Preparation method of self-sulfuration oil-soluble catalyst

Abstract

The invention discloses a preparation method of a self-sulfuration oil-soluble catalyst, sulfur-containing organic acid is used as an organic ligand, metal salt is used as catalytic active metal, the preparation method is simple, raw materials are wide in source and relatively low in price, and the prepared self-sulfuration oil-soluble catalyst is good in dispersity, high in stability and good in oil solubility, and can be used for preparing the self-sulfuration oil-soluble catalyst. The catalyst prepared by the method can be well dissolved in an oil product, is uniformly dispersed and is in full contact with a heavy oil system and hydrogen during reaction, and edge sites of the vulcanized catalyst have high catalytic hydrogenation activity.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and in particular relates to a method for preparing a low-temperature self-sulfurization oil-soluble catalyst for slurry bed hydrogenation. Background Art

[0002] One of the most important challenges facing humanity is the clean and efficient conversion of heavy oil into light fuels or chemical feedstocks. Slurry-bed hydrogenation processes using dispersed catalysts offer advantages such as strong feedstock adaptability, no bed clogging, and high conversion rates. These processes can cleanly process and utilize low-quality feedstocks such as residual oil, coal tar, and coal / heavy oil. Dispersed catalysts are free from intrapore diffusion limitations, making active sites more accessible to reactant molecules and resulting in higher metal utilization. However, to reduce operating costs, the catalyst dosage must be strictly controlled. High catalyst dispersion within the feedstock is required to effectively activate hydrogen molecules and prevent polycondensation between large hydrocarbon radicals, thereby increasing the yield of light components and suppressing coke formation.

[0003] Dispersed catalysts can be divided into two types: water-soluble and oil-soluble. The precursors of water-soluble catalysts are generally inorganic salts of metals such as Fe, Ni, and Mo. They are relatively cheap, but difficult to disperse in the raw materials, resulting in low catalytic activity. The precursors of oil-soluble catalysts are mainly metal organic salts, which can be dissolved or evenly dispersed in residual oil. They are used in small amounts and have high activity, making them ideal dispersed catalysts. The oil-soluble catalysts that are currently used more frequently include cyclopentane salts, fatty acid salts, organic amine salts, carbonyl salts, etc., such as nickel cyclopentaneate, iron cyclopentaneate, nickel oleate, cobalt oleate, molybdenum oleate, molybdenum hexacarbonyl, etc. The active phase of the dispersed catalyst is the metal sulfide after the precursor is sulfurized, such as FeS x 、NiS x , MoS2, etc.

[0004] When preparing oil-soluble catalysts, the key of the prior art is to select suitable organic ligands. On the one hand, it is necessary to ensure that the catalyst precursor has good oil solubility, and on the other hand, it is necessary to reduce the preparation cost as much as possible. Although the currently commonly used organic ligands, such as cyclohexane acid, oleic acid, isooctanoic acid, etc., can prepare catalyst precursors with good oil solubility, the organic ligand raw material sources used are limited and the catalyst preparation process is complicated, resulting in the high cost of the catalyst, which has become a key bottleneck affecting the promotion of slurry bed hydrogenation process. Therefore, it is necessary to adopt organic ligands with a wide range of sources and low prices to reduce the preparation cost of oil-soluble catalysts and further improve the technical and economic efficiency of slurry bed hydrogenation process. Summary of the Invention

[0005] In view of the above problems, the present invention provides a method for preparing a self-sulfurized oil-soluble catalyst. Compared with the existing technology, its preparation process is relatively simple, the raw material price is relatively low, and it can effectively reduce the operating cost of the heavy oil slurry bed hydrocracking process.

[0006] In order to achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0007] The method for preparing a self-sulfurized oil-soluble catalyst provided by the present invention comprises the following steps:

[0008] Weighing a sulfur-containing organic ligand and a metal source in a molar ratio of 2 to 5:1;

[0009] Dissolve the metal source in deionized water, heat and stir at 50-90°C for 2-8 hours to obtain a metal salt solution;

[0010] Add the sulfur-containing organic ligand into the reaction vessel and start stirring at room temperature;

[0011] The metal salt solution is added dropwise to a reaction vessel at 50-60° C., then heated to 100-120° C. to evaporate water for 6-7 hours, then heated to 180-220° C. and reacted for 2-5 hours to obtain a self-sulfurized oil-soluble catalyst.

[0012] Preferably, the sulfur-containing organic ligand is at least one of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and sodium dodecylbenzenesulfonate.

[0013] Preferably, the metal source includes at least one of a molybdenum source and a nickel source.

[0014] Preferably, the molybdenum source includes at least one of molybdenum trioxide, molybdic acid, and ammonium molybdate, and the nickel source includes at least one of nickel acetate, nickel nitrate, and nickel hydroxide.

[0015] Preferably, the sulfur-containing organic ligand and the metal salt are weighed according to the molar ratio of ligand to metal.

[0016] Preferably, the reaction container is a three-necked flask.

