CN110665499A - Low-content supported ruthenium metal catalyst and preparation method thereof - Google Patents
Low-content supported ruthenium metal catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 241000219793 Trifolium Species 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 12
- 229960001545 hydrotalcite Drugs 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000004993 emission spectroscopy Methods 0.000 description 9
- 238000009616 inductively coupled plasma Methods 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- 239000012279 sodium borohydride Substances 0.000 description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000003100 immobilizing effect Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- 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
Abstract
The invention discloses a low-content supported ruthenium metal catalyst and a preparation method thereof. The method is based on a hydrothermal principle, adopts a surface in-situ growth method and is applied to Al2O3Surface realization of M2+In-situ growth of Al-type hydrotalcite and introduction of divalent metal component M as cocatalyst2+(ii) a At the same time, the immobilization of the catalytically active metal component Ru is completed. When the low-content supported Ru metal catalyst prepared by the invention is used for the catalytic selective hydrogenation reaction process of preparing 1, 4-dimethyl cyclohexanedicarboxylate (DMCD) from dimethyl terephthalate (DMT), the DMT conversion rate is 93.5-98.2%, and the selectivity of DMCD is 95.1-96.9%. The DMT conversion rate, the DMCD selectivity and the DMCD yield of the catalyst are all superior to other metal Ru catalysts with equal loading capacity, and meanwhile, the invention effectively reduces the usage amount of noble metal RuAnd has obvious economic cost advantage.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a low-content supported ruthenium metal catalyst and a preparation method thereof, wherein the catalyst shows excellent catalytic activity and stability when applied to a reaction process of preparing 1, 4-cyclohexane dimethyl phthalate (DMCD) by selective hydrogenation of dimethyl terephthalate (DMT).
Background
As an important catalyst material, the supported catalyst has excellent heat and mass transfer performance, is suitable for continuous reaction and the like, is widely applied to petrochemical processes, particularly important reaction processes of selective hydrogenation, oxidation and the like of hydrocarbon substances such as olefin, aromatic hydrocarbon and the like, and the using amount of the supported catalyst accounts for more than 70 percent of the total amount of the catalyst.
In the petrochemical process, most of common supported metal catalysts are single metal catalysts, and the main active component of the supported metal catalysts is a specific metal element. Due to the single nature of the components, the material is easily influenced by solvation effect and metal component clustering effect in the actual preparation process, and the phenomena of active metal component microcrystal ice coagulation and the like occur in the subsequent heat treatment processes such as high-temperature roasting and the like, so that the dispersibility of the active metal component is reduced, the structural stability of the active metal component is poor, the energy consumption in the preparation process is high, the use amount of precious metal is large, and the like. Therefore, it has become an important issue to be solved urgently to reduce or even avoid the above problems through the rational design and controlled preparation of the catalytic material. Wherein, developing a novel carrier material, adding a proper auxiliary agent to regulate and control the physical texture of the material, and improving and optimizing the chemical performance of the material, thereby realizing the dispersion type, stabilized anchoring and solid-carrying of the catalytic active particles into an effective strategy and method. In addition, considering the rarity of precious metal resources, how to realize the efficient utilization of precious metal resources to reduce consumption has also become a very challenging research topic in the field of efficient heterogeneous catalysis.
In the actual industrial production process, a single-metal type noble metal palladium-based catalyst material (US Patent 4301046, US Patent 5414159 and US Patent 5286898) is mainly adopted in the reaction process of preparing 1, 4-cyclohexane dimethyl phthalate by selective hydrogenation of dimethyl terephthalate (DMT), wherein the using amount of the noble metal palladium is up to 1-5%, so that the cost of the catalyst material is higher, meanwhile, the single-metal palladium particles have smaller acting force with a carrier, so that the phenomena of shedding and poisoning are very easy to occur in the using process of the catalyst material, and in recent years, a report that metal ruthenium is applied to the reaction process is provided, wherein when ruthenium is used as an auxiliary agent of the noble metal palladium-based catalyst (US Patent 5286898), the catalytic performance of the noble metal palladium can be obviously improved; the prepared single-metal supported ruthenium-based catalyst material also has certain catalytic activity, but the usage amount of the single-metal supported ruthenium-based catalyst material is generally more than 2-10%, and the catalytic performance, especially the catalytic selectivity, of the single-metal supported ruthenium-based catalyst material needs to be improved (US Patent appl.20030153456, US Patent6187968 and US Patent 3027398).
