Viscosity-reducing magnetic-carrier catalyst for inferior heavy oil and preparation method and application thereof
阅读说明：本技术 劣质重油减粘磁载催化剂及其制备方法与应用 (Viscosity-reducing magnetic-carrier catalyst for inferior heavy oil and preparation method and application thereof ) 是由 何盛宝 杨良嵘 毕秦岭 朱向阳 李阳 倪善 王路海 邢慧芳 刘银东 安振涛 王丽 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减粘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、以及MoS-(2)和Ni混合层。制备方法包括：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、硫前驱体和镍前驱体加入无机溶剂中,加热反应,得到劣质重油减粘磁载催化剂。本发明催化剂可以用于劣质重油如加拿大油砂沥青加氢改质,且具有高活性,高减粘率,催化剂回收率可达95％以上。(The invention discloses a viscidity-reducing magnetic-carrier catalyst for inferior heavy oil, 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 a Ni mixed 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 to carry out 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, the sulfur precursor and the nickel precursor into an inorganic solvent, and heating for reaction to obtain the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil. The catalyst can be used for hydro-upgrading of inferior heavy oil such as Canadian oil sand asphalt, and has high activity and high viscosity reduction rate, and the recovery rate of the catalyst can reach more than 95 percent.)
1. The visbreaking magnetic-carried catalyst for poor-quality heavy oil is characterized by comprising Fe3O4Magnetic microspheres coated with Fe3O4SiO outside magnetic microsphere2Layer and MoS2And a Ni mixed layer.
2. The visbreaking magnetically supported catalyst for inferior heavy oil of claim 1, wherein the SiO is2Coated on Fe3O4Outside the magnetic microsphere, MoS2And a Ni mixed layer coated on SiO2And (6) outside the layer.
3. The visbreaking magnetically supported catalyst for inferior heavy oil of claim 2, wherein the Fe is present in the catalyst3O4The grain diameter of the magnetic microsphere is 20-200 nanometers, SiO2The thickness of the layer is 5-150 nm, MoS2And the thickness of the Ni mixed layer is 5-50 nm.
4. The visbreaking magnetic-supported catalyst for the inferior heavy oil of claim 2, wherein the particle size of the catalyst is 50-550 nm; the bulk density of the catalyst with the particle diameter of 50-100nm is 1.28-1.39g/cm3(ii) a The bulk density of the catalyst with the particle size of 320-370nm is 1.12-1.22g/cm3。
5. The preparation method of the visbreaking magnetic-supported catalyst for the inferior heavy oil is characterized by comprising the following steps of:
step 1, adding Fe3O4Adding the magnetic microspheres and the silicon precursor into a solvent, adjusting the pH value to carry out hydrolysis reaction to obtain SiO2Layer coated Fe3O4Magnetic microspheres.
Step 2, SiO2Layer coated Fe3O4Adding the magnetic microspheres, the molybdenum precursor, the sulfur precursor and the nickel precursor into an inorganic solvent, and heating for reaction to obtain the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil.
6. The method for preparing the visbreaking magnetic-supported catalyst for the inferior heavy oil of claim 5, wherein the Fe is Fe3O4The magnetic microsphere is prepared by carrying out thermal reaction on iron salt and a reducing agent.
7. The method for preparing the visbreaking magnetic-supported catalyst for the inferior heavy oil of claim 6, wherein 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.
8. The method for preparing the visbreaking magnetic-supported catalyst for the inferior heavy oil of claim 7, wherein Fe3O4In the preparation process of the magnetic microspheres, the mass ratio of the reducing agent to the ferric salt to the organic sodium salt to the polyethylene glycol to 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 ℃.
9. The method for preparing the visbreaking magnetic catalyst for 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 the pH value to 8-11.
