CN114950465A - Nickel-based catalyst, preparation method thereof and application thereof in olefin and alkyne saturation hydrogenation - Google Patents
Nickel-based catalyst, preparation method thereof and application thereof in olefin and alkyne saturation hydrogenation Download PDFInfo
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Abstract
The invention provides a nickel-based catalyst, a preparation method thereof and application thereof in olefin and alkyne saturation hydrogenation. The preparation method comprises the following steps: mixing high-purity pseudo-boehmite, an alcohol solvent, an organic vanadium precursor and polyethylene glycol, drying, roasting at a temperature of not more than 250 ℃ and roasting 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-iron-indium modified pseudo-boehmite; mixing the pseudo-boehmite modified by the vanadium-iron-indium with a solution containing a nickel source and a tungsten source, drying, rapidly heating, roasting and cooling to obtain the nickel-based catalyst. The 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 olefin and alkyne saturation hydrogenation.
Background
In an oil refining unit structure, the traditional operation units such as catalytic cracking, coking and the like occupy a certain proportion, and byproducts of the traditional operation units contain rich low-carbon alkane resources and are usually used as liquefied petroleum gas fuels, so that the chemical utilization rate is low, and huge waste is caused to enterprises. The continuous construction and perfection of the natural gas pipeline further consolidates and expands the status of natural gas in civil fuel and the share of silkworm-eating liquefied petroleum gas in civil fuel, further reduces the price of the liquefied petroleum gas, reduces the profit margin of the liquefied petroleum gas and finally influences the benefit of refining enterprises. Therefore, how to fully and reasonably utilize the low-carbon alkane resources and exploit the potential value of the low-carbon alkane and change the low-carbon alkane into a high-added-value product has become a problem to be solved urgently by refining enterprises and scientific researchers.
The low-carbon olefin is an important chemical raw material, and the dehydrogenation of the low-carbon alkane to prepare the olefin is an important direction for high-value comprehensive utilization of the low-carbon alkane and is a common technical means for preparing the olefin. With the increasing demand for polymer products in recent years, the production of the corresponding olefin monomers has also increased year by year. If the low-carbon alkane can be directly converted into the low-carbon olefin, the problem of insufficient source of the low-carbon olefin raw material is solved, and the utilization value of the low-carbon alkane is improved. However, there are large differences between different alkane dehydrogenation feeds. Some ethane, propane and isobutane dehydrogenation feedstocks come from oilfield associated gas, shale gas, etc., and have very low olefin content. Some dehydrogenation raw materials are derived from liquefied gas and ether in a catalytic cracking section and then are mixed with C, C and C, and hydrogen production by dehydrogenation still contains partial mono-olefin, alkyne and diene. The monoolefine, alkyne and dialkene contained in the raw material can be further deeply dehydrogenated in the dehydrogenation process, carbon deposit is easily formed on the catalyst, and the dehydrogenation active site is covered, so that the catalyst has great harm to the dehydrogenation catalyst. The dehydrogenation catalyst is generally a platinum or chromium-supported alumina catalyst, the platinum-based catalyst is expensive, and the chromium-based catalyst causes severe environmental pollution, so that in order to protect the smooth operation of the dehydrogenation process and reduce the frequency of replacing the catalyst, the conventional method is to pre-hydrogenate the dehydrogenation raw material before dehydrogenation to saturate mono-olefins, diolefins and alkynes therein. At present, the commercial hydrogenation catalyst mainly comprises supported noble metals such as platinum and palladium, has the characteristics of high activity and long service life, but has the defects of higher price and cost of the noble metals and causes greater 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 is greatly reduced, and the operating economy of a dehydrogenation device is improved.
Disclosure of Invention
Based on the defects in the prior art, the first object of the present invention is to provide a method for preparing a nickel-based catalyst; the second purpose of the invention is to provide the nickel-based catalyst prepared by the preparation method; the third purpose of the invention is to provide the application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation. The catalyst has high activity, high selectivity and high stability in olefin and alkyne saturation hydrogenation reaction, and can greatly reduce the cost of the catalyst and improve the operation economy of related devices of enterprises.