Disclosure of Invention
The invention aims to provide a low-content supported ruthenium metal catalyst and a preparation method thereof. Based on the hydrothermal principle, a surface in-situ growth method is adopted to grow on Al2O3Surface realization of M2+In-situ growth of Al-type hydrotalcite and introduction of divalent metal component M as cocatalyst2+(ii) a At the same time, the immobilization of the catalytically active metal component Ru is completed. And first complete M2+Al-type hydrotalcite on Al2O3In-situ growth of the surface, then immobilization of Ru, and Al2O3Compared with the direct immobilized Ru, the Ru metal catalyst prepared by the method has higher catalytic hydrogenation reaction activity and stability. The method can realize the purposes of improving the catalytic reaction performance of the catalyst and improving the catalytic reaction stability, and simultaneously effectively reduces the use amount of the noble metal Ru, and has obvious economic cost advantage.
The invention firstly adopts urea solution to react Al2O3The surface is activated to excite Al on the surface3+Source, then, introducing a divalent metal M2+To complete Al2O3Surface M2+Surface in-situ synthesis of Al-type hydrotalcite; meanwhile, a catalytic active metal Ru is introduced to synchronously realize the surface dispersion and immobilization. The assistant metal M is generated by the lattice positioning effect of hydrotalcite crystal2+Atoms and Al atoms are highly dispersed with each other and with Al2O3Firm combination; at the same time, since M2+Al-type hydrotalcite on Al2O3The surface is mainly in an oriented growth mode (namely a hydrotalcite layer plate and Al)2O3The included angle of the surfaces is generally greater than 0 deg., with many included angles approaching 90 deg.), and therefore, from M2+Al-type hydrotalcite is staggered and connected with each other to form a local confinement space similar to a grid, which provides possibility for the isolated dispersion of Ru particles; in addition, drying and baking are carried out subsequentlyEven during the reaction, M2+The Al-type hydrotalcite can be converted to contain M2+And Al, and the structure and the appearance of the composite metal oxide can be basically kept stable, which provides guarantee for stable solid loading of isolated and dispersed Ru particles.
The preparation method of the low-content supported ruthenium metal catalyst comprises the following specific preparation steps:
1)Al2O3activation of (2): firstly, preparing a urea solution with the concentration of 0.1-3.0mol/L by using deionized water; then, Al with a particle size of 10 to 60 mesh is added2O3Adding into the urea solution at a specific amount of 0.5-5.0g Al per 100mL urea solution2O3(ii) a Then, carrying out ultrasonic treatment for 5-15min at 30-60 ℃; finally, standing for 8-48h at 20-90 ℃;
2) weighing soluble divalent metal salt and Ru salt, dissolving in deionized water to prepare divalent metal ion M2+And a mixed salt solution of Ru ions, in which M is2+And Ru in a metal atom molar ratio of 25 to 100; then, adding the mixed salt solution into the mixed solution system obtained in the step 1), and enabling M to be in the mixed solution system2+The concentration of (A) is kept between 0.005 and 0.5 mol/L; then, carrying out ultrasonic treatment for 3-10min at 30-60 ℃; finally, standing for 6-24h at 60-150 ℃;
3) cooling the mixed solution obtained in the step 2) to room temperature; then filtering to obtain a solid material, washing with deionized water, and drying at 30-80 ℃ for 6-18 h; finally, roasting for 6-12h at the temperature of 300-600 ℃.
The Al is2O3The shape of the utility model is one or a mixture of a plurality of spherical, clover and sheet.
The Al is2O3The crystal form of (A) is any one or a mixture of more of delta, beta, gamma, theta and eta.
Said M2+Selected from Mg2+、Ni2+、Ca2+、Fe2+、Cu2+One or more of them.
