阅读说明：本技术 劣质重油改质磁载催化剂及其制备方法与应用 (Magnetic-carrier catalyst for modifying inferior heavy oil and preparation method and application thereof ) 是由 毕秦岭 杨良嵘 马安 朱向阳 王路海 倪善 许倩 邢慧芳 刘银东 安振涛 王丽涛 于 2020-05-07 设计创作，主要内容包括：本发明公开了一种劣质重油改质磁载催化剂及其制备方法与应用,该催化剂包括Fe-(3)O-(4)磁性微球,包覆于Fe-(3)O-(4)磁性微球外的SiO-(2)层和MoS-(2)层。该制备方法包括如下步骤：步骤1,将Fe-(3)O-(4)磁性微球和硅前驱体加入溶剂中,调节pH值,进行水解反应,得到SiO-(2)层包覆的Fe-(3)O-(4)磁性微球；以及步骤2,将SiO-(2)层包覆的Fe-(3)O-(4)磁性微球、钼前驱体和硫前驱体加入无机溶剂中,加热反应,得到劣质重油改质磁载催化剂。本发明制备的Fe-(3)O-(4)/SiO-(2)/MoS-(2)磁性催化剂尺寸均匀,用于劣质重油加氢改质具有高加氢活性,改质效果好,且可以利用其磁性通过外加磁场进行回收并重复利用,磁载催化剂回收率可达95％以上。(The invention discloses an inferior heavy oil modified magnetic-supported catalyst, a preparation method and application thereof, wherein the catalyst comprises Fe 3 O 4 Magnetic microspheres coated with Fe 3 O 4 SiO outside magnetic microsphere 2 Layer and MoS 2 And (3) a layer. The preparation method comprises the following steps: step 1, adding Fe 3 O 4 Adding the magnetic microspheres and the silicon precursor into a solvent, adjusting the pH value, and performing hydrolysis reaction to obtain SiO 2 Layer coated Fe 3 O 4 Magnetic microspheres; and step 2, SiO 2 Layer coated Fe 3 O 4 Adding the magnetic microspheres, the molybdenum precursor and the sulfur precursor into an inorganic solvent, and heating for reaction to obtain the inferior heavy oil modified magnetic-supported catalyst. Fe prepared by the invention 3 O 4 /SiO 2 /MoS 2 The magnetic catalyst has uniform size, high hydrogenation activity when used for hydrogenation modification of inferior heavy oil, good modification effect, and can be recovered and recycled by using the magnetism of the magnetic catalyst through an external magnetic field, and the recovery rate of the magnetic-supported catalyst can reach more than 95%.)

1. The magnetic carrier catalyst for modifying inferior heavy oil is characterized by comprising Fe₃O₄Magnetic microspheres coated with Fe₃O₄SiO outside magnetic microsphere₂Layer and MoS₂And (3) a layer.

2. The magnetic catalyst as claimed in claim 1, wherein the SiO is selected from the group consisting of₂Coated on Fe₃O₄Outside the magnetic microsphere, MoS₂Is coated on SiO₂And (6) outside the layer.

3. The magnetic catalyst as claimed in claim 2, wherein the Fe is selected from the group consisting of Fe, and Fe, wherein the Fe, and Fe is selected by weight, and Fe₃O₄The particle size of the magnetic microsphere is 20-200 nm.

4. The magnetic catalyst as claimed in claim 2, wherein the particle size of the catalyst is 25-500 nm; the bulk density of the catalyst with the particle diameter of 25-75nm is 1.28-1.39g/cm³The bulk density of the catalyst with the particle size of 220-270nm is 1.12-1.22g/cm³。

5. A preparation method of an inferior heavy oil modified magnetic-supported catalyst is characterized by comprising the following steps:

step 1, adding Fe₃O₄Adding magnetic microsphere and silicon precursor into solvent, and regulating pH value, hydrolysis reaction is carried out to obtain SiO₂Layer coated Fe₃O₄Magnetic microspheres;

step 2, SiO₂Layer coated Fe₃O₄Adding the magnetic microspheres, the molybdenum precursor and the sulfur precursor into an inorganic solvent, and heating for reaction to obtain the inferior heavy oil modified magnetic-supported catalyst.

