Preparation method of slurry reactor hydrogenation tungsten-based oil-soluble catalyst taking modified heteropoly acid as precursor

Abstract

The invention discloses a preparation method of a slurry reactor hydrogenation tungsten-based oil-soluble catalyst with modified heteropolyacid as a precursor, and belongs to the technical field of hydrocracking catalyst preparation, the chemical formula of the modified heteropolyacid precursor is [(CaHbOcXd) n [MeYfOgHh], n is greater than or equal to 1, [MeYfOgHh] is an anion of tungsten-based heteropolyacid, X comprises N or S, Y comprises P and / or Si, and n is greater than or equal to 1. M comprises a combination of W and any one or at least two of Mo, Fe, Co, Ni or Cr, and a: (b + c + d) < = 1: 2. The heteropoly acid is used as an active metal source, atomic-scale dispersion and uniform distribution are achieved, the modified precursor is good in dispersity, high in stability and good in oil solubility, ultra-high dispersion of active metal in raw oil can be achieved, and good hydrogenation performance and coke inhibition performance are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrocracking catalyst preparation, and particularly relates to a preparation method of a slurry bed hydrotungsten-based oil-soluble catalyst using a modified heteropolyacid as a precursor. Background Art

[0002] In recent years, the development of crude oil in China has gradually shown a trend of heavy and inferior quality. The proportion of heavy oil in crude oil is up to about 30% - 50% at most. In addition, among the newly discovered oil fields in each oil region, such as Tahe crude oil in Xinjiang and Huanxiling crude oil in Liaohe, they are all heavy oil and extra-heavy oil (API value < 10.0). This type of crude oil is mainly composed of hydrocarbons, is a dark black viscous liquid with a relatively large viscosity and low volatility, and has characteristics such as high molecular weight, high carbon-hydrogen ratio, and high sulfur content. China's demand for petroleum products is becoming increasingly urgent with the rapid development of the industrial society and economy, especially for light oil products. However, China's crude oil reserves are insufficient and generally heavy, mainly manifested as the continuous deterioration of crude oil quality, and the output of unconventional crude oil (such as oil sand asphalt, etc.) will be higher and higher. With the increasing demand for light oil products in China and the continuous tightening of relevant environmental protection laws and regulations, it has become very important to develop heavy oil upgrading technologies.

[0003] As a cutting-edge technology for the deep and efficient resource utilization of waste oil and inferior oil, the slurry bed hydrogenation technology has developed into more than a dozen processes so far. Germany started researching the slurry bed hydrogenation technology as early as 1929 and applied it to the process of coal liquefaction. During World War II, Germany realized the industrial production of two slurry bed hydrogenation units. In recent years, the slurry bed hydrogenation technology has developed rapidly in various countries around the world, especially in the aspect of heavy oil hydrogenation. Among them, the EST process of Eni Company and the VRSH technology of Chevron Company have been put into industrial production. Compared with other countries in the world, China's slurry bed hydrogenation technology started relatively late. The key to the development of the slurry bed hydrocracking process lies in the continuous progress of high-quality hydrogenation catalysts. Among them, oil-soluble catalysts can be effectively dispersed in heavy feedstocks, and the promoter metals play an effective synergy with the main metal, which is an ideal catalyst that shows excellent hydrogenation effects and effectively inhibits coking in the slurry bed hydrogenation reaction. Therefore, developing an oil-soluble tungsten-based catalyst with synergistic action of promoter metals and ultra-high dispersion is crucial for cost reduction and efficiency improvement of the slurry bed heavy oil hydrogenation process.

[0004] The specific technical solution provided by the present invention is as follows:

[0005] A preparation method of a slurry bed hydrotungsten-based oil-soluble catalyst using a modified heteropolyacid as a precursor provided by the present invention includes:

[0006] (1) First, dissolve a W-based heteropolyacid or heteropolyacid salt in a solvent to obtain a solution;

[0007] (2) Dissolve the modifier in an organic solvent to obtain a solution; dropwise add the modifier solution to the prepared W-based heteropolyacid or heteropolyacid salt solution according to the molar ratio of the modifier to the W-based heteropolyacid or heteropolyacid salt of 1:1 to 64, wherein the dropping rate is 1 to 5 ml / min, the stirring rate during the dropping process is 500 to 1000 r / min, and after the dropping is completed, keep the stirring rate and continue the reaction for 2 to 5 h;

[0008] (3) After the above reaction ends, let it stand for a preset time length and then separate the liquid to obtain the organic phase part. Then wash it a certain number of times with water, add anhydrous sodium sulfate for drying, stir, filter by suction, rotary evaporate to remove the solvent, and then obtain the W-based oil-soluble catalyst precursor after drying treatment.

