CN115814820A - Hydrogenation catalyst, preparation method thereof and preparation method of N, N-dimethylcyclohexylamine - Google Patents
Hydrogenation catalyst, preparation method thereof and preparation method of N, N-dimethylcyclohexylamine Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 88
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000005470 impregnation Methods 0.000 claims abstract description 57
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 56
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 48
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 41
- 239000011669 selenium Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 150000002940 palladium Chemical class 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 230000004913 activation Effects 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000007598 dipping method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012216 screening Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of catalysts, and provides a hydrogenation catalyst and a preparation method thereof, and a preparation method of N, N-dimethylcyclohexylamine. Firstly dipping a carrier in a selenium dioxide aqueous solution to obtain a dipping material; sequentially carrying out first drying, first grinding and first calcining on the impregnated material to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in a palladium salt solution to obtain an impregnation precursor; and sequentially carrying out second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst. The method comprises the steps of doping selenium into a carrier and then loading palladium to obtain the selenium-doped palladium-based catalyst. In the invention, the doped selenium can increase the dispersion degree of palladium on the surface of the carrier and generate a synergistic effect with the palladium, and is favorable for improving the activity of the catalyst and the selectivity of hydrogenation reaction when being used for preparing N, N-dimethylcyclohexylamine by taking cyclohexanone, dimethylamine and hydrogen as raw materials.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a hydrogenation catalyst and a preparation method thereof, and a preparation method of N, N-dimethylcyclohexylamine.
Background
N, N-dimethyl cyclohexylamine is a low-viscosity medium-activity amine catalyst, is mainly used as a catalyst for hard polyurethane foam, has catalytic action on gel and foam, is a strong initial catalyst for foam reaction, and can also be used as an auxiliary catalyst for molding soft foam, semi-hard foam and the like. Currently, cyclohexanone, dimethylamine and hydrogen are mainly used as raw materials to synthesize N, N-dimethylcyclohexylamine industrially.
Chinese patent publication No. CN104892429A discloses a method for synthesizing N, N-dimethylcyclohexylamine from cyclohexanone, ammonia, hydrogen and formaldehyde. The catalyst used in the method is a supported nickel catalyst doped with copper and chromium, the carrier is gamma-alumina, silicon dioxide and a molecular sieve, the loading capacity of nickel is 0.1-50%, the reaction is carried out in a two-stage fixed bed reactor connected in series, the reaction pressure is 6MPa, the first stage reaction temperature is 120 ℃, the second stage reaction temperature is 130 ℃, finally, the yield of N, N-dimethylcyclohexylamine is 84.2%, and the yield of N-methyldicyclohexylamine is 10.3%.
At present, the method for synthesizing N, N-dimethylcyclohexylamine by using cyclohexanone as a raw material mainly has the following problems: under the condition of micro excess of dimethylamine, the phenomena of incomplete conversion of cyclohexanone or generation of cyclohexanol by-products by hydrogenation of cyclohexanone still exist by using the existing catalyst, such as a palladium catalyst, cyclohexanone or cyclohexanol still remains in the final reaction product, and the conversion rate of cyclohexanone and the selectivity of dimethylcyclohexylamine are low.
Disclosure of Invention
In view of the above, the present invention provides a hydrogenation catalyst, a preparation method thereof, and a preparation method of N, N-dimethylcyclohexylamine. The hydrogenation catalyst provided by the invention has good catalytic effect, and the conversion rate of the raw material cyclohexanone and the selectivity of the product N, N-dimethylcyclohexylamine are high in the reaction of catalyzing the micro-excess synthesis of the N, N-dimethylcyclohexylamine from the dimethylamine.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnation material;
sequentially carrying out first drying, first grinding and first calcining on the impregnated material to obtain a selenium composite carrier;
carrying out second impregnation on the selenium composite carrier in a palladium salt solution to obtain an impregnation precursor;
and sequentially carrying out second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst.
Preferably, the carrier comprises an activated carbon carrier, an alumina carrier or a titanium dioxide carrier; the concentration of the selenium dioxide water solution is 1-5 g/L; the mass ratio of the carrier to the selenium dioxide aqueous solution is 1 (3-20).
