CN111871441A - Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof - Google Patents
Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof Download PDFInfo
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- CN111871441A CN111871441A CN202010727773.5A CN202010727773A CN111871441A CN 111871441 A CN111871441 A CN 111871441A CN 202010727773 A CN202010727773 A CN 202010727773A CN 111871441 A CN111871441 A CN 111871441A
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 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 title claims abstract description 104
- 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 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000013335 mesoporous material Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time 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
- 230000002431 foraging effect Effects 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
- 239000000243 solution Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of hydrogenated rosin preparation, and discloses a method for preparing hydrogenated rosin by rosin hydrogenation and a catalyst thereof. The method for preparing hydrogenated rosin by rosin hydrogenation comprises the steps of adding Ni/CxNy @ mSiO in a mixed solution of water and 200# solvent oil in a Juans type hollow amphiphilic nano catalyst2Under the catalytic action of (3), is filled with H2And catalyzing the hydrogenation of the rosin to prepare hydrogenated rosin. The Ni-based catalyst provided by the invention is Ni/CxNy @ mSiO2The catalyst has better catalytic activity and product selectivity, and the rosin hydrogenation reaction has mild reaction conditions and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of hydrogenated rosin preparation, and particularly relates to a method for preparing hydrogenated rosin by rosin hydrogenation and a catalyst thereof.
Background
Rosin is a solid remained after pine oil generated by exudation of pine plants is distilled and cooled, is generally yellow or brown in color, is a renewable chemical raw material, and is widely applied to the industries of materials, medicines, rubber, graphite and the like; china is a big country for rosin production, the yield reaches 679.87 ten thousand tons/year, but the utilization rate is low, and the rosin is directly exported without deep processing, thereby causing a great amount of economic loss. Rosin is a complex compound, the main component of which is abietic acid type resin acid, the abietic acid type resin acid has a pair of conjugated double bonds and a ternary phenanthrene ring skeleton structure, and has a plurality of isomers including pimaric acid, abietic acid, palustric acid, neoabietic acid and the like, and the abietic acid type resin acids have similar physicochemical properties.
The unsaturated conjugated double bonds of the longitudinal acid type resin acid are easy to oxidize, so that the use quality of the rosin is reduced, and the application of the rosin in industries such as rubber, graphite and the like is limited. In order to improve the quality of rosin, unsaturated double bonds of longitudinal acid resin tend to be saturated so as to be more stable, and the rosin is modified by disproportionation, hydrogenation and the like. Hydrogenated rosin generated after rosin hydrogenation can lead double bonds to be saturated so as to enable the double bonds to be more stable, and has better oxidation resistance and lighter color, so the hydrogenated rosin and derivatives thereof are widely applied to industries such as medicine, materials, chemical engineering and the like.
The traditional catalyst used for rosin hydrogenation is usually Pd/C, Ru/C or active components such as Ru, Rh and the like are added in the traditional Pd/C, Ru/C catalyst, but the catalysts belong to noble metal catalysts, not only the cost is high, but also the catalytic activity is relatively low; in addition, in these catalysts using activated carbon as a carrier, active metal particles are liable to fall off and run off, resulting in poor catalytic cycle effect. In conclusion, the invention provides a method for preparing hydrogenated rosin by hydrogenation of non-noble metal catalytic rosin under mild conditions, and has important significance.
Disclosure of Invention
The invention provides a method for preparing hydrogenated rosin by rosin hydrogenation, aiming at solving the problems of high catalyst cost, low catalytic activity under mild conditions and poor recycling effect in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first invention aim of the invention is to provide a catalyst for preparing hydrogenated rosin by rosin hydrogenation, which is prepared by the following method: adopting resorcinol and formaldehyde as carbon sources, ethylenediamine as nitrogen sources, hexadecyl trimethyl ammonium bromide as a template agent and tetraethoxysilane as a silicon source to synthesize 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 amphiphilic nano catalyst Ni/CxNy @ mSiO2。
Preferably, the preparation method of the catalyst specifically comprises the following steps:
1) juans type hollow amphiphilic nano 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 (ethyl orthosilicate), continuously stirring for 12h, then standing for 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) Juans type hollow amphiphilic nano catalyst Ni/CxNy @ mSiO2Weighing 200mg CxNy @ mSiO2Adding into a three-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 50mg NiCl2Continuously dispersing for 10min, and then weighing 30mg NaBH4Adding the mixture into a three-neck flask, and mechanically stirring the mixture for 2 hours at the temperature of 40 ℃ to obtain the stable amphiphilic nano catalyst Ni/CxNy @ mSiO2。
The traditional catalyst used for rosin hydrogenation is usually Pd/C, Ru/C or active components such as Ru, Rh and the like are added in the traditional Pd/C, Ru/C catalyst, but the catalysts belong to noble metal catalysts, not only the cost is high, but also the catalytic activity is relatively low; in addition, in these catalysts using activated carbon as a carrier, active metal particles are liable to fall off and run off, resulting in poor catalytic cycle effect. Therefore, the inventor provides an amphiphilic nano catalyst for rosin hydrogenation reaction, and simultaneously considers that the type of the supported non-noble metal in a catalytic system is strictly selected, so that the invention selects the non-noble metal Ni with catalytic activity and product selectivity obviously superior to other metals.
