CN111960911A - Method for preparing cis-pinane by hydrogenating alpha-pinene - Google Patents
Method for preparing cis-pinane by hydrogenating alpha-pinene Download PDFInfo
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- CN111960911A CN111960911A CN202010716952.9A CN202010716952A CN111960911A CN 111960911 A CN111960911 A CN 111960911A CN 202010716952 A CN202010716952 A CN 202010716952A CN 111960911 A CN111960911 A CN 111960911A
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- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 title claims abstract description 56
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 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 37
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 239000013335 mesoporous material Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910000510 noble metal Inorganic materials 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000011943 nanocatalyst Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B01J35/393—
-
- B01J35/50—
-
- 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
Abstract
The invention belongs to the technical field of cis-pinane preparation, and discloses a method for preparing cis-pinane by hydrogenating alpha-pinene. In aqueous solution, alpha-pinene loads nickel active particle catalyst Ni/CxNy @ mSiO in amphiphilic nano mesoporous material2Under the catalytic action of (3), is filled with H2And carrying out catalytic hydrogenation reaction to obtain the cis-pinane. The catalyst Ni/CxNy @ mSiO provided by the invention2The catalyst shows excellent catalytic activity and product selectivity to alpha-pinene hydrogenation catalytic reaction.
Description
Technical Field
The invention relates to a method for preparing cis-pinane by hydrogenating alpha-pinene.
Background
China has abundant rosin resources, and the main component alpha-pinene can be hydrogenated to obtain cis-pinane which is a chemical intermediate with important application in the fields of biological pharmacy, material synthesis, industrial essence, pesticide synthesis and the like. Therefore, the process for preparing cis-pinane by hydrogenating the alpha-pinene plays an important role in the fields of chemical engineering, biological medicine, materials and the like; in the prior art, most of catalysts used for industrially catalyzing alpha-pinene to carry out hydrogenation reaction to obtain cis-pinane are Pd/C, Ru/C or Raney nickel catalysts, however, the reaction conditions of the catalysts are too severe, and the cis-pinane and trans-pinane are low in cis-inverse ratio.
In recent years, Housheng et al have adopted RuCl3·3H2O is a metal precursor, polymers P123, F127 and TPGS-1000 are respectively used as stabilizing agents, and H is adopted2Ru nanoparticles prepared by the method as a reducing agent catalyze pinene hydrogenation reaction in a water phase, but the method has the problems of difficulty in separation of the catalyst and raw materials, poor repeatability and the like. Shelihua et al introduce amphiphilic functional group in the molecular sieve, prepare the amphiphilic catalyst of "micelle-like" mechanism, and apply it to alpha-pinene hydrogenation, have realized that mildly, high-efficiently, high-selectively catalyze alpha-pinene hydrogenation, the reusability of the catalyst is poor, the catalyst is difficult to separate question. Meanwhile, Quli et al adopt a cellulose derivative to load metal ruthenium nanoparticles to realize green, high-activity and high-selectivity catalysis of alpha-pinene hydrogenation to prepare the cis-pinane. Chinese patent application CN201910284586.1 discloses a method for preparing cis-pinane by alpha-pinene hydrogenation, which uses amphiphilic magnetic nano material to load ruthenium active particle Fe3O4@SiO2@C12@NH2The catalyst is/Ru, and H is filled2Catalyzing alpha-pinene hydrogenation to prepare cis-pinane. However, all the reaction systems described above use noble metals such as Ru as active nanoparticles, and the cost of noble metals limits the large-scale application of catalysts. Therefore, the method for preparing the cis-pinane by catalyzing the hydrogenation of the alpha-pinene by the supported non-noble metal nano particle catalyst under the mild condition becomes urgent.
Disclosure of Invention
The invention provides a method for preparing cis-pinane by hydrogenating alpha-pinene, aiming at solving the problems of high cost and difficult separation of a noble metal catalyst in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing cis-pinane by hydrogenating alpha-pinene comprises the step of loading alpha-pinene on an amphiphilic nano mesoporous material in an aqueous solution to form a nickel active particle catalyst Ni/CxNy @ mSiO2Under the catalytic action of (3), fill pressure H2And carrying out catalytic hydrogenation reaction to obtain the cis-pinane.
