CN115414942A - Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as well as preparation method and application thereof - Google Patents
Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN115414942A CN115414942A CN202211165225.3A CN202211165225A CN115414942A CN 115414942 A CN115414942 A CN 115414942A CN 202211165225 A CN202211165225 A CN 202211165225A CN 115414942 A CN115414942 A CN 115414942A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methylamine
- metal salt
- bis
- aminopropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 126
- 239000002184 metal Substances 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims abstract description 54
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 15
- 230000008014 freezing Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 35
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 30
- -1 isopropylidene amine Chemical class 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000011068 loading method Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005576 amination reaction Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- NPMCIHCQSNHBDX-UHFFFAOYSA-N 3-[2-cyanoethyl(methyl)amino]propanenitrile Chemical compound N#CCCN(C)CCC#N NPMCIHCQSNHBDX-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing the first water-soluble metal salt, the second water-soluble metal salt and water to obtain a mixed double-metal salt solution;dispersing a carbon-based substrate and an equal amount of nano-TiO in water 2 As catalyst load, ultrasonically stirring until the catalyst is completely dispersed, and then adding a corresponding amount of mixed double-metal salt solution; placing the mixed double-metal salt solution under a xenon lamp light source for irradiation and stirring reaction, freezing the irradiated mixed double-metal salt solution into a solid, and finally carrying out vacuum freeze drying on the solid to finally obtain the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine. The catalyst obtained by the invention simplifies facilities and operation in the synthesis production process of the N, N-bis (3-aminopropyl) methylamine, and has the characteristics of high activity and good selectivity. The preparation method of the catalyst has the characteristics of wide raw material source, simple operation, low cost and the like.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, a preparation method and application thereof.
Background
N, N-bis (3-aminopropyl) methylamine (BAPMA) having the formula:
BAPMA is an important fine organic chemical intermediate, and is widely applied to industries such as medicine, pesticide, dye, petrochemical industry, semiconductor manufacturing and polymer. Meanwhile, as an important precursor of pentamethyl dipropylene triamine, BAPMA is commonly used for producing and preparing reverse osmosis nanofiltration membranes, epoxy resin curing accelerators, schiff bases and complexes thereof, medical synthetic intermediates, printing and dyeing wastewater treatment and the like.
At present, N, N-bis (3-aminopropyl) methylamine is mainly obtained by carrying out catalytic hydrogenation on N, N-bis (cyanoethyl) methylamine, and catalysts with different active centers have differences in the process of reducing cyano groups by catalytic hydrogenation, catalytic activity, selectivity and the like.
Commercial scale nitrile hydrogenation mostly employs suspended catalysts such as raney nickel and raney cobalt. Hirano et al hydrogenated N, N-bis (cyanoethyl) methylamine using a nickel-cobalt bimetallic catalyst (Manufacturing method of nickel compound and catalytic converter null for production, JP-B No. 3156734 (P3156734) B2[ P ] 2001.) under mild conditions (80 ℃,4.5MPa,3.9 h) at a yield of 93%, but the catalyst shows poor reaction selectivity and the formation of various by-products.
Use of ZrO by Eidamshaus et al 2 Supported Ru CATALYST as CATALYST FOR fixed bed reaction (metal FOR HYDROGENATING nitrile IN THE reaction OF a RUTHENIUM CATALYST carbon ZrO 2 :,US20190169112[P]2019.) the hydrogenation of N, N-bis (cyanoethyl) methylamine is carried out at 100 ℃ and 140 bar. Although the conversion rate of the reaction is as high as 99%, the reaction conditions are harsh, the selectivity is poor, the product yield is 92% at most, the metal loading is as high as 15wt%, and the cost is high.
Relatively few reports have been made on the one-step synthesis of N, N-bis (3-aminopropyl) methylamine. Chen et al used raney nickel as a cyano hydrogenation catalyst (An efficient synthesis of N, N, N ', N', N "-pentamethyl isopropylidene amine) to synthesize N, N-bis (cyanoethyl) methylamine in one step in An autoclave from acrylonitrile and methylamine: firstly, aminating for 4 hours at normal temperature in a methanol solvent, then carrying out hydrogenation reaction under the alkaline reaction condition of 90 ℃ and 2MPa, and finally obtaining the N, N-bis (3-aminopropyl) methylamine with the yield of 85%. However, in the process, the raney nickel catalyst only catalyzes the hydrogenation process, resulting in a longer overall reaction time and lower efficiency.
