CN114950471B - Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene - Google Patents
Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene Download PDFInfo
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Abstract
The invention provides a nickel-based catalyst, a preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene. The preparation method comprises the following steps: mixing high-purity pseudo-boehmite, an alcohol solvent, an organic vanadium precursor and polyethylene glycol, and drying and roasting at the temperature of not more than 250 ℃ to obtain vanadium-containing pseudo-boehmite; mixing the pseudo-boehmite powder containing vanadium with a solution containing barium salt and manganese salt, and drying to obtain vanadium-barium-manganese modified pseudo-boehmite; mixing the vanadium-barium-manganese modified pseudo-boehmite with a solution containing nickel salt and potassium salt, 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 the selective hydrogenation reaction of acetylene in ethylene, and can reduce the total content of acetylene in ethylene raw materials to below 1ppmw on the premise of not carrying out 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 selective hydrogenation of acetylene in ethylene.
Background
Ethylene can undergo a series of chemical reactions such as decomposition, hydrogenation, hydration, oxidation, halogenation, carbonylation and the like, can also react with inorganic nitrogen, sulfur, aluminum, boron and other inorganic matters, and can also react with organic chemicals such as hydrocarbon, alcohol, aldehyde, acid and the like, wherein the most valuable chemical reactions are polymerization, oxidation, alkylation, halogenation, hydration, oligomerization, carbonylation and the like, and have wide application in the industries such as chemical industry, medicine, high polymer and the like. The polymerization product polyethylene of ethylene is petrochemical product with the largest consumption of ethylene, high-purity ethylene can be polymerized to generate polyethylene under the conditions of specific temperature, pressure and the existence of an initiator or a catalyst, and the raw material for producing the polyethylene is polymer grade ethylene. Ethylene mainly originates from naphtha cracking, and the cracked carbon two-fraction contains 0.5-2.5% of acetylene in mole fraction, and when producing polyethylene, a small amount of acetylene in ethylene reduces the activity of a polymerization catalyst and deteriorates the physical properties of the polymer, so that the acetylene content in ethylene must be reduced to a certain limit to be used as a monomer for synthesizing a high polymer. Acetylene separation and conversion are therefore one of the important links in the ethylene plant flow.
At present, a selective hydrogenation mode is often adopted to remove acetylene in ethylene, wherein a used selective hydrogenation catalyst of acetylene in ethylene is mainly a supported noble metal catalyst such as platinum and palladium. The supported noble metal as the selective hydrogenation catalyst for acetylene in ethylene has the characteristics of high activity, long service life and good selectivity, but has the defects of high price and high cost of the noble metal, and causes great pressure on the operation economy of application enterprises. Therefore, if a non-noble metal hydrogenation catalyst with high hydrogenation activity, good selectivity and excellent reaction performance can be developed successfully, the defects can be overcome, the investment cost of enterprises can be greatly reduced, and the running 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; a third object of the present invention is to provide the use of the nickel-based catalyst in the selective hydrogenation of acetylene in ethylene. The catalyst has high activity, high selectivity and high stability in the selective hydrogenation reaction of acetylene in ethylene, and simultaneously 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, 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 barium salt and manganese salt, and drying to obtain vanadium-barium-manganese modified pseudo-boehmite;
mixing the vanadium-barium-manganese modified pseudo-boehmite with a solution containing nickel salt and potassium salt, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the temperature rising rate of the roasting is not lower than 100 ℃/min, and the temperature of the roasting 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 barium and manganese added in the second step can generate oxides on the surface of the carrier after drying and decomposing to form a similar grid structure, the similar grid structure can improve the dispersity of active components, effectively fix subsequent nickel active components, prevent aggregation and growth of crystal grains in the roasting process, maintain the stability of a catalyst in the reaction process, meanwhile, the oxides formed on the surface of the catalyst by the barium and manganese can interact with hydrogenation active centers, d-layer electrons of the outer layer of manganese and the electron supply effect of the barium are utilized to inhibit ethylene molecular adsorption, ensure preferential adsorption of acetylene, promote timely desorption of hydrogenated ethylene to prevent excessive hydrogenation reaction and improve the selectivity of catalyst hydrogenation reaction; the nickel source added in the third step can form a highly dispersed selective hydrogenation active center after being decomposed in the roasting process, and the added potassium salt can further inhibit the adsorption of the nickel hydrogenation center on olefin and promote timely desorption after alkyne hydrogenation, so that the high selectivity of selective hydrogenation is ensured. 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 the formation of hot spots in the catalyst is prevented from polymerizing alkyne or olefin.