The alpha-pinene and the catalyst Ni/CxNy @ mSiO provided by the invention2Is 1000; the reaction temperature of the catalytic hydrogenation reaction is 60-70 ℃, the reaction time is 2H, and H in the reaction process2The pressure was 3 MPa.
After the catalytic hydrogenation reaction is finished, standing, aging and layering to separate the catalyst and the cis-pinane, extracting with an organic solvent such as n-heptane, and collecting an upper product.
In an ethanol medium, with CxNy @ mSiO2The formed nano particles are taken as a stabilizer, nickel particles are loaded on the amphiphilic nano mesoporous particles through reduction hydrogenation of nickel salt, and the nano particle ball catalyst Ni/CxNy @ mSiO with catalytic property is formed2In this catalytic system, CxNy @ mSiO2The catalyst can be used as an 'amphiphilic microreactor', so that catalytic reaction is carried out in a formed microenvironment, the reaction is promoted, the catalytic efficiency is improved, and the amphiphilic microreactor can provide the amphipathy and is important for the separation of the catalyst.
In consideration of the fact that the cost of noble metal supported by the catalyst is higher, the inventor selects non-noble metal as a supported metal atom, but the amphiphilic nano mesoporous material supported non-noble metal active particle catalyst provided by the invention has strict selection of non-noble metal, non-noble metal nickel (Ni) in a catalytic system enables the catalyst to show more excellent catalytic activity and product selectivity, the performance of the catalyst is obviously superior to that of other non-noble metals, the metal atoms supported by the catalyst are different, and the capacities of adsorbing and cracking hydrogen molecules are different, so that the activity of catalytic hydrogenation reaction is shownIn contrast, at the catalyst support CxNy @ mSiO2Under the provided amphiphilic environment, the Ni-based catalyst has the fastest speed of absorbing hydrogen, and the activity energy required by cracking hydrogen molecules is lower; in addition, in the preparation of the catalyst, the support CxNy @ mSiO was found2Can load more Ni nano particles to lead Ni/CxNy @ mSiO2The Ni-based catalyst provided by the invention has more catalytic active centers and is also an obvious advantage, and test data show that the Ni-based catalyst provided by the invention has better catalytic activity and product selectivity.
In the catalytic hydrogenation reaction, a solid catalyst-alpha-pinene oil phase-hydrogen forms a three-phase interface, so that mass transfer resistance is reduced, the reaction is facilitated, the catalytic hydrogenation reaction can be carried out under mild conditions, the mild reaction conditions enable the catalyst to have higher catalytic efficiency on alpha-pinene, the selectivity is better, the catalytic efficiency is reduced when the temperature is too high, mainly because the excessive temperature destroys the three-phase interface of the reaction, so that the catalytic activity is reduced, and the effective catalytic temperature of the catalyst is 60-70 ℃. In addition, after the reaction is finished, the catalyst is separated by standing and layering, the catalyst can be recycled, and the activity of the recovered catalyst can be still maintained.