6. The method for preparing the magnetic catalyst for upgrading the inferior heavy oil according to claim 5, wherein the Fe is Fe₃O₄The magnetic microsphere is prepared by carrying out solvothermal reaction on iron salt and a reducing agent.

7. The method for preparing the magnetic catalyst for upgrading the inferior heavy oil according to claim 6, wherein Fe is used₃O₄In the preparation process of the magnetic microspheres, the reducing agent is organic alcohol; fe₃O₄Organic sodium salt, polyethylene glycol and caustic alkali are also added in the preparation process of the magnetic microspheres.

8. The method for preparing the magnetic catalyst for upgrading the inferior heavy oil according to claim 7, wherein the Fe is Fe₃O₄In the preparation process of the magnetic microspheres, the mass ratio of the organic alcohol, the ferric salt, the organic sodium salt, the polyethylene glycol and the caustic alkali is 5-20: 1: 1-5: 4-10: 0.1-0.5; the iron salt is FeCl₃、FeCl₂The organic alcohol is one or two of ethylene glycol and propylene glycol, and the organic sodium salt is one or more of anhydrous sodium acetate, sodium stearate and sodium benzoate; the reaction temperature of the solvothermal reaction is 80-220 ℃.

9. The method for preparing the magnetic catalyst for upgrading the inferior heavy oil according to claim 5, wherein in the step 1, the silicon precursor is one or more of ethyl orthosilicate, sodium orthosilicate and sodium metasilicate, and Fe₃O₄The mass ratio of the magnetic microspheres to the solvent to the silicon precursor is 1:80-500: 8-25; adjusting pH to 8-11.

10. The method for preparing the magnetic catalyst for upgrading the inferior heavy oil according to claim 5, wherein in the step 2, the sulfur precursor is one or more of thiourea, thioacetamide and L-cysteine; the molybdenum precursor is one or more of ammonium molybdate tetrahydrate, sodium molybdate, potassium molybdate and sodium thiomolybdate; the SiO₂Layer coated Fe₃O₄The mass ratio of the magnetic microspheres to the molybdenum precursor to the sulfur precursor is 1:5-15: 10-30; the reaction temperature of the heating reaction is 160-240 ℃.

11. The use of the magnetically supported catalyst for upgrading inferior heavy oil according to any one of claims 1 to 4 in the hydro-upgrading of inferior heavy oil.

Technical Field

The invention relates to an inferior heavy oil modified magnetic-supported catalyst, a preparation method and application thereof, belonging to the field of inferior heavy oil hydro-modification.

Background

With the development of global economy, the demand for energy is still increasing. In current energy configurations, oil still dominates. However, with continuous exploitation and utilization of light crude oil, the trend of crude oil quality deterioration becomes more and more obvious, and the exploitation, storage, transportation and processing technology of inferior heavy oil is in urgent need of development. Because some inferior heavy oil such as canadian oil sand bitumen and venezuela heavy oil have high viscosity, do not flow at normal temperature and cannot directly enter an oil pipeline for conveying and processing, a new technology suitable for modifying the inferior heavy oil is developed, the viscosity of the heavy oil is reduced, and the storage and transportation of the inferior heavy oil are urgent and crucial.

The current technologies applied to heavy oil upgrading mainly comprise thermal viscosity reduction, delayed coking, solvent deasphalting, temporary (hydrogenation) viscosity reduction and the like. Because the crude oil enters a public pipeline and has the requirements on safety and stability, the oil product after thermal viscosity reduction and delayed coking can meet the requirement on the content of unsaturated hydrocarbon only by hydrotreating, and the solvent deasphalting has low utilization rate on the crude oil and can not meet the requirement on large-scale modification, the hydro-modification becomes a good choice. However, if the catalyst is separated by adopting the traditional rectification process after hydrogenation, the process is long and the catalyst is not easy to separate and recycle.

Magnetic loading and separation of the catalyst are commonly found in food processing, pharmacy and water treatment industries, and no report is found on the research of the catalyst for modifying high-viscosity inferior heavy oil. The high-efficiency hydrogenation catalyst such as molybdenum disulfide and the like which is reported in the prior publication is mainly concerned with the high activity and dispersity of the heavy oil hydrogenation catalyst in the research aspect. For example, CN103349999A discloses the preparation and application of an oil-soluble molybdenum sulfide-based catalyst, and no report is found on the research on the separation, recovery and reutilization of the catalyst; for another example: CN105435818A discloses a surface amphiphilic nano molybdenum disulfide hydrogenation catalyst, a preparation method and an application thereof, and is characterized in that ionic liquid is added into a synthesis system, so that the prepared molybdenum disulfide has good surface amphipathy, and has good dispersibility and catalytic activity in polar and non-polar systems.

