Isoparaffin solvent oil and preparation method thereof

Abstract

The invention provides isoparaffin solvent oil and a preparation method thereof.The preparation method comprises the steps that firstly, coal-based Fischer-Tropsch hydrofined oil with the distillation range of 170-340 DEG C is sequentially subjected to hydroisomerization and finishing, and a hydroisomerization-refined product is obtained; and carrying out normal-pressure rectification cutting on the hydroisomerization-refining product to obtain the isoparaffin solvent oil. The hydroisomerization catalyst is prepared by using the preparation method provided by the invention, the hydroisomerization catalyst has proper acidity and a proper micropore-mesopore ratio, and under the synergistic effect of the acidic site, the proper micropore-mesopore ratio and the loaded metal ions, the hydroisomerization effect of the hydroisomerization catalyst is improved. The catalyst can realize high-selectivity isomerization of the Fischer-Tropsch hydrofined oil in the distillation range, and can be smoothly desorbed from the catalyst after isomerization, so that re-cracking is effectively avoided to generate non-target fraction impurities. The preparation method is simple in process and low in cost, and opens up a new way for high-value utilization of the coal-based Fischer-Tropsch synthetic oil.

Description

Technical Field

[0001] The invention relates to the field of coal chemical industry, and in particular to an isoparaffin solvent oil and a preparation method thereof. Background Art

[0002] Isoparaffin solvent oil is widely used and can be used as a solvent for coatings, an auxiliary solvent for organic synthesis, an emulsifier for pesticides, an organic solvent, etc. Traditional solvent oil production mainly uses isobutane and olefins as raw materials, and obtains isoparaffin solvent oil through alkylation reaction, hydrogenation and distillation. This method can generally obtain isoparaffin solvent oil in the gasoline fraction range (30-180°C), but it is difficult to produce isoparaffin solvent oil in the kerosene or diesel fraction range (150-350°C).

[0003] Some of the prior art uses a raw material containing C8-C20 mainly normal alkanes, such as Fischer-Tropsch synthetic oil, to prepare a light white oil with an isoparaffin content of more than 50% by hydrogenation isomerization. The low-temperature performance and viscosity of the prepared light white oil are significantly improved. The Fischer-Tropsch synthetic oil in this method has a low olefin component content. There is also a prior art that uses distillate oil or light deoiling as a raw material and adopts a combined process of hydrotreatment-hydroisomerization-hydrogenation supplementary refining to produce isomerized light white oil. The yield of light isoparaffin fraction is more than 60%. However, the isoparaffin solvent oil products obtained by these methods are single, low in isoparaffin content, and poor in indicators such as pour point.

[0004] Coal-based Fischer-Tropsch hydrorefined oil is a by-product of the coal refining industry. It has the characteristics of low aromatic content, high saturated hydrocarbon content, high alkane and olefin content, high dry point, high hydrogen-to-carbon ratio, and low sulfur and nitrogen content. Therefore, it can be used as an important raw material oil for the production of solvent oil. However, FTS oil is mainly composed of normal alkanes and normal olefins, while solvent oil is mainly composed of aromatics and isoparaffins. The aromatic content and isoparaffin content of FTS oil are relatively low, so it is usually not easy to convert into isoparaffin solvent oil.

[0005] Therefore, the present invention is proposed to prepare isoparaffin solvent oil with high isoparaffin content and better pour point and other indicators by using coal-based Fischer-Tropsch hydrorefined oil as raw material. Summary of the invention

[0006] The main purpose of the present invention is to provide an isoparaffin solvent oil and a preparation method thereof, so as to solve the problems in the prior art that it is impossible to achieve efficient conversion of coal-based Fischer-Tropsch hydrorefined oil into isoparaffin solvent oil, and the prepared isoparaffin solvent oil has poor isoparaffin performance, insufficient pour point index and single isoparaffin solvent oil component.

[0007] In order to solve the above problems, the present invention provides a preparation method of isoparaffin solvent oil, which comprises: sequentially performing hydroisomerization and supplementary refining on coal-based Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340° C. to obtain a hydroisomerization-refined product; performing atmospheric distillation cutting on the hydroisomerization-refined product to obtain the isoparaffin solvent oil; wherein the hydroisomerization is performed under the catalytic action of a hydroisomerization catalyst, and the hydroisomerization catalyst is prepared by the following method: mixing a molecular sieve, an amine compound, and an alkali source and performing a hydrothermal reaction to obtain a hydrothermal product; the amine compound is one or more of an organic amine, a quaternary ammonium salt, and an amine salt; performing a first drying and a first roasting on the hydrothermal product to obtain a modified molecular sieve; mixing the modified molecular sieve with a first binder and water, adding a first acid solution to knead, standing, and performing a second drying and a second roasting to obtain a molded molecular sieve; after impregnating the molded molecular sieve in a first metal impregnation solution, sequentially performing a third drying and a third roasting to obtain a hydroisomerization catalyst.

[0008] Furthermore, in the preparation process of the hydroisomerization catalyst, the weight ratio of the molecular sieve, the amine compound and the alkali source is (25-50):1:(5-20); and / or the concentration of the alkali source is 0.05-2 mol / L; and / or the amine compound is selected from one or more of 1,6-hexanediamine, ethylenediamine, triethylamine, isopropylamine, 1,6-ethylpyridinium bromide, N-ethylpyridine, imidazole diquaternary ammonium salt, pyrrolidine, dimethylformamide, hexamethylammonium bromide and hexamethylammonium chloride; and / or the molecular sieve is a one-dimensional ten-membered ring structure molecular sieve, preferably the molecular sieve is one or more of ZSM-22 molecular sieve, ZSM-23 molecular sieve and ZSM-48 molecular sieve; and / or the alkali source is an aqueous solution of one or more of ammonia, sodium hydroxide and sodium carbonate.

[0009] Further, the molecular sieve is a ZSM-22 molecular sieve, and the amine compound is selected from one or more of 1,6-hexanediamine, ethylenediamine, 1,6-ethylpyridinium bromide, N-ethylpyridine and imidazole diquaternary ammonium salts; or, the molecular sieve is a ZSM-23 molecular sieve, and the amine compound is selected from one or more of pyrrolidine, isopropylamine and dimethylformamide; or, the molecular sieve is a ZSM-48 molecular sieve, and the amine compound is selected from one or more of hexamethylammonium bromide, hexamethylammonium chloride, 1,6-hexanediamine and triethylamine; preferably, the silicon-aluminum ratio of the ZSM-22 molecular sieve is 40-130, the silicon-aluminum ratio of the ZSM-23 molecular sieve is 40-150, and the silicon-aluminum ratio of the ZSM-48 molecular sieve is 80-300.

[0010] Furthermore, in the preparation process of the hydroisomerization catalyst, the temperature of the hydrothermal reaction is 60-100° C., and the reaction time is 0.5-2 h; and / or, after the hydrothermal reaction is completed, the hydrothermal product is first washed to neutrality, and then subjected to the first drying and the first calcination; more preferably, the washing is performed by centrifugal washing or filtration washing; and / or, the temperatures of the first drying, the second drying and the third drying are 80-120° C., respectively, and the times are 3-5 h, respectively, and the temperatures of the first calcination, the second calcination and the third calcination are 450-600° C., respectively, and the times are 8-12 h, respectively.

[0011] Furthermore, in the preparation process of the hydroisomerization catalyst, the first binder is selected from pseudo-boehmite and / or alumina; preferably, the first auxiliary agent is added during the mixing process of the modified molecular sieve, the first binder and water, and the first auxiliary agent is one or more of sesbania powder, starch and methyl cellulose; preferably, the first acid solution is one or more of nitric acid, phosphoric acid, hydrochloric acid and citric acid; preferably, the mass concentration of the first acid solution is 2-5%; preferably, the mass ratio of the added amount of the first acid solution to the first binder is 1:(7.5-10); preferably, the modified molecular sieve, the first binder and the first auxiliary agent are added to the first binder. The weight ratio of the modified molecular sieve to the first binder is (12-15):(7.5-10):1; preferably, the amount of water added is 50-60% of the sum of the weight of the modified molecular sieve and the first binder; preferably, the standing time is 3-5h; preferably, the metal type of the first metal impregnation solution is one or more of Pt, Pd, Ni, Ce, Zn, W, Mg, and Fe; the weight content of the modified molecular sieve in the hydroisomerization catalyst is 60-80%, and the weight loading of the metal is 0.3-1%, more preferably 0.3-0.6%; preferably, the specific surface area of ​​the hydroisomerization catalyst is 150-300m 2 / g, mechanical strength 10-15N / mm, total acid content 0.3-0.5mmol / g, weak acid proportion ≥60%, pore volume 0.3-0.5mL / g.