Preferably, the first and second calcinations are carried out under nitrogen atmosphere, and the temperature of the first and second calcinations is 200-250 ℃ independently, and the time is 3-6 h independently.
Preferably, the gas used for reduction activation is hydrogen or a mixed gas of hydrogen and nitrogen; the temperature of the reduction activation is 50-200 ℃, and the time is 1-3 h.
Preferably, the palladium salt in the palladium salt solution comprises palladium chloride, palladium nitrate or palladium acetate; the mass fraction of the palladium salt in the palladium salt solution is 10-30 g/L; the mass ratio of the selenium composite carrier to the palladium salt solution is 1 (5-20).
The invention also provides a hydrogenation catalyst prepared by the preparation method in the scheme, which comprises a carrier and palladium and selenium loaded on the carrier; the mass percent of palladium in the hydrogenation catalyst is 2-10%, and the mass percent of selenium is 0.1-5%.
The invention also provides a preparation method of the N, N-dimethylcyclohexylamine, which comprises the following steps:
mixing dimethylamine, cyclohexanone and a hydrogenation catalyst, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain the N, N-dimethylcyclohexylamine; the hydrogenation catalyst is the hydrogenation catalyst in the scheme.
Preferably, the mixing is: the dimethylamine is mixed with the hydrogenation catalyst, followed by addition of cyclohexanone.
Preferably, the mass ratio of the cyclohexanone to the hydrogenation catalyst is (5-500): 1, and the mass ratio of the dimethylamine to the cyclohexanone is (1-1.1): 1.
Preferably, the pressure of the hydrogenation reaction is 1-4 MPa;
the time of the hydrogenation reaction is calculated by adding cyclohexanone, the time of the hydrogenation reaction comprises the time of adding cyclohexanone and the time of continuing the reaction after adding cyclohexanone is finished, the time of adding cyclohexanone is 10-600 min, and the time of continuing the reaction is 30-200 min; the temperature of the hydrogenation reaction is 45-135 ℃.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnation material; sequentially carrying out first drying, first grinding and first calcining on the impregnated material to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in a palladium salt solution to obtain an impregnation precursor; and sequentially carrying out second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst. The method comprises the steps of doping selenium into a carrier and then loading palladium to obtain the selenium-doped palladium-based catalyst. In the invention, the doped selenium can increase the dispersion degree of palladium on the surface of the carrier and generate a synergistic effect with the palladium, thereby being beneficial to improving the activity of the catalyst and the selectivity of hydrogenation reaction.
The invention also provides the hydrogenation catalyst prepared by the preparation method in the scheme. The catalyst prepared by the invention has good catalytic hydrogenation effect, and the conversion rate of the raw material cyclohexanone and the selectivity of the product N, N-dimethylcyclohexylamine are high in the reaction of catalyzing the micro-excess synthesis of the N, N-dimethylcyclohexylamine by dimethylamine.
The invention also provides a preparation method of the N, N-dimethylcyclohexylamine. The preparation method provided by the invention adopts the hydrogenation catalyst in the scheme to catalyze the reaction of cyclohexanone, dimethylamine and hydrogen to obtain N, N-dimethylcyclohexylamine, and the conversion rate of the raw material cyclohexanone and the selectivity of the product N, N-dimethylcyclohexylamine are high. Experimental data of the embodiment of the invention show that the highest conversion rate of the raw material cyclohexanone is 99.9%, and the highest selectivity of the N, N-dimethylcyclohexylamine is 99.7%.
Detailed Description
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnation material; sequentially carrying out first drying, first grinding and first calcining on the impregnated material to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in a palladium salt solution to obtain an impregnation precursor; and sequentially carrying out second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst.
Unless otherwise specified, the starting materials for the preparation used in the present invention are commercially available.
The carrier is subjected to first impregnation in a selenium dioxide aqueous solution to obtain an impregnation material.
