阅读说明：本技术 一种油溶性悬浮床加氢催化剂的制备方法及其应用 (Preparation method and application of oil-soluble suspension bed hydrogenation catalyst ) 是由 柳云骐 管泽坤 陈彦飞 潘原 刘宾 柴永明 刘晨光 于 2020-06-17 设计创作，主要内容包括：本发明涉及一种油溶性悬浮床加氢催化剂的制备方法及其应用,属于石油加工技术领域；所述制备方法包括如下步骤：将金属盐与表面活性剂混合均匀,充分研磨；将上述混合物放入真空干燥箱,加热后得催化剂前驱体；将上述催化剂前驱体充分研磨,溶于油品,得到悬浮床加氢催化剂。本发明的油溶性悬浮床加氢催化剂的制备方法,采用低温固相反应方法,制备工艺简单,避免使用各种溶剂,无废水废气排放。同时,耗能少,对生产设备的要求低,装置设备投资少。(The invention relates to a preparation method and application of an oil-soluble suspension bed hydrogenation catalyst, belonging to the technical field of petroleum processing; the preparation method comprises the following steps: uniformly mixing metal salt and a surfactant, and fully grinding; putting the mixture into a vacuum drying oven, and heating to obtain a catalyst precursor; and fully grinding the catalyst precursor, and dissolving the catalyst precursor in an oil product to obtain the suspension bed hydrogenation catalyst. The preparation method of the oil-soluble suspension bed hydrogenation catalyst adopts a low-temperature solid-phase reaction method, has simple preparation process, avoids using various solvents and has no waste water and waste gas emission. Meanwhile, the energy consumption is low, the requirement on production equipment is low, and the equipment investment is low.)

1. A preparation method of an oil-soluble suspended bed hydrogenation catalyst is characterized by comprising the following steps:

s101: uniformly mixing the main agent of metal acid salt and the surfactant, and fully grinding to obtain a mixture; the surfactant is long-chain alkyl quaternary ammonium salt surfactant; the main agent metalate is one or a combination of several of ammonium heptamolybdate, ammonium tetramolybdate, sodium heptamolybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate;

s102: putting the mixture into a vacuum drying oven, and heating and drying to obtain a catalyst precursor;

s103: and fully grinding the catalyst precursor, and dissolving the catalyst precursor in an oil product to obtain the suspension bed hydrogenation catalyst.

2. The method for preparing the oil-soluble suspended bed hydrogenation catalyst according to claim 1, wherein the step S101 further comprises mixing the auxiliary metalate with the surfactant uniformly and grinding; the auxiliary agent metal acid salt is at least one of cobalt acetate, cobalt carbonate, cobalt nitrate, nickel carbonate and nickel nitrate; the molar ratio of the metal in the main agent metal acid salt to the metal in the auxiliary agent metal acid salt is 3: 1-1: 1.

3. the method for preparing the oil-soluble suspended bed hydrogenation catalyst as claimed in claim 1, wherein the long-chain alkyl quaternary ammonium salt surfactant comprises at least one or a combination of anionic surfactant, cationic surfactant and zwitterionic surfactant.

4. The method for preparing an oil-soluble suspended bed hydrogenation catalyst according to claim 3, wherein in the anionic surfactant, the number of carbon atoms in the polycarboalkyl chain is 5-18, and the number of the polycarboalkyl chain is 1-4.

5. The preparation method of the oil-soluble suspension bed hydrogenation catalyst according to claim 4, wherein the long-chain alkyl quaternary ammonium salt surfactant is dioctadecyl dimethyl ammonium chloride.

6. The method for preparing an oil-soluble suspended bed hydrogenation catalyst according to any one of claims 1 to 5, wherein the step S101 comprises the steps of:

s1011: fully grinding a single main agent metal acid salt or a mixture of the main agent metal acid salt and the auxiliary agent metal acid salt for 10-30 min;

s1012: fully grinding the long-chain alkyl quaternary ammonium salt surfactant for 10-30 min, wherein the addition of the long-chain alkyl quaternary ammonium salt surfactant is determined according to the total charge number of metal ions in the main agent metal acid salt, namely the total negative charge number of the long-chain alkyl amine ions is consistent with the total positive charge number of the metal ions, so that the final product is electrically neutral;

s1013: the two are stirred and mixed evenly, and are fully ground for 0.5h-1 h.

7. The method for preparing the oil-soluble suspended bed hydrogenation catalyst according to any one of claims 1 to 5, wherein in the step S102, the heating and drying temperature is 60 ℃ to 180 ℃, and the heating and drying time is 1h to 5 h.