Another object of the invention is to provide the catalyst Ni/CxNy @ mSiO2The preparation method comprises the steps of adopting resorcinol and formaldehyde as carbon sources, ethanediamine as nitrogen sources, hexadecyl trimethyl ammonium bromide as a template agent, tetraethoxysilane as a silicon source, and synthesizing the amphiphilic core-shell nano mesoporous material CxNy @ mSiO by high-temperature carbonization2Finally, nickel particles are loaded on the amphiphilic nano mesoporous core-shell material through reduction hydrogenation of nickel salt to form a stable catalyst Ni/CxNy @ mSiO2。
The catalyst Ni/CxNy @ mSiO2The preparation method specifically comprises the following steps:
1) the hollow Juans amphiphilic nano mesoporous material CxNy @ mSiO2Respectively weighing 0.16g CTAB (cetyl trimethyl ammonium bromide) and 5mL EDA (ethylenediamine) and dispersing in 50mL of mixed solution of ethanol and water, adding 0.12g resorcinol, ultrasonically dispersing for 30min, dropwise adding 0.24mL formaldehyde, stirring for reacting for 2h, and addingAdding 50mg CTAB, dropwise adding 0.8mL TEOS (tetraethyl orthosilicate), continuously stirring for 12h, standing and aging for 48h, centrifugally separating, and finally carbonizing at high temperature in an argon atmosphere to obtain the amphiphilic nano mesoporous material CxNy @ mSiO2；
2) Hollow Juans amphiphilic nano mesoporous material loaded nickel active particle catalyst Ni/CxNy @ mSiO2Weighing 50mg CxNy @ mSiO2Adding into a 100mL single-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 30mg NiCl2Continuously dispersing for 10min, and then weighing 30mg NaBH4Adding the solution into a 10mL centrifuge tube, adding 8mL ethyl acetate solution to completely dissolve the solution, dropwise adding the dissolved liquid into a single-neck flask, and magnetically stirring the solution at 40 ℃ for 2 hours to obtain the catalyst Ni/CxNy @ mSiO2。
Preferably, the volume ratio of ethanol to water in the mixed solution of ethanol and water is 3: 7.
The invention provides a method for preparing cis-pinane by hydrogenating alpha-pinene, wherein a hollow Juans amphiphilic nano mesoporous material loaded nickel active particle catalyst Ni/CxNy @ mSiO is used in the method2Presents better catalytic activity and product selectivity, and coordinates with various reaction conditions of catalytic hydrogenation reaction to ensure that the alpha-pinene conversion rate and the cis-pinane selectivity reach the best.
Detailed Description
The invention discloses a method for preparing cis-pinane by hydrogenating alpha-pinene, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
EXAMPLE 1 catalyst Ni/CxNy @ mSiO2Preparation of
S1Preparation of hollow Juans amphiphilic nano mesoporous material (CxNy @ mSiO)2): respectively weighing 0.16g of CTAB (cetyl trimethyl ammonium bromide) and 5mL of EDA (ethylenediamine) and dispersing in 50mL of mixed solution of ethanol and water (ethanol: water is 3:7), adding 0.12g of resorcinol, performing ultrasonic dispersion for 30min, dropwise adding 0.24mL of formaldehyde, stirring for reaction for 2h, adding 50mg of CTAB, dropwise adding 0.8mL of TEOS (tetraethyl orthosilicate), continuing stirring for 12h, standing for aging for 48h, performing centrifugal separation, and finally carbonizing at high temperature in an argon atmosphere to obtain the amphiphilic nano mesoporous material CxNy @ mSiO2；
S2Preparation of hollow Juans amphiphilic nano catalyst (Ni/CxNy @ mSiO)2): weighing 50mg CxNy @ mSiO2Adding into a 100mL single-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 30mg NiCl2Continuously dispersing for 10min, and then weighing 30mg NaBH4Adding the mixture into a 10mL centrifuge tube, adding 8mL ethyl acetate solution to completely dissolve the mixture, dropwise adding the dissolved liquid into a single-neck flask, and magnetically stirring the mixture for 2 hours at 40 ℃ to obtain the stable amphiphilic nano catalyst Ni/CxNy @ mSiO2。
Synthesized amphiphilic nano mesoporous material CxNy @ mSiO2Scanning by a scanning electron microscope and a transmission electron microscope obviously shows that the catalyst carrier prepared by the method has uniform size particles and larger specific surface area, can increase the contact area of a substrate and the catalyst and promote the reaction. Synthetic amphiphilic nano catalyst Ni/CxNy @ mSiO2The amphiphilic nano catalyst Ni/CxNy @ mSiO can be obviously seen through the scanning of a high-resolution transmission electron microscope2Lattice striations of supported metal nanoparticles nickel (Ni).
