CN109876852A - A PtO@MFI encapsulated structure catalyst for partial oxidation of methane to syngas and its preparation method and application - Google Patents
A PtO@MFI encapsulated structure catalyst for partial oxidation of methane to syngas and its preparation method and application Download PDFInfo
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Abstract
本发明属于甲烷催化转化技术领域，尤其是公开了一种甲烷部分氧化制合成气的封装结构催化剂及其制备方法。本发明所述的一种甲烷部分氧化制合成气封装结构催化剂的组成为：活性组分金属Pt的含量1 wt%～5 wt%，载体的含量95 wt%～99 wt%。其制备方法为：首先制备负载活性组分Pt的纳米二氧化硅，即PtO/SiO2纳米粒子；然后以PtO/SiO2纳米粒子为硅源，通过模板剂合成MFI结构分子筛；最后，将MFI结构分子筛焙烧，得到活性组分Pt被封装在分子筛中的核壳结构催化剂，即PtO@MFI。本发明所制得的PtO@MFI催化剂在甲烷部分氧化制合成气反应中活性和稳定性较高，且特有的封装结构进一步提高了催化剂的稳定性和活性组分的抗烧结性能。
The invention belongs to the technical field of methane catalytic conversion, and in particular discloses a packaged structure catalyst for producing synthesis gas by partial oxidation of methane and a preparation method thereof. The composition of the catalyst for partial oxidation of methane to syngas encapsulated structure is as follows: the content of active component metal Pt is 1 wt% to 5 wt%, and the content of carrier is 95 wt% to 99 wt%. The preparation method is as follows: firstly, nano-silicon dioxide loaded with active component Pt, namely PtO/SiO 2 nanoparticles, is prepared; then PtO/SiO 2 nanoparticles are used as silicon sources to synthesize MFI structural molecular sieves through a template; The structural molecular sieve is calcined to obtain a core-shell structure catalyst in which the active component Pt is encapsulated in the molecular sieve, namely PtO@MFI. The PtO@MFI catalyst prepared by the invention has high activity and stability in the partial oxidation of methane to syngas reaction, and the unique packaging structure further improves the stability of the catalyst and the anti-sintering performance of active components.
Description
Technical field
The invention belongs to methyl hydride catalyzed transformation technology field, a kind of methane portion oxidation synthesis gas is especially disclosed
PtO@MFI encapsulating structure catalyst and its preparation method and application.
Background technique
The high pollution of coal resources and the finiteness of petroleum resources promote the development and utilization of natural gas resource.Natural gas
Main component be methane, economically feasible methane utilization ways are to be catalytically conveted to synthesis gas.Methane portion oxidation
Preparing synthetic gas reacts mild heat release, more economical from the energy；Partial oxidation reaction of methane device is small in size, equipment investment is few；First
Alkane partial oxidation has suitable H2/ CO, the ratio are highly beneficial to downstream product especially methanol and Fiscber-Tropscb synthesis.Currently,
There are mainly two types of catalyst used in the reaction: one is load-type nickels, Co catalysts, although cost is relatively low, the catalyst
There is the problems such as easy carbon distribution of active component and sintering at high temperature；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 CN108722405A provides a kind of nanocatalyst with core-shell structure, and the catalyst is with your gold
Category nanoparticle is active component, to be capable of providing the metal oxide solid solution of Lacking oxygen as clad.It is said that the catalysis
Agent can either protect noble metal not to be sintered, but can provide a large amount of Lacking oxygens without influence catalyst activity, but technique compared with
For complexity.Chinese patent CN108579732A discloses a kind of Pt ZrO of hollow nucleocapsid meso-hole structure2Photo-thermal catalyst preparation
Method and application.By hollow ZrO2Nano particle is internally embedded Pt nanoparticle composition, but the catalyst is in pyroreaction
Under not can avoid still metal nanoparticle sintering.It is anti-that Chinese patent CN108636455A, which discloses one kind with core-shell structure MOF,
Answer the preparation and application of the carried noble metal base catalyst of container.Using the bimetallic Ni/Zn-MOF of core-shell structure as carrier, lead to
Regulation is crossed, noble metal nano particles can be encapsulated in the cavity between nucleocapsid, kernel can be used as carrier, evenly dispersed expensive
Metal palladium nano-particles, shell can play a protective role, and noble metal nano particles is inhibited to be lost, and having constructed has multilevel structure
Pd@Ni Zn-MOF.But the catalyst non-refractory reacts, high temperature flowering structure is collapsed serious.
