CN101294349A - Collagen fiber stem grafting tannic acid and method for loading palladium catalyst - Google Patents
Collagen fiber stem grafting tannic acid and method for loading palladium catalyst Download PDFInfo
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Abstract
The invention discloses a method for grafting collagenous fiber with tannin, which includes the following steps: the collagenous fiber is added into water by dry weight for dissolving, the vegetable tannin is added for reacting under room temperature for 2 to 6 hours, then crosslinking agent is added and the pH valve of the system is controlled to be 5.0 to 7.5, then the temperature is raised to 30 to 45 DEG C after the stirring reaction is carried out for 2 to 4 hours, and then the stirring reaction is carried out again for 2 to 6 hours, thus, the grafting is finally finished after filtering and washing. The invention also discloses a method for loading palladium catalyst in the process of grafting the collagenous fiber with the tannin, and the method includes the following steps: deionized water is added in the process of grafting the collagenous fiber with the tannin to be stirred for 2 to 4 hours, then palladium is added and the pH value of the system is controlled to be 3.5 to 5.5, then the stirring reaction is carried out under the temperature of 25 to 35 DEG C for 2 to 8 hours, and then the reaction is carried out again for 2 to 6 hours after the temperature is raised to 40 to 50 DEG C, and finally the un-reacted palladium is removed by filtering and washing or the reaction is continued to reduce the palladium to obtain the palladium nanometer catalyst loaded in the process of grafting the collagenous fiber with the tannin. The catalyst obtained by the method of the invention has the advantages of little possibility of falling off, high thermal stability, good accessibility of mass transfer, high catalytic reaction activity and good reusability.
Description
Technical field
The invention belongs to heterogeneous palladium metal catalyst preparing technical field, be specifically related to the method for a kind of collagen fiber stem grafting tannic acid and loaded palladium catalyst thereof.
Background technology
The basis of modern chemical industry is based upon on oil, coal, the natural gas catalyzed conversion basis, and catalyst be catalyzed conversion core (Yan Zifeng. nano-catalytic technology [M]. Chemical Industry Press, Beijing, 2003).A kind of as in the noble metal catalyst of Metal Palladium, with its catalytic activity height, selectivity is good, consumption is few, reaction time is short and advantage such as reaction condition gentleness, demonstrated in the Industrial Catalysis field crucial effect (Chen Qingling. nano-catalytic The Application of Technology progress. modern chemical industry .2004,24 (7): 20-25), and such catalyst is particularly suitable for series reaction such as catalytic hydrogenation, catalytic oxidation.
Palladium metal catalyst mainly is divided into homogeneous phase (homogeneous) and heterogeneous (heterogeneous) catalyst two classes.In actual applications; heterogeneous catalysis has convenient separation with respect to homogeneous catalyst; repeat usage height and noble metal reclaim significant advantages such as convenient, and therefore, the preparation heterogeneous catalysis all has crucial meaning for the utilization of resource and the protection of environment.At present, prepare the effective method of heterogeneous palladium metal catalyst and be exactly palladium catalyst with homogeneous phase by directly means such as absorption or chemical bond connection are immobilized on certain inert carrier, and use the carrier material of maximum heterogeneous catalysis to mainly contain mineral-type materials and organic class material.Mineral-type mainly contains activated carbon, molecular sieve (zeolite), metal oxide etc.; Organic class material is mainly based on synthetic class polymeric material, as poly--N-ethylene carboxamide, poly--the 2-vinylpyridine, styrene-divinylbenzene copolymer etc.
