CN114950465B - Nickel-based catalyst, preparation method thereof and application thereof in alkene and alkyne saturated hydrogenation - Google Patents
Nickel-based catalyst, preparation method thereof and application thereof in alkene and alkyne saturated hydrogenation Download PDFInfo
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a nickel-based catalyst, a preparation method thereof and application thereof in alkene and alkyne saturated hydrogenation. The preparation method comprises the following steps: mixing high-purity pseudo-boehmite, an alcohol solvent, an organic vanadium precursor and polyethylene glycol, and roasting at a temperature of not more than 250 ℃ to obtain vanadium-containing pseudo-boehmite; mixing vanadium-containing pseudo-boehmite powder with a solution containing an iron source and an indium source, and drying to obtain vanadium-indium modified pseudo-boehmite; mixing the ferrovanadium modified pseudo-boehmite with a solution containing a nickel source and a tungsten source, drying, rapidly heating, roasting and cooling to obtain the nickel-based catalyst. The preparation method of the nickel-based catalyst is simple and suitable for large-scale industrial production, and the prepared nickel-based catalyst has the characteristics of high activity, high selectivity, good stability and long service life for olefin and alkyne saturation hydrogenation reaction, and can reduce the total content of olefin and alkyne in alkane raw materials to below 1ppmw on the premise of no deep hydrogenation.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a nickel-based catalyst, a preparation method thereof and application thereof in alkene and alkyne saturation hydrogenation.
Background
In the oil refining unit structure, the traditional catalytic cracking, coking and other operation units occupy a considerable proportion, and byproducts of the oil refining unit structure contain abundant low-carbon alkane resources, and the oil refining unit structure is usually used as liquefied petroleum gas fuel, has low chemical utilization rate and causes huge waste for enterprises. The continuous construction and perfection of the natural gas pipeline further consolidates and expands the status of the natural gas in the civil fuel and the share of the predation liquefied petroleum gas in the civil fuel, further reduces the price of the liquefied petroleum gas, reduces the profit margin of the liquefied petroleum gas, and finally influences the benefits of the refining enterprises. Therefore, how to fully and reasonably utilize the low-carbon alkane resource, dig the potential value of the low-carbon alkane, and change the low-carbon alkane into a high-added-value product has become a subject to be solved urgently for refining enterprises and scientific researchers.
The low-carbon olefin is an important chemical raw material, and the preparation of olefin by low-carbon alkane dehydrogenation is an important direction of high-value comprehensive utilization of low-carbon alkane and is also a common technical means for preparing olefin. With the increasing demand for polymer products in recent years, the yields of the corresponding olefin monomers have been increased year by year. If the low-carbon alkane can be effectively and directly converted into the low-carbon alkene, the problem of insufficient sources of the low-carbon alkene raw materials is solved, and the utilization value of the low-carbon alkane is also improved. However, there is a large difference between different alkane dehydrogenation feeds. Some ethane, propane and isobutane dehydrogenation feeds are derived from oilfield associated gas, shale gas, etc., and have very low levels of olefins. Some dehydrogenation raw materials are derived from liquefied gas and ether in a catalytic cracking section, and then mixed with carbon three-carbon four, and still contain part of mono-olefin, alkyne and diene in dehydrogenation hydrogen production. The mono-olefin, alkyne and diene contained in the raw materials can be further deeply dehydrogenated in the dehydrogenation process, carbon deposit is easily formed on the catalyst, dehydrogenation active sites are covered, and the dehydrogenation catalyst is greatly damaged. The dehydrogenation catalyst is generally a platinum or chromium-supported alumina catalyst, the platinum-based catalyst is relatively expensive, and the chromium-based catalyst has serious environmental pollution, so that in order to protect smooth operation of the dehydrogenation process and reduce the frequency of replacing the catalyst, it is common practice to pretreat the dehydrogenation raw material before dehydrogenation to saturate mono-olefins, di-olefins and alkynes therein. The current commercial hydrogenation catalyst mainly comprises supported noble metals such as platinum and palladium catalysts, has the characteristics of high activity and long service life, but has the defects of high price and high cost of the noble metals, and causes great pressure on the operation economy of application enterprises. If a non-noble metal hydrogenation catalyst with high hydrogenation activity and excellent reaction performance can be developed successfully, the defects can be overcome, the investment cost of enterprises can be greatly reduced, and the operation economy of a dehydrogenation device can be improved.