Research shows that Zeolite Entrapped metal nanoparticle can effectively improve its anti-sintering property, but preparation process is general
It is more complex.
Summary of the invention
High, thermal stability difference problem that the purpose of the present invention is to solve current noble metal catalyst preparation costs, mentions
For one kind by conventional load type PtO/SiO2The MFI Zeolite Entrapped Pt base catalyst preparation that catalyst is prepared through hydrothermal crystallizing
Method, the catalyst show higher activity and anti-sintering property for methane portion oxidation synthesis gas reaction.
The specific technical solution of the present invention is as follows:
The present invention provides a kind of preparation methods of encapsulation type NanoPt catalyst, prepare support type using infusion process first
Then Pt base catalyst prepares MFI molecular sieve as silicon source using the nano silica for containing Pt, active component Pt is sealed in realization
In molecular sieve, to obtain the PtO@MFI encapsulating structure catalyst for methane portion oxidation synthesis gas.As than
Compared with using tradition PtO/SiO prepared by infusion process2It is good that catalyst catalytic performance can not show a candle to PtO@MFI catalyst performance.
In above-mentioned preparation method, the process of the MFI molecular sieve of the synthesis containing Pt specifically comprises the following steps:
1) the certain density tetrapropylammonium hydroxide solution of 5~25ml is measured, deionized water is added and is made into 40~60ml
0.1~0.5mol.L-1Solution；
2) 1~2g PtO/SiO is weighed2Nano particle is dissolved in the tetrapropylammonium hydroxide solution prepared, fills
Stirring, 1~2h of ultrasound is divided to reach and utmostly disperse；
3) above-mentioned solution is transferred in ptfe autoclave, 150~170 DEG C of rotation 1~3d of hydrothermal crystallizing, is turned
40~60r/min of 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, then roasting obtains PtO@MFI encapsulation in 400~550 DEG C of air
Structure catalyst.
As a kind of perferred technical scheme, during the MFI molecular sieve of the synthesis containing Pt, silicon source preferably loads work
The PtO/SiO of property component Pt2Nanoparticle, the PtO/SiO2Nanoparticle the preparation method is as follows:
1) 0.03~0.2g solubility platinum salt is weighed, is dissolved in 1.5~3ml deionized water and platinum salt solution is made；
2) 1~5g is weighed having a size of 15~50nm single crystalline Si O2, the platinum salt solution prepared in (1) is added drop-wise to nanometer dropwise
On silica, and it is sufficiently stirred；
3) ultrasonic, it vacuumizes, keeps platinum salt fully dispersed on silica；
4) it is dried in vacuo at 80~100 DEG C, then roasting obtains PtO/SiO in 400~550 DEG C of air2Nanometer
Grain.
Further preferred technical solution is, in above-mentioned preparation method, it is described solubility platinum salt be chloroplatinic acid, platinum nitrate,
One or more of platinum chloride, ammonium chloroplatinate.
Further preferred technical solution is, in above-mentioned preparation method, the Nano-meter SiO_22For 15~50nm of crystallite dimension
Single crystalline Si O2。
In preparation method of the present invention for the PtO@MFI catalyst of methane portion oxidation synthesis gas, by negative
Load type PtO/SiO2Catalyst prepares PtO@MFI encapsulating structure catalyst through a step hydrothermal crystallizing.The preparation method, uses first
Active component Pt is supported in nanometer silicon dioxide by dipping method, in the case where not introducing other silicon sources, using receiving
Rice silica supports obtain PtO/SiO as silicon source2Then micro porous molecular sieve template tetrapropyl hydrogen is added in nano particle
Amine-oxides, hydrothermal crystallizing form MFI structure, active component Pt are wrapped in molecular sieve, which can be achieved at the same time anti-
Sintering and reduction noble metal dosage reduce the purpose of cost.
