CN103240126A - A kind of heavy oil hydrogenation catalyst containing iron ore and its preparation and application - Google Patents

Abstract

The heavy oil hydrogenation catalyst comprises iron ore-containing ultrafine powder and a dispersion medium, wherein the weight percentage of the iron ore-containing ultrafine powder is 5-70% on the basis of the catalyst; the dispersion medium contains the following components: by taking a dispersion medium as a reference, 80-99 wt% of base oil, 0.05-10 wt% of surfactant and 0.05-10 wt% of solid thickening rheological agent, wherein the base oil is distillate oil with a boiling point range of 220-550 ℃. The heavy oil hydrogenation catalyst obtained by the invention has high catalytic activity solid content, has good mixing capability with the heavy oil raw oil, and has good catalytic effect in the heavy oil hydrocracking or upgrading of a suspension bed or a slurry bed.

Description

A kind of heavy oil hydrogenation catalyst containing iron ore and its preparation and application

technical field

The invention relates to a heavy oil hydrogenation catalyst. More specifically, it is a catalyst for iron-containing ore powder used for hydrogenation of heavy oil, as well as the preparation method and application of the catalyst.

Background technique

With the gradual scarcity of conventional oil resources, the proportion of heavy oil, especially low-quality heavy oil, in the total oil is increasing. How to efficiently convert heavy oil has become a huge challenge in the energy field. The heavy oil referred to above includes asphalt, oil sands, shale oil, residual oil with a boiling point higher than 524°C, etc. Its characteristics are: high asphaltene and residual carbon content, high metal nickel and vanadium content, the total content is generally not less than 200μg/g, high S and N compound content, and high apparent viscosity at normal temperature and pressure. Inferior heavy oil is prone to clogging pipelines and reactors and producing coke due to accumulation and sedimentation of heavy oil components during heat treatment or hydrotreating.

Slurry-bed hydroupgrading and hydrocracking of heavy oil are important efficient conversion methods for heavy oil. Compared with the hydrogenation process with fixed bed and ebullating bed reactor as the main body, the use of slurry bed reactor has the following advantages: effectively strengthen the uniform mixing of catalyst, hydrogen and heavy oil macromolecules, and improve the accessibility of catalyst active centers; easy to control The temperature and pressure of the reaction process realize steady-state operation; the reactor form is suitable for the processing of inferior heavy oil, and it is easy to control the reaction depth by adjusting the reaction conditions and process. Based on the above reasons, the research on heavy oil hydro-upgrading using slurry bed reactors has attracted the attention of researchers from various countries, and the research on catalysts suitable for slurry bed reactors has become an important research direction.

Catalysts for heavy oil slurry bed include oil-soluble catalysts, such as cobalt naphthenate, nickel naphthenate, molybdenum isooctanoate and other organic metal salts or organic metal complexes; water-soluble catalysts, such as iron nitrate, nickel nitrate, ferrous sulfate, One or more mixed inorganic salt solutions such as ammonium molybdate; solid powder catalysts, such as one or more mixtures of metal sulfides or oxides such as molybdenum, iron, nickel, cobalt, molybdenum-containing ore tailings, iron-containing Ores, etc., in order to improve their dispersibility in heavy oil, generally prepare them into powders with a certain particle size distribution, and use strong mechanical mixing. The use of the three catalysts each has advantages and disadvantages.

The oil-soluble catalyst is evenly mixed with heavy oil, and after online vulcanization, the effect of catalytic hydrocracking is good, but the proportion of active metal components such as metal molybdenum is low, generally less than 10% of the total mass of the catalyst, commonly used molybdenum naphthenate, metal molybdenum The mass proportion of it is only 6.5-9.0%. For example, CN 1362492 A proposes an oil-soluble heavy oil hydrocracking catalyst containing Mo, W, benzene and its derivative complexes. According to the embodiment of the invention, the molybdenum content in the catalyst obtained by the conventional method is 7.0%. Another example is that CN 1335367 A discloses an oil-soluble catalyst containing a heterocyclic sulfo compound, which is an organic solid product containing one or more metals such as Cr, Ni, Fe, Co, Mo, W, etc., and the metal content is lower than 9 %. CN101165140A and CN101165141A propose molybdenum isooctanoate and molybdenum naphthenate catalysts, which are viscous oily and have a metal mass percentage higher than 6%, and are used in the coal refining process. When this type of catalyst is used, in order to ensure the concentration of active metals in the raw oil, a large amount is added. On the one hand, the application cost is increased, and on the other hand, the properties of the raw oil itself are affected.