The prepared low-content supported ruthenium metal catalyst is applied to the reaction of preparing 1, 4-cyclohexane dimethyl phthalate (DMCD) by catalyzing the selective hydrogenation of dimethyl terephthalate (DMT).
The following are characterized by means such as X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and Scanning Electron Microscope (SEM): the low-content supported ruthenium metal catalyst Ru-M prepared by the invention2+Al-HTc/Al2O3Middle M2+Al-HTc is mainly located in Al2O3Ru is mainly located on the radial surface layer. The mass fraction of Ru in the resulting catalyst was found to be between 0.1 and 1.0 wt% by inductively coupled plasma emission spectroscopy (ICP-AES).
The preparation method of the invention can mix M2+The two processes of the growth of the Al-type hydrotalcite lamellar precursor and the immobilization of the catalytic active metal Ru are synchronously finished, and the auxiliary agent metal M takes the characteristics of hydrotalcite into consideration2+And Al are highly isolated and uniformly dispersed under the action of lattice positioning constraint, and obvious phenomena such as morphology transformation, structure transformation or collapse are not easy to occur in the subsequent drying, roasting and even reaction processes, and meanwhile, M is used2+The Al-type hydrotalcite laminate plates are staggered or connected with each other to form a local limited micro-space, so that important structural support and guarantee can be provided for realizing the dispersion type stabilization isolation and immobilization of Ru particles, and the Ru particles are not easy to migrate, aggregate or fall off on the surface in the processes of drying, roasting and catalytic reaction, so that the dispersion immobilization stability of the Ru particles is obviously improved and promoted; in addition, the use amount of the catalyst can be effectively reduced, and the material cost control is facilitated. The main catalytic active particles of the catalyst are metallic Ru nano particles with zero valence state; due to the synchronization of the synthesis of the carrier material and the immobilization process of the active metal component Ru, the obtained main catalytic active metal Ru particles have the characteristics of small particle size, narrow distribution, obvious inhibition on the formation of large particle size particles and the like, and the load stability of the main catalytic active metal Ru particles is obviously improved.
The low-content supported Ru metal catalyst (Ru-HTc/Al) prepared by the invention2O3) Catalytic selection for the preparation of dimethyl 1, 4-cyclohexanedicarboxylate (DMCD) from dimethyl terephthalate (DMT)During the hydrogenation reaction, the DMT conversion rate is 93.5-98.2%, and the DMCD selectivity is 95.1-96.9%. To prepare M first2+Al-HTc/Al2O3And then further immobilizing Ru (Ru/HTc/Al) to obtain a supported Ru catalyst2O3) And a supported Ru catalyst (Ru/Al) obtained by directly supporting Ru2O3) As a reference, when it was used in the selective hydrogenation of DMT to DMCD under the same Ru content and reaction conditions, the DMT conversion was 80.0-96.4% (Ru/HTc/Al), respectively2O3) And 44.9-58.3% (Ru/Al)2O3) The DMCD selectivity is 86.9-92.5% (Ru/HTc/Al)2O3) And 75.2-86.6% (Ru/Al)2O3). Therefore, the low-content supported Ru metal catalyst prepared by the method has more excellent catalytic activity and selectivity.
Drawings
FIG. 1 shows Ru-HTc/Al obtained in example 12O3The HRTEM electron micrograph of (1).
FIG. 2 shows Ru/Al obtained in example 22O3The HRTEM electron micrograph of (1).
FIG. 3 shows Ru/HTc/Al prepared in example 32O3The HRTEM electron micrograph of (1).
Detailed Description
Example 1:
1) weighing 2.0g of 20-40 mesh spherical theta-Al2O3Putting the urea into a urea solution (30mL) with the concentration of 2mol/L, uniformly mixing, and carrying out ultrasonic treatment for 5min at 40 ℃; then placing the mixture into a stainless steel type autogenous pressure kettle (the volume is 100mL, the inner lining is polytetrafluoroethylene), and standing the mixture for 24 hours at the temperature of 90 ℃;
2) adding Mg (NO) into the mixed solution obtained in the step 1)3)2And RuCl3The mixed salt solution of (4) (volume 20mL, concentration of Mg 5.0g/L, concentration of Ru 1.0 g/L); subsequently, ultrasonic treatment was carried out at 30 ℃ for 5 min; finally, standing for 24 hours at 130 ℃;
3) cooling the mixed solution obtained in the step 2), filtering to obtain a solid material, washing with deionized water, drying at 70 ℃ for 12h, and processing at 450 DEG CContinuously roasting for 8 hours under the condition of one part to obtain the catalyst Ru-HTc/Al2O3. The total active metal ruthenium content in the catalyst was 0.95 wt% as measured by inductively coupled plasma emission spectroscopy.