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): 0.002-0.1): 0.05-0.4.
According to a preferred embodiment of the first aspect, the barium salt includes one or both of barium nitrate and barium oxalate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the manganese salt includes one or both of manganese nitrate and manganese acetate, 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, barium salt and manganese salt of the pseudo-boehmite containing vanadium is 1 (0.001-0.05): 0.001-0.05.
According to a preferred embodiment of the first aspect, the nickel salt includes one or a combination of two or more of nickel nitrate, nickel acetate, nickel formate, but is not limited thereto.
According to a preferred embodiment of the first aspect, the potassium salt is selected from organic potassium salts, such as potassium acetate, but is not limited thereto.
According to a preferred embodiment of the first aspect, in the third step, the mass ratio of the dry-basis alumina, potassium salt and nickel salt of the vanadium-barium-manganese modified pseudo-boehmite is 1 (0.002-0.05): 0.01-0.0.05.
According to a preferred embodiment of the first aspect, in step one, the drying temperature is 100-250 ℃; 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 100-250 ℃ 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 rising rate is 100-200 ℃/min.
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 molding process is performed by extruding the strips and then drying.
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 use of the nickel-based catalyst described above in the selective hydrogenation of acetylene in ethylene.
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 for the selective hydrogenation of acetylene in ethylene is in the range of 20-90 ℃.
According to a preferred embodiment of the third aspect, H during the selective hydrogenation of acetylene in ethylene 2 The molar ratio of the catalyst to acetylene is 2.0-20.0.
According to a preferred embodiment of the third aspect, the total weight hourly space velocity of the hydrocarbon feedstock during the selective hydrogenation of acetylene in ethylene is 3-6h -1 。
According to a preferred embodiment of the third aspect, the reaction pressure of the selective hydrogenation of acetylene in ethylene is atmospheric pressure.
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 the selective hydrogenation reaction of acetylene in ethylene, and can reduce the total content of acetylene in ethylene 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 3) is added into the clear solution, and the mixture is stirred and mixed uniformly, dried at 100 ℃ for 10 hours under stirring, and then heated to 200 ℃ at a heating rate of 1 ℃/min and baked at 200 ℃ for 8 hours to obtain vanadium-containing pseudo-boehmite powder (about 680g in weight).
(2) Dissolving 10g of barium acetate and 10g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 10g of potassium acetate and 20g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 755 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 550 ℃ at the heating rate of 100 ℃/min and is roasted at 550 ℃ for 5min, and after roasting, liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
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.
The embodiment also provides an application of the nickel-based catalyst in acetylene selective hydrogenation reaction in ethylene, which specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 25 ℃, normal pressure and H 2 Molar amount of acetylene molar amount = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 3.0h -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.
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 3 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 5 hours at the temperature of 220 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight is about 620 g).
(2) 8g of barium nitrate and 15g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (about 630g in weight).
(3) Dissolving 5g of potassium acetate and 10g of nickel acetate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese 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 about 645 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 600 ℃ at a heating rate of 150 ℃/min and baked at 600 ℃ for 5min, and after baking, liquid nitrogen quenching (cooling rate of 150 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The embodiment also provides an application of the nickel-based catalyst in acetylene selective hydrogenation reaction in ethylene, which specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 50 ℃, normal pressure, H 2 Molar amount acetylene molar amount = 15.0:1, total weight hydrocarbon feedstock hourly space velocity 4.0h -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 6h.
