CN117753427A - Preparation method and application of catalyst - Google Patents
Preparation method and application of catalyst Download PDFInfo
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- CN117753427A CN117753427A CN202211126797.0A CN202211126797A CN117753427A CN 117753427 A CN117753427 A CN 117753427A CN 202211126797 A CN202211126797 A CN 202211126797A CN 117753427 A CN117753427 A CN 117753427A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 229930064664 L-arginine Natural products 0.000 claims abstract description 15
- 235000014852 L-arginine Nutrition 0.000 claims abstract description 15
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002059 L-arginyl group Chemical group O=C([*])[C@](N([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])N([H])C(=N[H])N([H])[H] 0.000 claims abstract description 3
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 104
- 238000006243 chemical reaction Methods 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 34
- 238000006356 dehydrogenation reaction Methods 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- 238000004176 ammonification Methods 0.000 description 15
- 229910002515 CoAl Inorganic materials 0.000 description 13
- 239000003245 coal Substances 0.000 description 13
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FZKDURCLMTYEER-UHFFFAOYSA-N cobalt lanthanum Chemical compound [Co].[Co].[Co].[La] FZKDURCLMTYEER-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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Abstract
The application discloses a preparation method and application of a catalyst, wherein the preparation method at least comprises the following steps: impregnating a carrier precursor into a mixture containing an active component precursor, an auxiliary agent precursor and a surfactant, drying and roasting to obtain the catalyst; the carrier precursor is at least one of alumina, magnesia and zirconia; the active component precursor is cobalt nitrate; the auxiliary agent precursor is lanthanum nitrate; the surfactant is L-arginine. Compared with a sample without L-arginine, the catalyst prepared by the invention has the advantages of higher acetonitrile selectivity, better stability and the like.
Description
Technical Field
The application relates to a preparation method and application of a catalyst, and belongs to the technical field of chemical catalyst preparation.
Background
Acetonitrile is an organic chemical raw material with quite wide application, is widely used as an extracting agent for extracting butadiene and isoprene from olefin and alkane in petrochemical industry, is also widely used as a synthetic raw material for organic synthesis, medicines, pesticides, surfactants, dyes and other fine chemicals, and is used as a mobile phase solvent for thin layer chromatography, paper chromatography, spectrum, polarography and High Performance Liquid Chromatography (HPLC), is recently used as a solvent for DNA synthesis and purification, is used as a solvent for organic EL material synthesis, is used as a cleaning solvent for chips, and has high requirements on the purity (more than or equal to 99.9%) of acetonitrile. Acetonitrile with purity more than or equal to 99.9% is popular in the market and has wide application, and the consumption rate of the acetonitrile exceeds 66%.
Today, acetonitrile is mainly recovered as a crude byproduct in the process of producing acrylonitrile by ammoxidation of propylene on a global scale, but only 20-30 kg of acetonitrile can be obtained from 1 ton of acrylonitrile, and the purity is not high, and particularly, acetonitrile with purity of more than or equal to 99.9% is difficult to reach. The production of acetonitrile by ammonification and dehydrogenation of ethanol is a beneficial supplement to the acetonitrile source. Compared with other acetonitrile obtaining methods, the method for producing acetonitrile by ammonification and dehydrogenation of ethanol has the advantages of simple process, low energy consumption, high atom utilization rate, high acetonitrile selectivity, less side reaction, less investment and low operation cost, and can realize industrialization.
The existing acetonitrile dehydrogenation ammonification method for preparing acetonitrile has the problems or defects of low ethanol conversion rate and acetonitrile selectivity, poor catalyst stability and the like.
Disclosure of Invention
The application aims to develop a CoLa/Al catalyst with high selectivity and stability, which is used for preparing acetonitrile by alcohol dehydrogenation and ammonification, and is a report that the catalyst is used for preparing acetonitrile by alcohol dehydrogenation and ammonification for the first time.