To examine the reactivity of the catalyst, first, 1.0g of Ru-HTc/Al was weighed2O3And the mixture was placed in a sodium borohydride solution (10mL, sodium borohydride content 1.0g) having a pH of 10.0, treated with continuous stirring at room temperature for 30min, filtered, washed 5 times with absolute ethanol, and then dried at 120 ℃ for 6 hours under a nitrogen atmosphere, and then the obtained solid was rapidly transferred to a reaction solution containing dimethyl terephthalate (DMT) and reacted for 6 hours using a liquid phase reaction vessel, resulting in a DMT conversion of 98.2% and a DMCD selectivity of 96.9%. Wherein the reaction temperature is 180 ℃, H2The pressure is 8.0MPa, the dosage of the raw material dimethyl terephthalate is 10mmol, and the dosage of the solvent ethyl acetate is 80 ml.
For comparison, Al is used2O3Ru metal catalyst (Ru/Al) obtained by directly immobilizing Ru2O3) And first HTc/Al was prepared2O3Then, the Ru metal catalyst (Ru/HTc/Al) was supported2O3) The ruthenium content was found to be 0.97 wt% and 0.96 wt% respectively by inductively coupled plasma emission spectroscopy. Under the same reaction conditions, the DMT conversion rate was 58.3% (Ru/Al), respectively2O3) And 96.4% (Ru/HTc/Al)2O3) The DMCD selectivity was 86.6% (Ru/Al), respectively2O3) And 92.5% (Ru/HTc/Al)2O3)。
Example 2:
firstly, weighing 1.5g of 30-50 meshes clover type gamma-Al2O3Putting the urea into a urea solution (40mL) with the concentration of 2.4mol/L, uniformly mixing, and carrying out ultrasonic treatment for 10min at 30 ℃; then, the mixture is placed into a stainless steel type autogenous pressure kettle (the volume is 100mL, the inner lining is polytetrafluoroethylene), and the mixture is kept stand for 18 hours at the temperature of 85 ℃;
then, Mg (NO) is added3)2·6H2O and RuCl3·3H2Mixed salt solution of O (volume 18mL, concentration of Mg)4.5g/L, concentration of Ru is 1.0 g/L); subsequently, ultrasonic treatment was carried out at 40 ℃ for 10 min; finally, standing for 12 hours at 130 ℃;
finally, after the obtained solution is cooled, filtering to obtain a solid material, washing with deionized water, drying at 60 ℃ for 12 hours, and continuously roasting at 400 ℃ for 6 hours to obtain the catalyst Ru-HTc/Al2O3. The total content of active metal ruthenium in the catalyst is 0.95 wt% measured by inductively coupled plasma emission spectroscopy;
to examine the reactivity of the catalyst, first, 1.2g of Ru-HTc/Al was weighed2O3After being placed in a sodium borohydride solution (10mL, the content of sodium borohydride is 1.0g) with the pH value of 10.0, the mixture is continuously stirred and treated for 30min at room temperature, and then is washed 5 times by absolute ethyl alcohol, and is dried for 6h at the temperature of 120 ℃ under a nitrogen atmosphere, and then the obtained solid is quickly transferred to a reaction liquid containing dimethyl terephthalate (DMT) to be reacted for 6h by using a liquid phase reaction kettle, so that the conversion rate of DMT is 97.2 percent, and the selectivity of DMCD is 96.2 percent. Wherein the reaction temperature is 180 ℃, H2The pressure is 6.0MPa, the dosage of the raw material dimethyl terephthalate is 10mmol, and the dosage of the solvent methanol is 100 ml.