In conclusion, many reported production routes of N, N-bis (3-aminopropyl) methylamine mostly use nitrile as a raw material and are obtained by hydrogenation, and the problems of poor selectivity, harsh conditions, high cost, low efficiency and the like exist, and continuous production is difficult to realize, so that the development of a technology capable of synthesizing N, N-bis (3-aminopropyl) methylamine in one step is a problem to be solved in the field.
Disclosure of Invention
The invention aims at providing a preparation method of a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine, wherein the catalyst obtained by the preparation method has the characteristics of simplifying facilities and operation in the production process of synthesizing the N, N-bis (3-aminopropyl) methylamine, high activity and good selectivity for the reaction of synthesizing the N, N-bis (3-aminopropyl) methylamine, and the preparation method of the catalyst has the characteristics of wide raw material source, simplicity in operation, low cost and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine comprises the following steps:
1) Mixing the first water-soluble metal salt, the second water-soluble metal salt and water to obtain a mixed double-metal salt solution; the first water-soluble metal salt is one or more of sodium nitrate, potassium nitrate and magnesium nitrate, and the second water-soluble metal salt is one or more of nickel nitrate, zinc nitrate and chromium nitrate;
2) Dispersing a carbon-based substrate and an equal amount of nano-TiO in water 2 As catalyst load, ultrasonically stirring until the catalyst load is completely dispersed, and then adding a corresponding amount of mixed double-metal salt solution, wherein the mass ratio of metal to the catalyst load in the mixed double-metal salt solution is 0.5-5.0 wt%;
3) Placing the mixed double-metal salt solution under a xenon lamp light source, irradiating and stirring for reaction for 3-6 h, wherein the current is 10-20A, freezing the irradiated mixed double-metal salt solution into a solid, and finally, carrying out vacuum freeze drying on the solid under the conditions of 0.001-0.01 MPa of vacuum degree and-60-50 ℃ to finally obtain the composite double-metal monatomic catalyst, namely the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine.
The preferred scheme is as follows: the carbon-based substrate is graphiteAlkene, graphene oxide, carbon nanotube, C 3 N 4 And one or more of nitrogen-doped graphene.
The preferred scheme is as follows: the freezing time of the irradiated mixed double-metal salt solution is 2-4 h, and the vacuum freeze-drying time of the solid is 23-25 h.
The second object of the present invention is to provide a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine obtained based on the above-mentioned preparation method.
The third purpose of the invention is to provide an application of the catalyst for preparing N, N-bis (3-aminopropyl) methylamine, which comprises the following steps:
adding a composite bimetallic monatomic catalyst, raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the composite bimetallic monatomic catalyst to the raw materials of the acrylonitrile and the methylamine is 1-5 wt%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, then stirring and reacting for 1.5-2.5 h at the reaction temperature of 80-100 ℃ and the reaction pressure of 0.5-2.0 MPa, introducing hydrogen, stirring and reacting for 1.5-2.5 h at the maintained pressure of 1.5-3 MPa and the temperature of 130-160 ℃; after the reaction is finished, opening the high-pressure kettle, adding a solvent to dissolve a reaction product and filtering to obtain the product N, N-bis (3-aminopropyl) methylamine.
The preferred scheme is as follows: the stirring reaction time is 2h.
The invention has the following technical effects:
1) The preparation principle of the composite type bimetal monatomic catalyst is as follows: in the process of preparing the catalyst by the photo-deposition method, when a material with photosensitivity is irradiated by ultraviolet light, an electron-hole pair which is easy to move and has extremely strong activity is generated, a photo-generated carrier pair can freely migrate to the surface of a crystal lattice or other reaction places in the crystal lattice to form a free hole and a free electron, the free hole and the free electron are immediately captured by surface species, various oxidation-reduction reactions are carried out, different metal atoms are anchored on a carrier, and the composite bimetallic monatomic catalyst is formed. The function of each step of operation in the preparation process of the catalyst is as follows: different kinds of metal salts are precursors of different active centers; tiO 2 2 And C 3 N 4 As the photosensitive material, there is used,generating electron holes under illumination; the carbon-based carrier with large specific surface area, special morphology and structure is added, so that a load surface can be provided, dispersion is facilitated, electrons are separated, and rapid recombination of electron holes is prevented; the vacuum freeze-drying step has the function of removing water in the system at low temperature, and simultaneously keeping a stable structure in the catalyst; the influence of the corresponding technical parameters on the successful preparation of the catalyst is as follows: the mass ratio of the metal to the carrier is controlled to be 0.5-5.0 wt%, when the mass ratio is too high, agglomeration is formed, and when the mass ratio is too low, the activity is insufficient; the illumination time is controlled to be 3-6 h, too low metal is not reduced, and too high metal affects the carrier structure; the metal salt is selected from sodium salt, potassium salt, magnesium salt, nickel salt, zinc salt and chromium salt which are respectively used as active centers of amination reaction and hydrogenation reaction. The key technical points are as follows: the mass ratio of the metal to the load carrier controls the dispersion degree of the metal on the surface of the carrier; the light irradiation time influences the reduction valence state of the metal; the selection of the metal salt influences the type of the active center, and the active site of the previous step can be used as a cocatalyst of the next step, so that the hydrogenation selectivity is improved. In conclusion, the successful preparation of the catalyst of the present invention ensures a one-step synthesis of N, N-bis (3-aminopropyl) methylamine.