Catalysts used in the ammonification and dehydrogenation of ethanol to produce acetonitrile are divided into two classes: dehydrogenation/hydrogenation catalysts and dehydration catalysts. The dehydrogenation/hydrogenation catalyst mostly comprises Ni, cu, fe, cr, co, rh, zr, pb, ag and the like as main active components, wherein nickel is the most widely used. In generalIt is also necessary to add a second and a third component as cocatalysts, such as Cu, co, na, mg and Ca, and rare earth elements, which exhibit good catalytic activity under suitable reaction conditions, and the introduction of cocatalysts can also improve the product distribution. Al (Al) 2 O 3 、SiO 2 HZSM-5 and the like are often used as a catalyst for dehydration condensation reaction because of their certain acidity on the surface. Wherein Al is 2 O 3 Is an excellent catalyst for alcohol dehydration, and is a carrier used in a large amount in the industry in metal carrier catalysts.
According to one aspect of the present application, there is provided a method of preparing a catalyst, the method comprising at least the steps of:
impregnating a carrier precursor into a mixture containing an active component precursor, an auxiliary agent precursor and a surfactant, drying and roasting to obtain the catalyst;
the carrier precursor is at least one of alumina, magnesia and zirconia;
the active component precursor is cobalt nitrate; the auxiliary agent precursor is lanthanum nitrate; the surfactant is L-arginine.
Optionally, the mass of the surfactant is 1.0-3.0 wt% of the mass of the carrier precursor, and the mass of the surfactant is based on the mass of the L-arginine.
Alternatively, the surfactant has a mass with an upper limit independently selected from 3.0wt%, 2.8wt%, 2.5wt%, 2.0wt%, 1.5wt% and a lower limit independently selected from 1.0wt%, 1.2wt%, 1.5wt%, 2.0wt% of the mass of the carrier precursor.
Optionally, the mass of the auxiliary agent precursor is 0.1-1.0 wt% of the mass of the carrier precursor, and the mass of the auxiliary agent precursor is calculated by the mass of lanthanum element in lanthanum nitrate.
Alternatively, the mass of the auxiliary precursor is such that the upper limit of the mass of the carrier precursor is independently selected from 1.0wt%, 0.9wt%, 0.8wt%, 0.7wt%, 0.6wt%, 0.5wt%, and the lower limit is independently selected from 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%.
Optionally, the mass of the active component precursor is 5-30wt% of the mass of the carrier precursor, and the mass of the active component precursor is calculated by the mass of cobalt element in cobalt nitrate.
Alternatively, the mass of the active component precursor is such that the upper limit of the mass of the carrier precursor is independently selected from 30wt%, 25wt%, 20wt%, 15wt%, 10wt%, and the lower limit is independently selected from 5wt%, 10wt%, 15wt%, 20wt%, 25wt%.
Optionally, the impregnating is vacuum isovolumetric impregnating; the soaking time is 2-5 h.
Optionally, the vacuum degree of the vacuum isovolumetric impregnation is 1-10 Pa.
Optionally, the time of the soaking is selected from any value of 2h, 3h, 4h and 5h or a range value between any two points.
Optionally, the temperature of the drying is 110-130 ℃; the drying time is 6-12 h.
Optionally, the temperature of the drying is selected from any value of 110 ℃, 115 ℃,120 ℃, 125 ℃,130 ℃ or a range value between any two points.
Optionally, the time of drying I is selected from any value of 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or a range of values between any two points.
Optionally, the roasting temperature is 500-700 ℃; the roasting atmosphere is an air atmosphere; the roasting time is 2-4 h.
Optionally, the baking temperature is selected from any value of 500 ℃,550 ℃,600 ℃, 650 ℃,700 ℃ or any value between any two points.
Optionally, the firing time is selected from any of 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or a range between any two of the foregoing.
According to another aspect of the present application, there is provided a catalyst prepared by the preparation method described above.
According to yet another aspect of the present application, there is provided a method for preparing acetonitrile by dehydrogenating and ammonifying ethanol, comprising at least the following steps:
mixing raw materials containing ethanol and ammonia gas, contacting with a catalyst, and reacting to obtain a product containing acetonitrile;
the catalyst is selected from the catalyst prepared by the preparation method or at least one of the catalysts.
