CN109908945A - A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application - Google Patents
A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application Download PDFInfo
- Publication number
- CN109908945A CN109908945A CN201910237412.XA CN201910237412A CN109908945A CN 109908945 A CN109908945 A CN 109908945A CN 201910237412 A CN201910237412 A CN 201910237412A CN 109908945 A CN109908945 A CN 109908945A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- pto
- porous structure
- hierarchical porous
- synthesis gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to methyl hydride catalyzed transformation technology fields, a kind of Pt metal by 1~5 wt% of the hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas of the present invention and, the carrier of 95~99 wt% forms, its preparation method is first to synthesize silicate-1 zeolite molecular sieve, then using soluble platinum salt as active component, by activity component impregnation on the silicate-1 zeolite molecular sieve carrier prepared, again using the silicate-1 zeolite molecular sieve containing Pt metal as silicon source, under lye etching action, active component Pt is encapsulated in multistage porous molecular sieve.Catalyst made from the method for the present invention, its encapsulating structure effectively prevents active component to be sintered at high temperature, hierarchical porous structure makes reaction gas and reaction product be easier to spread, and increases its contact probability with active component, to significantly improve the activity and anti-sintering property of catalyst.
Description
Technical field
The invention belongs to methyl hydride catalyzed transformation technology fields, more particularly, to a kind of methane portion oxidation synthesis gas PtO@
S-1 multistage porous molecular sieve and its preparation method and application.
Background technique
In gas chemical industry field, the application of methane can generally be divided into directly conversion and indirect reformer, but methane is direct
The problem of converting generally existing conversion ratio and low yield.Methane indirect reformer is first converted into synthesis gas, is then with synthesis gas
Raw material produces chemical products.Thus methane is converted into synthesis gas and is particularly important.The technique that methane is converted into synthesis gas has two
Carbonoxide reforming process, steam reforming process and methane portion oxidation method etc., methane portion oxidation method is more economical in contrast.First
Alkane partial oxidation is mild exothermic reaction, and energy consumption is smaller；Partial oxidation reaction of methane device is small in size, and has suitable H2/
CO, the ratio are highly beneficial to downstream product especially methanol and F-T synthesis.Currently, catalyst used in the reaction mainly has
Two kinds: one is load-type nickels, Co catalysts, are conducive to industrial production although cost is relatively low, which deposits at high temperature
The problems such as carbon distribution is with sintering, this will greatly limit its application；Another kind is loaded noble metal catalyst, although seldom hair
The problem of raw carbon distribution, but active component sintering can reduce the atom utilization of metal to further increase cost.
Chinese patent CN108636455A is disclosed a kind of to be urged by the carried noble metal base of reaction vessel of core-shell structure MOF
The preparation and application of agent.It, can be by noble metal nano by regulation using the bimetallic Ni/Zn-MOF of core-shell structure as carrier
Particle is encapsulated in the cavity between nucleocapsid, and kernel can be used as carrier, evenly dispersed precious metal palladium nano particle, and shell can be with
It plays a protective role, inhibits noble metal nano particles to be lost, constructed the Pd@Ni Zn-MOF with multilevel structure, but this is urged
Agent is not suitable for and pyroreaction, and catalyst structure collapses serious under high temperature.Chinese patent CN107983401A discloses one kind and relates to
And the monoatomic layer Pd catalyst and its preparation method and application of ZSM-5 encapsulation, solve noble metal catalyst system in the prior art
Standby at high cost, atom utilization is low and the technical problem of pyroreaction stability difference, and preparation method is that palladium complex is added
In molecular sieve gel, disperse Metal Palladium in ZSM-5 molecular sieve by a crystallization method, in high temperature furnace under oxygen atmosphere
Roasting, so as to the more active sites of exposure, reduces noble metal and uses so that Metal Palladium forms single atomic dispersion inside molecular sieve
Amount reduces catalyst preparation cost, but microporous molecular mesh size is limited, and reaction gas and reaction product contact not with active component
Sufficiently.Chinese patent CN105107497B discloses the gold nano catalyst and its synthetic method of a kind of multiple encapsulation of multilevel structure.