Disclosure of Invention
Based on the drawbacks of the prior art, a first object of the present invention is to provide a method for preparing a nickel-based catalyst; the second object of the present invention is to provide a nickel-based catalyst prepared by the preparation method; the third object of the invention is to provide the application of the nickel-based catalyst in olefin and alkyne saturated hydrogenation. The catalyst has high activity, high selectivity and high stability in olefin and alkyne saturated hydrogenation reaction, and meanwhile, the cost of the catalyst can be greatly reduced, and the operation economy of related devices of enterprises is improved.
In order to achieve the above object, the present invention provides the following technical solutions.
In a first aspect, the present invention provides a method for preparing a nickel-based catalyst, comprising the steps of:
mixing high-purity pseudo-boehmite, an alcohol solvent, an organic vanadium precursor and polyethylene glycol, and drying and roasting to obtain vanadium-containing pseudo-boehmite; wherein the roasting temperature is not more than 250 ℃;
mixing the vanadium-containing pseudo-boehmite powder with a solution containing an iron source and an indium source, and drying to obtain vanadium-iron-indium modified pseudo-boehmite;
mixing the ferrovanadium modified pseudo-boehmite with a solution containing a nickel source and a tungsten source, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the temperature rising rate of the roasting is not lower than 20 ℃/s, and the roasting temperature is not lower than 500 ℃.
In the preparation process of the nickel-based catalyst, the vanadium source and the polyethylene glycol substance are added in the first preparation process, so that the specific surface area of the final preparation catalyst can be effectively increased, and conditions are provided for the dispersion of active components; the iron and indium added in the second step can generate oxides on the surface of the carrier after being dried and decomposed to form a similar grid structure, the similar grid structure can effectively fix the subsequent nickel and tungsten active components by interacting with vanadium-containing active centers, prevent aggregation growth of crystal grains in the roasting process of the nickel and tungsten active components, maintain the stability of the catalyst in the reaction process, meanwhile, the oxides formed on the surface of the catalyst by the iron and indium two components can interact with hydrogenation active centers, and the d-space electron orbits of the oxides are utilized to strengthen the adsorption of olefins on the surface of the catalyst, so that the hydrogenation reaction efficiency of the catalyst is improved; the nickel and tungsten source added in the third step can form nickel-tungsten mixed active center after being decomposed in the roasting process, and tungsten can effectively enhance the hydrogenation activity of nickel and ensure the saturation hydrogenation activity of alkane. In addition, the roasting temperature in the first step is controlled to be not higher than 250 ℃ so that all polyethylene glycol can not be decomposed in the roasting in the first step, part of polyethylene glycol can be carbonized due to rapid heating in the roasting process in the third step, and stable graphite-like carbon is formed in partial areas while cross-linked pore channels are formed in the catalyst, so that heat released in the reaction process can be rapidly led out of the catalyst in the hydrogenation reaction process, the hydrogenation activity of the catalyst is kept stable, and hot spots are prevented from forming in the catalyst.
In the technical scheme of the invention, the high-purity pseudo-boehmite is selected from common high-purity pseudo-boehmite, and the high-purity pseudo-boehmite is usually Na in raw materials 2 Pseudoboehmite having an O content of not more than 100 ppmw.
According to a preferred embodiment of the first aspect, the alcohol solvent includes one or a combination of two or more of ethanol, propanol and butanol, but is not limited thereto.
According to a preferred embodiment of the first aspect, the organic vanadium precursor includes one or both of vanadyl acetylacetonate and vanadyl sulfate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the polyethylene glycol has a degree of polymerization of not more than 1000.
According to a preferred embodiment of the first aspect, the high purity pseudo-boehmite has a dry alumina content of 70wt% to 80wt% and a specific surface area of not less than 200m 2 Per gram, pore volume is more than or equal to 0.5mL/g, pore diameter is more than or equal to 10nm, na 2 The O content is less than or equal to 0.01 percent. The pseudo-boehmite has high purity, high specific surface area and mesopores.
According to a preferred embodiment of the first aspect, in the first step, the mass ratio of the dry alumina, the alcohol solvent, the organic vanadium precursor and the polyethylene glycol of the high-purity pseudo-boehmite is 1 (0.2-0.8): 0.001-0.1): 0.05-0.4.