Optionally, the molar ratio of ammonia gas to ethanol is 8-2: 1, a step of;
the mass airspeed of the ethanol is 0.1 to 1.0h -1 ；
The pressure of the reaction is 0.1-0.2 MPa;
the temperature of the reaction is 400-470 ℃.
Optionally, the mass space velocity of the ethanol is selected from 0.1h -1 、0.2h -1 、0.3h -1 、0.4h -1 、0.5h -1 、0.6h -1 、0.7h -1 、0.8h -1 、0.9h -1 、1.0h -1 Any value in (2) or a range between any two points.
Alternatively, the pressure of the reaction is selected from any value of 0.1MPa, 0.15MPa, 0.2MPa or a range between any two points.
Alternatively, the temperature of the reaction is selected from any value or range of values between any two points of 400 ℃, 430 ℃, 450 ℃, 460 ℃, 470 ℃.
The beneficial effects that this application can produce include:
cobalt and lanthanum in the prepared CoLa/Al catalyst are uniformly distributed in the catalyst, and are not easy to agglomerate in the reaction process, so that the problems of diffusion of reactants and products in the catalyst, the reaction performance of the catalyst and the like are further affected.
The catalyst prepared by the invention can be applied to the process of preparing acetonitrile by alcohol dehydrogenation and ammoniation, and has the advantages of higher acetonitrile selectivity, better stability and the like compared with the conventional catalyst without L-arginine CoLa/Al.
Drawings
FIG. 1 is a graph of 20Co/Al of the present application 2 O 3 TEM and HRTEM images of catalyst (A: 20Co/Al 2 O 3 TEM image of catalyst; b:20Co/Al 2 O 3 HRTEM diagram of catalyst).
FIG. 2 is a 20Co0.125La/Al plot of the present application 2 O 3 TEM and HRTEM images of the catalyst (C: 20Co0.125La/Al 2 O 3 TEM image of catalyst; d:20Co0.125La/Al 2 O 3 HRTEM diagram of catalyst).
FIG. 3 is a 20Co0.25La/Al plot of the present application 2 O 3 TEM and HRTEM images of the catalyst (E: 20Co0.25La/Al 2 O 3 TEM image of catalyst; f:20Co0.25La/Al 2 O 3 HRTEM diagram of catalyst).
FIG. 4 is a 20Co0.5La/Al alloy of the present application 2 O 3 TEM and HRTEM images of the catalyst (G: 20Co0.5La/Al 2 O 3 TEM image of catalyst; h:20Co0.5La/Al 2 O 3 HRTEM diagram of catalyst).
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the examples of the present application, agilent 7890A GC analysis, FID detector, hydrogen gas as carrier gas was used.
In the examples of the present application, catalyst activity evaluation indexes, i.e., ethanol conversion, ammonia conversion and acetonitrile selectivity, were all calculated based on mass:
calculation of the conversion of the main reactants and the selectivity to acetonitrile:
ethanol conversion:
ammonia conversion rate:
acetonitrile selectivity:
in the above formula, m represents mass.
Comparative example 1
9.86g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 3 hours at 25 ℃, the carrier is dried for 6 hours at 120 ℃ in an oven, and the Co content in the catalyst Cat-A prepared by roasting for 3 hours at 700 ℃ is 20wt%.
Comparative example 2
9.86g Co (NO) 3 ) 2 ·6H 2 O and 0.120. 0.120g L-arginine were dissolved in 5.5g of water, 7.975g of alumina was placed in a closed vessel, the impregnation liquid was sucked into the carrier by a vacuum isovolumetric impregnation method, the vacuum was applied at 10Pa, then the impregnation was carried out at 25℃for 3 hours, the drying was carried out at 120℃for 6 hours, and the Co content in the catalyst Cat-B obtained by baking at 700℃for 3 hours was 20wt%.
Comparative example 3
9.86g Co (NO) 3 ) 2 ·6H 2 O and 0.079g La (NO) 3 ) 2 ·6H 2 O is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 3 hours at 25 ℃, the carrier is dried for 6 hours at 120 ℃ in an oven, and the Co and La contents in the catalyst Cat-C prepared by roasting for 3 hours at 700 ℃ are 20wt% and 0.25wt% respectively.
