CN110124656B - Catalyst for converting vegetable oil into lubricating oil and preparation method thereof - Google Patents

Catalyst for converting vegetable oil into lubricating oil and preparation method thereof Download PDF

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CN110124656B
CN110124656B CN201910480378.9A CN201910480378A CN110124656B CN 110124656 B CN110124656 B CN 110124656B CN 201910480378 A CN201910480378 A CN 201910480378A CN 110124656 B CN110124656 B CN 110124656B
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catalyst
aluminum
sio
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CN110124656A (en
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陈新庆
薛文杰
丘明煌
孙予罕
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Shanghai Advanced Research Institute of CAS
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/40—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
    • C10M109/02—Reaction products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C10M2207/2895—Partial esters containing free hydroxy groups used as base material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The present invention provides a method for preparing a catalyst for converting vegetable oil into lubricating oil, the method at least comprising: firstly, mixing a silicon source and deionized water, uniformly stirring, and adding acid to a first pH value to obtain silica sol; then mixing an aluminum source and deionized water, and uniformly stirring to obtain an aluminum solution; then mixing the aluminum solution and the silica sol, and then adding alkali to a second PH value to obtain aluminum-silica mixed sol; then washing, drying and calcining the aluminum-silicon mixed sol in sequence to obtain SiO2‑Al2O3A carrier; finally loading a metal load precursor solution to the SiO2‑Al2O3On a carrier, and then calcining to obtain SiO supported by metal oxide2‑Al2O3A catalyst. The invention provides a novel preparation method of a catalyst for converting vegetable oil into lubricating oil, and the prepared catalyst has better catalytic performance when used for oligomerization reaction of methyl ricinoleate.

Description

Catalyst for converting vegetable oil into lubricating oil and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of oligomerization catalysts, and particularly relates to a catalyst for converting vegetable oil into lubricating oil and a preparation method thereof.
Background
Lubricating oil is blood which is supposed to maintain normal operation of a machine, and plays a significant role in the development of modern socioeconomic performance. Most of the traditional lubricating oil takes mineral oil as base oil, which plays a great role in reducing friction and wear, saving energy, prolonging the service life of machines and meeting the lubricating requirements under harsh working conditions, however, when the lubricating oil is used in large quantity, the lubricating oil inevitably enters the environment through various ways such as transportation, leakage, sputtering, overflow or improper discharge and the like, seriously pollutes soil and water resources and destroys the ecological environment and ecological balance. From the trend of social development, the environment-friendly lubricating oil gradually replaces the existing mineral-based lubricating oil. The environment-friendly lubricating oil mainly takes bio-based lubricating oil as a main component, and is modified by taking vegetable oil as base oil or is lubricating oil which can be decomposed into water and carbon dioxide by active microorganisms in a relatively short time. Compared with traditional mineral lubricating oil, the natural renewable and biodegradable properties of the vegetable oil can provide obvious benefits of environmental and economic sustainable development, and the vegetable oil has the advantages of low volatility, high flash point, high viscosity index, excellent lubricating property and the like. Therefore, bio-based lubricating oils mainly derived from vegetable oils are the main power of environmental protection lubricating oils. However, the disadvantages of vegetable oils, such as poor low temperature flow (pour point), poor oxidation stability, poor bio-tolerance and poor hydrolytic stability, may limit their direct use as lubricant base stocks.
By chemically modifying the vegetable oil, it is possible to improve its properties. Pramab Ghosh et al developed a method for synthesizing environmentally friendly lubricant additives using a small amount of polymeric material by copolymerizing castor oil with dodecyl acrylate in varying percentages, which is thermally stable, cost effective, and performs better. Kotte Kamalakar et al prepared low pour point lubricant base stocks using castor oil by synthesizing acyloxyricinoleic polyol esters.
In this work, we propose a new strategy for the preparation of lubricating oils by oligomerization of methyl ricinoleate. As starting material, methyl ricinoleate may be dehydrated to form double bonds and then polymerized to form oligomers under the action of a catalyst.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a solution for the above-mentioned problemsProvides a catalyst for converting vegetable oil into lubricating oil and a preparation method thereof, and the metal oxide loaded SiO prepared by the preparation method of the invention2-Al2O3The catalyst can be applied to oligomerization of methyl ricinoleate, lubricating oil prepared by the reaction has excellent performance, and the catalyst has high selectivity in oligomerization.