In the present invention, the support preferably includes an activated carbon support, an alumina support or a titania support. In the invention, the mesh number of the activated carbon carrier is preferably 200 to 400 meshes, more preferably 300 to 350 meshes; the specific surface area of the activated carbon carrier is preferably 1000-1500 m 2 (iv)/g, more preferably 1100 to 1300m 2 /g。
In the present invention, the activated carbon support is preferably nitric acid-treated activated carbon; the kind of the activated carbon is preferably coconut shell carbon.
In the present invention, the nitric acid treatment is preferably: adding activated carbon into a nitric acid solution, boiling, and filtering to obtain a filter cake;
and washing the filter cake with pure water until the pH value is 6-7, and drying to obtain the active carbon treated by the nitric acid.
In the present invention, the mass fraction of the nitric acid solution is preferably 2 to 15%, more preferably 9 to 10%; the mass of the nitric acid solution is preferably 10 to 20 times, more preferably 14 to 18 times that of the activated carbon; the boiling time is preferably 100 to 150min, more preferably 110 to 130min, and still more preferably 120min. According to the invention, the content of the impurity metal ions on the surface of the activated carbon can be reduced through nitric acid acidification, and the specific surface area and the pore structure of the activated carbon are improved.
In the present invention, the alumina support is preferably γ -alumina; the mesh number of the alumina carrier is preferably 100 to120 meshes; the specific surface area of the alumina carrier is preferably 100-500 m 2 A ratio of 200 to 300 m/g is more preferable 2 /g。
In the present invention, the titania support is preferably of the type P25 for commercial use, and the titania support has a specific surface area of preferably 50m 2 /g。
In the invention, the concentration of the selenium dioxide aqueous solution is preferably 1 to 5g/L, and more preferably 2 to 3g/L; the mass ratio of the carrier to the selenium dioxide aqueous solution is preferably 1 (3-20), more preferably 1 (5-10). In the present invention, the first dipping is preferably ultrasonic dipping, and the power of the ultrasonic dipping is preferably 40 to 100W, more preferably 60 to 100W, and further preferably 100W; the temperature of the ultrasonic impregnation is preferably 25-40 ℃, and more preferably 30-35 ℃; the time for the ultrasonic immersion is preferably 30 to 60min, and more preferably 40 to 60min.
After the impregnating material is obtained, the impregnating material is sequentially subjected to first drying, first grinding and first calcining to obtain the selenium composite carrier.
In the present invention, the temperature of the first drying is preferably 60 to 130 ℃, more preferably 70 to 120 ℃. In the present invention, the mesh number of the material obtained by the first grinding is preferably 100 to 400 mesh. In the invention, when the carrier is preferably an activated carbon carrier, the mesh number of the material obtained by the first grinding is preferably 200-400 meshes; when the carrier is preferably an alumina carrier or a titania carrier, the mesh number of the first ground material is preferably 100 to 150 mesh, more preferably 110 to 120 mesh.
In the present invention, the first calcination is preferably performed under a nitrogen atmosphere; the temperature of the first calcination is preferably 200 to 250 ℃, more preferably 210 to 230 ℃, and the time of the first calcination is preferably 3 to 6 hours, more preferably 4 to 5 hours.
After the selenium composite inorganic carrier is obtained, the selenium composite inorganic carrier is subjected to second impregnation in a palladium salt solution to obtain an impregnation precursor.
In the present invention, the palladium salt in the palladium salt solution preferably includes palladium chloride, palladium nitrate or palladium acetate. In the present invention, when the palladium salt is preferably palladium chloride, the palladium salt solution is preferably a hydrochloric acid solution of palladium chloride, and the concentration of hydrochloric acid in the hydrochloric acid solution of palladium chloride is preferably 1 to 3mol/L, and more preferably 1.5 to 2mol/L; when the palladium salt is preferably palladium nitrate, the palladium salt solution is preferably an aqueous solution of palladium nitrate; when the palladium salt is preferably palladium acetate, the palladium salt solution is preferably a solution of palladium acetate in methylene chloride.
