CN103566932B - A kind of powdery Pd/SiO2Catalysts and its preparation method and application - Google Patents
A kind of powdery Pd/SiO2Catalysts and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of powdery Pd/SiO2Catalyst, component by following percentage by weight forms: 90～99.98% granular colloidal silica, 0.01～5% palladium metal component and 0.01～5% co-catalyst, described co-catalyst is one or more in lithium, sodium, potassium, chromium, manganese, zinc, silver, titanium, lead, bismuth, and the granularity of described granular colloidal silica is 150～500 orders. This catalyst is the hydrogenation reaction at reactor for the larger alkynol compounds of molecular weight, and the alkalescence that can eliminate current use lindlar catalyst is strong, isomery, the shortcoming such as the side reactions such as polymerization are many, and pin material rate is high, and specific surface is little, and adsorptivity is low, poor selectivity. The invention also discloses this powdery Pd/SiO2The preparation method of catalyst and the application in the hydrogenation reaction of alkynol compounds. Be applied to alkynol compounds hydrogenation and produce when enols used, conversion ratio and selective high.
Description
Technical field
The invention belongs to load hydrogenation catalyst field, be specifically related to a kind of powdery Pd/SiO2Catalyst and preparation thereofMethods and applications.
Background technology
The selective hydrogenation of alkynol compounds is produced enols usedly has an important application industrial, especially in dimensionRaw element and spices preparation field. Taking linalool as example, this compound has higher economic worth, it can be used as senior spices orThe raw materials of essence is also the important intermediate of synthesising complex E and vitamin A. Gone out by oil C5 fraction separated productSend out that to prepare linalool through 6-methyl-5-hepten-2-one (dehydrolinalool) be current artificial synthetic a kind of important work of linaloolSkill route. Dehydrolinalool through the main side effect of selective hydrogenation linalool processed as shown in the formula shown in III and formula IV. Shown in formula IVThe side reaction of consecutive hydrogenation very easily follow generation with main reaction, therefore hydrogenation reaction is high to selectively having of all catalystRequirement.
In the prior art, the suitability for industrialized production of preparing linalool from dehydrolinalool through selective hydrogenation is mostly anti-in liquid phase autoclaveAnswer in device and carry out in mode intermittently, hydrogenation catalyst generally adopts Lindlar catalyst (a kind of taking whiting as carryingBody, the loaded catalyst taking metal Pd and Pb as active component). In order to improve reaction selectivity, early stage Lindlar catalysisAgent also must make catalyst absorption or directly in reaction system, add the compounds such as a certain amount of pyridine or quinoline, and this is for virtueThe preparation of camphor tree alcohol has fatal shortcoming, and it will cause product variable color and bring peculiar smell, and grievous injury is as spices or perfume (or spice)Form and aspect and the flavouring essence quality of the linalool product of essence raw material. In later stage improved Lindlar catalyst activity component, further addEntered metal Bi, this is for optionally improving and played certain positive role.
" Pb, the synthetic linalool of Bi modification Pd catalyst " (" fine chemistry industry ", the 20th volume, the 8th phase) literary composition discloses oneBatch process is prepared the method for linalool by dehydrolinalool selective hydrogenation, hydrogenation catalyst adopts improved Lindlar catalysisAgent, with the CaCO of powdery3For carrier, load active component metal Pd, Pb and Bi. Throw at strict control hydrogen and dehydrolinaloolUnder the prerequisite of material ratio, do not add the compound such as pyridine or quinoline in catalyst and reaction system, best experimental result is dehydrogenation virtue camphor treeThe conversion ratio of alcohol reaches 99%, linalool selectively reach 98%. But with CaCO3For the catalyst acid labile of carrier, alkaliProperty is strong, and the side reactions such as isomery, polymerization are many, and pin material rate is high, and specific area is little, and adsorptivity is low, poor selectivity.
Summary of the invention
The invention provides a kind of powdery Pd/SiO2Catalyst, this powdery Pd/SiO2Catalyst is for alkynol compoundsWhen hydrogenation is produced in enols used reaction, catalytic activity is higher, and side reaction is few, has effectively avoided excessive hydrogenation,Improve the selective of product.