It is respectively synthesized mesoporous SiO2Nanometer bead, gold nano cluster solution and polystyrene sphere lotion；Then by mesoporous SiO2Nanometer is small
Ball disperses in deionized water, excessively gold nano cluster solution to be added, sufficiently obtains Jie of load gold nano cluster after load
Hole SiO2Bead aqueous solution；Take the mesoporous SiO of polystyrene sphere lotion Yu load gold nano cluster2The mixing of bead solution, ultrasound
Silicon source is added after dispersion thereto, is placed in baking oven and stands aging, then obtain the Jenner of the multiple encapsulation of hierarchical porous structure after calcining
Rice catalyst.
Stabilized metal can be improved in inert material encapsulation active metal, but the duct of inert material is mostly micropore at present,
Reactant and product diffusion are influenced to a certain extent, and then influence catalytic conversion efficiency.
Summary of the invention
The purpose of the present invention is to solve the dispersions of conventional load type Pt base catalyst activity component unevenly, and noble metal is former
Sub- utilization rate is not high, is easy to happen active component sintering at high temperature, and microporous molecular mesh size is limited, reactant, product with
The problem of active component insufficient contact.The present invention provides a kind of hierarchical porous structure Zeolite Entrapped Pt metal catalyst preparations
Method is used for methane portion oxidation synthesis gas, and catalytic activity and stability all significantly improve.
A kind of PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas of the present invention, which is characterized in that institute
Stating PtO@S-1 hierarchical porous structure molecular sieve is using the PtO/S-1 nanoparticle of the Pt containing active component as silicon source, in leading for template
To under etching action, by desiliconization and crystallization process again, active component Pt is encapsulated in molecular sieve and is made.
Second object of the present invention is to provide a kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure point
Son sieve and preparation method thereof, which is characterized in that active component Pt is supported on to the S-1 prepared using dipping method
(silicate-1) on carrier, in the case where not introducing other silicon sources, use PtO/S-1 as silicon source, template, mould is added
Directed agents and aqueous slkali are played the role of in plate agent simultaneously, and water-heat process desiliconization carries out simultaneously with crystallization again, by active component Pt packet
It is rolled in molecular sieve, while molecular sieve forms hierarchical porous structure, increases while realizing anti-sintering and raising noble metal utilisation
The contact probability of reaction gas and active component, to effectively improve the activity and stability of catalyst.
Technical solution used by preparation method of the present invention specifically, a kind of methane portion oxidation synthesis gas PtO@S-
The preparation method of 1 hierarchical porous structure molecular sieve, which is characterized in that using the PtO/S-1 nanoparticle of the Pt containing active component as silicon source,
Under the guiding of template and etching action, by desiliconization and crystallization process again, active component Pt is encapsulated in molecular sieve, is made
Obtain PtO@S-1 hierarchical porous structure molecular sieve.
A preferred technical solution is that the preparation method further includes the steps that preparing S-1 zeolite molecular sieve and by S-1
Zeolite molecular sieve prepares the step of PtO/S-1 nanoparticle.
Further, the step of preparation S-1 zeolite molecular sieve are as follows:
1) a certain amount of template solution is measured, deionized water is added, is mixed and is made into certain density solution；
2) appropriate tetraethyl orthosilicate is measured, measured tetraethyl orthosilicate is slowly dropped in the above-mentioned solution 1) prepared,
2~3 h of stirring at normal temperature, the ethyl alcohol that 70~80 DEG C of evaporation hydrolysis generate；
3) plus deionized water is to original volume, then transfers the solution into ptfe autoclave, 170 DEG C of hydrothermal crystallizings
3 d, centrifugation, excessive deionized water are washed to neutrality；
4) in 80~100 DEG C of air-dried overnights, then roasting obtains S-1 zeolite molecules in 400~550 DEG C of air
Sieve.
Further, the template is tetrapropylammonium hydroxide, 4-propyl bromide, cetyl trimethyl bromination
Any one in ammonium.