When using a water-soluble catalyst, it is generally necessary to dissolve the precursor salt containing the active metal in the aqueous solution. In order to improve the dispersibility of the aqueous solution in the raw material oil, in addition to improving the physical stirring intensity, as described in CN 1295112 A, a multi- The method that water-soluble catalyst is dispersed on-line by stage shear pump or static mixer; Or need to add dispersant and surfactant component, as Petroleum University proposes two kinds of catalyst liquid sol systems in patent CN 101024186 A and CN 101011663 A, The difference is that the former is a water-in-oil system, and the latter is an oil-in-water system. Metal sulfides such as Mo, Ni, Fe, and Co are complexed and dispersed in the sol system. The metal content is generally lower than 15% of the total mass. Larger, but also to remove water in the process of use, complex operation.

When using a solid powder catalyst, its advantage is that it is easy to control the catalyst concentration, but its disadvantage is that the catalyst has poor dispersibility in heavy oil.

Contents of the invention

The object of the present invention is to provide a heavy oil hydrogenation catalyst containing iron ore, its preparation method and application. What is to be solved is that in the slurry bed or suspension bed hydrogenation process using a solid powder catalyst, the solid powder catalyst will The technical problem of poor stable dispersion performance in raw oil.

The heavy oil hydrogenation catalyst is composed of iron-containing ore ultrafine powder and a dispersion medium, based on the catalyst, the mass percentage of iron-containing ore ultrafine powder is 5-70%; the dispersion medium contains the following components : Based on the dispersion medium, 80-99% by weight of base oil, 0.05-10% by weight of surfactant, 0.05-10% by weight of solid thickening rheological agent, the base oil has a boiling point range of 220°C-550°C ℃ distillate oil.

The iron-containing ore superfine powder is a mixed powder of one or more ores selected from bauxite, pyrite, limonite, magnetite, hematite and siderite, and the iron-containing ore superfine powder is The average particle size of the fine powder is less than 80 μm.

Based on the catalyst, the mass percentage of the iron-containing ore ultrafine powder is 15-50%; preferably 20-45%. The average particle size of the iron-containing ore ultra-fine powder is less than 40 μm, more preferably less than 3 μm.

The bauxite is boehmite, also known as boehmite, the molecular formula of aluminum is Al ₂ O ₃ .H ₂ O, and the mass fraction of iron is 10-25% calculated as iron oxide. The main component of the pyrite is FeS ₂ , and the mass fraction of sulfide is 20-80%. The main chemical formula of the limonite is nFe ₂ O ₃ .mH ₂ O (n=1-3, m=1-4), and the mass fraction of Fe ₂ O ₃ in the ore is 20-40%. The molecular formula of the main component of the magnetite is Fe ₃ O ₄ , wherein the mass fraction of Fe ₃ O ₄ is 20-60%. The molecular formula of the main component of the hematite is Fe ₂ O ₃ , and the mass fraction of Fe ₂ O ₃ in the ore is 40-60%. The molecular formula of the main component of the siderite is FeCO ₃ , and the Fe content in the ore is 10-35% calculated according to Fe ₂ O ₃ . The iron-containing ore powder is directly prepared by mechanical crushing and grinding.

The base oil is selected from one or more of diesel oil, kerosene, and wax oil.

Described surfactant is ionic surfactant and/or nonionic surfactant, and ionic surfactant is selected from sodium oleate, sodium dodecylbenzenesulfonate, sodium petroleum sulfonate and fatty acid quaternary ammonium salt One or more of them, and the nonionic surfactant is one or more of polyethylene glycol, polyvinyl alcohol or octylphenol polyoxyethylene ether (OP).

The number average molecular weight of the polyethylene glycol (PEG) is 400-6000, which can be one or more of PEG400, PEG600, PEG1000, PEG2000, PEG6000, and the polyvinyl alcohol is polyvinyl alcohol with a low degree of polymerization.

Based on the dispersion medium, the amount of the surfactant is 0.1-5.0% by weight, preferably 0.3-2.0% by weight.