The present invention also provides a kind of powdery Pd/SiO2The preparation method of catalyst, this preparation method is prepared easily, activityUniform component distribution.
The present invention also provides a kind of described powdery Pd/SiO2Catalyst is at alkynol compounds selective hydrogenationIn application.
A kind of powdery Pd/SiO2Catalyst, is made up of the component of following percentage by weight:
Granular colloidal silica 90～99.98%
Palladium metal component 0.01～5%
Co-catalyst 0.01～5%
Described co-catalyst is one or more in lithium, sodium, potassium, chromium, manganese, zinc, silver, titanium, lead, bismuth;
The granularity of described granular colloidal silica is 150～500 orders.
The present invention, taking granular colloidal silica as carrier, has been adsorbed Pd at the surfaces externally and internally of silica gel, has made Powdered Pd/SiO2UrgeAgent, the nearly neutral feature of Powdered silica gel used, can reduce the generation of the side reaction such as isomery, polymerization greatly; LargerPore be convenient to the diffusion in catalyst granules inside of alkynol compounds that molecular weight is larger, this can not only improve catalysisThe activity of agent, and reduced the enols used time stopping of product in catalyst duct, thus avoid excessively addingHydrogen, has improved product selectivity.
As preferably, described powdery Pd/SiO2Catalyst, is made up of the component of following percentage by weight:
Granular colloidal silica 94～97%
Palladium metal component 1～2%
Co-catalyst 2～4%
Described co-catalyst is Ag.
When the Ag that adds special ratios is as co-catalyst, the powdery Pd/SiO obtaining2Catalyst is for the selection of alkynolWhen property hydrogenation, conversion ratio is high, selectively good, and both can reach more than 99%.
As preferably, described powdery Pd/SiO2Catalyst, is made up of the component of following percentage by weight:
When adding the Bi of special ratios and Mn or Bi and Zn as co-catalyst, the powdery Pd/SiO obtaining2CatalystWhile being used for the selective hydrogenation of alkynol, conversion ratio is high, and selectively good, both can reach more than 99%.
As preferably, described powdery Pd/SiO2Catalyst, is made up of the component of following percentage by weight:
When adding the Pb of special ratios and Cr as co-catalyst, the powdery Pd/SiO obtaining2Catalyst is used for alkynolWhen selective hydrogenation, conversion ratio is high, and selectively good, both can reach more than 99%.
As preferably, the specific surface of described granular colloidal silica is 100～400m2/ g, most probable aperture is 2～40nm, holeAppearance is 0.5～1.5ml/g, while adopting such carrier, can effectively avoid the over-hydrogenation of alkynol, improves the selection of reactionProperty.
The present invention also provides a kind of above-mentioned powdery Pd/SiO2The preparation method of catalyst, comprises the steps:
(1) dried granular colloidal silica is immersed in the dipping solution of palladium presoma, stirs 0.5-4h at 5-95 DEG C, soFinal vacuum suction filtration;
(2) filter cake step (1) being obtained, 50-150 DEG C of oven dry in air dry oven, makes palladium presoma uniform loadTo the surfaces externally and internally of silica-gel carrier, obtain dry catalyst;
(3) catalyst after step (2) oven dry is reduced, obtain described powdery Pd/SiO2Catalyst.
The dipping solution of described palladium presoma refers to the acid solution that contains various soluble palladium salt, for example chlorinationPalladium-hydrochloric acid solution, its concrete concentration is without strict especially requirement. Adopt the method while preparing, can make described palladium component (with helpCatalytic component) be scattered in equably the surface of described catalyst, with traditional Lindlar catalyst CaCO used3CarrierCompare, the feature that granular colloidal silica used is acidproof can reduce the requirement to maceration extract pH, reduces difficulty prepared by catalyst.