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, drying and roasting to obtain vanadium-containing pseudo-boehmite; wherein the roasting temperature is not more than 250 ℃;
mixing 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 pseudoboehmite modified by the vanadium-iron-indium with a solution containing a nickel source and a tungsten source, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the heating 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 are added in the first preparation process, so that the specific surface area of the finally prepared catalyst can be effectively improved, and conditions are provided for dispersion of active components; the second step, the added iron and indium can generate oxides on the surface of the carrier after being dried and decomposed to form a similar grid structure, the interaction of the similar grid structure and the vanadium-containing active center can effectively fix subsequent nickel and tungsten active components, prevent the aggregation and growth of crystal grains in the roasting process of the nickel and tungsten active components and 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 components can interact with the hydrogenation active center, and the d-empty electron orbit of the oxides can be utilized to strengthen the adsorption of olefin on the surface of the catalyst, so that the hydrogenation reaction efficiency of the catalyst is improved; and the nickel and tungsten source added in the third step can form a 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 of the first step is controlled not to exceed 250 ℃, so that all polyethylene glycol can not be decomposed by the roasting of the first step, part of polyethylene glycol can be carbonized due to rapid temperature rise in the roasting process of the third step, cross-linked pore channels are formed in the catalyst, and stable graphite-like carbon is formed in a part of regions, and the graphite-like carbon can rapidly guide heat released in the reaction process out of the catalyst in the hydrogenation reaction process, thereby being beneficial to keeping the hydrogenation activity of the catalyst stable and preventing hot spots from being formed 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 generally Na in the raw material 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 higher than 1000.
According to a preferred embodiment of the first aspect, the high purity pseudoboehmite has a dry alumina content of 70 wt% to 80 wt% and a specific surface area of 200m or more 2 The pore volume is more than or equal to 0.5mL/g, the pore diameter is more than or equal to 10nm, Na 2 The content of O is less than or equal to 0.01 percent. The pseudoboehmite has high purity, high specific surface area and mesopores.
According to a preferred embodiment of the first aspect, in the step one, 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 iron nitrate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the indium source is selected from indium salts; 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 alumina, the iron source and the indium source of the vanadium-containing pseudo-boehmite is 1 (0.001-0.08): 0.001-0.08).
According to a preferred embodiment of the first aspect, the nickel source is selected from nickel salts; 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 selected from salts containing tungsten; 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-based alumina, the tungsten source and the nickel source of the ferrovanadium indium modified pseudoboehmite is 1 (0.002-0.05) to 0.02-0.1.
According to a preferred embodiment of the first aspect, in step one, the drying temperature is 180-; the drying time is 8-20 h.
According to a preferred embodiment of the first aspect, in the first step, the roasting temperature is 200-.
According to a preferred embodiment of the first aspect, in the second step, the drying temperature is 180 ℃ and 250 ℃, and the drying time is 8-20 h.
According to a preferred embodiment of the first aspect, in step three, the temperature of drying is 80-120 ℃; the drying time is 8-20 h.
According to a preferred embodiment of the first aspect, in the third step, the calcination temperature is 550-650 ℃, the calcination time is 1-10min, and the temperature rise rate of the calcination is 20-200 ℃/s.
According to a preferred embodiment of the first aspect, in step three, the cooling rate is 100-.
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 of preparing the nickel-based catalyst further comprises: in the third step, the dried product is molded and then roasted;
more preferably, the forming process is carried out by extrusion and/or drying after tabletting.
According to a preferred embodiment of the first aspect, the mixing in the first step, the second step and the third step is realized by stirring; more preferably, the mixing is achieved by stirring in a water bath at a temperature not exceeding 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 monoolefin and diolefine) and alkyne saturation hydrogenation reaction.
According to a preferred embodiment of the third aspect, the nickel-based catalyst is reduced with pure hydrogen at high temperature before use;
more preferably, the high temperature is 300-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 for the olefin and alkyne saturation hydrogenation reaction is 250-500 ℃.
According to a preferred embodiment of the third aspect, during the saturated hydrogenation of the alkenes and alkynes, H 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, the total weight hourly space velocity of the hydrocarbon feedstock during the saturated hydrogenation reaction of the olefin and the alkyne is 3-6h -1 。
According to a preferred embodiment of the third aspect, the reaction pressure of the olefin and alkyne saturation hydrogenation reaction is from normal pressure to 5.0 MPa.
The invention has the beneficial effects that:
the nickel-based catalyst has the characteristics of high activity, high selectivity, good stability and long service life for olefin (including monoolefin and diolefin) and alkyne saturation hydrogenation reaction, and can reduce the total content of olefin (including monoolefin and diolefin) and alkyne in alkane raw materials to below 1ppmw on the premise of no deep hydrogenation.
