carrier; the inert carrier includes one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the second hydrogenation active component is selected from one or more of nickel, molybdenum, tungsten, and cobalt. In the method of the present invention, a non-precious metal catalyst is used as a hydrofining catalyst, which avoids the need to set up a gas stripping tower between the hydrotreatment reaction zone and the hydrofining reaction zone, thereby simplifying the process and making the operation easier.

[0060] According to the present invention, the hydrodegassing catalyst can be selected from one or more of any catalysts in the prior art that can achieve this function, and can be a commercially available product or prepared by any existing method. For example, the hydrodegassing catalyst of the present invention can be prepared by the methods described in patents CN 102051232A, CN 103805266A and CN 1952074A. In a preferred embodiment, the hydrodegassing catalyst can be a non-precious metal catalyst; the hydrorefining catalyst contains a molecular sieve, a third hydrogenation active component and an inert carrier. The inert carrier comprises one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the third hydrogenation active component is selected from the metal component of Group VIB and / or the metal component of Group VIII; the molecular sieve is ZSM-3, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-37, MCM-37, MCM-68, β molecular sieve, USY or mordenite.

[0061] The present invention is further illustrated by the following examples, but the present invention is not limited thereto.

[0062] The properties of the raw materials used in the examples and comparative examples of the present invention are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] The catalysts used in the examples and comparative examples of the present invention are prepared by the following method.

[0067] Preparation Example 1

[0068] Hydrogenation treatment catalyst A was prepared by the following method: 2000 g of aluminum hydroxide powder (dry rubber powder produced by the catalyst factory of Changling Branch, 72 wt% on a dry basis) was weighed and extruded into cylindrical strips with an circumscribed circle diameter of 1.3 mm using an extruder. The wet strips were dried at 120°C for 4 hours and calcined at 600°C for 3 hours to obtain carrier Sl.

[0069] Weigh 200 g of carrier S1, and impregnate the carrier with an aqueous solution containing 29.0 g of ammonium fluoride (analytical pure, a product of Beijing Chemical Plant) for 2 hours, dry at 120° C. for 3 hours, and roast at 420° C. for 3 hours to obtain a fluorine-containing aluminum oxide carrier. The above carrier is impregnated with 170 ml of an aqueous solution containing 16.3 g of ammonium paramolybdate (chemically pure, a product of Beijing Chemical Plant) for 3 hours, dried at 120° C. for 8 hours, and then impregnated with 162 ml of an aqueous solution containing 30.2 g of nickel nitrate (analytical pure, a product of Beijing Chemical Plant), 131.5 g of ammonium metatungstate (industrial grade, a product of Sichuan Zigong Cemented Carbide Plant) and 18.5 g of phosphoric acid for 3 hours. The wet strip is dried at 120° C. for 4 hours and roasted at 450° C. for 4 hours to obtain catalyst A, whose composition is determined by X-ray fluorescence method.

[0070] Based on the dry weight of the hydroprocessing catalyst A, the mass fraction of nickel is 2.9%, the mass fraction of tungsten is 28.9%, the mass fraction of molybdenum is 3.1%, and the rest is the fluorine-containing alumina carrier, and the mass fraction of fluorine is 3.5% based on the dry weight of the hydroprocessing catalyst A. The acidity of the catalyst or the carrier is characterized by pyridine adsorption-infrared spectroscopy, and the ratio of pyridine infrared B acid to L acid measured by the alumina carrier at 200°C is 0.614.

[0071] Preparation Example 2

[0072] Hydrogenation treatment catalyst B was prepared by the following method: 2000 g of aluminum hydroxide powder (dry rubber powder produced by the catalyst factory of Changling Branch, 72 wt% on a dry basis) was weighed and extruded into cylindrical strips with an circumscribed circle diameter of 1.3 mm using an extruder. The wet strips were dried at 120°C for 4 hours and calcined at 600°C for 3 hours to obtain carrier Sl.

[0073] Weigh 200 g of carrier S1, and soak the carrier in 175 ml of an aqueous solution containing 52.8 g of ammonium fluoride (analytical pure, a product of Beijing Chemical Plant) for 2 hours, dry at 120° C. for 3 hours, and roast at 420° C. for 3 hours to obtain a fluorine-containing aluminum oxide carrier. The above carrier was soaked in 170 ml of an aqueous solution containing 17.6 g of ammonium paramolybdate (chemically pure, a product of Beijing Chemical Plant) for 3 hours, dried at 120° C. for 8 hours, and then soaked in 162 ml of an aqueous solution containing 28.6 g of nickel nitrate (analytical pure, a product of Beijing Chemical Plant), 129.5 g of ammonium metatungstate (industrial grade, a product of Sichuan Zigong Cemented Carbide Plant) and 12.8 g of phosphoric acid for 3 hours. The wet strip was dried at 120° C. for 4 hours and roasted at 450° C. for 4 hours to obtain catalyst C, whose composition was determined by X-ray fluorescence.

