A preparation method of cosmetic grade white oil

Abstract

The present invention provides a method for preparing cosmetic-grade white oil, the method comprising the following steps: (1) after mixing raw oil with hydrogen, sequentially performing a first catalytic reaction and a second catalytic reaction to obtain a reaction product; the catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfide catalysts; (2) the reaction product is sequentially subjected to gas-liquid separation and distillation to obtain the cosmetic-grade white oil. The catalyst used in the preparation method of the present invention is low in cost, the preparation process is simple, and the cosmetic-grade white oil finally obtained has low viscosity and high quality. Moreover, the application of the preparation method of the present invention only requires changing the catalyst grading scheme of the original reactor or adding a supplementary refining reactor, without adding a circulating hydrogen system, which is beneficial to the upgrading and transformation of white oil production enterprises.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, and in particular to a method for preparing cosmetic-grade white oil. Background Art

[0002] Mineral oil is also known as white mineral oil or white oil. Commonly used ones include industrial grade white oil, cosmetic grade white oil, medical grade white oil, food grade white oil, etc. Among them, food grade white oil, cosmetic grade white oil and pharmaceutical grade white oil are collectively referred to as high-grade white oil. At present, industrial white oil is in a situation of oversupply and competition is fierce. Due to its production limitations, there are not many manufacturers of high-grade white oil. However, as market demand gradually increases, it has attracted great attention from refineries.

[0003] High-grade white oil has very strict requirements on the aromatic content. The high-pressure hydrogenation process has a more obvious effect on the dearomaticization of oil products. Therefore, the production of food-grade white oil mostly adopts the high-pressure hydrogenation process. Depending on the nature of the raw materials, one or more stages of hydrogenation are used to prepare high-grade white oil.

[0004] The prior art proposes to use vacuum distillate oil, solvent refined deasphalted oil and Fischer-Tropsch oil as raw materials, carry out hydrogenation treatment, distillation separation to obtain hydrogenated tail oil as raw material, adopt high-pressure hydrogenation supplementary refining process, and directly produce food-grade white oil products by high-pressure hydrogenation supplementary refining; it is also proposed to use distillate oil or cracking tail oil for two-stage hydrogenation to produce food-grade white oil; it is also proposed to use vacuum distillate oil, solvent refined deasphalted oil and Fischer-Tropsch oil as raw materials, adopt single-stage or tandem hydrogenation treatment process, and use modified nickel-based or precious metal hydrogenation supplementary refining catalyst to prepare high-grade white oil.

[0005] CN111518589A discloses a production process of food-grade white oil, which uses lubricating oil base oil, industrial white oil, hydrocracking tail oil, hydroisomerization dewaxing product oil and the like as raw oils, adopts a precious metal catalyst, and obtains a reaction product by a series hydrogenation. After the high-pressure and low-pressure gas-liquid separation, the reaction product is subjected to vacuum distillation and side-line stripping to obtain food-grade white oil products of different viscosity grades.

[0006] CN111334330A discloses a white oil for poultry vaccine injection and a preparation method thereof. The atmospheric and vacuum distillate oil of paraffin-based crude oil and the atmospheric and vacuum distillate oil of cycloalkyl crude oil are mixed to obtain a mixed fraction. The hydrogenation pre-refined product is subjected to hydrogenation treatment, isomerization decondensation and precious metal hydrogenation supplementary refining in sequence under a hydrogen partial pressure of 15.0 to 20.0 MPa, and a 290 to 370°C fraction of the hydrogenation supplementary refining product is taken to obtain the white oil for poultry vaccine injection.

[0007] CN1769380A discloses a one-stage hydrogenation method for producing premium white oil, which uses a sulfurized hydrogenation catalyst to supplement a refined catalyst to prepare a premium white oil hydrogenation method. However, this method is only suitable for producing industrial white oil, that is, preparing raw materials for producing high-grade white oil.

[0008] However, the above methods all use highly active reduced precious metal or nickel catalysts, which have strict requirements on the sulfur and nitrogen content of the raw materials and are relatively expensive. In addition, the industrial device needs to be equipped with separate circulation facilities, and the construction and production costs of the device are relatively high.