In recent years, with natural polymer or synthetic high polymer is that carrier manufacturing heterogeneous catalysis has caused people's extensive concern (Guibal E.Heterogeneous catalysis on chitosan-based materials:a review.Prog.Polym.Sci.2005,30:71-109., Patel D R, Ram R N.Hydrogenation of nitrobenzene using polymeranchored Pd (II) complexes as catalyst.J.Mol.Catal.A:Chem.1998,130:57-64.).Its reason is, can give the different functional group of macromolecule on the one hand makes it have the binding ability stronger with the catalyst center metal, on the other hand, because carrier functional group is to the coordination of catalyst center metal, make it have higher activity, selectivity and good stable (Baiker A.Progress in asymmetric heterogeneous catalysis:designof novel chirally modified platinum metal catalysts.J.Mol.Catal.A:Chem.1997,115:473-93., Tada M, Iwasawa Y.Advanced chemical design with supported metal complexesfor selective catalysis.Chem.Commun.2006,27:2833-2844.).Starch derivatives (Huang K, XueL, Hu Y C, Huang M Y, Jiang Y Y.Catalytic behaviors of silica-supportedstarch-polysulfosiloxane-Pt complexes in asymmetric hydrogenation of4-methyl-2-pentanone.React.Funct.Polym.2002,50:199-203.), gelatin (Zhang X, Geng Y, Han B, Ying M Y, Huang M Y, Jiang Y Y.Asymmetric hydrogenation of ketones catalyzedby zeolite-supported gelatin Fe-complex.Polym.Adv.Technol.2001,12:642-6.), alginates or alginic acid (Wei W L, Zhu H Y, Zhao C L, Huang M Y, Jiang Y Y.Asymmetric hydrogenationof furfuryl alcohol catalyzed by a biopolymer-metal complex, silica-supported alginicacid-amino acid-Pt complex.React.Funct.Polym.2004,59:33-39.), cellulose (Mastrorilli P, Nobile C F.Supported catalyst from polymerizable transition metal complexes.Coordination Chem.Rev.2005,248:377-395), chitin or shitosan (Chiessi E, Pispisa B.Polymer-supported catalysis:oxidation of catecholamines by Fe (III) and Cu (II) complexesimmobilized to chitosan.J.Mol.Catal.1994 87:177-194.) waits as the carrier of natural macromolecular material as catalyst.Because special composition and the space structure of natural polymer, usually has stereoselectivity, be special chirality character, (Macquarrie D J is with a wide range of applications in chirality is synthetic, Hardy J JE.Applications of functionalized chitosan in catalysis.Ind.Eng.Chem.Res.2005,44:8499-8520.).
Yet, be difficult to be used for actual Industrial Catalysis system by the loaded catalyst of above-mentioned natural polymer, thereby do not see the report of industrial applications as preparing carriers because the mechanical property of natural macromolecular material itself is relatively poor.
Summary of the invention
One of purpose of the present invention provides a kind of method that can be used for preparing the collagen fiber stem grafting tannic acid of loaded catalyst.
Two of purpose of the present invention provides materials with hide glue fibril grafting vegatable tannin with method for preparing as carrier, with a kind of method of palladium load on it.
Three of purpose of the present invention provides a kind of new heterogeneous collagenous fibres branch tannin loaded palladium catalyst.
To achieve the object of the present invention, the inventor finds on the basis of having carried out big quantity research, derive from ox, sheep, the materials with hide glue fibril of livestock animals skins such as pig is mainly assembled by type i collagen, has regular fibre structure, if with its carrier as catalyst, also should have fibre structure (carbon fiber, silk fiber) the good mass-transfer performance of catalyst, lower pressure falls, diffusional resistance is little, and good operating characteristic (Matatov-Meytal Yu, Sheintuch M.Catalytic fibers and cloths.Appl.Catal.A:General, 2002,231:1-16.), yet, because materials with hide glue fibril itself is to precious metal ion (palladium, platinum, gold) binding ability is not strong, come off easily, cause catalytic activity low, thereby limited its range of application as catalyst carrier material.Vegatable tannin is the natural polyphenols of a class, to most of metal ion, comprises that precious metal ion all has very strong affinity, and ortho position phenolic hydroxyl group functional groups a large amount of in the tannin molecule can combine with metallic ion coordination.Simultaneously, vegatable tannin can be grafted on the materials with hide glue fibril surface securely through covalently bound mode under the crosslinking agent effect.Therefore, materials with hide glue fibril can improve the binding ability to metal ion, particularly precious metal ion greatly after the tannin graft modification.