CN107349940A discloses a preparation method and application of a Z-type magnetic nano composite material molybdenum disulfide/cobalt tetraoxydipherase photocatalyst. The method is characterized in that the method respectively prepares the CoFe by using solvothermal method and hydrothermal method₂O₄Magnetic nanoparticles and molybdenum disulfide nanosheets. The magnetic molybdenum disulfide catalyst is prepared, but the magnetic core is not coated by a protective layer, and the magnetic molybdenum disulfide catalyst is only applied to a sewage system with mild conditions and low viscosity and cannot be used for high-temperature (400 ℃) high-viscosity inferior heavy oil hydrotreating.

Disclosure of Invention

The invention mainly aims to provide an inferior heavy oil modification magnetic-carrier catalyst, and a preparation method and application thereof, so as to overcome the defects that the inferior heavy oil modification catalyst is difficult to recover, and the catalyst cannot be used under inferior conditions in the prior art.

In order to achieve the aim, the invention provides a magnetic carrier catalyst for modifying inferior heavy oilCatalyst, the catalyst comprising Fe₃O₄Magnetic microspheres coated with Fe₃O₄SiO outside magnetic microsphere₂Layer and MoS₂And (3) a layer.

In one embodiment, the SiO₂Coated on Fe₃O₄Outside the magnetic microsphere, MoS₂Is coated on SiO₂And (6) outside the layer.

In one embodiment, the Fe₃O₄The particle size of the magnetic microsphere is 20-200 nm.

In one embodiment, the catalyst has a particle size of 25 to 500 nm; the bulk density of the catalyst with the particle diameter of 25-75nm is 1.28-1.39g/cm³The bulk density of the catalyst with the particle size of 220-270nm is 1.12-1.22g/cm³。

In order to achieve the above purpose, the invention further provides a preparation method of the magnetic-supported catalyst for modifying inferior heavy oil, which comprises the following steps:

step 1, adding Fe₃O₄Adding the magnetic microspheres and the silicon precursor into a solvent, adjusting the pH value, and performing hydrolysis reaction to obtain SiO₂Layer coated Fe₃O₄Magnetic microspheres;

step 2, SiO₂Layer coated Fe₃O₄Adding the magnetic microspheres, the molybdenum precursor and the sulfur precursor into an inorganic solvent, and heating for reaction to obtain the inferior heavy oil modified magnetic-supported catalyst.

In one embodiment, the Fe₃O₄The magnetic microsphere is prepared by carrying out solvothermal reaction on iron salt and a reducing agent.

In one embodiment, Fe₃O₄In the preparation process of the magnetic microspheres, the reducing agent is organic alcohol; fe₃O₄Organic sodium salt, polyethylene glycol and caustic alkali are also added in the preparation process of the magnetic microspheres.

In one embodiment, Fe₃O₄In the preparation process of the magnetic microspheres, the mass ratio of the organic alcohol, the ferric salt, the organic sodium salt, the polyethylene glycol and the caustic alkali is 5-20: 1: 1-5: 4-10: 0.1-0.5; the iron salt is FeCl₃、FeCl₂The organic alcohol is one or two of ethylene glycol and propylene glycol, and the organic sodium salt is one or more of anhydrous sodium acetate, sodium stearate and sodium benzoate; the reaction temperature of the thermal reaction is 80-220 ℃.

In one embodiment, in step 1, the silicon precursor is one or more of ethyl orthosilicate, sodium orthosilicate and sodium metasilicate, and Fe₃O₄The mass ratio of the magnetic microspheres to the solvent to the silicon precursor is 1:80-500: 8-25; adjusting pH to 8-11.