[0074] Based on the dry weight of the hydroprocessing catalyst C, the mass fraction of nickel is 2.7%, the mass fraction of tungsten is 27.5%, the mass fraction of molybdenum is 3.2%, and the rest is the fluorine-containing alumina carrier, and the mass fraction of fluorine is 6.2% based on the dry weight of the catalyst C. The acidity of the catalyst or the carrier is characterized by pyridine adsorption-infrared spectroscopy, and the ratio of pyridine infrared B acid to L acid measured by the alumina carrier at 200°C is 1.39.

[0075] Preparation Example 3

[0076] Hydroprocessing catalyst C was prepared by the following method: 2000 g of aluminum hydroxide powder (dry rubber powder produced by the catalyst factory of Changling Branch, 72 wt% on a dry basis) was weighed and extruded into cylindrical strips with an circumscribed circle diameter of 1.3 mm using an extruder. The wet strips were dried at 120°C for 4 hours and calcined at 600°C for 3 hours to obtain carrier Sl.

[0077] Weigh 200 g of carrier S1, and impregnate the carrier with an aqueous solution containing 30.6 g of ammonium fluoride (analytical grade, product of Beijing Chemical Plant) for 2 hours, dry at 120° C. for 3 hours, and roast at 420° C. for 3 hours to obtain a fluorine-containing aluminum oxide carrier. The above carrier is impregnated with 170 ml of an aqueous solution containing 19.1 g of ammonium paramolybdate (chemically pure, product of Beijing Chemical Plant) for 3 hours, dried at 120° C. for 8 hours, and then impregnated with 162 ml of an aqueous solution containing 35.4 g of nickel nitrate (analytical grade, product of Beijing Chemical Plant), 145.2 g of ammonium metatungstate (industrial grade, product of Sichuan Zigong Cemented Carbide Plant) and 18.5 g of phosphoric acid for 3 hours. The wet strip is dried at 120° C. for 4 hours and roasted at 450° C. for 4 hours to obtain catalyst C, whose composition is determined by X-ray fluorescence method.

[0078] Based on the dry weight of the hydroprocessing catalyst C, the mass fraction of nickel is 3.2%, the mass fraction of tungsten is 3.5%, the mass fraction of molybdenum is 30.3%, and the rest is the fluorine-containing alumina carrier, and the mass fraction of fluorine is 3.5% based on the dry weight of the hydroprocessing catalyst C. The acidity of the catalyst or the carrier is characterized by pyridine adsorption-infrared spectroscopy, and the ratio of pyridine infrared B acid to L acid measured by the alumina carrier at 200°C is 0.616.

[0079] Preparation Example 4

[0080] Hydrogenation treatment catalyst D was prepared by the following method: 2000 g of aluminum hydroxide powder (dry rubber powder produced by the catalyst factory of Changling Branch, 72 wt% on a dry basis) was weighed and extruded into cylindrical strips with an circumscribed circle diameter of 1.3 mm using an extruder. The wet strips were dried at 120°C for 4 hours and calcined at 600°C for 3 hours to obtain carrier Sl.

[0081] Weigh 200 g of carrier S1, and impregnate the carrier with an aqueous solution containing 62.4 g of ammonium fluoride (analytical pure, a product of Beijing Chemical Plant) for 2 hours, dry at 120° C. for 3 hours, and roast at 420° C. for 3 hours to obtain a fluorine-containing aluminum oxide carrier. The above carrier is impregnated with 174 ml of an aqueous solution containing 18.9 g of ammonium paramolybdate (chemically pure, a product of Beijing Chemical Plant) for 3 hours, dried at 120° C. for 8 hours, and then impregnated with 192 ml of an aqueous solution containing 30.7 g of nickel nitrate (analytical pure, a product of Beijing Chemical Plant), 137.8 g of ammonium metatungstate (industrial grade, a product of Sichuan Zigong Cemented Carbide Plant), and 16.8 g of phosphoric acid for 3 hours. The wet strip is dried at 120° C. for 4 hours and roasted at 450° C. for 4 hours to obtain catalyst D, whose composition is determined by X-ray fluorescence.