Thus, the inventor at first provides a kind of method that can be used for preparing the collagen fiber stem grafting tannic acid of loaded catalyst, this method is will join in 100～500 parts of water for 20 parts with the collagenous fibres of dry weight basis earlier to dissolve, added 10～60 parts of vegatable tannin normal-temperature reaction then 2～6 hours, add 1.5～10 parts of crosslinking agents again, and hierarchy of control pH is 5.0～7.5, stirring reaction is after 2～4 hours under the normal temperature, be warming up to 30～45 ℃, stirring reaction is 2～6 hours again, filtration and washing get final product, and wherein the used umber of material is weight portion.
Used vegatable tannin is that acacia mearnsii tannin, Baybery tannin, larch tannin, horse account for any in yearning between lovers tannin, the tea tannin in this method.
Used crosslinking agent is any in glutaraldehyde, formaldehyde, the 7-ethyl bicyclo oxazolidine in this method.
It is 75～87 ℃ that prepared collagen fiber stem grafting tannic acid records thermal denaturation temperature with differential thermal analyzer (DSC).
Secondly, provide a kind of method of collagen fiber stem grafting tannic acid loaded palladium catalyst, the processing step and the condition of this method are as follows:
(1) will join in 100～500 parts of water for 20 parts with the collagenous fibres of dry weight basis earlier and dissolve, added 10～60 parts of vegatable tannin normal-temperature reaction then 2～6 hours, add 1.5～10 parts of crosslinking agents again, and hierarchy of control pH is 5.0～7.5, stirring reaction is after 2～4 hours under the normal temperature, be warming up to 30～45 ℃, stirring reaction is 2～6 hours again, filters and wash to get final product;
(2) be to add 100～500 parts of deionized waters in 80% the collagen fiber stem grafting tannic acid 100 parts of moistures, stirred 2～4 hours, add 1～20 part of palladium salt, and hierarchy of control pH value is 3.5～5.5, in 25～35 ℃ of stirring reactions of temperature 2～8 hours, be warming up to 40～50 ℃ then, reacted again 2～6 hours, filter, washing, promptly get collagen fiber supported palladium catalyst CFGT-Pd (II) after removing unreacted palladium salt.It is 75～85 ℃ that this catalyst records its thermal denaturation temperature with differential thermal analyzer.
The inventor also reduces the materials with hide glue fibril loaded palladium catalyst that above method obtains, be that to add concentration in 80% the collagen fiber stem grafting tannic acid loaded palladium catalyst be 200～300 parts of 0.1mol/L reductants promptly 100 parts of moistures, and 35～45 ℃ of reactions of temperature 2～6 hours, filtration washing, being drying to obtain particle diameter is the collagen fiber stem grafting tannic acid supported palladium nanocatalyst CFGT-Pd (0) of 2～8nm.It is 75～85 ℃ that this catalyst records its thermal denaturation temperature with differential thermal analyzer.
The used umber of material is weight portion in the above method.
Used vegatable tannin is that acacia mearnsii tannin, Baybery tannin, larch tannin, horse account for any in yearning between lovers tannin, the tea tannin in this method.
Used crosslinking agent is any in glutaraldehyde, formaldehyde, the 7-ethyl bicyclo oxazolidine in this method.
Used palladium salt is any in palladium bichloride, palladium, the potassium chloropalladite in this method.
Used reductant can be selected conventional reductant for use in this method, and as methyl alcohol, hydrazine hydrate, sodium borohydride, what wherein reduction effect was preferable is sodium borohydride.
Collagen fiber stem grafting tannic acid loaded palladium catalyst provided by the invention (comprising CFGT-Pd (II) and CFGT-Pd (0)) is a heterogeneous catalysis, can be used for the synthetic reaction of catalytic hydrogenation, catalytic oxidation and fine chemicals.