[0017] Preferably, the metal salt solution is added at a rate of 2 to 5 ml / min at 50 to 60°C.

[0018] Preferably, the metal salt solution is added at a rate of 3 ml / min at 50-60°C.

[0019] Preferably, after obtaining the self-sulfurized oil-soluble catalyst, the following steps are further included:

[0020] Weigh 1000 μg / g (based on active metal) of oil-soluble catalyst, add it to base oil, stir evenly, and then add it to the autoclave;

[0021] Perform gas replacement operation on the autoclave, and fill 2MPa, 2MPa, and 4MPa hydrogen into the autoclave in sequence and discharge them. After the gas replacement is completed, fill 6MPa hydrogen into the autoclave and carry out the vulcanization reaction at the vulcanization temperature. When the autoclave reacts for 1 to 3 hours, the reaction is completed;

[0022] After the reaction is completed, the temperature is rapidly cooled, the autoclave is placed in a cold water container and cooled to room temperature, the gas in the autoclave is discharged and the sulfide product is taken out;

[0023] The sulfidation product was centrifuged and washed 3 to 4 times with tetrahydrofuran solvent. When the upper layer of the centrifuge tube was clear and transparent, it was centrifuged and washed with anhydrous ethanol.

[0024] After washing, excess anhydrous ethanol is removed by steam stripping and drying to finally obtain a powdery catalytic active phase.

[0025] Preferably, the base oil is 400N base oil.

[0026] Preferably, the vulcanization temperature is 310°C to 380°C.

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

[0028] The present invention provides a method for preparing a self-sulfurizing oil-soluble catalyst. The method uses a sulfur-containing organic acid as an organic ligand and a metal salt as its catalytically active metal. The preparation method is simple, the raw materials are widely available and relatively inexpensive, and the prepared self-sulfurizing oil-soluble catalyst has good dispersibility and high stability, good oil solubility, can be well dissolved in oil products, and is evenly dispersed. During the reaction, it is in full contact with the heavy oil system and hydrogen, and the catalyst edge sites after sulfurization have high catalytic hydrogenation activity.

[0029] In addition to the technical problems solved by the embodiments of the present invention described above, the technical features that constitute the technical solutions, and the beneficial effects brought about by the technical features of these technical solutions, other technical problems that can be solved by the shielding structure, power system and vehicle provided by the embodiments of the present invention, other technical features included in the technical solutions, and the beneficial effects brought about by these technical features will be further described in detail in the specific implementation methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the XRD pattern of the self-sulfurized oil-soluble molybdenum-based catalyst of Example 1 of the present invention.

[0031] Figure 2 This is the XRD pattern of the self-sulfurized oil-soluble nickel-based catalyst of Example 3 of the present invention. DETAILED DESCRIPTION

[0032] To make the objectives, technical solutions, and advantages of the present invention more apparent, the present invention will be described in further detail below. It is apparent that the embodiments described are only a portion of the embodiments of the present invention, rather than all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0033] The preparation method of a self-sulfurized oil-soluble catalyst of the present invention will be described in detail below with reference to specific examples.

[0034] Example 1

[0035] A method for preparing a self-sulfurized oil-soluble molybdenum-based catalyst. The active ingredient of the self-sulfurized oil-soluble catalyst prepared by the preparation method is molybdenum, and the weight content of molybdenum in the oil-soluble catalyst is 11.38%. The preparation method is as follows:

[0036] (1) Dissolve 9.5 g of oxalic acid in 100 g of deionized water, add molybdenum trioxide at a molar ratio of oxalic acid to molybdenum of 1:1, and stir at 90°C for 8 h until the molybdenum trioxide is completely dissolved to obtain a colorless transparent liquid;

[0037] (2) Weigh 73.80 g of dodecylbenzenesulfonic acid and add it to a three-necked flask, and start stirring at room temperature; then add the colorless transparent liquid in step (1) dropwise at 50° C. at a dropping rate of 3 ml / min, and stir vigorously. After the addition is completed, heat the mixture to 110° C., evaporate the water for 6 h to dry the water, and then heat the mixture to 180° C. and continue the reaction for 3 h to obtain a self-sulfurized oil-soluble molybdenum-based catalyst.

[0038] Example 2

[0039] A method for preparing a self-sulfurized oil-soluble molybdenum-based catalyst. The active ingredient of the self-sulfurized oil-soluble catalyst prepared by the preparation method is molybdenum, and the weight content of molybdenum in the oil-soluble catalyst is 10.38%. The preparation method is as follows:

[0040] (1) Dissolve 9.5 g of oxalic acid in 100 g of deionized water, add molybdenum trioxide at a molar ratio of oxalic acid to molybdenum of 1:1, and stir at 90°C for 8 h until the molybdenum trioxide is completely dissolved to obtain a colorless transparent liquid;

[0041] (2) Weigh 97.95 g of dodecylbenzenesulfonic acid into a three-necked flask and start stirring at room temperature; then add the colorless transparent liquid in step (1) dropwise at 50° C. at a dropping rate of 3 ml / min and stir vigorously. After the addition is completed, heat the mixture to 110° C., evaporate water for 6 h to dry the water, then heat the mixture to 180° C. and continue the reaction for 3 h to obtain a self-sulfurized oil-soluble molybdenum-based catalyst.