[0012] Further, the supplementary refining is carried out under the action of a supplementary refining catalyst, and the supplementary refining catalyst is prepared by the following method: using alumina as a carrier, mixing it with a second binder, and then adding a second acid solution and water to knead to obtain a modified carrier; after the modified carrier is impregnated in a second metal impregnation solution, a fourth drying and a fourth calcination are carried out in sequence to obtain a supplementary refining catalyst; preferably, the alumina is a mixture of γ-alumina and macroporous alumina, and more preferably the weight ratio of the two is (2-5):1; preferably, the second binder is SB powder; preferably, the second acid solution is nitric acid; preferably, the mass concentration of the second acid solution is 2-5%; preferably, the weight ratio of the added amount of the second acid solution to the second binder is 1:(7.5-10); preferably, In the process of mixing alumina with the second binder, a second auxiliary agent is also added, and the second auxiliary agent is sesbania powder and / or starch; preferably, the weight ratio of alumina, the second binder and the second auxiliary agent is (20-30):(3-5):1; preferably, the amount of water added is 60-70% of the sum of the weight of the carrier and the second binder; preferably, the temperature of the fourth drying is 80-100°C, the time is 3-6h, and the temperature of the fourth calcination is 400-500°C, and the time is 3-6h; preferably, the metal in the second metal impregnation solution is one or more of Pt, Pd, Ni and W; preferably, the metal weight loading of the supplementary refined catalyst is 0.3-0.5%; preferably, the specific surface area of ​​the supplementary refined catalyst is 150-300m 2 / g, the mechanical strength is 12-15N / mm, and the pore volume is 0.3-0.5mL / g; preferably, the ratio of mesopores to non-mesopores in the hydroisomerization catalyst is (15-40):(60-85).

[0013] Furthermore, the saturated hydrocarbon content of the Fischer-Tropsch hydrorefined oil is ≥ 99%.

[0014] Furthermore, the hydroisomerization and supplementary refining are carried out in a trickle bed reactor, which is provided with a hydroisomerization bed and a supplementary refining bed from top to bottom, the hydroisomerization bed is filled with a hydroisomerization catalyst, and the supplementary refining bed is filled with a supplementary refining catalyst. The gas-liquid mixture of Fischer-Tropsch hydrorefined oil and hydrogen enters from the upper part of the trickle bed reactor and passes through the hydroisomerization bed and the supplementary refining bed in sequence to carry out hydroisomerization and supplementary refining in sequence; preferably, the ratio of the loading amount of the hydroisomerization catalyst to the loading amount of the supplementary refining catalyst is (1-3):1; preferably, the temperature of the hydroisomerization bed is 220-320°C, preferably 240-300°C, and the temperature of the supplementary refining bed is 220-300°C, preferably 220-280°C; preferably, the volumetric space velocity of the gas-liquid mixture in the trickle bed reactor is 0.5-5h -1 , preferably 1 to 3 hours -1; The volume ratio of hydrogen to oil in the gas-liquid mixture is (500-1500):1, preferably (600-1000):1; the hydrogen partial pressure is 1-6MPa, preferably 2-5MPa.

[0015] Furthermore, during the atmospheric distillation process, isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 are cut to form.

[0016] According to another aspect of the present invention, there is also provided an isoparaffin solvent oil, which is prepared by the above-mentioned preparation method.

[0017] The present invention provides an isoparaffin solvent oil and a preparation method thereof, the preparation method comprising: firstly, sequentially performing hydroisomerization and supplementary refining on a coal-based Fischer-Tropsch hydrorefined oil having a distillation range of 170 to 340°C to obtain a hydroisomerization-refined product; and subjecting the hydroisomerization-refined product to atmospheric distillation cutting to obtain the isoparaffin solvent oil. The hydroisomerization catalyst and the supplementary refining catalyst are both prepared using the preparation method of the present invention, in particular, the hydroisomerization catalyst prepared by the present invention not only has suitable acidity, but also has a suitable micropore-mesopore ratio. Under the synergistic effect of the acidic site, the loaded metal and the suitable micropore-mesopore ratio, the obtained hydroisomerization catalyst can achieve high-selective isomerization for the Fischer-Tropsch hydrorefined oil having a distillation range of 170 to 340°C, and at the same time, it can ensure that it can be smoothly desorbed from the catalyst after isomerization, and can effectively avoid cracking again to generate non-target fraction impurities. In addition, the hydroisomerization catalyst and supplementary refining catalyst prepared by this method have simple preparation process, low cost, and are easy to industrialize, which opens up a new way for the high-value utilization of coal-based Fischer-Tropsch synthetic oil. At the same time, it also reduces the dependence on fossil fuels in the preparation of isoparaffin solvent oil, and provides strong technical support for the realization of green chemical production. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0019] Figure 1 The production process flow chart of preparing isoparaffin solvent oil according to the present invention is shown;

[0020] Figure 2 A schematic diagram of a hydroisomerization-supplementary refining reactor is shown; the above-mentioned figure includes the following figure marks: 1. upper buffer zone; 2. upper gas-liquid distributor; 3. hydroisomerization catalyst zone; 4. first catalyst support zone; 5. lower buffer zone; 6. lower gas-liquid distributor; 7. supplementary refining catalyst zone; 8. second catalyst support zone. DETAILED DESCRIPTION

[0021] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0022] As described in the background technology section of the present invention, Fischer-Tropsch hydrorefined oil is a by-product of the coal refining industry, and has the characteristics of low aromatic content, high saturated hydrocarbon content, high alkane and olefin content, high dry point, high hydrogen-to-carbon ratio, and low sulfur and nitrogen content, and can be used as a feedstock oil for producing solvent oil. However, it is difficult to achieve efficient conversion of Fischer-Tropsch hydrorefined oil to isoparaffin solvent oil in the prior art, and the isoparaffins in the isoparaffin solvent oil prepared from Fischer-Tropsch hydrorefined oil have poor performance, insufficient pour point index, and a single component of isoparaffin solvent oil.

[0023] In order to solve this problem, the present invention provides a method for preparing isoparaffin solvent oil, and its process flow chart is as follows: Figure 1 As shown, it includes: sequentially performing hydroisomerization and supplementary refining on Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340° C. to obtain a hydroisomerization-refined product; performing atmospheric distillation cutting on the hydroisomerization-refined product to obtain an isoparaffin solvent oil; wherein the hydroisomerization is performed under the catalytic action of a hydroisomerization catalyst, and the hydroisomerization catalyst is prepared by the following method: mixing a molecular sieve, an amine compound, and an alkali source and performing a hydrothermal reaction to obtain a hydrothermal product; the amine compound is one or more of an organic amine, a quaternary ammonium salt, and an amine salt; performing a first drying and a first roasting on the hydrothermal product to obtain a modified molecular sieve; mixing the modified molecular sieve with a first binder and water, adding a first acid solution to knead, standing, and performing a second drying and a second roasting to obtain a molded molecular sieve; after impregnating the molded molecular sieve in a first metal impregnation solution, sequentially performing a third drying and a third roasting to obtain a hydroisomerization catalyst.

[0024] The present application uses Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340° C. as a starting raw material, and utilizes a prepared hydroisomerization catalyst having a specific catalytic effect on the Fischer-Tropsch hydrorefined oil to catalyze the hydroisomerization reaction, thereby greatly improving the isomerization efficiency and conversion rate. Combined with subsequent supplementary refining and atmospheric distillation cutting treatment, high-quality isoparaffin solvent oil with high isoparaffin content, low aromatic content, low pour point, low sulfur and low odor is obtained. The isoparaffin solvent oil is suitable for a variety of industrial applications, such as paints, coatings, adhesives, cleaning agents, etc., and due to its environmentally friendly characteristics, it can effectively reduce pollution to the environment and improve the safety and efficiency of industrial production.