To achieve the above and other related objects, the present invention provides a method for preparing a catalyst for converting vegetable oil into lubricating oil, the method comprising at least:
mixing a silicon source and deionized water, uniformly stirring, and adding acid to a first pH value to obtain silica sol;
mixing an aluminum source and deionized water, and uniformly stirring to obtain an aluminum solution;
mixing the aluminum solution and the silica sol, and then adding alkali to a second pH value to obtain aluminum-silica mixed sol;
washing, drying and calcining the aluminum-silicon mixed sol in sequence to obtain SiO2-Al2O3A carrier;
loading a metal-loading precursor solution to the SiO2-Al2O3On a carrier, and then calcining to obtain SiO supported by metal oxide2-Al2O3A catalyst.
As an optimized solution of the preparation method of the catalyst for converting vegetable oil into lubricating oil of the present invention, the silicon source comprises a mixture of one or more of sodium silicate, silica sol and ethyl orthosilicate.
As an optimized solution of the preparation method of the catalyst for converting vegetable oil into lubricating oil of the present invention, the aluminum source comprises one or more of aluminum isopropoxide, aluminum nitrate and aluminum trichloride.
As an optimized aspect of the method for preparing the catalyst for converting vegetable oil into lubricating oil of the present invention, the acid includes one of hydrochloric acid and nitric acid.
As an optimized aspect of the method for preparing the catalyst for converting vegetable oil into lubricating oil of the present invention, the base comprises a mixture of one or more of ammonia water and sodium hydroxide.
As an optimized scheme of the preparation method of the catalyst for converting the vegetable oil into the lubricating oil, the first pH value is between 1 and 3, and the second pH value is between 8 and 10.
As an optimized proposal of the preparation method of the catalyst for converting the vegetable oil into the lubricating oil, the calcining temperature is between 400 and 600 ℃, and the calcining time is between 2 and 6 hours, so as to obtain the SiO2-Al2O3And (3) a carrier.
As an optimized scheme of the preparation method of the catalyst for converting vegetable oil into lubricating oil, the SiO2-Al2O3The molar ratio of silicon to aluminum of the carrier is between 1:9 and 9: 1.
As an optimized scheme of the preparation method of the catalyst for converting vegetable oil into lubricating oil, the metal load precursor solution is loaded to the SiO by adopting an impregnation method2-Al2O3On a carrier.
As an optimized aspect of the preparation method of the catalyst for converting vegetable oil into lubricating oil of the present invention, the metal load precursor includes a mixture of one or more of nitrate, chloride and metal complex salt.
As an optimized scheme of the preparation method of the catalyst for converting vegetable oil into lubricating oil, the metal load precursor solution is loaded to the SiO2-Al2O3Calcining the carrier at 400-600 ℃ for 2-6 hours to obtain the SiO supported by the metal oxide2-Al2O3A catalyst.
As an optimized aspect of the method for preparing the catalyst for converting vegetable oil into lubricating oil of the present invention, the metal oxide-supported SiO2-Al2O3In a catalyst, the goldThe metal oxide comprises NiO and MoO3CeO, PdO and ZnO.
As an optimized aspect of the method for preparing the catalyst for converting vegetable oil into lubricating oil of the present invention, the metal oxide-supported SiO2-Al2O3In the catalyst, the loading amount of the metal oxide is between 0.5 and 7 percent.
The invention also provides a catalyst for converting vegetable oil into lubricating oil, which is prepared by the preparation method.
The invention further provides an application of the catalyst in methyl ricinoleate oligomerization reaction, wherein the reaction temperature of the methyl ricinoleate oligomerization reaction is 160-240 ℃, the reaction pressure is 1-2 bar, the flow rate of N2 is 30-50 mL/min, and the flow rate of the reactants is 0.009-0.021 mL/min.