[0009] Optionally, the W-based heteropolyacid or heteropolyacid salt includes at least one of Anderson type, Keggin type, Standberg type, Dawson type, Weakley type, Finke type, substituted type, sandwich type, and heteropoly blue.

[0010] Optionally, the modifier includes at least one of fatty amine hydrochloride, fatty-based imidazoline acetate, alkyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, imidazole-type ammonium salt, polyquaternary ammonium salt, dialkyldimethylammonium chloride, alkylpyridinium chloride, alkylaminoacetate, alkyldimethylaminoacetate, gemini quaternary ammonium salt, and multi-headed quaternary ammonium salt.

[0011] Optionally, the dropping rate of the modifier solution dropwise added to the prepared W-based heteropolyacid or heteropolyacid salt solution is 1 to 5 ml / min, the stirring rate during the dropping process is 500 to 1000 r / min, and after the dropping is completed, keep the stirring rate and continue the reaction for 2 to 5 h.

[0012] Optionally, the organic solvent includes at least one of dichloromethane, chloroform, n-heptane, toluene, and tetrahydrofuran.

[0013] Optionally, the oil-soluble tungsten-based catalyst solution is mixed with crude oil through a static mixer and enters from the bottom of the slurry bed reactor together with hydrogen for heavy oil hydrocracking reaction.

[0014] Optionally, the catalyst addition amount is 500 to 1500 ppm, the reaction temperature is 330 to 460 °C, the reaction pressure is 5 to 20 MPa, and the liquid hourly space velocity is 0.2 to 1.5 h -1 , and the volume ratio of hydrogen to the raw material is 300 to 1500.

[0015] Optionally, the crude oil is one or more of paraffinic crude oil, intermediate crude oil, and naphthenic crude oil.

[0016] The beneficial effects of the present invention are as follows:

[0017] (1) A preparation method of an organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation provided by the present invention, the chemical formula of the modified heteropolyacid precursor is [(C a H b O c X d ) n [M e Y f O g H h , where n≥1, [M e Y f O g H h is the anion of the heteropolyacid, X includes N or S, Y includes P and / or Si, M includes any one or at least two combinations of W and Mo, Fe, Co, Ni or Cr, a:(b + c + d) ≤ 1:2. As the main agent metal, W can be flexibly proportioned with other promoter metals to achieve atomic-level dispersion, uniform distribution, strong synergy, better realize the synergy of bimetal or polymetal, and obtain a highly active catalyst.

[0018] (2) A preparation method of an organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation provided by the present invention, the preparation method is simple, the raw materials are widely sourced and reasonably priced. After modification, the precursor not only has good dispersibility but also high stability, can be well dissolved in the heavy oil system, has good oil solubility, can achieve ultra-high dispersion of the active metal in the feed oil, and has good hydrogenation performance and coke inhibition performance. Detailed implementation mode

[0019] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention. Brief description of the drawings

[0020] Figure 1 It is the dispersion diagram of Example 1 dissolved in toluene.

[0021] Figure 2 It is the high-resolution transmission electron microscope image of the catalyst of Example 1.

[0022] Figure 3 It is the HAADF-STEM-EDS mapping image of the catalyst of Example 1.

[0023] The preparation method of an organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation of the present invention will be described in detail below in conjunction with specific embodiments.

[0024] Example 1

[0025] This example provides a Keggin-type NiW heteropolyacid modified as a slurry bed catalyst precursor, and the catalyst precursor is prepared by the following method:

[0026] (1) Add 50 ml of an aqueous solution containing 2.49 g of nickel acetate to 100 ml of an aqueous solution containing 9.87 g of sodium tungstate and 0.425 g of disodium hydrogen phosphate. After adjusting the pH to 6.5 with acetic acid, heat under reflux for 2 h, then perform hot filtration. Add 4 g of potassium acetate to the filtrate, separate out the green crystals, wash and dry them;

[0027] (2) First, take 0.1 mol of K 6 Na[Ni 3 (H 2 O) 3 PW 10 O 39 ·H 2 O]·12H 2 O and dissolve it in 50 ml of deionized water to obtain a solution;

[0028] (3) Weigh 0.7 mol of dioctadecyldimethylammonium bromide and dissolve it in 50 ml of dichloroethane. Slowly add it drop by drop to the heteropolyacid salt solution in step (2) at a dropping rate of 3 ml / min and a stirring rate of 700 r / min. After the addition is completed, continue the reaction for 4 h while maintaining the stirring rate;

[0029] (4) After the above reaction ends, let it stand for a preset time length and then separate the organic phase. Then wash it 3 times with water, add anhydrous sodium sulfate for drying, stir, filter by suction, rotary evaporate to remove the solvent, and then obtain the NiW-based oil-soluble catalyst precursor after drying treatment.