10. The method for preparing the visbreaking magnetic catalyst for 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 nickel precursor is one or more of nickel acetate tetrahydrate, nickel chloride hexahydrate, nickel sulfate hexahydrate and nickel nitrate hexahydrate; the SiO2Layer coated Fe3O4The mass ratio of the magnetic microspheres to the molybdenum precursor to the nickel precursor to the sulfur precursor is 1:5-15:1-10: 10-30; the reaction temperature of the heating reaction is 160-240 ℃.
11. The use of the visbreaking magnetically supported catalyst for heavy oil of low quality according to any one of claims 1 to 4 in the hydro-upgrading of heavy oil of low quality.
Technical Field
The invention relates to a viscidity-reducing magnetic-carrier catalyst for inferior heavy oil, a preparation method and application thereof, belonging to the field of modification of inferior heavy oil.
Background
With the development of global economy, the demand for energy is still increasing. In current energy configurations, oil still dominates. However, as light crude oil is continuously produced and utilized, the quality of the crude oil becomes worse and worse. Heavy oils of low quality are not suitable for transportation and subsequent processing, and therefore, it is necessary to develop a technique for upgrading inferior crude oils, to reduce the viscosity of heavy oils, and to improve the API gravity.
The current technologies applied to heavy oil upgrading mainly comprise thermal viscosity reduction, delayed coking, solvent deasphalting, hydrogenation viscosity reduction and the like. Because the crude oil enters a public pipeline and has the requirements on safety and stability, and the oil product after thermal viscosity reduction and delayed coking also needs to be subjected to hydrotreating to meet the requirement on the content of unsaturated hydrocarbons, the hydro-upgrading is 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.
The magnetic loading and separation of the catalyst are commonly found in food processing, pharmacy and water treatment industries, and the research on viscosity reduction of high-viscosity inferior heavy oil is not reported. The research on the currently published and reported molybdenum disulfide heavy oil hydrogenation catalyst is mainly concerned about high activity and dispersity of the catalyst, and the separation, recovery and reutilization of the catalyst are not reported. CN105435818A discloses a surface amphiphilic nano molybdenum disulfide hydrogenation catalyst, a preparation method and application thereof. The 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. Although the catalyst prepared by the invention has good dispersibility and activity, the separation and recycling of the catalyst still need to be further researched.
CN107349940A discloses a preparation method and application of a Z-type magnetic nano composite material molybdenum disulfide/cobalt tetraoxydipherase photocatalyst. The method respectively prepares CoFe by solvothermal method and hydrothermal method2O4Magnetic nanoparticles and molybdenum disulfide nanosheets. The magnetic-loaded molybdenum disulfide catalyst is prepared, is only applied to a sewage system with mild conditions and low viscosity, is applied to environments with high temperature, high sulfur and the like, and magnetic cores are easy to demagnetize.
Disclosure of Invention
The invention mainly aims to provide a visbreaking magnetic-supported catalyst for inferior heavy oil and a preparation method and application thereof, so as to solve the problems of difficult separation and recovery, limited application conditions and the like of heavy oil upgrading catalysts in the prior art.
In order to achieve the aim, the invention provides a visbreaking magnetic-supported catalyst for inferior heavy oil, which comprises Fe3O4Magnetic microspheres coated with Fe3O4SiO outside magnetic microsphere2Layer and MoS2And a Ni mixed layer.
The visbreaking magnetic-carrier catalyst for the inferior heavy oil, disclosed by the invention, is characterized in that SiO2Coated on Fe3O4Outside the magnetic microsphere, MoS2And a Ni mixed layer coated on SiO2And (6) outside the layer.
According to the inventionThe visbreaking magnetic carrier catalyst for poor heavy oil is Fe3O4The grain diameter of the magnetic microsphere is 20-200 nanometers, SiO2The thickness of the layer is 5-150 nm, MoS2And the thickness of the Ni mixed layer is 5-50 nm.