2) The composite bimetallic monatomic catalyst prepared by the invention has the following effects on the synthesis of N, N-bis (3-aminopropyl) methylamine: facilities and operation in the production process of synthesizing N, N-bis (3-aminopropyl) methylamine are simplified, two sets of production devices are required in the traditional production process, amination and hydrogenation operation are separated, and equipment and operation are complex; in the invention, only one reactor is adopted, amination and hydrogenation are carried out in sequence, and an intermediate product does not need to be separated, so that equipment and intermediate operation steps are reduced; the method has the characteristics of high activity and good selectivity for the reaction of synthesizing N, N-bis (3-aminopropyl) methylamine, raney nickel or noble metal catalyst is used for hydrogenation in the traditional operation, the acceleration effect on the amination reaction is avoided, the yield is lower than 93%, and the selectivity is lower than 94%; the catalyst of the invention has promoting effect on amination and hydrogenation at the same time, the yield is higher than 94.1%, and the selectivity is higher than 96.2%; in addition, the preparation method of the catalyst has the characteristics of wide raw material source, simple operation, low cost and the like, the transition metal salt and the carbon-based carrier are cheaper and easily obtained than noble metal, the price of the noble metal catalyst commonly used in industrialization is 1.5 times of that of the transition metal in the invention, and the metal utilization rate (nearly 100 percent) of the catalyst is greatly higher than that of the traditional catalyst; the traditional industrial catalyst needs complex operations such as high-temperature roasting, and the like, and the catalyst is finished at normal temperature and normal pressure, so that the operation is simple.
3) The invention utilizes a composite bimetallic monatomic catalyst to prepare and synthesize N, N-bis (3-aminopropyl) methylamine, and the catalytic principle is as follows: the method comprises the following steps that (1) a Michael addition reaction is carried out on acrylonitrile and methylamine at a sodium atom active site of a catalyst, transition hydrogen bonds are formed by the acrylonitrile, cyano groups and active hydrogen on amino groups, lone pair electrons on nitrogen are subjected to nucleophilic attack on carbon atoms on a beta position, and a cyano-containing intermediate is formed through conjugate addition and rearrangement; the intermediate is continuously hydrogenated at the active site of the nickel atom of the catalyst to generate amine. The invention has the following effects in each step of operation in the process of synthesizing N, N-bis (3-aminopropyl) methylamine: the nitrogen replacement is used for exhausting air in the reactor to prevent products from being oxidized or generating danger; amination reaction is carried out in the process of stirring and reacting for 1.5-2.5 h at the reaction temperature of 80-100 ℃ and the reaction pressure of 0.5-2.0 MPa, hydrogenation reaction is carried out in the process of stirring and reacting for 1.5-2.5 h at the maintenance pressure of 1.5-3 MPa and the temperature of 130-160 ℃, and a solvent is added to dissolve a reaction product and filter the reaction product so as to separate the product and obtain a product with higher purity; the influence of the corresponding technical parameters on the successful synthesis of the N, N-bis (3-aminopropyl) methylamine is as follows: if the reaction temperature is too low and the reaction activity is not enough, if the reaction temperature is too high and the deamination of the reaction intermediate is accelerated, byproducts are increased; the catalyst dosage is too low, the active center is insufficient, the dosage is too high, the cost is increased, and waste is caused; reaction pressure influences the reaction effect, and hydrogen pressure high energy improves reaction rate, but too high pressure promotion rate effect is not obvious, has danger in the operation even, and its key technology point has: the temperature in the reaction process influences the activity and the selectivity, and the optimal temperature is 80-100 ℃ and 130-160 ℃; the mass ratio of the proper catalyst dosage to the reactants is 1-5 wt%; the reaction pressure in the hydrogenation process is 1.5-3 MPa.