As described above, the catalyst for converting vegetable oil into lubricating oil and the method for preparing the same of the present invention include at least: mixing a silicon source and deionized water, uniformly stirring, and adding acid to a first pH value to obtain silica sol; mixing an aluminum source and deionized water, and uniformly stirring to obtain an aluminum solution; mixing the aluminum solution and the silica sol, and then adding alkali to a second pH value to obtain aluminum-silica mixed sol; washing, drying and calcining the aluminum-silicon mixed sol in sequence to obtain SiO2-Al2O3A carrier; loading a metal-loading precursor solution to the SiO2-Al2O3On a carrier, and then calcining to obtain SiO supported by metal oxide2-Al2O3A catalyst. The invention provides a novel preparation method of a catalyst for converting vegetable oil into lubricating oil, and the prepared catalyst has better catalytic performance when used for oligomerization reaction of methyl ricinoleate.
Drawings
FIG. 1 is a process diagram of the preparation method of the catalyst for converting vegetable oil into lubricating oil according to the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to the attached drawings. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
The present invention provides a method for preparing a catalyst for converting vegetable oil into lubricating oil, the method at least comprising:
step S1 is performed first, a silicon source and deionized water are mixed, stirred uniformly, and an acid is added to a first PH to obtain a silica sol.
As an example, the silicon source includes a mixture of one or more of sodium silicate, silica sol, and ethyl orthosilicate.
As an example, the first pH value is between 1 and 3. Preferably, the first PH is 2.
As an example, the acid includes one of hydrochloric acid and nitric acid.
Then, step S2 is performed, and the aluminum source and the deionized water are mixed and stirred uniformly to obtain an aluminum solution.
Illustratively, the aluminum source comprises a mixture of one or more of aluminum isopropoxide, aluminum nitrate, and aluminum trichloride.
In the step, an aluminum source and deionized water can be mixed and heated to a certain temperature, and stirred to completely dissolve the aluminum source. For example, it may be dissolved completely by heating to 40 ℃ and stirring for 1 hour.
The operation sequence of steps S1 and S2 is not limited, and step S1 may be performed first, and step S2 may be performed second, step S2 may be performed first, and step S1 may be performed second, or step S1 and step S2 may be performed simultaneously.
Then, step S3 is performed to mix the aluminum solution and the silica sol, and then an alkali is added to a second PH value to obtain an aluminum-silica mixed sol.
As an example, the second pH value is between 8 and 10. Preferably, the first PH is 8.
Illustratively, the base comprises a mixture of one or more of aqueous ammonia and sodium hydroxide.
And step S4 is executed, the aluminum-silicon mixed sol is washed, dried and calcined in sequence to obtain SiO2-Al2O3And (3) a carrier.
In this step, the aluminum-silica mixed sol may be left to stand for a certain period of time, for example, for 1 hour, before being subjected to filtration washing.
As an example, in this step, the calcination temperature is between 400 ℃ and 600 ℃, and the calcination time is between 2 hours and 6 hours, so as to obtain the SiO2-Al2O3And (3) a carrier. Preferably, the calcining temperature is 500-600 ℃, and the calcining time is 2-4 hours, so as to obtain the SiO2-Al2O3And (3) a carrier.
As an example, the SiO2-Al2O3The molar ratio of silicon to aluminum of the carrier is between 1:9 and 9: 1.
Finally, step S5 is executed to load the metal load precursor solution to the SiO2-Al2O3On a carrier, and then calcining to obtain SiO supported by metal oxide2-Al2O3A catalyst.
As an example, the metal support precursor solution is loaded to the SiO using a dipping method2-Al2O3On a carrier.
By way of example, the metal support precursor includes a mixture of one or more of nitrates, chlorides, and metal complex salts.
As an example, the metal support precursor solution is supported to the SiO2-Al2O3Calcining the carrier at 400-600 ℃ for 2-6 hours to obtain the SiO supported by the metal oxide2-Al2O3A catalyst. Preferably, the calcination is carried out at 500 to 600 ℃ for 2 to 4 hours to obtain metal oxide-supported SiO2-Al2O3A catalyst. The solvent may be evaporated to dryness at a certain temperature before calcination.
As an example, the metal oxide supported SiO2-Al2O3In the catalyst, the metal oxide comprises NiO and MoO3CeO, PdO and ZnO.
As an example, the metal oxide supported SiO2-Al2O3In the catalyst, the loading amount of the metal oxide is between 0.5 and 7 percent. For example, the metal oxide loading is between 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 0.5%, 3.5%, 5%, 6%, 7%, and the like.
The invention also provides a catalyst for converting vegetable oil into lubricating oil, which is prepared by the preparation method and has better catalytic performance when used for oligomerization of methyl ricinoleate.