In an ethanol medium, with CxNy @ mSiO2The formed nano-particles are taken as a stabilizer, nickel particles are loaded on the amphiphilic mesoporous nano-particles by the principle of nickel salt reduction hydrogenation, 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 performed in a formed microenvironment, the reaction can be promoted, the catalytic efficiency is improved, and the hydrophilicity and hydrophobicity can be provided, so that the catalyst is important for separation of the catalyst; the inventor unexpectedly finds that the selectivity of hydrogenated rosin prepared by catalytic hydrogenation of a Juans type hollow amphiphilic nano catalyst to non-noble metal is also strict, compared with other metals, the non-noble metal nickel (Ni) in a catalytic system enables the catalyst to show excellent catalytic activity and product selectivity, the performance of the catalyst is obviously superior to that of other metals, metal atoms loaded on the catalyst are different, and the capacity of adsorbing and cracking hydrogen molecules is different, so that the catalytic hydrogenation reaction shown is different in activity, and CxNy @ mSiO is a catalyst carrier2Under 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 has more catalytic active centers and is also an obvious advantage, and the final catalytic result experimental data clearly show that the Ni-based catalyst provided by the invention has better catalytic activity and product selectivity.
The second invention aims to provide a method for preparing hydrogenated rosin by hydrogenating rosin, which is to add Ni/CxNy @ mSiO in Juans type hollow amphiphilic nano catalyst in mixed solution of water and 200# solvent oil2Under the catalytic action of (3), is filled with H2And catalyzing the hydrogenation of the rosin to prepare hydrogenated rosin.
Preferably, the rosin is reacted with the catalyst Ni/CxNy @ mSiO2In a mass ratio of 25: 1.
Preferably, the reaction temperature of the catalytic rosin hydrogenation reaction is 120-200 ℃, the reaction time is 2-8 h, and the hydrogen pressure in the reaction process is 2-8 MPa. More preferably, the reaction temperature of the catalytic rosin hydrogenation reaction is 130-150 ℃, the reaction time is 4h, and the hydrogen pressure in the reaction process is 4 MPa.
After the catalytic rosin hydrogenation reaction is finished, standing, aging and layering to separate the catalyst from the hydrogenated rosin, dispersing the catalyst in the bottom water phase, separating oil phase supernatant to obtain a product hydrogenated rosin, and recycling the catalyst in the bottom water phase for continuous reuse.
Catalyst Ni/CxNy @ mSiO2Adding into a reaction kettle, adding a certain amount of rosin, and filling with H under a certain pressure2The hydrogenation reaction is carried out, in the hydrogenation reaction, a solid catalyst, rosin oil phase and hydrogen form a three-phase interface, the mass transfer resistance is reduced, the reaction is favorably carried out, the catalytic hydrogenation reaction can be carried out under mild conditions, the rosin hydrogenation has higher catalytic efficiency and better selectivity, after the reaction is finished, the mixture is stood, aged and layered, and the catalyst can be recycled.
The addition of water in the reaction system is favorable for separating the hydrophilic catalyst from the substrate, but the catalytic efficiency of the catalytic reaction is obviously influenced because the catalytic reaction occurs in a water phase, and the catalyst Pd/CxNy @ mSiO provided by the invention2The catalyst is amphiphilic, and can be well contacted with a substrate in an oil phase by utilizing the lipophilicity of the catalyst, so that the separation of the catalyst and the substrate can be well realized while high catalytic activity is ensured. The catalyst Ni/CxNy @ mSiO provided by the invention2And on the premise of the process for preparing hydrogenated rosin by rosin hydrogenation, the proportion condition of 200# solvent oil and water in the reaction can be optimized, and meanwhile, the reaction condition for preparing hydrogenated rosin by rosin hydrogenation is cooperated, so that the catalytic efficiency of the catalytic reaction can be improved to a certain extent by adding water in the preparation process of hydrogenated rosin.
The invention provides a rosin hydrogenation methodThe invention provides a method for preparing hydrogenated rosin and a catalyst thereof, and a Ni-based catalyst Ni/CxNy @ mSiO2The catalyst has the advantages of good catalytic activity and product selectivity, low cost because the catalytic activity center particles are non-noble metal nickel (Ni), simple separation and good reusability. Test results show that the conversion rate of the rosin reaches more than 92%, the tetrahydroabietic acid in the product meets the requirements of special-grade rosin, the amphiphilic catalyst is recycled for more than 4 times, and the conversion rate of the rosin is still more than 90%. According to the technical scheme, the rosin hydrogenation reaction provided by the invention is mild in reaction condition and environment-friendly.
