CN109317178A - A kind of loaded catalyst and preparation method thereof adding hydrogen preparation hydrogenated styrene-butadiene rubber for heterogeneous solution - Google Patents
A kind of loaded catalyst and preparation method thereof adding hydrogen preparation hydrogenated styrene-butadiene rubber for heterogeneous solution Download PDFInfo
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Abstract
The present invention relates to a kind of loaded catalysts and preparation method thereof for adding hydrogen preparation hydrogenated styrene-butadiene rubber (HSBR) for butadiene-styrene rubber (SBR) heterogeneous solution.The present invention passes through urea first or the thermal polymerization of cyanamide class presoma prepares the mesoporous carbonitride (g-C of graphite-phase3N4), PdCl is then added2Solution simultaneously passes through chemical reduction method, and Pd doping g-C is prepared3N4Nanomaterial loadings type catalyst.The carrier of the method for the present invention synthesis has typical two-dimensional layered structure, is conducive to the diffusion of styrene butadiene rubber polymeric molecule and improves the accessibility of metal.The loaded catalyst is applied in the hydrogenation reaction of butadiene-styrene rubber, the hydrogenated styrene-butadiene rubber of high quality can be obtained, products obtained therefrom degree of hydrogenation is greater than 95%, and selectivity is 100%, and without phenomenon is crosslinked, is better than commercial catalysts Pd/SiO2, which is of great significance to the development of butadiene-styrene rubber heterogeneous catalysis.
Description
Technical field
The invention belongs to nano material noble metal catalyst preparation fields, and in particular to one kind adds hydrogen system for butadiene-styrene rubber
Loaded catalyst of hydrogenated styrene-butadiene rubber and preparation method thereof.
Background technique
HSBR(hydrogenated styrene-butadiene rubber) be by SBR(butadiene-styrene rubber) selective catalytic hydrogenation unsaturation carbon-to-carbon double bond and protect
It stays phenyl ring to be prepared, makes HSBR that there is excellent heatproof, weather-proof, oxytolerant, heat-resisting ageing-resisting and good after hydrogenation modification
Good tensile property, and the service life of HSBR polymer is extended, it is widely used in producing high-grade elastomer, modifying plastics, gluing
Agent, lubricating oil viscosity index improver, filler material of wire and cable etc..
The preparation process of HSBR mainly has at present: solution hydrogenation (including homogeneous catalysis and heterogeneous catalysis) and SBR emulsion
Add hydrogen.The homogeneous hydrogenation in solution hydrogenation technique accounts for leading position at present, but homogeneous catalyst is easily by dioxygen oxidation in air
And lose activity, catalyst amount is big, and stability is poor, and catalyst separates difficulty with hydrogenation products HSBR, increases noble metal
Dosage originally greatly increased so that being hydrogenated into, more seriously remaining catalyst also will affect its service performance in HSBR,
These factors limit the mass production and extensive use of HSBR to a certain extent.In heterogeneous catalytic reaction system, urge
Agent and glue are two-phase, have well solved the separation and recovery problem of catalyst, moreover it is possible to be effectively prevented from noble metal and polymerize
Residual in object shows good prospects for commercial application.
The carrier structure of catalyst plays very important effect in SBR hydrogenation reaction.Maria Lu in 1994 | za
(Holleben M L A V, Silva S M, the Mauler R S. Hydrogenation such as Ambros yon Holleben
of styrene-butadiene rubber by hydrogen transfer from limonene[J]. Polymer
Bulletin, 1994,33 (2): 203-208.) by loaded catalyst of Pd/C it is applied to SBR hydrogenation reaction, but SBR
Degree of hydrogenation is only capable of reaching 71%；Jen-Ray Chang and Shi-Ming Huang(And J R C, Huang S M. Pd/Al2O3
Catalysts for Selective Hydrogenation of Polystyrene-block-polybutadiene-
block-polystyrene Thermoplastic Elastomers[J]. Industrial & Engineering
Chemistry Research, 1998,37 (4): 1220-1227.) with Pd/Al2O3For catalyst, reaction temperature 80oC,
Degree of hydrogenation is only capable of reaching 78% when reaction time is 50 h, and the HSBR that both carriers are prepared easily crosslinks phenomenon.