Drawings
Fig. 1 is an XRD spectrum of the nickel-based catalyst prepared in example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1:
this 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, produced by Sasol/Condea company, the content of dry alumina is 75 wt%, and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the clear solution is stirred and mixed uniformly, the mixture is dried for 10 hours at the temperature of 200 ℃ under the stirring condition, the temperature is raised to 200 ℃ at the heating rate of 1 ℃/min after the drying, and the mixture is roasted for 6 hours at the temperature of 200 ℃ to obtain the vanadium-containing pseudo-boehmite powder (the weight is about 680 g).
(2) Dissolving 15g of ferric nitrate and 15g of indium nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clarified solution, stirring and mixing uniformly, and drying at 180 ℃ for 10h under the stirring condition to obtain vanadium-iron-indium modified pseudo-boehmite powder (the 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 pseudo-boehmite powder modified by the vanadium iron indium obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying at 80 ℃ for 20h under the stirring condition to obtain nickel-based catalyst precursor powder (the weight is about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 550 ℃ at the heating rate of 100 ℃/s, roasting the powder at 550 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain 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 crystal phase of the sample of example 1 is mainly alumina, and the overall intensity of the diffraction peak is low and the peak shape is short, indicating that the alumina in the sample does not form large crystal grains and may still exist in an amorphous form. In addition, no obvious nickel oxide crystal diffraction peak is found on the sample, which indicates that the nickel oxide on the prepared sample exists in a highly dispersed form. Diffraction peaks of other oxides of vanadium, iron, indium and the like do not appear, and the auxiliary agent and the active component are kept in a high dispersion state.
The embodiment also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into 10-20 mesh particles, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cmCarrying out olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight, total molar weight of alkene and alkyne 5.0:1, total weight hourly space velocity of hydrocarbon raw material 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and the space velocity of hydrogen of 2000h -1 And the reduction time is 4 h. The results are shown in Table 3.
Example 2:
this embodiment provides a nickel-based catalyst and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) dissolving 10g vanadyl acetylacetonate and 50g polyethylene glycol 600 in 150g absolute ethyl alcohol to form a clear solution, adding 700g high-purity pseudo-boehmite (Nanjing Ginko nanotechnology Co., Ltd., dry alumina content 73 wt%, and the rest physicochemical properties are shown in Table 2), stirring and mixing uniformly, drying at 100 ℃ for 15h under stirring, heating to 220 ℃ at a heating rate of 1 ℃/min after drying, and roasting at 220 ℃ for 8 hours to obtain vanadium-containing pseudo-boehmite powder (weight about 620 g).
(2) Dissolving 6g of ferric nitrate and 20g of indium nitrate in 500g of deionized water to obtain a clear solution; and (2) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 12h at 200 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (the 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 pseudo-boehmite powder modified by the vanadium iron indium obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying for 15h at 100 ℃ under the stirring condition to obtain nickel-based catalyst precursor powder (the weight is about 640 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 600 ℃ at the heating rate of 150 ℃/s, roasting the powder at 600 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 200 ℃/s) to obtain the nickel-based catalyst.
The embodiment also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight, total molar weight of alkene and alkyne is 8.0:1, and total weight hourly space velocity of hydrocarbon raw material is 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 450 ℃ and the hydrogen space velocity of 4000h -1 And the reduction time is 2 h. The results are shown in Table 3.
Example 3:
this 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 ethanol to form a clear solution, 670g of high-purity pseudo-boehmite (the content of dry alumina is 78 wt% and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the clear solution is stirred and mixed uniformly, the mixture is dried for 8 hours at 230 ℃ under the stirring condition, the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min after the drying, and the mixture is roasted for 10 hours at the temperature of 250 ℃ to obtain the vanadium-containing pseudo-boehmite powder (the weight is about 670 g).
(2) Dissolving 35g of ferric nitrate and 8g of indium nitrate in 500g of deionized water to obtain a clear solution; and (2) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 15h at 220 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (the weight is 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 pseudo-boehmite powder modified by the vanadium iron indium obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying at 120 ℃ for 10h under the stirring condition to obtain nickel-based catalyst precursor powder (the weight is about 710 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 650 ℃ at the heating rate of 200 ℃/s, roasting the powder at 650 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain the nickel-based catalyst.
The embodiment also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight of olefin and alkyne, total molar weight of olefin and alkyne is 10.0:1, and total weight hourly space velocity of hydrocarbon raw material is 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and the space velocity of hydrogen gas of 2000h -1 And the reduction time is 4 h. The results are shown in Table 3.