According to a preferred embodiment of the first aspect, the iron source is selected from iron salts; more preferably, the iron source is selected from ferric nitrate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the indium source is an indium salt; more preferably, the indium source is indium nitrate, but is not limited thereto.
According to a preferred embodiment of the first aspect, in the second step, the mass ratio of the dry-basis alumina, the iron source and the indium source of the pseudo-boehmite containing vanadium is 1 (0.001-0.08): 0.001-0.08.
According to a preferred embodiment of the first aspect, the nickel source is a nickel salt; more preferably, the nickel source is nickel nitrate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the tungsten source is a salt containing tungsten element; more preferably, the tungsten source is ammonium metatungstate, but is not limited thereto.
According to a preferred embodiment of the first aspect, in the third step, the mass ratio of the dry alumina, the tungsten source and the nickel source of the ferrovanadium modified pseudo-boehmite is 1 (0.002-0.05): 0.02-0.1.
According to a preferred embodiment of the first aspect, in step one, the drying temperature is 180-250 ℃; the drying time is 8-20h.
According to a preferred embodiment of the first aspect, in step one, the firing temperature is 200-250 ℃, the firing time is 4-10 hours, and the firing temperature rise rate is not higher than 2 ℃/min.
According to a preferred embodiment of the first aspect, in step two, the drying temperature is 180-250 ℃ and the drying time is 8-20h.
According to a preferred embodiment of the first aspect, in step three, the drying temperature is 80-120 ℃; the drying time is 8-20h.
According to a preferred embodiment of the first aspect, in step three, the firing temperature is 550-650 ℃, the firing time is 1-10min, and the firing temperature rise rate is 20-200 ℃/s.
According to a preferred embodiment of the first aspect, in step three, the cooling rate is in the range of 100-500 ℃/s.
According to a preferred embodiment of the first aspect, in step three, the cooling is performed by means of liquid nitrogen quenching.
According to a preferred embodiment of the first aspect, the method for preparing a nickel-based catalyst further comprises: in the third step, the dried product is molded and then baked;
more preferably, the shaping treatment is performed by means of extrusion and/or drying after tabletting.
According to a preferred embodiment of the first aspect, the mixing in step one, step two and step three is achieved by stirring; more preferably, the mixing is achieved by stirring under water bath conditions of not more than 80 ℃.
In a second aspect, the invention also provides the nickel-based catalyst prepared by the preparation method.
In a third aspect, the invention also provides the application of the nickel-based catalyst in olefin (including mono-olefin and diene) and alkyne saturated hydrogenation reaction.
According to a preferred embodiment of the third aspect, the nickel-based catalyst is reduced with pure hydrogen at elevated temperature prior to use;
more preferably, the high temperature is 300-500 ℃, and the gas hourly space velocity of the hydrogen is 200-10000h -1 The reduction time is 1-6 hours.
According to a preferred embodiment of the third aspect, the reaction temperature of the alkene and alkyne saturation hydrogenation is in the range of 250-500 ℃.
According to a preferred embodiment of the third aspect, H during the olefin, alkyne saturation hydrogenation 2 The molar ratio to the sum of alkyne and alkene is 2.0-20.0:1.
According to a preferred embodiment of the third aspect, an olefin,In the alkyne saturated hydrogenation reaction process, the total weight hourly space velocity of the hydrocarbon raw material is 3-6h -1 。
According to a preferred embodiment of the third aspect, the reaction pressure of the alkene, alkyne saturation hydrogenation reaction is from atmospheric pressure to 5.0MPa.
The invention has the beneficial effects that:
the preparation method of the nickel-based catalyst is simple and effective, is suitable for large-scale industrial production, and the prepared nickel-based catalyst has the characteristics of high activity, high selectivity, good stability and long service life for olefin (including mono-olefin and diene) and alkyne saturated hydrogenation reaction, and can reduce the total content of olefin (including mono-olefin and diene) and alkyne in alkane raw materials to below 1ppmw on the premise of not generating deep hydrogenation.