[0030] Example 2

[0031] This example provides a sandwich-type CoW heteropolyacid modified as a slurry bed catalyst precursor, and the catalyst precursor is prepared by the following method:

[0032] (1) Dissolve 0.095 g of CoCl 2 and 1.0 g of K 8 [γ-SiW 10 O 36 in 20 ml of 1 mol·L -1 KCl solution, and then slowly add drop by drop 0.1 mol·L -1HCl solution was added until pH = 4.5, the mixture was heated to 50 °C for half an hour, cooled to room temperature, and slowly evaporated to obtain dark purple crystals;

[0033] (2) First, the K 10 [Co 2 (H 2 O) 2 (γ-SiW 10 O 35 ) 2 ·H 2 O]·8.25H 2 O of 0.1 mol was dissolved in deionized water to obtain a solution;

[0034] (3) 0.8 mol of dioctadecyl dimethyl ammonium bromide was weighed and dissolved in 50 ml of dichloroethane, and it was added dropwise to the heteropolyacid salt solution in step (2) at a dropping rate of 3 ml / min and a stirring rate of 700 r / min. After the dropping was completed, the stirring rate was maintained and the reaction continued for 4 h;

[0035] (4) After the above reaction was completed, the organic phase was separated by liquid separation after standing for a preset time length, then washed 3 times with water, dried with anhydrous sodium sulfate, stirred, filtered by suction, the solvent was removed by rotary evaporation, and then dried to obtain the CoW-based oil-soluble catalyst precursor.

[0036] Example 3

[0037] This example provides a Keggin-type MoW heteropolyacid modified as a slurry bed catalyst precursor, and the catalyst precursor is prepared by the following method:

[0038] (1) 182 g of sodium tungstate (Na 2 WO 4 ,2H 2 O) and 11 g of Na 2 SiO 3 ,5H 2 O were dissolved in 300 mL of hot water (60 °C), 195 mL of hydrochloric acid was added, boiled for 1 hour, cooled to room temperature, and solid KCl (about 50 g) was added to precipitate potassium salts, and then filtered and separated;

[0039] (2) 6 mL of nitric acid was added to 10 mL of Na 2 MoO 4 solution, and then 10 g of K 8 [SiW 11 O 39 was added in portions to precipitate a yellow solid;

[0040] (3) First, the H 4 [SiMo 1W 11 O 40 ] Take 0.1 mol and dissolve it in 50 ml of deionized water to obtain a solution;

[0041] (4) Weigh 0.4 mol of dioctadecyl dimethyl ammonium bromide and dissolve it in 50 ml of dichloroethane, and add it dropwise to the heteropolyacid salt solution in step (3) at a dropping speed of 3 ml / min and a stirring rate of 700 r / min. After the dropping is completed, the stirring rate is maintained and the reaction is continued for 4 hours;

[0042] (5) After the above reaction is completed, the mixture is allowed to stand for a preset time and then separated to obtain an organic phase, which is then washed with water three times, dried by adding anhydrous sodium sulfate, stirred, filtered, and evaporated to remove the solvent, and then dried to obtain a MoW-based oil-soluble catalyst precursor.

[0043] Example 4

[0044] This embodiment provides a lacuna Keggin-type W-based heteropoly acid modified as a slurry bed catalyst precursor, and the catalyst precursor is prepared by the following method:

[0045] (1) 120 g Na 2 WO 4 ·2H 2 O was dissolved in 150 mL of water and stirred until the solid was completely dissolved. Then 4.0 mL (85%) of phosphoric acid was added dropwise. Under vigorous stirring, 22.5 mL of 0.40 mol of acetic acid was added dropwise to produce a large amount of white precipitate. The final pH of the solution was 7.5 ± 0.3. The solution was stirred for 1 h, and the precipitate was filtered and dried.

[0046] (2) First, the Na obtained in step (1) 9 [PW 9 O 34 ]·7H 2 Take 0.1 mol of O and dissolve it in deionized water to obtain a solution;

[0047] (3) Weigh 0.9 mol of dioctadecyl dimethyl ammonium bromide and dissolve it in 50 ml of dichloroethane, and add it dropwise to the heteropolyacid salt solution in step (2) at a dropping speed of 3 ml / min and a stirring rate of 700 r / min. After the dropping is completed, the stirring rate is maintained and the reaction is continued for 4 hours;

[0048] (4) After the above reaction is completed, the mixture is allowed to stand for a preset time and then separated to obtain an organic phase, which is then washed with water three times, dried by adding anhydrous sodium sulfate, stirred, filtered, and evaporated to remove the solvent, and then dried to obtain a W-based oil-soluble catalyst precursor.