Example 1
9.86g Co (NO) 3 ) 2 ·6H 2 O，0.079g La(NO 3 ) 2 ·6H 2 O, 0.120-g L-arginine is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, impregnating solution is sucked into a carrier by adopting a vacuum isovolumetric impregnation method, vacuumizing is 10Pa, then impregnating is carried out for 3 hours at 25 ℃, drying is carried out for 6 hours at 120 ℃, and roasting is carried out for 3 hours at 700 ℃ to obtain the catalyst CatThe Co and La contents in D were 20wt% and 0.25wt%, respectively.
Example 2
2.47g Co (NO) 3 ) 2 ·6H 2 O，0.032g La(NO 3 ) 2 ·6H 2 O,0.08 and g L-arginine is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 2 hours at 25 ℃, the carrier is dried for 8 hours at 130 ℃, and the Co and La contents in the catalyst Cat-E prepared by roasting for 4 hours at 500 ℃ are 5wt% and 0.1wt% respectively.
Example 3
14.79g of Co (NO 3 ) 2 ·6H 2 O，0.316g La(NO 3 ) 2 ·6H 2 O, 0.240. 0.240g L-arginine is dissolved in 5.5g of water, 7.975g of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 5 hours at 25 ℃, the carrier is dried for 12 hours at 110 ℃, and the Co and La contents in the catalyst Cat-F prepared by roasting at 600 ℃ for 2 hours are 30wt% and 1.0wt% respectively.
Example 4
7.40g Co (NO) 3 ) 2 ·6H 2 O，0.158g La(NO 3 ) 2 ·6H 2 O, 0.160-G L-arginine is dissolved in 5.5G of water, 7.975G of alumina is placed in a closed container, the impregnating solution is sucked into the carrier by adopting a vacuum isovolumetric impregnation method, the vacuum is pumped to 10Pa, then the carrier is impregnated for 4 hours at 25 ℃, the carrier is dried for 12 hours at 110 ℃, and the Co and La contents in the catalyst Cat-G prepared by roasting for 4 hours at 550 ℃ are 15wt% and 0.5wt% respectively.
Example 5
The catalysts prepared in comparative examples 1 and 2 were subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 3h. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the product adopts AgilThe analysis of the ent 7890A GC FID detector with hydrogen as carrier gas gave the specific evaluation results shown in Table 1.
Example 6
The catalyst prepared in comparative example 3 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 3h. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 7
The catalyst prepared in comparative example 3 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 98h. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 8
The catalyst prepared in example 1 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 3h. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 9
The catalyst prepared in example 1 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, and the catalyst is heated up at a speed of 3 ℃/min under the ammonia conditionAnd (3) heating to 430 ℃, introducing ethanol, and reacting for 98 hours. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.5h -1 The molar ratio of ammonia gas to ethanol is 6:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 10
The catalyst prepared in example 2 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 430 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 26h. The reaction conditions are as follows: the temperature is 430 ℃, the pressure is 0.2MPa, and the ethanol mass airspeed is 0.1h -1 The molar ratio of ammonia gas to ethanol is 2:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 11
The catalyst prepared in example 3 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 470 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 4h. The reaction conditions are as follows: the temperature is 470 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 1.0h -1 The molar ratio of ammonia gas to ethanol is 8:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Example 12
The catalyst prepared in example 4 was subjected to evaluation of the reaction performance of ethanol dehydrogenation ammonification to acetonitrile on a fixed bed reactor. The diameter of the reactor is 14mm, the catalyst loading amount is 4g, the temperature is raised to 400 ℃ at the temperature rising rate of 3 ℃/min under the ammonia condition, ethanol is introduced, and the reaction time is 20h. The reaction conditions are as follows: the temperature is 400 ℃, the pressure is 0.1MPa, and the ethanol mass airspeed is 0.3h -1 The molar ratio of ammonia gas to ethanol is 4:1. the product was analyzed using an Agilent 7890A GC FID detector with hydrogen as carrier gas and specific evaluation results are shown in table 1.