Drawings
Fig. 1 is an XRD spectrum of the nickel-based catalyst prepared in example 1.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
the embodiment provides a nickel-based catalyst and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethyl alcohol to form a clear solution, 670g of high-purity pseudo-boehmite (SB powder, manufactured by Sasol/Condea company, 75wt% of dry alumina content and the rest of physicochemical properties shown in Table 2) is added into the clear solution, and the mixture is stirred and mixed uniformly, dried at 200 ℃ for 10 hours under stirring, and then heated to 200 ℃ at a heating rate of 1 ℃/min and baked at 200 ℃ for 6 hours to obtain vanadium-containing pseudo-boehmite powder (about 680g in weight).
(2) 15g of ferric nitrate and 15g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 10 hours at 180 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 10g of ammonium metatungstate and 40g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 20 hours at 80 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying for 8 hours at 100 ℃, then heating to 550 ℃ at a heating rate of 100 ℃/s, roasting for 5 minutes at 550 ℃, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The XRD spectrum of the nickel-based catalyst prepared in this example is shown in FIG. 1.
As can be seen from FIG. 1, the sample of example 1 prepared had a crystalline phase based on alumina, and the diffraction peaks were of lower overall intensity and shorter peak shape, indicating that the alumina in the sample did not form larger grains, and may still exist in an amorphous form. In addition, no significant diffraction peaks of nickel oxide crystals were found on the samples, indicating that the nickel oxide on the prepared samples was present in a highly dispersed form. Other diffraction peaks of oxides of vanadium, iron, indium and the like do not appear, which indicates that the auxiliary agent and the active component keep a higher dispersion state.
The embodiment also provides the application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 5.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and hydrogen space velocity of 2000h -1 And the reduction time is 4 hours. The results are shown in Table 3.
Example 2:
the embodiment provides a nickel-based catalyst and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) 10g of vanadyl acetylacetonate and 50g of polyethylene glycol 600 are taken and dissolved in 150g of absolute ethyl alcohol to form a clear solution, 700g of high-purity pseudo-boehmite (the dry basis alumina content is 73wt percent and the rest physicochemical properties are shown in Table 2 of Nanjing Ji bin nanotechnology Co., ltd.) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 15 hours at the temperature of 100 ℃ under the stirring condition, and the temperature is raised to 220 ℃ at the heating rate of 1 ℃/min and is baked for 8 hours at the temperature of 220 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight is about 620 g).
(2) 6g of ferric nitrate and 20g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 12 hours at 200 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight is about 625 g).
(3) 2.5g of ammonium metatungstate and 30g of nickel nitrate are dissolved in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 15 hours at 100 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight is about 640 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying at 100 ℃ for 8 hours, then heating to 600 ℃ at a heating rate of 150 ℃/s, roasting at 600 ℃ for 5 minutes, and quenching by adopting liquid nitrogen (cooling rate of 200 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The embodiment also provides the application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 8.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 450 ℃ and hydrogen gas spaceThe speed is 4000h -1 And the reduction time is 2h. The results are shown in Table 3.
Example 3:
the embodiment provides a nickel-based catalyst and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethyl alcohol to form a clear solution, 670g of high-purity pseudo-boehmite (the dry basis alumina content is 78wt percent and the rest physicochemical properties are shown in Table 2 of Shandong catalytic technology Co., ltd.) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 8 hours at the temperature of 230 ℃ under the stirring condition, and the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min and the mixture is baked for 10 hours at the temperature of 250 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight is about 670 g).
(2) 35g of ferric nitrate and 8g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 15 hours at 220 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight about 690 g).
(3) Dissolving 10g of ammonium metatungstate and 40g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 10 hours at 120 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 710 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying for 8 hours at 100 ℃, then heating to 650 ℃ at a heating rate of 200 ℃/s, roasting for 5 minutes at 650 ℃, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The embodiment also provides the application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass of total moles of alkene and alkyneMolar mass = 10.0:1, total weight hourly space velocity of hydrocarbon feedstock 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and hydrogen space velocity of 2000h -1 And the reduction time is 4 hours. The results are shown in Table 3.
Comparative example 1:
the comparative example provides a nickel-based catalyst and a preparation method thereof, which are different from example 1 in that the pseudo-boehmite used is common pseudo-boehmite, and the preparation method is as follows:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethyl alcohol to form a clear solution, 670g of common pseudo-boehmite (the content of dry basis alumina is 75wt% of that of Shandong catalytic technology Co., ltd., and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 10 hours at 200 ℃ under stirring, and the temperature is raised to 200 ℃ at a heating rate of 1 ℃/min and is baked for 6 hours at 200 ℃ to obtain vanadium-containing pseudo-boehmite powder (about 680g in weight).