The visbreaking magnetic-carrying catalyst for the inferior heavy oil, disclosed by the invention, has the advantages that the particle size of the catalyst is 50-550 nm; the bulk density of the catalyst with the particle diameter of 50-100nm is 1.28-1.39g/cm3(ii) a The bulk density of the catalyst with the particle size of 320-370nm is 1.12-1.22g/cm3。
In order to achieve the purpose, the invention also provides a preparation method of the visbreaking magnetic-supported catalyst for the 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 to carry out hydrolysis reaction to obtain SiO2Layer coated Fe3O4Magnetic microspheres;
step 2, SiO2Layer coated Fe3O4Adding the magnetic microspheres, the molybdenum precursor, the sulfur precursor and the nickel precursor into an inorganic solvent, and heating for reaction to obtain the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil.
The invention relates to a preparation method of a visbreaking magnetic-supported catalyst for inferior heavy oil, wherein Fe3O4The magnetic microsphere is prepared by carrying out thermal reaction on iron salt and a reducing agent.
The invention relates to a preparation method of a visbreaking magnetic-supported catalyst for inferior heavy oil, wherein 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.
The invention relates to a preparation method of a visbreaking magnetic-supported catalyst for inferior heavy oil, wherein Fe3O4In the preparation process of the magnetic microspheres, the mass ratio of the reducing agent to the ferric salt to the organic sodium salt to the polyethylene glycol to the caustic alkali is 5-20: 1: 1-5: 4-10: 0.1-0.5; the iron salt is FeCl3、FeCl2One or two of, the organic alcohol isOne or two of ethylene glycol and propylene glycol, wherein 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 ℃.
The invention relates to a preparation method of a visbreaking magnetic-supported catalyst for inferior heavy oil, wherein in step 1, a silicon precursor is one or more of ethyl orthosilicate, sodium orthosilicate or sodium metasilicate, and Fe3O4The mass ratio of the magnetic microspheres to the solvent to the silicon precursor is 1:80-500: 8-25; adjusting the pH value to 8-11.
The preparation method of the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil, disclosed by the invention, comprises the following steps of (1) in step 2, wherein 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 nickel precursor is one or more of nickel acetate tetrahydrate, nickel chloride hexahydrate, nickel sulfate hexahydrate and nickel nitrate hexahydrate; the SiO2Layer coated Fe3O4The mass ratio of the magnetic microspheres to the molybdenum precursor to the nickel precursor to the sulfur precursor is 1:5-15:1-10: 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 visbreaking magnetic-supported catalyst for the inferior heavy oil in hydro-upgrading of the inferior heavy oil.
The invention has the beneficial effects that:
the invention provides a viscidity-reducing magnetic-carrier catalyst for inferior heavy oil, which has magnetic carrier, can be separated out for recycling by a magnetic separation method directly after the inferior heavy oil is modified, has simple process and high catalyst utilization rate, and can greatly reduce the modification cost; the poor-quality heavy oil viscosity-reducing magnetic-carrying catalyst can be used under severe conditions because the protective layer is used for coating the magnetic core.
According to the viscosity-reducing magnetic-carrier catalyst for the inferior heavy oil, the nickel component is added, so that the viscosity-reducing effect of the catalyst is remarkably improved, and the double targets of efficient viscosity reduction of the inferior heavy oil and efficient separation of the catalyst can be better realized.
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 the visbreaking magnetic carrier catalyst (Fe) for the inferior heavy oil of the present invention3O4/SiO2/MoS2+ Ni) transmission electron micrograph.
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 a visbreaking magnetic-supported catalyst for 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 to carry out hydrolysis reaction to obtain SiO2Layer coated Fe3O4Magnetic microspheres;
step 2, SiO2Layer coated Fe3O4Adding the magnetic microspheres, the molybdenum precursor, the sulfur precursor and the nickel precursor into an inorganic solvent, and heating for reaction to obtain the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil.
