阅读说明：本技术 用于煤/重油加氢共炼的脂肪酸镍油溶性催化剂及其应用 (Fatty acid nickel oil-soluble catalyst for coal/heavy oil hydrogenation co-refining and application thereof ) 是由 邓文安 翟若浩 杜峰 李传 罗辉 李庶峰 杨腾飞 李珺 于 2020-06-24 设计创作，主要内容包括：本发明公开用于煤/重油加氢共炼的脂肪酸镍油溶性催化剂及其应用,该催化剂活性成分为镍,镍在催化剂中的重量含量为6％～20％,其制备方法包括以下步骤：将反应所需的脂肪酸溶于乙醇中,并与碱液充分混合,并加入溶剂反应；配制镍盐水溶液,并逐滴滴加至反应体系中滴加完成后继续反应；反应结束,迅速分液,弃掉水相,油相加入适量甲苯或二甲苯洗涤后旋蒸脱溶剂后干燥,即得。本发明提供的脂肪酸镍类煤/重油加氢共炼油溶性催化剂,具有良好的油溶性,能较好地溶解在劣质油品中,反应时与煤/重油体系和氢气充分接触,硫化后的催化剂边缘位点具有较高催化加氢活性及抑焦活性,煤转化率高。(The invention discloses a fatty acid nickel oil-soluble catalyst for coal/heavy oil hydrogenation co-refining and application thereof, wherein the active component of the catalyst is nickel, the weight content of the nickel in the catalyst is 6-20%, and the preparation method comprises the following steps: dissolving fatty acid required by the reaction in ethanol, fully mixing with alkali liquor, and adding a solvent for reaction; preparing a nickel salt aqueous solution, dropwise adding the nickel salt aqueous solution into a reaction system, and continuing to react after dropwise adding is finished; and after the reaction is finished, quickly separating liquid, removing the water phase, adding a proper amount of toluene or xylene into the oil phase, washing, then, rotationally evaporating to remove the solvent, and drying to obtain the catalyst. The fatty acid nickel-based coal/heavy oil hydrogenation co-refining oil soluble catalyst provided by the invention has good oil solubility, can be well dissolved in an inferior oil product, is fully contacted with a coal/heavy oil system and hydrogen during reaction, has high catalytic hydrogenation activity and coke inhibition activity at edge sites of the vulcanized catalyst, and is high in coal conversion rate.)

1. The fatty acid nickel oil soluble catalyst for coal/heavy oil hydrogenation co-refining is characterized in that the active component of the catalyst is nickel, the weight percentage content of the nickel in the catalyst is 6-20%, and the preparation method comprises the following steps:

(1) dissolving fatty acid required by the reaction in ethanol, fully mixing the fatty acid with alkali liquor, adding a solvent, and reacting at the temperature of 60-95 ℃ for 2-5 hours;

(2) Preparing a nickel salt aqueous solution, dropwise adding the nickel salt aqueous solution into a reaction system, controlling the dropwise adding speed to be 1-10 ml/min, controlling the reaction temperature to be 60-95 ℃, and continuing to react for 2-5 hours after the dropwise adding is finished;

(3) and after the reaction is finished, quickly separating liquid, removing a water phase, adding a proper amount of toluene or xylene into an oil phase, washing, then, rotationally evaporating to remove the solvent, and drying to obtain the fatty acid nickel oil-soluble catalyst.

2. The nickel fatty acid oil-soluble catalyst for coal/heavy oil hydrogenation co-refining of claim 1, wherein: the fatty acid is caprylic acid, lauric acid, myristic acid, palmitic acid or stearic acid.

3. The nickel fatty acid oil-soluble catalyst for coal/heavy oil hydrogenation co-refining of claim 1, wherein: the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or ammonia aqueous solution; the molar ratio of the fatty acid to the alkali in the alkali liquor is 1: 0.8-1: 1.5.

4. the nickel fatty acid oil-soluble catalyst for coal/heavy oil hydrogenation co-refining of claim 1, wherein: the solvent is n-hexane, toluene, xylene or n-heptane; the molar ratio of the fatty acid to the solvent is 1: 1.6-1: 3.

5. the nickel fatty acid oil-soluble catalyst for coal/heavy oil hydrogenation co-refining of claim 1, wherein: and (2) determining the pH value of the system after the reaction in the step (1) is finished, and maintaining the pH value of the system between 6 and 9.