Comparative example 1:
the present comparative example provides a nickel-based catalyst and a preparation method thereof, which is different from example 1 in that the adopted pseudoboehmite is a general pseudoboehmite, 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 (SB powder, produced by Sasol/Condea company, the content of dry alumina is 75 wt%, and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the clear solution is stirred and mixed uniformly, the mixture is dried for 10 hours at the temperature of 200 ℃ under the stirring condition, the temperature is raised to 200 ℃ at the heating rate of 1 ℃/min after the drying, and the mixture is roasted for 6 hours at the temperature of 200 ℃ to obtain the vanadium-containing pseudo-boehmite powder (the weight is about 680 g).
(2) Dissolving 15g of ferric nitrate and 15g of indium nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clarified solution, stirring and mixing uniformly, and drying at 180 ℃ for 10h under the stirring condition to obtain vanadium-iron-indium modified pseudo-boehmite powder (the 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 pseudo-boehmite powder modified by the vanadium iron indium obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying at 80 ℃ for 20h under the stirring condition to obtain nickel-based catalyst precursor powder (the weight is about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 550 ℃ at the heating rate of 100 ℃/s, roasting the powder at 550 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain the nickel-based catalyst.
The comparative example also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight, total molar weight of alkene and alkyne 5.0:1, total weight hourly space velocity of hydrocarbon raw material 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and the space velocity of hydrogen gas of 2000h -1 And the reduction time is 4 h. The results are shown in Table 3.
Comparative example 2:
this comparative example provides a nickel-based catalyst and a method for preparing the same, which is different from example 2 in that polyethylene glycol is not added, and the preparation method is as follows:
(1) dissolving 10g vanadyl acetylacetonate in 150g of absolute ethanol to form a clear solution, adding 700g of high-purity pseudo-boehmite (Nanjing Ginko nanotechnology Co., Ltd., dry alumina content 73 wt%, and the balance of physicochemical properties shown in Table 2), stirring and mixing uniformly, drying at 200 ℃ for 15h under stirring, heating to 220 ℃ at a heating rate of 1 ℃/min after drying, and roasting at 220 ℃ for 6 hours to obtain vanadium-containing pseudo-boehmite powder (weight about 570 g).
(2) Dissolving 6g of ferric nitrate and 20g of indium nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clarified solution, stirring and mixing uniformly, and drying for 12h at 200 ℃ under the stirring condition to obtain vanadium iron indium modified pseudo-boehmite powder (weight is about 575 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 indium modified pseudo-boehmite powder obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying at 100 ℃ for 15h under the stirring condition to obtain nickel-based catalyst precursor powder (with the weight of about 590 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 600 ℃ at the heating rate of 150 ℃/s, roasting the powder at 600 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 200 ℃/s) to obtain the nickel-based catalyst.
The comparative example also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight of olefin and alkyne, total molar weight of olefin and alkyne, 8.0:1, total weight hourly space velocity of hydrocarbon raw material 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 450 ℃ and the hydrogen space velocity of 4000h -1 And the reduction time is 2 h. The results are shown in Table 3.
Comparative example 3:
this comparative example provides a nickel-based catalyst and a method for preparing the same, which is different from example 3 in that ammonium metatungstate is not added, and the method for preparing the same is as follows:
(1) 30g of vanadyl acetylacetonate and 100g of polyethylene glycol 200 are dissolved in 200g of absolute ethanol to form a clear solution, 670g of high-purity pseudo-boehmite (the content of dry alumina is 78 wt% and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the clear solution is stirred and mixed uniformly, the mixture is dried for 8 hours at 230 ℃ under the stirring condition, the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min after the drying, and the mixture is roasted for 10 hours at the temperature of 250 ℃ to obtain the vanadium-containing pseudo-boehmite powder (the weight is about 670 g).
(2) Dissolving 35g of ferric nitrate and 8g of indium nitrate in 500g of deionized water to obtain a clear solution; and (2) adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clear solution, stirring and mixing uniformly, and drying for 15h at 220 ℃ under the stirring condition to obtain the vanadium-iron-indium modified pseudo-boehmite powder (the weight is about 690 g).
(3) 40g of nickel nitrate is dissolved in 500g of deionized water to obtain a clear solution; adding the pseudo-boehmite powder modified by the vanadium iron indium obtained in the step (2) into the clarified solution, stirring and mixing uniformly, and drying at 120 ℃ for 10h under the stirring condition to obtain nickel-based catalyst precursor powder (the weight is about 700 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 650 ℃ at the heating rate of 200 ℃/s, roasting the powder at 650 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain the nickel-based catalyst.