The present invention has following advantage:
1, since the present invention not only the instrumentality by crosslinking agent will be grafted to the collagenous fibres surface to the vegatable tannin that metal ion has a high reaction activity, but also collagenous fibres self have been carried out to a certain degree crosslinked, thereby palladium (Pd (II)) can be securely fixed on the collagenous fibres by complex bound mode, obtain the heterogeneous collagen fiber supported palladium catalyst (CFGT-Pd (II)) of difficult drop-off, its heat endurance is improved greatly.
2, because the present invention can obtain by chemical method the CFGT-Pd (II) of preparation the palladium nanocatalyst of support type with Pd (II) reduction back, it is CFGT-Pd (0), and the Pd (0) on the CFGT-Pd (0) mainly is evenly distributed on the outer surface of collagenous fibres with the nano particle of polymolecularity, thereby not only particle diameter is less to make this catalyst, be difficult between the particle reuniting, and palladium nano-particles is again the outer surface that is securely fixed in collagenous fibres, make the more accessible activity of such catalysts of the substrate molecule site of catalytic reaction, promptly have the sensible degree of good mass transfer, so its catalytic reaction activity is higher.
3, because collagen fiber stem grafting tannic acid loaded palladium catalyst provided by the invention, comprise CFGT-Pd (II) and CFGT-Pd (0)) all have better chemical stability, thereby after being used for catalytic reaction, catalyst is easy to separate with reaction system, and has good repeat performance.
4, because catalyst carrier used in the present invention is the materials with hide glue fibril with regular fibre structure, adding the present invention has carried out crosslinked with crosslinking agent to it, thereby can improve the mechanical property of natural macromolecular material itself greatly, make the present invention can be used in actual Industrial Catalysis system as the loaded catalyst of preparing carriers with natural polymer.
5, because the inventive method is that palladium (Pd (II)) is supported on the materials with hide glue fibril in complex bound mode, its loading not only is easy to regulation and control, and with CFGT-Pd (0) nano particle that obtains after Pd (II) reduction, its bin stability height is stored also more convenient.
6, method technology provided by the invention is simple, and control is easy, and it is low to consume energy, thereby can reduce production costs greatly.
Description of drawings
Fig. 1 is the stereoscan photograph (SEM) of pigskin collagen fibre grafting tea tannin loaded palladium catalyst;
Fig. 2 is the transmission electron microscope photo (TEM) of pigskin collagen fibre grafting tea tannin supported palladium nanocatalyst;
Fig. 3 is the stereoscan photograph of cattle-hide collagen fibers grafting tea tannin loaded palladium catalyst;
Fig. 4 is the transmission electron microscope photo of cattle-hide collagen fibers grafting tea tannin supported palladium nanocatalyst;
Fig. 5 is that pigskin collagen fibre grafting tea tannin loaded palladium catalyst (CFGT-Pd (II) and CFGT-Pd (0)) is used for propenyl catalytic hydrogenation reaction conversion ratio graph of a relation over time;
The propenyl catalytic hydrogenation reaction conversion ratio that Fig. 6 is used for the different solvents system for pigskin collagen fibre grafting tea tannin supported palladium nanocatalyst is graph of a relation over time;
Fig. 7 is used for conversion ratio that the propenyl catalytic hydrogenation reaction reuses number of times graph of a relation over time for pigskin collagen fibre grafting tea tannin supported palladium nanocatalyst;
Fig. 8 is used for nitrobenzene catalytic hydrogenation system aniline reaction conversion ratio graph of a relation over time for cattle-hide collagen fibers grafting tea tannin supported palladium nanocatalyst;
Fig. 9 conversion ratio that is five kinds of different tannin supported palladium nanocatalysts of cattle-hide collagen fibers grafting in the manufacturing process of aniline through nitrobenzene hydrogenation reaction is graph of a relation over time.
The specific embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
What deserves to be explained is that in addition the used umber of following examples is weight portion.