How to solve the separation problem of catalyst and inhibit crosslinked polymer phenomenon to be production high-performance HSBR
Critical issue.Two-dimensional material causes researchers and widely pays close attention at present, class graphene carbonitride (g-C3N4) there is typical case
Two-dimensional layered structure and richness N characteristic, external surface area exposure height increase the contact probability of reaction molecular and active sites,
Improve reaction efficiency.Pd/g-C at present3N4Nano material is applied primarily to photocatalysis field (Ni Z, Dong F, Huang
H, et al. New insights into how Pd nanoparticles influence the photocatalytic
oxidation and reduction ability of g-C3N4 nanosheets[J]. Catalysis Science &
Technology, 2016,6 (16)) and phenol catalytic hydrogenation reaction (Li Y, Xu X, Zhang P, et al.
Highly selective Pd@mpg-C3N4 catalyst for phenol hydrogenation in aqueous
Phase [J] Rsc Advances, 2013,3 (27): 10973-10982.) in, it is not up to the present applied to also gather
In the hydrogenation reaction of adduct molecule.Therefore, the present invention utilizes g-C3N4The characteristics of, prepare the Pd/g-C with high activity3N4It is non-
Homogeneous catalyst, this HSBR product for being used to produce high added value to loaded catalyst have a very important significance and make
With value.
Summary of the invention
In order to solve the above technical problems, it is an object of the invention to develop one kind to add hydrogen preparation hydrogenation for heterogeneous solution
Loaded catalyst of butadiene-styrene rubber and preparation method thereof.Carrier g- is obtained by high-temperature calcination urea or cyanamide class presoma
C3N4, then supported active metals Pd, prepares the heterogeneous catalysis of high dispersive high activity.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of loaded catalyst Pd/g-C adding hydrogen preparation hydrogenated styrene-butadiene rubber for heterogeneous solution3N4Preparation method,
Specifically includes the following steps:
(1) g-C3N4The preparation of carrier: urea or cyanamide class presoma are placed in alumina crucible with cover, placed it in
In 400-800 in Muffle furnaceoC temperature lower calcination 2-6 h, heating rate 2 oC/min obtains the class of yellow after being cooled to room temperature
Graphene carbonitride (g-C3N4).
(2) Pd/g-C3N4The preparation of nano material: the g-C for taking step (1) to synthesize3N4Support dispersion in deionized water,
0.5 h of ultrasound is slowly added to the PdCl dissolved with HCl under stirring2Solution, 30oC continues to be suspended after stirring 0.5 h
Liquid；Then it is alkalinity with the pH that the NaOH solution of 1 mol/L adjusts suspension, excessive NaBH quickly is added dropwise under stirring4
Solution, the reaction was continued 1-5 h；Dispersion liquid is filtered, is washed, ethyl alcohol is washed, is dried in vacuo to get Pd/g-C is arrived3N4Nanometer material
Material, tem analysis show that the mean size of nano Pd particle particle is 3 nm or so.
The cyanamide class presoma includes one of cyanamide, cyanamid dimerization and melamine.
G-C in step (2)3N4Mass ratio with deionized water is 1:50-300.
The concentration of the HCl solution is 0.5-5 mol/L.
The pH of the suspension is 9-12.
In the above preparation method, using chemical reduction method supported active metals Pd, active metal Pd on a support material
Load capacity be 0.1-10 wt%, it is preferable that load capacity be 0.1-5 wt%.
The application of loaded catalyst made from preparation method as described above: a certain amount of SBR is dissolved in organic molten
Certain density glue is made into agent to be placed in autoclave, the mass ratio of organic solvent and butadiene-styrene rubber is 100-10:1,
Then a certain amount of loaded catalyst Pd/g-C is added3N4, stir evenly, the mass ratio of loaded catalyst and butadiene-styrene rubber is
0.1-1:1；It is depressed in 30-80 DEG C, 0.5-6 MPa hydrogen, reacts 0.5-12 h；Centrifugation point is carried out to reaction solution after reaction
From recycling loaded catalyst is for hydrogenation reaction next time.
Preferably, organic solvent is one in normal heptane, normal octane, toluene, hexamethylene, methylene chloride and chloroform
Kind or several mixed solvents.It is highly preferred that organic solvent is normal heptane, normal octane and hexamethylene.