[0082] Based on the dry weight of the hydroprocessing catalyst D, the mass fraction of nickel is 2.7%, the mass fraction of tungsten is 27.7%, the mass fraction of molybdenum is 3.3%, and the rest is alumina support. Based on the dry weight of the hydroprocessing catalyst D, the mass fraction of fluorine is 6.9% in terms of elements. The acidity of the catalyst or support is characterized by pyridine adsorption-infrared spectroscopy, and the ratio of pyridine infrared B acid to L acid measured by the alumina support at 200°C is 1.720.

[0083] Preparation Example 5

[0084] Hydroprocessing catalyst E was prepared by the following method: 2000 g of aluminum hydroxide powder (dry rubber powder produced by the catalyst factory of Changling Branch, 72 wt% on a dry basis) was weighed and extruded into cylindrical strips with an circumscribed circle diameter of 1.3 mm using an extruder. The wet strips were dried at 120°C for 4 hours and calcined at 600°C for 3 hours to obtain carrier Sl.

[0085] Weigh 200 g of carrier S1, impregnate the carrier with 170 ml of an aqueous solution containing 46.3 g of ammonium paramolybdate (chemically pure, a product of Beijing Chemical Plant) for 3 hours, dry at 120°C for 8 hours, and then impregnate with 162 ml of an aqueous solution containing 40.8 g of nickel nitrate (analytical pure, a product of Beijing Chemical Plant), 110.5 g of ammonium metatungstate (industrial grade, a product of Sichuan Zigong Cemented Carbide Plant), and 14.2 g of phosphoric acid for 3 hours. Dry the wet strip at 120°C for 4 hours and calcine at 450°C for 4 hours to obtain catalyst C, whose composition is determined by X-ray fluorescence.

[0086] Based on the dry weight of the hydroprocessing catalyst E, the mass fraction of nickel is 4.1%, the mass fraction of tungsten is 25.1%, the mass fraction of molybdenum is 9.2%, and the rest is alumina support, calculated as oxide. The acidity of the catalyst or support is characterized by pyridine adsorption-infrared spectroscopy, and the ratio of pyridine infrared B acid to L acid measured by the alumina support at 200°C is 0.06.

[0087] The hydrodecondensation catalyst and hydrotreating catalyst are RDW-1 and RJW-3 developed by the Petrochemical Research Institute respectively.

[0088] Example 1

[0089] like Figure 1 As shown, light white oil and industrial white oil are prepared by the following method:

[0090] In the presence of hydrogen, the raw material is contacted with a hydroprocessing catalyst A for hydroprocessing to obtain a hydroprocessing product;

[0091] S2. In the presence of hydrogen, the hydrotreated product is contacted with a hydrodecondensation catalyst RDW-1 to perform a hydrodecondensation treatment to obtain a hydrodecondensation treated product;

[0092] S3, in the presence of hydrogen, contacting the hydrodecondensation product with a hydrorefining catalyst RJW-3 for hydrorefining treatment to obtain a hydrorefined oil;

[0093] S4. Fractionate the hydrorefined oil to obtain light white oil and industrial white oil.

[0094] The operating conditions of each step are shown in Table 2, and the properties of the obtained products are shown in Table 3.

[0095] Table 2

[0096] Process conditions Hydroprocessing Hydrodecondensation Hydrotreating Hydrogen partial pressure / MPa 15.0 15.0 15.0 Reaction temperature / ℃ 310 330 280 <![CDATA[Space velocity per hour -1 > 1.0 2.0 2.0 Hydrogen to oil ratio / (v / v) 600：1 600：1 600：1

[0097] Table 3

[0098]

[0099] Example 2

[0100] Industrial white oil and light white oil were prepared by the same method as in Example 1, except that the conditions of the hydrotreatment, hydrodecondensation treatment and hydrofining treatment were different from those in Example 1, as shown in Table 4. The properties of the obtained products are shown in Table 5.

[0101] Table 4

[0102] Process conditions Hydroprocessing Hydrodecondensation Hydrotreating Hydrogen partial pressure / MPa 12.0 12.0 12.0 Reaction temperature / ℃ 340 340 280 <![CDATA[Space velocity per hour -1 > 1.0 1.0 1.0 Hydrogen to oil ratio / (v / v) 600：1 600：1 600：1

[0103] Table 5

[0104]

[0105] Example 3

[0106] Industrial white oil and light white oil were prepared by the same method as in Example 1, except that hydrotreating catalyst B was used instead of hydrotreating catalyst A in step S1. The properties of the obtained products are shown in Table 6.

[0107] Table 6

[0108]

[0109]

[0110] Example 4

[0111] Industrial white oil and light white oil were prepared by the same method as in Example 1, except that hydrotreating catalyst C was used instead of hydrotreating catalyst A in step S1. The properties of the obtained products are shown in Table 7.