Embodiment 1
Choose tannery not tanning pigskin leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water then, obtain moisture and be 80% pigskin collagen fiber, taking by weighing 100 parts of these collagenous fibres joins in 100 parts of deionized waters and dissolves, added 30 parts of tea tannin normal-temperature reaction then 2 hours, add 7 parts of glutaraldehydes again, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 7.0 with concentration, stirring reaction is after 2 hours under the normal temperature, be warming up to 35 ℃, stirring reaction is 3 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after the tea tannin grafting.
100 parts of moistures is to add 150 parts of deionized waters in 80% the collagen fiber stem grafting tea tannin, stirred 2 hours, add 3 parts of palladium bichlorides (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 3.5 with concentration, in 30 ℃ of stirring reactions of temperature 3 hours, be warming up to 40 ℃ then, reacted again 2 hours, filter, spend deionised water, promptly get collagenous fibres tea tannin loaded palladium catalyst (CFGT-Pd (II)) after removing unreacted palladium salt.
It is 80 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer; The stereoscan photograph of this catalyst as shown in Figure 1, regular as seen from the figure fibre structure shows that this catalyst is the fibrous type catalyst.
Embodiment 2
In 100 parts of moistures that embodiment 1 prepares is that to add concentration in 80% the collagen fiber stem grafting tea tannin loaded palladium catalyst be 200 parts of 0.1mol/L sodium borohydride solutions, and 35 ℃ of reactions of temperature 2 hours, filtration is also used absolute ethanol washing, promptly gets the collagen fiber stem grafting tea tannin supported palladium nanocatalyst that particle diameter is 2～8nm in 8 hours 35 ℃ of vacuumizes then.
The transmission electron microscope photo of this catalyst as shown in Figure 2, as seen from the figure, the particle diameter that loads on the palladium nano-particles on the collagenous fibres is 2～3nm.
Embodiment 3
Choose tannery not tanning ox-hide leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water, obtain moisture and be 80% cattle-hide collagen fibers.Taking by weighing 100 parts of these collagenous fibres joins in 300 parts of deionized waters and dissolves, added 50 parts of tea tannin normal-temperature reaction then 3 hours, add 6 parts in formaldehyde again, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 5.0 with concentration, stirring reaction is after 3 hours under the normal temperature, be warming up to 30 ℃, stirring reaction is 2 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after the tea tannin grafting.
100 parts of moistures is to add 200 parts of deionized waters in 80% the collagen fiber stem grafting tea tannin, stirred 4 hours, add 6 parts of palladium (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 4.0 with concentration, in 25 ℃ of stirring reactions of temperature 4 hours, be warming up to 45 ℃ then, reacted again 6 hours, filter, spend deionised water, promptly get collagen fiber stem grafting tea tannin loaded palladium catalyst (CFGT-Pd (II)) after removing unreacted palladium salt.
It is 85 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer; The stereoscan photograph of this catalyst as shown in Figure 2, regular as seen from the figure fibre structure shows that this catalyst is the fibrous type catalyst.
Embodiment 4
In 100 parts of moistures that embodiment 3 prepares is that to add concentration in 80% the collagen fiber stem grafting tannic acid loaded palladium catalyst be 300 parts of 0.1mol/L sodium borohydride solutions, and 45 ℃ of reactions of temperature 6 hours, filtration is also used absolute ethanol washing, promptly gets the collagen fiber stem grafting tea tannin supported palladium nanocatalyst that particle diameter is 2～8nm in 8 hours 35 ℃ of vacuumizes then.
The transmission electron microscope photo of this catalyst as shown in Figure 4, as seen from the figure, the particle diameter that loads on the palladium nano-particles on the collagenous fibres is 4～8nm.
Embodiment 5
Choose tannery not tanning ox-hide leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water, obtain moisture and be 80% cattle-hide collagen fibers.Taking by weighing 100 parts of these collagenous fibres joins in 200 parts of deionized waters and dissolves, added 20 parts of acacia mearnsii tannin normal-temperature reaction then 4 hours, add 6 parts of 7-ethyl bicyclo oxazolidines again, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 6.0 with concentration, stirring reaction is after 2 hours under the normal temperature, be warming up to 35 ℃, stirring reaction is 5 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after the acacia mearnsii tannin grafting.