[0025] In the preparation method of the above-mentioned specific hydroisomerization catalyst, the molecular sieve is first modified by a hydrothermal reaction using a specific amine compound and an alkali source, wherein the addition of the amine compound can control the amount of desiliconization during the preparation of the molecular sieve, and avoid excessive desiliconization of the catalyst during the alkali treatment process, thereby causing the skeleton to collapse. The amine compound, the alkali source and the molecular sieve are mixed and subjected to a hydrothermal product formed by hydrothermal treatment, and then dried and calcined to obtain a modified molecular sieve, which has a large specific surface area and an appropriate micropore-mesoporous ratio, which is conducive to subsequent metal loading, and the obtained hydroisomerization catalyst will also have better catalytic and diffusion performance during the catalytic process, further improving the target product yield. Then the obtained modified molecular sieve is mixed with the first binder, water and acid solution and kneaded to form a molded molecular sieve carrier with a certain mechanical strength for loading the first metal. In the process of impregnation with metal impregnation solution, the formed molecular sieve carrier has excellent metal adsorption and fixation performance due to the above-mentioned modification operation. After the metal loading process is completed, the obtained hydroisomerization catalyst is not only suitable in acidity, but also has suitable pores. Under the synergistic effect of acid sites, loaded metals and suitable micropore-mesopore ratio, the Fischer-Tropsch hydrorefined oil can achieve high-selective isomerization, and at the same time, it can ensure that it can be smoothly desorbed from the catalyst after isomerization, and can effectively avoid cracking again to generate non-target fraction impurities. Under the action of preparing specific catalysts, the high catalytic activity, selectivity and stability of the isomerization reaction are guaranteed, and it has the isomerization ability suitable for Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340°C, so that the Fischer-Tropsch hydrorefined oil can be efficiently and high-yield converted into high-quality isoparaffin solvent oil. At the same time, it is precisely because of the use of the above-mentioned specific hydroisomerization catalyst that the preparation process of the isoparaffin solvent oil of the present invention is relatively simple and easy to operate. High-quality isoparaffin solvent oil of different fractions can be obtained only through hydroisomerization, supplementary refining and atmospheric distillation cutting. In addition, the process conditions such as reaction temperature and pressure during the operation are also relatively milder, providing a more economical and efficient solution for industrial production.

[0026] In a preferred embodiment, during the preparation of the hydroisomerization catalyst, the weight ratio of the molecular sieve, the amine compound and the alkali source is (25-50):1:(5-20); and / or the concentration of the alkali source is 0.05-2 mol / L; and / or the amine compound is selected from one or more of 1,6-hexanediamine, ethylenediamine, triethylamine, isopropylamine, 1,6-ethylpyridinium bromide, N-ethylpyridine, imidazole diquaternary ammonium salts, pyrrolidine, dimethylformamide, hexamethylammonium bromide and hexamethylammonium chloride; and / or the molecular sieve is a one-dimensional ten-membered ring structure molecular sieve, preferably the molecular sieve is one or more of ZSM-22 molecular sieve, ZSM-23 molecular sieve and ZSM-48 molecular sieve; and / or the alkali source is an aqueous solution of one or more of ammonia, sodium hydroxide and sodium carbonate. By modifying the molecular sieve with amine compounds and bases, the modified molecular sieve carrier can have suitable acid properties and a suitable micropore-mesopore ratio structure. By optimizing the ratio of amine compounds and alkali sources and the type of molecular sieves in the catalyst preparation process, the obtained hydroisomerization catalyst can have better selectivity for Fischer-Tropsch hydrorefined oil raw materials, and can further improve the activity and stability of the catalyst, thereby obtaining higher conversion rate and selectivity in the hydroisomerization reaction, which is suitable for large-scale industrial production.

[0027] In a preferred embodiment, the molecular sieve is a ZSM-22 molecular sieve, and the amine compound is selected from one or more of 1,6-hexanediamine, ethylenediamine, 1,6-ethylpyridinium bromide, N-ethylpyridine and imidazole diquaternary ammonium salts; or, the molecular sieve is a ZSM-23 molecular sieve, and the amine compound is selected from one or more of pyrrolidine, isopropylamine and dimethylformamide; or, the molecular sieve is a ZSM-48 molecular sieve, and the amine compound is selected from one or more of hexamethylammonium bromide, hexamethylammonium chloride, 1,6-hexanediamine and triethylamine; preferably, the silicon-aluminum ratio of the ZSM-22 molecular sieve is 40-130, the silicon-aluminum ratio of the ZSM-23 molecular sieve is 40-150, and the silicon-aluminum ratio of the ZSM-48 molecular sieve is 80-300. In the process of modifying molecular sieves with amine compounds, different amine compounds are selected and matched with molecular sieves with different silicon-aluminum ratios. This can make the acid sites, pore sizes and metal active components of the obtained hydroisomerization catalyst better matched with the Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340°C, further improve the specific catalytic function of the catalyst and achieve efficient conversion of the raw materials.

[0028] In a preferred embodiment, during the preparation of the hydroisomerization catalyst, the temperature of the hydrothermal reaction is 60-100°C, and the reaction time is 0.5-2h; and / or, after the hydrothermal reaction is completed, the hydrothermal product is first washed to neutrality, and then the first drying and the first calcination are performed; more preferably, the washing is performed by centrifugal washing or filtration washing; and / or, the temperatures of the first drying, the second drying, and the third drying are 80-120°C, respectively, and the time is 3-5h, respectively, and the temperatures of the first calcination, the second calcination, and the third calcination are 450-600°C, respectively, and the time is 8-12h. The hydrothermal reaction process is to allow the molecular sieve and the added amine compound and the base to fully react, so that the modified molecular sieve has a suitable acidity and micropore-mesopore ratio, and thus the catalyst has better specific catalytic activity. Accurately controlling the conditions of the hydrothermal reaction and subsequent drying and calcination treatment within the above range can further improve the above effect.

[0029] In a preferred embodiment, during the preparation of the hydroisomerization catalyst, the first binder is selected from pseudo-boehmite and / or alumina; preferably, the first auxiliary agent is added during the mixing of the modified molecular sieve, the first binder and water, and the first auxiliary agent is one or more of sesbania powder, starch and methyl cellulose; preferably, the first acid solution is one or more of nitric acid, phosphoric acid, hydrochloric acid and citric acid; preferably, the mass concentration of the first acid solution is 2-5%; preferably, the mass ratio of the first acid solution added to the first binder is 1:(7.5-10); preferably, the weight ratio of the modified molecular sieve, the first binder and the first auxiliary agent is (12-15):(7.5-10):1; preferably, the amount of water added is 50-60% of the sum of the weight of the modified molecular sieve and the first binder. Preferably, the standing time is 3-5h. In the process of preparing the formed molecular sieve, the above-mentioned binders and additives are selected and their dosage is controlled within the above-mentioned range, so that a catalyst with high specific surface area, good mechanical strength and suitable acidity can be prepared, and the catalytic performance of the catalyst in the hydroisomerization reaction can be further improved, wherein the standing still plays the role of standing aging. Preferably, the metal type of the first metal impregnation solution is one or more of Pt, Pd, Ni, Ce, Zn, W, Mg, and Fe; the weight content of the modified molecular sieve in the hydroisomerization catalyst is 60-80%, and the metal weight loading is 0.3-1%, more preferably 0.3-0.6%. Controlling the metal loading within the above-mentioned range can make the catalytic performance of the obtained catalyst better. Preferably, the specific surface area of ​​the hydroisomerization catalyst is 150-300m 2 / g, mechanical strength 10-15N / mm, total acid content 0.3-0.5mmol / g, weak acid proportion ≥60%, pore volume 0.3-0.5mL / g. The method for preparing a hydroisomerization catalyst according to the present invention can make the acid sites and active metals in the prepared catalyst better match, and at the same time control the specific surface area and pore volume of the catalyst within the above range, so that the hydroisomerization catalyst can have a better specific effect on the isoparaffin solvent oil in the range of kerosene or diesel fractions prepared from Fischer-Tropsch hydrorefined oil, and can significantly improve the yield and purity of the isoparaffin solvent oil during use. Preferably, the first metal impregnation solution is one or more of dichlorotetraammineplatinum aqueous solution, platinum chloride aqueous solution, palladium chloride aqueous solution, nickel nitrate aqueous solution, cerium nitrate aqueous solution, zinc nitrate aqueous solution, tungsten nitrate aqueous solution, magnesium nitrate aqueous solution and iron nitrate aqueous solution.