[0112] Table 7

[0113]

[0114] Comparative Example 1

[0115] Industrial white oil and light white oil were prepared by the same method as in Example 1, except that hydrotreating catalyst D was used instead of hydrotreating catalyst A in step S1. The properties of the obtained products are shown in Table 8.

[0116] Table 8

[0117]

[0118] Comparative Example 2

[0119] Industrial white oil and light white oil were prepared by the same method as in Example 1, except that hydroprocessing catalyst E was used instead of hydroprocessing catalyst A. The properties of the obtained products are shown in Table 9.

[0120] Table 9

[0121]

[0122] The method of the invention has small investment, simple process and convenient operation. The prepared white oil product has low aromatic content and can meet the requirements of light white oil and industrial white oil for pour point. The yield of light white oil and industrial white oil is high.

[0123] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0124] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0125] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for producing light white oil and industrial white oil, the method comprising: S1. In the presence of hydrogen, the crude oil is contacted with a hydroprocessing catalyst for hydroprocessing to obtain a hydroprocessing product; The feedstock oil contains straight-run kerosene fraction and / or straight-run diesel fraction; the conditions of the hydrotreatment include: hydrogen partial pressure of 15-20 MPa, temperature of 280-310°C, volume space velocity of 0.5-1 h -1 , the volume ratio of hydrogen to oil is (300-600):1; S2. In the presence of hydrogen, the hydrotreated product is contacted with a hydrodecondensation catalyst to perform a hydrodecondensation treatment to obtain a hydrodecondensation treated product; the conditions of the hydrodecondensation treatment include: a hydrogen partial pressure of 15-18 MPa, a temperature of 280-330° C., and a volume space velocity of 0.5-2 h -1 , the volume ratio of hydrogen to oil is (300-600):1; S3. In the presence of hydrogen, the hydrodecondensation product is contacted with a hydrorefining catalyst for hydrorefining treatment to obtain a hydrorefined oil; the conditions of the hydrorefining treatment include: a hydrogen partial pressure of 15-18 MPa, a temperature of 260-280° C., and a volume space velocity of 0.5-2 h -1 , the volume ratio of hydrogen to oil is (300-600):1; S4, separating the hydrorefined oil to obtain the light white oil and industrial white oil; The hydroprocessing catalyst is a non-precious metal catalyst; the hydroprocessing catalyst contains an alumina carrier and a first hydrogenation active component, the alumina carrier contains fluorine, and the ratio of B acid to L acid of pyridine infrared measured at 200°C of the alumina carrier is 0.16-1.35; the first hydrogenation active component is a VIB group metal and / or a VIII group metal; based on the dry weight of the hydroprocessing catalyst, the fluorine content is 1-6% by weight.

2. The method according to claim 1, wherein: The first hydrogenation active component is selected from one or more of Co, Ni, Mo and W; Based on the dry weight of the hydroprocessing catalyst, the content of the first hydrogenation active component is 1-35% by weight in terms of oxide.

3. The method according to claim 1, wherein: The distillation range of the raw oil is 120-400°C, and the pour point is -27°C to 50°C.

4. The method according to claim 1, wherein: The method comprises: contacting the feedstock oil with the hydroprocessing catalyst in a hydroprocessing reaction zone to perform the hydroprocessing; then contacting the obtained hydroprocessing product with the hydrodecompression catalyst in a hydrodecompression reaction zone to perform the hydrodecompression treatment; and then contacting the hydrodecompression product with the hydrodecompression catalyst in a hydrorefining reaction zone to perform the hydrorefining treatment; The feedstock oil contains a straight-run kerosene fraction and a straight-run diesel fraction, and the straight-run kerosene fraction and the straight-run diesel fraction are alternately fed into the hydroprocessing reaction zone in a switching feed manner.

5. The method according to claim 1, wherein: In step S4, the separation includes: distilling the hydrorefined oil to obtain light white oil and industrial white oil.

6. The method according to claim 1, wherein: The hydrotreating catalyst is a non-precious metal catalyst; The hydrotreating catalyst contains a second hydrogenation active component and an inert carrier; The inert carrier includes one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the second hydrogenation active component is selected from one or more of nickel, molybdenum, tungsten and cobalt.

7. The method according to claim 1, wherein: The hydrodegradation catalyst is a non-precious metal catalyst; The hydrofining catalyst contains a molecular sieve, a third hydrogenation active component and an inert carrier; The inert carrier comprises one or more of silicon oxide, aluminum oxide, titanium oxide and magnesium oxide; the third hydrogenation active component is selected from the metal component of Group VIB and / or the metal component of Group VIII; the molecular sieve is selected from ZSM-3, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAPO-37, MCM-37, MCM-68, β molecular sieve, USY or mordenite.

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