In above-mentioned technical proposal, by S-1 zeolite molecular sieve prepare PtO/S-1 nanoparticle the step of it is as follows:
1) 0.03~0.2 mass parts solubility platinum salt is weighed, is dissolved in 1.5~3 parts by volume deionized waters and platinum salt is made
Solution；
2) the S-1 zeolite molecular sieve made in 1~5 mass parts claim 3 is weighed, 1) the middle platinum salt solution prepared is dripped dropwise
It is added on S-1 zeolite molecular sieve, and is sufficiently stirred；
3) ultrasonic, vacuumizing keeps platinum salt fully dispersed on S-1；
4) it is dried in vacuo at 80~100 DEG C, then roasting obtains PtO/S-1 nanometers in 400~550 DEG C of air
Grain.
Further, the soluble platinum salt is one or more of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate.
In above-mentioned technical proposal, multistage porous molecular sieve is synthesized as silicon source using PtO/S-1 nanoparticle again, is specifically included as follows
Step:
1) a certain amount of template solution is measured, deionized water is added, is mixed and is made into certain density solution；
2) PtO/S-1 nano particle described in 1~2 mass parts claim 4 is weighed, the template solution prepared is dissolved in
In, it is sufficiently stirred, 1~2 h of ultrasound is reached and utmostly dispersed；
3) above-mentioned solution is transferred in 100 ml ptfe autoclaves, 150~170 DEG C of rotation hydrothermal crystallizings 12~
For 24 hours, 40~60 r/min of revolving speed；
4) it is centrifugated above-mentioned solution, is sufficiently washed with excessive deionized water to neutrality；
5) dry at 80~100 DEG C in air, it then roasts and obtains in air atmosphere in 400~550 DEG C of Muffle furnaces
PtO@S-1 hierarchical porous structure encapsulating material.
Further, the preferred tetrapropylammonium hydroxide of the template, 4-propyl bromide, cetyl trimethyl bromination
Any one in ammonium.
The invention further relates to the PtO@S-1 hierarchical porous structure molecules of the methane portion oxidation synthesis gas of above method preparation
Sieve is preparing the application in synthesis gas using fixed bed reactors, which is characterized in that reaction process includes oxidation pretreatment process
With partial oxidation reaction of methane process；The temperature of the oxidation pretreatment process is 200~300 DEG C, 2~3 h of oxidization time,
The oxidation pretreatment process carries out in pure oxygen atmosphere；Air speed is 10800~14400 during the methanation reaction
ml·h-1·g-1, methane/oxygen charge ratio is 2/1, and reaction temperature is 700~800 DEG C.
The present invention realizes constructing for micropore-mesopore multistage catalytic system, and it is unsmooth to solve encapsulated catalysts reaction channel
The problem of, compared with the existing technology, there is following prominent characteristics:
(1) encapsulation type NanoPt catalyst prepared by the present invention, reduces Pt aggregation significantly, and active component Pt dispersion is more equal
It is even, the atom utilization of active component Pt is increased, obtained catalyst activity and stability all significantly improve；
(2) present invention is directed agents and aqueous slkali using template, and desiliconization is carried out simultaneously with crystallization process again, effectively reduced
Silicon source consumption, improves yield；
(3) present invention is to form pore structure abundant in pore creating material, then crystallization process using template, effectively increases reaction
The contact probability of gas and active component improves the activity of catalyst；
(4) without being re-introduced into other silicon sources, catalyst preparation is conveniently easy to get the present invention.
Detailed description of the invention
Fig. 1 schemes for the TEM of PtO@S-1 hierarchical porous structure molecular sieve obtained in embodiment 1.TEM figure in Fig. 1 is shown
Multi-stage porous encapsulating structure is presented in PtO@S-1 catalyst, and active component platinum is encapsulated in molecular sieve, and its particle size distribution is equal
Even, dispersion degree is preferable.
Fig. 2 is the nitrogen adsorption desorption curve of PtO@S-1 hierarchical porous structure molecular sieve obtained in embodiment 1.Display is deposited in figure
In apparent H2 type hysteresis loop, illustrate to introduce meso-hole structure in S-1 molecular sieve.