The solid thickening rheological agent is selected from one or more of amorphous silica, magnesium aluminate, magnesium silicate, and organic bentonite, and the particle size of the solid thickening rheological agent is less than 100 μm, preferably less than 20 μm, More preferably less than 1 μm.

Based on the dispersion medium, the amount of the solid thickening rheological agent is 0.1-5.0% by weight, preferably 0.5-3.0% by weight.

The preparation method of above-mentioned any one catalyst, comprises:

(1) Base oil is mixed with solid thickening rheological agent and homogenized with a shearing machine;

(2) Heating to 40-120°C for 0.5-3 hours;

(3) drop to room temperature, add surfactant, stir at room temperature until the system is homogeneous, and obtain a dispersion medium;

(4) Add the superfine iron-containing ore powder into the dispersion medium obtained in step (3), and disperse by shearing or high-speed stirring.

The dispersion medium of the catalyst of the present invention may also contain polar additives, based on the dispersion medium, the amount of polar additives is 0.05 to 10% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight %. Alcohol components are included in the polar additives. The alcohol component is selected from one or more of ethanol, ethylene glycol, propylene glycol, glycerol, and dipolyethylene glycol.

The preparation method of above-mentioned any one containing the catalyst of polar additive is:

(1) Base oil is mixed with solid thickening rheological agent and homogenized with a shearing machine;

(2) Heating to 40-120°C for 0.5-3 hours;

(3) drop to room temperature, add surfactant and polar additive, stir at room temperature until the system is homogeneous, and obtain a dispersion medium;

(4) Add the superfine iron-containing ore powder into the dispersion medium obtained in step (3), and disperse by shearing or high-speed stirring.

An application of any one of the catalysts above, where the catalyst is applied in the hydrogenation process of heavy oil in a slurry bed or a suspension bed.

The heavy oil hydrogenation catalyst obtained by the invention not only has high catalytic activity solid content, but also has good mixing ability with heavy oil raw material oil, and the catalyst has good dispersibility in raw material oil, reflecting good heavy oil hydrogenation catalytic activity. It has a good catalytic effect in the hydrocracking or upgrading of heavy oil in suspended bed or slurry bed. Although the hydrogenation activity is lower than that of the catalyst system containing molybdenum and nickel, it is more economical.

Detailed ways

The use effect of the present invention is further illustrated below through examples. Embodiment 1～4 illustrates the preparation method of dispersion medium, embodiment 5～8 illustrates the preparation method of catalyst, embodiment 9～14 illustrates the heavy oil hydrocracking effect of catalyst, and with oil-soluble molybdenum isooctanoate catalyst, commercially available _MoS2 Catalysts were compared.

Example 1

Weigh 38 g of diesel oil, add 1.0 g of organic bentonite (domestic, organic matter content 15-20% by weight), and homogenize with a shearing machine. Then heated and stirred on an 80° C. oil bath for 2 hours. The obtained homogeneous mixed oil was cooled to room temperature, added 0.5g PEG 600, added 0.2g sodium dodecylbenzenesulfonate, and homogenized at room temperature to obtain dispersion medium A.

Example 2

Weigh 42 g of kerosene, add 0.8 g of fumed silica (particle size less than 1 μm), and homogenize with a shearing machine. At room temperature, add 0.2 g of sodium oleate, 0.4 g of PEG2000, and 1.0 g of analytically pure ethanol. Homogenize at room temperature to obtain dispersion medium B.

Example 3

Weigh 30 g of diesel oil, 12 g of white oil, and add 1.2 g of organic bentonite (domestic, organic matter content 15-20% by weight). Homogenization is performed on a shearing machine. At room temperature, add 0.2 g of sodium oleate, 0.4 g of OP-7, and 1.0 g of analytically pure ethanol. Homogenize at room temperature to obtain dispersion medium C.

Example 4

Weigh 21g of diesel oil and 21g of white oil, and add 0.5g of fumed silica (particle size less than 1μm). Homogenization is performed on a shearing machine. At room temperature, add 0.4g PEG 4000 and add 1.5g analytically pure propylene glycol. Homogenize at room temperature to obtain dispersion medium D.