6. The nickel fatty acid oil-soluble catalyst for coal/heavy oil hydrogenation co-refining of claim 1, wherein: the nickel salt is nickel nitrate, nickel sulfate or nickel chloride; the molar ratio of the fatty acid to the nickel salt is 1: 1-1: 5, the mass percentage concentration of the nickel salt water solution is 35-50%.

7. The method for preparing the fatty acid nickel oil-soluble catalyst for hydrogenation co-refining of coal/heavy oil according to any one of claims 1 to 6 in coal/heavy oilThe application in hydrogenation co-refining is characterized in that: the total amount of metals added into the raw material of the fatty acid nickel-based catalyst is 500-1500 mu g.g of the raw material^-1。

Technical Field

The invention relates to the technical field of hydrocracking agents in petrochemical industry, and particularly relates to a nickel fatty acid oil-soluble catalyst suitable for coal/heavy oil hydrogenation co-refining and application thereof.

Background

The coal/heavy oil hydrogenation co-refining technology is developed on the basis of a direct coal liquefaction technology, and is a technology for co-processing coal and heavy oil, and the basis of the technology is a single direct coal liquefaction technology and a heavy oil hydrocracking technology. The catalyst is a core technology for coal/heavy oil hydrogenation co-refining and direct coal liquefaction, can effectively reduce the reaction severity, improve the utilization rate of activated hydrogen and the quality of liquid products, improve the product quality, improve the conversion rate of coal, and improve the economy of a liquefaction process, and is a research hotspot of the current coal/heavy oil hydrogenation co-refining technology. The development of the coal/heavy oil hydrogenation co-refining catalyst mainly goes through two stages of a non-uniform solid powder catalyst and a uniformly dispersed catalyst, wherein the uniformly dispersed catalyst comprises a water-soluble dispersed catalyst and an oil-soluble dispersed catalyst. Both catalysts are present in the form of metal particles and their sulphides during the reaction. The active metal is generally a transition metal of groups IVB, VB, VIB, VIIB and VIIIB, and most commonly Fe, Ni and Mo.

Solid powder catalysts present significant disadvantages: one is that the tail oil contains a large amount of solid particles and is difficult to utilize and process; one is its low dispersion and short life. The dispersion process of the water-soluble catalyst is complex, the hydrogenation activity is low, and the coal conversion rate is low; compared with water-soluble catalyst, the oil-soluble catalyst has simple dispersing process, high hydrogenation activity and obvious coke inhibiting effect. Therefore, the development of an oil-soluble coal/heavy oil hydrogenation co-refining catalyst which is easier to prepare has become a topic of great interest.

CN109289932A discloses a nickel-based high-dispersion emulsion catalyst, a preparation method and application thereof, relates to the technical field of coal/heavy oil hydrogenation co-refining catalysts, and provides a catalyst with high hydrogenation coke-inhibiting activity for coal/heavy oil hydrogenation co-refining; the preparation method of the catalyst comprises the following steps: 1) heating and dissolving a hydrophilic surfactant and nickel salt in deionized water with the mass of 0.3-3 times: 2) placing the oleophilic surfactant and the wax oil into a container, heating to 50-80 ℃, and stirring at the rotating speed of 1000-4000 r/min; 3) slowly adding the water phase into a container containing the oil phase, shearing and dispersing for 5-15 min at 50-80 ℃, and cooling to room temperature after dispersion is completed to obtain the nickel-based high-dispersion emulsion catalyst. The catalyst prepared by the method has mild process conditions, low use cost and cheap and easily-obtained raw materials, and is suitable for large-scale process production. However, the oil solubility of the catalyst is improved by physical means, so that the requirement of an emulsifier is large, and the stability of the catalyst is required to be further improved.

CN109647535A discloses a preparation method of a coal-supported iron-based catalyst, which relates to the technical field of coal/heavy oil hydrogenation co-refining catalysts and provides a catalyst with higher catalytic activity for coal/heavy oil hydrogenation co-refining; the preparation method of the catalyst comprises the following steps: 1) mixing and dispersing the coal powder and the mixed salt solution uniformly under stirring to obtain a dispersion liquid; 2) dropwise adding 1.5-3 mol/L alkaline solution into the dispersion liquid under stirring, carrying out precipitation reaction for 2-3 h until the pH value is 6-9, and obtaining a precipitate after the reaction is finished; 3) introducing air into the precipitate for oxidation reaction, wherein the oxidation time is 1-3 h; and after the reaction is finished, carrying out pressure reduction, suction filtration, washing, drying, grinding and screening particles of 200-500 meshes to obtain the coal-supported iron-based catalyst. The catalyst introduces the synergistic effect of bimetal or trimetal, and has high active component loading amount and high catalytic activity. However, the preparation method of the catalyst is complex in synthesis process, and the concentration of the raw material liquid needs to be accurately controlled.