Table 1 is the N of PtO/S-1 and PtO@S-1 hierarchical porous structure molecular sieve obtained in embodiment 12Adsorption desorption characterization knot
Fruit.Hierarchical porous structure molecular sieve PtO@S-1 is shown compared with S-1 molecular sieve by data in table 4, mesopore surface area increases, and
Pore structure is more abundant, and mesopore surface area and mesoporous pore volume increase are conducive to methane portion oxidation synthesis gas reaction
It carries out.
Specific embodiment
Embodiment 1
Catalyst preparation: measuring 16.5 ml, 25 wt% tetrapropylammonium hydroxide solution, and 34 ml deionized waters are mixed
It is made into certain density TPAOH solution；15.4 ml tetraethyl orthosilicates are measured, measured tetraethyl orthosilicate is slowly added dropwise
In the solution prepared to above-mentioned (1), 3 h of stirring at normal temperature, the ethyl alcohol that 80 DEG C of evaporation hydrolysis generate；Add deionized water to original
Then volume transfers the solution into ptfe autoclave, 170 DEG C of 3 d of hydrothermal crystallizing, centrifugation, excessive deionized water
It washs to neutrality；In 100 DEG C of air-dried overnights, then roasting obtains S-1 zeolite molecular sieve in 550 DEG C of air.
0.03 g chloroplatinic acid is weighed, is dissolved in 1.5 ml deionized waters and platinum acid chloride solution is made；Weigh the S-1 that 3 g make
The platinum acid chloride solution prepared is added drop-wise on S-1 zeolite molecular sieve dropwise, and is sufficiently stirred by zeolite molecular sieve；Ultrasound vacuumizes
1 h keeps platinum acid chloride solution fully dispersed on S-1；It is dry in 100 DEG C of vacuum, then roasted in 400 DEG C of air
To PtO/S-1 nano particle.10 ml, 25 wt% tetrapropylammonium hydroxide solution is measured, deionized water is added and is made into 60 ml
The solution of 0.2 M；2 g PtO/S-1 nano particles are weighed, is dissolved in the tetrapropylammonium hydroxide solution prepared, fills
Stirring, 1 h of ultrasound is divided to reach and utmostly disperse；Above-mentioned solution is transferred to 100 ml ptfe autoclaves
In, 170 DEG C of rotations 12 h of hydrothermal crystallizing, 60 r/min of revolving speed；It is centrifugated above-mentioned solution, is sufficiently washed with excessive deionized water
It washs to neutrality；100 DEG C of dryings in air, then to obtain PtO S-1 more for roasting in air atmosphere in 400 DEG C of Muffle furnaces
Grade pore structure molecular sieve.
Transmission electron microscope observing is carried out to obtained PtO@S-1 hierarchical porous structure molecular sieve, result is as shown in Figure 1.
The N of PtO@S-1 hierarchical porous structure molecular sieve2Adsorption-desorption curve and pore structure are as shown in Figure 2 and Table 1.
1 PtO/S-1 and PtO@S-1 hierarchical porous structure molecular sieve N of table2Adsorption desorption characterization result
Catalyst performance evaluation: before reaction, catalyst aoxidizes 3 h in 300 DEG C of oxygen, in continuous sample introduction fixed bed reactors
In reacted, 700 DEG C of reaction temperature, unstripped gas form CH4/O2=2/1 (molar ratio), 10800 mlh of air speed-1·g-1,
Product uses gas chromatographic analysis after condensation water removal.The results are shown in Table 2 for embodiment 1.