The PtO@MFI that methane portion oxidation synthesis gas is used for prepared by the above method is utilized the invention further relates to a kind of
Encapsulating structure catalyst, which is characterized in that the composition of the PtO@MFI encapsulating structure catalyst are as follows: activity component metal Pt's
Content 1wt%~5wt%, vector contg 95wt%~99wt%.
In addition, the present invention also provides the above-mentioned PtO@MFI encapsulating structure catalysis for methane portion oxidation synthesis gas
Application of the agent in fixed bed reactors, which is characterized in that 300~700 DEG C, 2~3h of oxidization time of the temperature of oxidized portion, institute
Oxidation process is stated to carry out in pure oxygen atmosphere；The reaction velocity of methanation portion is 10800~14400mlh-1·g-1, first
Alkane/oxygen feeding is than 2/1, and 600~800 DEG C of reaction temperature.
Compared with prior art, the present invention has following prominent characteristics:
(1) encapsulation type NanoPt catalyst prepared by the present invention substantially reduces Pt aggregation, so that active component Pt dispersion is more
Uniformly, active component Pt has biggish opposite specific surface area, increases the touch opportunity of catalyst active center and reactant,
Obtained catalyst activity and stability all significantly improves；
(2) specific surface area and cellular structure the ratio SiO of MFI shell2Richer, reactant, product pass through on MFI shell
Duct diffuses out, and diffusion rate increases, and can adjust by adjusting hole density, average pore size；
(3) present invention is template and aqueous slkali using tetrapropylammonium hydroxide, and desiliconization carries out simultaneously with crystallization process again,
The consumption of silicon source is effectively reduced, yield is improved；
(4) present invention uses carrier silicas as the silicon source of further crystallization, on the basis for not introducing other silicon sources
Upper realization Zeolite Entrapped active component.
Detailed description of the invention
Fig. 1 is PtO@MFI catalyst transmission electron microscope picture freshly prepared in the embodiment of the present invention 1.
Fig. 2 is the PtO@MFI catalyst transmission electron microscope picture after reacting in the embodiment of the present invention 1.
Specific embodiment
Below by specific embodiment combination attached drawing, the following further describes the technical solution of the present invention, but of the invention
Embodiment is without being limited thereto.
Embodiment 1
Catalyst preparation: 0.03g H is weighed2PtCl6·6H2O, is dissolved in 1.5ml deionized water that platinum salt is made is molten
Liquid；Weigh single crystalline Si O of the 3g having a size of 15nm2, the platinum acid chloride solution prepared is added drop-wise in nano silica dropwise, and
It is sufficiently stirred；Ultrasonic 1h, vacuumizing 1h, to realize chloroplatinic acid on silica fully dispersed；It is dried in 100 DEG C of vacuum
Then night roasts 3h in 400 DEG C of air and obtains PtO/SiO2Nano particle.10ml 25wt%TPAOH solution is measured, is added
50ml deionized water is made into 60ml 0.2mol.L-1Solution；Weigh 2g PtO/SiO2Nano particle is dissolved in and prepares
It in TPAOH solution, is sufficiently stirred, ultrasound 2h is reached and utmostly dispersed；Above-mentioned solution is transferred to 100ml polytetrafluoroethyl-ne
In alkene reaction kettle, 170 DEG C of rotations hydrothermal crystallizing 3d, revolving speed 60r/min；It is centrifugated solution, is sufficiently washed with excessive deionized water
It washs to neutrality；It is dried overnight at 100 DEG C in air, then roasts 3h in 400 DEG C of air and obtain PtO@MFI encapsulating structure and urge
Agent.
Transmission electron microscope observing is carried out to obtained PtO@MFI encapsulating structure catalyst, result is as depicted in figs. 1 and 2.