The present invention also provides the methods that SBR selectivity heterogeneous hydrogenation catalyst recycles and reuses, and will return after reaction
The catalyst of receipts is scattered in hexamethylene, 60oC is refluxed overnight, and centrifuge separation is used for next secondary response.
The beneficial effects of the present invention are:
1) method of above-mentioned SBR heterogeneous hydrogenation provided by the invention, the degree of hydrogenation of SBR reach 95% or more, and selectivity is reachable
100%。
2) it is cheaply easy to have the following characteristics that (1) prepares raw material used in carrier for the made loaded catalyst of the present invention
, and operating process is simple；(2) carrier is typical two-dimensional layered structure, and richness N characteristic electron makes carrier and active component
Pd binding force is stronger；(3) active component particles are small, be uniformly dispersed, stability is strong, and when reaction is not easy to reunite；(4) carrier and SBR
Intermolecular π-π interaction is so that SBR molecule is easier to close to active component；(5) catalyst recycling is simple.
Detailed description of the invention
Fig. 1 is the mesoporous nitridation carbon carrier (a) that embodiment 1 obtains and mesoporous carbonitride loaded nanometer palladium catalyst (b)
XRD diagram；
Fig. 2 is the TEM of mesoporous nitridation carbon carrier (left side) and mesoporous carbonitride loaded nanometer palladium catalyst (right side) that embodiment 1 obtains
Figure；
Fig. 3 is silica supports (a), comparative example 1 obtains catalyst Pd/SiO2(c) and comparative example 2 obtains catalyst Pd/N-
SiO2(b) XRD diagram；
Fig. 4 is embodiment 1, the infrared spectrogram of the HSBR that comparative example 1 obtains and SBR.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, embodiment below will
The present invention is more comprehensively described, but should not be understood as that limiting the scope of the invention.
In embodiment, XRD diagram is obtained by Japanese KYOWAGLAS-XA H-12 type X-ray diffractometer；TEM image is by Japan
2100 LaB6 transmission electron microscope of JEM obtains；Infrared spectrum is obtained by U.S.'s NICOLET is50 type FTIR spectrum instrument.
Embodiment 1
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace 550o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 1.0 wt%
Agent Pd/g-C3N4.By 1.0 g carrier g-C3N4It is scattered in 100 mL deionized waters, 0.5 h of ultrasonic disperse；Under stirring
It is slowly added to the PdCl dissolved with the HCl of 1 mol/L2Solution, 30oC continues to obtain suspension after stirring 0.5 h；Then with 1
The pH that the NaOH solution of mol/L adjusts suspension is 10, and excessive NaBH quickly is added dropwise under stirring4Solution, the reaction was continued 3
h；Dispersion liquid is filtered, is washed, ethyl alcohol is washed, is dried in vacuo to get the heterogeneous catalysis for being 1.0 wt% to load capacity
Pd/g-C3N4.1g SBR is dissolved in 80 g hexamethylenes, 1g catalyst Pd/g-C is taken3N4It is added in glue, it is anti-in high pressure
It answers and carries out catalytic hydrogenation reaction in kettle.Reaction condition are as follows: temperature 60 C, 1 MPa of Hydrogen Vapor Pressure, 2.5 h of reaction time.Reaction knot
Shu Hou, Pd/g-C3N4Catalyst centrifuge separation adds ethyl alcohol coagulation into glue and obtains product HSBR, and degree of hydrogenation is listed in Table 1 below.
Embodiment 2
A certain amount of melamine is weighed in crucible with cover, is put in Muffle furnace in 550o4 h of C temperature lower calcination, heating
Rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 2.0 wt%
Pd/g-C3N4.By 1.0 g carrier g-C3N4It is scattered in 100 mL deionized waters, 0.5 h of ultrasonic disperse；Delay under stirring
It is slow that the PdCl dissolved with the HCl of 1 mol/L is added2Solution, 30oC continues to obtain suspension after stirring 0.5 h；Then with 1
The pH that the NaOH solution of mol/L adjusts suspension is 10, and excessive NaBH quickly is added dropwise under stirring4Solution, the reaction was continued 3
h；Dispersion liquid is filtered, is washed, ethyl alcohol is washed, is dried in vacuo to get the heterogeneous catalysis for being 2.0 wt% to load capacity
Pd/g-C3N4.Using the identical reaction condition of embodiment 1, its catalytic hydrogenation property to SBR is investigated, degree of hydrogenation is listed in Table 1 below.