Drawings
FIG. 1 is an SEM image of a catalyst Na-GO-Ni of the present invention;
FIG. 2 is an XRD spectrum of the catalyst Na-GO-Ni of the present invention.
As can be seen from fig. 1: the graphene oxide carrier is in a corrugated shape, and the preparation process does not obviously influence the appearance of the graphene oxide carrier; the surface of the substrate is white photosensitizer titanium dioxide with different particle sizes; no obvious metallic Na, ni polymer or particle is seen, which indicates that the metal has better atomic-scale dispersity.
As can be seen from fig. 2: after comparing with the X-ray diffraction standard card, only the characteristic peak of the photosensitizer titanium dioxide is observed, but the characteristic peaks of Na and Ni crystals are not observed, which shows that no Na and Ni nano crystal grains exist in the catalyst, and further verifies that the metal dispersion degree is higher.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
1. Preparation of composite bimetallic monatomic catalyst
In the following catalyst expression method, graphene is represented by G, graphene oxide is represented by GO, and graphitic carbon nitride is represented by C 3 N 4 It is shown that nitrogen-doped graphene is denoted by NG and carbon nanotubes are denoted by C. The vacuum degree of the vacuum freeze dryer is 0.001 to 0.01MPa, and the temperature is-60 to-50 ℃.
Preparation example 1, the preparation process of the composite bimetallic monatomic catalyst Na-G-Ni is as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 2.48mg of second water-soluble metal salt nickel nitrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding a mixed double-metal salt solution, and keeping the metal content in the mixed double-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source for irradiation, stirring and reacting for 3h, wherein the current is 10A, placing the solution after the irradiation in a refrigerator for freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound type bimetal monatomic catalyst Na-G-Ni with the metal content of 1.0 wt%.
Preparation example 2, the preparation process of the composite type bimetallic monatomic catalyst Mg-G-Zn is as follows:
1) Uniformly mixing and dispersing 5.34mg of first water-soluble metal salt magnesium nitrate, 1.46mg of second water-soluble metal salt zinc nitrate hexahydrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding a mixed double-metal salt aqueous solution, and keeping the metal content in the mixed double-metal salt aqueous solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source for irradiation, stirring and reacting for 3h, wherein the current is 10A, placing the solution after the irradiation in a refrigerator for freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the composite type bimetal monatomic catalyst Mg-G-Zn with the metal content of 1.0 wt%.
Preparation example 3, the preparation process of the composite type bimetal monatomic catalyst K-G-Cr is as follows:
1) 1.29mg of first water-soluble metal salt potassium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water are mixed and dispersed uniformly to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding a mixed double-metal salt aqueous solution, and keeping the metal content in the mixed double-metal salt aqueous solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source for irradiation, stirring and reacting for 3h, wherein the current is 10A, placing the solution after the irradiation in a refrigerator for freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound type bimetal monatomic catalyst K-G-Cr with the metal content of 1.0 wt%.
Preparation example 4, the preparation process of the composite bimetallic monatomic catalyst Na-GO-Cr is as follows:
1) Mixing and uniformly dispersing 20mg of first water-soluble metal salt sodium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene oxide substrate and the same amount of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding a corresponding amount of mixed double-metal salt aqueous solution, and keeping the metal in the mixed double-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 3h, wherein the current is 10A, placing the irradiated solution in a refrigerator, freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound bimetallic monatomic catalyst Na-GO-Cr with the metal content of 1.0 wt%.
Preparation example 5 composite bimetallic monatomic catalyst Na-C 3 N 4 -Zn was prepared as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 20mg of second water-soluble metal salt zinc nitrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) 100mg of graphitic carbon nitride material C was added to 20ml of deionized water 3 N 4 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding mixed double-metal salt aqueous solution, and keeping the metal in the mixed double-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 3h, wherein the current is 10A, placing the irradiated solution in a refrigerator, freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier, and drying for 23h to obtain the compound type bimetallic monatomic catalyst Na-GO-Zn with the metal content of 1.0 wt%.