Example 2 hydrogenation of alpha-pinene to produce cis-pinane
Weighing 1g of alpha-pinene, adding the alpha-pinene into a stainless steel mechanical stirring kettle, adding 4mL of water, weighing 20mg of amphiphilic catalyst, uniformly mixing, replacing gas in the kettle for 4 times by 1MPa hydrogen, then flushing 3MPa hydrogen, mechanically stirring for reaction for 2h at 60 ℃, standing after the reaction is finished, separating the catalyst from a product, extracting by n-heptane, collecting an upper product phase, and carrying out quantitative analysis by adopting a chromatography, wherein the conversion rate of the alpha-pinene is 95.6%, and the selectivity of the cis-pinane is 96.5%.
EXAMPLE 3 hydrogenation of alpha-pinene to produce cis-pinane
Weighing 1g of alpha-pinene, adding the alpha-pinene into a stainless steel mechanical stirring kettle, adding 4mL of water, weighing 20mg of amphiphilic catalyst, uniformly mixing, replacing gas in the kettle for 4 times by 1MPa hydrogen, then flushing 3MPa hydrogen, mechanically stirring for reaction at 70 ℃ for 2h, after the reaction is finished, standing to separate the catalyst from a product, extracting by toluene, collecting an upper layer product phase, and carrying out quantitative analysis by adopting a chromatography, wherein the conversion rate of the alpha-pinene is 97.1%, and the selectivity of cis-pinane is 98.5%.
EXAMPLE 4 Recycling of the catalyst
Weighing 1g of alpha-pinene, adding the alpha-pinene into a stainless steel high-pressure reaction kettle, adding 4mL of water, weighing 20mg of amphiphilic nano catalyst, uniformly mixing, replacing gas in the kettle by 1MPa hydrogen for 4 times, then flushing 3MPa hydrogen, mechanically stirring at 60 ℃ for reaction for 2h, after the reaction is finished, separating the catalyst from a product, recycling the separated catalyst, repeating the experiment steps for 7 times, wherein the alpha-pinene conversion rate is 95.2%, the selectivity of the homeopinane is 96.5%, and the catalyst has good reusability.
Example 5 selection of temperature for hydrogenation of alpha-pinene to produce cis-pinane
Weighing 1g of alpha-pinene, adding the alpha-pinene into a stainless steel mechanical reaction kettle, adding 4mL of water, weighing 20mg of amphiphilic nano catalyst, uniformly mixing, replacing gas in the kettle for 4 times by 1MPa of hydrogen, then flushing 3MPa of hydrogen, reacting for 1h under magnetic stirring at 100 ℃, standing after the reaction is finished, separating the catalyst from a substrate, extracting by n-heptane, collecting an upper product phase, and carrying out quantitative analysis by adopting a chromatography, wherein the conversion rate of the alpha-pinene is 24.5%, and the selectivity of the cis-pinane is 96.6%; the catalytic efficiency is reduced when the temperature is too high, mainly because the three-phase interface of the reaction is damaged by the too high temperature, the catalytic activity is reduced, and the effective catalytic temperature of the catalyst is 60-70 ℃.
Comparative example
Adding 1g of alpha-pinene, 20mg of different catalysts shown in table 1 and 4mL of water into a stainless steel mechanical reaction kettle, uniformly mixing, replacing 4 times with 1MPa hydrogen, flushing with 3MPa hydrogen, reacting for 2 hours under magnetic stirring at 60 ℃, separating the catalyst and the product by centrifugation after the reaction is finished, extracting the product phase with n-heptane, and performing quantitative analysis on the product by chromatography, wherein the conversion rate of alpha-pinene and the selectivity of cis-pinane are shown in table 1.
TABLE 1 Effect of different catalysts on the catalytic hydrogenation of alpha-pinene
The data in table 1 show that the catalyst designed by the invention has excellent catalytic activity and product selectivity for the alpha-pinene hydrogenation catalytic reaction under the same conditions when hydrogen is used as a reducing agent, and the effect of the catalyst is obviously superior to other non-noble metal catalysts and also obviously superior to industrial Reny Ni catalysts; meanwhile, the catalyst is superior to a noble metal catalyst Pd/C in selectivity.
