CN111545195A - Recyclable Ru nano catalyst, preparation method thereof and application thereof in preparation of cis-pinane - Google Patents
Recyclable Ru nano catalyst, preparation method thereof and application thereof in preparation of cis-pinane Download PDFInfo
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- CN111545195A CN111545195A CN202010425799.4A CN202010425799A CN111545195A CN 111545195 A CN111545195 A CN 111545195A CN 202010425799 A CN202010425799 A CN 202010425799A CN 111545195 A CN111545195 A CN 111545195A
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 43
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XOKSLPVRUOBDEW-DJLDLDEBSA-N (1r,4s,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-DJLDLDEBSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 7
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims abstract description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- -1 terpenoid compounds Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229930006728 pinane Natural products 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- XOKSLPVRUOBDEW-IWSPIJDZSA-N (1r,4r,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-IWSPIJDZSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000003408 phase transfer catalysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000011924 stereoselective hydrogenation Methods 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Images
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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B01J35/40—
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- 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
Abstract
The invention relates to a method for preparing cis-pinane by hydrogenating alpha-pinene, belonging to the technical field of deep processing of terpenoid compounds. The invention adopts polyethylene glycol (PEG) as a stabilizer to prepare the Ru nano catalyst which has high activity and selectivity and can be recycled and used for catalyzing the selective hydrogenation of alpha-pinene to prepare cis-pinane. The Ru nano catalyst with stable PEG is used as one phase, and the mixed solvent of toluene and n-heptane is used as the other phase to form a Ru nano catalytic system with a temperature control function, so that the hydrogenation reaction and the nano catalyst separation process of 'high-temperature mixing and dissolving reaction and low-temperature cooling separation' are realized. The system realizes the high-efficiency recycling of the Ru nano catalyst and higher cis-pinane selectivity in the process of catalyzing the selective hydrogenation of alpha-pinene to prepare the cis-pinane.
Description
Technical Field
The invention belongs to the technical field of catalyst application and deep processing of terpenoid compounds, and relates to a method for preparing cis-pinane by selective hydrogenation of alpha-pinene, in particular to a method for preparing cis-pinane by catalyzing selective hydrogenation of alpha-pinene by using Ru nanoparticles stabilized by PEG as a catalyst.
Background
The catalytic hydrogenation of pinene to prepare pinane is an important reaction process in the production of terpene perfumes. The turpentine (mainly containing alpha-pinene and beta-pinene) is used as a raw material to produce spices such as linalool, geraniol and dihydromyrcenol, wherein pinane is an important synthetic intermediate. Pinane has four isomers of cis-form and trans-form, as shown in figure 1.
Wherein P1 and P2 are cis-pinane, P3 and P4 are trans-pinane, and are enantiomers of each other. Generally, if the cis-pinane content in the production of terpene perfumes is lower than 97%, side reactions in subsequent reactions are increased, and the separation difficulty is increased; the yield is low and the product quality is seriously influenced. The mechanism of this oxidation and hydration process of cis-pinane over trans-pinane has been demonstrated. The method for producing terpene perfume by using pinene as raw material must synthesize cis-pinane firstly, so that the selective catalytic hydrogenation of pinene for preparing high-purity cis-pinane is very important, and this is the fundamental guarantee of high quality of downstream products.
To efficiently and selectively produce cis-pinane, the selection of the hydrogenation catalytic process is critical. There are many reports on this aspect. Pinene hydrogenation catalysts can be mainly classified into nickel-based catalysts and noble metal catalysts according to composition, and catalytic processes can be classified into homogeneous catalytic processes and heterogeneous catalytic processes. The nickel-based catalyst mainly selects Raney nickel or nano nickel with high hydrogenation activity as a catalyst and is carried out in a batch reactor, but the hydrogenation reaction is an exothermic reaction and the high activity of the nickel catalyst, so that the temperature distribution in the reactor is not uniform, local hot spots exist, and the phenomenon is very obvious in the industrial amplification of the reactor. The reaction temperature is the key for generating the cis-pinane through the stereoselective hydrogenation of the pinene, so that the purity fluctuation of the cis-pinane product is large. The noble metal catalyst is widely applied to the selective hydrogenation reaction of olefin due to the characteristics of high activity and high selectivity. The noble metals used in the catalytic hydrogenation of pinene mainly comprise rhodium, ruthenium, palladium and the like. The noble metal catalysts are mainly classified into homogeneous complex catalysts, heterogeneous supported catalysts and nanoparticle catalysts. The Ru nano catalyst has high activity and high selectivity, is easy to prepare, and has mild reaction conditions, so the Ru nano catalyst has high potential industrial application value. However, the problems of easy agglomeration and difficult separation and recovery of the nano-particle catalyst generally exist. The invention adopts the Ru nano catalyst with stable PEG and the mixed solvent to form a temperature control phase transfer catalysis system, so that the Ru nano particles are not easy to agglomerate and achieve the purposes of easy separation and recovery and recycling on the basis of keeping the high activity and high selectivity of the catalysis performance of the Ru nano particles.