100 parts of moistures is to add 150 parts of deionized waters in 80% the collagen fiber stem grafting acacia mearnsii tannin, stirred 2 hours, add 17 parts of potassium chloropalladites (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 4.0 with concentration, in 30 ℃ of stirring reactions of temperature 6 hours, be warming up to 45 ℃ then, reacted again 4 hours, filter, spend deionised water, promptly get collagen fiber stem grafting acacia mearnsii tannin loaded palladium catalyst (CFGT-Pd (II)) after removing unreacted palladium salt.
It is 83 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer.
Embodiment 6
Choose tannery not tanning ox-hide leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water, obtain moisture and be 80% cattle-hide collagen fibers.Taking by weighing 100 parts of these collagenous fibres joins in 250 parts of deionized waters and dissolves, added 30 parts of Baybery tannin normal-temperature reaction then 4 hours, add 2 parts in formaldehyde again, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 7.0 with concentration, stirring reaction is after 3 hours under the normal temperature, be warming up to 40 ℃, stirring reaction is 4 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after the Baybery tannin grafting.
100 parts of moistures is to add 150 parts of deionized waters in 80% the collagen fiber stem grafting Baybery tannin, stirred 2 hours, add 12 parts of palladium bichlorides (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 4.0 with concentration, in 30 ℃ of stirring reactions of temperature 6 hours, be warming up to 45 ℃ then, reacted again 4 hours, filter, spend deionised water, promptly get collagen fiber stem grafting Baybery tannin loaded palladium catalyst (CFGT-Pd (II)) after removing unreacted palladium salt.
It is 82 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer.
Embodiment 7
Choose tannery not tanning ox-hide leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water, obtain moisture and be 80% cattle-hide collagen fibers.Taking by weighing 100 parts of these collagenous fibres joins in 500 parts of deionized waters and dissolves, added 20 parts of larch tannin normal-temperature reaction then 6 hours, add concentration again and be 8 parts of 30% glutaraldehydes, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 6.5 with concentration, stirring reaction is after 4 hours under the normal temperature, be warming up to 35 ℃, stirring reaction is 6 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after the larch tannin grafting.
100 parts of moistures is to add 150 parts of deionized waters in 80% the collagen fiber stem grafting larch tannin, stirred 3 hours, add 3 parts of palladium bichlorides (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 5.5 with concentration, in 25 ℃ of stirring reactions of temperature 8 hours, be warming up to 50 ℃ then, reacted again 6 hours, filter, spend deionised water, promptly get collagen fiber stem grafting larch tannin loaded palladium catalyst (CFGT-Pd (II)) after removing unreacted palladium salt.
It is 83 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer.
Embodiment 8
Choose tannery not tanning ox-hide leftover bits be raw material, be crushed to granularity 0.5～2mm, fully wash with deionized water, obtain moisture and be 80% cattle-hide collagen fibers.Taking by weighing 100 parts of these collagenous fibres joins in 400 parts of deionized waters and dissolves, add 30 portions of horses then and accounted for yearning between lovers tannin normal-temperature reaction 5 hours, add 7 parts of 7-ethyl bicyclo oxazolidines again, and be that the hydrochloric acid hierarchy of control pH of 0.1mol/L is 7.0 with concentration, stirring reaction is after 2 hours under the normal temperature, be warming up to 35 ℃, stirring reaction is 4 hours again, filters and fully wash with deionized water the collagenous fibres (CFGT) that promptly obtain after horse accounts for the grafting of yearning between lovers tannin.