Embodiment 3
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace in 600o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 2.0 wt%
Agent Pd/g-C3N4.By 1.0 g carrier g-C3N4It is scattered in 100 mL deionized waters, 0.5 h of ultrasonic disperse；Under stirring
It is slowly added to the PdCl dissolved with the HCl of 1 mol/L2Solution, 30oC continues to obtain suspension after stirring 0.5 h；Then with 1
The pH that the NaOH solution of mol/L adjusts suspension is 10, and excessive NaBH quickly is added dropwise under stirring4Solution, the reaction was continued 3
h；Dispersion liquid is filtered, is washed, ethyl alcohol is washed, is dried in vacuo to get the heterogeneous catalysis for being 2.0 wt% to load capacity
Pd/g-C3N4.1g SBR is dissolved in 80 g hexamethylenes, 1g catalyst Pd/g-C is taken3N4It is added in glue, it is anti-in high pressure
It answers and carries out catalytic hydrogenation reaction in kettle.Reaction condition are as follows: temperature 60 C, 1 MPa of Hydrogen Vapor Pressure, 2.5 h of reaction time.Reaction knot
Shu Hou, Pd/g-C3N4Catalyst centrifuge separation adds ethyl alcohol coagulation into glue and obtains product HSBR, and degree of hydrogenation is listed in Table 1 below.
Embodiment 4
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace in 550o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 0.1 wt%
Agent Pd/g-C3N4.Remaining step is same as Example 1.Using the identical reaction condition of embodiment 1, its catalysis to SBR is investigated
Hydrogenation, degree of hydrogenation are listed in Table 1 below.
Embodiment 5
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace in 550o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 0.3 wt%
Agent Pd/g-C3N4.Remaining step is same as Example 1.Using the identical reaction condition of embodiment 1, its catalysis to SBR is investigated
Hydrogenation, degree of hydrogenation are listed in Table 1 below.
Embodiment 6
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace in 550o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 0.5 wt%
Agent Pd/g-C3N4.Remaining step is same as Example 1.Using the identical reaction condition of embodiment 1, its catalysis to SBR is investigated
Hydrogenation, degree of hydrogenation are listed in Table 1 below.
Embodiment 7
A certain amount of ground urea is weighed in crucible with cover, is put in Muffle furnace in 550o4 h of C temperature lower calcination rises
Warm rate is 2oC/min is cooled to room temperature.With PdCl2Solution is preceding body fluid, the heterogeneous catalysis that preparation load capacity is 1.5 wt%
Agent Pd/g-C3N4.Remaining step is same as Example 1.Using the identical reaction condition of embodiment 1, its catalysis to SBR is investigated
Hydrogenation, degree of hydrogenation are listed in Table 1 below.
Embodiment 8
Catalyst synthesis step is same as Example 1, obtains the heterogeneous catalysis Pd/g-C that load capacity is 1.0 wt%3N4.It will
3g SBR is dissolved in 80 g hexamethylenes, takes 1g catalyst Pd/g-C3N4It is added in glue, is urged in a high pressure reaction kettle
Change hydrogenation reaction.Reaction condition are as follows: temperature 60 C, 1 MPa of Hydrogen Vapor Pressure, 4 h of reaction time.After reaction, Pd/g-C3N4
Catalyst centrifuge separation adds ethyl alcohol coagulation into glue and obtains product HSBR, and degree of hydrogenation is listed in Table 1 below.
Embodiment 9
Catalyst synthesis step is same as Example 7, obtains the heterogeneous catalysis Pd/g-C that load capacity is 1.5 wt%3N4.It will
1g SBR is dissolved in 80 g hexamethylenes, takes 0.5 g catalyst Pd/g-C3N4It is added in glue, carries out in a high pressure reaction kettle
Catalytic hydrogenation reaction.Reaction condition are as follows: temperature 60 C, 1 MPa of Hydrogen Vapor Pressure, 4 h of reaction time.After reaction, Pd/g-
C3N4Catalyst centrifuge separation adds ethyl alcohol coagulation into glue and obtains product HSBR, and degree of hydrogenation is listed in Table 1 below.