In one embodiment, in step 2, the sulfur precursor is one or more of thiourea, thioacetamide and L-cysteine; the molybdenum precursor is one or more of ammonium molybdate tetrahydrate, sodium molybdate, potassium molybdate and sodium thiomolybdate; the SiO₂Layer coated Fe₃O₄The mass ratio of the magnetic microspheres to the molybdenum precursor to the sulfur precursor is 1:5-15: 10-30; the reaction temperature of the heating reaction is 160-240 ℃.

In order to achieve the purpose, the invention further provides an application of the magnetic-supported catalyst for upgrading the inferior heavy oil in the hydro-upgrading of the inferior heavy oil.

The invention has the beneficial effects that:

the magnetic-carrier catalyst for modifying inferior heavy oil is Fe₃O₄As magnetic nuclei, Fe₃O₄Compared with other magnetic cores, e.g. CoFe₂O₄Easy to obtain and low in cost; the catalyst of the invention is made of SiO₂Layer coated Fe₃O₄The magnetic core is protected so as to be difficult to demagnetize at high temperature; the catalyst is applied to hydro-upgrading of high-temperature (above 400 ℃) high-viscosity inferior heavy oil, can realize the effect of efficient upgrading and viscosity reduction of inferior heavy oil, and is easy to recycle. Therefore, the magnetic-supported catalyst has great application potential in the aspects of modifying the inferior heavy oil such as Canadian oil sand asphalt, Venezuela extra heavy oil, Liaohe heavy oil, Cramay heavy oil and the like and reducing the storage and transportation cost.

The catalyst of the invention utilizes the magnetic supported catalyst, can be separated for recycling by a magnetic separation method directly after the inferior heavy oil is modified, has simple process and high utilization rate of the catalyst, and can greatly reduce the modification cost.

Drawings

FIG. 1 is Fe of the present invention₃O₄Transmission electron micrographs of magnetic microspheres;

FIG. 2 shows Fe of the present invention₃O₄/SiO₂(SiO₂Layer coated Fe₃O₄Magnetic microspheres);

FIG. 3 shows Fe of the present invention₃O₄/SiO₂/MoS₂Transmission electron micrograph of catalyst.

Detailed Description

The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.

The invention discloses a preparation method of an inferior heavy oil modified magnetic-supported catalyst, which comprises the following steps:

step 1, adding Fe₃O₄Adding the magnetic microspheres and the silicon precursor into a solvent, adjusting the pH value, and performing hydrolysis reaction to obtain SiO₂Layer coated Fe₃O₄Magnetic microspheres;

step 2, SiO₂Layer coated Fe₃O₄Adding the magnetic microspheres, the molybdenum precursor and the sulfur precursor into an inorganic solvent, and heating for reaction to obtain the inferior heavy oil modified magnetic-supported catalyst.

Fe of the invention₃O₄The magnetic microspheres can be prepared by a solvothermal method, specifically can be prepared by carrying out thermal reaction on iron salt and a reducing agent, and can also be added with organic sodium salt, polyethylene glycol, caustic alkali and the like in the preparation process. As a preferred embodiment, Fe₃O₄The preparation method of the magnetic microsphere comprises the following steps: mixing several materials including reducing agent, iron salt, organic sodium salt, polyethylene glycol and caustic alkaliAdding the mixture into a reactor according to the mass ratio, uniformly mixing at 10-45 ℃, preparing an initial reaction mixture, adding the initial reaction mixture into a reaction kettle, and heating and reacting at 80-220 ℃ for 12-24 hours to obtain Fe₃O₄Cooling the mixture of the magnetic microspheres and the reaction solvent to 12-35 ℃, separating and recovering the mixture by using a magnet, washing, freeze-drying and storing for later use.

Wherein, the reducing agent can be organic alcohol, preferably ethylene glycol, propylene glycol or a mixture of the two; the ferric salt can be ferric trichloride, ferric dichloride or a mixture of the ferric trichloride and the ferric dichloride; the organic sodium salt can be one or more of sodium acetate, sodium stearate and sodium benzoate; the polyethylene glycol of the present invention is not particularly limited, and commercially available products such as polyethylene glycol 6000; the caustic alkali can be one or more of sodium hydroxide, potassium hydroxide and ammonia water.