Example 5

Take bauxite powder whose average particle size is less than 40 μm, weigh 3.0 g and place it in a test tube. Weigh 5.0g of dispersion medium A into the same test tube, stir and vibrate with a glass rod, after the powder is evenly infiltrated, let it stand for 12 hours, and no obvious sedimentation occurs. Catalyst C1 is obtained.

Example 6

Take the mixed powder of hematite ore and magnetite, the average particle size of which is less than 10 μm, weigh 5.0 g and place it in a test tube. Weigh 8.0g of dispersion medium B into the same test tube, stir and vibrate with a glass rod, after the powder is evenly infiltrated, let it stand for 12 hours, no obvious sedimentation occurs. Catalyst C2 is obtained.

Example 7

Take limonite ore and siderite powder whose average particle size is less than 20 μm, weigh 5.0 g and place it in a test tube. Weigh 12.0g of dispersion medium C into the same test tube, stir and vibrate with a glass rod, and wait for the powder to infiltrate evenly, let it stand for 6 hours, and no obvious sedimentation occurs. Catalyst C3 is obtained.

Example 8

Take pyrite powder whose average particle size is less than 30 μm, weigh 4.0 g and place it in a test tube. Weigh 10.0g of dispersion medium D into the same test tube, stir and vibrate with a glass rod, after the powder is evenly infiltrated, let it stand for 8 hours, no obvious sedimentation occurs. Catalyst C4 is obtained.

Embodiment 9～14 and comparative example 1～2

The effect of the catalyst of the present invention on heavy oil hydrotreating is as follows. The raw oil is a kind of atmospheric residue with high content of asphaltenes and metals, and its properties are shown in Table 1.

Table 1

project Raw material property data project Raw material property data Density (20℃), g/ ^cm3 0.9914 Elemental analysis, weight % Kinematic viscosity, mm ² /s C 85.38 80℃ 304.5 h 10.77 100℃ 102.1 S 2.11 Carbon residue, wt% 16.6 N 0.50 Ash content, wt% 0.052 Metal analysis, μg/g Total acid value, mgKOH/g 0.3 Ni 35.9 Saturated hydrocarbons, wt% 30.8 V 201 Aromatics, weight % 36.2 Ca 5.7 Colloid, % by weight 22.1 Fe Fe 15.0 Asphaltenes, % by weight 10.9

The evaluation indicators for catalyst hydrocracking performance include: conversion rate of heavy oil, yield of liquid products, coke formation rate (yield of toluene insoluble matter). The indicators are defined as follows:

Heavy oil conversion rate = mass of components below 524°C (including gas) / mass of feedstock oil × 100%;

Liquid product yield=liquid product mass/raw material oil mass×100%.

Coke formation rate = mass of toluene insoluble matter / mass of raw material oil × 100%;

The reactor used was a 0.5-liter high-pressure stirred tank. The catalyst is vulcanized online during the heating process of the reaction, that is, sublimed sulfur is added to the reaction system as a vulcanizing agent, and the vulcanization temperature is 300-350°C.

Reaction conditions: reaction temperature 410-440°C, initial hydrogen partial pressure 5.00-9.00MPa, reaction pressure 9.50-17.00MPa, heavy oil raw material addition 120g, sublimated sulfur 0.1g, stirring speed 400r/min, reaction time 30-60min, The amount of catalyst added is as described in Table 2. Its reaction effect and comparative example effect are as described in Table 2.

Table 2

*: Calculated according to the mass of ore powder

**: Calculated according to the metal sulfide MoS ₂ , the commercially available MoS ₂ is 1000-1500 mesh, and the average particle size is 10-15 μm.

***: Calculated value after deducting catalyst mass

As can be seen from Table 2, from the reaction effect, the use effect of the catalyst provided by the present invention is close to that of the commercially available MoS2. For example, when the pyrite powder used in the catalyst _C4 is reacted at 415-420°C for 40 minutes, the reaction process produces coke The yield is 1.0% by weight. When other ore powders are used, the liquid yield is close to 90%, and the coke formation rate is close to 2% by weight. The effect is slightly worse than that of Comparative Examples 1 and 2, but the coke formation rate is much lower than that of Comparative Example 3 in which ore powder is directly used. Considering the relatively high price of the oil-soluble molybdenum-based catalyst and MoS ₂ , the combination of economical efficiency and application effect of the catalyst of the present invention is advantageous.