[0030] In a preferred embodiment, the supplementary refining is carried out under the action of a supplementary refining catalyst, and the supplementary refining catalyst is prepared by the following method: using alumina as a carrier, mixing it with a second binder, and then adding a second acid solution and water to knead to obtain a modified carrier; after the modified carrier is impregnated in a second metal impregnation solution, a fourth drying and a fourth calcination are carried out in sequence to obtain a supplementary refining catalyst. The supplementary refining catalyst prepared by the above preparation method can effectively improve the refining effect of the catalyst and remove impurities in the hydrogenation isomerization product. Preferably, the alumina is a mixture of γ-alumina and macroporous alumina, and more preferably the weight ratio of the two is (2 to 5): 1; preferably, the second binder is SB powder; preferably, the concentration of the second acid solution is 2 to 5%; preferably, the amount of the second acid solution added is 1: (7.5 to 10) of the weight ratio of the second binder; preferably, a second auxiliary agent is also added in the process of mixing the alumina and the second binder, and the second auxiliary agent is sesbania powder and / or starch; preferably, the weight ratio of alumina, the second binder and the second auxiliary agent is (20 to 3 0):(3-5):1; preferably, the amount of water added is 60-70% of the sum of the weight of the carrier and the second binder; preferably, the temperature of the fourth drying is 80-100°C, the time is 3-6h, and the temperature of the fourth calcination is 400-500°C, the time is 3-6h; preferably, the metal in the second metal impregnation solution is one or more of Pt, Pd, Ni and W; preferably, the metal weight loading of the supplementary refined catalyst is 0.3-0.5%; preferably, the specific surface area of ​​the supplementary refined catalyst is 150-300m 2 / g, mechanical strength 12~15N / mm, pore volume 0.3~0.5mL / g. Selecting the above-mentioned specific component types and controlling the specific addition amount within the above-mentioned range can make the obtained supplementary refining catalyst more effective and further improve the purity and quality of the prepared isoparaffin solvent oil. Preferably, the ratio of mesopores to non-mesopores in the hydroisomerization catalyst is (15~40):(60~85). Controlling the ratio of mesopores to non-mesopores in the hydroisomerization catalyst within the above-mentioned range can make the catalyst have better specificity for coal-based Fischer-Tropsch hydrorefined oil with a distillation range of 170~340°C, so that it can better synthesize isoparaffin solvent oil.

[0031] In a preferred embodiment, the saturated hydrocarbon weight content of the Fischer-Tropsch hydrorefined oil is ≥ 99%. Selecting a Fischer-Tropsch hydrorefined oil with a high saturated hydrocarbon content as a raw material can ensure a high conversion rate and selectivity of the hydroisomerization reaction, which is beneficial to improving the yield and purity of isoparaffin solvent oil, and is suitable for preparing high-purity isoparaffin solvent oil.

[0032] In a preferred embodiment, hydroisomerization and supplementary refining are carried out in a trickle bed reactor, which is provided with a hydroisomerization bed and a supplementary refining bed from top to bottom, the hydroisomerization bed is filled with a hydroisomerization catalyst, and the supplementary refining bed is filled with a supplementary refining catalyst. The gas-liquid mixture of Fischer-Tropsch hydrorefined oil and hydrogen enters from the upper part of the trickle bed reactor and passes through the hydroisomerization bed and the supplementary refining bed in sequence to carry out hydroisomerization and supplementary refining in sequence; preferably, the ratio of the loading amount of the hydroisomerization catalyst to the loading amount of the supplementary refining catalyst is (1-3):1; preferably, the temperature of the hydroisomerization bed is 220-320°C, preferably 240-300°C, and the temperature of the supplementary refining bed is 220-300°C, preferably 220-280°C; preferably, the volumetric space velocity of the gas-liquid mixture in the trickle bed reactor is 0.5-5h -1 , preferably 1 to 3 hours -1 ; The volume ratio of hydrogen to oil in the gas-liquid mixture is (500-1500):1, preferably (600-1000):1; the hydrogen partial pressure is 1-6MPa, preferably 2-5MPa. The volume space velocity is the ratio of the feed volume of crude oil to the catalyst loading volume. The use of a trickle bed reactor can effectively improve the reaction efficiency, reduce the amount of catalyst used, and reduce production costs. At the same time, by controlling the reaction conditions within the above range, the yield and purity of isoparaffin solvent oil can be further improved, which is especially suitable for large-scale industrial production of isoparaffin solvent oil. The specific structure of the above-mentioned trickle bed reactor can be designed according to the two-stage bed structure described above. Preferably, as Figure 2As shown, the trickle bed reactor has a reaction chamber, and a hydroisomerization bed 3 and a supplementary refining bed 7 are sequentially arranged inside the reaction chamber from top to bottom. In the specific reaction process, the Fischer-Tropsch hydrorefined oil A and hydrogen B are introduced into the reaction chamber from the top of the chamber, and the hydroisomerization reaction and the supplementary refining reaction are carried out successively; more preferably, in order to improve the uniformity of gas-liquid feed distribution, make the reaction more stable and efficient, and make the mass transfer and heat transfer more uniform, preferably, an upper gas-liquid distributor 2 is also arranged above the hydroisomerization bed 3 near the top inlet, which is connected to the top inlet of the chamber and has a plurality of gas-liquid outlets arranged in an array; similarly, a lower gas-liquid distributor 6 is also arranged between the hydroisomerization bed 3 and the supplementary refining bed 7 and near the supplementary refining bed 7.

[0033] In addition, in order to support the bed, e.g. Figure 2 As shown, a first catalyst support 4 is preferably provided at the lower portion of the hydroisomerization bed 3, a second catalyst support area 8 is provided at the lower portion of the supplementary refining bed 7, an upper buffer zone 1 is provided between the upper gas-liquid distributor 2 and the top wall of the cavity, and a lower buffer zone 5 is also provided between the lower gas-liquid distributor 6 and the first catalyst support 4 near the lower gas-liquid distributor 6, which can prevent the isomerization product from entering the gas-liquid distributor too quickly and playing a buffering role due to uneven catalyst distribution caused by large impact.

[0034] In a preferred embodiment, during the atmospheric distillation process, isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 are cut. The atmospheric distillation separation process can reduce energy consumption and improve production efficiency. By controlling the cutting temperature, isoparaffin solvent oils of different distillation ranges can be obtained, thereby meeting the specific needs of different fields for solvent oils. For example, IP40 is suitable for fast-drying coatings, while IP120 is suitable for paints that require longer drying time.

[0035] According to another aspect of the present invention, an isoparaffin solvent oil is also provided, which is prepared by the above preparation method. The obtained isoparaffin solvent oil not only has a low pour point, but also has a relatively low aromatic content, bromine index and sulfur content. In addition, the isoparaffin solvent oil has various types and can be widely used in the fields of paints, coatings, inks, adhesives, cleaning agents, etc., effectively improving the added value and market competitiveness of the products.

[0036] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0037] It should be further explained that there are three kinds of raw materials used in the preparation of isoparaffin solvent oil in the present invention, including coal-based hydrorefined oil A, coal-based hydrorefined oil B and coal-based hydrorefined oil C. The physical properties of the three raw materials are shown in Table 1. The structure of the trickle bed reactor used in the present invention is as follows: Figure 2 shown.