For comparison, Al is used2O3Ru metal catalyst (Ru/Al) obtained by directly immobilizing Ru2O3) And first HTc/Al was prepared2O3Then, the Ru metal catalyst (Ru/HTc/Al) was supported2O3) The ruthenium content was found to be 0.96 wt% and 0.95 wt% respectively by inductively coupled plasma emission spectroscopy. Under the same reaction conditions, the DMT conversion rate was 52.4% (Ru/Al), respectively2O3) And 86.5% (Ru/HTc/Al)2O3) The DMCD selectivity was 89.5% (Ru/Al), respectively2O3) And 91.1% (Ru/HTc/Al)2O3)。
Example 3:
firstly, weighing 2.5g of 20-50 mesh flaky beta-Al2O3Putting the urea into urea solution (30mL) with the concentration of 3.0mol/L, uniformly mixing, and carrying out ultrasonic treatment for 8min at the temperature of 30 ℃; then, the stainless steel mold is put in to generate pressureStanding for 18h at 90 ℃ in a kettle (the volume is 100mL, and the lining is polytetrafluoroethylene);
then, Mg (NO) is added3)2·6H2O and RuCl3·3H2Mixed salt solution of O (volume 20mL, Mg concentration of 5.0g/L, Ru concentration of 0.9 g/L); subsequently, ultrasonic treatment was carried out at 25 ℃ for 10 min; finally, standing for 24 hours at 130 ℃;
finally, after the obtained solution is cooled, filtering to obtain a solid material, washing with deionized water, drying at 70 ℃ for 8h, and continuously roasting at 450 ℃ for 8h to obtain the catalyst Ru-HTc/Al2O3. The total content of active metal ruthenium in the catalyst is 0.84 wt% measured by inductively coupled plasma emission spectroscopy;
to examine the reactivity of the catalyst, first, 1.5g of Ru-HTc/Al was weighed2O3And the resulting mixture was placed in a sodium borohydride solution (10mL, sodium borohydride content 1.5g) having a pH of 9.0, treated with continuous stirring at room temperature for 30min, filtered, washed 5 times with absolute ethanol, and then dried at 120 ℃ for 6 hours under a nitrogen atmosphere, and then the resulting solid was rapidly transferred to a reaction solution containing dimethyl terephthalate (DMT) and reacted for 6 hours using a liquid phase reaction vessel, resulting in a DMT conversion of 95.3% and a DMCD selectivity of 86.2%. Wherein the reaction temperature is 200 ℃, H2The pressure is 6.0MPa, the dosage of the raw material dimethyl terephthalate is 10mmol, and the dosage of the solvent isopropanol is 80 ml.
For comparison, Al is used2O3Ru metal catalyst (Ru/Al) obtained by directly immobilizing Ru2O3) And first HTc/Al was prepared2O3Then, the Ru metal catalyst (Ru/HTc/Al) was supported2O3) The ruthenium content was 0.84 wt% and 0.85 wt% as determined by inductively coupled plasma emission spectroscopy, respectively. Under the same reaction conditions, the DMT conversion rate was 34.5% (Ru/Al), respectively2O3) And 83.1% (Ru/HTc/Al)2O3) The DMCD selectivity was 65.6% (Ru/Al), respectively2O3) And 75.8% (Ru/HTc/Al)2O3)。
Example 4:
firstly, weighing 2.0g of 10-40 mesh irregular granular theta-Al2O3Putting the urea into a urea solution (30mL) with the concentration of 2.5mol/L, uniformly mixing, and carrying out ultrasonic treatment for 5min at 25 ℃; then, the mixture is placed into a stainless steel type autogenous pressure kettle (the volume is 100mL, the inner lining is polytetrafluoroethylene), and the mixture is kept stand for 24 hours at the temperature of 90 ℃;
then, Mg (NO) is added3)26H2O and RuCl33H2Mixed salt solution of O (volume 15mL, Mg concentration of 5.0g/L, Ru concentration of 0.9 g/L); subsequently, ultrasonic treatment was carried out at 25 ℃ for 5 min; finally, standing for 24 hours at 130 ℃;
finally, after the obtained solution is cooled, filtering to obtain a solid material, washing with deionized water, drying at 70 ℃ for 12h, and continuously roasting at 450 ℃ for 8h to obtain the catalyst Ru-HTc/Al2O3. The total content of active metal ruthenium in the catalyst is 0.90 wt% measured by inductively coupled plasma emission spectroscopy;