Preparation example 6, the preparation process of the composite bimetallic monatomic catalyst Na-NG-Ni is as follows:
1) Mixing and uniformly dispersing 9.25mg of first water-soluble metal salt sodium nitrate, 7.30mg of second water-soluble metal salt zinc nitrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of nitrogen-doped graphene NG and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding mixed double-metal salt aqueous solution, and keeping the metal in the mixed double-metal salt solution: catalyst loading =5.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 3h, wherein the current is 10A, placing the irradiated solution in a refrigerator, freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the composite type bimetallic monatomic catalyst Na-NG-Ni with the metal content of 5.0 wt%.
Preparation example 7, the preparation process of the composite bimetallic monatomic catalyst Na-G-Ni was as follows:
1) Mixing and uniformly dispersing 0.92mg of first water-soluble metal salt sodium nitrate, 1.24mg of second water-soluble metal salt nickel nitrate and 5ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding a mixed double-metal salt solution, and keeping the metal content in the mixed double-metal salt solution: catalyst loading =0.5wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 6h, wherein the current is 20A, placing the irradiated solution in a refrigerator, freezing for 2h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound type bimetallic monatomic catalyst Na-G-Ni with the metal content of 0.5 wt%.
Preparation example 8, the preparation process of the composite bimetallic monatomic catalyst Mg-G-Zn is as follows:
1) Uniformly mixing and dispersing 5.34mg of first water-soluble metal salt magnesium nitrate, 1.46mg of second water-soluble metal salt zinc nitrate hexahydrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding mixed double-metal salt aqueous solution, and keeping the metal in the mixed double-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 4h, wherein the current is 15A, placing the irradiated solution in a refrigerator, freezing for 3h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the composite type bimetallic monatomic catalyst Mg-G-Zn with the metal content of 1.0 wt%.
Preparation example 9 preparation of a composite bimetallic monatomic catalyst K-C-Cr:
1) 1.29mg of first water-soluble metal salt potassium nitrate, 3.85mg of second water-soluble metal salt chromium nitrate nonahydrate and 10ml of deionized water are mixed and dispersed uniformly to obtain a mixed double-metal salt solution;
2) Adding 50mg of carbon nanotube substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonically stirring until the dispersion is complete, then adding mixed double-metal salt aqueous solution, and keeping the metal in the mixed double-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 3h, wherein the current is 10A, placing the irradiated solution in a refrigerator, freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound type bimetallic monatomic catalyst K-C-Cr with the metal content of 1.0 wt%.
Preparation example 10, a preparation process of the composite bimetallic monatomic catalyst Na-GO-Ni was as follows:
1) Uniformly mixing and dispersing 1.85mg of first water-soluble metal salt sodium nitrate, 2.48mg of second water-soluble metal salt nickel nitrate and 10ml of deionized water to obtain a mixed double-metal salt solution;
2) Adding 50mg of graphene oxide substrate and 50mg of nano TiO into 20ml of deionized water 2 As catalyst loading, ultrasonic stirring is carried out until the dispersion is complete, and then mixed double metal salt solution is addedMaintaining the metal in the mixed bi-metal salt solution: catalyst loading =1.0wt% mass ratio;
3) Placing the mixed solution under a xenon lamp light source, irradiating, stirring and reacting for 3h, wherein the current is 10A, placing the irradiated solution in a refrigerator, freezing for 4h until the solution becomes solid, and finally placing the solution in a vacuum drier for drying for 24h to obtain the compound bimetallic monatomic catalyst Na-GO-Ni with the metal content of 1.0 wt%.
2. Synthesis of N, N-bis (3-aminopropyl) methylamine by continuous Process example
The synthesis method takes acrylonitrile and methylamine as raw materials, and the synthesis reaction equation is as follows:
the specific synthesis steps are as follows:
example 1, 100mg of a composite bimetallic monatomic catalyst Na-G-Ni with a metal content of 1.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 1.5MPa and the temperature of 130 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 94.1 percent, and the selectivity is 96.2 percent.
Example 2, 100Mg of composite bimetallic monatomic catalyst Mg-G-Zn with the metal content of 1.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 90 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 2.0MPa and the temperature of 130 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 95.3 percent, and the selectivity is 98.6 percent.
Example 3, 100mg of a composite bimetallic monatomic catalyst K-G-Cr with a metal content of 1.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 100 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 2.5MPa and the temperature of 130 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 96.0 percent and the selectivity is 97.6 percent.
Example 4, 100mg of a composite type bimetal monatomic catalyst Na-GO-Cr with the metal content of 1.0wt%, acrylonitrile and methylamine which are used as raw materials are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 85 ℃ and the reaction pressure of 0.5 MPa; then hydrogen is introduced, and the mixture is stirred and reacts for 2 hours under the pressure of 2.0MPa and the temperature of 140 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 96.5 percent, and the selectivity is 97.9 percent.