As preferably, in step (1), described dipping solution also comprises the soluble-salt of co-catalyst, and described is solvableProperty salt cation be the cation of described cocatalyst component, anion is Cl-Or NO3 -Deng, now, the powder preparingShape Pd/SiO2Catalyst is for hydrogenation reaction, selectively high.
The method of the reduction in step (3) is known by those skilled in the art, for example, can enter by the following methodOK:
(A) high-temperature heating under flowing hydrogen; Or
(B) stir at hydrazine hydrate solution or alkaline formaldehyde solution, then lotion is extremely neutral, and vacuum drying.
The present invention also provides a kind of described powdery Pd/SiO2Catalyst is in the hydrogenation reaction of alkynol compoundsApplication, described alkynol compounds optionally generates enols used, selectively more than 98%;
The structure of described alkynol compounds is suc as formula shown in (I):
Described enols used structure is suc as formula shown in (II):
In formula (I) and (II), R is H, C1～C20Alkyl or C1～C20Thiazolinyl; As preferably, described R is C5～C20Alkyl or C5～C20Thiazolinyl. Use described powdery Pd/SiO2Catalyst, can make the enols used higher choosing that hasSelecting property, avoids the further hydrogenation of olefinic double bonds.
As preferably, described alkynol compounds is selected from 3,7-dimethyl-6-alkene-1-octyne-3-alcohol, 3,7-diformazanBase-1-octyne-3-alcohol, 3,7,11-trimethyl-1-dodecyne-3-alcohol, 3,7,11-trimethyl-10-alkene-1-dodecyne-3-alcohol, 3,7,11-trimethyl-6,10-diene-1-dodecyne-3-alcohol, 3,7,11, phytanetriol 4-alkene-1-16 carbonAlkynes-3-alcohol, 3,7,11,15-tetramethyl-6,10,14-triolefin-1-hexadecine-3-alcohol or 3,7,11, phytanetriol-tenSix carbynes-3-alcohol. Described powdery Pd/SiO2When catalyst is used for these alkynol compounds, conversion ratio and selectiveHigher.
As preferably, described hydrogenation reaction is carried out in tank reactor, and reaction temperature is 20～200 DEG C, reaction pressurePower is 0.5～4.0MPa, and reaction dissolvent is C2-C4Alcoholic solvent, the volume of described reaction dissolvent and described alkynol compoundsThan being 0.5-5:1, described powdery Pd/SiO2The consumption of catalyst is 0.1%～5% of described alkynol compounds quality.
As further preferred, described alkynol compounds is 3-butyne-2-alcohol, described powdery Pd/SiO2UrgeAgent, is made up of the component of following percentage by weight:
Now, 3-butyne-2-alcohol conversion ratio and selectively can reaching more than 99%.
As other preferably, described alkynol compounds is linalool, described powdery Pd/SiO2Catalyst, byThe component composition of following percentage by weight:
Granular colloidal silica 94～97%
Palladium metal component 1～2%
Ag2～4%。
Now, the conversion ratio of described linalool can reach 100%, selectively can reach more than 99%.
As other preferably, described alkynol compounds be 3,7,11-trimethyl-1-dodecyne-3-alcohol or3,7,11, phytanetriol-hexadecine-3-alcohol, described powdery Pd/SiO2Catalyst, by the group of following percentage by weightBe grouped into:
Carbyne-3-alcohol or 3,7,11, the conversion ratio of phytanetriol-hexadecine-3-alcohol can reach more than 99%, selectsProperty can reach more than 98.5%.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) replace CaCO with granular colloidal silica3As carrier, be applied to the hydrogenation containing triple bond class organic compound such as linaloolWhen reaction, overcome the acid labile of current Lindlar catalyst, alkalescence is strong, isomery, and the side reactions such as polymerization are many, and pin material rate is high, thanSurface area is little, the low series of problems that waits of adsorptivity;
(2), by having added specific co-catalyst, greatly improved the selective hydrogenation of alkynol compounds and generated enolThe conversion ratio of compounds and selective.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
The preparation technology (one) of catalyst: (1) will process dried silica-gel carrier 98.15g, be immersed in containing palladium ionIn the maceration extract of 1.00g, lead ion 0.60g, chromium ion 0.25g, at 35 DEG C of stirring and adsorbing 2.5h, then vacuum filtrations;
(2) filter cake step (1) being obtained, 55 DEG C of oven dry in air dry oven, arrive metal precursor uniform loadThe surfaces externally and internally of silica-gel carrier;
(3) catalyzer with water after step (2) oven dry is closed to hydrazine and reduce, and extremely neutral with deionized water washing,Obtain catalyst A. Preparation method and the catalyst A of catalyst B, C are similar, and the ratio that difference is various active components is notWith.