The reaction result of 2 PtO@S-1 hierarchical porous structure encapsulating material of table progress methane portion oxidation
Embodiment 2
Catalyst preparation: weighing 3.6 g of 4-propyl bromide, 34 ml deionized waters, be added sodium hydroxide adjust pH value to 10~
14；15.4 ml tetraethyl orthosilicates are measured, measured tetraethyl orthosilicate is slowly dropped to the solution that above-mentioned (1) prepares
In, 3 h of stirring at normal temperature, the ethyl alcohol that 80 DEG C of evaporation hydrolysis generate；Add deionized water to original volume, then transfers the solution into
In ptfe autoclave, 170 DEG C of 3 d of hydrothermal crystallizing are centrifuged, and excessive deionized water is washed to neutrality；In 100 DEG C of skies
It is dried overnight in gas, then roasting obtains S-1 zeolite molecular sieve in 550 DEG C of air.0.03 g platinum nitrate is weighed, by it
It is dissolved in 1.5 ml deionized waters and platinum nitrate solution is made；Weigh the S-1 zeolite molecular sieve that 3 g make, the nitric acid that will be prepared
Platinum solution is added drop-wise to dropwise on S-1 zeolite molecular sieve, and is sufficiently stirred；Ultrasound, vacuumizing 1 h makes platinum nitrate solution on S-1
It is fully dispersed；Dry in 100 DEG C of vacuum, then roasting obtains PtO/S-1 nano particle in 400 DEG C of air.It weighs
6.5 g of 4-propyl bromide is mixed with 60 ml deionized waters, and sodium hydroxide is added and adjusts pH value to 10~14；Weigh 2 g
PtO/S-1 nano particle is dissolved in the 4-propyl bromide solution prepared, is sufficiently stirred, 1 h of ultrasound is reached
Utmostly disperse；Above-mentioned solution is transferred in 100 ml ptfe autoclaves, 170 DEG C of rotation hydrothermal crystallizings 12
H, 60 r/min of revolving speed；It is centrifugated above-mentioned solution, is sufficiently washed with excessive deionized water to neutrality；It does for 100 DEG C in air
Dry, then roasting obtains PtO S-1 hierarchical porous structure molecular sieve in air atmosphere in 400 DEG C of Muffle furnaces.
Catalyst performance evaluation: reference implementation example 1,750 DEG C of reaction temperature, remaining reaction condition is identical, embodiment 2
The results are shown in Table 3.
The reaction result of 3 PtO@S-1 hierarchical porous structure encapsulating material of table progress methane portion oxidation
Embodiment 3
Catalyst preparation: weighing 3.6 g of cetyl trimethylammonium bromide, and 34 ml deionized waters are added sodium hydroxide and adjust pH
It is worth to 10~14；15.4 ml tetraethyl orthosilicates are measured, measured tetraethyl orthosilicate is slowly dropped to above-mentioned (1) and is prepared
Solution in, stirring at normal temperature 3 h, the ethyl alcohol that 80 DEG C of evaporation hydrolysis generate；Add deionized water to original volume, then by solution
It is transferred in ptfe autoclave, 170 DEG C of 3 d of hydrothermal crystallizing, is centrifuged, excessive deionized water is washed to neutrality；100
DEG C air-dried overnight, then roasting obtains S-1 zeolite molecular sieve in 550 DEG C of air.0.03 g platinum chloride is weighed,
It is dissolved in 1.5 ml deionized waters and platinum chloride solution is made；The S-1 zeolite molecular sieve that 3 g make is weighed, by what is prepared
Platinum chloride solution is added drop-wise to dropwise on S-1 zeolite molecular sieve, and is sufficiently stirred；Ultrasound, vacuumizing 1 h makes platinum chloride solution exist
S-1 is upper fully dispersed；Dry in 100 DEG C of vacuum, then roasting obtains PtO/S-1 nano particle in 400 DEG C of air.
6.5 g of cetyl trimethylammonium bromide is weighed, is mixed with 60 ml deionized waters, addition sodium hydroxide adjusting pH value to 10~
14；2 g PtO/S-1 nano particles are weighed, is dissolved in the cetyl trimethylammonium bromide solution prepared, sufficiently stirs
It mixes, 1 h of ultrasound is reached and utmostly dispersed；Above-mentioned solution is transferred in 100 ml ptfe autoclaves, 170
DEG C rotation 12 h of hydrothermal crystallizing, 60 r/min of revolving speed；It is centrifugated above-mentioned solution, is sufficiently washed into excessive deionized water
Property；100 DEG C of dryings in air, then roasting obtains PtO S-1 multi-stage porous knot in air atmosphere in 400 DEG C of Muffle furnaces
Structure molecular sieve.
Catalyst performance evaluation: reference implementation example 1, the results are shown in Table 4 for embodiment 3.