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 3 of Shandong catalytic technology Co., ltd.) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 15 hours at 230 ℃ under stirring, and the temperature is raised to 250 ℃ at a heating rate of 1 ℃/min and the mixture is baked for 6 hours at 250 ℃ to obtain vanadium-containing pseudo-boehmite powder (the weight is about 670 g).
(2) Dissolving 5g of barium acetate and 15g of manganese acetate 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 100 ℃ under the stirring condition to obtain the vanadium-barium-manganese modified pseudo-boehmite powder (weight is about 685 g).
(3) 10g of potassium acetate and 15g of nickel formate are dissolved in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese 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);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 650 ℃ at a heating rate of 200 ℃/min and baked at 650 ℃ for 5min, and after baking, liquid nitrogen quenching (cooling rate of 250 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The embodiment also provides an application of the nickel-based catalyst in acetylene selective hydrogenation reaction in ethylene, which specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 45 ℃ and normal pressure H 2 Molar weight of propyne plus allene total molar weight = 20.0:1, total weight of hydrocarbon feedstock hourly space velocity 6.0h -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 6h.
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 3) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried at 100 ℃ for 10 hours under stirring, and the temperature is raised to 200 ℃ at a heating rate of 1 ℃/min and is roasted at 200 ℃ for 8 hours, so that vanadium-containing pseudo-boehmite powder (about 680g in weight) is obtained.
(2) Dissolving 10g of barium acetate and 10g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 10g of potassium acetate and 20g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (weight is about 725 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 550 ℃ at the heating rate of 100 ℃/min and is roasted at 550 ℃ for 5min, and after roasting, liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The comparative example also provides the application of the nickel-based catalyst in the selective hydrogenation reaction of acetylene in ethylene, and specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 25 ℃, normal pressure and H 2 Molar amount of acetylene molar amount = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 3.0h -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 2:
this comparative example provides a nickel-based catalyst and a preparation method thereof, which is different from example 1 in that polyethylene glycol 200 is not added, and the preparation method is as follows:
(1) 30g of vanadyl acetylacetonate was dissolved in 200g of absolute ethanol to form a clear solution, and 670g of high-purity pseudo-boehmite (SB powder, manufactured by Sasol/Condea Co., ltd., dry basis alumina content 75% by weight, the remaining physicochemical properties were shown in Table 3) was added thereto, and the mixture was stirred and mixed uniformly, dried at 100℃for 10 hours under stirring, and after drying, the temperature was raised to 200℃at a heating rate of 1℃per minute and calcined at 200℃for 8 hours to obtain a vanadium-containing pseudo-boehmite powder (weight of about 580 g).
(2) Dissolving 10g of barium acetate and 10g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (weight is about 595 g).
(3) Dissolving 10g of potassium acetate and 20g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (weight is about 625 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 550 ℃ at the heating rate of 100 ℃/min and is roasted at 550 ℃ for 5min, and after roasting, liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The comparative example also provides the application of the nickel-based catalyst in the selective hydrogenation reaction of acetylene in ethylene, and specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 25 ℃, normal pressure and H 2 Molar amount of acetylene molar amount = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 3.0h -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 3:
this comparative example provides a nickel-based catalyst and a method for preparing the same, which is different from example 1 in that no potassium metasalt is 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 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 3) is added into the clear solution, and the mixture is stirred and mixed uniformly, dried at 100 ℃ for 10 hours under stirring, and then heated to 200 ℃ at a heating rate of 1 ℃/min and baked at 200 ℃ for 8 hours to obtain vanadium-containing pseudo-boehmite powder (about 680g in weight).
(2) Dissolving 10g of barium acetate and 10g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (weight is about 695 g).