[0009] Therefore, it is of great significance to develop a method for preparing cosmetic-grade white oil using a non-precious metal catalyst and without the need for a separate hydrogen circulation facility. Summary of the invention

[0010] In order to solve the above technical problems, the present invention provides a method for preparing cosmetic grade white oil, which uses a non-precious metal sulfide catalyst for catalytic reaction, and obtains low-viscosity cosmetic grade white oil by controlling the carrier of the supplementary refining catalyst. The preparation method provided by the present invention only needs to change the catalyst grading scheme of the original reactor or add a supplementary refining reactor, and does not need to add a circulating hydrogen system, which is conducive to the upgrading and transformation of production enterprises.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] The present invention provides a method for preparing cosmetic-grade white oil, the preparation method comprising the following steps:

[0013] (1) After the feedstock oil and hydrogen are mixed, a first catalytic reaction and a second catalytic reaction are sequentially performed to obtain a reaction product;

[0014] The catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfided catalysts;

[0015] The catalyst used in the second catalytic reaction includes a supplementary refined catalyst; the carrier of the supplementary refined catalyst includes γ-Al2O3 containing 0.5% to 20% by mass of SiO2;

[0016] (2) The reaction product is subjected to gas-liquid separation and distillation in sequence to obtain the cosmetic grade white oil; the kinematic viscosity of the cosmetic grade white oil at 40° C. is 7.6 to 12.4 mm 2 / s.

[0017] The preparation method of the cosmetic-grade white oil of the present invention adopts a non-precious metal sulfurized catalyst, and the catalyst cost is low; the preparation method has low requirements on the sulfur content and nitrogen content in the raw oil, and the obtained cosmetic-grade white oil has high quality, low viscosity, and high commercial utilization value; and the application of the preparation method of the present invention only requires changing the catalyst grading scheme of the original reactor or adding a supplementary refining reactor, without adding a circulating hydrogen system, the transformation investment is small, and it is convenient for the transformation and upgrading of the production enterprise.

[0018] The carrier of the supplementary refining catalyst in the present invention includes γ-Al2O3 containing 0.5% to 20% SiO2 by mass, which can make the final cosmetic grade white oil have a good oil structure and low viscosity, and meet the index requirements of 10# cosmetic grade white oil in the SH0007-2015 standard. When the mass percentage of SiO2 in the carrier is too low, the acidity of the supplementary refining catalyst is weak, and the aromatic molecules in the raw oil cannot be adsorbed, the dearomatization effect is poor, and the quality of the cosmetic grade white oil is poor; when the mass percentage of SiO2 in the carrier is too high, the cracking performance of the supplementary refining catalyst is enhanced, and the yield of the cosmetic grade white oil is reduced.

[0019] The carrier of the supplementary refined catalyst in the present invention includes γ-Al2O3 containing SiO2 with a mass percentage of 0.5% to 20%, for example, it can be 0.5%, 1%, 3%, 5%, 10%, 15%, 17% or 20%, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the kinematic viscosity of the cosmetic grade white oil at 40°C is 7.6 to 12.4 mm 2 / s, for example, it can be 7.6mm 2 / s、7.9mm 2 / s, 8mm 2 / s、8.2mm 2 / s, 9mm 2 / s, 10mm 2 / s or 12.4mm 2 / s, etc., but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0020] Preferably, the feedstock oil includes any one of lubricating oil base oil, industrial white oil or hydrogenated modified diesel.

[0021] Preferably, the catalyst used in the first catalytic reaction in step (1) comprises a hydrodegradation catalyst.

[0022] Preferably, the hydrodegradation catalyst comprises a first active metal oxide, a first metal oxide promoter and a first carrier.

[0023] Preferably, the first active metal oxide comprises Group VIII and / or Group VIB metal oxides, preferably NiO and / or WO3.

[0024] The present invention does not limit the first metal oxide promoter in the hydrodegradation catalyst, and any metal oxide known in the art that can be used in a catalyst can be used.

[0025] Preferably, the first support comprises a molecular sieve.

[0026] Preferably, the mass percentages of the components in the hydrodecondensation catalyst are respectively: NiO: 1.0-6.0%, for example, 1%, 1.5%, 2%, 3%, 5%, 5.5% or 6%, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; WO3: 0-15%, for example, 0%, 1%, 2%, 5%, 10%, 13% or 15%, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; Metal oxide additive: 1.0%-5.4%, for example, 1%, 1.5%, 2%, 3%, 5% or 5.4%, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; Molecular sieve: 8-40%, for example, 8%, 10%, 20%, 30%, 35% or 40%, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0027] The present invention preferably comprises 1.0-6.0% by mass content of NiO and 0-15% by mass content of WO3 in the hydrodecondensation catalyst, and the ultraviolet absorbance of polycyclic aromatic hydrocarbons in the obtained cosmetic-grade white oil at a wavelength of 260-420 mm is ≤0.1, which meets the index requirements of 10# cosmetic-grade white oil in the SH0007-2015 standard.