The reaction result of 4 PtO@S-1 hierarchical porous structure encapsulating material of table progress methane portion oxidation
Comparative example 1
Catalyst preparation: measuring 16.5 ml, 25 wt% tetrapropylammonium hydroxide solution, and 34 ml deionized waters are mixed
It is made into certain density TPAOH solution；15.4 ml tetraethyl orthosilicates are measured, measured tetraethyl orthosilicate is slowly added dropwise
In the solution prepared to above-mentioned (1), 3 h of stirring at normal temperature, the ethyl alcohol that 80 DEG C of evaporation hydrolysis generate；Add deionized water to original
Then volume transfers the solution into ptfe autoclave, 170 DEG C of 3 d of hydrothermal crystallizing, centrifugation, excessive deionized water
It washs to neutrality；In 100 DEG C of air-dried overnights, then roasting obtains S-1 zeolite molecular sieve in 550 DEG C of air.
0.03 g chloroplatinic acid is weighed, is dissolved in 1.5 ml deionized waters and platinum acid chloride solution is made；Weigh the S-1 that 3 g make
The platinum acid chloride solution prepared is added drop-wise on S-1 zeolite molecular sieve dropwise, and is sufficiently stirred by zeolite molecular sieve；Ultrasound vacuumizes
1 h keeps platinum acid chloride solution fully dispersed on S-1；It is dry in 100 DEG C of vacuum, then roasted in 400 DEG C of air
To PtO/S-1 nano particle.
Catalyst performance evaluation: reference implementation example 1.Methane conversion is 43.55%, carbon monoxide selective 63.61%,
Hydrogen selective is 55.54%, hence it is evident that lower than the performance of PtO@S-1 hierarchical porous structure encapsulating material.
The foregoing is merely presently preferred embodiments of the present invention, does not limit the scope of implementation of the present invention according to this, Fan Yibenfa
Any modifications, equivalent replacements, and improvements made by bright the scope of the patents and description etc. should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas, which is characterized in that
Using the PtO/S-1 nanoparticle of the Pt containing active component as silicon source, under the guiding of template and etching action, by desiliconization and again
Active component Pt is encapsulated in molecular sieve by crystallization process, and PtO@S-1 hierarchical porous structure molecular sieve is made.
2. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 1
Method, which is characterized in that the preparation method further includes the steps that preparing S-1 zeolite molecular sieve and by S-1 zeolite molecular sieve system
The step of standby PtO/S-1 nanoparticle.
3. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 2
Method, which is characterized in that the step of the preparation S-1 zeolite molecular sieve are as follows:
1) a certain amount of template solution is measured, deionized water is added, is mixed and is made into certain density solution；
2) appropriate tetraethyl orthosilicate is measured, measured tetraethyl orthosilicate is slowly dropped in the above-mentioned solution 1) prepared,
2~3 h of stirring at normal temperature, the ethyl alcohol that 70~80 DEG C of evaporation hydrolysis generate；
3) plus deionized water is to original volume, then transfers the solution into ptfe autoclave, 170 DEG C of hydrothermal crystallizings
3 d, centrifugation, excessive deionized water are washed to neutrality；
4) in 80~100 DEG C of air-dried overnights, then roasting obtains S-1 zeolite molecules in 400~550 DEG C of air
Sieve.
4. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 3
Method, which is characterized in that the template is tetrapropylammonium hydroxide, 4-propyl bromide, cetyl trimethylammonium bromide
In any one.
5. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 2
Method, which is characterized in that the step of PtO/S-1 nanoparticle is prepared by S-1 zeolite molecular sieve are as follows: 1) weigh 0.03~0.2 matter
Part solubility platinum salt is measured, is dissolved in 1.5~3 parts by volume deionized waters and platinum salt solution is made；
2) the S-1 zeolite molecular sieve made in 1~5 mass parts claim 3 is weighed, 1) the middle platinum salt solution prepared is dripped dropwise
It is added on S-1 zeolite molecular sieve, and is sufficiently stirred；
3) ultrasonic, vacuumizing keeps platinum salt fully dispersed on S-1；
4) it is dried in vacuo at 80~100 DEG C, then roasting obtains PtO/S-1 nanometers in 400~550 DEG C of air
Grain.
6. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 5
Method, which is characterized in that the solubility platinum salt is one or more of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate.