(2) 15g of ferric nitrate and 15g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 10 hours at 180 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 10g of ammonium metatungstate and 40g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 20 hours at 80 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying for 8 hours at 100 ℃, then heating to 550 ℃ at a heating rate of 100 ℃/s, roasting for 5 minutes at 550 ℃, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The comparative example also provides application of the nickel-based catalyst in alkene and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 5.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and hydrogen space velocity of 2000h -1 And the reduction time is 4 hours. The results are shown in Table 3.
Comparative example 2:
this comparative example provides a nickel-based catalyst and a preparation method thereof, which is different from example 2 in that polyethylene glycol is not added, and the preparation method is as follows:
(1) 10g of vanadyl acetylacetonate is dissolved in 150g of absolute ethyl alcohol to form a clear solution, 700g of high-purity pseudo-boehmite (the dry alumina content is 73wt percent and the rest of physicochemical properties are shown in Table 2) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 15h at 200 ℃ under stirring, and the dried mixture is heated to 220 ℃ at a heating rate of 1 ℃/min and is baked for 6h at 220 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight of the pseudo-boehmite powder is about 570 g).
(2) 6g of ferric nitrate and 20g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 12 hours at 200 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (about 575g in weight).
(3) 2.5g of ammonium metatungstate and 30g of nickel nitrate are dissolved in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 15h at 100 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight is about 590 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying at 100 ℃ for 8 hours, then heating to 600 ℃ at a heating rate of 150 ℃/s, roasting at 600 ℃ for 5 minutes, and quenching by adopting liquid nitrogen (cooling rate of 200 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The comparative example also provides application of the nickel-based catalyst in alkene and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 8.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 450 ℃ and hydrogen space velocity of 4000h -1 And the reduction time is 2h. The results are shown in Table 3.
Comparative example 3:
this comparative example provides a nickel-based catalyst and a preparation method thereof, which is different from example 3 in that ammonium metatungstate is not added, and the preparation method is as follows:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethyl alcohol to form a clear solution, 670g of high-purity pseudo-boehmite (the dry basis alumina content is 78wt percent and the rest physicochemical properties are shown in Table 2 of Shandong catalytic technology Co., ltd.) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 8 hours at the temperature of 230 ℃ under the stirring condition, and the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min and the mixture is baked for 10 hours at the temperature of 250 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight is about 670 g).
(2) 35g of ferric nitrate and 8g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 15 hours at 220 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight about 690 g).
(3) Dissolving 40g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 10 hours at 120 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 700 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying for 8 hours at 100 ℃, then heating to 650 ℃ at a heating rate of 200 ℃/s, roasting for 5 minutes at 650 ℃, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The comparative example also provides application of the nickel-based catalyst in alkene and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and hydrogen space velocity of 2000h -1 And the reduction time is 4 hours. The results are shown in Table 3.
Comparative example 4:
the present comparative example provides a nickel-based catalyst and a preparation method thereof, which are different from example 1 in that each metal precursor of the comparative example is added at one time, not performed in several times, and the preparation method is as follows:
dissolving 30g of vanadyl acetylacetonate, 100g of polyethylene glycol 200, 15g of ferric nitrate, 15g of indium nitrate, 10g of ammonium metatungstate and 40g of nickel nitrate in 500g of absolute ethyl alcohol, adding 670g of high-purity pseudo-boehmite (SB powder, manufactured by Sasol/Condea company, with 75 weight percent of dry alumina content and the rest of physicochemical properties shown in Table 2) into the mixture after the dissolution is completed, stirring and mixing the mixture uniformly, drying the mixture for 20h at 80 ℃ under stirring conditions, heating the mixture to 200 ℃ at a heating rate of 1 ℃/min, and roasting the mixture at 200 ℃ for 8h to obtain nickel-based catalyst precursor powder (weight of about 725 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying for 8 hours at 100 ℃, then heating to 550 ℃ at a heating rate of 100 ℃/s, roasting for 5 minutes at 550 ℃, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The comparative example also provides application of the nickel-based catalyst in alkene and alkyne saturation hydrogenation, which comprises the following specific steps:
crushing a nickel-based catalyst into particles with 10-20 meshes, and filling 2.0g into a reaction tube with an inner diameter of 1.4cm, an outer diameter of 1.7cm and a total length of 72cm to perform olefin and alkyne saturated hydrogenation reaction; the reaction conditions were as follows: 450 ℃, normal pressure, H 2 Molar mass: total molar mass of alkene and alkyne = 5.0:1, total weight of hydrocarbon feedstock hourly space velocity 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition of the reaction is shown in table 1, and the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and hydrogen space velocity of 2000h -1 And the reduction time is 4 hours.