In the present invention, the mass fraction of the palladium salt in the palladium salt solution is preferably 10 to 30g/L, and more preferably 10 to 20g/L. In the present invention, the mass ratio of the selenium composite carrier to the palladium salt solution is preferably 1 (5 to 20), and more preferably 1 (6 to 12).
In the present invention, the second dipping is preferably ultrasonic dipping, and the power of the ultrasonic dipping is preferably 40 to 100W, more preferably 60 to 100W, and further preferably 100W; the temperature of the ultrasonic impregnation is preferably 25-40 ℃, and more preferably 30-35 ℃; the time for the ultrasonic immersion is preferably 30 to 60min, and more preferably 40 to 60min.
According to the invention, the selenium dioxide and the palladium salt can be fully and uniformly adsorbed into the carrier respectively by preferably adopting an ultrasonic impregnation mode, and selenium is loaded firstly, then palladium is loaded, so that the dispersion degree of palladium is favorably improved, and the catalytic activity of the hydrogenation catalyst is favorably improved.
After the impregnated precursor is obtained, the impregnated precursor is subjected to second drying, second grinding, second calcining and reduction activation in sequence to obtain the hydrogenation catalyst.
In the present invention, the temperature of the second drying is preferably 80 to 130 ℃, more preferably 100 to 120 ℃.
The second drying and second grinding processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art.
After said second grinding, the present invention also preferably comprises sieving the obtained material. The screening process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In the present invention, the mesh number of the material obtained by screening is preferably 100 to 400 mesh. In the invention, when the carrier is preferably an activated carbon carrier, the mesh number of the materials obtained by screening is preferably 200-400 meshes; when the carrier is preferably an alumina carrier or a titanium dioxide carrier, the mesh number of the sieved material is preferably 100-150 meshes, and more preferably 110-120 meshes.
In the present invention, the second calcination is preferably performed under a nitrogen atmosphere; the temperature of the second calcination is preferably 200 to 250 ℃, and more preferably 210 to 230 ℃; the time of the second calcination is preferably 3 to 6 hours, more preferably 4 to 5 hours.
In the present invention, both the first calcination and the second calcination are preferably performed in a tube furnace.
In the present invention, the gas used for the reduction activation is hydrogen or a mixed gas of hydrogen and nitrogen, and the volume ratio of hydrogen to nitrogen in the mixed gas of hydrogen and nitrogen is preferably (1 to 9): 1, and more preferably (1 to 3): 1.
In the present invention, the temperature of the reduction activation is preferably 50 to 200 ℃, more preferably 80 to 200 ℃; the time for the reduction activation is preferably 1 to 3 hours, more preferably 2 to 3 hours. In the present invention, the reduction activation is preferably performed in a tube furnace. In the present invention, it is preferable that the reduction activation is followed by purging, the gas used for purging is preferably high-purity nitrogen, the temperature of the high-purity nitrogen is preferably 50 to 60 ℃, and the time of purging is preferably 0.5 to 1 hour, and more preferably 1 hour. The method blows away the active hydrogen remained on the surface of the catalyst after reduction activation through blowing so as to prevent the catalyst after reduction activation from being oxidized when encountering air and losing or reducing the catalytic activity.
The present invention preferably enables removal of moisture from the material by the first stage calcination and the second calcination, and then enables reduction of palladium in a compound state to metallic palladium by reduction activation.
The invention also provides a hydrogenation catalyst prepared by the preparation method in the scheme, which comprises an inorganic carrier and palladium and selenium loaded on the carrier; the mass percent of palladium in the hydrogenation catalyst is 2-10%, preferably 3-5%; the mass percent of selenium is 0.1-5%, preferably 0.2-3%.
The invention also provides a preparation method of the N, N-dimethylcyclohexylamine, which comprises the following steps: mixing a dimethylamine raw material, cyclohexanone and a hydrogenation catalyst, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain N, N-dimethylcyclohexylamine; the hydrogenation catalyst is the hydrogenation catalyst in the scheme.
In the present invention, the mixing is preferably: the dimethylamine is mixed with the hydrogenation catalyst prior to addition of cyclohexanone.