Fe of the invention3O4The magnetic microsphere is prepared by a solvothermal method, specifically is prepared by carrying out thermal reaction on iron salt and a reducing agent, and organic sodium salt, polyethylene glycol and caustic alkali are added in the preparation process. As a preferred embodiment, Fe3O4The preparation process of the magnetic microsphere comprises the following steps: adding ferric salt, a reducing agent, organic sodium salt, polyethylene glycol and caustic alkali into a reactor according to a mass ratio, uniformly mixing at 10-45 ℃, preparing an initial reaction mixture, adding into a reaction kettle, and adding at 80-220 DEG CCarrying out thermal reaction for 12-24 hours to obtain Fe3O4Cooling the mixture of magnetic microsphere and reaction solvent to 12-45 deg.C, separating and recovering with magnet, washing, and freeze drying to obtain Fe3O4Magnetic microspheres.
Wherein, the reducing agent is preferably organic alcohol, more preferably ethylene glycol, propylene glycol or a mixture of the two; in the present invention, the organic alcohol may also serve as a reaction solvent at the same time to subject the iron salt and the reducing agent to a solvothermal reaction. The iron salt preferably comprises iron trichloride, iron dichloride, or a mixture of both; the organic sodium salt preferably comprises one or more of sodium acetate, sodium stearate and sodium benzoate; the caustic alkali preferably comprises one or more of sodium hydroxide and potassium hydroxide. The polyethylene glycol of the present invention is not particularly limited, and may be a commercially available product, for example, polyethylene glycol 6000.
In one embodiment, the organic alcohol, iron salt, organic sodium salt, polyethylene glycol and caustic alkali are used as the reactants in a mass ratio of 5-20: 1: 1-5: 4-10: 0.1-0.5, adding into a reactor for mixing, and preferably adding the mixture in a mass ratio of 6-18: 1: 2-4: 3-9: 0.15-0.45. Fe3O4The particle size of the magnetic microspheres can be controlled by adjusting the proportion of reaction materials, the reaction time, the reaction temperature and the like.
In one embodiment, the molar concentration of the iron salt in the initial reaction mixture is 0.01 to 0.5mol/L, the molar concentration of the organic sodium salt is 0.1 to 1mol/L, the molar concentration of the polyethylene glycol is 0.0001 to 0.1mol/L, and the molar concentration of the caustic alkali is 0.1 to 0.5 mol/L.
Step 1 of the invention is to prepare SiO by hydrolysis reaction2Coated Fe3O4Magnetic microspheres, i.e. Fe3O4/SiO2Magnetic nanoparticles, specifically Fe obtained by the above method3O4Adding the magnetic microspheres and the silicon precursor into a solvent, adjusting the pH value to carry out hydrolysis reaction to obtain SiO2Layer coated Fe3O4Magnetic microspheres. As a preferred technical solution, step 1 is: the Fe obtained above is added3O4Adding magnetic microsphere into organic solvent such as anhydrous ethanol, sequentially adding silicon precursor and adjusting pH valueStirring the mixture for 2 to 8 hours at a temperature of between 12 and 35 ℃ to obtain a precipitate, namely 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 ethyl orthosilicate, and can also be water-soluble silicates such as sodium orthosilicate and sodium metasilicate; the pH regulator may be any one of ammonia water or alkali salt of lithium, sodium and potassium capable of forming soluble salt with silicate, and preferably the pH regulator is adjusted to 8-11.
In one embodiment, Fe3O4The mass ratio of the magnetic microspheres to the organic solvent to the silicon precursor to the pH regulator is 1:80-500:8-25:7-18, preferably 1:90-450:10-20: 8-16. SiO of the invention2The coating thickness can be controlled by adjusting the dosage of the silicon precursor and the pH value regulator, the hydrolysis temperature, the hydrolysis time and the like.
Step 2 of the invention is to prepare the visbreaking magnetic-supported catalyst of the inferior heavy oil by using hydrothermal reaction, namely Fe3O4/SiO2/MoS2+ Ni magnetically supported catalyst, in particular SiO2Layer coated Fe3O4Adding the magnetic microspheres, the molybdenum precursor, the sulfur precursor and the nickel precursor into an inorganic solvent, and heating for reaction to obtain the viscosity-reducing magnetic-supported catalyst for the inferior heavy oil.
