CN117582995B - Catalyst for synthesizing methacrylonitrile and preparation method thereof - Google Patents
Catalyst for synthesizing methacrylonitrile and preparation method thereof Download PDFInfo
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- CN117582995B CN117582995B CN202311521070.7A CN202311521070A CN117582995B CN 117582995 B CN117582995 B CN 117582995B CN 202311521070 A CN202311521070 A CN 202311521070A CN 117582995 B CN117582995 B CN 117582995B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 52
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 33
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 18
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 15
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 15
- 239000012300 argon atmosphere Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- -1 nitrile compound Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing methacrylonitrile and a preparation method thereof, belonging to the technical field of catalysts, and comprising the following components in parts by weight: 2.5-3.5 parts of cobalt nitrate, 10-15 parts of zinc nitrate, 22-27 parts of 2-methylimidazole, 0.9-1.7 parts of manganese nitrate, 8-13 parts of ferrous nitrate and 6-8 parts of copper nitrate; the catalyst is of a core-shell structure obtained by sintering a composite organic metal frame; the core-shell structure takes C-Co/Mn as a core body and C-Fe/Cu as a shell. The invention provides a catalyst for synthesizing methacrylonitrile and a preparation method thereof, and aims to solve the problems of low catalyst activity and harsh reaction conditions.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for synthesizing methacrylonitrile and a preparation method thereof.
Background
The nitrile compound is an organic matter containing an organic group-CN, is a general precursor for preparing nitrogen-containing functional compounds, and is also an important intermediate for dyes, medicines, pesticides, natural products and various fine chemicals; methacrylonitrile is a colorless liquid with chronic toxicity, is mainly used as an intermediate product for producing products such as Polymethacrylimide (PMI), methyl Methacrylate (MMA) and the like, and is an important chemical raw material; hydrocyanic acid or metal cyanide is needed in the production process of the nitrile compound, so that a large amount of toxic pollutants are generated, and the environment is damaged, therefore, the development of an efficient and environment-friendly catalyst for synthesizing the nitrile compound is extremely important, and most reactions need high pressure, high temperature and poor selectivity; the high-temperature calcination can enable N element doped in the C framework of the ZIF-67 material to show N-type transmission behavior, the material has more positive charges, which is favorable for absorbing more oxygen, but the high-temperature calcination can cause collapse of the ZIF structure, agglomeration of Co nano particles is generated, and the activity of the Co nano particles is reduced.
The prior art mainly has the following problems: 1. the catalyst for synthesizing the methacrylonitrile has low activity and poor stability; 2. the synthesis condition of the methacrylonitrile is harsh, the synthesis cost is high and the yield is low.
Disclosure of Invention
Aiming at the situation, the invention provides a catalyst for synthesizing methacrylonitrile and a preparation method thereof, and aims to solve the problems of low catalyst activity and harsh reaction conditions.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a catalyst for synthesizing methacrylonitrile and a preparation method thereof, wherein the catalyst for synthesizing methacrylonitrile comprises the following components in parts by weight: 2.5-3.5 parts of cobalt nitrate, 10-15 parts of zinc nitrate, 22-27 parts of 2-methylimidazole, 0.9-1.7 parts of manganese nitrate, 8-13 parts of ferrous nitrate and 6-8 parts of copper nitrate; the catalyst is of a core-shell structure obtained by sintering a composite organic metal frame; the core-shell structure takes C-Co/Mn as a core body and C-Fe/Cu as a shell;
preferably, the preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
S1, dissolving cobalt nitrate in ionized water to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution;
S2, uniformly mixing the cobalt nitrate solution obtained in the step S1 and the 2-methylimidazole solution, stirring in a water bath at the speed of 300rpm and the temperature of 30-40 ℃ for 5-7h, and filtering and drying to obtain ZIF-67;
s3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at the power of 80-120w for 100-120min, then reacting for 1h at the temperature of 100 ℃ in a reaction kettle, filtering, drying, and calcining at the temperature of 300 ℃ for 80-120min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Preferably, in S1, the addition amount of cobalt nitrate in water is 0.15-17g/mL.
Preferably, in S1, the addition amount of 2-methylimidazole in water is 0.13-16g/mL.
Preferably, in S2, the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution is 1:8-10.