As a preferred embodiment, the reducing agent, iron salt, organic sodium salt, polyethylene glycol and caustic alkali are mixed according to the mass ratio of 5-20: 1: 1-5: 4-10: 0.1-0.5, and the mass ratio is more preferably 6-18: 1: 2-4: 3-9: 0.15-0.45. Fe of the invention₃O₄The particle size of the magnetic microspheres can be controlled by adjusting the material ratio, the reaction time, the reaction temperature and the like. It should be noted that the reducing agent of the present invention can also be used as a solvent for the solvothermal reaction of the present invention, so as to provide a medium for the smooth progress of the reaction.

In one embodiment, the molar concentration of the iron salt in the initial reaction mixture is 0.01-0.5mol/L, the molar concentration of the organic sodium salt is 0.1-1mol/L, the molar concentration of the polyethylene glycol is 0.0001-0.1mol/L, and the molar concentration of the caustic alkali is 0.1-0.5 mol/L.

Step 1 of the invention is to prepare SiO by hydrolysis reaction₂Coated Fe₃O₄Magnetic microspheres, i.e. Fe₃O₄/SiO₂Magnetic nanoparticles, as a preferred technical solution, SiO₂Coated Fe₃O₄The preparation method of the magnetic microsphere comprises the following steps: mixing Fe₃O₄Adding the magnetic microspheres into an organic solvent such as absolute ethyl alcohol, sequentially adding a silicon precursor and a pH value regulator, and stirring at 12-35 ℃ for 2-E8 hours later, the precipitate is Fe₃O₄/SiO₂And separating and recovering the magnetic nano particles by using a magnet after the reaction is finished, washing, freeze-drying and storing for later use.

Wherein, the silicon precursor can be tetraethoxysilane and can also be replaced by other kinds of silicon salts such as water-soluble silicate such as sodium orthosilicate, sodium metasilicate and the like; the pH regulator may be any one of ammonia water and alkali salts of lithium, sodium and potassium capable of forming soluble salts with silicate.

As a preferred technical scheme, the Fe-based catalyst provided by the invention₃O₄The mass ratio of the magnetic microspheres, the organic solvent, the silicon precursor and the pH value regulator is 1:80-500:8-25:7-18, and the more preferable mass ratio is 1:90-450:10-20: 8-16. SiO of the invention₂The coating thickness of the layer can be controlled by adjusting the dosage of the silicon precursor and the pH value regulator, hydrolysis time and the like.

In one embodiment, the pH adjusting agent adjusts the pH of the mixture to 8-11.

Step 2 of the invention is to prepare the magnetic-supported catalyst for modifying the inferior heavy oil, namely Fe, by hydrothermal reaction₃O₄/SiO₂/MoS₂The catalyst is magnetically supported. As a preferred technical scheme, the step 2 of the invention is as follows: mixing SiO₂Layer coated Fe₃O₄Dispersing the magnetic microspheres into an inorganic solvent such as distilled water again, sequentially adding a molybdenum precursor and a sulfur precursor, uniformly stirring, adding into a reaction kettle, heating to 160-240 ℃, reacting for 4-24 hours, cooling to 12-35 ℃, separating and recovering by using a magnet after the reaction is finished, washing, and freeze-drying to obtain solid powder, namely Fe₃O₄/SiO₂/MoS₂The catalyst is magnetically supported.

Wherein, the sulfur precursor can be thiourea, and can also be replaced by other kinds of sulfur-containing salts, such as thioacetamide, L-cysteine, and the like. The molybdenum precursor may be ammonium molybdate tetrahydrate, or may be replaced by other molybdenum salts, such as thioacetamide, L-cysteine, sodium molybdate, sodium thiomolybdate, potassium thiomolybdate, etc.

As a preferred technical scheme, the inventionFe₃O₄/SiO₂The mass ratio of the magnetic nano-particles to the molybdenum precursor to the sulfur precursor is 1:5-15:10-30, preferably 1:8-14.12: 29.

In one embodiment, the step 2 of the present invention is mixing the mixture uniformly with Fe₃O₄/SiO₂The molar concentration of the magnetic nano-particles is 0.1-10mol/L, the molar concentration of the sulfur precursor is 0.5-2mol/L, and the molar concentration of the molybdenum precursor is 0.01-0.1 mol/L.