Disclosure of Invention
The invention aims to provide a recyclable Ru nano catalyst, a preparation method thereof and application thereof in catalyzing alpha-pinene to selectively hydrogenate and prepare cis-pinane. The invention adopts polyethylene glycol (PEG) as a stabilizer to prepare the Ru nano catalyst which has high activity and selectivity and can be recycled and used for catalyzing the selective hydrogenation of alpha-pinene to prepare cis-pinane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a recyclable Ru nano catalyst is prepared by taking Ru salt as a catalyst precursor, reducing by a reducing agent to prepare metal Ru nano particles, and adding PEG as a stabilizer.
Further, the molecular weight of PEG is 600 to 10000, with PEG6000 being most preferred.
Further, the mass ratio of the Ru salt to the PEG6000 is 1: 10000-1: 30000.
The method specifically comprises the following steps:
(1) weighing Ru salt and PEG, adding into a stainless steel autoclave, and sealing the stainless steel autoclaveLeak detection, three times of N2Displacing air within the device;
(2) heating to 90 deg.C and maintaining the temperature, stirring at 500r/min for 2 h;
(3) reuse H2Gas in the kettle of the gas replacement device is replaced for 3 times, and then 4MPa of H is introduced2Gas; reducing for 8 hours at the stirring speed and temperature of the step (2);
(4) cooling to remove H2And obtaining the Ru nano catalyst with stable PEG.
The application of the recyclable Ru nano catalyst in catalyzing selective hydrogenation of α -pinene to prepare cis-pinane is specifically that the Ru nano catalyst and a mixed solvent composed of toluene and n-heptane are added into a stainless steel autoclave, then α -pinene is added, and H is subjected to hydrogenation treatment2Reacting in the atmosphere, and carrying out hydrogenation reaction for 9h at the stirring speed of 500 r/min.
Further, the mass ratio of toluene to n-heptane was 3: 1.
Further, the above is at H2The reaction temperature in the reaction under the atmosphere is 130 ℃ and H2The pressure was 3 MPa.
Further, the molar ratio of the Ru nano catalyst to the alpha-pinene is 1: 100-1: 1000.
The invention has the following remarkable advantages:
(1) the Ru nano catalyst prepared by the invention has higher catalytic hydrogenation activity and cis-pinane selectivity in the selective hydrogenation reaction of alpha-pinene, shows better stability under the action of polyethylene glycol (PEG) serving as a stabilizer, and prevents the agglomeration of nano particles. And can realize convenient separation, recovery and recycling in a temperature-controlled phase transfer catalytic system formed by the mixed solvent of toluene and n-heptane.
(2) The Ru nano catalyst with stable PEG prepared by the invention, a toluene and n-heptane mixed solvent form a temperature control phase transfer catalysis system, and the Ru nano catalyst has the characteristics of high-temperature mixing and low-temperature phase splitting. The Ru nano catalyst is uniformly dispersed in a reaction system in the reaction process, so that a homogeneous reaction effect is achieved. And (3) cooling to room temperature after the reaction is finished, and recovering the system into two phases, namely one phase of the PEG-stabilized Ru nano catalyst and the other phase of the product and the mixed solvent. The PEG-stabilized Ru nano catalyst can be separated out through simple phase separation and can be recycled.
Drawings
FIG. 1 Structure of four isomers of pinane;
FIG. 2 TEM image and particle size distribution plot of PEG-stabilized Ru nanocatalysts of the present invention;
FIG. 3 shows the recycling effect of the PEG-stabilized Ru nanocatalyst of the invention. (X represents the conversion of alpha-pinene and S represents the cis-pinane selectivity)
Detailed description of the invention
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1
0.01g of RuCl was weighed3·xH2O and 25g PEG6000 are added into a stainless steel high-pressure autoclave, the stainless steel high-pressure autoclave is sealed and leak-tested, and N is led in for three times2Displacing air within the device. Heating to 90 deg.C and maintaining the temperature, and stirring at 500r/min for 2 h. Reuse H2Gas in the kettle of the gas replacement device is replaced for 3 times, and then 4MPa of H is introduced2Gas, reduced for 8h at the above stirring rate and temperature. Cooling to remove H2And obtaining the Ru nano catalyst with stable PEG. As shown in FIG. 2, which is a Transmission Electron Micrograph (TEM), the average particle diameter was 2.3 nm.