In the present invention, the dimethylamine is preferably mixed in the form of liquid dimethylamine or an aqueous dimethylamine solution. In the present invention, the purity of the liquid dimethylamine is preferably 98% or more. In the present invention, the mass fraction of dimethylamine in the dimethylamine aqueous solution is preferably 35 to 42%.
In the present invention, the step of mixing the dimethylamine and the hydrogenation catalyst preferably comprises: the hydrogenation catalyst was added to the reactor, the reactor was purged with high-purity nitrogen gas at room temperature to remove air, then the dimethylamine was added to the reactor, hydrogen gas was fed into the reactor, and then stirring and heating were carried out.
In the present invention, the reactor preferably comprises a tank reactor or a loop reactor; the pressure of the hydrogen in the reactor is preferably 0.5 to 3MPa, more preferably 1 to 3MPa; the rotation speed of the stirring is preferably 100 to 800r/min, more preferably 400 to 600r/min, and the end temperature of the heating is preferably 40 to 90 ℃, more preferably 40 to 60 ℃. In the present invention, the mass ratio of the cyclohexanone to the hydrogenation catalyst is preferably (5 to 500): 1, more preferably (100 to 400): 1, and the mass ratio of the dimethylamine to the cyclohexanone is preferably (1 to 1.1): 1, more preferably (1 to 1.05): 1.
In the invention, the cyclohexanone is preferably added dropwise; the dropping rate is preferably 0.0001 to 25kg/min.
In the present invention, the pressure of the hydrogenation reaction is preferably 1 to 4MPa, more preferably 1 to 3MPa. In the present invention, the time of the hydrogenation reaction is preferably calculated from the time of adding cyclohexanone, and the time of the hydrogenation reaction preferably includes the time of adding cyclohexanone and the time of continuing the reaction after the addition of cyclohexanone is completed. In the invention, the time for adding cyclohexanone is preferably 10-600 min, more preferably 30-500 min, and more preferably 60-300 min; the time for continuing the reaction after the cyclohexanone is added is preferably 30-200 min, and more preferably 60-120 min. In the present invention, the temperature of the hydrogenation reaction is preferably 45 to 135 ℃, more preferably 115 to 125 ℃.
After the hydrogenation reaction, the method also preferably comprises the step of carrying out post-treatment on the obtained feed liquid; the post-treatment preferably comprises cooling and filtering the feed liquid to obtain filtrate; the filtrate preferably comprises N, N-dimethylcyclohexylamine. In the present invention, the temperature of the cooled feed liquid is preferably 40 ℃ or lower. The cooling and filtering processes are not particularly limited in the present invention and may be performed by processes well known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Adding 5.5g of activated carbon into 100g of dilute nitric acid solution with the mass fraction of 10%, wherein the mesh number of the activated carbon carrier is 300 meshes, and the specific surface area is 1210m 2 Heating and boiling for 120min, filtering, washing a filter cake with pure water until the pH value is 6-7, and drying the activated carbon washed with the pure water at 85 ℃ for 12h for later use;
weighing 0.039g of selenium dioxide, and dissolving in 20g of purified water to obtain a selenium dioxide aqueous solution; adding the activated carbon after acid treatment into a selenium dioxide aqueous solution, and performing ultrasonic impregnation with the ultrasonic power of 100W, the impregnation temperature of 30 ℃ and the impregnation time of 60min, so as to obtain an impregnation material after the impregnation is completed;
drying the impregnated material at 80 ℃ for 8h, grinding the dried material into powder with the mesh number of 300 meshes, placing the powder in a tubular furnace, introducing nitrogen for protection, and keeping the temperature at 250 ℃ for 5h to obtain a selenium composite carrier;
adding 4.9g of selenium composite carrier into 20.8mL of palladium chloride hydrochloric acid solution with palladium content of 0.0125g/mL, wherein the concentration of hydrochloric acid is 1.6mol/L, carrying out ultrasonic impregnation with the ultrasonic power of 100W, ensuring that the impregnation temperature is 30 ℃, the impregnation time is 60min, and obtaining an impregnation precursor after the impregnation is finished;
drying the impregnated precursor at 80 ℃ for 8h, grinding the dried material into powder, screening, and screening the obtained powder with the mesh number of 120 meshes; and (2) placing the powder in a tube furnace, introducing nitrogen for protection, keeping the temperature at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing the unactivated catalyst in high-purity hydrogen at 200 ℃ for 2 hours, blowing the catalyst for 1 hour by adopting high-purity nitrogen at 50 ℃ after the reduction is finished, cooling to room temperature, and taking out the catalyst to obtain the hydrogenation catalyst. The hydrogenation catalyst contained 5% by mass of palladium and 0.5% by mass of selenium.