The invention further provides an application of the catalyst in methyl ricinoleate oligomerization reaction, wherein the reaction temperature of the methyl ricinoleate oligomerization reaction is 160-240 ℃, the reaction pressure is 1-2 bar, the flow rate of N2 is 30-50 mL/min, and the flow rate of the reactants is 0.009-0.021 mL/min.
It should be noted that castor oil, vegetable oil, can be esterified with methanol to obtain methyl ricinoleate, which can be dehydrated to form double bonds and then oligomerized to dimers and trimers by the catalyst of the present invention to obtain the lubricating oil.
Preferably, the reaction temperature of the methyl ricinoleate oligomerization reaction is 160-200 ℃, the reaction pressure is 1-2 bar, the flow rate of N2 is 30-40 mL/min, and the flow rate of the reactant is 0.01-0.021 mL/min.
For a more detailed understanding of the technical content, the features and the effects of the present invention, the technical solutions of the present invention will be described in further detail with reference to the accompanying drawings and the specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1:
0.8mL of tetraethoxysilane is transferred by a pipette and added into 0.4mL of water at 40 ℃ to be uniformly stirred, and simultaneously, a certain amount of nitric acid is absorbed by a suction tube and slowly dripped into the solution to ensure that the pH value reaches 2, so that silica sol appears. Then, 25.92g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 15.6mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 1SiO in a muffle furnace at 550 ℃ for 3 hours2-9Al2O3And (3) sampling. Weighing 1.5g of 1SiO by using a balance scale2-9Al2O3The sample is mixed with 0.1932g of ammonium molybdate by an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 7 percent3/1SiO2-9Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 2:
2.4mL of tetraethoxysilane is transferred by a pipette and added into 1.2mL of water at 40 ℃ and stirred evenly, and simultaneously a certain amount of nitric acid is absorbed by a suction tube and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. 18.81g of aluminum nitrate nonahydrate were weighed on an analytical balance, added to 14.8mL of deionized water, and heated to 40 ℃ to completely dissolve the aluminum nitrate nonahydrate. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then sucking a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, 40Standing for 1 hour, filtering and washing, drying, and then obtaining 3SiO in a muffle furnace at 550 ℃ for 3 hours2-7Al2O3And (3) sampling. Weighing 1.5g3SiO with balance2-7Al2O3The sample is mixed with 0.1932g of ammonium molybdate by an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 7 percent3/3SiO2-7Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 3:
4.0mL of tetraethoxysilane is transferred by a pipette and added into 2.0mL of water at 40 ℃ and stirred evenly, and simultaneously a certain amount of nitric acid is absorbed by a suction tube and slowly dripped into the solution to ensure that the pH value reaches 2, so that silica sol appears. 13.44g of aluminum nitrate nonahydrate were weighed on an analytical balance and added to 14.0mL of deionized water, and the mixture was heated to 40 ℃ to completely dissolve the aluminum nitrate nonahydrate. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 5SiO in a muffle furnace at 550 ℃ for 3 hours2-5Al2O3And (3) sampling. Weighing 1.5g of 5SiO by using a balance scale2-5Al2O3The sample is mixed with 0.1932g of ammonium molybdate by an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 7 percent3/5SiO2-5Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 4:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Reuse of2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and heated to 40 ℃ to completely dissolve the aluminum nitrate nonahydrate. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3The sample is mixed with 0.1932g of ammonium molybdate by an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 7 percent3/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Table 1 shows the results of oligomerization of the methyl ricinoleate products of examples 1-4, the effect of the respective 7% Mo catalysts loaded at different Si/Al ratios on oligomerization of the methyl ricinoleate.
TABLE 1
Figure BDA0002083632690000061
Figure BDA0002083632690000071
As can be seen from Table 1, the catalysts of examples 1-4 gave high conversion of methyl ricinoleate and good selectivity of methyl ricinoleate oligomers. Specifically, as the silica to alumina ratio increased, the conversion of methyl ricinoleate increased, while the selectivity of methyl ricinoleate oligomers decreased.