The preparation technology (two) of catalyst: (1) will process dried silica-gel carrier 90.95g, be immersed in palladium ionIn the maceration extract of 5.00g, bismuth ion 3.20g, zinc ion 0.85g, at 90 DEG C of stirring and adsorbing 0.5h, then vacuum filtrations;
(2) filter cake step (1) being obtained, 120 DEG C of flash bakings in air dry oven, make metal precursor evenly negativeBe downloaded to the surfaces externally and internally of silica-gel carrier;
(3) catalyzer with water after step (2) oven dry is closed to hydrazine and reduce, and extremely neutral with deionized water washing,Obtain catalyst D.
Prepare according to the method described above a series of catalyst, typical catalyst as shown in the table 1.
Table 1 catalyst title and metal composition list
| Catalyst title | Carrier silica gel ratio is the each amount of metal % of 100%- |
| Catalyst A | Pd1.0%；Pb0.6%；Cr0.25% |
| Catalyst B | Pd2.6%；Ag3.0% |
| Catalyst C | Pd2.0%；Bi1.86%；Mn0.65% |
| Catalyst D | Pd5.0%；Bi3.2%；Zn0.85% |
Embodiment 1
Catalyst A, in the selective hydrogenation of 2L tank reactor catalysis 3-butyne-2-alcohol liquid phase, is 20-35 in reaction temperatureDEG C, reaction pressure is 2.0MPa, catalyst amount is under 1.2% condition of alkynol quality, and after reacting completely, GC analysis resultFor: 3-butyne-2-alcohol conversion ratio 99.9% in raw material, in hydrogenation products, enol is selectively 99.6%.
Embodiment 2
Catalyst B, in the selective hydrogenation of 2L tank reactor catalytic dehydrogenation linalool liquid phase, is 25-60 in reaction temperatureDEG C, reaction pressure is 2.0MPa, and the volume ratio of alcohol solvent and dehydro aromatic laurolol is 1:1, and catalyst amount is dehydro aromatic laurololUnder 1% condition of quality, after reacting completely, GC analysis result is: dehydro aromatic laurolol conversion ratio 100% in raw material, hydrogenation productsMiddle linalool is selectively 99.4%.
Embodiment 3
Catalyst C is in 2L tank reactor catalysis 3,7, the selective hydrogenation of 11-trimethyl-1-dodecyne-3-alcohol liquid phase,Be 35-55 DEG C in reaction temperature, reaction pressure is 2.2MPa, and the volume ratio of alcohol solvent and alkynol raw material is 1:1, and catalyst is usedUnder 1% the condition that amount is alkynol quality, after reacting completely, GC analysis result is: in raw material 3,7, and 11-trimethyl-1-12 carbonAlkynes-3-alcohol conversion 99.95%, in hydrogenation products, enol is selectively 99.2%.
Embodiment 4
Catalyst D is in 2L tank reactor catalysis 3,7,11, and phytanetriol-hexadecine-3-alcohol liquid phase selectively addsHydrogen, is 40-65 DEG C in reaction temperature, and reaction pressure is 2.5MPa, and the volume ratio of alcohol solvent and alkynol raw material is 1:1, catalysisAgent consumption is under 1% condition of alkynol quality, and after reacting completely, GC analysis result is: in raw material 3,7,11, and 15-tetramethyl-1-hexadecine-3-alcohol conversion 99.86%, in hydrogenation products, enol is selectively 98.9%.