Detailed Description
The invention discloses a method for preparing hydrogenated rosin by rosin hydrogenation and a catalyst thereof, 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
S1And amphiphilic nano mesoporous material CxNy @ mSiO2Respectively weighing 0.16g of CTAB (cetyl trimethyl ammonium bromide) and 5mL of ethylenediamine (ethylene diamine) and dispersing in 50mL of mixed solution of ethanol and water (ethanol: water is 3:7), then adding 0.12g of resorcinol, performing ultrasonic dispersion for 30min, dropwise adding 0.24mL of formaldehyde, stirring for reaction for 2h, then adding 50mg of CTAB, dropwise adding 0.8mL of TEOS (ethyl orthosilicate), continuing stirring for 12h, then standing for aging for 48h, performing centrifugal separation, and finally performing high-temperature carbonization in an argon atmosphere to obtain the amphiphilic nano mesoporous material CxNy @ mSiO2；
S2Amphiphilic nano catalyst Ni/CxNy @ mSiO2The preparation of (1) is that 200mg CxNy @ mSiO is weighed2Adding into a three-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 50mg NiCl2Continuously dispersing for 10min, and then weighing 30mgNaBH4Adding the mixture into a three-neck flask, and mechanically stirring the mixture for 2 hours at the temperature of 40 ℃ to obtain the stable amphiphilic nano catalyst Ni/CxNy @ mSiO2。
Example 2 hydrogenation of rosin to hydrogenated rosin
Weighing 1g of rosin, adding the rosin into a stainless steel mechanical stirring kettle, then adding 4mL of water and 6mL of 200# solvent oil, and weighing 40mg of amphiphilic catalyst Ni/CxNy @ mSiO2Mixing uniformly, replacing gas in the kettle for 4 times by 1MPa hydrogen, then filling 4MPa hydrogen, mechanically stirring and reacting for 4 hours at 140 ℃, standing for a period of time after the reaction is finished, separating a catalyst from a product, collecting an upper layer product, and carrying out quantitative analysis by adopting a chromatography method, wherein the conversion rate of rosin reaches 94.78%, the selectivity of tetrahydroabietic acid in the product is 61.80%, and the selectivity of dihydroabietic acid is 35.12%, so that the requirement of special-grade rosin is met.
Example 3 hydrogenation of rosin to hydrogenated rosin
Weighing 1g of rosin, adding the rosin into a stainless steel mechanical stirring kettle, then adding 4mL of water and 6mL of 200# solvent oil, and weighing 40mg of amphiphilic catalyst Ni/CxNy @ mSiO2Mixing uniformly, replacing gas in the kettle for 4 times by 1MPa hydrogen, then flushing 2MPa hydrogen, mechanically stirring and reacting for 2h at 120 ℃, standing, aging and layering after the reaction is finished, separating a catalyst from a product, collecting an upper layer product, and carrying out quantitative analysis by adopting a chromatography method, wherein the conversion rate of rosin reaches 92.09%, the selectivity of tetrahydroabietic acid in the product is 61.17%, and the selectivity of dihydroabietic acid is 29.09%, so that the requirement of special-grade rosin is met.
Example 4 hydrogenation of rosin to hydrogenated rosin
Weighing 1g of rosin, adding the rosin into a stainless steel mechanical stirring kettle, then adding 4mL of water and 6mL of 200# solvent oil, and weighing 40mg of amphiphilic catalyst Ni/CxNy @ mSiO2Mixing, replacing gas in the kettle with 1MPa hydrogen for 4 times, and flushingAdding 8MPa hydrogen, mechanically stirring and reacting for 8h at 180 ℃, standing, aging and layering after the reaction is finished, separating the catalyst from the product, collecting the upper layer product, and carrying out quantitative analysis by adopting chromatography, wherein the conversion rate of the rosin reaches 97.23%, the selectivity of the tetrahydroabietic acid in the product is 53.10%, and the selectivity of the dihydrolongitudinal acid is 34.67%, and the tetrahydroabietic acid is slightly less than the dihydrolongitudinal acid due to the temperature relationship, but all the tetrahydroabietic acid meets the requirements of special-grade rosin.
EXAMPLE 5 Recycling of the catalyst
Weighing 1g of rosin, adding the rosin into a stainless steel mechanical stirring kettle, then adding 4mL of water and 6mL of 200# solvent oil, and weighing 40mg of amphiphilic catalyst Ni/CxNy @ mSiO2Mixing uniformly, replacing gas in the kettle for 4 times by 1MPa hydrogen, then flushing 4MPa hydrogen, mechanically stirring and reacting for 4 hours at 140 ℃, standing, aging and layering after the reaction is finished to separate the catalyst from the product, recycling the separated catalyst, repeating the experimental steps, recycling the amphiphilic catalyst for 4 times, and ensuring that the conversion rate of the rosin is still more than 90 percent.