[0038] Table 1

[0039] project A B C Distillation range, ℃ 170～250 220～310 220～340 IBP 172.9 221.7 223.2 5％ 183.0 238.9 253.1 10％ 185.1 244.3 263.5 50％ 201.2 266.4 295.6 90％ 228.4 289.2 319.1 95％ 236.3 296.0 325.7 FBP 248.4 303.4 335.3 Saturated hydrocarbon content, % 99 99 99

[0040] (I) Preparation of Hydroisomerization Catalyst

[0041] Preparation of hydroisomerization catalyst Y1-1: ZSM-22 molecular sieve with a silicon-aluminum ratio of 40 was mixed with 1,6-hexanediamine and ammonia water and stirred at 80°C for 1h to perform a hydrothermal reaction, and then centrifuged and washed twice to obtain a hydrothermal product, wherein the concentration of ammonia water was 1mol / L, and the weight ratio of molecular sieve, 1,6-hexanediamine and ammonia water was 30:1:10; the obtained hydrothermal product was dried at 100°C for 4h, and then calcined at 550°C for 10h to obtain a modified ZSM-22 molecular sieve. The obtained modified molecular sieve was mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier was first aged at room temperature for 4h, dried at 120°C for 3h, and then calcined at 550°C for 10h to obtain a formed molecular sieve; wherein the first binder was alumina, the first auxiliary agent was methyl cellulose, the first acid solution was nitric acid, and the mass concentration of nitric acid was 3%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 55% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in a solution of tetraammine dichloroplatinum and cerium nitrate, and then dried at 100°C for 4h and calcined at 450°C for 10h to obtain a hydroisomerization catalyst Y1-1 with Pt and Ce loadings of 0.5% and 0.1% respectively.

[0042] Preparation of hydroisomerization catalyst Y1-2: ZSM-22 molecular sieve with a silicon-aluminum ratio of 70 was mixed with 1,6-hexanediamine and ammonia water and stirred at 80°C for 1 hour for hydrothermal reaction, and then filtered and washed twice to obtain a hydrothermal product, wherein the concentration of ammonia water was 1 mol / L, and the weight ratio of molecular sieve, 1,6-hexanediamine and ammonia water was 30:1:10; the obtained hydrothermal product was dried at 100°C for 4 hours, and then calcined at 550°C for 10 hours to obtain a modified ZSM-22 molecular sieve. The obtained modified molecular sieve was mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier was first aged at room temperature for 4 hours, dried at 100°C for 3 hours, and then calcined at 550°C for 10 hours to obtain a formed molecular sieve; wherein the first binder was alumina, the first auxiliary agent was methyl cellulose, the first acid solution was nitric acid, and the mass concentration of nitric acid was 3%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 60% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in a chloroplatinic acid solution, and then dried at 100°C for 4h and calcined at 450°C for 10h to obtain a hydroisomerization catalyst Y1-2 with a Pt loading of 0.5%.

[0043] Preparation of hydroisomerization catalyst Y1-3: ZSM-22 molecular sieve with a silicon-aluminum ratio of 40 is mixed with ethylenediamine and sodium hydroxide and stirred at 60°C for 2h to perform a hydrothermal reaction, and then filtered and washed twice to obtain a hydrothermal product, wherein the concentration of sodium hydroxide is 0.05mol / L, and the weight ratio of molecular sieve, ethylenediamine and sodium hydroxide is 25:1:5; the obtained hydrothermal product is dried at 80°C for 5h, and then calcined at 500°C for 12h to obtain a modified ZSM-22 molecular sieve. The obtained modified molecular sieve is mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier is first aged at room temperature for 3h, dried at 120°C for 3h, and then calcined at 600°C for 10h to obtain a formed molecular sieve; wherein the first binder is boehmite, the first auxiliary agent is sesbania powder, the first acid solution is phosphoric acid, and the mass concentration of phosphoric acid is 5%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 58% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in a tetraammine dichloroplatinum solution, and then dried at 100°C for 4h and calcined at 550°C for 10h to obtain a hydroisomerization catalyst Y1-3 with a Pt loading of 1%.

[0044] Preparation of hydroisomerization catalyst Y1-4: ZSM-22 molecular sieve with a silicon-aluminum ratio of 130 was mixed with 1,6-ethylpyridinium bromide and sodium carbonate and stirred at 100°C for 0.5h to carry out a hydrothermal reaction, and then centrifuged and washed twice to obtain a hydrothermal product, wherein the concentration of sodium carbonate was 2 mol / L, and the weight ratio of the molecular sieve, 1,6-ethylpyridinium bromide and sodium carbonate was 50:1:20; the obtained hydrothermal product was dried at 120°C for 3h, and then calcined at 600°C for 10h to obtain a modified ZSM-22 molecular sieve. The obtained modified molecular sieve is mixed with the first binder, water, the first auxiliary agent and the first acid solution, kneaded and formed, and the formed carrier is first aged at room temperature for 5 hours, dried at 80°C for 5 hours, and then calcined at 500°C for 12 hours to obtain a formed molecular sieve; wherein the first binder is alumina, the first auxiliary agent is starch, the first acid solution is hydrochloric acid, the mass concentration of hydrochloric acid is 2%, the mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 12:10:1, the mass ratio of the added first acid solution to the first binder is 1:7.5, and the amount of water added is 60% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to immerse the formed molecular sieve in a dichlorotetraammineplatinum solution, and then dried at 100°C for 4 hours and calcined at 450°C for 10 hours to obtain a hydroisomerization catalyst Y1-4 with a Pt loading of 0.3%.

[0045] Preparation of hydroisomerization catalyst Y1-5: The difference between the preparation of hydroisomerization catalyst Y1-5 and the preparation of hydroisomerization catalyst Y1-1 is that the amine compound used is N-ethylpyridine.

[0046] Preparation of hydroisomerization catalyst Y1-6: The difference between the preparation of hydroisomerization catalyst Y1-6 and the preparation of hydroisomerization catalyst Y1-1 is that the amine compound is an imidazole diquaternary ammonium salt.

[0047] Preparation of hydroisomerization catalyst Y1-7: The difference between the preparation of hydroisomerization catalyst Y1-7 and the preparation of hydroisomerization catalyst Y1-1 is that the silicon-aluminum ratio is 140, and the amine compound is selected from hexamethylammonium bromide.

[0048] Preparation of hydroisomerization catalyst Y2-1: ZSM-23 molecular sieve with a silicon-aluminum ratio of 60 is mixed with dimethylformamide and ammonia water and stirred at 80°C for 1h to perform a hydrothermal reaction, and then filtered and washed twice to obtain a hydrothermal product, wherein the concentration of ammonia water is 0.5mol / L, and the weight ratio of molecular sieve, dimethylformamide and ammonia water is 30:1:15; the obtained hydrothermal product is dried at 100°C for 4h, and then calcined at 550°C for 10h to obtain a modified ZSM-23 molecular sieve. The obtained modified molecular sieve is mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier is first aged at room temperature for 4h, dried at 100°C for 3h, and then calcined at 550°C for 10h to obtain a formed molecular sieve; wherein the first binder is alumina, the first auxiliary agent is methyl cellulose, the first acid solution is nitric acid, and the mass concentration of nitric acid is 3%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 53% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in a chloroplatinic acid solution, and then dried at 100°C for 4h and calcined at 550°C for 10h to obtain a hydroisomerization catalyst Y2-1 with a Pt loading of 0.5%.

[0049] Preparation of hydroisomerization catalyst Y2-2: ZSM-23 molecular sieve with a silicon-aluminum ratio of 100 is mixed with dimethylformamide and ammonia water and stirred at 80°C for 1h to perform a hydrothermal reaction, and then filtered and washed twice to obtain a hydrothermal product, wherein the concentration of ammonia water is 0.5mol / L, and the weight ratio of molecular sieve, dimethylformamide and ammonia water is 30:1:15; the obtained hydrothermal product is dried at 100°C for 4h, and then calcined at 550°C for 10h to obtain a modified ZSM-23 molecular sieve. The obtained modified molecular sieve is mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier is first aged at room temperature for 4h, dried at 100°C for 3h, and then calcined at 550°C for 10h to obtain a formed molecular sieve; wherein the first binder is alumina, the first auxiliary agent is methyl cellulose, the first acid solution is nitric acid, and the mass concentration of nitric acid is 3%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 50% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in dichlorotetraammineplatinum and nickel nitrate solutions, and then dried at 100°C for 4h and calcined at 550°C for 10h to obtain a hydroisomerization catalyst Y2-2 with Pt and Ni loadings of 0.5% and 0.3%, respectively.

[0050] Preparation of hydroisomerization catalyst Y2-3: The main differences between the preparation of hydroisomerization catalyst Y2-3 and the preparation of hydroisomerization catalyst Y2-1 are that the silicon-aluminum ratio of the ZSM-23 molecular sieve is 40, and the amine compound is pyrrolidine.