Example 2
The amount of selenium dioxide was adjusted to 0.078g, and the preparation conditions were the same as in example 1. The mass percent of palladium and the mass percent of selenium in the obtained hydrogenation catalyst are respectively 5% and 1%.
Example 3
Weighing 0.039g of selenium dioxide, and dissolving in 20g of purified water to obtain a selenium dioxide aqueous solution; adding 5.5g of gamma-alumina into the selenium dioxide aqueous solution, wherein the mesh number of the gamma-alumina is 120 meshes, and the specific surface area is 210m 2 Performing ultrasonic impregnation with the ultrasonic power of 100W at the impregnation temperature of 30 ℃ for 60min to obtain an impregnation material after the impregnation is finished;
drying the impregnated material at 100 ℃ for 8h, grinding the dried material into powder with the mesh number of 120 meshes, placing the powder in a tubular furnace, introducing nitrogen for protection, and keeping the temperature at 250 ℃ for 5h to obtain a selenium composite carrier;
adding 4.9g of selenium composite carrier into 20.8mL of palladium chloride hydrochloric acid solution with the palladium content of 0.0125g/mL and the hydrochloric acid concentration of 1.6mol/L, carrying out ultrasonic impregnation with the ultrasonic power of 100W, ensuring the impregnation temperature to be 30 ℃, and the impregnation time to be 60min, and obtaining an impregnation precursor after the impregnation is finished;
drying the impregnated precursor at 120 ℃ for 8h, grinding the dried material into powder, screening, and screening the powder with the mesh number of 120 meshes; placing the powder in a tube furnace, introducing nitrogen for protection, keeping the temperature at 250 ℃ for 5h to obtain an unactivated catalyst, then reducing the unactivated catalyst in high-purity hydrogen at 200 ℃ for 2h, purging the catalyst for 1h by adopting high-purity nitrogen at 50 ℃ after the reduction is finished, cooling the catalyst to room temperature, and taking the catalyst out to obtain the hydrogenation catalyst. The hydrogenation catalyst contained 5% by mass of palladium and 0.5% by mass of selenium.
Example 4
The amount of selenium dioxide was adjusted to 0.078g, and the preparation conditions were the same as in example 3. The mass percent of palladium and the mass percent of selenium in the obtained hydrogenation catalyst are respectively 5% and 1%.
Example 5
Weighing 0.039g of selenium dioxide, and dissolving in 20g of purified water to obtain a selenium dioxide aqueous solution; 5.5g of titanium dioxide (commercial P25 type) are added to an aqueous selenium dioxide solution, the specific surface area of the titanium dioxide support being 50m 2 Performing ultrasonic impregnation with the ultrasonic power of 100W at about 30 ℃ for 60min to obtain an impregnated material after the impregnation is finished;
drying the impregnated material at 100 ℃ for 8h, grinding the dried material into powder with the mesh number of 120 meshes, placing the powder in a tubular furnace, introducing nitrogen for protection, and keeping the temperature at 250 ℃ for 5h to obtain a selenium composite inorganic carrier;
adding 4.9g of selenium composite inorganic carrier into 20.8mL of palladium chloride hydrochloric acid solution with the palladium content of 0.0125g/mL and the hydrochloric acid concentration of 1.6mol/L, carrying out ultrasonic impregnation with the ultrasonic power of 100W, ensuring the impregnation temperature to be about 30 ℃, and the impregnation time to be 60min, and obtaining an impregnation precursor after the impregnation is finished;
drying the impregnated precursor at 120 ℃ for 8h, grinding the dried material into powder, screening, and screening the powder with the mesh number of 120 meshes; and (2) placing the powder in a tube furnace, introducing nitrogen for protection, keeping the temperature at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing the unactivated catalyst in high-purity hydrogen at 200 ℃ for 2 hours, blowing the catalyst for 1 hour by adopting high-purity nitrogen at about 50 ℃ after the reduction is finished, cooling to room temperature, and taking out the catalyst to obtain the hydrogenation catalyst. The hydrogenation catalyst contained 5% by mass of palladium and 0.5% by mass of selenium.