[0028] Preferably, the pressure of the first catalytic reaction in step (1) is 10.0 to 20.0 MPa, for example, 10 MPa, 11 MPa, 13 MPa, 15 MPa, 17 MPa, 19 MPa or 20 MPa, etc., but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 12.0 to 18.0 MPa.

[0029] Preferably, the temperature of the first catalytic reaction is 270-410°C, for example, it can be 270°C, 280°C, 300°C, 320°C, 350°C or 410°C, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 280-380°C.

[0030] Preferably, the hydrogen-to-oil volume ratio of the first catalytic reaction is (300-2000):1, for example, it can be 300:1, 500:1, 800:1, 1000:1, 1300:1, 1500:1 or 2000:1, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably (500-1200):1.

[0031] Preferably, the volume space velocity of the first catalytic reaction is 0.2 to 3.0 h -1 , for example, it can be 0.2h -1 、0.5h -1 、0.8h -1 , 1h -1 , 1.5h -1 , 2h -1 or 3h -1 etc., but are not limited to the listed values. Other values ​​not listed in the numerical range are also applicable, preferably 0.3 to 2.0 h -1 .

[0032] Preferably, the supplementary refined catalyst in step (1) further comprises a second active metal oxide and a second metal oxide promoter.

[0033] Preferably, the second active metal oxide comprises a Group VIII and / or Group VIB metal oxide, preferably any one or a combination of at least two of WO3, MoO3, CoO or NiO, wherein typical but non-limiting combinations are a combination of WO3 and MoO3; a combination of CoO and NiO; a combination of WO3 and MoO3 or a combination of NiO, WO3 and MoO3.

[0034] Preferably, the second metal oxide additive comprises any one of P, F, B, Ti or Zr or a combination of at least two thereof, wherein typical but non-limiting combinations include a combination of P and F; a combination of B and Ti; a combination of ZrP and F or a combination of B, Ti and Zr.

[0035] Preferably, the mass percentage of each component in the supplementary refined catalyst is: Group VIB metal oxide: 15-35%, for example, 15%, 18%, 20%, 25%, 30%, 32% or 35%, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; Group VIII metal oxide: 4.0-10.0%, for example, 4%, 5%, 6%, 8%, 9%, 9.5% or 10%, etc., but not limited to the listed values, and the values ​​are also applicable. Other unlisted values ​​within the value range are also applicable; second metal oxide additive: 1.0-10%, for example, it can be 1%, 3%, 6%, 8%, 9%, 9.5% or 10%, etc., but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable; carrier: 50-80%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc., but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] Preferably, the pressure of the second catalytic reaction in step (1) is 10.0 to 20.0 MPa, for example, 10 MPa, 11 MPa, 13 MPa, 15 MPa, 17 MPa, 19 MPa or 20 MPa, etc., but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 12.0 to 18.0 MPa.

[0037] Preferably, the temperature of the second catalytic reaction is 240-360°C, for example, it can be 240°C, 250°C, 280°C, 300°C, 320°C, 350°C or 360°C, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 250-340°C.

[0038] Preferably, the hydrogen-to-oil volume ratio of the second catalytic reaction is (200-1200):1, for example, it can be 200:1, 300:1, 500:1, 800:1, 1000:1 or 1200:1, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably (500-800):1.

[0039] Preferably, the volume space velocity of the second catalytic reaction is 0.3 to 3.5 h -1 , for example, it can be 0.3h -1 、0.5h -1 , 1h -1 , 2h -1 , 2.5h -1 , 3h -1 or 3.5h -1etc., but are not limited to the listed values. Other values ​​not listed in the numerical range are also applicable, preferably 0.5 to 2.0 h -1 .

[0040] Preferably, the gas-liquid separation in step (2) includes a first separation and a second separation.

[0041] Preferably, the first separation pressure is 12-16 MPa, for example, 12 MPa, 13 MPa, 15 MPa, 17 MPa or 18 MPa, but is not limited to the listed values, and is preferably 14-16 MPa.

[0042] Preferably, the second separation pressure is 0.1-0.6 MPa, for example, 0.1 MPa, 0.3 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa or 0.6 MPa, but is not limited to the listed values, and is preferably 0.2-0.5 MPa.