Comparative example 1
The amphiphilic catalyst in table 1 was prepared by the same method as in example 1, 1g of rosin was weighed and added to a stainless steel mechanical stirred tank, 4mL of water and 6mL of 200# solvent oil were then added, 40mg of the prepared amphiphilic catalyst or the industrially conventional catalyst Pd/C, Ru/C was weighed and mixed uniformly, the gas in the tank was replaced with 1MPa hydrogen for 4 times, then 4MPa hydrogen was flushed, the reaction was mechanically stirred at 140 ℃ for 4 hours, after the reaction was completed, the mixture was allowed to stand or centrifuged for layering, and the upper product phase was collected for quantitative analysis by chromatography, and the conversion rate and selectivity of rosin were as shown in table 1.
TABLE 1 Effect of different catalysts on rosin hydroconversion and selectivity
The data in Table 1 show that the metal in the catalytic system plays a key role in improving the selectivity and the catalytic efficiency, and compared with the traditional catalysts Pd/C and R, the method for preparing hydrogenated rosin by rosin hydrogenation provided by the inventionThe u/C has higher catalytic efficiency on rosin, and the traditional catalyst adopts activated carbon as a carrier, so that active metal particles are easy to fall off and run off, and the catalytic recycling effect is poor; CxNy @ mSiO in catalytic system2The supported metals have different types and different catalytic effects, and the data in Table 1 show that the catalyst Ni/CxNy @ mSiO provided by the invention2The supported non-noble metal atom Ni has stronger capability of absorbing and cracking hydrogen molecules than other metal atoms, 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.
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. The catalyst for preparing hydrogenated rosin by hydrogenating rosin is characterized by being prepared by the following method: adopting resorcinol and formaldehyde as carbon sources, ethylenediamine as nitrogen sources, hexadecyl trimethyl ammonium bromide as a template agent and tetraethoxysilane as a silicon source to synthesize 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 amphiphilic nano catalyst Ni/CxNy @ mSiO2。
2. The catalyst according to claim 1, wherein the preparation method of the catalyst comprises the following steps:
1) juans type hollow amphiphilic nano material CxNy @ mSiO20.16g CTAB (cetyltrimethylammonium bromide) and 5mL EDA (ethylenediamine) were weighed and dispersed in 50mL ethanol and waterAdding 0.12g of resorcinol into a mixed solution, performing ultrasonic dispersion for 30min, dropwise adding 0.24mL of formaldehyde, stirring for reaction for 2h, then adding 50mg of CTAB, dropwise adding 0.8mL of TEOS (tetraethyl orthosilicate), continuously stirring for 12h, standing for aging for 48h, performing centrifugal separation, and finally performing high-temperature carbonization in an argon atmosphere to obtain the amphiphilic nano mesoporous material CxNy @ mSiO2；
2) Juans type hollow amphiphilic nano catalyst Ni/CxNy @ mSiO2Weighing 200mg CxNy @ mSiO2Adding into a three-neck flask, ultrasonically dispersing in ethanol solution at room temperature, and adding 50mg NiCl2Continuously dispersing for 10min, and then weighing 30mg NaBH4Adding the mixture into a three-neck flask, and mechanically stirring the mixture for 2 hours at the temperature of 40 ℃ to obtain the stable amphiphilic nano catalyst Ni/CxNy @ mSiO2。
3. The method for preparing hydrogenated rosin by rosin hydrogenation is characterized in that in a mixed solution of water and 200# solvent oil, a Juans type hollow amphiphilic nano catalyst Ni/CxNy @ mSiO2Under the catalytic action of (3), is filled with H2And catalyzing the hydrogenation of the rosin to prepare hydrogenated rosin.
4. The method of claim 3, wherein the rosin is reacted with the catalyst Ni/CxNy @ mSiO2In a mass ratio of 25: 1.
5. The method for preparing hydrogenated rosin by rosin hydrogenation according to claim 3, wherein the reaction temperature of the catalytic rosin hydrogenation reaction is 120-200 ℃, the reaction time is 2-8 h, and the hydrogen pressure in the reaction process is 2-8 MPa.
6. The method for preparing hydrogenated rosin by hydrogenating rosin according to claim 3 or 5, wherein the reaction temperature of the catalytic rosin hydrogenation reaction is 130-150 ℃, the reaction time is 4 hours, and the hydrogen pressure in the reaction process is 4 MPa.
7. The method of claim 3 wherein after the catalytic rosin hydrogenation reaction is complete, the catalyst is separated from the hydrogenated rosin by standing, aging and layering.
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