8. The method for preparing an oil-soluble suspended bed hydrogenation catalyst according to any one of claims 1-5, wherein in step S103, the oil product comprises at least one of lube base oil, straight-run diesel, catalytic cracking diesel, coker diesel and liquid wax.

9. An oil soluble suspended bed hydrogenation catalyst obtainable by the process of any one of claims 1 to 8.

10. Use of the oil soluble hydrocracking catalyst of claim 9 in a slurry hydrogenation process.

Technical Field

The invention belongs to the technical field of petroleum processing, and particularly relates to a preparation method and application of an oil-soluble suspension bed hydrogenation catalyst.

Background

With the increasing demand of petroleum and the increasing shrinkage of the reserves of light crude oil easy to be extracted in shallow layer, the crude oil is more and more serious in heavy and inferior quality, wherein the average content of residual oil can reach more than 50 percent. The residual oil consists of saturated components, aromatic components, colloid and asphaltene, and the key to how to improve the conversion rate of the residual oil (especially the colloid and the asphaltene in the residual oil) is to efficiently utilize petroleum resources, improve energy efficiency, reduce environmental pollution and national dependence on international crude oil, and one of the effective ways to break the key is to develop a heavy oil hydrogenation technology. Because the residual oil contains colloid asphaltene and trace metals which are easy to coke, the problems of quick catalyst deactivation, short service life and the like easily occur in the heavy oil hydroconversion process, particularly in the fixed bed heavy oil hydrogenation process due to coking and metal deposition. The heavy oil suspension bed hydrogenation process is a heavy oil lightening process for treating inferior residual oil (high metal, high carbon residue, high sulfur, high nitrogen and high viscosity) by adopting an unsupported catalyst, has high conversion rate and high yield of light oil, and can effectively avoid catalyst deactivation caused by coke deposition.

The heavy oil suspension bed hydrogenation process is not industrialized on a large scale at present, and the technical breakthrough point is mainly focused on the development aspect of high-performance catalysts. In the early heavy oil suspension bed hydrogenation process, solid particles or powder is mainly used as a catalyst, the catalyst is low in activity and large in addition amount, equipment is seriously abraded, and meanwhile, tail oil contains a large amount of solid particles and is difficult to treat and utilize. The oil-soluble catalyst can be uniformly dispersed in the heavy oil and fully contacts with the heavy oil and hydrogen, so that the catalytic activity is high, the addition amount of the catalyst is small, and the operation cost is reduced, thereby being popular with domestic and foreign experts, scholars and enterprises.

Chinese patent CN201410216485.8 discloses that an oil-soluble composite hydrocracking catalyst is prepared by heating a reduced metal element compound serving as a metal source, organic amine and carbon disulfide in a reaction medium for reaction, and filtering and washing the obtained product. Chinese patent CN201510848631.3 discloses that metal salt reacts with carboxylic acid organic matter, alcohol and vulcanizing agent together to obtain oil-soluble catalyst. Chinese patent CN01106013.1 discloses that the oil soluble catalyst is prepared by reacting Mo and W metal with phenylhydroxylamine and its derivatives. Chinese patent 201510275523.1 discloses that oil-soluble bimetallic catalyst is prepared by adding a small amount of glycol into nickel nitrate and ammonium molybdate, adjusting the PH, precipitating in aqueous solution, filtering the precipitate, mixing with oleic acid, and heating for reaction. Although the oil-soluble catalysts show excellent hydrocracking performance and coke inhibition performance, organic solvents or organic media are used as reactants or reaction sites in the preparation process, the environment is polluted, personal injury is easily caused, operation steps such as filtering, washing, purifying and the like are required, and the preparation process is complicated.

Therefore, the method has important significance for preparing the oil-soluble suspended bed hydrogenation catalyst with higher activity by adopting nontoxic and harmless reactants and simplified reaction steps. In view of the above defects of the existing oil-soluble catalyst, the invention aims to provide a preparation method and application of an oil-soluble suspended bed hydrogenation catalyst, which can solve the problems of safety and environmental protection and the defect of complicated preparation process in the prior art.

The principle on which the invention is based is as follows: the preparation method of the oil-soluble suspension bed hydrogenation catalyst uses a low-temperature solid-phase reaction method, adopts metal acid salt and long-chain alkyl quaternary ammonium salt surfactant to stir and mix uniformly, and fully grinds for a sufficient time to ensure that the metal acid salt and the long-chain alkyl quaternary ammonium salt surfactant are in full contact reaction. When in use, the catalyst precursor is ground and dissolved in petroleum fraction, and is directly added into a reactor to generate a catalytic hydrogenation active phase in situ in the reactor without the separation, dispersion and presulfurization processes of the catalyst. On the premise of saving operation cost and simplifying operation steps, the catalyst is well dispersed at the reaction temperature, can achieve molecular-level dispersion, and further is less in use amount when the same treatment effect is achieved.