The comparative example also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure, H 2 Molar weight of olefin and alkyne, total molar weight of olefin and alkyne is 10.0:1, and total weight hourly space velocity of hydrocarbon raw material is 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and the space velocity of hydrogen gas of 2000h -1 And the reduction time is 4 h. 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 divided, and the preparation method is as follows:
25g of vanadyl acetylacetonate, 100g of polyethylene glycol 200, 10g of cerium nitrate, 10g of lanthanum nitrate, 10g of ammonium metatungstate and 40g of nickel nitrate are dissolved in 500g of absolute ethanol, 670g of high-purity pseudo-boehmite (SB powder, produced by Sasol/Condea company, the content of dry alumina is 75 wt%, and the rest physical and chemical properties are shown in Table 2) is added after the complete dissolution, the mixture is stirred and mixed uniformly, the mixture is dried for 20 hours at 80 ℃ under the stirring condition, the dried mixture is heated to 200 ℃ at the heating rate of 1 ℃/min and is roasted for 8 hours at the temperature of 200 ℃ to obtain nickel-based catalyst precursor powder (the weight is about 725 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 550 ℃ at the heating rate of 100 ℃/s, roasting the powder at 550 ℃ for 5min, and quenching the roasted powder by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain the nickel-based catalyst.
The comparative example also provides an application of the nickel-based catalyst in olefin and alkyne saturation hydrogenation reaction, which specifically comprises the following steps:
crushing the nickel-based catalyst into particles of 10-20 meshes, and filling 2.0g of the particles into a reaction tube with the inner diameter of 1.4cm, the outer diameter of 1.7cm and the total length of 72cm to perform olefin and alkyne saturation hydrogenation reaction; the reaction conditions were as follows: 450 deg.C, normal pressure H 2 Molar weight, total molar weight of alkene and alkyne 5.0:1, total weight hourly space velocity of hydrocarbon raw material 5.0h -1 (ii) a The composition of the raw materials for the reaction is shown in table 1, the nickel-based catalyst is reduced by hydrogen before the reaction, and the reduction conditions are as follows: 350 ℃ and the space velocity of hydrogen gas of 2000h -1 And the reduction time is 4 h.
Comparative example 5:
the present comparative example provides a nickel-based catalyst and a method for preparing the same, which are different from example 1 in the temperature rise rate and the calcination time at the time of calcination, and in the present comparative example, the temperature rise rate is 5 ℃/min and the calcination time is 4 hours in the calcination process of the step (3).
The comparative example also provides the application of the nickel-based catalyst in the olefin and alkyne saturation hydrogenation reaction, and the difference from the example 1 is only that the nickel-based catalyst is used for the nickel-based catalyst provided by the comparative example.
Comparative example 6:
this example provides a nickel-based catalyst and a method for preparing the same, which are different from example 1 in the calcination step, 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, produced by Sasol/Condea company, the content of dry alumina is 75 wt%, and the rest physicochemical properties are shown in Table 2) is added into the clear solution, the clear solution is stirred and mixed uniformly, the mixture is dried for 10 hours at the temperature of 200 ℃ under the stirring condition, the temperature is raised to 550 ℃ at the heating rate of 100 ℃/s after the drying, the mixture is roasted for 5 minutes at the temperature of 550 ℃, and the vanadium-containing pseudo-boehmite powder (the weight is about 680g) is obtained.
(2) Dissolving 15g of ferric nitrate and 15g of indium nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-containing pseudo-boehmite powder obtained in the step (1) into the clarified solution, stirring and mixing uniformly, and drying at 180 ℃ for 10h under the stirring condition to obtain vanadium-iron-indium modified pseudo-boehmite powder (the 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 pseudoboehmite powder modified by the vanadium-iron-indium obtained in the step (2) into the clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (with the weight of about 720 g);
and tabletting the obtained nickel-based catalyst precursor powder, drying the powder at 100 ℃ for 8 hours, heating the powder to 200 ℃ at the heating rate of 1 ℃/min, roasting the powder at 200 ℃ for 6 hours, and quenching the roasted product by adopting liquid nitrogen (the cooling rate is 250 ℃/s) to obtain the nickel-based catalyst.
The comparative example also provides the application of the nickel-based catalyst in the olefin and alkyne saturation hydrogenation reaction, and the difference from the example 1 is only that the nickel-based catalyst is used for the nickel-based catalyst provided by the comparative example.