Embodiment 10
Catalyst synthesis step is same as Example 1, obtains the heterogeneous catalysis Pd/g-C that load capacity is 1.0 wt%3N4.It will
1g SBR is dissolved in 80 g toluene, takes 1g catalyst Pd/g-C3N4It is added in glue, is catalyzed in a high pressure reaction kettle
Hydrogenation reaction.Reaction condition are as follows: temperature 60 C, 1 MPa of Hydrogen Vapor Pressure, 2.5 h of reaction time.After reaction, Pd/g-C3N4
Catalyst centrifuge separation adds ethyl alcohol coagulation into glue and obtains product HSBR, and degree of hydrogenation is listed in Table 1 below.
Comparative example 1
This comparative example uses a kind of unmodified silica (SiO2) be carrier and urged using general Pd prepared by infusion process
Agent, to be compared with embodiment 1.
Using silica as carrier, PdCl2HCl solution be maceration extract (HCl concentration is 1M-5M), using isometric leaching
Stain method prepares the loaded catalyst that load capacity is 1.0 wt%, maceration extract is added drop-wise in silica dropwise, after mixing evenly
Pd is obtained in drying at room temperature2+/SiO2, by the Pd after drying2+/SiO2It is transferred in Muffle furnace, in 480 in air atmosphereoC roasting
Burn 4 h；140 after being cooled to room temperatureoC、H2Reductase 12 h under atmosphere, obtaining load capacity is 1.0 wt% loaded catalysts.Catalysis
SBR adds hydrogen to prepare HSBR, and to compare with embodiment, SBR Hydrogenation Experiment condition is same as Example 1.Degree of hydrogenation is listed in
In table 1.
Comparative example 2
This comparative example uses process-NH2The SiO of modification2It is silane coupled with aminoethyl amino propyl trimethoxy silane for carrier
Agent is to carrier S iO2Progress-NH2Modification；Use carrying method preparation load capacity identical with comparative example 1 for 1.0 wt% support types
Catalyst.It is compared with embodiment 1, according to the method for hydrotreating and reaction condition in embodiment 1, is catalyzed SBR and hydrogen is added to prepare
HSBR.Degree of hydrogenation is listed in Table 1 below.
Catalyst prepared by embodiment 1-10 and comparative example 1-2 adds hydrogen to obtain the HSBR of different degrees of hydrogenation for SBR,
Degree of hydrogenation and selectivity are listed in table 1.Fig. 1 is that the mesoporous nitridation carbon carrier (a) that embodiment 1 obtains and mesoporous carbonitride load nanometer
The XRD diagram of palladium catalyst (b), the characteristic diffraction peak at 2 θ=27.6 ° illustrate that there is carrier the interlayer of aromatic system to stack knot
Structure, the characteristic diffraction peak at 2 θ=13.6 ° represent the stacked structure in face；After loading Pd, it is lower than instrument since Pd particle is too small
The detectable limit of device and do not occur the peak of Pd, while also illustrating that the dispersion of Pd nano particle is fine.
Fig. 2 is the mesoporous nitridation carbon carrier (left side) and mesoporous carbonitride loaded nanometer palladium catalyst (right side) that embodiment 1 obtains
TEM figure.As shown in Figure 2, carrier is in layer structure, and the catalyst agent active group obtained using the method provided by the present invention
Divide even particle distribution, particle size is small, and partial size statistics particle size about concentrates on 2.9 nm.
Fig. 3 is silica supports (a), comparative example 1 obtains catalyst Pd/SiO2(c) and comparative example 2 obtains catalyst
Pd/N-SiO2(b) XRD diagram.As shown, the loaded catalyst Pd/SiO that comparative example 1 obtains2There is Pd nano particle
Characteristic diffraction peak, illustrate active component Pd dispersion it is poor, particle size is also larger.