Claims (16)

1. the heavy-oil hydrogenation catalyst of an iron-stone is characterized in that, described heavy-oil hydrogenation catalyst is made up of iron-stone superfines and decentralized medium, is benchmark with the catalyst, and the mass percent example of iron-stone superfines is 5～70%; Described decentralized medium contains following composition: be benchmark with the decentralized medium, the base oil of 80～99 weight %, 0.05 the surfactant of～10 weight %, 0.05～10 weight % solid thickener rheology agent, described base oil are boiling spread at 220 ℃-550 ℃ distillate.

2. according to the described catalyst of claim 1, it is characterized in that, described iron-stone superfines is for being selected from one or more ore mixed-powders in bauxite, pyrite, limonite, magnetic iron ore, bloodstone and the siderite, and the average grain diameter of iron-stone superfines is less than 80 μ m.

3. according to the described catalyst of claim 1, it is characterized in that, is benchmark with the catalyst, and the mass percent example of iron-stone superfines is 15～50%; The average grain diameter of iron-stone superfines is less than 40 μ m.

4. according to the described catalyst of claim 1, it is characterized in that described base oil is selected from one or more in diesel oil, kerosene, the wax oil.

5. according to the described catalyst of claim 1, it is characterized in that, described surfactant is ionic surfactant and/or nonionic surface active agent, ionic surfactant is selected from one or more in enuatrol, neopelex, petroleum sodium sulfonate and the fatty acid quaternary ammonium salt, and nonionic surface active agent is one or more in polyethylene glycol, polyvinyl alcohol, the sim alkylphenol APEO.

6. according to the described catalyst of claim 5, it is characterized in that the number-average molecular weight of described polyethylene glycol is 400-6000, polyvinyl alcohol is polyvinyl alcohol with low degree of polymerization.

7. according to the described catalyst of claim 1, it is characterized in that, is benchmark with the decentralized medium, and the consumption of described surfactant is 0.1～5.0 weight %.

8. according to the described catalyst of claim 1, it is characterized in that described solid thickener rheology agent is selected from one or more in amorphous silica, magnesium aluminate, magnesium silicate, the organobentonite, the particle diameter of solid thickener rheology agent is less than 100 μ m.

9. according to the described catalyst of claim 8, it is characterized in that the particle diameter of described solid thickener rheology agent is less than 20 μ m.

10. according to the described catalyst of claim 1, it is characterized in that, is benchmark with the decentralized medium, and the consumption of described solid thickener rheology agent is 0.1～5.0 weight %.

11. according to the described catalyst of claim 1, it is characterized in that, also contain polar additive in the decentralized medium, be benchmark with the decentralized medium, the consumption of polar additive is 0.05～10 weight %, comprises the alcohols component in the described polar additive.

12., it is characterized in that described alcohols component is selected from ethanol, ethylene glycol, propane diols, glycerine, two polyethylene glycol one or more according to the described catalyst of claim 11.

13. according to claim 11 or 12 described catalyst, it is characterized in that, be benchmark with the decentralized medium, the consumption of polar additive is 0.1～5.0 weight %.

14. any Preparation of catalysts method of claim 1-10 comprises:

(1) base oil is mixed with the solid thickener rheology agent and homogenize with cutter;

(2) be heated to 40～120 ℃, handled 0.5～3 hour;

(3) be down to room temperature, add surfactant, at room temperature be stirred to the system homogeneous phase, obtain decentralized medium;

(4) the iron-stone superfines is added in step (3) the gained decentralized medium, and shear and disperse or the high-speed stirred dispersion.

15. any Preparation of catalysts method of claim 11-13 comprises:

(1) base oil is mixed with the solid thickener rheology agent and homogenize with cutter;

(2) be heated to 40～120 ℃, handled 0.5～3 hour;

(3) be down to room temperature, add surfactant and polar additive, at room temperature be stirred to the system homogeneous phase, obtain decentralized medium;

(4) the iron-stone superfines is added in step (3) the gained decentralized medium, and shear and disperse or the high-speed stirred dispersion.

16. any Application of Catalyst of claim 1-13, described catalyst are applied to starch in the heavy-oil hydrogenation process of attitude bed or suspension bed.