Example 6
The amount of selenium dioxide was adjusted to 0.078g, and the preparation conditions were the same as in example 5. The mass percent of palladium and the mass percent of selenium in the obtained hydrogenation catalyst are respectively 5% and 1%.
Comparative example 1
In the preparation process, activated carbon after acid treatment is not added into a selenium dioxide aqueous solution for ultrasonic impregnation, and is directly added into a palladium chloride hydrochloric acid solution for ultrasonic impregnation, and the rest conditions are the same as in example 1, so that the mass percent of palladium in the obtained catalyst is 5%.
Comparative example 2
During the preparation process, the gamma-alumina is not added into the selenium dioxide aqueous solution for ultrasonic impregnation, but is directly added into the palladium chloride hydrochloric acid solution for ultrasonic impregnation, the rest preparation conditions are the same as those in example 3, and the mass percent of palladium in the obtained catalyst is 5%.
Comparative example 3
In the preparation process, titanium dioxide is not added into the selenium dioxide aqueous solution for ultrasonic impregnation, but is directly added into the palladium chloride hydrochloric acid solution for ultrasonic impregnation, and the rest preparation conditions are the same as those in example 5, so that the mass percent of palladium in the obtained catalyst is 5%.
Application example 1
Adding 0.3g of hydrogenation catalyst obtained in examples 1-6 and catalyst obtained in comparative examples 1-3 into a 300mL reaction kettle respectively, screwing the reaction kettle, blowing by using high-purity nitrogen for 5min at room temperature, removing air in the reaction kettle, pumping 35g of liquid dimethylamine into the reaction kettle by using a plunger pump, pumping hydrogen into the reaction kettle until the pressure in the reactor is 0.5MPa, starting stirring at the rotating speed of 600r/min, heating to 55 ℃, supplementing hydrogen into the reactor until the pressure is 2MPa, dripping 70g of cyclohexanone into the reaction kettle by using a advection pump for 240min, controlling the reaction temperature to be 115 ℃, keeping the hydrogen pressure at 2.5MPa, continuing to react for 120min after the dripping of the cyclohexanone is finished, cooling the reaction kettle to be below 40 ℃ after the reaction is finished, filtering and recovering the catalyst, and carrying out gas chromatography on the obtained filtrate. The gas chromatographic analysis conditions were: HP-5 chromatographic column, vaporizing chamber temperature 260 deg.C, FID detector temperature 280 deg.C, column box temperature raising program of 80 deg.C for 2min,10 deg.C/min for 260 deg.C for 5min. And respectively calculating the cyclohexanone conversion rate, the selectivity of the N, N-dimethylcyclohexylamine and the selectivity of the cyclohexanol according to the detection result. The catalytic effects of the hydrogenation catalysts obtained in examples 1 to 6 and the catalysts obtained in comparative examples 1 to 3 are shown in Table 1.