(3) Dissolving 20g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (weight about 715 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 550 ℃ at the heating rate of 100 ℃/min and is roasted at 550 ℃ for 5min, and after roasting, liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The comparative example also provides the application of the nickel-based catalyst in the selective hydrogenation reaction of acetylene in ethylene, and specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 25 ℃, normal pressure and H 2 Molar amount of acetylene molar amount = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 3.0h -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 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, 10g of barium acetate, 10g of manganese acetate, 10g of potassium acetate and 20g of nickel nitrate in 500g of absolute ethyl alcohol, adding 670g of high-purity pseudo-boehmite (SB powder, produced by Sasol/Condea company, and having 75 weight percent of dry alumina content and the rest of physicochemical properties shown in Table 3) into the mixture after the complete dissolution, stirring and mixing uniformly, drying the mixture at 100 ℃ for 10 hours under stirring conditions, heating the mixture to 200 ℃ at a heating rate of 1 ℃/min, and roasting the mixture at 200 ℃ for 8 hours to obtain nickel-based catalyst precursor powder (weight of about 725 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical) and dried at 100 ℃ for 8 hours, then the temperature is raised to 550 ℃ at the heating rate of 100 ℃/min and is roasted at 550 ℃ for 5min, and after roasting, liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted, so that the nickel-based catalyst can be obtained.
The comparative example also provides the application of the nickel-based catalyst in the selective hydrogenation reaction of acetylene in ethylene, and specifically comprises the following steps:
crushing a nickel-based catalyst into 10-20 mesh particles, 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 acetylene selective hydrogenation reaction in ethylene; the reaction conditions were as follows: 25 ℃, normal pressure and H 2 Molar amount of acetylene molar amount = 10.0:1, total weight of hydrocarbon feedstock hourly space velocity 3.0h -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 step (3) is 5 ℃/min and the calcination time is 4 hours.
The present comparative example also provides for the use of the above-described nickel-based catalyst in the selective hydrogenation of acetylene in ethylene, differing from example 1 only in the use of the nickel-based catalyst as provided for the present comparative example.
Comparative example 6:
the comparative example provides a nickel-based catalyst and a preparation method thereof, 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 (SB powder, manufactured by Sasol/Condea company, 75wt% of dry basis alumina content and the rest of physicochemical properties shown in Table 3) is added into the clear solution, the mixture is stirred and mixed uniformly, the mixture is dried for 10 hours at 100 ℃ under stirring, the temperature is raised to 550 ℃ at a heating rate of 100 ℃/min and the mixture is roasted for 5 minutes at 550 ℃, and liquid nitrogen quenching (cooling rate of 200 ℃/s) is adopted after roasting, so that vanadium-containing pseudo-boehmite powder (about 570g in weight) is obtained.
(2) Dissolving 10g of barium acetate and 10g of manganese acetate 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-barium-manganese modified pseudo-boehmite powder (weight is about 585 g).
(3) Dissolving 10g of potassium acetate and 20g of nickel nitrate in 500g of deionized water to obtain a clear solution; adding the vanadium-barium-manganese modified pseudo-boehmite powder obtained in the step (2) into a clear solution, stirring and mixing uniformly, and drying at 80 ℃ for 20 hours under the stirring condition to obtain nickel-based catalyst precursor powder (weight is about 600 g);
the obtained nickel-based catalyst precursor powder is extruded and formed (phi=2 mm cylindrical), dried for 8 hours at 100 ℃, then heated to 200 ℃ at a heating rate of 1 ℃/min, baked for 8 hours at 200 ℃, and naturally cooled to obtain the nickel-based catalyst.
The present comparative example also provides for the use of the above-described nickel-based catalyst in the selective hydrogenation of acetylene in ethylene, differing from example 1 only in the use of the nickel-based catalyst as provided for the present comparative example.
Table 1 shows the composition of each of the raw materials for the selective hydrogenation of acetylene in ethylene in the examples and comparative examples; table 2 shows data such as specific surface area of the nickel-based catalyst in examples and comparative examples; table 3 shows the physicochemical properties of pseudo-boehmite used in the examples and comparative examples; table 4 shows the comparison of the evaluation results of the selective hydrogenation of acetylene in ethylene of examples and comparative examples.