Preferably, in S3, the ultrasonic power is 80-120W and the reaction time is 100-120min.
Preferably, in S4, the volume ratio of the methanol solution to the 2-methylimidazole methanol solution is 1:1-1.3.
The beneficial effects obtained by the invention are as follows: according to the invention, a mode of preparing a carbon skeleton composite catalyst with a core-shell structure is provided, so that a composite catalyst with larger specific surface area and pore volume and higher low-temperature activity is obtained, a Co is used as a core to synthesize ZIF-67, mn is loaded on the ZIF-67 through an impregnation method to obtain Mn/ZIF-67, a Mn/ZIF-67 is used as a core to synthesize ZIF-8@Mn/ZIF-67 on the ZIF-67, C-Zn@C-Co/Mn is obtained through calcination, fe 2+ and Cu 2+ are replaced by reduced Zn, the atomic replacement proportion is controlled by controlling the addition amount of ferrous nitrate and copper nitrate, and then high-temperature calcination evaporation Zn is carried out again for a shorter time to obtain C-Fe/Cu@C-Co/Mn; the C-Fe/Cu@C-Co/Mn has large specific surface area and high pore volume, is favorable for oxygen absorption and reaction, reduces crystallinity by utilizing strong interaction between two metals, inhibits crystallization of metal oxide in a core body, realizes increase of the specific surface area inside, and can well protect Co/Mn core body due to the fact that porous carbon structure is reserved outside Zn evaporation, improves the stability of a catalyst, and further improves the product yield and the service life of the catalyst.
Drawings
FIG. 1 is a graph showing the results of the methacrylonitrile yields when the experiments of examples 1 to 5 and comparative example 1 were carried out 1 time;
FIG. 2 is a graph showing the results of the methacrylonitrile yields when the experiments of examples 1 to 5 and comparative example 1 were carried out 40 times;
Fig. 3 is an SEM image of the catalytic experiment of example 1 after 40 runs.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
Example 1
The catalyst for synthesizing the methacrylonitrile comprises the following components in parts by weight: 3.5 parts of cobalt nitrate, 15 parts of zinc nitrate, 27 parts of 2-methylimidazole, 1.7 parts of manganese nitrate, 13 parts of ferrous nitrate and 8 parts of copper nitrate.
The preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
s1, dissolving cobalt nitrate in ionized water according to the addition amount of 17g/mL to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water according to the addition amount of 16g/mL to obtain a 2-methylimidazole solution;
s2, uniformly mixing the cobalt nitrate solution obtained in the step S1 with a 2-methylimidazole solution in a volume ratio of 1:10, stirring in a water bath at a speed of 300rpm and a temperature of 40 ℃ for 7 hours, and filtering and drying to obtain ZIF-67;
S3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at 120w for 120min, then reacting for 1h at 100 ℃ in a reaction kettle, filtering, drying, and calcining at 300 ℃ for 120min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1.3, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Example 2
The catalyst for synthesizing the methacrylonitrile comprises the following components in parts by weight: 2.5 parts of cobalt nitrate, 10 parts of zinc nitrate, 22 parts of 2-methylimidazole, 0.9 part of manganese nitrate, 8 parts of ferrous nitrate and 6 parts of copper nitrate.
The preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
S1, dissolving cobalt nitrate in ionized water according to the addition amount of 0.15g/mL to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water according to the addition amount of 13g/mL to obtain a 2-methylimidazole solution;
s2, uniformly mixing the cobalt nitrate solution obtained in the step S1 with a 2-methylimidazole solution in a volume ratio of 1:8, stirring in a water bath at a speed of 300rpm and a temperature of 30 ℃ for 5 hours, and filtering and drying to obtain ZIF-67;
s3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at 80w for 100min, then reacting for 1h at 100 ℃ in a reaction kettle, filtering, drying, and calcining at 300 ℃ for 80min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Example 3
The catalyst for synthesizing the methacrylonitrile comprises the following components in parts by weight: 3 parts of cobalt nitrate, 12 parts of zinc nitrate, 25 parts of 2-methylimidazole, 1.5 parts of manganese nitrate, 10 parts of ferrous nitrate and 7 parts of copper nitrate.
The preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
s1, dissolving cobalt nitrate in ionized water according to the addition amount of 0.16g/mL to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water according to the addition amount of 15g/mL to obtain a 2-methylimidazole solution;
S2, uniformly mixing the cobalt nitrate solution obtained in the step S1 with a 2-methylimidazole solution according to a volume ratio of 1:9, stirring in a water bath at a speed of 300rpm and a temperature of 35 ℃ for 6 hours, and filtering and drying to obtain ZIF-67;
S3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at 100w for 110min, then reacting for 1h at 100 ℃ in a reaction kettle, filtering, drying, and calcining at 300 ℃ for 100min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Example 4
The catalyst for synthesizing the methacrylonitrile comprises the following components in parts by weight: 2.7 parts of cobalt nitrate, 12 parts of zinc nitrate, 24 parts of 2-methylimidazole, 1.2 parts of manganese nitrate, 9 parts of ferrous nitrate and 6 parts of copper nitrate.
The preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
S1, dissolving cobalt nitrate in ionized water according to the addition amount of 0.16g/mL to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water according to the addition amount of 14g/mL to obtain a 2-methylimidazole solution;
s2, uniformly mixing the cobalt nitrate solution obtained in the step S1 with a 2-methylimidazole solution in a volume ratio of 1:8, stirring in a water bath at a speed of 300rpm and a temperature of 32 ℃ for 5.5 hours, and filtering and drying to obtain ZIF-67;
s3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at 90w power for 100min, then reacting for 1h at 100 ℃ in a reaction kettle, filtering, drying, and calcining at 300 ℃ for 100min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1.1, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Example 5
The catalyst for synthesizing the methacrylonitrile comprises the following components in parts by weight: 3.3 parts of cobalt nitrate, 14 parts of zinc nitrate, 26 parts of 2-methylimidazole, 1.6 parts of manganese nitrate, 12 parts of ferrous nitrate and 7.5 parts of copper nitrate.
The preparation method of the catalyst for synthesizing the methacrylonitrile specifically comprises the following steps:
s1, dissolving cobalt nitrate in ionized water according to the addition amount of 0.16g/mL to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water according to the addition amount of 15g/mL to obtain a 2-methylimidazole solution;
s2, uniformly mixing the cobalt nitrate solution obtained in the step S1 with a 2-methylimidazole solution according to a volume ratio of 1:9, stirring in a water bath at a speed of 300rpm and a temperature of 38 ℃ for 7 hours, and filtering and drying to obtain ZIF-67;
s3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at 110w for 115min, then reacting for 1h at 100 ℃ in a reaction kettle, filtering, drying, and calcining at 300 ℃ for 110min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1.3, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
Comparative example 1
This comparative example provides a catalyst which differs from example 1 only in that all components do not contain 2-methylimidazole, i.e. the product is prepared without a core-shell structure, and is only sintered, and the remaining components and the component contents are the same as in example 1.
Experimental example
1. Preparation experiments
Sequentially adding the catalysts obtained in the examples 1-3 and the comparative example 1 and tertiary butanol into a polytetrafluoroethylene-lined pressure kettle, sealing the reaction kettle, filling ammonia gas of 0.7MPa, filling oxygen gas into the kettle to pressure of 2.5MPa, reacting at 130 ℃ for 20 hours, cooling to room temperature after the reaction is finished, and slowly deflating and depressurizing; after the test is finished, the catalyst is recovered for the next experiment, and when the experiment is carried out for 1 time and 40 times, an internal standard is added into the reaction liquid for gas chromatographic analysis, and the yield of the methacrylonitrile is calculated.
Methacrylonitrile yield = methacrylonitrile yield/methacrylonitrile theoretical yield x 100%
FIG. 1 is a graph showing the results of the methacrylonitrile yields when the experiments of examples 1 to 5 and comparative example 1 were carried out 1 time; as shown in the figure, when the experiment was conducted 1 time, the methacrylonitrile yields of examples 1 to 5 and comparative example 1 were 93.26%, 92.66%, 91.35%, 91.18%, 92.37%, 53.29%, respectively; when the experiment is carried out for 1 time, the yield of the methacrylonitrile in the examples 1-5 is obviously higher than that in the comparative example 1, the catalyst prepared by calcining the organometallic framework has larger specific surface area and pore volume, the absorption of oxygen and the reaction are facilitated, and the synergistic effect among metals also increases the adsorption amount of oxygen on the catalyst.