TABLE 1 catalytic Effect of hydrogenation catalysts obtained in examples 1 to 6 and catalysts obtained in comparative examples 1 to 3
| Item | Conversion of cyclohexanone/% | N, N-dimethylcyclohexylamine selectivity% | Cyclohexanol selectivity/%% |
| Example 1 | 99.9 | 99.7 | 0.01 |
| Example 2 | 98.9 | 99.7 | 0.01 |
| Example 3 | 100 | 91.2 | 8.6 |
| Example 4 | 100 | 94.6 | 5.2 |
| Example 5 | 100 | 95.7 | 4.1 |
| Example 6 | 100 | 96.4 | 3.4 |
| Comparative example 1 | 94.6 | 98.9 | 0.2 |
| Comparative example 2 | 100 | 81.4 | 18.4 |
| Comparative example 3 | 100 | 86.2 | 13.6 |
According to the detection results in table 1, comparing the data of examples 1 and 2 and comparative example 1, the data of examples 3 and 4 and comparative example 2, and the data of examples 5 and 6 and comparative example 3, respectively, it can be seen that the doping with selenium before the carrier supports palladium is beneficial to improving the selectivity of N, N-dimethylcyclohexylamine and the activity of cyclohexanone in the reaction and improving the hydrogenation catalytic effect of the catalyst. According to the invention, activated carbon is used as a carrier, selenium is doped, and then palladium is loaded, so that the obtained catalyst has the best catalytic hydrogenation effect, the selectivity of N, N-dimethylcyclohexylamine can reach 99.7%, the selectivity of cyclohexanol is 0.01%, and the generation of by-products can be reduced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps:
carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnation material;
sequentially carrying out first drying, first grinding and first calcining on the impregnated material to obtain a selenium composite carrier;
carrying out second impregnation on the selenium composite carrier in a palladium salt solution to obtain an impregnation precursor;
and sequentially carrying out second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst.
2. The production method according to claim 1, wherein the support comprises an activated carbon support, an alumina support, or a titania support; the concentration of the selenium dioxide aqueous solution is 1-5 g/L, and the mass ratio of the carrier to the selenium dioxide aqueous solution is 1 (3-20).
3. The method according to claim 1, wherein the first calcination and the second calcination are carried out under a nitrogen atmosphere, and the temperatures of the first calcination and the second calcination are independently 200 to 250 ℃ and the times are independently 3 to 6 hours.
4. The production method according to claim 1, wherein the gas used for the reduction activation is hydrogen gas or a mixed gas of hydrogen gas and nitrogen gas; the temperature of the reduction activation is 50-200 ℃, and the time is 1-3 h.
5. The method according to claim 1, wherein the palladium salt in the palladium salt solution includes palladium chloride, palladium nitrate, or palladium acetate; the mass fraction of the palladium salt in the palladium salt solution is 10-30 g/L; the mass ratio of the selenium composite carrier to the palladium salt solution is 1 (5-20).
6. The hydrogenation catalyst prepared by the preparation method of any one of claims 1 to 5, which comprises a carrier and palladium and selenium loaded on the carrier; the mass percent of palladium in the hydrogenation catalyst is 2-10%, and the mass percent of selenium is 0.1-5%.
7. A preparation method of N, N-dimethylcyclohexylamine is characterized by comprising the following steps:
mixing dimethylamine, cyclohexanone and a hydrogenation catalyst, and carrying out hydrogenation reaction in a hydrogen atmosphere to obtain the N, N-dimethylcyclohexylamine;
the hydrogenation catalyst is the hydrogenation catalyst of claim 6.
8. The method of claim 7, wherein the mixing is: the dimethylamine is mixed with the hydrogenation catalyst prior to addition of cyclohexanone.
9. The production method according to claim 7, wherein the mass ratio of the cyclohexanone to the hydrogenation catalyst is (5-500): 1, and the mass ratio of the dimethylamine to the cyclohexanone is (1-1.1): 1.
10. The production method according to claim 8 or 9, wherein the pressure of the hydrogenation reaction is 1 to 4MPa;
the time of the hydrogenation reaction is calculated by adding cyclohexanone, the time of the hydrogenation reaction comprises the time of adding cyclohexanone and the time of continuing the reaction after adding cyclohexanone is finished, the time of adding cyclohexanone is 10-600 min, and the time of continuing the reaction is 30-200 min; the temperature of the hydrogenation reaction is 45-135 ℃.
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