Catalyst performance evaluation: before reaction, catalyst aoxidizes 3h in 300 DEG C of oxygen, in continuous sample introduction fixed bed reaction
It is reacted in device, 700 DEG C of reaction temperature, unstripped gas forms CH4/O2=2/1 (molar ratio), air speed 10800mlh-1·g-1,
Product uses gas chromatographic analysis after condensation water removal.The results are shown in Table 1 for embodiment 1.
1 PtO@MFI catalyst of table (300 DEG C of oxidation processes, 700 DEG C of reactions) carries out partial oxidation reaction of methane result
Fig. 1 and Fig. 2 is PtO@MFI encapsulating structure catalyst TEM figure obtained in embodiment 1.TEM figure in Fig. 1 is shown
The active component platinum of the PtO@MFI catalyst of brand-new is wrapped in MFI molecular sieve, and its particle size distribution is uniform, average
Partial size is 3nm or so, and dispersion degree is preferable.TEM figure in Fig. 2 show reaction after PtO@MFI catalyst structure not by
It destroys, little crystal grain high dispersive is still presented in active component in molecular sieve, has no that active component is reunited after pyroreaction.
Embodiment 2
Catalyst preparation: 0.03g PtN is weighed2O6, it is dissolved in 1.5ml deionized water and platinum salt solution is made；It weighs
Single crystalline Si O of the 3g having a size of 20nm2, the platinum nitrate solution prepared is added drop-wise in nano silica dropwise, and is sufficiently stirred
It mixes；Ultrasonic 1h, vacuumizing 1h, to realize platinum nitrate solution on silica fully dispersed；It is dried overnight in 100 DEG C of vacuum,
Then 3h is roasted in 400 DEG C of air obtain PtO/SiO2Nano particle.10ml 25wt%TPAOH solution is measured, is added
50ml deionized water is made into 60ml 0.2molL-1Solution；Weigh 2g PtO/SiO2Nano particle is dissolved in and prepares
TPAOH solution in, be sufficiently stirred, ultrasound 2h is reached and utmostly dispersed；Above-mentioned solution is transferred to 100ml poly- four
In vinyl fluoride reaction kettle, 170 DEG C of rotations hydrothermal crystallizing 3d, revolving speed 60r/min；It is centrifugated solution, is filled with excessive deionized water
Divide washing to neutrality；It is dried overnight at 100 DEG C in air, 3h is then roasted in 400 DEG C of air and obtains PtO@MFI encapsulation knot
Structure catalyst.
Catalyst performance evaluation: reference implementation example 1, the results are shown in Table 2 for embodiment 2.
2 PtO@MFI catalyst of table (250 DEG C of oxidation processes, 750 DEG C of reactions) carries out partial oxidation reaction of methane result
Embodiment 3
Catalyst preparation: 0.03g Pt is weighed2Cl4, it is dissolved in 1.5ml deionized water and platinum salt solution is made；It weighs
Single crystalline Si O of the 3g having a size of 50nm2, the platinum chloride solution prepared is added drop-wise in nano silica dropwise, and is sufficiently stirred
It mixes；Ultrasonic 1h, vacuumizing 1h, to realize platinum chloride solution on silica fully dispersed；It is dried overnight in 100 DEG C of vacuum,
Then 3h is roasted in 400 DEG C of air obtain PtO/SiO2Nano particle.10ml 25wt%TPAOH solution is measured, 50ml is added
Deionized water is made into 60ml 0.2molL-1Solution；Weigh 2g PtO/SiO2Nano particle is dissolved in and prepares
It in TPAOH solution, is sufficiently stirred, ultrasound 2h is reached and utmostly dispersed；Above-mentioned solution is transferred to 100ml polytetrafluoroethyl-ne
In alkene reaction kettle, 170 DEG C of rotations hydrothermal crystallizing 3d, revolving speed 60r/min；It is centrifugated solution, is sufficiently washed with excessive deionized water
It washs to neutrality；It is dried overnight at 100 DEG C in air, then roasts 3h in 400 DEG C of air and obtain PtO@MFI encapsulating structure and urge
Agent.