The non-noble metal atom Ni loaded by the catalyst provided by the invention has stronger capability of adsorbing and cracking hydrogen molecules, and the catalyst carrier CxNy @ mSiO2Under the amphiphilic environment, the Ni-based catalyst has the fastest hydrogen adsorption capacity and speed, the activity required by cracking hydrogen molecules is lower, and simultaneously, the carrier CxNy @ mSiO2Can load more Ni nano particles to lead Ni/CxNy @ mSiO2Has more catalytic active centers; therefore, the invention provides a catalyst Ni/CxNy @ mSiO2The catalyst shows excellent catalytic activity and product selectivity to alpha-pinene hydrogenation catalytic reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for preparing cis-pinane by hydrogenating alpha-pinene is characterized in that in aqueous solution, the alpha-pinene loads a nickel active particle catalyst Ni/CxNy @ mSiO in an amphiphilic nano mesoporous material2Under the catalytic action of (3), fill pressure H2And carrying out catalytic hydrogenation reaction to obtain the cis-pinane.
2. The process for the hydrogenation of α -pinene to produce cis-pinane of claim 1, wherein the α -pinene is hydrogenated with the catalyst Ni/CxNy @ mSiO2In a mass ratio of 50: 1.
3. The method for preparing cis-pinane by hydrogenating alpha-pinene according to claim 1, wherein the reaction temperature of the catalytic hydrogenation reaction is 60-70 ℃, the reaction time is 2 hours, and H in the reaction process2The pressure was 3 MPa.
4. The method for preparing cis-pinane by hydrogenating alpha-pinene according to claim 1, wherein after the catalytic hydrogenation reaction is finished, the catalyst is separated from the cis-pinane by standing, aging and layering.
5. The process for the hydrogenation of α -pinene to produce cis-pinane of claim 1, wherein the catalyst is Ni/CxNy @ mSiO2The preparation method comprises the steps of adopting resorcinol and formaldehyde as carbon sources, ethanediamine as nitrogen sources, hexadecyl trimethyl ammonium bromide as a template agent, tetraethoxysilane as a silicon source, and synthesizing the amphiphilic core-shell nano mesoporous material CxNy @ mSiO by high-temperature carbonization2Finally, nickel particles are loaded on the amphiphilic nano mesoporous core-shell material through reduction hydrogenation of nickel salt to form a stable catalyst Ni/CxNy @ mSiO2。
6. The process for the hydrogenation of α -pinene to produce cis-pinane of claim 1 or claim 5, wherein the catalyst is Ni/CxNy @ mSiO2The preparation method specifically comprises the following steps:
1) the hollow Juans amphiphilic nano mesoporous material CxNy @ mSiO2Respectively weighing 0.16g of CTAB (cetyl trimethyl ammonium bromide) and 5mL of EDA (ethylenediamine) and dispersing in 50mL of mixed solution of ethanol and water, then adding 0.12g of resorcinol, ultrasonically dispersing for 30min, dropwise adding 0.24mL of formaldehyde, stirring for reacting for 2h, then adding 50mg of CTAB, dropwise adding 0.8mL of TEOS (tetraethoxysilane), continuing stirring for 12h, then standing and aging for 48h, centrifugally separating, and finally carbonizing at high temperature in an argon atmosphere to obtain the amphiphilic nano mesoporous material CxNy @ mSiO2；
2) Hollow Juans amphiphilic nano mesoporous material loaded nickel active particle catalyst Ni/CxNy @ mSiO2Weighing 50mg CxNy @ mSiO2Adding into a 100mL single-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 30mg NiCl2Continuously dispersing for 10min, and then weighing 30mg NaBH4Adding the solution into a 10mL centrifuge tube, adding 8mL ethyl acetate solution to completely dissolve the solution, dropwise adding the dissolved liquid into a single-neck flask, and magnetically stirring the solution at 40 ℃ for 2 hours to obtain the catalyst Ni/CxNy @ mSiO2。
7. The method for preparing cis-pinane by hydrogenating alpha-pinene according to claim 6, wherein the volume ratio of ethanol to water in the mixed solution of ethanol and water is 3: 7.
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