[0043] Preferably, the fraction with a temperature ≥280°C in the distillation of step (2) is the cosmetic-grade white oil, for example, it can be 280°C, 290°C, 300°C, 320°C, 350°C or 400°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0044] Preferably, the cosmetic grade white oil in step (2) meets the index requirements of 10# cosmetic grade white oil in the SH0007-2015 standard.

[0045] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0046] (1) After the feedstock oil and hydrogen are mixed, a first catalytic reaction and a second catalytic reaction are sequentially performed to obtain a reaction product;

[0047] The catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfided catalysts;

[0048] The catalyst used in the second catalytic reaction includes a supplementary refined catalyst; the carrier of the supplementary refined catalyst includes γ-Al2O3 containing 0.5% to 20% by mass of SiO2;

[0049] The feedstock oil includes any one of lubricating oil base oil, industrial white oil or hydrogenated modified diesel; the catalyst used in the first catalytic reaction includes a hydrodegradation catalyst;

[0050] The hydrodecondensation catalyst comprises a first active metal oxide, a first metal oxide promoter and a first carrier; the first active metal oxide comprises a Group VIII and / or Group VIB metal oxide, preferably NiO and / or WO3; the first carrier comprises a molecular sieve; the mass percentage of each component in the hydrodecondensation catalyst is respectively NiO: 1.0-6.0%, WO3: 0-15%, metal oxide promoter: 1.0%-5.4% and molecular sieve: 8-40%; the pressure of the first catalytic reaction is 10.0-20.0MPa, the temperature is 270-410°C, the hydrogen-to-oil volume ratio is (300-2000):1, and the volume space velocity is 0.2-3.0h -1 ;

[0051] The supplemental refining catalyst also includes a second active metal oxide and a second metal oxide promoter;

[0052] The second active metal oxide comprises a Group VIII and / or Group VIB metal oxide, preferably any one or a combination of at least two of WO3, MoO3, CoO or NiO; the second metal oxide promoter comprises any one or a combination of at least two of P, F, B, Ti or Zr; the mass percentage of each component in the supplementary refined catalyst is respectively Group VIB metal oxide: 15-35%, Group VIII metal oxide: 4.0-10.0%, second metal oxide promoter: 1.0-10% and carrier: 50-80%; the pressure of the second catalytic reaction is 10.0-20.0MPa, the temperature is 240-360°C, the hydrogen-to-oil volume ratio is (200-1200): 1, and the volume space velocity is 0.3-3.5h -1 ;

[0053] (2) The reaction product is sequentially subjected to a first separation at a pressure of 12 to 16 MPa, a second separation at a pressure of 0.1 to 0.6 MPa, and distillation, and the fraction with a temperature of ≥280° C. is the cosmetic grade white oil; the kinematic viscosity of the cosmetic grade white oil at 40° C. is 7.6 to 12.4 mm 2 / s; the cosmetic grade white oil meets the index requirements of 10# cosmetic grade white oil in SH0007-2015 standard.

[0054] Compared with the prior art, the present invention has at least the following beneficial effects:

[0055] (1) The preparation method of the cosmetic-grade white oil provided by the present invention has low cost, simple process, and low requirements on the sulfur content and nitrogen content in the raw oil. The finally obtained cosmetic-grade white oil has low viscosity, high quality, and high commercial value;

[0056] (2) The method for preparing cosmetic-grade white oil provided by the present invention only requires changing the catalyst grading scheme of the original reactor or adding a supplementary refining reactor, without adding a circulating hydrogen system, which is conducive to the upgrading and transformation of production enterprises and is suitable for large-scale promotion and application. DETAILED DESCRIPTION

[0057] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0058] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0059] The preparation method of the hydrodecondensation catalyst in the following examples comprises the following steps:

[0060] Weigh the pore volume of 1.095mL / g and the specific surface area of ​​328m produced by aluminum sulfate method respectively. 2 / g, 500g of pseudo-boehmite with a dry basis of 71%, 18.4g of nitric acid with a concentration of 65%, 10g of sesbania powder, 89g of starch, 43.7g of copper nitrate trihydrate auxiliary agent and 754g of deionized water were added into a roller and rolled and mixed, and extruded into cylindrical strips with an outer diameter of 6mm and an inner hollow diameter of 2.5mm, and the strips were dried to a solid content of 65% under constant humidity and temperature conditions.

[0061] A punching device is used to punch evenly arranged circular through holes with a diameter of 1.5 mm on the surface of the cylindrical strip, and particles with a length of 3 mm to 10 mm are made. After drying at 130° C. for 8 hours, the particles are calcined at 900° C. for 3 hours to obtain a carrier support.

[0062] 15.53 g of aluminum sulfate, 663 g of silica sol containing 30% silicon oxide, 4.45 g of sodium hydroxide, 3.75 g of triethylamine and 165.6 g of water were weighed respectively to prepare a ZSM-5 molecular sieve mother liquor; half of the prepared molecular sieve mother liquor was used to impregnate the above-mentioned carrier support, the impregnated material was placed on the upper part of a gas phase reactor, deionized water was added to the bottom of the gas phase reactor, and the reaction was carried out at 180°C for 36 hours. After the reaction was completed, the material was washed with deionized water to neutrality, and dried at 130°C for 8 hours. The dried material was then impregnated with the remaining molecular sieve mother liquor, the impregnated material was placed on the upper part of a gas phase reactor, deionized water was added to the bottom of the gas phase reactor, and the reaction was carried out at 180°C for 36 hours. After the reaction was completed, the material was washed with deionized water to neutrality, and dried at 130°C for 8 hours. Then, it was calcined at 550°C for 3 hours to obtain a catalyst carrier containing a ZSM-5 molecular sieve membrane.

[0063] 50.4 g of nickel nitrate and 83.3 g of ammonium metatungstate were weighed separately to prepare a mixed solution containing 0.043 g / mL of nickel oxide and 0.128 g / mL of tungsten trioxide, and the above catalyst carrier was impregnated. After the impregnation, the material was dried at 120°C for 8 h and calcined at 450°C for 3 h to obtain a hydrodecondensation catalyst.

[0064] The preparation method of the supplementary refined catalyst in the following examples comprises the following steps:

[0065] The pore volume produced by aluminum sulfate method was 1.095 mL / g, and the specific surface area was 328 m 2 / g pseudo-boehmite 500g (dry basis 71%), nitric acid 18.4g (65%), sesbania powder 10g and deionized water 694g were added to a roller mill for rolling and mixing, extruded into strips, dried at 120°C for 10 hours, and then calcined at 750°C for 3 hours to obtain a clover-shaped catalyst carrier for standby use. The carrier properties are pore volume 0.757mL / g, specific surface area 235m 2 / g water absorption: 0.90mL / g.

[0066] 90 mL of calcium nitrate solution containing 0.02 g / mL of calcium oxide was prepared, 100 g of the above carrier was weighed and impregnated therein, and dried at 140° C. for 8 hours. After drying, the water absorption rate of the calcium-containing carrier was 88 mL / g.

[0067] The catalyst composition is MoO322%, NiO3.5%, P2.0%, and Mo-Ni-P solution is prepared based on the water absorption of the calcium-containing carrier for standby use, wherein the MoO3 concentration is 0.344 g / mL, the NiO concentration is 0.055 g / mL, and the P concentration is 0.031 g / mL;

[0068] The volume ratio of the pre-prepared catalyst Mo-Ni catalyst in the catalyst is 40%. 35.2 mL of the above solution was measured, and after starting the stirring, 26.5 g of isooctane (density 0.6919), 5.0 g of polyoxyethylene glycol octylphenyl ether (density 1.06), and 8.0 g of n-pentanol (density 0.82) were added respectively, and after mixing evenly, the mixture was stirred for 50 min to obtain 88 mL of oil-in-water type microemulsion with a particle size of <6 nm;

[0069] Weigh 100 g of the calcium-containing carrier, impregnate the carrier with 88 mL of the microemulsion, dry at 120° C. for 8 hours, and then calcine at 450° C. for 3 hours to obtain a catalyst semi-finished product with the following properties: pore volume 0.655 mL / g, water absorption 0.67 mL / g.

[0070] The catalyst composition is WO332%, NiO5.5%, and W-Ni solution is prepared based on the water absorption rate of the carrier for use, wherein the WO3 concentration is 0.582g / mL and the NiO concentration is 0.10g / mL;

[0071] The volume ratio of the pre-prepared catalyst W-Ni catalyst in the catalyst is 60%. 52.8 mL of W-Ni solution is taken to impregnate the above-mentioned semi-finished catalyst, dried at 120° C. for 10 hours, and then calcined at 500° C. for 3 hours to obtain a supplementary refined catalyst.

[0072] Example 1

[0073] This embodiment provides a method for preparing cosmetic-grade white oil, the preparation method comprising the following steps:

[0074] (1) After the hydrogenated reformed diesel is mixed with hydrogen, a first catalytic reaction and a second catalytic reaction are sequentially carried out to obtain a reaction product; the first catalytic reaction and the second catalytic reaction are carried out in a hydrogenation experimental device produced by Mairui Experimental Equipment Co., Ltd.; the catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfide catalysts; the catalyst used in the second catalytic reaction is a supplementary refined catalyst; the mass percentage of each component in the supplementary refined catalyst is NiO: 5%, WO3: 22%, MoO3: 9%; the second metal oxide additive is P: 1.2% and the carrier: 62.8%; the carrier is γ-Al2O3 containing SiO2 with a mass percentage of 9%, a pore volume of 0.421 mL / g, and a specific surface area of ​​192 m 2 / g;

[0075] The catalyst used in the first catalytic reaction is a hydrodegassing catalyst; the mass percentages of the components in the hydrodegassing catalyst are respectively NiO: 1.92%, WO311.32%, metal oxide additive: 1.76% and molecular sieve: 35.4%; the loading amount of the two catalysts is 200 mL, and the new hydrogen passes through once;

[0076] The first catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 290°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 1.0 h -1 ;

[0077] The second catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 320°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 0.5 h -1 ;

[0078] (2) The reaction product is sequentially subjected to a first separation at a pressure of 15 MPa, a second separation at a pressure of 0.3 MPa, and distillation, and the fraction with a temperature ≥ 280°C is the cosmetic grade white oil.

[0079] Example 2

[0080] This embodiment provides a method for preparing cosmetic-grade white oil. The hydrodegradation catalyst and supplementary refining catalyst used are the same as those in Example 1. The preparation method comprises the following steps:

[0081] (1) After the hydrogenated reformed diesel is mixed with hydrogen, a first catalytic reaction and a second catalytic reaction are sequentially performed to obtain a reaction product; the first catalytic reaction and the second catalytic reaction are performed in a hydrogenation experimental device produced by Mairui Experimental Equipment Co., Ltd.; the catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfurized catalysts; the catalyst used in the second catalytic reaction is a supplementary refined catalyst; the catalyst used in the first catalytic reaction is a hydrodegassing catalyst; the loading amount of the two catalysts is 200 mL, and the new hydrogen passes through once;

[0082] The first catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 290°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 1.0 h -1 ;

[0083] The second catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 320°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 0.4 h -1 ;

[0084] (2) The reaction product is sequentially subjected to a first separation at a pressure of 15 MPa, a second separation at a pressure of 0.3 MPa, and distillation, and the fraction with a temperature ≥ 280°C is the cosmetic grade white oil.

[0085] Example 3

[0086] This embodiment provides a method for preparing cosmetic-grade white oil. The hydrodegradation catalyst and supplementary refining catalyst used are the same as those in Example 1. The preparation method comprises the following steps:

[0087] (1) After 60N lubricating oil base oil is mixed with hydrogen, a first catalytic reaction and a second catalytic reaction are sequentially performed to obtain a reaction product; the first catalytic reaction and the second catalytic reaction are performed in a hydrogenation experimental device produced by Mairui Experimental Equipment Co., Ltd.; the catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfurized catalysts; the catalyst used in the second catalytic reaction is a supplementary refined catalyst; the catalyst used in the first catalytic reaction is a hydrodegassing catalyst; the loading amount of the two catalysts is 200 mL, and the new hydrogen passes through once;

[0088] The first catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 290°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 1.0 h -1 ;

[0089] The second catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 310°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 0.5 h -1 ;

[0090] (2) The reaction product is sequentially subjected to a first separation at a pressure of 15 MPa, a second separation at a pressure of 0.3 MPa, and distillation, and the fraction with a temperature ≥ 280°C is the cosmetic grade white oil.

[0091] Example 4

[0092] This embodiment provides a method for preparing cosmetic-grade white oil. The hydrodegradation catalyst and supplementary refining catalyst used are the same as those in Example 1. The preparation method comprises the following steps:

[0093] (1) A lubricating oil base oil obtained by hydrodeacidification-furfural clay refining of a conventional second-line distillate oil, named as 3# raw material, is mixed with hydrogen and subjected to a first catalytic reaction and a second catalytic reaction in sequence to obtain a reaction product; the first catalytic reaction and the second catalytic reaction are carried out in a hydrogenation experimental device produced by Mairui Experimental Equipment Co., Ltd.; the catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfurized catalysts; the catalyst used in the second catalytic reaction is a supplementary refining catalyst; the catalyst used in the first catalytic reaction is a hydrodegassing catalyst; the loading amount of the two catalysts is 200 mL, and new hydrogen passes through once;

[0094] The first catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 290°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 1.0 h -1 ;

[0095] The second catalytic reaction was carried out at a pressure of 15 MPa, a temperature of 310°C, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 0.4 h -1 ;

[0096] (2) The reaction product is sequentially subjected to a first separation at a pressure of 15 MPa, a second separation at a pressure of 0.3 MPa, and distillation, and the fraction with a temperature ≥ 280°C is the cosmetic grade white oil.

[0097] Example 5

[0098] This embodiment provides a method for preparing cosmetic-grade white oil. The preparation method is the same as that of Embodiment 1 except that the mass percentage of WO3 in the supplementary refining catalyst is 12%.

[0099] Example 6

[0100] This embodiment provides a method for preparing cosmetic-grade white oil. The preparation method is the same as that of Embodiment 1 except that the mass percentage of WO3 in the supplementary refining catalyst is 40%.

[0101] Comparative Example 1

[0102] This comparative example provides a method for preparing cosmetic-grade white oil, which is the same as Example 1 except that the supplementary refining catalyst is replaced by a commercially available high-nickel catalyst.

[0103] The mass percentage of each component in the commercially available high-nickel catalyst is NiO: 0.11%, Ni: 43.4%, the pore volume is 0.34mL / g, and the specific surface area is 158m 2 / g.

[0104] Comparative Example 2

[0105] This comparative example provides a method for preparing cosmetic-grade white oil, which is the same as Example 1 except that the carrier in the supplementary refined catalyst is γ-Al2O3 containing 0.2% by mass of SiO2.

[0106] Comparative Example 3

[0107] This comparative example provides a method for preparing cosmetic-grade white oil. The preparation method is the same as Example 1 except that the carrier in the supplementary refined catalyst is γ-Al2O3 containing 30% by mass of SiO2.

[0108] The composition and properties of the raw material oil in the above examples and comparative examples are shown in Table 1.

[0109] Table 1

[0110]

[0111] The 20°C density, 40°C kinematic viscosity and ultraviolet absorbance of polycyclic aromatic hydrocarbons at a wavelength of 260-420 mm of the cosmetic-grade white oils obtained in the above examples and comparative examples are shown in Table 2.

[0112] Table 2

[0113]

[0114] From Table 2 we can see that:

[0115] (1) It can be seen from Examples 1 to 6 that the cosmetic-grade white oil finally obtained by the preparation method of the cosmetic-grade white oil provided by the present invention has low viscosity and high quality, meets the index requirements of 10# cosmetic-grade white oil in SH0007-2015, and has high commercial value;

[0116] (2) Combining Example 1 with Examples 5 to 6, it can be seen that the mass percentage of the Group VIB metal oxide WO3 in Example 5 is relatively low, and the ultraviolet absorbance of the polycyclic aromatic hydrocarbons is increased to 0.550 cm; the mass percentage of the Group VIB metal oxide WO3 in Example 65 is relatively high, and the ultraviolet absorbance of the polycyclic aromatic hydrocarbons is relatively low, only 0.035 cm, and the performance of the cosmetic grade white oil is better, but the cost of the supplementary refining catalyst is greatly increased; this shows that the present invention limits the content of the Group VIB metal oxide in the supplementary refining catalyst to a specific range, and can obtain a cosmetic grade white oil with better quality, and can also make the cost of the supplementary refining catalyst lower;

[0117] (3) From the perspective of Example 1 and Comparative Example 1, it can be seen that the quality of the cosmetic-grade white oil finally obtained by the preparation method of the cosmetic-grade white oil provided by the present invention in Example 1 is comparable to that of the cosmetic-grade white oil obtained by the expensive commercially available high-nickel catalyst in Comparative Example 1, and the preparation cost of the present invention is lower.

[0118] (4) It can be seen from Example 1 and Comparative Examples 2 to 3 that the mass percentage of SiO2 in the carrier of the supplementary refining catalyst of Comparative Example 2 is relatively low, and the cosmetic-grade white oil with a satisfactory aromatic content cannot be obtained; the mass percentage of SiO2 in the carrier of the supplementary refining catalyst of Comparative Example 3 is relatively high, and the yield of the cosmetic-grade white oil product is significantly reduced, affecting the overall economic benefits; this shows that the present invention limits the mass percentage of SiO2 in the carrier of the supplementary refining catalyst to a specific range, and obtains a cosmetic-grade white oil with high quality and high yield.

[0119] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing cosmetic grade white oil, characterized in that: The preparation method comprises the following steps: (1) After the feedstock oil and hydrogen are mixed, a first catalytic reaction and a second catalytic reaction are sequentially performed to obtain a reaction product; The raw material oil is a 60N lubricating oil base oil or a lubricating oil base oil obtained by hydrodeacidification-furfural white clay refining of a conventional second-line distillate oil; The pressure of the first catalytic reaction is 12.0-18.0 MPa; the temperature of the first catalytic reaction is 280-300°C; the hydrogen-oil volume ratio of the first catalytic reaction is 500:1; the volume space velocity of the first catalytic reaction is 0.8-1.5 h -1 ; The pressure of the second catalytic reaction is 12.0-18.0 MPa; the temperature of the second catalytic reaction is 300-320°C; the hydrogen-oil volume ratio of the second catalytic reaction is 500:1; the volume space velocity of the second catalytic reaction is 0.3-0.5 h -1 ; The catalysts used in the first catalytic reaction and the second catalytic reaction are both non-precious metal sulfided catalysts; The catalyst used in the second catalytic reaction includes a supplementary refined catalyst; the carrier of the supplementary refined catalyst includes γ-Al2O3 containing 0.5% to 20% by mass of SiO2; (2) the reaction product is subjected to gas-liquid separation and distillation in sequence to obtain the cosmetic grade white oil; The gas-liquid separation includes a first separation and a second separation; the pressure of the first separation is 12-16 MPa; the pressure of the second separation is 0.1-0.6 MPa; The kinematic viscosity of the cosmetic grade white oil at 40°C is 9 to 10 mm 2 / s; the ultraviolet absorbance of the polycyclic aromatic hydrocarbons in the cosmetic-grade white oil at a wavelength of 260 to 420 mm is 0.051 to 0.062 cm.

2. The preparation method according to claim 1, characterized in that: The catalyst used in the first catalytic reaction in step (1) includes a hydrodecondensation catalyst.

3. The preparation method according to claim 2, characterized in that: The hydrodegradation catalyst comprises a first active metal oxide, a first metal oxide promoter and a first carrier.

4. The preparation method according to claim 3, characterized in that: The first active metal oxide comprises Group VIII and / or Group VIB metal oxides.

5. The preparation method according to claim 4, characterized in that: The first active metal oxide includes NiO and / or WO3.

6. The preparation method according to claim 3, characterized in that: The first support comprises a molecular sieve.

7. The preparation method according to claim 3, characterized in that: The mass percentage of each component in the hydrodecondensation catalyst is respectively NiO: 1.0-6.0%, WO3: 0-15%, metal oxide auxiliary agent: 1.0%-5.4% and molecular sieve: 8-40%.

8. The preparation method according to claim 1, characterized in that: The supplementary refined catalyst in step (1) further comprises a second active metal oxide and a second metal oxide promoter.

9. The preparation method according to claim 8, characterized in that: The second active metal oxide comprises a Group VIII and / or Group VIB metal oxide.

10. The preparation method according to claim 9, characterized in that: The second active metal oxide is any one of WO3, MoO3, CoO or NiO, or a combination of at least two thereof.

11. The preparation method according to claim 8, characterized in that: The second metal oxide additive includes any one of P, F, B, Ti or Zr or a combination of at least two thereof.

12. The preparation method according to claim 8, characterized in that: The mass percentages of the components in the supplementary refined catalyst are respectively 15-35% of Group VIB metal oxide, 4.0-10.0% of Group VIII metal oxide, 1.0-10% of the second metal oxide additive and 50-80% of the carrier.

13. The preparation method according to claim 1, characterized in that: The fraction with a temperature of ≥280° C. in the distillation of step (2) is the cosmetic grade white oil.

14. The preparation method according to claim 1, characterized in that: The cosmetic grade white oil in step (2) meets the index requirements of 10# cosmetic grade white oil in the SH0007-2015 standard.

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