As a preferred technical scheme, the step 2 is as follows: mixing Fe3O4/SiO2Dispersing the magnetic nano particles into distilled water again, sequentially adding a molybdenum precursor, a sulfur precursor and a nickel precursor according to a proportion, 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, washing, freeze-drying to obtain solid powder, namely Fe3O4/SiO2/MoS2+ Ni magnetically supported catalyst.
Wherein the molybdenum precursor can be one or more of ammonium molybdate tetrahydrate, thioacetamide, L-cysteine, sodium molybdate, potassium molybdate, sodium thiomolybdate and potassium thiomolybdate; the sulfur precursor can be one or more of thiourea, thioacetamide and L-cysteine; the nickel precursor can be one or more of nickel acetate tetrahydrate, nickel chloride hexahydrate, nickel sulfate hexahydrate and nickel nitrate hexahydrate.
In one embodiment, Fe3O4/SiO2The mass ratio of the magnetic nanoparticles to the molybdenum precursor to the nickel precursor to the sulfur precursor is 1:5-15:1-10:10-30, preferably 1:8-14:2-8: 12-29.
In one embodiment, the mixture formed in step 2 is 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, the molar concentration of the molybdenum precursor is 0.01-0.1mol/L, and the molar concentration of the nickel precursor is 0.01-0.2 mol/L.
The poor-quality heavy oil viscosity-reducing magnetic-carrier catalyst prepared by the method is Fe3O4/SiO2/MoS2+ Ni magnetically supported catalyst comprising Fe3O4Magnetic microspheres coated with Fe3O4SiO outside magnetic microsphere2Layer and MoS2And a Ni mixed layer. Wherein, SiO2Coated on Fe3O4Outside the magnetic microsphere, MoS2And a Ni mixed layer coated on SiO2And (6) outside the layer. The particle size of the catalyst is 50-550nm, preferably 50-350 nm; the bulk density of the catalyst having a particle diameter of 50nm is 1.28 to 1.39g/cm3(ii) a The bulk density of the catalyst with the particle size of 350nm is 1.12-1.22g/cm3。
In one embodiment, Fe3O4The grain diameter of the magnetic microsphere is 20-200 nanometers, SiO2The thickness of the layer is 5-150 nm, MoS2And the thickness of the Ni mixed layer is 5-50 nm.
The poor-quality heavy oil viscosity-reducing magnetic-carrier catalyst prepared by the method is Fe3O4/SiO2/MoS2The Ni magnetic-carried catalyst has good application effect in the normal slag hydrogenation modification of the Canadian oil sand asphalt at 350 ℃, and the kinematic viscosity of the oil product at 100 ℃ is 860mm from 850-2The/s is reduced to 33-43mm2/s。
The catalyst Fe prepared by the method3O4/SiO2/MoS2+ Ni pairThe catalyst has good application effect of reducing viscosity in normal slag at 350 ℃ in Canadian oil sand asphalt by hydrogen, and the recovery rate of the catalyst can reach more than 95% at 100 ℃ after hydrogenation reaction.
The catalyst Fe prepared by the method3O4/SiO2/MoS2The slag reduction of the Ni is more than 420 ℃ for the Canadian oil sand asphalt, and the modification effect is better than that of Fe without nickel3O4/SiO2/MoS2The catalyst has a kinematic viscosity at 100 ℃ of 1940-2The/s is reduced to 320-330mm2S, using catalyst Fe under the same conditions3O4/SiO2/MoS2The time is reduced by 2 to 4 percent; the recovery rate of the catalyst can reach more than 95 percent at 100 ℃. Therefore, the viscosity-reducing magnetic-carrier catalyst for the inferior heavy oil is added with the nickel component, so that the viscosity-reducing effect of the catalyst is obviously improved, and the double targets of high-efficiency viscosity reduction of the inferior heavy oil and high-efficiency separation of the catalyst can be better realized.