[0042] Example 3

[0043] A method for preparing a self-sulfurized oil-soluble nickel-based catalyst. The active ingredient of the self-sulfurized oil-soluble catalyst prepared by the preparation method is nickel, and the weight content of nickel in the oil-soluble catalyst is 8.91%. The preparation method is as follows:

[0044] (1) Dissolve 12.44 g of nickel acetate in 100 g of deionized water and stir at 50 °C for 2 h until all the nickel acetate is dissolved.

[0045] (2) Weigh 37.33 g of dodecylbenzenesulfonic acid and add it to a three-necked flask, and start stirring at room temperature; then add the nickel acetate aqueous solution in step (1) dropwise at 50° C. at a dropping rate of 3 ml / min, and stir vigorously. After the dropwise addition is completed, heat the mixture to 110° C., evaporate the water for 6 h to dry the water, and then heat the mixture to 180° C. and continue the reaction for 3 h to obtain a self-sulfurized oil-soluble nickel-based catalyst.

[0046] 500 ppm of the self-sulfurized oil-soluble catalyst prepared in Examples 1 to 3 above was added to 200 g of palmitic acid oil for hydrogenation reaction. The reaction results are shown in Table 1 below.

[0047] Table 1: Palmitic acid oil conversion and hydrogenation product yield

[0048]

[0049]

[0050] 300 ppm of the self-sulfurized oil-soluble catalyst prepared in Examples 1 to 3 was added to 200 g of Marui residue oil to carry out heavy oil hydrogenation reaction. The reaction results are shown in Table 2 below.

[0051] Table 2: Distribution of Marui Residue Products

[0052]

[0053]

[0054] It should be noted that IBP refers to the Initial Boiling Point, which is the temperature at which the mixture begins to distill the first drop of liquid.

[0055] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a self-sulfurized oil-soluble catalyst, characterized in that: The following steps are involved: Weighing a sulfur-containing organic ligand and a metal source in a molar ratio of 2 to 5:1; Dissolve the metal source in deionized water, heat and stir at 50-90°C for 2-8 hours to obtain a metal salt solution; Add the sulfur-containing organic ligand into the reaction vessel and start stirring at room temperature; The metal salt solution is added dropwise to a reaction vessel at 50-60° C., then heated to 100-120° C. to evaporate water for 6-7 hours, then heated to 180-220° C. and reacted for 2-5 hours to obtain a self-sulfurized oil-soluble catalyst.

2. The preparation method according to claim 1, characterized in that The sulfur-containing organic ligand is at least one of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and sodium dodecylbenzenesulfonate.

3. The preparation method according to claim 1, characterized in that The metal source includes at least one of a molybdenum source and a nickel source.

4. The preparation method according to claim 3, characterized in that The molybdenum source includes at least one of molybdenum trioxide, molybdic acid, and ammonium molybdate, and the nickel source includes at least one of nickel acetate, nickel nitrate, and nickel hydroxide.

5. The preparation method according to claim 1, characterized in that The reaction container is a three-necked flask.

6. The preparation method according to claim 1, characterized in that The metal salt solution is added at a rate of 2 to 5 ml / min at a temperature of 50 to 60° C.

7. The preparation method according to claim 7, characterized in that The metal salt solution is added at a rate of 3 ml / min at a temperature of 50-60°C.

8. The preparation method according to claim 1, characterized in that After obtaining the self-sulfurized oil-soluble catalyst, The following steps are involved: Weigh the oil-soluble catalyst, add it to the base oil, stir evenly, and then add it to the high-pressure reactor; The autoclave is subjected to a gas replacement operation. 2MPa, 2Mpa, and 4MPa hydrogen are sequentially charged into the autoclave and discharged. After the gas replacement is completed, 6MPa hydrogen is charged into the autoclave. The vulcanization reaction is carried out at the vulcanization temperature. After the autoclave has reacted for 1 to 3 hours, the reaction is completed. After the reaction is completed, the temperature is quickly cooled, the autoclave is placed in a cold water container and cooled to room temperature, the gas in the autoclave is discharged and the sulfide product is taken out; The sulfide product was centrifuged and washed 3 to 4 times with tetrahydrofuran solvent. When the upper layer of the centrifuge tube was clear and transparent, it was centrifuged and washed with anhydrous ethanol. After washing, excess anhydrous ethanol is removed by steam stripping and drying to finally obtain a powdery catalytic active phase.

9. The preparation method according to claim 8, characterized in that The base oil is 400N base oil.

10. The preparation method according to claim 8, characterized in that The vulcanization temperature is 310°C to 380°C.

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