[0051] Preparation of hydroisomerization catalyst Y2-4: The main difference between the preparation of hydroisomerization catalyst Y2-4 and the preparation of hydroisomerization catalyst Y2-1 is that the silicon-aluminum ratio of the ZSM-23 molecular sieve is 150, and the amine compound is isopropylamine.

[0052] Preparation of hydroisomerization catalyst Y2-5: The main differences between the preparation of hydroisomerization catalyst Y2-5 and the preparation of hydroisomerization catalyst Y2-1 are that the silicon-aluminum ratio of the ZSM-23 molecular sieve is 160, and the amine compound is dimethylformamide.

[0053] Preparation of Hydroisomerization Catalyst Y3-1:

[0054] The ZSM-48 molecular sieve with a silicon-aluminum ratio of 105 is mixed with hexamethylammonium bromide and ammonia water and stirred at 80°C for 1 hour to perform a hydrothermal reaction, and then filtered and washed twice to obtain a hydrothermal product, wherein the concentration of ammonia water is 0.1 mol / L, and the weight ratio of the molecular sieve, hexamethylammonium bromide and ammonia water is 30:1:20; the obtained hydrothermal product is dried at 100°C for 4 hours, and then calcined at 550°C for 10 hours to obtain a modified ZSM-48 molecular sieve. The obtained modified molecular sieve is mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded to form it. The formed carrier is first aged at room temperature for 4 hours, dried at 100°C for 3 hours, and then calcined at 550°C for 10 hours to obtain a formed molecular sieve; wherein the first binder is aluminum oxide, the first auxiliary agent is methyl cellulose, the first acid solution is nitric acid, and the mass concentration of nitric acid is 3%. The mass ratio of the modified molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 53% of the sum of the weight of the modified molecular sieve and the first binder. Finally, the saturated impregnation method is used to impregnate the formed molecular sieve in a solution of tetraammine dichloroplatinum and cerium nitrate, and then dried at 100°C for 4h and calcined at 500°C for 5h to obtain a hydroisomerization catalyst Y3-1 with Pt and Ce loadings of 0.5% and 0.4%, respectively.

[0055] Preparation of hydroisomerization catalyst Y3-2: The difference between the preparation of hydroisomerization catalyst Y3-2 and the preparation of hydroisomerization catalyst Y3-1 is that the silicon-aluminum ratio of the ZSM-48 molecular sieve is 130.

[0056] Preparation of hydroisomerization catalyst Y3-3: The difference between the preparation of hydroisomerization catalyst Y3-3 and the preparation of hydroisomerization catalyst Y3-1 is that the silicon-aluminum ratio of the ZSM-48 molecular sieve is 80, and the amine compound is hexamethylammonium chloride.

[0057] Preparation of hydroisomerization catalyst Y3-4: The difference between the preparation of hydroisomerization catalyst Y3-4 and the preparation of hydroisomerization catalyst Y3-1 is that the silicon-aluminum ratio of the ZSM-48 molecular sieve is 300, and the amine compound is 1,6-hexanediamine.

[0058] Preparation of hydroisomerization catalyst Y3-5: The difference between the preparation of hydroisomerization catalyst Y3-5 and the preparation of hydroisomerization catalyst Y3-1 is that the amine compound is triethylamine.

[0059] Preparation of hydroisomerization catalyst Y3-6: The difference between the preparation of hydroisomerization catalyst Y3-6 and the preparation of hydroisomerization catalyst Y3-1 is that the silicon-aluminum ratio of the ZSM-48 molecular sieve is 310, and the amine compound is pyrrolidine.

[0060] (II) Preparation of supplementary refined catalyst

[0061] Preparation of supplementary refined catalyst J: γ-alumina and macroporous alumina are mixed in a mass ratio of 3:1 as a carrier, and the carrier, the second binder, the second acid solution, the second auxiliary agent and water are mixed and kneaded to obtain a modified carrier; wherein the second binder is SB powder, the second auxiliary agent is sesbania powder, the second acid solution is nitric acid with a mass concentration of 3%, the amount of the second acid solution added is the weight ratio of the second binder is 1:8, the weight ratio of the carrier, the second binder and the second auxiliary agent is 25:4:1, and the amount of water added is 70% of the sum of the weight of the carrier and the second binder. The kneaded molecular sieve is first aged at room temperature for 4 hours, dried at 100°C for 3 hours, and then calcined at 550°C for 4 hours to obtain a modified carrier. The obtained modified carrier is impregnated in a chloroplatinic acid solution by a saturated impregnation method, dried at 100°C for 4 hours, and calcined at 450°C for 10 hours to obtain a supplementary refined catalyst J with a Pt loading of 0.3%.

[0062] Example 1

[0063] Coal-based hydrorefined oil A is used as raw material, Y3-1 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 260°C, the temperature of the supplementary refining reaction is 240°C, and the feed space velocity in the trickle bed reactor is 1h -1 , hydrogen-to-oil ratio is 800:1, and hydrogen partial pressure is 4MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 2.

[0064] Table 2

[0065]

[0066]

[0067] Example 2

[0068] Coal-based hydrorefined oil B is used as raw material, Y1-1 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 280°C, the temperature of the supplementary refining reaction is 220°C, and the feed space velocity in the trickle bed reactor is 0.8h -1 , the hydrogen-oil ratio is 1000:1, and the hydrogen partial pressure is 3MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 3.

[0069] Table 3

[0070]

[0071] Example 3

[0072] Coal-based hydrorefined oil C is used as raw material, Y2-1 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 270°C, the temperature of the supplementary refining reaction is 235°C, and the feed space velocity in the trickle bed reactor is 1.2h -1 , the hydrogen-oil ratio is 600:1, and the hydrogen partial pressure is 5MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 4.

[0073] Table 4

[0074]

[0075] Example 4

[0076] Coal-based hydrorefined oil C is used as raw material, Y3-2 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 260°C, the temperature of the supplementary refining reaction is 245°C, and the feed space velocity in the trickle bed reactor is 1h -1, hydrogen-oil ratio is 800:1, hydrogen partial pressure is 4MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 5.

[0077] Table 5

[0078]

[0079] Example 5

[0080] Coal-based hydrorefined oil A is used as raw material, Y1-2 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 280°C, the temperature of the supplementary refining reaction is 230°C, and the feed space velocity in the trickle bed reactor is 1h -1 , hydrogen-to-oil ratio is 800:1, and hydrogen partial pressure is 4MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 6.

[0081] Table 6

[0082]

[0083] Example 6

[0084] Coal-based hydrorefined oil A is used as raw material, Y2-2 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 270°C, the temperature of the supplementary refining reaction is 225°C, and the feed space velocity is 1.2h -1 , the hydrogen-oil ratio is 600:1, and the hydrogen partial pressure is 5MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 7.

[0085] Table 7

[0086]

[0087] Example 7

[0088] The difference from Example 1 is that Y1-4 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The performance of each grade of isoparaffin solvent oil prepared was tested, and the results are shown in Table 8.

[0089] Table 8

[0090]

[0091] Example 8

[0092] The difference from Example 1 is that Y1-5 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The performance of each grade of isoparaffin solvent oil prepared was tested, and the results are shown in Table 9.

[0093] Table 9

[0094]

[0095] Example 9

[0096] The difference from Example 1 is that Y1-6 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The performance of each grade of isoparaffin solvent oil prepared was tested, and the results are shown in Table 10.

[0097] Table 10

[0098]

[0099] Example 10

[0100] The difference from Example 1 is that Y2-4 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The performance of each grade of isoparaffin solvent oil prepared was tested, and the results are shown in Table 11.

[0101] Table 11

[0102]

[0103] Embodiment 11

[0104] The difference from Example 1 is that Y3-3 is a hydroisomerization catalyst and J is a supplementary refining catalyst. The performance of the prepared isoparaffin solvent oils of various grades is tested. The results are shown in Table 12.

[0105] Table 12

[0106]

[0107]

[0108] Example 12

[0109] The difference from Example 1 is that Y3-4 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The performance of the prepared isoparaffin solvent oils of various grades is tested, and the results are shown in Table 13.