100 parts of moistures is that 80% collagen fiber stem grafting horse accounts for and adds 150 parts of deionized waters in the yearning between lovers tannin, stirred 2 hours, add 10 parts of palladium bichlorides (earlier with 50 parts of deionized water dissolvings), and be that the hydrochloric acid hierarchy of control pH value of 0.1mol/L is 5.0 with concentration, in 30 ℃ of stirring reactions of temperature 3 hours, be warming up to 45 ℃ then, reacted again 4 hours, filter, spend deionised water, remove and promptly get the collagen fiber stem grafting horse after the unreacted palladium salt and account for yearning between lovers tannin loaded palladium catalyst (CFGT-Pd (II)).
It is 83 ℃ that this catalyst records thermal denaturation temperature with differential thermal analyzer.
Application examples 1
Should use-case be that pigskin collagen fibre grafting tea tannin loaded palladium catalyst (CFGT-Pd (II) and CFGT-Pd (0)) is used for propenyl catalytic hydrogenation system normal propyl alcohol.
In the autoclave of being furnished with automatic constant-temperature controller and magnetic stirring apparatus, add the 30mL methanol solution earlier, with by the embodiment 1 preparation fiber-loaded palladium catalyst of pigskin collagen (CFGT-Pd (II)) 0.03g (dry weight), after feeding hydrogen and replacing three times, stir-activating is 30 minutes under the 0.08MPa hydrogen pressure, add the 10mmol propenyl then, reacted 2 hours down for 30 ℃ in hydrogen pressure 0.08MPa, still temperature.The catalytic hydrogenation reaction of the fiber-loaded palladium nanocatalyst of pigskin collagen (CFGT-Pd (0)) carries out under the same conditions among the embodiment 2, and detects catalytic hydrogenation reaction degree, result such as Fig. 5, Fig. 6, Fig. 7 and shown in Figure 8 with gas chromatograph respectively.As shown in Figure 5, CFGT-Pd (II) and CFGT-Pd (0) have very high catalytic activity and higher selectivity for the olefinic double bonds hydrogenation of propenyl, but when the reaction time was 90min, CFGT-Pd (II) was 3085molmol to the transformation frequency (TOF value) of reaction substrate
-1h
-1, the selectivity of chromatograph target product normal propyl alcohol is 72.6%, and CFGT-Pd (0) is when the reaction time is 60min, is 3398molmol to the TOF value of substrate
-1h
-1, the selectivity of chromatograph target product is 77.1%.This shows that for the olefinic double bonds hydrogenation reaction of propenyl, the catalytic activity of CFGT-Pd (0) is higher than CFGT-Pd (II).As can be seen from Fig. 6, in the reaction system of methanol, catalyst is the highest to the selectivity of target product, reaches 79.15%; And in aqueous systems, have only 58.55%.The reusability of catalyst (CFGT-Pd (0)) as shown in Figure 7, catalyst still has advantages of high catalytic activity after reusing 4 times, shows that therefore this catalyst has better chemical stability and reusable ability.
Application examples 2
Should use-case be that cattle-hide collagen fibers grafting tea tannin supported palladium nanocatalyst (CFGT-Pd (0)) is used for nitrobenzene catalytic hydrogenation system aniline.
In the autoclave of being furnished with automatic constant-temperature controller and magnetic stirring apparatus, add the 25mL ethanolic solution, add cattle-hide collagen fibers grafting tea tannin supported palladium nanocatalyst (CFGT-Pd (0)) 0.025g (dry weight) simultaneously by embodiment 4 preparations, after feeding hydrogen and replacing three times, stir-activating is 60 minutes under the 1.0MPa hydrogen pressure, add 2.5mmol nitrobenzene then, reacted 3 hours down for 35 ℃ in hydrogen pressure 1.0MPa, still temperature, and detecting the catalytic hydrogenation reaction degree with gas chromatograph, its result is as shown in Figure 8.As seen from Figure 8, (CFGT-Pd (0)) has advantages of high catalytic activity and high selectivity for the hydrogenation of nitrobenzene, reacts 2 hours down at 35 ℃, and catalyst is 511molmol to the transformation frequency (TOF value) of reaction substrate
-1h
-1, the conversion ratio of nitrobenzene is 100%.In addition, the selectivity of chromatograph target product aniline is 100%, does not almost have accessory substance to generate.In addition, use the catalytic rate influence of prepared CFGT-Pd (0) the p-nitrophenyl hydrogenation system aniline of the different tannin of cattle-hide collagen fibers grafting bigger simultaneously, grafting tea tannin p-nitrophenyl hydrogenation rate maximum wherein, and the grafting horse accounts for its hydrogenation rate minimum of yearning between lovers tannin, as shown in Figure 9.