Comparative example 5:
the comparative example provides a nickel-based catalyst and a method for producing the same, which are different from example 1 in the temperature rising rate at the time of calcination and the calcination time, and in the comparative example, the temperature rising rate during the calcination in the (3) th step is 5 deg.c/min and the calcination time is 4 hours.
The present comparative example also provides the use of the above-described nickel-based catalyst in olefin and alkyne saturation hydrogenation reactions, differing from example 1 only in the use of the nickel-based catalyst as provided in the present comparative example.
Comparative example 6:
this example provides a nickel-based catalyst and a method for producing the same, which are different from example 1 in that the calcination steps are different, and this comparative example reverses the calcination processes of the first and third steps in example 1:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethyl alcohol to form a clear solution, 670g of high-purity pseudo-boehmite (SB powder, manufactured by Sasol/Condea company, 75wt% of dry alumina content and the rest of physicochemical properties shown in Table 2) is added into the clear solution, and the mixture is stirred and mixed uniformly, dried at 200 ℃ for 10 hours under stirring, and then heated to 550 ℃ at a heating rate of 100 ℃/s and baked for 5 minutes at 550 ℃ to obtain vanadium-containing pseudo-boehmite powder (about 680g in weight).
(2) 15g of ferric nitrate and 15g of indium nitrate are dissolved in 500g of deionized water to obtain a clear solution; and (3) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 10 hours at 180 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 10g of ammonium metatungstate and 40g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the ferrovanadium modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying for 20 hours at 80 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, forming and drying at 100 ℃ for 8 hours, then heating to 200 ℃ at a heating rate of 1 ℃/min, roasting at 200 ℃ for 6 hours, and quenching by adopting liquid nitrogen (cooling rate of 250 ℃/s) after roasting, thus obtaining the nickel-based catalyst.
The present comparative example also provides the use of the above-described nickel-based catalyst in olefin and alkyne saturation hydrogenation reactions, differing from example 1 only in the use of the nickel-based catalyst as provided in the present comparative example.
Table 1 shows the composition of each raw material for olefin and alkyne saturation hydrogenation reactions in examples and comparative examples; table 2 shows the physicochemical properties of pseudo-boehmite used in the examples and comparative examples; table 3 shows the results of the evaluation of the alkene and alkyne saturated hydrogenation reactions in the examples and comparative examples; table 4 shows data such as specific surface areas of the nickel-based catalysts in examples and comparative examples.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
From the data of specific surface area, pore volume and most probable pore diameter of the prepared partial sample, the catalyst prepared strictly according to the preparation method of the invention has the characteristics of high specific surface area, pore volume and most probable pore diameter. The method of changing the addition sequence of the metal precursor, the roasting sequence, the roasting condition and the like can have adverse effects on the structure of the prepared catalyst.
The evaluation result shows that the catalyst prepared by the method has good alkene and alkyne saturated hydrogenation activity, and the alkene and alkyne content in the raw material can be reduced to less than 1ppmw by hydrogenation in the reaction process. As can be seen from the reactivity of the comparative example, the preparation process of the nickel-based catalyst disclosed by the invention can prepare the advantages of high saturated hydrogenation activity and stable reaction activity, which proves that the structure of the catalyst prepared by the method disclosed by the invention is suitable for saturated hydrogenation reaction.