Example 5 composite type bimetal single atom catalyst Na-C with 1.0wt% of metal content 3 N 4 100mg of Zn, acrylonitrile and methylamine which are raw materials are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2 percent; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 2.0MPa and the temperature of 150 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 94.4 percent and the selectivity is 96.9 percent.
Example 6, 100mg of a composite bimetallic monatomic catalyst Na-NG-Ni with a metal content of 5.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 90 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 2.0MPa and the temperature of 160 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 94.3 percent and the selectivity is 95.7 percent.
Example 7, 100mg of composite bimetallic monatomic catalyst Na-NG-Ni with a metal content of 5.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 1.0 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 2.0MPa and the temperature of 150 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 95.0 percent and the selectivity is 97.7 percent.
Example 8, 100mg of a composite bimetallic monatomic catalyst Na-NG-Ni with a metal content of 5.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 1%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the temperature of 150 ℃ under the condition of maintaining the pressure of 1.5MPa; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 94.0 percent and the selectivity is 96.7 percent.
Example 9, 100mg of composite bimetallic monatomic catalyst Na-NG-Ni with a metal content of 5.0wt%, raw materials of acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 5%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 95 ℃ and the reaction pressure of 2.0 MPa; then hydrogen is introduced, and the mixture is stirred and reacted for 2 hours under the maintained pressure of 3MPa and the temperature of 150 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 94.5 percent and the selectivity is 96.5 percent.
Example 10, 100mg of a composite bimetallic monatomic catalyst Na-GO-Ni with a metal content of 1.0wt%, raw materials acrylonitrile and methylamine are added into an autoclave, and the mass ratio of the catalyst to the raw materials is 2%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, and then stirring and reacting for 2 hours at the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa; then introducing hydrogen, and stirring and reacting for 2h at the maintained pressure of 1.5MPa and the temperature of 130 ℃; after the reaction is finished, the high-pressure kettle is opened, a solvent is added to dissolve a reaction product and the reaction product is filtered to obtain a product N, N-bis (3-aminopropyl) methylamine, wherein the yield is 95.1 percent, and the selectivity is 96.5 percent.
The composite bimetallic single-atom catalyst obtained in the preparation example can be effectively used for synthesizing N, N-bis (3-aminopropyl) methylamine, and the yield and the selectivity of the N, N-bis (3-aminopropyl) methylamine basically reach over 95 percent.
Comparative example 1-1, the following catalyst preparation conditions in catalyst preparation example 1 were changed: the metal content was 10.0wt%, and other preparation conditions were kept constant, and the procedure for the synthesis reaction of N, N-bis (3-aminopropyl) methylamine was identical to that of example 1 described above. The result obtained was that N, N-bis (3-aminopropyl) methylamine was in a yield of 54.5% and a selectivity of 65.2%.
Comparative examples 1-2, the following catalyst preparation conditions in catalyst preparation example 1 were changed: activated carbon was used as a carbon-based substrate, and other preparation conditions were kept unchanged, and the procedure for the synthesis reaction of N, N-bis (3-aminopropyl) methylamine was identical to that of example 1 described above. The obtained N, N-bis (3-aminopropyl) methylamine had a yield of 44.5% and a selectivity of 54.6%.
Comparative example 2-1, catalyst preparation is identical to catalyst preparation example 1, and the procedure for the synthesis reaction of N, N-bis (3-aminopropyl) methylamine is the same as in example 1 above, except that "the reaction temperature of 80 ℃ and the reaction pressure of 0.5 MPa" in example 1 were changed to "60 ℃, atmospheric pressure", and the remaining reaction conditions were maintained. The obtained N, N-bis (3-aminopropyl) methylamine had a yield of 34.5% and a selectivity of 40.2%.
