CN115814820B - 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 78
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 title abstract description 23
- 238000005470 impregnation Methods 0.000 claims abstract description 72
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 56
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 39
- 239000011669 selenium Substances 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 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 40
- 239000000463 material Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 72
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 42
- 238000001354 calcination Methods 0.000 abstract description 24
- 150000002940 palladium Chemical class 0.000 abstract description 22
- 230000004913 activation Effects 0.000 abstract description 15
- 239000012266 salt solution Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 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
- 239000000706 filtrate Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 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
- 239000012298 atmosphere Substances 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
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000005086 pumping 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
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and provides a hydrogenation catalyst, a preparation method thereof and a preparation method of N, N-dimethylcyclohexylamine. The method comprises the steps of carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnating compound; sequentially carrying out first drying, first grinding and first calcining on the impregnating compound to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in 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. According to the invention, selenium is doped into a carrier and palladium is loaded, so that the selenium-doped palladium-based catalyst is obtained. In the invention, the doped selenium can increase the dispersity of palladium on the surface of the carrier and generate a synergistic effect with the palladium, and is beneficial to improving the activity of the catalyst and the selectivity of hydrogenation reaction in the preparation of N, N-dimethyl cyclohexylamine by taking cyclohexanone, dimethylamine and hydrogen as raw materials.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, 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 of rigid polyurethane foam, has catalytic action on gel and foaming, is a strong initial catalyst for foam reaction, and can also be used as auxiliary catalysts for molding soft foam, semi-rigid foam and the like. At present, the N, N-dimethylcyclohexylamine is synthesized by mainly taking cyclohexanone, dimethylamine and hydrogen as raw materials in industry.
Chinese patent publication No. CN104892429a discloses a method for synthesizing N, N-dimethylcyclohexane using cyclohexanone, ammonia, hydrogen and formaldehyde as raw materials. 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 load of nickel is 0.1% -50%, the reaction is carried out in two sections of fixed bed reactors connected in series, the reaction pressure is 6MPa, the reaction temperature in the first section is 120 ℃, the reaction temperature in the second section is 130 ℃, and finally, the yield of N, N-dimethyl cyclohexane is 84.2%, and the yield of N-methyl dicyclohexylamine is 10.3%.
At present, in the method for synthesizing N, N-dimethyl cyclohexane by using cyclohexanone as a raw material, the main problems are as follows: under the condition of little excessive dimethylamine, the existing catalyst, such as palladium catalyst, still has the phenomenon that cyclohexanone is converted incompletely or the cyclohexanone is hydrogenated to form cyclohexanol byproducts, and the final reaction product still has cyclohexanone or cyclohexanol residues, so that the conversion rate of cyclohexanone and the selectivity of dimethylcyclohexylamine are lower.
Disclosure of Invention
In view of this, the present invention provides a hydrogenation catalyst, a process for producing the same and a process for producing N, N-dimethylcyclohexylamine. The hydrogenation catalyst provided by the invention has good catalytic effect, and has high conversion rate of raw material cyclohexanone and selectivity of product N, N-dimethyl cyclohexylamine in the reaction of catalyzing the micro-excess synthesis of N, N-dimethyl cyclohexylamine by 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 the carrier in a selenium dioxide aqueous solution to obtain an impregnating compound;
sequentially carrying out first drying, first grinding and first calcining on the impregnating compound to obtain a selenium composite carrier;
carrying out second impregnation on the selenium composite carrier in palladium salt solution to obtain an impregnation precursor;
and sequentially performing 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 titania carrier; the concentration of the selenium dioxide aqueous 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 calcination and the second calcination are performed under a nitrogen atmosphere, and the temperature of the first calcination and the second calcination is independently 200-250 ℃ and the time is independently 3-6 h.
Preferably, the gas used for the reduction and activation is hydrogen or a mixed gas of hydrogen and nitrogen; the reduction and activation temperature 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 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 of the scheme, which comprises a carrier and palladium and selenium loaded on the carrier; the mass percentage of palladium in the hydrogenation catalyst is 2-10%, and the mass percentage 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: mixing the dimethylamine and the hydrogenation catalyst, and then adding cyclohexanone.