[0110] Table 13

[0111]

[0112] Embodiment 13

[0113] The difference from Example 1 is that Y3-5 is a hydroisomerization catalyst and J is a supplementary refining catalyst. The performance of each grade of isoparaffin solvent oil prepared was tested. The results are shown in Table 14.

[0114] Table 14

[0115]

[0116]

[0117] Embodiment 14

[0118] Coal-based hydrorefined oil A is used as raw material, Y1-3 is used as a hydroisomerization catalyst, and J is used as a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 220°C, the temperature of the supplementary refining reaction is 300°C, and the feed space velocity in the trickle bed reactor is 0.5h -1 , the hydrogen-oil ratio is 500:1, and the hydrogen partial pressure is 1 MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 15.

[0119] Table 15

[0120]

[0121] Embodiment 15

[0122] Coal-based hydrorefined oil A is used as raw material, Y1-3 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 320°C, the temperature of the supplementary refining reaction is 220°C, and the feed space velocity in the trickle bed reactor is 5h -1 , the hydrogen-oil ratio is 1500:1, and the hydrogen partial pressure is 6MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 16.

[0123] Table 16

[0124]

[0125]

[0126] Example 16

[0127] Coal-based hydrorefined oil A is used as raw material, Y1-3 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 240°C, the temperature of the supplementary refining reaction is 280°C, and the feed space velocity in the trickle bed reactor is 1h -1 , the hydrogen-oil ratio is 600:1, and the hydrogen partial pressure is 1 MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 17.

[0128] Table 17

[0129]

[0130] Embodiment 17

[0131] Coal-based hydrorefined oil A is used as raw material, Y1-3 is a hydroisomerization catalyst, and J is a supplementary refining catalyst. The raw material is introduced into a trickle bed reactor to carry out a hydroisomerization reaction in a hydroisomerization bed layer, and a hydroisomerization reaction is carried out in a supplementary refining bed layer to obtain a hydroisomerization-refined product; wherein the temperature of the hydroisomerization reaction is 300°C, the temperature of the supplementary refining reaction is 220°C, and the feed space velocity in the trickle bed reactor is 3h -1 , the hydrogen-oil ratio is 1000:1, and the hydrogen partial pressure is 6MPa. Finally, the hydroisomerization-refining product is cut into different grades of isoparaffin solvent oil in the atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil is tested. The results are shown in Table 18.

[0132] Table 18

[0133]

[0134] Embodiment 18

[0135] The difference from Example 1 is that Y1-7 is a hydroisomerization catalyst and J is a supplementary refining catalyst. The performance of the prepared isoparaffin solvent oils of various grades is tested. The results are shown in Table 19.

[0136] Table 19

[0137]

[0138] Embodiment 19

[0139] The difference from Example 1 is that Y2-5 is a hydroisomerization catalyst and J is a supplementary refining catalyst. The performance of the prepared isoparaffin solvent oils of various grades is tested. The results are shown in Table 20.

[0140] Table 20

[0141]

[0142] Embodiment 20

[0143] The difference from Example 1 is that Y3-6 is a hydroisomerization catalyst and J is a supplementary refining catalyst. The performance of the prepared isoparaffin solvent oils of various grades is tested, and the results are shown in Table 21.

[0144] Table 21

[0145]

[0146] Comparative Example 1

[0147] The difference from Example 1 is that the hydroisomerization catalyst used is hydroisomerization catalyst D, wherein the preparation method of hydroisomerization catalyst D is:

[0148] The ZSM-22 molecular sieve with a silicon-aluminum ratio of 100 is mixed with a first binder, water, a first auxiliary agent and a first acid solution, and kneaded into a mold. The molded carrier is first aged at room temperature for 4 hours, dried at 120°C for 3 hours, and then calcined at 550°C for 10 hours to obtain a molded molecular sieve; wherein the first binder is alumina, the first auxiliary agent is methyl cellulose, the first acid solution is nitric acid, and the mass concentration of nitric acid is 3%. The mass ratio of the ZSM-22 molecular sieve to the first binder and the first auxiliary agent is 15:7.5:1, the mass ratio of the added first acid solution to the first binder is 1:10, and the amount of water added is 60% of the sum of the weight of the ZSM-22 and the first binder. Finally, the saturated impregnation method is used to impregnate the molded molecular sieve in a dichlorotetraammineplatinum solution, and then dried at 100°C for 4 hours and calcined at 450°C for 10 hours to obtain a hydroisomerization catalyst D with a Pt loading of 0.5%.

[0149] The prepared hydroisomerization-refined product was cut into different grades of isoparaffin solvent oil in an atmospheric pressure tower, and the performance of each grade of isoparaffin solvent oil was tested. The results are shown in Table 22.

[0150] Table 22

[0151]

[0152] The prepared hydroisomerization catalysts Y1-1, Y1-2, Y1-3, Y1-4, Y1-5, Y1-6, Y1-7, Y2-1, Y2-2, Y2-3, Y2-4, Y2-5, Y3-1, Y3-2, Y3-3, Y3-4, Y3-5, Y3-6 and D were tested for relevant properties, and the results are shown in Table 23; the prepared J was tested for relevant properties, and the results are shown in Table 24. The isoparaffin solvent oils prepared in Examples 1 to 20 and Comparative Example 1 were tested for relevant properties, and the results are shown in Table 25.

[0153] Table 23-1

[0154]

[0155]

[0156] Table 23-2

[0157]

[0158] Table 24

[0159] project J <![CDATA[Specific surface area, m 2 / g]]> 200 Pore ​​volume, mL / g 0.4 Mechanical strength, N / mm 14

[0160] Table 25-1

[0161]

[0162]

[0163] Table 25-2

[0164]

[0165]

[0166] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0167] Examples 1 to 17 are methods for preparing hydroisomerization catalysts according to the present invention, and the preparation parameters of the hydroisomerization catalysts are controlled within the preferred range. The isoparaffin solvent oils prepared have not only a higher yield, but also a higher isoparaffin content. Moreover, the aromatic content, bromine index, sulfur content and pour point of the isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 formed by cutting the obtained isoparaffin solvent oil are lower, indicating that they have better quality. The preparation parameters for preparing the hydroisomerization catalysts in Examples 18 to 20 are not within the preferred range, and the yield of the isoparaffin solvent oils prepared by the corresponding catalysts and the quality of the isoparaffin solvent oils formed by cutting are slightly worse.

[0168] In Comparative Example 1, the method for preparing a hydroisomerization catalyst according to the present invention was not used to prepare a hydroisomerization catalyst. The prepared hydroisomerization catalyst was used to prepare isoparaffin solvent oil. Not only was the yield of isoparaffin solvent oil low, but the isoparaffin content therein and the quality of the isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 formed by cutting were also much worse.

[0169] In summary, the preparation method of the hydroisomerization catalyst proposed in the present invention is used to prepare a hydroisomerization catalyst with suitable acidity and a suitable micropore-mesopore ratio. Under the synergistic effect of suitable acid sites, micropore-mesopore ratio and metal catalyst, the obtained hydroisomerization catalyst can achieve high selectivity isomerization for Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340 ° C, and at the same time, it can ensure that it can be smoothly desorbed from the catalyst after isomerization, and can effectively avoid cracking again to generate non-target fraction impurities. In combination with the preparation method of the isoparaffin solvent oil proposed in the present invention, the obtained isoparaffin solvent oil can not only have a higher yield, but also a higher isoparaffin content. The isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 formed by cutting the obtained isoparaffin solvent oil all have better quality.

[0170] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing isoparaffin solvent oil, characterized in that: The preparation method comprises: The coal-based Fischer-Tropsch hydrorefined oil with a distillation range of 170 to 340° C. is subjected to hydroisomerization and supplementary refining in sequence to obtain a hydroisomerization-refining product; The hydroisomerization-refining product is subjected to atmospheric distillation cutting to obtain the isoparaffin solvent oil; Wherein, the hydroisomerization is carried out under the catalytic action of a hydroisomerization catalyst, and the hydroisomerization catalyst is prepared by the following method: The molecular sieve, the amine compound and the alkaline source are mixed and subjected to a hydrothermal reaction to obtain a hydrothermal product; the amine compound is one or more of an organic amine, a quaternary ammonium salt and an amine salt; The hydrothermal product is subjected to a first drying and a first calcination to obtain a modified molecular sieve; The modified molecular sieve is mixed with a first binder and water, and a first acid solution is added to knead and stand, and a second drying and a second calcination are performed to obtain a molded molecular sieve; After the shaped molecular sieve is impregnated in the first metal impregnation solution, a third drying and a third calcination are performed in sequence to obtain the hydroisomerization catalyst.