Based on the principle, the technical scheme of the invention is as follows:

the invention provides a preparation method of an oil-soluble suspension bed hydrogenation catalyst, which comprises the following steps:

s101: uniformly mixing the main agent of metal acid salt and the surfactant, and fully grinding to obtain a mixture; the surfactant is long-chain alkyl quaternary ammonium salt surfactant; the main agent metalate is one or a combination of several of ammonium heptamolybdate, ammonium tetramolybdate, sodium heptamolybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate;

s102: putting the mixture into a vacuum drying oven, and heating and drying to obtain a catalyst precursor;

s103: and fully grinding the catalyst precursor, and dissolving the catalyst precursor in an oil product to obtain the suspension bed hydrogenation catalyst.

Further, the step S101 further includes an auxiliary agent metal acid salt, which is uniformly mixed with the surfactant together with the main agent metal acid salt and is ground; the auxiliary agent metal acid salt is at least one of cobalt acetate, cobalt carbonate, cobalt nitrate, nickel carbonate and nickel nitrate; the molar ratio of the metal in the main agent metal acid salt to the metal in the auxiliary agent metal acid salt is 3: 1-1: 1.

further, the long-chain alkyl quaternary ammonium salt surfactant at least comprises one or a combination of more of an anionic surfactant, a cationic surfactant and a zwitterionic surfactant; more preferably, in the anionic surfactant, the number of carbon atoms in the polycarboalkyl chain is 5 to 18, and the number of the polycarboalkyl chain is 1 to 4; still more preferably, the long-chain alkyl quaternary ammonium salt surfactant is dioctadecyl dimethyl ammonium chloride.

Further, the step S101 includes the steps of:

s1011: fully grinding a single main agent metal acid salt or a mixture of the main agent metal acid salt and the auxiliary agent metal acid salt for 10-30 min;

s1012: fully grinding the long-chain alkyl quaternary amine salt surfactant for 10-30 min, wherein the addition of the long-chain alkyl quaternary amine salt surfactant is determined according to the total charge number of metal ions in the main agent metal acid salt, namely the total negative charge number of the long-chain alkyl amine ions is consistent with the total positive charge number of the metal ions, so that the final product is electrically neutral.

S1013: the two are stirred and mixed evenly, and are fully ground for 0.5h-1 h.

Further, in the step S102, the heating and drying temperature is 60 ℃ to 180 ℃, and the heating and drying time is 1h to 5 h.

Further, in step S103, the oil product at least includes one of lubricating base oil, straight-run diesel oil, catalytic cracking diesel oil, coking diesel oil, and liquid wax oil.

The second invention provides the oil-soluble suspension bed hydrogenation catalyst obtained by the preparation method.

The third invention provides the application of the oil-soluble suspension bed hydrogenation catalyst in the suspension bed hydrogenation process. When the catalyst is used, a certain volume of the oil-soluble suspension bed hydrogenation catalyst is directly added into inferior heavy oil, a hydrogenation active component is generated in situ by utilizing a sulfur-containing compound in the heavy oil in the reaction process, the hydrogenation activity is excellent, and the dosage of the catalyst is 50-2000 [ mu ] g/g calculated by metal; the operating conditions of the suspension bed hydrogenation reactor are as follows: the reaction pressure is 5MPa to 25MPa, the reaction temperature is 380 ℃ to 480 ℃, and the volume space velocity is 0.2h^-1-1.5h^-1The volume ratio of hydrogen to oil is 200-1000.

Compared with the prior art, the preparation method of the oil-soluble suspension bed hydrogenation catalyst has the following beneficial effects:

(1) the method adopts a low-temperature solid-phase reaction method, namely reactants are all solid phases at normal temperature, no solution system participates, the complicated operations such as filtration, purification and the like are avoided, the synthesis process is simple, the conditions are mild, the energy consumption is low, the preparation cost of the catalyst is reduced, and the low-cost large-scale industrial production is facilitated.

(2) The oil-soluble suspension bed hydrogenation catalyst prepared by the invention is dissolved in an oil product in advance, and is directly added for reaction during reaction, so that the molecular level dispersion can be quickly and stably achieved, and the start-up time and the catalyst use amount are reduced.

Detailed Description

The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.