The technical solution of the present invention is further described in detail by specific examples below.
Example 1
500ml of ethylene glycol was added to the reaction vessel, followed by 29g of FeCl3·6H2O, 60g of anhydrous sodium acetate, 128g of polyethylene glycol 6000 and 5.9g 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/SiO2Separating and recovering the magnetic nanoparticles with a magnet after the magnetic nanoparticles are finished, and freeze-drying. Weighing 1g of Fe3O4/SiO2Dispersing the magnetic nano particles into 300ml of distilled water again, adding 10g of ammonium molybdate tetrahydrate, 5.6g of nickel acetate tetrahydrate and 22.8g of thiourea in sequence, stirring uniformly, adding the uniformly mixed reactants into a reaction kettle, heating at 180 ℃ for reaction for 10 hours, cooling to 25 ℃, and adding the reactant after the reaction is finishedSeparating and recovering the magnet, washing, freezing and drying to obtain Fe3O4/SiO2/MoS2+ Ni catalyst. Wherein, Fe3O4The transmission electron microscope of the magnetic microsphere is shown in the attached figure 1; fe3O4/SiO2(SiO2Layer coated Fe3O4Magnetic microspheres) see fig. 2; fe3O4/SiO2/MoS2See FIG. 3 for a transmission electron micrograph of the + Ni catalyst. As can be seen from the transmission electron micrograph, Fe3O4The magnetic microspheres have uniform particle size distribution, the particle size is between 50 and 130, and the average particle size is about 120 nm; SiO 22The particle size is slightly increased after the coating, and the thickness of the coating is about 10 nm; performing MoS2The particle diameter of the catalyst after being supported is further increased.
Fe to be prepared3O4/SiO2/MoS2The + Ni catalyst is used for a Canadian oil sand asphalt 350 ℃ normal slag hydrogenation catalysis viscosity reduction experiment, and under the conditions of 400 ℃, hydrogen pressure of 15.2MPa and catalyst addition of 500ppm, the kinematic viscosity of the oil sand asphalt at 100 ℃ is controlled from original 850mm2The/s is reduced to 34mm2The viscosity reduction reaches 96 percent, which shows that the catalyst has better hydrogenation catalysis viscosity reduction function; the viscid oil is magnetically separated at 100 ℃, and the recovery rate of the catalyst is 95.2%.
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 1:8.5, not the former 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 96.1 percent, and the recovery rate of the catalyst reaches 95.9 percent. 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 different from example 1, the silicon precursor added in the second step was sodium orthosilicate,Fe3O4the ratio of nanoparticles to their mass was 1:24, 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 viscosity reduction rate of the oil sand asphalt is 96.2 percent, and the recovery rate of the catalyst reaches 95.0 percent. When the thickness of the coating layer was increased, the magnetic properties of the catalyst were reduced compared to example 1, and the final catalyst recovery rate was lowered. The thickness change 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 1:5.6, instead of 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 95.8 percent, and the recovery rate of the catalyst reaches 95 percent. When the content of active metal is reduced, the cracking effect of the catalyst is weakened, the viscosity reduction rate of oil is slightly reduced, and the recovery rate of the catalyst is slightly reduced compared with that of example 1.
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 1:14, 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 96.6 percent, and the recovery rate of the catalyst reaches 96 percent. When the content of active metal is increased, compared with the example 1, the cracking effect of the catalyst is enhanced, the viscosity reduction rate of oil products is increased, and further the recovery rate of the catalyst is increased.
Example 6
Example 6 differs from example 1 in that the nickel precursor added in step three is nickel chloride hexahydrate, Fe3O4/SiO2The ratio of nanoparticles to their mass was 1:2.1, not 1: 7.6, i.e., the nickel metal content is low, 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 95.9 percent, and the oil sand asphalt is catalyzedThe recovery rate of the agent reaches 95 percent. When the nickel metal content is decreased, the cracking effect of the catalyst is slightly reduced, the viscosity reduction rate of the oil product is decreased, and the recovery rate of the catalyst is decreased as compared with example 1.