7. the system of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 1 or 2
Preparation Method, which is characterized in that multistage porous molecular sieve is synthesized as silicon source using PtO/S-1 nanoparticle again, is specifically comprised the following steps:
1) a certain amount of template solution is measured, deionized water is added, is mixed and is made into certain density solution；
2) PtO/S-1 nano particle described in 1~2 mass parts claim 4 is weighed, the template solution prepared is dissolved in
In, it is sufficiently stirred, 1~2 h of ultrasound is reached and utmostly dispersed；
3) above-mentioned solution is transferred in 100 ml ptfe autoclaves, 150~170 DEG C of rotation hydrothermal crystallizings 12~
For 24 hours, 40~60 r/min of revolving speed；
4) it is centrifugated above-mentioned solution, is sufficiently washed with excessive deionized water to neutrality；
5) dry at 80~100 DEG C in air, it then roasts and obtains in air atmosphere in 400~550 DEG C of Muffle furnaces
PtO@S-1 hierarchical porous structure encapsulating material.
8. the preparation of the PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas according to claim 7
Method, which is characterized in that the template is tetrapropylammonium hydroxide, 4-propyl bromide, cetyl trimethylammonium bromide
In any one.
9. a kind of PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas, which is characterized in that the PtO@S-
1 hierarchical porous structure molecular sieve is using the PtO/S-1 nanoparticle of the Pt containing active component as silicon source, in the guiding and etching of template
Under effect, by desiliconization and crystallization process again, active component Pt is encapsulated in molecular sieve and is made.
10. a kind of PtO@S-1 hierarchical porous structure molecular sieve of methane portion oxidation synthesis gas as claimed in claim 9 is utilizing
Fixed bed reactors prepare the application in synthesis gas, which is characterized in that application process includes oxidation pretreatment process and methane portion
Divide oxidation reaction process；The temperature of the oxidation pretreatment process is 200~300 DEG C, 2~3 h of oxidization time, the oxidation
Pretreatment process carries out in pure oxygen atmosphere；Air speed is 10800~14400 mlh during the methanation reaction-1·g-1, methane/oxygen charge ratio is 2/1, and reaction temperature is 700~800 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910237412.XA CN109908945A (en) | 2019-03-27 | 2019-03-27 | A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910237412.XA CN109908945A (en) | 2019-03-27 | 2019-03-27 | A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109908945A true CN109908945A (en) | 2019-06-21 |
Family
ID=66967141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910237412.XA Pending CN109908945A (en) | 2019-03-27 | 2019-03-27 | A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109908945A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138706A (en) * | 2020-09-15 | 2020-12-29 | 大连理工大学 | Sulfur-tolerant hydrogenation catalyst for hydrogen transfer system and preparation method thereof |
| CN113457718A (en) * | 2021-06-25 | 2021-10-01 | 复旦大学 | Magnetic functional zeolite molecular sieve catalyst and preparation method thereof |
| CN114345396A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Molecular sieve in-situ packaging active component type oxygen carrier and preparation method and application thereof |
| CN114784306A (en) * | 2022-05-06 | 2022-07-22 | 青岛创启新能催化科技有限公司 | Preparation method of anode catalyst Pt/C for fuel cell |
| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056633A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method of SiO2-coated core-shell structure catalyst |
| CN106669768A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application |
| CN108273547A (en) * | 2017-12-28 | 2018-07-13 | 中国华能集团公司 | A method of carried molecular sieve catalyst is prepared using vacuum impregnation technology |
| CN108607600A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of catalyst of molecular sieve carried high dispersive noble metal and its preparation and application |
-
2019
- 2019-03-27 CN CN201910237412.XA patent/CN109908945A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056633A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method of SiO2-coated core-shell structure catalyst |
| CN108607600A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of catalyst of molecular sieve carried high dispersive noble metal and its preparation and application |