When catalyst in above-described embodiment 1-4 is applied mechanically 12 batches continuously at lab scale, selective, the conversion ratio of reaction have no brightAobvious change.
Listed reaction condition in above-described embodiment 1-4, is only preferred embodiments of the present invention, not to skill of the present inventionArt scheme is done any type of restriction.
Claims (4)
1. a powdery Pd/SiO2Catalyst, is characterized in that, is made up of the component of following percentage by weight:
The granularity of described granular colloidal silica is 150～500 orders;
Described powdery Pd/SiO2The preparation method of catalyst, comprises the following steps:
(1) dried granular colloidal silica is immersed in the dipping solution of palladium presoma, stirs 0.5-4h at 5-95 DEG C, then trueEmpty suction filtration;
(2) filter cake step (1) being obtained, 50-150 DEG C of oven dry in air dry oven, makes palladium presoma uniform load to siliconThe surfaces externally and internally of glue carrier, obtains dry catalyst;
(3) catalyst after step (2) oven dry is reduced, obtain described powdery Pd/SiO2Catalyst;
In step (1), in described dipping solution, also comprise the soluble-salt of co-catalyst, described co-catalyst be chromium andPlumbous;
The specific surface of described granular colloidal silica is 100～400m2/ g, most probable aperture is 2～40nm, pore volume is 0.5～1.5ml/g。
2. a powdery Pd/SiO as claimed in claim 12The application of catalyst in the hydrogenation reaction of alkynol compounds,It is characterized in that, described alkynol compounds optionally generates enols used, selectively more than 98%;
The structure of described alkynol compounds is suc as formula shown in (I):
Described enols used structure is suc as formula shown in (II):
In formula (I) and (II), R is H, C1～C20Alkyl or C1～C20Thiazolinyl.
3. powdery Pd/SiO according to claim 22The application of catalyst in the hydrogenation reaction of alkynol compounds, itsBe characterised in that, described alkynol compounds is selected from 3,7-dimethyl-6-alkene-1-octyne-3-alcohol, 3,7-dimethyl-1-octyne-3-alcohol, 3,7,11-trimethyl-1-dodecyne-3-alcohol, 3,7,11-trimethyl-10-alkene-1-dodecyne-3-alcohol, 3,7,11-trimethyl-6,10-diene-1-dodecyne-3-alcohol, 3,7,11, phytanetriol 4-alkene-1-hexadecine-3-alcohol, 3,7,11,15-tetramethyl-6,10,14-triolefin-1-hexadecine-3-alcohol or 3,7,11, phytanetriol-hexadecine-3-Alcohol.
4. according to the powdery Pd/SiO described in claim 2 or 32The application of catalyst in the hydrogenation reaction of alkynol compounds,It is characterized in that, described hydrogenation reaction is carried out in tank reactor, and reaction temperature is 20～200 DEG C, and reaction pressure is 0.5～4.0MPa, reaction dissolvent is C2-C4Alcoholic solvent, the volume ratio of described reaction dissolvent and described alkynol compounds is0.5-5:1, described powdery Pd/SiO2The consumption of catalyst is 0.1%～5% of described alkynol compounds quality.
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| CN105175231B (en) * | 2015-09-22 | 2018-03-16 | 山东新和成药业有限公司 | A kind of method that propargyl ethanol selective hydrogenation prepares allyl alcohol |
| CN106748658A (en) * | 2016-12-27 | 2017-05-31 | 重庆建峰工业集团有限公司 | A kind of method that alkynol semihydrogenation prepares enol |
| CN110743590B (en) * | 2019-10-21 | 2023-01-24 | 西安凯立新材料股份有限公司 | High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof |
| CN111018672B (en) * | 2019-12-09 | 2023-01-13 | 万华化学集团股份有限公司 | Method for preparing linalool |
| CN113788737B (en) * | 2021-08-25 | 2024-06-25 | 万华化学集团股份有限公司 | Three-bond partial hydrogenation method and catalyst thereof |
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