Application example 1
Adding 10g of PEG 6000-stable Ru nano catalyst and a mixed solvent consisting of 3g of toluene and 1g of n-heptane into a stainless steel autoclave, adding 1.3g of α -pinene, and reacting at 130 ℃ and H2The hydrogenation reaction is carried out for 9 hours under the pressure of 3MPa and the stirring speed of 500r/min, the conversion rate of α -pinene is 98.9 percent, and the cis-pinane selectivity can reach 96.8 percent.
Application example 2
10g of PEG 6000-stable Ru nano catalyst and a mixed solvent consisting of 3g of toluene and 1g of n-heptane are added into a stainless steel autoclave, and 1.3g of α -pinene is addedAt a reaction temperature of 130 ℃ and H2The method comprises the steps of carrying out hydrogenation reaction for 9 hours under the pressure of 3MPa and the stirring rate of 500r/min, cooling a reaction kettle to room temperature after the reaction is finished, naturally separating a reaction mixture into two phases, wherein the upper layer is a mixed solvent and a product phase, and the lower layer is a PEG-stable Ru nano catalyst phase, separating the two phases through simple phase separation operation (such as decantation), recovering the Ru nano catalyst, adding a mixed solvent consisting of 3g of toluene and 1g of n-heptane and 1.3g of α -pinene into the lower PEG-stable Ru nano catalyst phase, carrying out hydrogenation reaction under the reaction conditions, namely, recycling the Ru nano catalyst, and carrying out recycling 7 times of the Ru nano catalyst, wherein the effect of recycling is shown in figure 3, which shows that the catalytic performance of the Ru nano catalyst is basically kept unchanged in the recycling process.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a recyclable Ru nano catalyst is characterized by comprising the following steps: ru salt is used as a catalyst precursor, metal Ru nano particles are prepared by reduction of a reducing agent, and polyethylene glycol (PEG) is added as a stabilizing agent to prepare the recyclable Ru nano catalyst.
2. The method for preparing a recyclable Ru nanocatalyst as claimed in claim 1, wherein: the method specifically comprises the following steps:
(1) weighing Ru salt and PEG, adding into a stainless steel autoclave, sealing the stainless steel autoclave, detecting leakage, and introducing N three times2Displacing air within the device;
(2) heating to 90 deg.C and maintaining the temperature, stirring at 500r/min for 2 h;
(3) reuse H2Gas in the kettle of the gas replacement device is replaced for 3 times, and then 4MPa of H is introduced2Gas; reducing for 8 hours at the stirring speed and temperature of the step (2);
(4) cooling to remove H2And obtaining the Ru nano catalyst with stable PEG.
3. The method for preparing a recyclable Ru nanocatalyst as claimed in claim 1, wherein: the mass ratio of the Ru salt to the PEG6000 is 1: 10000-1: 30000.
4. The method for preparing a recyclable Ru nanocatalyst as claimed in claim 1, wherein: the PEG has a molecular weight of 600 to 10000.
5. A recyclable Ru nanocatalyst prepared by the method of any one of claims 1-4.
6. The application of the recyclable Ru nano-catalyst prepared by the method of any one of claims 1-4 in the preparation of cis-pinane by catalyzing selective hydrogenation of α -pinene is characterized in that the Ru nano-catalyst and a mixed solvent composed of toluene and n-heptane are added into a stainless steel autoclave together, α -pinene is added, and H is subjected to hydrogenation treatment2Reacting in the atmosphere, and carrying out hydrogenation reaction for 9h at the stirring speed of 500 r/min.
7. Use according to claim 6, characterized in that: the mass ratio of toluene to n-heptane was 3: 1.
8. Use according to claim 6, characterized in that: said at H2The reaction temperature in the reaction under the atmosphere is 130 ℃ and H2The pressure was 3 MPa.
9. Use according to claim 6, characterized in that: the molar ratio of the Ru nano catalyst to the alpha-pinene is 1: 100-1: 1000.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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