Table 1 reactivity of catalyst for catalyzing alcohol dehydrogenation ammonification to prepare acetonitrile
| Catalyst numbering | Cat-A | Cat-B | Cat-C | Cat-C | Cat-D | Cat-D | Cat-E | Cat-F | Cat-G |
| Reaction pressure (Mpa) | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.20 | 0.10 | 0.10 |
| Ethanol weight space velocity (h) -1 ) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.1 | 1.0 | 0.3 |
| Reaction temperature (. Degree. C.) | 430 | 430 | 430 | 430 | 430 | 430 | 430 | 470 | 400 |
| Molar ratio of ammonia to alcohol | 6:1 | 6:1 | 6:1 | 6:1 | 6:1 | 6:1 | 2:1 | 8.0 | 4.0 |
| Reaction time (h) | 3 | 3 | 3 | 98 | 3 | 98 | 26 | 4 | 20 |
| Ethanol conversion (%) | 99.02 | 99.12 | 99.42 | 96.72 | 99.99 | 99.95 | 99.78 | 99.65 | 99.50 |
| Acetonitrile selectivity (%) | 78.60 | 79.20 | 82.10 | 77.66 | 84.40 | 84.20 | 84.13 | 84.74 | 85.13 |
The experimental results in Table 1 show that the addition of L-arginine alone versus Co/Al 2 O 3 The upper reaction performance is not greatly influenced (Cat-A vs Cat-B), and the addition of lanthanum can promote Co/Al 2 O 3 Upper reaction performance (Cat-A vs Cat-C), compared with the alumina carrier supported cobalt lanthanum catalyst (Cat-C) prepared by adding L-arginine under the condition that L-arginine is not added in the catalyst preparation process, the alumina carrier supported cobalt lanthanum catalyst prepared by adding L-arginineThe acetonitrile on (Cat-D) has higher selectivity and better stability, and the prepared Cat-E, cat-F and Cat-G catalysts have excellent reaction performance under the examined reaction conditions.
TABLE 2 Co/Al with different La contents 2 O 3 Structural Properties of the catalyst
| S BET a (m 2 /g) | V b (cm 3 /g) | |
| 20Co/Al 2 O 3 | 80 | 0.548 |
| 20Co0.125La/Al 2 O 3 | 95 | 0.537 |
| 20Co0.25La/Al 2 O 3 | 97 | 0.533 |
| 20Co0.50La/Al 2 O 3 | 91 | 0.512 |
In table 2 a refers to the specific surface area; b is the accumulated desorption pore volume. From Table 2The experimental results of (a) show that N is used 2 Physical adsorption of La modified Co/Al 2 O 3 The porous structure and specific surface area of the sample were characterized. As can be seen, with 20Co/Al 2 O 3 The La modified catalyst has a larger specific surface area and smaller pore volume than the catalyst, possibly as a result of better dispersion of the crystallites at the catalyst surface. It can be seen that in Co/Al 2 O 3 The specific surface area of the catalyst can be increased by adding La into the catalyst, so that the reaction performance is improved.
FIG. 1 is Co/Al 2 O 3 TEM and HRTEM characterization of the catalyst (A is 20Co/Al 2 O 3 TEM image of catalyst; b is 20Co/Al 2 O 3 HRTEM diagram of catalyst). As can be seen, at 20Co/Al 2 O 3 The catalyst has large Co 3 O 4 Or CoAl 2 O 4 High resolution transmission electron microscopy analysis of particles to identify particles as Co 3 O 4 Or CoAl 2 O 4 Corresponding to Co 3 O 4 Or CoAl 2 O 4 (2 2 2 0) crystal plane of (a).
FIG. 2 is 20Co0.125La/Al 2 O 3 Catalyst TEM and HRTEM characterization (C20 Co0.125La/Al 2 O 3 TEM image of catalyst; d is 20Co0.125La/Al 2 O 3 HRTEM diagram of catalyst). It can be seen that Co in the catalyst after La addition 3 O 4 Or CoAl 2 O 4 The particles of (C) seem to be more than 20Co/Al 2 O 3 The smaller the average particle size, the better the dispersibility of the active component in the catalyst after La addition. Meanwhile, the high-resolution transmission electron microscope analysis identifies that the particles are still Co 3 O 4 Or CoAl 2 O 4 With 20Co/Al 2 O 3 The catalyst is kept consistent and corresponds to Co 3 O 4 Or CoAl 2 O 4 (2 2 2 0) crystal plane of (a).