Table 1 shows the composition of each raw material for olefin and alkyne saturation hydrogenation in examples and comparative examples; table 2 shows the physical properties of pseudo-boehmite used in examples and comparative examples; table 3 shows the results of the olefin and alkyne saturation hydrogenation evaluation in the examples and comparative examples; table 4 shows data of specific surface area, etc. of the nickel-based catalysts in examples and comparative examples.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
From the data of the specific surface area, the pore volume and the most probable pore diameter of the prepared part of samples, the catalyst prepared strictly according to the preparation method of the invention has the characteristics of high specific surface area and large pore volume and most probable pore diameter. Changing the order of addition of the metal precursors, changing the calcination order, changing the calcination conditions, etc., can adversely affect the structure of the catalyst.
According to the evaluation result, the catalyst prepared by the method has good olefin and alkyne saturation hydrogenation reaction activity, and the olefin and alkyne content in the raw material can be reduced to below 1ppmw in a hydrogenation mode in the reaction process. Compared with the reaction activity of the comparative example, the preparation process of the nickel-based catalyst disclosed by the invention can prepare the advantages of high saturation hydrogenation activity and stable reaction activity, which shows that the structure of the catalyst prepared by the method disclosed by the invention is suitable for the saturation hydrogenation reaction.
Claims (10)
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, drying and roasting to obtain vanadium-containing pseudo-boehmite; wherein the roasting temperature is not more than 250 ℃;
mixing 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 pseudo-boehmite modified by the vanadium-iron-indium with a solution containing a nickel source and a tungsten source, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the heating 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,
the alcohol solvent comprises one or the combination of more than two of ethanol, propanol and butanol;
the organic vanadium precursor comprises one or two of vanadyl acetylacetonate and vanadyl sulfate;
the polymerization degree of the polyethylene glycol is not higher than 1000;
the high-purity pseudo-boehmite contains dry-based alumina 70-80 wt% and has a specific surface area of more than or equal to 200m 2 The pore volume is more than or equal to 0.5mL/g, the pore diameter is more than or equal to 10nm, Na 2 The content of O is less than or equal to 0.01 percent.
3. The production method according to any one of claims 1 or 2, wherein the mass ratio of the dry alumina, the alcohol solvent, the organic vanadium precursor and the polyethylene glycol of the high purity pseudoboehmite is 1 (0.2-0.8): 0.001-0.1): 0.05-0.4.
4. The production method according to claim 1,
the iron source is iron salt; preferably, the iron source is ferric nitrate;
the indium source is indium salt; preferably, the indium source is indium nitrate.
5. The preparation method according to claim 1 or 4, wherein the mass ratio of the dry alumina, the iron source and the indium source of the vanadium-containing pseudo-boehmite is 1 (0.001-0.08) to (0.001-0.08).
6. The production method according to claim 1,
the nickel source is nickel salt; preferably, the nickel source is nickel nitrate;
the tungsten source is salt containing tungsten element; preferably, the tungsten source is ammonium metatungstate.
7. The preparation method according to claim 1 or 6, wherein the mass ratio of the dry alumina, the tungsten source and the nickel source of the ferrovanadium indium modified pseudoboehmite is 1 (0.002-0.05) to (0.02-0.1).
8. The production method according to claim 1,
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-;
in the third step, the drying temperature is 80-120 ℃, the time is 8-20h, the roasting temperature is 550-650 ℃, the time is 1-10min, the heating rate is 20-200 ℃/s, and the cooling rate is 100-500 ℃/s.
9. A nickel-based catalyst obtained by the production method according to any one of claims 1 to 8.
10. The use of the nickel-based catalyst of claim 9 in olefin, alkyne saturation hydrogenation reactions;
preferably, the nickel-based catalyst is reduced with pure hydrogen at high temperature before 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 h;
preferably, the reaction temperature of the olefin and alkyne saturation hydrogenation reaction is 250-500 ℃;
preferably, H is introduced during the saturated hydrogenation reaction of olefin and alkyne 2 The mol ratio of the olefin to the total amount of the introduced olefin and alkyne is 2.0-20.0: 1;
preferably, the total weight hourly space velocity of the hydrocarbon raw material in the olefin and alkyne saturation hydrogenation reaction process is 3-6h -1 ；
Preferably, the reaction pressure of the olefin and alkyne saturation hydrogenation reaction is normal pressure-5.0 MPa.
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