Comparative examples 2-2, catalyst preparation was identical to catalyst preparation example 1, and the procedure for the synthesis reaction of N, N-bis (3-aminopropyl) methylamine used in example 1 was the same as that of example 1 above, except that "introducing hydrogen gas, stirring the reaction at 150 ℃ under a maintained pressure of 2.0MPa for 2 hours" in example 1 was changed to "introducing hydrogen gas, stirring the reaction at 100 ℃ under a maintained pressure of 0.5MPa for 1 hour", and the remaining reaction conditions were kept unchanged. The obtained result was that the yield of N, N-bis (3-aminopropyl) methylamine was 39.2%, and the selectivity was 46.5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (6)
1. A preparation method of a catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine is characterized by comprising the following steps:
1) Mixing the first water-soluble metal salt, the second water-soluble metal salt and water to obtain a mixed double-metal salt solution; the first water-soluble metal salt is one or more of sodium nitrate, potassium nitrate and magnesium nitrate, and the second water-soluble metal salt is one or more of nickel nitrate, zinc nitrate and chromium nitrate;
2) Dispersing a carbon-based substrate and an equal amount of nano-TiO in water 2 As catalyst load, ultrasonically stirring until the catalyst load is completely dispersed, and then adding a corresponding amount of mixed double-metal salt solution, wherein the mass ratio of metal to the catalyst load in the mixed double-metal salt solution is 0.5-5.0 wt%;
3) Placing the mixed double-metal salt solution under a xenon lamp light source, irradiating and stirring for reaction for 3-6 h, wherein the current is 10-20A, freezing the irradiated mixed double-metal salt solution into a solid, and finally, carrying out vacuum freeze drying on the solid under the conditions of 0.001-0.01 MPa of vacuum degree and-60-50 ℃ to finally obtain the composite double-metal monatomic catalyst, namely the catalyst for synthesizing the N, N-bis (3-aminopropyl) methylamine.
2. The process for producing a catalyst for the synthesis of N, N-bis (3-aminopropyl) methylamine as claimed in claim 1, wherein: said carbon-based groupThe bottom is graphene, graphene oxide, carbon nano tube and C 3 N 4 And one or more of nitrogen-doped graphene.
3. The method for producing a catalyst for the synthesis of N, N-bis (3-aminopropyl) methylamine as claimed in claim 1, wherein: the freezing time of the irradiated mixed double-metal salt solution is 2-4 h, and the vacuum freeze-drying time of the solid is 23-25 h.
4. A catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine obtained by the production method according to any one of claims 1 to 3.
5. Use of a catalyst according to claim 4 for the preparation of N, N-bis (3-aminopropyl) methylamine, characterized in that the process is as follows:
adding a composite type bimetal monatomic catalyst, raw materials of acrylonitrile and methylamine into an autoclave, wherein the mass ratio of the composite type bimetal monatomic catalyst to the raw materials of the acrylonitrile and the methylamine is 1-5 wt%; performing gas replacement on the inner cavity of the high-pressure kettle by using nitrogen, stirring and reacting for 1.5-2.5 h at the reaction temperature of 80-100 ℃ and the reaction pressure of 0.5-2.0 MPa, introducing hydrogen, stirring and reacting for 1.5-2.5 h at the maintained pressure of 1.5-3 MPa and the temperature of 130-160 ℃; after the reaction is finished, opening the high-pressure kettle, adding a solvent to dissolve a reaction product and filtering to obtain the product N, N-bis (3-aminopropyl) methylamine.
6. Use of a catalyst according to claim 5 for the preparation of N, N-bis (3-aminopropyl) methylamine wherein: the stirring reaction time is 2h.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311262299.3A CN117323996A (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
CN202211165225.3A CN115414942B (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211165225.3A CN115414942B (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311262299.3A Division CN117323996A (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115414942A true CN115414942A (en) | 2022-12-02 |
CN115414942B CN115414942B (en) | 2023-10-31 |
Family
ID=84204447
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311262299.3A Pending CN117323996A (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
CN202211165225.3A Active CN115414942B (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311262299.3A Pending CN117323996A (en) | 2022-09-23 | 2022-09-23 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN117323996A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115947340A (en) * | 2023-01-06 | 2023-04-11 | 西北大学 | Metal nitrogen-doped graphene quantum dot composite material, preparation method and application |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190169112A1 (en) * | 2016-09-08 | 2019-06-06 | Basf Se | METHOD FOR HYDROGENATING NITRILES IN THE PRESENCE OF A RUTHENIUM CATALYST CARRIED ON ZrO2 |