2. The method for preparing isoparaffin solvent oil according to claim 1, characterized in that: During the preparation of the hydroisomerization catalyst, the weight ratio of the molecular sieve, the amine compound and the alkali source is (25-50):1:(5-20); and / or, The concentration of the alkali source is 0.05-2 mol / L; and / or, The amine compound is selected from one or more of 1,6-hexanediamine, ethylenediamine, triethylamine, isopropylamine, 1,6-ethylpyridinium bromide, N-ethylpyridine, imidazole diquaternary ammonium salt, pyrrolidine, dimethylformamide, hexamethylammonium bromide and hexamethylammonium chloride; and / or, The molecular sieve is a one-dimensional ten-membered ring structure molecular sieve, preferably the molecular sieve is one or more of ZSM-22 molecular sieve, ZSM-23 molecular sieve and ZSM-48 molecular sieve; and / or, The alkali source is an aqueous solution of one or more of ammonia, sodium hydroxide and sodium carbonate.

3. The method for preparing isoparaffin solvent oil according to claim 2, characterized in that: The molecular sieve is the ZSM-22 molecular sieve, and the amine compound is selected from one or more of the 1,6-hexanediamine, the ethylenediamine, the 1,6-ethylpyridinium bromide, the N-ethylpyridine and the imidazole diquaternary ammonium salt; or, The molecular sieve is the ZSM-23 molecular sieve, and the amine compound is selected from one or more of the pyrrolidine, isopropylamine and dimethylformamide; or, The molecular sieve is the ZSM-48 molecular sieve, and the amine compound is selected from one or more of the hexamethylammonium bromide, the hexamethylammonium chloride, the 1,6-hexanediamine and the triethylamine; Preferably, the silicon-aluminum ratio of the ZSM-22 molecular sieve is 40-130, the silicon-aluminum ratio of the ZSM-23 molecular sieve is 40-150, and the silicon-aluminum ratio of the ZSM-48 molecular sieve is 80-300.

4. The method for preparing the isoparaffin solvent oil according to any one of claims 1 to 3, characterized in that: During the preparation of the hydroisomerization catalyst, the temperature of the hydrothermal reaction is 60 to 100° C., and the reaction time is 0.5 to 2 h; and / or, After the hydrothermal reaction is completed, the hydrothermal product is first washed to neutrality, and then the first drying and the first calcination are performed; more preferably, the washing is performed by centrifugal washing or filtration washing; and / or, The temperatures of the first drying, the second drying and the third drying are 80-120° C. and the times are 3-5 hours respectively. The temperatures of the first calcination, the second calcination and the third calcination are 450-600° C. and the times are 8-12 hours respectively.

5. The method for preparing the isoparaffin solvent oil according to any one of claims 1 to 4, characterized in that: During the preparation of the hydroisomerization catalyst, the first binder is selected from pseudo-boehmite and / or alumina; Preferably, a first auxiliary agent is added during the mixing of the modified molecular sieve, the first binder and water, wherein the first auxiliary agent is one or more of sesbania powder, starch and methyl cellulose; Preferably, the first acid solution is one or more of nitric acid, phosphoric acid, hydrochloric acid and citric acid; Preferably, the mass concentration of the first acid solution is 2-5%; Preferably, the mass ratio of the added amount of the first acid solution to the first binder is 1:(7.5-10); Preferably, the weight ratio of the modified molecular sieve, the first binder and the first auxiliary agent is (12-15): (7.5～10):1； Preferably, the amount of water added is 50-60% of the sum of the weight of the modified molecular sieve and the first binder; Preferably, the standing time is 3 to 5 hours; Preferably, the metal type of the first metal impregnation solution is one or more of Pt, Pd, Ni, Ce, Zn, W, Mg, and Fe; the weight content of the modified molecular sieve in the hydroisomerization catalyst is 60-80%, and the metal weight loading is 0.3-1%, more preferably 0.3-0.6%; Preferably, the hydroisomerization catalyst has a specific surface area of ​​150 to 300 m 2 / g, mechanical strength 10-15N / mm, total acid content 0.3-0.5mmol / g, weak acid proportion ≥60%, pore volume 0.3-0.5mL / g.

6. The method for preparing the isoparaffin solvent oil according to any one of claims 1 to 5, characterized in that: The supplementary refining is carried out under the action of a supplementary refining catalyst, and the supplementary refining catalyst is prepared by the following method: Alumina is used as a carrier, mixed with a second binder, and then a second acid solution and water are added for kneading to obtain a modified carrier; After the modified support is impregnated in a second metal impregnation solution, fourth drying and fourth calcination are performed in sequence to obtain the supplementary refined catalyst; Preferably, the alumina is a mixture of γ-alumina and macroporous alumina, and more preferably the weight ratio of the two is (2-5):1; Preferably, the second binder is SB powder; Preferably, the second acid solution is nitric acid; Preferably, the mass concentration of the second acid solution is 2-5%; Preferably, the weight ratio of the added amount of the second acid solution to the second binder is 1:(7.5-10); Preferably, a second auxiliary agent is added during the mixing of the alumina and the second binder, and the second auxiliary agent is sesbania powder and / or starch; Preferably, the weight ratio of the aluminum oxide, the second binder and the second auxiliary agent is (20-30): (3～5):1； Preferably, the amount of water added is 60-70% of the sum of the weight of the carrier and the second binder; Preferably, the temperature of the fourth drying is 80-100°C, the time is 3-6 hours, and the temperature of the fourth calcination is 400-500°C, the time is 3-6 hours; Preferably, the metal in the second metal impregnation solution is one or more of Pt, Pd, Ni and W; Preferably, the metal weight loading of the supplementary refined catalyst is 0.3-0.5%; Preferably, the specific surface area of ​​the supplementary refined catalyst is 150 to 300 m 2 / g, mechanical strength is 12-15N / mm, pore volume is 0.3-0.5mL / g; Preferably, the ratio of mesopores to non-mesopores in the hydroisomerization catalyst is (15-40):(60-85).

7. The method for preparing the isoparaffin solvent oil according to any one of claims 1 to 6, characterized in that: The saturated hydrocarbon content of the Fischer-Tropsch hydrorefined oil is ≥99%.

8. The method for preparing isoparaffin solvent oil according to claim 7, characterized in that: The hydroisomerization and supplementary refining are carried out in a trickle bed reactor, wherein the trickle bed reactor is provided with a hydroisomerization bed layer and a supplementary refining bed layer in sequence from top to bottom, the hydroisomerization bed layer is filled with the hydroisomerization catalyst, and the supplementary refining bed layer is filled with the supplementary refining catalyst, and the gas-liquid mixture of the Fischer-Tropsch hydrorefined oil and hydrogen enters from the upper part of the trickle bed reactor and passes through the hydroisomerization bed layer and the supplementary refining bed layer in sequence, so as to carry out the hydroisomerization and supplementary refining in sequence; Preferably, the ratio of the loading amount of the hydroisomerization catalyst to the loading amount of the supplementary refining catalyst is (1-3):1; Preferably, the temperature of the hydroisomerization bed is 220-320°C, preferably 240-300°C, and the temperature of the supplementary refining bed is 220-300°C, preferably 220-280°C; Preferably, the volumetric space velocity of the gas-liquid mixture in the trickle bed reactor is 0.5 to 5 h -1 , preferably 1 to 3 hours -1 ; The hydrogen-oil volume ratio of the gas-liquid mixture is (500-1500):1, preferably (600-1000):1; the hydrogen partial pressure is 1-6MPa, preferably 2-5MPa.

9. The method for preparing the isoparaffin solvent oil according to any one of claims 1 to 6, characterized in that: During the atmospheric distillation process, isoparaffin solvent oils IP40, IP60, IP80, IP100 and IP120 are cut and formed.

10. An isoparaffin solvent oil, characterized in that: The method is prepared according to any one of claims 1 to 9.

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