[0049] The W-based oil-soluble catalysts prepared in the above Examples 1 to 4 were subjected to oil solubility tests, and good oil solubility was exhibited in both toluene, base oil, and aviation kerosene. Figure 1 The photo of the catalyst precursor prepared in Example 1 of the present invention dissolved in toluene is given. It can be seen that it dissolves well in toluene and the solution is clear. By adding 500 ppm of the W-based oil-soluble catalysts prepared in the above Examples 1 to 4 to 100 g of Marlim residue oil for heavy oil hydrotreating reaction, the reaction results are shown in the following table.

[0050] Table 1: Basic property parameters of the oil for evaluating the activity of the molybdenum organic acid oil-soluble catalyst

[0051]

[0052]

[0053] Table 2: Product distribution of Marlim residue oil hydrotreating reaction

[0054]

[0055] According to Table 1 and Table 2 above, it can be seen that under the action of the W-based oil-soluble catalyst prepared in the examples of the present invention, the coking rate in the products after the hydrotreating reaction of Marlim residue oil is significantly reduced. Figure 2 、 3 The HRTEM image and HAADF-STEM-EDS mapping image after the use of the hydrotreating catalyst prepared in Example 1 of the present invention are given. It can be seen that its size is small and the Ni and W elements are evenly distributed.

[0056] Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the embodiments of the present invention. Thus, if these modifications and variations of the embodiments of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these changes and modifications.

Claims

1. A method for preparing a slurry bed hydrogenation tungsten-based oil-soluble catalyst using a modified heteropoly acid as a precursor, characterized in that: Here are the steps: (1) firstly dissolving a W-based heteropoly acid or a heteropoly acid salt in a solvent to obtain a solution; (2) dissolving the modifier in an organic solvent to obtain a solution; adding the modifier solution dropwise to the prepared W-based heteropolyacid or heteropolyacid solution according to a molar ratio of the modifier to the W-based heteropolyacid or heteropolyacid salt of 1:1-64, wherein the dropping rate is 1-5 ml / min, the stirring rate during the dropping process is 500-1000 r / min, and after the dropping is completed, the stirring rate is maintained to continue the reaction for 2-5 hours; (3) After the above reaction is completed, the mixture is allowed to stand for a preset time and then separated to obtain an organic phase, which is then washed with water for a certain number of times, dried by adding anhydrous sodium sulfate, stirred, filtered, and evaporated to remove the solvent, and then dried to obtain a W-based oil-soluble catalyst precursor.

2. The method for preparing a slurry bed hydrogenation tungsten-based oil-soluble catalyst using a modified heteropoly acid as a precursor according to claim 1, characterized in that: The W-based heteropoly acid or heteropoly acid salt includes at least one of Anderson type, Keggin type, Standberg type, Dawson type, Weakley type, Finke type, substituted type, sandwich type, and heteropoly blue.

3. The method for preparing a slurry bed hydrogenation tungsten-based oil-soluble catalyst using a modified heteropoly acid as a precursor according to claim 1, characterized in that: The modifier includes at least one of fatty amine hydrochloride, fatty imidazoline acetate, alkyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, imidazole type ammonium salt, polyquaternary ammonium salt, dialkyl dimethyl ammonium chloride, alkyl pyridinium chloride, alkyl amino acetate, alkyl dimethyl amino acetate, Jimiqi gemini quaternary ammonium salt and polyquaternary ammonium salt.

4. The method for preparing a slurry bed hydrogenation tungsten-based oil-soluble catalyst using a modified heteropoly acid as a precursor according to claim 1, characterized in that: The modifier solution is added dropwise to the prepared W-based heteropolyacid or heteropolyacid salt solution at a dropping rate of 1-5 ml / min, and the stirring rate during the dropping process is 500-1000 r / min. After the dropping is completed, the stirring rate is maintained to continue the reaction for 2-5 hours.

5. The slurry bed hydrogenation preparation method using modified heteropoly acid as precursor according to claim 1, characterized in that: The organic solvent includes at least one of dichloromethane, chloroform, n-heptane, toluene and tetrahydrofuran.

6. An application of a tungsten-based oil-soluble catalyst, prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The oil-soluble tungsten-based catalyst solution is mixed with crude oil through a static mixer and enters the bottom of the slurry bed reactor together with hydrogen to carry out heavy oil hydrocracking reaction.

7. The use of a tungsten-based catalyst according to claim 6, characterized in that: The catalyst addition amount is 500-1500ppm, the reaction temperature is 330-460℃, the reaction pressure is 5-20MPa, and the liquid hourly volume space velocity is 0.2-1.5h -1 , the volume ratio of hydrogen to raw material is 300-1500.

8. The use of a tungsten-based oil-soluble catalyst according to claim 6 or 7, characterized in that: The crude oil is one of paraffin-based crude oil, intermediate-based crude oil and naphthenic crude oil.

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