Fe obtained by the above method₃O₄/SiO₂/MoS₂Magnetically supported catalyst with Fe₃O₄The magnetic microsphere is magnetic core, SiO₂Coated on Fe₃O₄Outside the magnetic microsphere, MoS₂Is coated on SiO₂Outside the layer, the catalyst has high hydro-upgrading activity to the inferior heavy oil, can be suitable for harsh hydrogenation environment of the inferior heavy oil, and can be recycled by utilizing an external magnetic field due to superparamagnetism, so that the hydro-upgrading cost is reduced.

As a preferred technical scheme, the particle diameter of the inferior heavy oil modified magnetic-supported catalyst is 50-500nm, preferably 50-250 nm; the 50nm catalyst bulk density is 1.28-1.39g/cm³250nm catalyst bulk density of 1.12-1.22g/cm³，Fe₃O₄The magnetic microsphere has a particle diameter of 20-200nm and SiO₂The thickness of the layer is 5-150 nm, MoS₂The thickness of the layer is 5-50 nm.

Fe obtained by the above preparation method₃O₄/SiO₂/MoS₂The catalyst has good application effect in the hydro-upgrading of the 350 ℃ normal slag of Canadian oil sand asphalt and the 350 ℃ normal slag of Venezuela inferior heavy oil, and the 100 ℃ kinematic viscosity of the Canadian oil sand asphalt can be 860mm from 850-²The/s is reduced to 40-52mm²The 350 ℃ normal slag kinematic viscosity of the venezuela inferior heavy oil can be 430mm²The/s is reduced to 35-42mm²/s，。

Fe obtained by the above preparation method₃O₄/SiO₂/MoS₂The magnetic carrier is used for carrying the catalyst,after the Canadian oil sand asphalt or Venezuela poor-quality heavy oil is subjected to hydrogenation modification at 350 ℃ and normal slag, the catalyst can be separated and recovered by magnetic force at 100 ℃, and the separation recovery rate reaches more than 95%.

The catalyst is formed by utilizing magnetic loading, and is directly separated out by a magnetic separation method for recycling after modification, so that the process is simple, the utilization rate of the catalyst is high, and the modification cost can be greatly reduced.

The invention discloses Fe₃O₄/SiO₂/MoS₂The preparation method of the magnetic catalyst and the application result of the magnetic catalyst in the aspect of hydro-upgrading of the inferior heavy oil have the advantages that the catalyst can realize double aims of efficient viscosity reduction of the inferior heavy oil and efficient separation of the catalyst.

The technical solution of the present invention will be further described in detail by specific examples.

Example 1

500ml of ethylene glycol was added to the reaction vessel, and 30g of FeCl was added₃·6H₂O, 60g of anhydrous sodium acetate, 130g of polyethylene glycol 6000 and 6g of sodium hydroxide are uniformly stirred at 25 ℃, then the solution is added into a reaction kettle for reaction, and the reaction is carried out for 15 hours at 200 ℃ to prepare Fe₃O₄Cooling the nanoparticles to 25 deg.C, separating and recovering with magnet, washing, and freeze drying. Fe to be prepared₃O₄Dispersing the nano particles into 500ml of absolute ethyl alcohol again, adding 20ml of ethyl orthosilicate and 25ml of ammonia water in sequence, and stirring for 3 hours at 25 ℃ to prepare Fe₃O₄/SiO₂And (4) separating and recovering the magnetic nanoparticles by using a magnet after the magnetic nanoparticles are finished, washing, and freeze-drying. Weighing 1g of Fe₃O₄/SiO₂Dispersing the magnetic nano particles into 300ml of distilled water again, sequentially adding 10g of ammonium molybdate tetrahydrate and 22.8g of thiourea, uniformly stirring, adding the uniformly mixed reactants into a reaction kettle, heating and reacting at 180 ℃ for 10 hours, cooling to 25 ℃, separating and recovering by using a magnet after the reaction is finished, washing, and freeze-drying to obtain Fe₃O₄/SiO₂/MoS₂Magnetically carrying the catalyst, and storing for later use. Wherein, Fe₃O₄Magnetic microFIG. 1 shows a transmission electron microscope of the ball; fe₃O₄/SiO₂(SiO₂Layer coated Fe₃O₄Magnetic microspheres) see fig. 2; fe₃O₄/SiO₂/MoS₂The transmission electron micrograph of the catalyst is shown in FIG. 3. As can be seen from the transmission electron micrograph, Fe₃O₄The magnetic microspheres have uniform particle size distribution, average particle size of about 300nm and SiO₂The particle size is increased after the layer is coated, and the thickness of the coating layer is about 5 nm; performing MoS₂The particle diameter of the catalyst after being supported is further increased.