FIG. 2 is a graph showing the results of the methacrylonitrile yields when the experiments of examples 1 to 5 and comparative example 1 were carried out 40 times; as shown in the figure, when the experiment was conducted 40 times, the methacrylonitrile yields of examples 1 to 5 and comparative example 1 were 90.11%, 89.66%, 90.27%, 90.03%, 90.16%, 17.76%, respectively; when the experiment was conducted 40 times, the yields of methacrylonitrile of examples 1-5 were significantly higher than those of comparative example 1, and the data yield of comparative FIG. 1 was significantly lower than that of comparative example 1, indicating that examples 1-5 could be reused, calcining the converted highly porous carbon shell, acting to protect the center Co/Mn nanoparticles, and helping to preserve their activity.
FIG. 3 is an SEM image after 40 times of the catalytic experiment of example 1; as shown in the figure, the product particles are still good in dispersibility after the catalytic experiment is carried out for 40 times, no obvious aggregation phenomenon occurs, and the catalyst has good stability.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (6)
1. A catalyst for methacrylonitrile synthesis, characterized in that: comprises the following components in parts by weight: 2.5-3.5 parts of cobalt nitrate, 10-15 parts of zinc nitrate, 22-27 parts of 2-methylimidazole, 0.9-1.7 parts of manganese nitrate, 8-13 parts of ferrous nitrate and 6-8 parts of copper nitrate; the catalyst is of a core-shell structure obtained by sintering a composite organic metal frame; the core-shell structure takes C-Co/Mn as a core body and C-Fe/Cu as a shell;
the preparation method of the catalyst for synthesizing the methacrylonitrile comprises the following steps: the method specifically comprises the following steps:
S1, dissolving cobalt nitrate in ionized water to obtain a cobalt nitrate solution, and dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution;
S2, uniformly mixing the cobalt nitrate solution obtained in the step S1 and the 2-methylimidazole solution, stirring in a water bath at the speed of 300rpm and the temperature of 30-40 ℃ for 5-7h, and filtering and drying to obtain ZIF-67;
s3, dissolving the ZIF-67 obtained in the step S2 in methanol, adding manganese nitrate, performing ultrasonic treatment at the power of 80-120w for 100-120min, then reacting for 1h at the temperature of 100 ℃ in a reaction kettle, filtering, drying, and calcining at the temperature of 300 ℃ for 80-120min to obtain Mn/ZIF-67;
s4, adding the Mn/ZIF-67 obtained in the step S3 and zinc nitrate into a methanol solution, adding 0.06g/mL of a 2-methylimidazole methanol solution in a volume ratio of 1:1, stirring in a water bath, filtering and drying to obtain ZIF-8@Mn/ZIF-67;
s5, calcining the ZIF-8@Mn/ZIF-67 obtained in the S4 at 800 ℃ for 120min in an argon atmosphere to obtain C-Zn@C-Co/Mn;
s6, adding ferrous nitrate and copper nitrate into the C-Zn@C-Co/Mn obtained in the S5, soaking for 12 hours, filtering, drying, and calcining for 30 minutes at 950 ℃ in an argon atmosphere to obtain C-Fe/Cu@C-Co/Mn;
S7, cooling the C-Fe/Cu@C-Co/Mn obtained in the step S6 to room temperature to obtain the catalyst for synthesizing the methacrylonitrile.
2. The catalyst for methacrylonitrile synthesis according to claim 1, characterized in that: in S1, the addition amount of cobalt nitrate in water is 0.15-17g/mL.
3. The catalyst for methacrylonitrile synthesis according to claim 2, characterized in that: in S1, the addition amount of 2-methylimidazole in water is 0.13-16g/mL.
4. A catalyst for the synthesis of methacrylonitrile in accordance with claim 3, characterized in that: in S2, the volume ratio of the cobalt nitrate solution to the 2-methylimidazole solution is 1:8-10.
5. The catalyst for methacrylonitrile synthesis according to claim 4, wherein: in S3, the ultrasonic power is 80-120W, and the reaction time is 100-120min.
6. The catalyst for methacrylonitrile synthesis according to claim 5, wherein: in S4, the volume ratio of the methanol solution to the 2-methylimidazole methanol solution is 1:1-1.3.
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