Fig. 4 is embodiment 1, the infrared spectrogram of the HSBR that comparative example 1 obtains and SBR, utilizes infrared spectrum absorption peak
Intensity obtains degree of hydrogenation.As shown in figure 4, the HSBR that HSBR and degree of hydrogenation of the degree of hydrogenation up to 96.2% are 60.5%, in 700 cm-1
The phenyl ring absorption peak strength at place does not all change, in 820-900 cm-1Between there is not the absorption peak of cyclohexyl, explanation yet
Phenyl ring is not hydrogenated, i.e., selectivity is 100%.In 970 and 910 cm-1The absorption peak at place represents 1,4- double bond group and 1,
2- double bond group, in embodiment 1,910 cm-1Absorption peak completely disappear, illustrate 1,2- double bond substantially by complete hydrogenation, 970
cm-1Absorption peak strength decline it is obvious, illustrate that Isosorbide-5-Nitrae-double bond content significantly reduces；In comparative example 2,970 and 910 cm-1Suction
Receiving peak intensity has decline, but reduction amplitude is much smaller with respect to embodiment 2, illustrates that degree of hydrogenation is lower.Meanwhile adding after hydrogen 723
cm-1There is new peak, belongs to-[CH2]n(wherein n > 4) structure, emerging knot after C=C adds hydrogen to be saturated as in strand
Structure.
1 SBR degree of hydrogenation of table and selectivity
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Claims (9)
1. a kind of preparation method for the loaded catalyst for adding hydrogen preparation hydrogenated styrene-butadiene rubber for butadiene-styrene rubber heterogeneous solution,
It is characterized by: urea or cyanamide class presoma are placed in alumina crucible with cover, place it in Muffle furnace, through high temperature
Calcining obtains carrier graphite phase carbon nitride g-C3N4；Then it is urged by chemical reduction method in supported on carriers active metal Pd
Agent Pd/g-C3N4。
2. preparation method according to claim 1, it is characterised in that: the cyanamide class presoma includes cyanamide, two
One of poly cyanamid and melamine.
3. preparation method according to claim 1, it is characterised in that: heating rate is 2 in Muffle furnace oC/min。
4. preparation method according to claim 1, it is characterised in that: calcination temperature 400-800oC, calcination time 2-
6 h。
5. preparation method according to claim 1, it is characterised in that: chemical reduction method is in supported on carriers active metal
The specific method of Pd includes: by g-C3N4In deionized water, PdCl is added in ultrasonic disperse2Solution stirs after 30 min with 1
It is alkalinity that the NaOH solution of mol/L, which adjusts pH, uses NaBH4Solution is by Pd2+It is reduced to Pd0, then it is filtered, washes, ethyl alcohol
It washes, be dried in vacuo, obtain Pd/g-C3N4。
6. preparation method according to claim 5, it is characterised in that: g-C3N4Mass ratio with deionized water is 1:50-
300, reaction condition 30 oThe load capacity of C, active metal Pd are 0.1-10 wt%, and the partial size of Pd is 2.9nm.
7. preparation method according to claim 5, it is characterised in that: pH is 9-12 after NaOH solution is adjusted.
8. a kind of application of loaded catalyst made from preparation method as claimed in claim 1, feature exist
In: butadiene-styrene rubber dissolution is made into glue in organic solvent, is subsequently placed in autoclave, organic solvent and butadiene-styrene rubber
Mass ratio is 100-10:1；Then loaded catalyst Pd/g-C is added3N4, the mass ratio of catalyst and butadiene-styrene rubber is 0.1-
1:1, in 30-80oC, 0.5-6 MPa hydrogen is depressed, and reacts 0.5-12h；Reaction solution is centrifuged after reaction.
9. application as claimed in claim 8, it is characterised in that: the organic solvent is normal heptane, normal octane, toluene, hexamethylene
One or more of alkane, methylene chloride and chloroform.
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| CN111135850A (en) * | 2020-01-17 | 2020-05-12 | 福州大学 | Application of three-dimensional ordered macroporous carbon nitride supported palladium catalyst in catalytic hydrogenation of styrene unsaturated copolymer |
| CN111203260A (en) * | 2020-02-25 | 2020-05-29 | 广州中国科学院沈阳自动化研究所分所 | Monoatomic palladium-supported carbon nitride catalyst, preparation thereof and application thereof in removing NO |
| CN113842940A (en) * | 2021-09-27 | 2021-12-28 | 太原理工大学 | Catalyst for preparing methanol by low-temperature conversion of low-concentration coal bed gas and method for preparing methanol |
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| CN107790168A (en) * | 2017-10-31 | 2018-03-13 | 北京化工大学 | A kind of preparation method of hydrogenation catalyst and fluorescence saturated rubber with fluorescence |
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