Example 5:
transferring 7.20mL of tetraethoxysilane into 3.6mL of water by using a pipette, uniformly stirring at 40 ℃, simultaneously sucking a certain amount of nitric acid by using a suction tube, slowly and dropwise adding the nitric acid into the solution to enable the pH value to reach 2, and obtainingAnd (3) silica sol. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3The sample is mixed with 0.1380g of ammonium molybdate by adopting an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 5 percent3/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 6:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3Mixing the sample with 0.0828g of ammonium molybdate by an immersion method, stirring for 24 hours at room temperature, stirring and evaporating at 100 ℃, and then roasting for 3 hours at 500 ℃ to obtain MoO with the loading of 3%3/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 7:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3The sample is mixed with 0.0276g of ammonium molybdate by an immersion method and stirred for 24 hours at room temperature, then stirred and evaporated to dryness at 100 ℃, and then roasted for 3 hours at 500 ℃ to obtain MoO with the load of 1 percent3/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 8:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3Mixing the sample with 0.0138g of ammonium molybdate by an immersion method, stirring for 24 hours at room temperature, stirring and evaporating at 100 ℃, and then roasting for 3 hours at 500 ℃ to obtain MoO with the load of 0.5 percent3/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Table 2 shows the results of oligomerization of methyl ricinoleate from the products of examples 4-8, respectively the effect of different loadings on oligomerization of methyl ricinoleate.
TABLE 2
Figure BDA0002083632690000081
Figure BDA0002083632690000091
As can be seen from Table 2, as the Mo content decreases, the MoO content decreases3The dispersibility of (A) is improved, and the selectivity of the methyl ricinoleate oligomer is increased.
Example 9:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3Mixing the sample with 0.025g of palladium chloride by adopting an immersion method, stirring for 24 hours at room temperature, then stirring and evaporating to dryness at 100 ℃, and then roasting for 3 hours at 500 ℃ to obtain 1% of PdO/9SiO2-1Al2O3A catalyst. Tabletting the catalyst, sieving 20-40 mesh particles, and oligomerizing methyl ricinoleate in a fixed bed reactor at 200 deg.cThe flow rate of N2 was 30mL/min and the flow rate of the reactants was 0.018 mL/min.
Example 10:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3Mixing the sample with 0.046g of cerium nitrate hexahydrate by adopting an impregnation method, stirring for 24 hours at room temperature, then stirring and evaporating at 100 ℃, and then roasting for 3 hours at 500 ℃ to obtain 1% CeO/9SiO2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 11:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3The sample was mixed with 0.068g of zinc nitrate hexahydrate by dipping for 24 hours at room temperature, then evaporated to dryness at 100 ℃ with stirring, and then baked at 500 ℃Firing for 3 hours to obtain ZnO/9SiO with the loading of 1 percent2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Example 12:
7.20mL of tetraethoxysilane is transferred by a pipette, added to 3.6mL of water and stirred evenly at 40 ℃, and simultaneously, a certain amount of nitric acid is absorbed by a pipette and slowly dripped into the solution to ensure that the pH value reaches 2, and silica sol appears. Then, 2.69g of aluminum nitrate nonahydrate was weighed on an analytical balance and added to 13.4mL of deionized water, and the mixture was heated to 40 ℃ to be completely dissolved. The two were then mixed and heated at 40 ℃ with stirring for 1 h. Then absorbing a certain amount of ammonia water by a suction pipe to adjust the pH value of the solution to 8 to generate alumina sol, standing for 1 hour at 40 ℃, filtering and washing, drying, and then obtaining 9SiO in a muffle furnace at 550 ℃ for 3 hours2-1Al2O3And (3) sampling. Weighing 1.5g of 9SiO by using a balance scale2-1Al2O3Mixing the sample with 0.074g of nickel nitrate hexahydrate by an impregnation method, stirring at room temperature for 24 hours, then stirring at 100 ℃ to dry, and then roasting at 500 ℃ for 3 hours to obtain NiO/9SiO with the loading of 1%2-1Al2O3A catalyst. After the catalyst is tabletted, particles of 20-40 meshes are screened, and the oligomerization reaction of methyl ricinoleate is carried out in a fixed bed reactor, wherein the reaction temperature is 200 ℃, the flow rate of N2 is 30mL/min, and the flow rate of reactants is 0.018 mL/min.
Table 3 shows the results of oligomerization of methyl ricinoleate from the products of examples 9-12, respectively, as a function of the effect of different supported metals on the oligomerization of methyl ricinoleate.