Claims (23)
1. A method for preparing a nickel-based catalyst, comprising the steps of:
mixing high-purity pseudo-boehmite, an alcohol solvent, an organic vanadium precursor and polyethylene glycol, and drying and roasting to obtain vanadium-containing pseudo-boehmite; wherein the roasting temperature is not more than 250 ℃, and polyethylene glycol is not completely decomposed; wherein the dry-basis alumina content of the high-purity pseudo-boehmite is 70-80 wt% and the specific surface area is more than or equal to 200m 2 Per gram, pore volume is more than or equal to 0.5mL/g, pore diameter is more than or equal to 10nm, na 2 The O content is less than or equal to 0.01wt%;
mixing the vanadium-containing pseudo-boehmite powder with a solution containing an iron source and an indium source, and drying to obtain vanadium-iron-indium modified pseudo-boehmite;
mixing the ferrovanadium modified pseudo-boehmite with a solution containing a nickel source and a tungsten source, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the temperature rising rate of the roasting is not lower than 20 ℃/s, and the roasting temperature is not lower than 500 ℃.
2. The production method according to claim 1, wherein the alcohol solvent comprises one or a combination of two or more of ethanol, propanol, and butanol.
3. The method of claim 1, wherein the organic vanadium precursor comprises one or both of vanadyl acetylacetonate and vanadyl sulfate.
4. The production method according to claim 1, wherein the polyethylene glycol has a degree of polymerization of not more than 1000.
5. The preparation method according to any one of claims 1 to 4, wherein the mass ratio of the dry-based alumina of the high-purity pseudo-boehmite, the alcohol solvent, the organic vanadium precursor and the polyethylene glycol is 1 (0.2 to 0.8): (0.001 to 0.1): (0.05 to 0.4).
6. The preparation method of claim 1, wherein the iron source is an iron salt.
7. The method according to claim 1, wherein the iron source is ferric nitrate.
8. The preparation method of claim 1, wherein the indium source is indium salt.
9. The method according to claim 1, wherein the indium source is indium nitrate.
10. The preparation method according to any one of claims 1, 6 to 9, wherein the mass ratio of the dry-basis alumina of the pseudo-boehmite containing vanadium, the iron source and the indium source is 1 (0.001-0.08): (0.001-0.08).
11. The preparation method of claim 1, wherein the nickel source is nickel salt.
12. The preparation method of claim 1, wherein the nickel source is nickel nitrate.
13. The preparation method of claim 1, wherein the tungsten source is a tungsten-containing salt.
14. The preparation method of claim 1, wherein the tungsten source is ammonium metatungstate.
15. The preparation method according to any one of claims 1, 12 to 14, wherein the mass ratio of the dry-basis alumina of the ferrovanadium-modified pseudo-boehmite, the tungsten source and the nickel source is 1 (0.002 to 0.05): 0.02 to 0.1.
16. The preparation method according to claim 1, wherein,
in the first step, the drying temperature is 180-250 ℃, the time is 8-20h, the roasting temperature is 200-250 ℃, the time is 4-10h, and the heating rate is not higher than 2 ℃/min;
in the second step, the drying temperature is 180-250 ℃ and the drying time is 8-20h;
in the third step, the drying temperature is 80-120 ℃, the baking time is 8-20h, the baking temperature is 550-650 ℃, the baking time is 1-10min, the heating rate is 20-200 ℃/s, and the cooling rate of cooling is 100-500 ℃/s.
17. A nickel-based catalyst prepared by the preparation method of any one of claims 1-16.
18. Use of the nickel-based catalyst of claim 17 in olefin and alkyne saturation hydrogenation reactions.
19. Use according to claim 18, whichThe nickel-based catalyst is reduced at high temperature by adopting pure hydrogen before use; wherein the high temperature is 300-500 ℃, and the gas hourly space velocity of the hydrogen is 200-10000h -1 The reduction time is 1-6h.
20. The use according to claim 18, wherein the reaction temperature of the alkene, alkyne saturation hydrogenation is 250-500 ℃.
21. The use according to claim 18, wherein during the saturated hydrogenation of olefins and alkynes, H is introduced 2 The molar ratio of the catalyst to the total of the olefin and alkyne is 2.0-20.0:1.
22. The use according to claim 18, wherein the total weight hourly space velocity of the hydrocarbon feedstock during the olefin/alkyne saturation hydrogenation reaction is from 3 to 6 hours -1 。
23. The use according to claim 18, wherein the reaction pressure of the alkene, alkyne saturation hydrogenation is from atmospheric pressure to 5.0MPa.
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