to examine the reactivity of the catalyst, first, 1.0g of Ru-HTc/Al was weighed2O3And the mixture was placed in a sodium borohydride solution (10mL, sodium borohydride content 1.0g) having a pH of 10.0, treated with continuous stirring at room temperature for 30min, filtered, washed 5 times with absolute ethanol, and then dried at 120 ℃ for 6 hours under a nitrogen atmosphere, and then the obtained solid was rapidly transferred to a reaction solution containing dimethyl terephthalate (DMT) and reacted for 6 hours using a liquid phase reaction vessel, with the result that the conversion of DMT was 78.3% and the selectivity of DMCD was 96.5%. Wherein the reaction temperature is 150 ℃, H2The pressure is 6.0MPa, the dosage of the raw material dimethyl terephthalate is 10mmol, and the dosage of the solvent ethyl acetate is 80 ml.
For comparison, Al is used2O3Ru metal catalyst (Ru/Al) obtained by directly immobilizing Ru2O3) And first HTc/Al was prepared2O3Then, the Ru metal catalyst (Ru/HTc/Al) was supported2O3) The ruthenium content was 0.88 wt% and 0.92 wt% as determined by inductively coupled plasma emission spectroscopy, respectively. In the same wayUnder the reaction conditions, the DMT conversion rate was 40.7% (Ru/Al), respectively2O3) And 66.4% (Ru/HTc/Al)2O3) The DMCD selectivity was 89.5% (Ru/Al), respectively2O3) And 92.4% (Ru/HTc/Al)2O3)。
Claims (5)
1. A preparation method of a low-content supported ruthenium metal catalyst is characterized by comprising the following specific preparation steps:
1)Al2O3activation of (2): firstly, preparing a urea solution with the concentration of 0.1-3.0mol/L by using deionized water; then, Al with a particle size of 10 to 60 mesh is added2O3Adding into the urea solution at a specific amount of 0.5-5.0gAl per 100mL of urea solution2O3(ii) a Then, carrying out ultrasonic treatment for 5-15min at 30-60 ℃; finally, standing for 8-48h at 20-90 ℃;
2) weighing soluble divalent metal salt and Ru salt, dissolving in deionized water to prepare divalent metal ion M2+And a mixed salt solution of Ru ions, in which M is2+And Ru in a metal atom molar ratio of 25 to 100; then, adding the mixed salt solution into the mixed solution system obtained in the step 1), and enabling M to be in the mixed solution system2+The concentration of (A) is kept between 0.005 and 0.5 mol/L; then, carrying out ultrasonic treatment for 3-10min at 30-60 ℃; finally, standing for 6-24h at 60-150 ℃;
3) cooling the mixed solution obtained in the step 2) to room temperature; then filtering to obtain a solid material, washing with deionized water, and drying at 30-80 ℃ for 6-18 h; finally, roasting for 6-12h at the temperature of 300-600 ℃.
2. The method of claim 1, wherein said Al is selected from the group consisting of2O3The shape of the utility model is one or a mixture of a plurality of spherical, clover and sheet.
3. The method for preparing a low-content supported ruthenium metal catalyst according to claim 1, wherein the catalyst is prepared by the method comprisingIn the above-mentioned Al2O3The crystal form of (A) is any one or a mixture of more of delta, beta, gamma, theta and eta.
4. The method for preparing a low-content supported ruthenium metal catalyst as claimed in claim 1, wherein M is2+Selected from Mg2+、Ni2+、Ca2+、Fe2+、Cu2+One or more of them.
5. Use of the low content supported ruthenium metal catalyst prepared according to any one of claims 1 to 4 for the selective hydrogenation of dimethyl terephthalate to dimethyl 1, 4-cyclohexanedicarboxylate.
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