TABLE 3
Figure BDA0002083632690000101
As can be seen from Table 3, MoO3Has higher selectivity to the methyl ricinoleate oligomer.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. Use of a catalyst for oligomerization of methyl ricinoleate, characterized in that the catalyst is prepared by a process comprising at least:
mixing a silicon source and deionized water, uniformly stirring, and adding acid to a first pH value to obtain silica sol;
mixing an aluminum source and deionized water, and uniformly stirring to obtain an aluminum solution;
mixing the aluminum solution and the silica sol, and then adding alkali to a second pH value to obtain aluminum-silica mixed sol;
washing, drying and calcining the aluminum-silicon mixed sol in sequence to obtain SiO2-Al2O3A carrier; the SiO2-Al2O3The molar ratio of silicon to aluminum of the carrier is between 1:9 and 9: 1;
loading a metal-loading precursor solution to the SiO2-Al2O3On a carrier, and then calcining to obtain SiO supported by metal oxide2-Al2O3A catalyst; the metal oxide-supported SiO2-Al2O3In the catalyst, the metal oxide comprises NiO and MoO3One of CeO, PdO and ZnO; the metal oxide-supported SiO2-Al2O3In the catalyst, the loading amount of the metal oxide is between 0.5 and 7 percent;
the reaction temperature of the oligomerization reaction of the methyl ricinoleate is between 160 and 240 ℃, and the reaction pressure is between 1 and 2 barsM, N2The flow rate is between 30mL/min and 50mL/min, and the flow rate of the reaction product is between 0.009mL/min and 0.021 mL/min.
2. Use according to claim 1, characterized in that: the silicon source comprises one or a mixture of more of sodium silicate, silica sol and tetraethoxysilane.
3. Use according to claim 1, characterized in that: the aluminum source comprises a mixture of one or more of aluminum isopropoxide, aluminum nitrate and aluminum trichloride.
4. Use according to claim 1, characterized in that: the acid comprises one of hydrochloric acid and nitric acid.
5. Use according to claim 1, characterized in that: the alkali comprises one or more of ammonia water and sodium hydroxide.
6. Use according to claim 1, characterized in that: the first pH value is between 1 and 3, and the second pH value is between 8 and 10.
7. Use according to claim 1, characterized in that: in the preparation of the SiO2-Al2O3When the carrier is used, the calcining temperature is between 400 and 600 ℃, and the calcining time is between 2 and 6 hours.
8. Use according to claim 1, characterized in that: loading the metal load precursor solution to the SiO by adopting an impregnation method2-Al2O3On a carrier.
9. Use according to claim 1, characterized in that: the metal support precursor includes a mixture of one or more of nitrates, chlorides, and metal complex salts.
10. Use according to claim 1, characterized in that: loading the metal-loading precursor solution to the SiO2-Al2O3Calcining the carrier at 400-600 ℃ for 2-6 hours to obtain the SiO supported by the metal oxide2-Al2O3A catalyst.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642661A (en) * 1969-10-21 1972-02-15 Exxon Research Engineering Co Sio2-al2o3-nio catalyst and its preparation
CN102764656A (en) * 2012-08-06 2012-11-07 久泰能源科技有限公司 High-efficiency hydrogenation catalyst and method for preparing same
CN106190592A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of method that biodiesel catalytic hydrogenation prepares biological lubricant
CN107233881A (en) * 2017-05-16 2017-10-10 北京化工大学 Microspheroidal silica/alumina base noble metal catalyst and preparation method thereof
CN108359519A (en) * 2018-02-27 2018-08-03 合肥择浚电气设备有限公司 A kind of preparation method of electrical equipment lubricating oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642661A (en) * 1969-10-21 1972-02-15 Exxon Research Engineering Co Sio2-al2o3-nio catalyst and its preparation
CN102764656A (en) * 2012-08-06 2012-11-07 久泰能源科技有限公司 High-efficiency hydrogenation catalyst and method for preparing same
CN106190592A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of method that biodiesel catalytic hydrogenation prepares biological lubricant
CN107233881A (en) * 2017-05-16 2017-10-10 北京化工大学 Microspheroidal silica/alumina base noble metal catalyst and preparation method thereof
CN108359519A (en) * 2018-02-27 2018-08-03 合肥择浚电气设备有限公司 A kind of preparation method of electrical equipment lubricating oil

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