CN201710802071.7 discloses a self-vulcanizing oil-soluble NiMo catalyst, a preparation method and application thereof, wherein the preparation of a molybdenum-based precursor and the preparation method of a nickel-based precursor are introduced as follows: 1) reacting a sulfur-molybdenum source with an organic acid to obtain a molybdenum-based precursor; 2) reacting nickel salt with organic amine to obtain a nickel-based precursor; 3) Dissolving the molybdenum-based precursor and the nickel-based precursor in a dispersion aid to obtain a self-vulcanized oil-soluble NiMo catalyst; the catalyst prepared by the method does not need a vulcanization process, has excellent hydrogenation performance, and is suitable for a low-cost slurry bed hydrogenation process of high-sulfur inferior heavy oil. However, the preparation process of the catalyst is complicated, and the raw material addition ratio needs to be accurately controlled.

Therefore, aiming at the different defects in the invention, a high-dispersion oil-soluble catalyst which has simple preparation process, wide raw material source, reasonable price and obvious hydrogenation and coking inhibition effects needs to be further researched.

Disclosure of Invention

The invention provides an oil-soluble catalyst suitable for coal/heavy oil hydrogenation co-refining of fatty acid nickel and application thereof, wherein the oil-soluble catalyst is an oil-soluble catalyst and has the characteristics of simple dispersion process, high hydrogenation activity and obvious coke inhibition effect.

In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:

the invention provides a nickel oil-soluble catalyst suitable for coal/heavy oil hydrogenation co-refining fatty acid, the active component of the catalyst is nickel, the weight content of nickel in the catalyst is 6-20%, and the preparation method comprises the following steps:

(1) dissolving fatty acid required by the reaction in ethanol, fully mixing the fatty acid with alkali liquor, adding a solvent, and reacting at the temperature of 60-95 ℃ for 2-5 hours;

(2) preparing a nickel salt aqueous solution, dropwise adding the nickel salt aqueous solution into a reaction system, controlling the dropwise adding speed to be 1-10 ml/min, controlling the reaction temperature to be 60-95 ℃, and continuing to react for 2-5 hours after the dropwise adding is finished;

(3) and after the reaction is finished, quickly separating liquid, removing a water phase, adding a proper amount of toluene or xylene into an oil phase, washing, then, rotationally evaporating to remove the solvent, and drying to obtain the fatty acid nickel oil-soluble catalyst.

Wherein, preferably, the fatty acid is caprylic acid, lauric acid, myristic acid, palmitic acid or stearic acid.

Wherein, preferably, the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or ammonia aqueous solution; the molar ratio of the fatty acid to the alkali in the alkali liquor is 1: 0.8-1: 1.5.

wherein, preferably, the solvent is n-hexane, toluene, xylene or n-heptane; the molar ratio of the fatty acid to the solvent is 1: 1.6-1: 3.

Preferably, the pH value of the system is measured after the reaction in the step (1) is finished, and the pH value of the system is maintained between 6 and 9.

Wherein, preferably, the nickel salt is nickel nitrate, nickel sulfate or nickel chloride; the molar ratio of the fatty acid to the nickel salt is 1: 1-1: 5, the mass percentage concentration of the nickel salt water solution is 35-50%.

The application of the oil-soluble catalyst for hydrogenating and co-refining the fatty acid nickel and the heavy oil in the hydrogenation and co-refining of the coal and the heavy oil is realized, wherein the total amount of metals added into the raw material of the fatty acid nickel-based catalyst is 500-1500 mu g.g.g.g of the raw material^-1。

Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:

1. the catalyst prepared by the invention has the advantages of simple synthesis method, wide raw material source, reasonable price, mild conditions and strong stability;

2. the fatty acid nickel-based coal/heavy oil hydrogenation co-refining oil soluble catalyst provided by the invention has good oil solubility, can be well dissolved in an inferior oil product, is uniformly dispersed, is fully contacted with a coal/heavy oil system and hydrogen during reaction, has high catalytic hydrogenation activity and coke inhibition activity at the edge site of the vulcanized catalyst, and is high in coal conversion rate.

Detailed Description

The technical solutions of the present invention will be described clearly and completely below with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.