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 1:28, namely the silicon content is higher than 1:8-25, and other steps and parameters are the same as those of the embodiment 1. As can be seen from the data in Table 3, the recovery rate of the magnetically supported catalyst was reduced due to the excessive thickness of the silicon coating layer.
Comparative example 2
Comparative example 2 differs from example 1 in that the molybdenum precursor added in step three is sodium thiomolybdate, Fe3O4/SiO2The mass ratio of the nano particles to the nano particles is 1:4.2, 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. As can be seen from the data in Table 3, the catalyst viscosity reduction rate is reduced due to the lower active metal content.
Comparative example 3
Comparative example 3 different from example 1, the nickel precursor added in step three is nickel acetate tetrahydrate, Fe3O4/SiO2The ratio of nanoparticles to their mass was 1:1.4, not 1: 7.4, other steps and parameters were the same as in example 1, and therefore, it was found from the data in Table 3 that the viscosity reducing effect was slightly inferior, about 1.3% lower than that of example 1.
In examples 1 to 6 and comparative examples 1 to 3, the catalyst evaluation conditions, i.e., the reaction pressure, the reaction temperature, and the amount of the catalyst added were slightly adjusted according to the actual operation conditions, as shown in Table 3.
Comparative example 4
Using Fe3O4/SiO2/MoS2The catalyst was prepared in the same manner as in example 1 except that no nickel precursor was added in the final catalyst loading step.
Comparative example 5
The catalyst preparation procedure was the same as in example 1.
Comparative examples 4 and 5 the canadian oil sands bitumen 350 ℃ common slag in example 1 was replaced in the catalyst evaluation with reduced slag for canadian oil sands bitumen greater than 420 ℃. The oil residue reducing product has lower quality and higher viscosity. The reaction temperature, reaction pressure and catalyst addition were evaluated in Table 3, and the evaluation results were obtained as the average of three experiments. From the viewpoint of modification effect, Fe3O4/SiO2/MoS2+ Ni catalyst hydro-upgrading viscosity-reducing effect ratio Fe3O4/SiO2/MoS2Good catalyst and 2.80% reduction in viscosity. Fe to illustrate Nickel addition3O4/SiO2/MoS2The Ni catalyst has better viscosity-reducing effect on inferior heavy oil with similar property.
The raw materials used in the above examples and comparative examples are typical canadian oil sand bitumen with 350 ℃ normal slag and canadian oil sand bitumen greater than 420 ℃ slag reduction in inferior heavy oil, and the basic properties are shown in tables 1 and 2. The viscosity reduction effect is tested by using an intermittent autoclave hydrogen evaluation device, and the magnetic separation and recovery are carried out by using a neodymium iron boron strong magnet and an external magnetic field. The viscosity-reducing effect and the magnetic separation recovery effect 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 table 1.
TABLE 1 basic properties of canadian oil sand bitumen at 350 deg.C for normal slag
The basic physical properties of the canadian oil sand bitumen at the temperature of more than 420 ℃ for slag reduction are shown in table 2.
TABLE 2 basic physical properties of canadian oil sand bitumen greater than 420 ℃ for slag reduction
The viscosity reducing effect and magnetic separation recovery data are shown in table 3 below.
TABLE 3 detackification Effect and magnetic separation recovery data
The above examples and application effects illustrate that the catalyst Fe prepared by the method of the present invention3O4/SiO2/MoS2The + Ni can be used for upgrading heavy oil with relatively poor quality, such as residual oil at 350 ℃ in Canadian oil sand, has higher visbreaking rate when reducing slag at 420 ℃ in heavy oil with relatively poor quality, such as Canadian oil sand, and has higher recovery rate of the catalyst, so that the catalyst can be recycled. In addition, the addition of the nickel component in the catalyst further improves the viscosity reduction effect of the catalyst.
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.