Preferably, the mass ratio of the cyclohexanone to the hydrogenation catalyst is (5-500): 1, and the mass ratio of dimethylamine to cyclohexanone is (1-1.1): 1.
Preferably, the pressure of the hydrogenation reaction is 1-4 MPa;
the hydrogenation reaction time is calculated by starting the addition of cyclohexanone, and comprises the addition time of cyclohexanone and the continuous reaction time after the addition of cyclohexanone is finished, wherein the addition time of cyclohexanone is 10-600 min, and the continuous reaction time 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 the carrier in a selenium dioxide aqueous solution to obtain an impregnating compound; sequentially carrying out first drying, first grinding and first calcining on the impregnating compound to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in palladium salt solution to obtain an impregnation precursor; and sequentially performing second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst. According to the invention, selenium is doped into a carrier and palladium is loaded, so that the selenium-doped palladium-based catalyst is obtained. In the invention, the doped selenium can increase the dispersity of palladium on the surface of the carrier, and has a synergistic effect with palladium, thereby being beneficial to improving the activity of the catalyst and the selectivity of hydrogenation reaction.
The invention also provides a hydrogenation catalyst prepared by the preparation method. The catalyst prepared by the invention has good catalytic hydrogenation effect, and has high conversion rate of raw material cyclohexanone and selectivity of product N, N-dimethyl cyclohexylamine in the reaction of catalyzing the micro-excess synthesis of N, N-dimethyl cyclohexylamine by dimethylamine.
The invention also provides a preparation method of the N, N-dimethyl cyclohexane. The preparation method provided by the invention adopts the hydrogenation catalyst to catalyze the reaction of cyclohexanone, dimethylamine and hydrogen to obtain the N, N-dimethyl cyclohexane, and the conversion rate of raw material cyclohexanone and the selectivity of the product N, N-dimethyl cyclohexane are high. Experimental data of the embodiment of the invention show that the conversion rate of raw material cyclohexanone is 99.9% at the highest, and the selectivity of N, N-dimethylcyclohexylamine is 99.7% at the highest.
Detailed Description
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: carrying out first impregnation on the carrier in a selenium dioxide aqueous solution to obtain an impregnating compound; sequentially carrying out first drying, first grinding and first calcining on the impregnating compound to obtain a selenium composite carrier; carrying out second impregnation on the selenium composite carrier in palladium salt solution to obtain an impregnation precursor; and sequentially performing second drying, second grinding, second calcining and reduction activation on the impregnated precursor to obtain the hydrogenation catalyst.
The preparation raw materials used in the invention are all commercially available unless otherwise specified.
The method comprises the step of carrying out first impregnation on a carrier in a selenium dioxide aqueous solution to obtain an impregnating compound.
In the present invention, the carrier preferably includes an activated carbon carrier, an alumina carrier, or a titania carrier. In the invention, the mesh number of the activated carbon carrier is preferably200 to 400 mesh, more preferably 300 to 350 mesh; the specific surface area of the active carbon carrier is preferably 1000-1500 m 2 Preferably 1100-1300 m 2 /g。
In the present invention, the activated carbon support is preferably nitric acid-treated activated carbon; the type of the activated carbon is preferably coconut shell carbon.
In the present invention, the nitric acid treatment is preferably: adding active carbon into 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 nitric acid treated activated carbon.
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 of the mass of the activated carbon; the boiling time is preferably 100 to 150 minutes, more preferably 110 to 130 minutes, and still more preferably 120 minutes. The invention can reduce the content of the impurity metal ions on the surface of the activated carbon and improve the specific surface area and pore structure of the activated carbon by nitric acid acidification.
In the present invention, the alumina carrier is preferably gamma-alumina; the mesh number of the alumina carrier is preferably 100-120 meshes; the specific surface area of the alumina carrier is preferably 100-500 m 2 Preferably 200 to 300m 2 /g。
In the present invention, the type of the titania carrier is preferably a commercial P25 type, and the specific surface area of the titania carrier is preferably 50m 2 /g。
In the present invention, the concentration of the selenium dioxide aqueous solution is preferably 1 to 5g/L, 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 impregnation is preferably ultrasonic impregnation, and the power of the ultrasonic impregnation is preferably 40 to 100W, more preferably 60 to 100W, and further preferably 100W; the temperature of the ultrasonic impregnation is preferably 25-40 ℃, more preferably 30-35 ℃; the time of the ultrasonic impregnation is preferably 30 to 60 minutes, more preferably 40 to 60 minutes.
After the impregnating material is obtained, the impregnating material is subjected to first drying, first grinding and first calcination in sequence 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 present invention, when the carrier is preferably an activated carbon carrier, the mesh number of the material obtained by the first grinding is preferably 200 to 400 mesh; when the support is preferably an alumina support or a titania support, the mesh number of the material obtained by the first grinding 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 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 hydrochloric acid concentration in the hydrochloric acid solution of palladium chloride is preferably 1 to 3mol/L, 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 dichloromethane solution of palladium acetate.
In the present invention, the mass fraction of the palladium salt in the palladium salt solution is preferably 10 to 30g/L, 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 (5-20), more preferably 1 (6-12).
In the present invention, the second impregnation is preferably ultrasonic impregnation, and the power of the ultrasonic impregnation is preferably 40 to 100W, more preferably 60 to 100W, and further preferably 100W; the temperature of the ultrasonic impregnation is preferably 25-40 ℃, more preferably 30-35 ℃; the time of the ultrasonic impregnation is preferably 30 to 60 minutes, more preferably 40 to 60 minutes.
According to the invention, selenium dioxide and palladium salt can be fully and uniformly adsorbed into the carrier by ultrasonic impregnation, and selenium and palladium are loaded firstly, so that the dispersity of palladium is improved, and the catalytic activity of the hydrogenation catalyst is improved.
After the impregnated precursor is obtained, the impregnated precursor is subjected to second drying, second grinding, second calcining and reduction activation in sequence, so that the hydrogenation catalyst is obtained.
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, and may be performed by processes well known to those skilled in the art.
After the second grinding, the present invention also preferably includes sieving the resulting material. The process of the screening is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the mesh number of the material obtained by the screening is preferably 100 to 400 mesh. In the present invention, when the carrier is preferably an activated carbon carrier, the mesh number of the material obtained by the screening is preferably 200 to 400 mesh; when the support is preferably an alumina support or a titania support, the mesh number of the material obtained by the sieving is preferably 100 to 150 mesh, more preferably 110 to 120 mesh.
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 ℃, more preferably 210 to 230 ℃; the second calcination time 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 and 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, 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 reductive activation is preferably performed in a tube furnace. In the present invention, the reduction activation is preferably followed by purging, the gas used for the purging is preferably high-purity nitrogen, the temperature of the high-purity nitrogen is preferably 50-60 ℃, and the time of the purging is preferably 0.5-1 h, and more preferably 1h. The active hydrogen remained on the surface of the catalyst after reduction and activation is blown away by blowing, so that the catalyst after reduction and activation is prevented from being oxidized by air and losing or reducing the catalytic activity.
The invention can remove moisture in the material by the first stage calcination and the second calcination, and then the palladium in a compound state can be reduced into metallic palladium by reduction activation.
The invention also provides a hydrogenation catalyst prepared by the preparation method of the scheme, which comprises an inorganic carrier and palladium and selenium loaded on the carrier; the mass percentage of palladium in the hydrogenation catalyst is 2-10%, preferably 3-5%; the mass percentage 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 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: mixing the dimethylamine and the hydrogenation catalyst, and then adding 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 not less than 98%. In the present invention, the mass fraction of dimethylamine in the aqueous dimethylamine 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 at room temperature to remove air, after which the dimethylamine was added to the reactor, hydrogen was introduced into the reactor, and then stirred and heated.
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 stirring speed is preferably 100 to 800r/min, more preferably 400 to 600r/min, and the heating end temperature 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 dimethylamine to cyclohexanone is preferably (1 to 1.1): 1, more preferably (1 to 1.05): 1.
In the invention, the adding mode of the cyclohexanone is preferably dropwise adding; 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 hydrogenation reaction time is preferably calculated from the time when cyclohexanone is added, and the hydrogenation reaction time preferably includes the time when cyclohexanone is added and the time when the reaction is continued after cyclohexanone is added. In the present invention, the time for adding cyclohexanone is preferably 10 to 600 minutes, more preferably 30 to 500 minutes, and still more preferably 60 to 300 minutes; the time for continuing the reaction after the completion of the addition of cyclohexanone is preferably 30 to 200 minutes, more preferably 60 to 120 minutes. 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 invention also preferably comprises post-treatment of the obtained feed liquid; the post-treatment preferably comprises cooling and filtering the feed liquid to obtain a 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 solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
Adding 5.5g of active carbon into 100g of 10% dilute nitric acid solution, wherein the mesh number of the active carbon carrier is 300 meshes, and the specific surface area is 1210m 2 Heating and boiling for 120min, filtering, washing the filter cake with pure water until the pH value is between 6 and 7, and drying the activated carbon washed by the pure water at 85 ℃ for 12h for later use;
0.039g of selenium dioxide is weighed and dissolved in 20g of purified water to obtain a selenium dioxide aqueous solution; adding the activated carbon subjected to acid treatment into a selenium dioxide aqueous solution, carrying out ultrasonic impregnation, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60 minutes, and the impregnation material is obtained after the impregnation is completed;
drying the impregnating material at 80 ℃ for 8 hours, grinding the dried material into powder with 300 meshes, placing the powder in a tube furnace, introducing nitrogen for protection, and maintaining at 250 ℃ for 5 hours 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, carrying out ultrasonic impregnation with hydrochloric acid concentration of 1.6mol/L, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60min, and obtaining an impregnation precursor after the impregnation is completed;
drying the impregnated precursor at 80 ℃ for 8 hours, grinding the dried material into powder, screening, and screening the powder with 120 meshes; placing the powder in a tube furnace, introducing nitrogen for protection, maintaining at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing in high-purity hydrogen at 200 ℃ for 2 hours, purging with high-purity nitrogen at 50 ℃ for 1 hour after the reduction is completed, cooling to room temperature, and taking out to obtain the hydrogenation catalyst. The mass percent of palladium in the hydrogenation catalyst is 5 percent, and the mass percent of selenium is 0.5 percent.
Example 2
The amount of selenium dioxide was adjusted to 0.078g, and the other preparation conditions were the same as in example 1. The mass percentage of palladium in the obtained hydrogenation catalyst is 5 percent, and the mass percentage of selenium is 1 percent.
Example 3
0.039g of selenium dioxide is weighed and dissolved in 20g of purified water to obtain a selenium dioxide aqueous solution; adding 5.5g of gamma-alumina with 120 meshes and specific surface area of 210m into selenium dioxide water solution 2 Carrying out ultrasonic impregnation, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60min, and the impregnation material is obtained after the impregnation is completed;
drying the impregnating material at 100 ℃ for 8 hours, grinding the dried material into powder with the mesh number of 120 meshes, placing the powder in a tube furnace, introducing nitrogen for protection, and maintaining at 250 ℃ for 5 hours 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, carrying out ultrasonic impregnation with hydrochloric acid concentration of 1.6mol/L, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60min, and obtaining an impregnation precursor after the impregnation is completed;
drying the impregnated precursor at 120 ℃ for 8 hours, 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, maintaining at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing in high-purity hydrogen at 200 ℃ for 2 hours, purging with high-purity nitrogen at 50 ℃ for 1 hour after the reduction is completed, cooling to room temperature, and taking out to obtain the hydrogenation catalyst. The mass percent of palladium in the hydrogenation catalyst is 5 percent, and the mass percent of selenium is 0.5 percent.
Example 4
The amount of selenium dioxide was adjusted to 0.078g, and the other preparation conditions were the same as in example 3. The mass percentage of palladium in the obtained hydrogenation catalyst is 5 percent, and the mass percentage of selenium is 1 percent.
Example 5
0.039g of selenium dioxide is weighed and dissolved in 20g of purified water to obtain a selenium dioxide aqueous solution; 5.5g of titanium dioxide (commercial P25 type) are added to the aqueous selenium dioxide solution, the specific surface area of the titanium dioxide carrier being 50m 2 Carrying out ultrasonic impregnation, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be about 30 ℃, the impregnation time is 60 minutes, and the impregnation material is obtained after the impregnation is completed;
drying the impregnating material at 100 ℃ for 8 hours, grinding the dried material into powder with the mesh number of 120 meshes, placing the powder in a tube furnace, introducing nitrogen for protection, and keeping at 250 ℃ for 5 hours 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 palladium content of 0.0125g/mL, carrying out ultrasonic impregnation with hydrochloric acid concentration of 1.6mol/L, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be about 30 ℃, the impregnation time is 60min, and obtaining an impregnation precursor after the impregnation is completed;
drying the impregnated precursor at 120 ℃ for 8 hours, 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, maintaining at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing in high-purity hydrogen at 200 ℃ for 2 hours, purging with high-purity nitrogen at about 50 ℃ for 1 hour after the reduction is completed, cooling to room temperature, and taking out to obtain the hydrogenation catalyst. The mass percent of palladium in the hydrogenation catalyst is 5 percent, and the mass percent of selenium is 0.5 percent.
Example 6
The amount of selenium dioxide was adjusted to 0.078g, and the other preparation conditions were the same as in example 5. The mass percentage of palladium in the obtained hydrogenation catalyst is 5 percent, and the mass percentage of selenium is 1 percent.
Comparative example 1
In the preparation process, the activated carbon subjected to 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, wherein the mass percentage of palladium in the obtained catalyst is 5%.
Comparative example 2
In the preparation process, gamma-alumina is not added into selenium dioxide aqueous solution for ultrasonic impregnation, and is directly added into palladium chloride hydrochloric acid solution for ultrasonic impregnation, and the rest preparation conditions are the same as those in example 3, wherein the mass percentage of palladium in the obtained catalyst is 5%.
Comparative example 3
In the preparation process, titanium dioxide is not added into selenium dioxide aqueous solution for ultrasonic impregnation, and is directly added into palladium chloride hydrochloric acid solution for ultrasonic impregnation, and the rest preparation conditions are the same as in example 5, wherein the mass percentage of palladium in the obtained catalyst is 5%.
Application example 1
Adding 0.3g of the hydrogenation catalyst obtained in examples 1-6 and the catalyst obtained in comparative examples 1-3 into a 300mL reaction kettle respectively, screwing the reaction kettle, purging the reaction kettle with high-purity nitrogen at room temperature for 5min, exhausting air in the reaction kettle, pumping 35g of liquid dimethylamine into the reaction kettle by a plunger pump, filling hydrogen into the reaction kettle to a pressure of 0.5MPa, starting stirring at a rotating speed of 600r/min, heating to 55 ℃, supplementing hydrogen to a pressure of 2MPa in the reaction kettle, dripping 70g of cyclohexanone into the reaction kettle by a advection pump for 240min, controlling the reaction temperature to 115 ℃, keeping the hydrogen pressure to 2.5MPa, continuing to react for 120min after the cyclohexanone dripping is finished, cooling the reaction kettle to below 40 ℃, filtering, recovering the catalyst, and performing gas chromatographic analysis on the obtained filtrate. The gas chromatographic analysis conditions were: HP-5 chromatographic column, vaporization chamber temperature 260 ℃, FID detector temperature 280 ℃, column box temperature program 80 ℃ for 2min,10 ℃/min temperature to 260 ℃ for 5min. And respectively calculating the cyclohexanone conversion rate, the selectivity of N, N-dimethylcyclohexylamine and the selectivity of 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
| Project | Cyclohexanone conversion/% | 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 of table 1, the data of examples 1, 2 and 1, the data of examples 3, 4 and 2, and the data of examples 5, 6 and 3, respectively, it can be seen that doping with selenium before palladium loading is carried out on the carrier, which is beneficial to improving the selectivity of N, N-dimethyl cyclohexylamine and the activity of cyclohexanone in the reaction and improving the hydrogenation catalytic effect of the catalyst. According to the invention, the active carbon is used as a carrier, the palladium is loaded after selenium doping, the catalytic hydrogenation effect of the obtained catalyst is optimal, the selectivity of N, N-dimethylcyclohexylamine can reach 99.7%, the selectivity of cyclohexanol is 0.01%, and the catalyst is more beneficial to reducing the generation of byproducts.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps:
adding 5.5g of active carbon into 100g of 10% dilute nitric acid solution, wherein the mesh number of the active carbon carrier is 300 meshes, and the specific surface area is 1210m 2 /g, heating and boiling for 120minFiltering, washing a filter cake with pure water until the pH value is between 6 and 7, and drying the activated carbon washed by the pure water at 85 ℃ for 12 hours for later use;
0.039g of selenium dioxide is weighed and dissolved in 20g of purified water to obtain a selenium dioxide aqueous solution; adding the activated carbon subjected to acid treatment into a selenium dioxide aqueous solution, carrying out ultrasonic impregnation, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60 minutes, and the impregnation material is obtained after the impregnation is completed;
drying the impregnating material at 80 ℃ for 8 hours, grinding the dried material into powder with 300 meshes, placing the powder in a tube furnace, introducing nitrogen for protection, and maintaining at 250 ℃ for 5 hours 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, carrying out ultrasonic impregnation with hydrochloric acid concentration of 1.6mol/L, wherein the ultrasonic power is 100W, the impregnation temperature is ensured to be 30 ℃, the impregnation time is 60min, and obtaining an impregnation precursor after the impregnation is completed;
drying the impregnated precursor at 80 ℃ for 8 hours, grinding the dried material into powder, screening, and screening the powder with 120 meshes; placing the powder in a tube furnace, introducing nitrogen for protection, maintaining at 250 ℃ for 5 hours to obtain an unactivated catalyst, then reducing in high-purity hydrogen at 200 ℃ for 2 hours, purging with high-purity nitrogen at 50 ℃ for 1 hour after the reduction is completed, cooling to room temperature, and taking out to obtain a hydrogenation catalyst; the mass percent of palladium in the hydrogenation catalyst is 5 percent, and the mass percent of selenium is 0.5 percent.
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| CN104271238A (en) * | 2012-03-27 | 2015-01-07 | 国际壳牌研究有限公司 | A selenium-containing hydroprocessing catalyst, its use, and method of preparation |
| CN110433802A (en) * | 2018-05-04 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof and the catalyst are used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde |
| CN110711605A (en) * | 2019-10-13 | 2020-01-21 | 西安凯立新材料股份有限公司 | Active carbon carrier treatment method, preparation method and application of palladium-carbon catalyst |
| CN114054061A (en) * | 2020-08-06 | 2022-02-18 | 台州学院 | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof |
| CN115312790A (en) * | 2022-08-03 | 2022-11-08 | 中山大学 | Preparation and application of binary palladium-tin nano-alloy catalyst loaded on selenium-doped MXene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104271238A (en) * | 2012-03-27 | 2015-01-07 | 国际壳牌研究有限公司 | A selenium-containing hydroprocessing catalyst, its use, and method of preparation |
| CN110433802A (en) * | 2018-05-04 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof and the catalyst are used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde |
| CN110711605A (en) * | 2019-10-13 | 2020-01-21 | 西安凯立新材料股份有限公司 | Active carbon carrier treatment method, preparation method and application of palladium-carbon catalyst |
| CN114054061A (en) * | 2020-08-06 | 2022-02-18 | 台州学院 | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof |
| CN115312790A (en) * | 2022-08-03 | 2022-11-08 | 中山大学 | Preparation and application of binary palladium-tin nano-alloy catalyst loaded on selenium-doped MXene |
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