Fe to be prepared₃O₄/SiO₂/MoS₂The magnetic-carrier catalyst is used for the hydro-upgrading experiment of Canadian oil sand asphalt (the basic physical properties are shown in Table 1), and the kinematic viscosity of the oil sand asphalt at 100 ℃ is changed from original 850mm under the conditions of about 400 ℃, about 16Mpa of hydrogen pressure and about 500ppm of catalyst addition²The/s is reduced to 42mm²The viscosity reduction rate reaches 95.1 percent, which shows that the catalyst has better hydrogenation modification activity; the modified oil is subjected to magnetic separation at 100 ℃, and the recovery rate of the magnetic-supported catalyst is 95.3%.

Example 2

Example 2 differs from example 1 in that the silicon precursor added in step two is sodium orthosilicate, Fe₃O₄The ratio of nanoparticles to their mass is 1:8, not 1: 20, i.e., the cladding layer is thin, the other steps and parameters are the same as those of example 1. The evaluation result shows that the viscosity reduction rate of the oil sand asphalt is 95.1%, and the recovery rate of the catalyst reaches 95.5%. When the thickness of the coating layer is decreased, the content of the nonmagnetic substance outside the magnetic core is decreased, and the magnetic property of the catalyst is enhanced and the recovery rate is improved as compared with example 1. And the thickness of the coating layer has little influence on the viscosity reducing effect of the oil product.

Example 3

Example 3 differs from example 1 in that the silicon precursor added in step two is sodium orthosilicate, Fe₃O₄The ratio of nanoparticles to their mass was 1:25, not 1: 20, i.e., the clad layer is thicker, the other steps and parameters are the same as those of example 1. The evaluation result shows that the oil sand asphaltThe viscosity reduction rate is 95.2%, and the recovery rate of the catalyst reaches 95.0%. When the thickness of the coating layer was increased, the content of nonmagnetic substances outside the magnetic core was increased, and the magnetic property of the catalyst was reduced and the recovery rate was lowered compared to example 1. And the thickness of the coating layer has little influence on the viscosity reducing effect of the oil product.

Example 4

Example 4 unlike example 1, the molybdenum precursor added in step three was sodium thiomolybdate, Fe₃O₄/SiO₂The ratio of nanoparticles to their mass was 1:5, not 1: 10, i.e. the active metal content is lower, the other steps and parameters are the same as in example 1. The evaluation result shows that the viscosity reduction rate of the oil sand asphalt is 94.9 percent, and the recovery rate of the catalyst reaches 94.6 percent. When the content of active metal is reduced, the cracking activity of the catalyst is weakened, and compared with the example 1, the viscosity reduction rate of oil products is reduced, so that the recovery rate of the catalyst is reduced.

Example 5

Example 5 differs from example 1 in that the molybdenum precursor added in step three is sodium thiomolybdate, Fe₃O₄/SiO₂The ratio of nanoparticles to their mass was 1:15, not 1: 10, i.e. the active metal content is higher, the other steps and parameters are the same as in example 1. The evaluation result shows that the viscosity reduction rate of the oil sand asphalt is 95.5%, and the recovery rate of the catalyst reaches 95.8%. When the content of active metal is increased, the cracking activity of the catalyst is enhanced, and compared with the example 1, the viscosity reduction rate of oil products is increased, so that the recovery rate of the catalyst is increased.

Comparative example 1

Comparative example 1 differs from example 1 in that the silicon precursor added in step two is ethyl orthosilicate, Fe₃O₄The ratio of the nano particles to the silicon nanoparticles is 1:27, namely the silicon content is higher than 1:8-25, and other steps and parameters are the same as those of the embodiment 1. Because the silicon coating layer is too thick, the recovery rate of the magnetic-carried catalyst is reduced.

Comparative example 2

Comparative example 2 differs from example 1 in that the molybdenum precursor added in step three is sodium thiomolybdate, Fe₃O₄/SiO₂Nanoparticles and methods of making the sameThe mass ratio is 1:4, namely the content of molybdenum is lower than 1:5-15, and other steps and parameters are the same as those of the embodiment 1. The viscosity reduction rate of the catalyst is reduced due to the lower content of active metal.

Comparative example 3

The oil-soluble catalyst is prepared according to CN105435818, and the preparation method comprises the following steps: adding 0.1mmol/L sodium dithiomolybdate, 1.5mmol/L hydroxylamine hydrochloride and 0.5mmol/L benzimidazole into 100ml deionized water, and uniformly stirring to prepare an initial reaction mixture; the concentration of molybdenum in the initial reaction mixture was 1 mol/L. Transferring the initial reaction mixture into a high-pressure synthesis kettle, and crystallizing for 12 hours at 180 ℃; and after crystallization is finished, cooling the reactant to room temperature, and separating a solid product to obtain the surface amphiphilic nano molybdenum disulfide hydrogenation catalyst. The catalyst is oil soluble and has no magnetism, so that the catalyst has no recovery effect.

Comparative example 4

Comparative example 4 is different from example 1 in that comparative example 4 is the same as the catalyst of example 1, but comparative example 4 is used for modifying Venezuela heavy oil (physical properties are shown in table 2), example 1 is used for modifying Canadian oil sand bitumen, and the modification effect of comparative example 4 is similar to that of example 1 in view of modification effect, which shows that the catalyst also has good modification effect on other inferior heavy oil with similar properties.

Application effects

The catalysts prepared in examples 1-5 and comparative examples 1-4 were used in heavy oil hydrogenation catalysis viscosity reduction experiments, and a batch autoclave hydro-upgrading test evaluation was performed at a certain reaction temperature, reaction pressure and catalyst addition (see table 3). Wherein the catalyst modification objects of examples 1-5 and comparative examples 1-3 are 350 ℃ common slag of Canadian oil sand bitumen, and the catalyst modification object of comparative example 4 is 350 ℃ common slag of Venezuela inferior heavy oil. The catalyst can be subjected to magnetic separation and recovery after the inferior heavy oil is modified, the magnetic separation and recovery are carried out by applying a magnetic field to neodymium iron boron strong magnet, the visbreaking oil containing the magnetic-loaded catalyst nanoparticles after the hydrogenation evaluation of the batch autoclave is subjected to magnetic separation at 100 ℃, and the recovery rate of the catalyst can reach more than 95%.

Basic properties of canadian oil sand bitumen at 350 ℃ and venezuela inferior heavy oil at 350 ℃ used in the above examples and comparative examples are shown in tables 1 and 2, and viscosity-reducing effects and magnetic separation recovery data of the catalysts of examples 1 to 5 and comparative examples 1 to 4 for heavy oil are shown in table 3. The data in the table are the average of the results of three tests.

The basic physical properties of the canadian oil sand bitumen at 350 ℃ in normal slag are shown in the following table 1:

TABLE 1 basic properties of canadian oil sand bitumen at 350 deg.C for normal slag

The basic physical properties of the Venezuela poor-quality heavy oil at 350 ℃ and normal slag are shown in the following table 2:

TABLE 2 basic physical properties of 350 deg.C normal slag of Venezuela inferior heavy oil

TABLE 3 catalyst visbreaking Effect and magnetic separation recovery data for the examples and comparative examples

From the above examples, comparative examples and application effect data, it can be seen that Fe prepared by the process of the present invention₃O₄/SiO₂/MoS₂The magnetic-supported catalyst is used for hydrogenation modification of the current most viscous heavy oil, namely Canadian oil sand asphalt, and has better hydrogenation modification activity and magnetic separation recovery effect when the addition amount is about 500 ppm; the effect is better when the emulsion is used in Venezuela extra heavy oil (the viscosity is slightly lower at the same temperature, and the emulsion is compared with that of comparative examples 4 and 5).

Fe prepared by the method of the invention₃O₄/SiO₂/MoS₂Magnetic carrier catalyst for improving low-quality heavy oil such as Venezuela superheavy oil, Liaohe heavy oil and Cramay heavy oil by using Canada oil sand asphaltHas great application potential in the aspects of reducing viscosity and storage and transportation cost.

The catalyst of the invention also has wide popularization and application potential in the aspect of recycling the catalyst of the slurry bed.

The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.