CN113501761A (en) * | 2021-07-16 | 2021-10-15 | 万华化学集团股份有限公司 | Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method |
CN113877630A (en) * | 2021-10-11 | 2022-01-04 | 万华化学集团股份有限公司 | Catalyst for preparing bis [ (3-dimethylamino) propyl ] amine and application thereof |
CN114471646A (en) * | 2021-12-22 | 2022-05-13 | 湘潭大学 | Preparation method and application of single-atom iron-series metal loaded on surface of titanium carbide |
CN114950486A (en) * | 2022-04-22 | 2022-08-30 | 北京科技大学 | Preparation method of bifunctional metal active site photocatalyst |
-
2022
- 2022-09-23 CN CN202311262299.3A patent/CN117323996A/en active Pending
- 2022-09-23 CN CN202211165225.3A patent/CN115414942B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190169112A1 (en) * | 2016-09-08 | 2019-06-06 | Basf Se | METHOD FOR HYDROGENATING NITRILES IN THE PRESENCE OF A RUTHENIUM CATALYST CARRIED ON ZrO2 |
CN113501761A (en) * | 2021-07-16 | 2021-10-15 | 万华化学集团股份有限公司 | Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method |
CN113877630A (en) * | 2021-10-11 | 2022-01-04 | 万华化学集团股份有限公司 | Catalyst for preparing bis [ (3-dimethylamino) propyl ] amine and application thereof |
CN114471646A (en) * | 2021-12-22 | 2022-05-13 | 湘潭大学 | Preparation method and application of single-atom iron-series metal loaded on surface of titanium carbide |
CN114950486A (en) * | 2022-04-22 | 2022-08-30 | 北京科技大学 | Preparation method of bifunctional metal active site photocatalyst |
Non-Patent Citations (1)
Title |
---|
祁建磊;徐琴琴;孙剑飞;周丹;银建中;: "石墨烯基单原子催化剂的合成、表征及分析", 化学进展, no. 05, pages 11 - 24 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115947340A (en) * | 2023-01-06 | 2023-04-11 | 西北大学 | Metal nitrogen-doped graphene quantum dot composite material, preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN117323996A (en) | 2024-01-02 |
CN115414942B (en) | 2023-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101602644B (en) | Method for synthesizing decalin | |
CN111115649B (en) | Preparation method of BCN nanosheet, BCN nanosheet prepared by preparation method and application of BCN nanosheet | |
CN109482235B (en) | Preparation method and application of N-doped mesoporous carbon supported metal nano catalyst | |
CN110385146B (en) | Ni0.85Se/PDA/g-C3N4Composite photocatalyst and application thereof | |
CN111960948B (en) | Synthesis process of tetrabutylammonium bromide | |
WO2022021506A1 (en) | Preparation of ultrathin porous carbon nitride nano-photocatalyst and applications thereof in photocatalytically oxidizing fructose to synthesize lactic acid | |
Ergen et al. | One-pot reductive amination of aldehydes with nitroarenes using formic acid as the hydrogen donor and mesoporous graphitic carbon nitride supported AgPd alloy nanoparticles as the heterogeneous catalyst | |
CN113019393B (en) | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound | |
CN115414942B (en) | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof | |
CN115007186B (en) | Carbon nitride-based site-specific double-single-atom catalyst, preparation and application thereof | |
CN111153768A (en) | Synthetic method of isohexide | |
CN114733520B (en) | Preparation method and application of supported nano gold catalyst | |
CN112569969A (en) | Synthesis and application method of BiOBr photocatalyst containing optically controlled oxygen vacancies | |
CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
US20240189799A1 (en) | Catalyst for decomposition of ammonia, manufacturing method therefor, and method for producing hydrogen using same | |
CN114849694A (en) | Catalyst based on metal-loaded tungsten oxide hydrogenated nitroarene and preparation method and application thereof | |
Pan et al. | Size-tunable carbon-doped Ni nanoparticles for switchable reductive amination of biomass-derived carbonyl compounds to primary amines and secondary imines | |
CN107999072B (en) | Photo-thermal catalyst, preparation method thereof and method for catalyzing cyclohexane oxidation | |
CN114588940B (en) | Nickel-based catalyst for hydrogenation of phenolic compounds, and preparation method and application thereof | |
CN117019147A (en) | Synthesis method of high-dispersity supported catalyst and method for preparing furfuryl alcohol by catalyzing furfural by using high-dispersity supported catalyst | |
CN112746288B (en) | Preparation method of reduced graphene oxide loaded metal monatomic catalyst | |
CN115254156B (en) | Supported Ru monoatomic alloy catalyst and application thereof | |
CN114774969A (en) | MoO2/Ni-NC nano composite electrocatalyst and preparation method and application thereof | |
CN113578346A (en) | Copper/silver alloy nano catalyst and preparation method and application thereof | |
CN113926487A (en) | Fullerol/palladium nano composite photocatalyst and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |