CN113731468A - Preparation method and application of catalyst for preparing 1, 2-cyclohexane dibutyl phthalate through dibutyl phthalate hydrogenation - Google Patents
Preparation method and application of catalyst for preparing 1, 2-cyclohexane dibutyl phthalate through dibutyl phthalate hydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- ANSWCYTXKAIJOK-UHFFFAOYSA-N dibutyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1CCCCC1C(=O)OCCCC ANSWCYTXKAIJOK-UHFFFAOYSA-N 0.000 claims description 5
- VHTIMVUUVHEYJA-UHFFFAOYSA-N dibutyl cyclohexane-1,1-dicarboxylate Chemical compound CCCCOC(=O)C1(C(=O)OCCCC)CCCCC1 VHTIMVUUVHEYJA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229960002380 dibutyl phthalate Drugs 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000002161 passivation Methods 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZVJGQCRBIFNMAD-UHFFFAOYSA-N 1,2-dibutylcyclohexane Chemical compound CCCCC1CCCCC1CCCC ZVJGQCRBIFNMAD-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method and application of a catalyst for preparing 1, 2-cyclohexane dibutyl phthalate through dibutyl phthalate hydrogenation. When the catalyst is used in synthesis reaction, the selectivity of the 1, 2-cyclohexane dibutyl phthalate can be obviously improved, and the activity stability and the porous structure of the catalyst can be obviously improved.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a preparation method and application of a catalyst for preparing 1, 2-dibutyl cyclohexane dicarboxylate by dibutyl phthalate hydrogenation.
Background
The active carbon has developed pore channel structure, large specific surface area, excellent property of being widely used for low price, stable acid and alkali resistance, developed pore structure, huge specific surface area and excellent adsorption performance. In addition, the noble metal loaded on the activated carbon is easy to recover through the combustion of the carbon carrier, the specific surface area, the pore structure and the surface functional group of the activated carbon can influence the properties of the catalyst, and the parameters of the carbon carrier can be modified through physical and chemical treatment methods, so that the catalyst has larger adjustment and adaptation range.
Dibutyl 1, 2-cyclohexane dicarboxylate (CDADE) is a hydrogenation product of dibutyl phthalate (DBP), and is characterized by quite low element mobility and excellent toxicological characteristics, is particularly suitable for sensitive materials such as PVC, and is a PVC plasticizer with excellent performance for toys, medical instruments and food contact. The Michael and the group thereof prepare Ru catalysts loaded on different carriers, and the yield of the product is about 99.3 percent; tyndager et Al discusses Pt-Ru/Al2O3The hydrogenation effect of the catalyst, the conversion rate and the selectivity are 98.6 percent and 95.3 percent respectively; rojun language investigates Ni/Al2O3The conversion rate and selectivity of the DBP hydrogenation reaction obtained by the catalyst are respectively 99.93 percent and 92.47 percent, the catalyst can reach a high catalyst, but the selectivity is low, and the noble metal ruthenium as an active center is difficult to recover and has high cost. In order to solve the problems of low selectivity and difficult precious metal recovery, the invention designs and prepares the selective hydrogenation catalyst which takes the modified activated carbon as the carrier and loads the monatomic ruthenium, improves the selectivity under the condition of ensuring the conversion rate, and simultaneously reduces the recovery difficulty of the precious metal ruthenium and the production cost.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the defects of the prior art, the invention adopts the following technical scheme:
a preparation method of a catalyst for preparing 1, 2-cyclohexane dibutyl phthalate by hydrogenating dibutyl phthalate comprises the following preparation steps:
(1) adding activated carbon into 40mL of concentrated acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h; the surface of the active carbon is oxidized in the stirring process, more unsaturated sites are exposed, and the doping of nitrogen and the loading of ruthenium atoms are facilitated.
(2) Centrifugally separating the solution stirred in the step (1), collecting a sample, washing the sample with distilled water, carrying out vacuum drying at 80 ℃ overnight, adding the dried solid into an ethanol solution of ethylenediamine or melamine for ultrasonic treatment for 30min, standing for 6h, washing, and drying at 120 ℃ for 4 h; the nitrogen source was doped into the activated carbon by standing to obtain stable monatomic anchor sites.
(3) Adding a ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4h at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
preferably, the activated carbon in the step (1) is used as a carrier, and the acid used is 60-65% of nitric acid, sulfuric acid or a mixed acid of the nitric acid and the sulfuric acid.
Preferably, the N source used in step (2) is one or two of ethylenediamine and melamine in ethanol solution.
Preferably, the activated carbon is impregnated by using an ethanol solution of ethylenediamine in the step (2), and the deionized water is used after being evaporated; the mass ratio of the activated carbon to the ethylenediamine is 5: 1-2: 1.
preferably, the calcining step in the step (4) is to calcine the solid at 300 ℃ for 1h under high-purity argon and then raise the temperature to 800 ℃ for 2 h.
The catalyst is used in the hydrogenation reaction of benzene ring for preparing the dibutyl cyclohexane dicarboxylate by the hydrogenation of the dibutyl phthalate. Reacting in a fixed bed reactor, adding 0.5g of catalyst into a 6mm reaction tube, checking the airtightness of the device, reducing and passivating the catalyst at 250 ℃, and reacting for 2 hours at 90 ℃ and under the pressure of 2.0-2.5 MPa.
The method has the beneficial effects that in order to increase unsaturated vacancies in the activated carbon and increase the anchoring of ruthenium atoms, ethylenediamine or melamine is used as a nitrogen source to dope nitrogen atoms on the surface of the activated carbon after oxidation treatment, an isometric impregnation method is adopted to load ruthenium monoatomic active centers, and the metal precursor is decomposed at a stepped calcination temperature, and meanwhile, the dispersion degree of atoms on the surface of the carrier is improved at a high temperature. The catalyst prepared by the invention has the advantages of good structure, uniform metal distribution, good surface distribution state and the like. The catalyst is used in the reaction for preparing the dibutyl cyclohexanedicarboxylate by catalyzing the dibutyl phthalate hydrogenation, which is not only beneficial to the recovery of the catalyst and the reduction of the preparation cost, but also can show the selectivity of the dibutyl cyclohexanedicarboxylate. The catalyst prepared by the invention has the advantages of good structure, uniform metal distribution, good surface distribution state and the like. The conversion rate of dibutyl phthalate can reach 99.7%, and the selectivity of 1, 2-cyclohexane butyl phthalate can reach 98.6%.
Detailed Description
The following examples further illustrate the present invention.
Example 1
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5g of the catalyst was placed in a fixed bed reactor, the airtightness of the apparatus was checked, and reduction and passivation were carried out at 250 ℃. The catalyst is reacted for 2 hours at 90 ℃ and 2.0MPa, and the conversion rate is 99.7 percent and the selectivity is 98.6 percent by sampling and measuring.
Example 2
Changing the acid species
(1) Adding 10g of activated carbon into 40mL of 60% sulfuric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst is reacted for 2 hours at 90 ℃ and 2.0MPa, the conversion rate is 98.9 percent and the selectivity is 99.2 percent by sampling and determining.
Example 3
Melamine instead of ethylenediamine
(1) Adding 10g of activated carbon into 40mL of 60% sulfuric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then carrying out vacuum drying at 80 ℃ overnight, mixing 2g of melamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst is reacted for 2 hours at 90 ℃ and 2.0MPa, the conversion rate is 96.9 percent and the selectivity is 99.6 percent by sampling and determining.
Comparative example 1
Varying the amount of ruthenium used
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10mL0.5g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4h at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst is reacted for 2 hours at 90 ℃ and 2.0MPa, and the conversion rate is 99.7 percent and the selectivity is 94.2 percent by sampling and determining.
Comparative example 2
Changing the reaction pressure
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst was reacted at 90 ℃ under 1.0MPa for 2h, with a sample taken to determine a conversion of 89.7% and a selectivity of 96.2%.
Comparative example 3
By varying the reaction temperature
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst was reacted at 120 ℃ under 1.0MPa for 2h, with a sample taken to determine a conversion of 95.6% and a selectivity of 89.2%.
Comparative example 4
Replacement of active centres
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 2g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of nickel nitrate aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst was reacted at 90 ℃ under 1.0MPa for 2h, with a sample taken to determine a conversion of 98.6% and a selectivity of 95.4%.
Comparative example 5
Changing the amount of ethylenediamine
(1) Adding 10g of activated carbon into 40mL of 60% nitric acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) filtering the solution stirred in the step (1) by suction, collecting a solid sample, washing the solid sample by distilled water to be neutral, then drying the solid sample overnight in vacuum at 80 ℃, mixing 1g of ethylenediamine by 10mL of ethanol, dropwise adding the mixture into the dried solid, carrying out ultrasonic treatment for 30min, standing for 6h, washing, and drying for 4h at 120 ℃;
(3) dropwise adding 10ml of 0.3g of ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4 hours at the temperature of 80 ℃ in vacuum;
(4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h;
0.5 catalyst is taken and placed in a fixed bed reactor, the airtightness of the device is checked, and reduction and passivation are carried out at 250 ℃. The catalyst was reacted at 90 ℃ under 2.0MPa for 2h, with a sample taken to determine a conversion of 95.7% and a selectivity of 97.6%.
In comparative example 1, the amount of the metal precursor was increased as compared to example 1, resulting in a decrease in catalytic effect, indicating that an excessive amount of the metal precursor causes agglomeration of metal atoms to affect the formation of isolated single metal atoms.
Compared with the comparative example 4 and the example 1, nickel is used as an active center instead of ruthenium, and the catalytic effect of the metal ruthenium on the dibutyl phthalate hydrogenation reaction in the nitrogen-doped carbon coordination environment is better than that of the metal nickel from the results of conversion rate and selectivity.
The reduction in the amount of ethylenediamine used compared to comparative example 5 and example 1, with a corresponding decrease in the catalytic effect, indicates that the nitrogen doping has a positive synergistic effect on the catalytic effect of the ruthenium monoatomic species.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A preparation method of a catalyst for preparing 1, 2-cyclohexane dibutyl phthalate by hydrogenating dibutyl phthalate is characterized by comprising the following steps: the preparation steps are as follows:
(1) adding activated carbon into 40mL of concentrated acid solution, carrying out ultrasonic treatment for 30min, and then placing the solution in a water bath kettle to be heated and stirred for 8 h;
(2) centrifugally separating the solution stirred in the step (1), collecting a sample, washing the sample with distilled water, carrying out vacuum drying at 80 ℃ overnight, adding the dried solid into an ethanol solution of ethylenediamine or melamine for ultrasonic treatment for 30min, standing for 6h, washing, and drying at 120 ℃ for 4 h;
(3) adding a ruthenium trichloride aqueous solution into the solid obtained in the step (2), soaking overnight, and drying for 4h at the temperature of 80 ℃ in vacuum;
(4) and (4) calcining the solid obtained in the step (3) at the temperature of 300 ℃ for 1h under high-purity argon, and then heating to 800 ℃ for 2 h.
2. The method of claim 1 for preparing a catalyst for dibutyl 1, 2-cyclohexanedicarboxylate hydrogenation, wherein the method comprises the following steps: and (2) taking the activated carbon in the step (1) as a carrier, wherein the acid is 60-65% of nitric acid, sulfuric acid or a mixed acid of the nitric acid and the sulfuric acid.
3. The method of claim 1 for preparing a catalyst for dibutyl 1, 2-cyclohexanedicarboxylate hydrogenation, wherein the method comprises the following steps: the N source used in the step (2) is an ethanol solution of one or a mixture of ethylene diamine and melamine.
4. The method of claim 1 for preparing a catalyst for dibutyl 1, 2-cyclohexanedicarboxylate hydrogenation, wherein the method comprises the following steps: in the step (2), the active carbon is impregnated by using an ethanol solution of ethylenediamine, and deionized water is used after evaporation; the mass ratio of the activated carbon to the ethylenediamine is 5: 1-2: 1.
5. the method of claim 1 for preparing a catalyst for dibutyl 1, 2-cyclohexanedicarboxylate hydrogenation, wherein the method comprises the following steps: in the calcining step in the step (4), the solid is calcined at the temperature of 300 ℃ for 1h under high-purity argon, and then the temperature is raised to 800 ℃ for 2 h.
6. Use of a catalyst according to any one of claims 1 to 5, wherein: the catalyst is used in the hydrogenation reaction of benzene ring for preparing the dibutyl cyclohexane dicarboxylate by the hydrogenation of the dibutyl phthalate.
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| CN115445609A (en) * | 2022-09-30 | 2022-12-09 | 浙江工业大学 | A kind of activated carbon supported ruthenium catalyst and its preparation method and application |
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