Claims (8)
1, a kind of method of collagen fiber stem grafting tannic acid, this method is will join in 100～500 parts of water for 20 parts with the collagenous fibres of dry weight basis earlier to dissolve, added 10～60 parts of vegatable tannin normal-temperature reaction then 2～6 hours, add 1.5～10 parts of crosslinking agents again, and hierarchy of control pH is 5.0～7.5, stirring reaction is after 2～4 hours under the normal temperature, be warming up to 30～45 ℃, stirring reaction is 2～6 hours again, filters and wash to get final product, and wherein the used umber of material is weight portion.
2, the method for collagen fiber stem grafting tannic acid according to claim 1, used vegatable tannin is that acacia mearnsii tannin, Baybery tannin, larch tannin, horse account for any in yearning between lovers tannin, the tea tannin in this method.
3, the method for collagen fiber stem grafting tannic acid according to claim 1 and 2, used crosslinking agent is any in glutaraldehyde, formaldehyde, the 7-ethyl bicyclo oxazolidine in this method.
4, a kind of method of collagen fiber stem grafting tannic acid loaded palladium catalyst, the processing step and the condition of this method are as follows:
(1) will join in 100～500 parts of water for 20 parts with the collagenous fibres of dry weight basis earlier and dissolve, added 10～60 parts of vegatable tannin normal-temperature reaction then 2～6 hours, add 1.5～10 parts of crosslinking agents again, and hierarchy of control pH is 5.0～7.5, stirring reaction is after 2～4 hours under the normal temperature, be warming up to 30～45 ℃, stirring reaction is 2～6 hours again, filters and wash to get final product;
(2) be to add 100～500 parts of deionized waters in 80% the collagen fiber stem grafting tannic acid 100 parts of moistures, stirred 2～4 hours, add 1～20 part of palladium salt, and hierarchy of control pH value is 3.5～5.5, in 25～35 ℃ of stirring reactions of temperature 2～8 hours, is warming up to 40～50 ℃ then, reacted again 2～6 hours, filter, washing, promptly get collagen fiber supported palladium catalyst after removing unreacted palladium salt
Wherein the used umber of material is weight portion.
5, the method for collagen fiber stem grafting tannic acid loaded palladium catalyst according to claim 4, this method is to be that to add concentration in 80% the collagen fiber stem grafting tannic acid loaded palladium catalyst be 200～300 parts of 0.1mol/L reductants 100 parts of moistures, and 35～45 ℃ of reactions of temperature 2～6 hours, filtration washing, being drying to obtain particle diameter is the collagen fiber stem grafting tannic acid supported palladium nanocatalyst of 2～8nm, and wherein the used umber of material is weight portion.
6, according to the method for claim 4 or 5 described collagen fiber stem grafting tannic acid loaded palladium catalysts, used vegatable tannin is that acacia mearnsii tannin, Baybery tannin, larch tannin, horse account for any in yearning between lovers tannin, the tea tannin in this method.
7, according to the method for claim 4 or 5 described collagen fiber stem grafting tannic acid loaded palladium catalysts, used crosslinking agent is any in glutaraldehyde, formaldehyde, the 7-ethyl bicyclo oxazolidine in this method.
8, according to the method for claim 4 or 5 described collagen fiber stem grafting tannic acid loaded palladium catalysts, used palladium salt is any in palladium bichloride, palladium, the potassium chloropalladite in this method.
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