FIG. 3 is 20Co0.25La/Al 2 O 3 Catalyst TEM and HRTEM characterization (E20 Co0.25La/Al 2 O 3 TEM image of catalyst; f:20Co0.25La/Al 2 O 3 HRTEM diagram of catalyst). It can be seen that the catalyst after La additionMiddle Co 3 O 4 Or CoAl 2 O 4 The particles of (C) seem to be more than 20Co/Al 2 O 3 Is small in (2), and Co at a La addition of 0.25 in these four catalysts 3 O 4 Or CoAl 2 O 4 The particles of (2) are the smallest and the dispersion of the active ingredient is the best. High resolution transmission electron microscope analysis identifies the particles as Co 3 O 4 Or CoAl 2 O 4 Corresponding to Co 3 O 4 Or CoAl 2 O 4 (2 2 2 0) crystal plane of (a).
FIG. 4 is 20Co0.5La/Al 2 O 3 Catalyst TEM and HRTEM characterization (G is 20Co0.5La/Al 2 O 3 TEM image of catalyst; h is 20Co0.5La/Al 2 O 3 HRTEM diagram of catalyst). It can be seen that Co in the catalyst after La addition 3 O 4 Or CoAl 2 O 4 The particles of (C) seem to be more than 20Co/Al 2 O 3 The active components are well dispersed due to the small size of the active components. High resolution transmission electron microscope analysis identifies the particles as Co 3 O 4 Or CoAl 2 O 4 Corresponding to Co 3 O 4 Or CoAl 2 O 4 The (1 1 1) crystal plane of (2).
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for preparing a catalyst, comprising at least the steps of:
impregnating a carrier precursor into a mixture containing an active component precursor, an auxiliary agent precursor and a surfactant, drying and roasting to obtain the catalyst;
the carrier precursor is at least one of alumina, magnesia and zirconia;
the active component precursor is cobalt nitrate; the auxiliary agent precursor is lanthanum nitrate; the surfactant is L-arginine.
2. The method according to claim 1, wherein the mass of the surfactant is 1.0 to 3.0wt% of the mass of the carrier precursor, and the mass of the surfactant is based on the mass of L-arginine.
3. The preparation method according to claim 1, wherein the mass of the auxiliary precursor is 0.1-1.0 wt% of the mass of the carrier precursor, and the mass of the auxiliary precursor is calculated by the mass of lanthanum element in lanthanum nitrate.
4. The preparation method according to claim 1, wherein the mass of the active component precursor is 5 to 30wt% of the mass of the carrier precursor, and the mass of the active component precursor is calculated as the mass of cobalt element in cobalt nitrate.
5. The method of claim 1, wherein the impregnation is vacuum isovolumetric impregnation; the soaking time is 2-5 h.
6. The method according to claim 5, wherein the vacuum degree of the vacuum isovolumetric impregnation is 1 to 10Pa.
7. The method according to claim 1, wherein the temperature of the drying is 110 to 130 ℃;
the drying time is 6-12 h.
8. The method according to claim 1, wherein the baking temperature is 500 to 700 ℃; the roasting atmosphere is an air atmosphere;
the roasting time is 2-4 h.
9. The method for preparing acetonitrile by dehydrogenating and ammonifying ethanol is characterized by at least comprising the following steps:
mixing raw materials containing ethanol and ammonia gas, contacting with a catalyst, and reacting to obtain a product containing acetonitrile;
the catalyst is at least one catalyst selected from the group consisting of catalysts produced by the production method according to any one of claims 1 to 8.
10. The use according to claim 9, wherein the molar ratio of ammonia to ethanol is 8-2: 1, a step of;
the mass airspeed of the ethanol is 0.1 to 1.0h -1 ；
The pressure of the reaction is 0.1-0.2 MPa;
the temperature of the reaction is 400-470 ℃.
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