| CN106669768A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application |
| CN108273547A (en) * | 2017-12-28 | 2018-07-13 | 中国华能集团公司 | A method of carried molecular sieve catalyst is prepared using vacuum impregnation technology |
Non-Patent Citations (3)
| Title |
|---|
| CHANG LIU ET AL.: "Palladium Nanoparticles Encapsulated in a Silicalite-1 Zeolite Shell for Size-Selective Catalysis in Liquid-Phase Solution", 《CHEMCATCHEM》 * |
| 周吉萍等: "Pd/A12O3催化剂上甲烷氧化反应的研究", 《第十届全国催化学术会议论文集》 * |
| 陈国华等: "甲烷部分氧化制合成气Pt/Al2O3催化剂的表征及其反应性能评价", 《光谱实验室》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138706A (en) * | 2020-09-15 | 2020-12-29 | 大连理工大学 | Sulfur-tolerant hydrogenation catalyst for hydrogen transfer system and preparation method thereof |
| CN113457718A (en) * | 2021-06-25 | 2021-10-01 | 复旦大学 | Magnetic functional zeolite molecular sieve catalyst and preparation method thereof |
| CN113457718B (en) * | 2021-06-25 | 2022-10-11 | 复旦大学 | Magnetic functional zeolite molecular sieve catalyst and preparation method thereof |
| CN114345396A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Molecular sieve in-situ packaging active component type oxygen carrier and preparation method and application thereof |
| CN114784306A (en) * | 2022-05-06 | 2022-07-22 | 青岛创启新能催化科技有限公司 | Preparation method of anode catalyst Pt/C for fuel cell |
| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN115805097B (en) * | 2022-12-01 | 2024-03-01 | 中触媒新材料股份有限公司 | Large-grain Zn@Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109908945A (en) | A kind of methane portion oxidation synthesis gas PtO@S-1 hierarchical porous structure molecular sieve and its preparation method and application | |
| CN109908904A (en) | A kind of monatomic catalyst of transition metal and its preparation method and application | |
| CN109453773A (en) | A kind of load type double-metal catalyst with core-casing structure and preparation method thereof | |
| CN110975864B (en) | Preparation method of carbon-doped and metal-monoatomic-supported catalyst, product and application thereof | |
| CN107321351B (en) | Preparation method of efficient catalyst for methane/carbon dioxide reforming reaction | |
| CN107020147A (en) | A kind of MFI structure sheet molecular sieve catalyst, the preparation method and the usage of package metals oxide or metal nanoparticle | |
| CN111135840A (en) | Preparation method of supported monatomic dispersed noble metal catalyst | |
| CN108940346A (en) | Beta-unsaturated ketone selective hydrocatalyst and its preparation method and application | |
| CN113151856B (en) | Preparation of high-entropy alloy phosphide nanoparticle catalyst and application of high-entropy alloy phosphide nanoparticle catalyst in hydrogen production by water electrolysis | |
| CN109277109A (en) | Composite catalyst and preparation method thereof, application | |
| CN106000443A (en) | Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis | |
| CN108654638A (en) | A kind of hud typed Co based Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN109420515A (en) | A kind of preparation method of high-dispersion loading type metallic catalyst | |
| CN113559916A (en) | Molecular sieve encapsulated noble metal catalyst and preparation method and application thereof | |
| CN109289886B (en) | PdIn alloy catalyst and preparation method thereof, application | |
| CN111215122A (en) | Palladium-based methane catalytic combustion catalyst, preparation and application | |
| CN107670694A (en) | A kind of metal load type catalyst and its preparation method and application | |
| CN114272927A (en) | Preparation method of zirconium dioxide modified layered porous vermiculite supported nickel-based catalyst | |
| CN114768859A (en) | Nickel-silicon catalyst suitable for dry reforming of methane and preparation method thereof | |
| CN111111676B (en) | Coated nickel-based catalyst and preparation method thereof | |
| CN114345336B (en) | Transition metal molybdenum modified palladium silver-alumina catalyst, and preparation method and application thereof | |
| CN109876852A (en) | A kind of PtO@MFI encapsulating structure catalyst and its preparation method and application for methane portion oxidation synthesis gas | |
| CN107185525B (en) | Octahedral Pt nanoparticle loaded gamma-Al2O3Process for preparing form catalyst | |
| CN114308061A (en) | NiAu bimetallic alloy nano catalyst and synthesis and application thereof | |
| CN114308063A (en) | PtCo/Co3O4-x-Al2O3Multi-interface structure catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190621 |