TABLE 1
TABLE 2
| Sample of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 5 | Comparative example 6 |
| Specific surface area/m 2 ·g -1 | 152.6 | 167.4 | 169.8 | 129.7 | 114.8 | 129.8 | 21.4 |
| Pore volume/mL.g -1 | 0.54 | 0.57 | 0.60 | 0.50 | 0.41 | 0.38 | 0.08 |
| Most probable pore size/nm | 10.9 | 11.8 | 12.1 | 11.0 | 8.1 | 9.3 | 2.5 |
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.
As shown by the evaluation result, the catalyst prepared by the method has good acetylene selective hydrogenation reaction activity, and the acetylene content in the polymerization-grade ethylene raw material can be reduced to below 1ppmw by hydrogenation in the reaction process. As can be seen from 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 saturated hydrogenation activity, stable reaction activity and high selectivity, which proves that the structure of the catalyst prepared by the method disclosed by the invention is suitable for the selective hydrogenation reaction of acetylene in ethylene.
Claims (20)
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 barium salt and manganese salt, and drying to obtain vanadium-barium-manganese modified pseudo-boehmite;
mixing the vanadium-barium-manganese modified pseudo-boehmite with a solution containing nickel salt and potassium salt, drying, roasting and cooling to obtain a nickel-based catalyst; wherein the temperature rising rate of the roasting is not lower than 100 ℃/min, and the temperature of the roasting 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-basis alumina of pseudo-boehmite, the alcohol solvent, the organic vanadium precursor and the polyethylene glycol is 1 (0.2 to 0.8): (0.002 to 0.1): (0.05 to 0.4).
6. The method of claim 1, wherein the barium salt comprises one or both of barium nitrate and barium oxalate.
7. The preparation method according to claim 1, wherein the manganese salt comprises one or both of manganese nitrate and manganese acetate.
8. The preparation method according to any one of claims 1, 6 and 7, wherein the mass ratio of the dry-basis alumina, barium salt and manganese salt of the vanadium-containing pseudo-boehmite is 1 (0.001-0.05): 0.001-0.05.
9. The preparation method according to claim 1, wherein the nickel salt comprises one or a combination of two or more of nickel nitrate, nickel acetate and nickel formate.
10. The preparation method according to claim 1, wherein the potassium salt is an organic potassium salt.
11. The preparation method according to claim 1, wherein the potassium salt is potassium acetate.
12. The preparation method according to any one of claims 1, 9 to 11, wherein the mass ratio of the dry-basis alumina, potassium salt and nickel salt of the vanadium barium manganese modified pseudo-boehmite is 1 (0.002-0.05): (0.01-0.0.05).
13. The preparation method according to claim 1, wherein,
in the first step, the drying temperature is 100-250 ℃, 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 100-250 ℃ 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 100-200 ℃/min, and the cooling rate of cooling is 100-500 ℃/s.
14. A nickel-based catalyst prepared by the preparation method of any one of claims 1 to 13.
15. Use of the nickel-based catalyst of claim 14 in the selective hydrogenation of acetylene in ethylene.
16. Use according to claim 15, wherein the nickel-based catalyst is reduced with pure hydrogen at high temperature prior to 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 1-12h.
17. Use according to claim 15, wherein the reaction temperature of the selective hydrogenation of acetylene in ethylene is 20-90 ℃.
18. The use according to claim 15, wherein during the selective hydrogenation of acetylene in ethylene, H is introduced 2 The molar ratio of the propylene hydrocarbon to the sum of the propylene diene is 2.0 to 20.0.
19. The use according to claim 15, wherein the total weight hourly space velocity of the hydrocarbon feedstock during the selective hydrogenation of acetylene in ethylene is 3-6h -1 。
20. The use according to claim 15, wherein the reaction pressure of the selective hydrogenation of acetylene in ethylene is atmospheric pressure.
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