Catalyst performance evaluation: reference implementation example 1, the results are shown in Table 3 for embodiment 3.
3 PtO@MFI catalyst of table (300 DEG C of oxidation processes, 800 DEG C of reactions) carries out partial oxidation reaction of methane result
Comparative example 1
Catalyst preparation: 0.03g H is weighed2PtCl6·6H2O, is dissolved in 1.5ml deionized water that platinum salt is made is molten
Liquid；Weigh single crystalline Si O of the 3g having a size of 50nm2, the platinum acid chloride solution prepared is added drop-wise in nano silica dropwise, and
It is sufficiently stirred；Ultrasonic 1h, vacuumizing 1h, to realize chloroplatinic acid on silica fully dispersed；It is dried in 100 DEG C of vacuum
Then night roasts 3h in 400 DEG C of air and obtains PtO/SiO2Nano particle.
Catalyst performance evaluation: reference implementation example 1, the results are shown in Table 4 for embodiment 4.
4 PtO/SiO of table2Catalyst (300 DEG C of oxidation processes, 700 DEG C of reactions) carries out partial oxidation reaction of methane result
Comparative example 1 prepares loaded catalyst using conventional impregnation method, in long-time reaction process, under catalyst activity
Drop, deactivation cause may be the catalyst activity component sintering of exposure caused by high temperature.The experimental results showed that produced by the present invention
Catalyst has excellent anti-sintering property, can effectively improve traditional supported catalysts at high temperature existing sintering and
Carbon deposition phenomenon, to improve the stability and service life of catalyst.
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 (8)
1. a kind of preparation method of the PtO@MFI encapsulating structure catalyst for methane portion oxidation synthesis gas, feature exist
In, using the nano silica of load active component Pt as silicon source, pass through template guiding role, synthesize the MFI molecule containing Pt
Sieve, then removes template, obtains the PtO@MFI catalyst that active component Pt is encapsulated in molecular sieve.
2. the catalyst of the PtO@MFI encapsulating structure according to claim 1 for methane portion oxidation synthesis gas
Preparation method, which is characterized in that the process of the MFI molecular sieve of the synthesis containing Pt includes the following steps:
1) 0.1~0.5 molL is prepared-1Tetrapropylammonium hydroxide solution；
2) nano silica of the load active component Pt of 1~2 mass parts is dissolved in the step 1) institute of 40~60 parts by volume
It in the tetrapropylammonium hydroxide solution of preparation, is sufficiently stirred, 1~2 h of ultrasound；
3) step 2 acquired solution is transferred in ptfe autoclave, 150~170 DEG C of rotation hydrothermal crystallizings 1~3
D, 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, then roasting obtains PtO@MFI encapsulating structure in 400~550 DEG C of air
Catalyst.
3. the preparation method of the PtO@MFI catalyst according to claim 2 for methane portion oxidation synthesis gas,
It is characterized in that, the nano silica of the load active component Pt is PtO/SiO2Nanoparticle.
4. the system of the PtO@MFI encapsulating structure catalyst according to claim 3 for methane portion oxidation synthesis gas
Preparation Method, which is characterized in that the PtO/SiO2Nanoparticle the preparation method is as follows:
1) the soluble platinum salt for weighing 0.03~0.2 mass parts, is dissolved in the deionized water of 1.5~3 parts by volume and is made
Platinum salt solution；
2) Nano-meter SiO_2 of 1~5 mass parts is weighed2, the platinum salt solution prepared in step 1) is added drop-wise to the Nano-meter SiO_2 dropwise2On,
And it is sufficiently stirred；
3) ultrasonic, it vacuumizes, keeps platinum salt fully dispersed on silica；
4) it is dried in vacuo at 80~100 DEG C, then roasting obtains PtO/SiO in 400~550 DEG C of air2Nanometer
Grain.
5. the system of the PtO@MFI encapsulating structure catalyst according to claim 4 for methane portion oxidation synthesis gas
Preparation Method, which is characterized in that the solubility platinum salt is one of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate or several
Kind.
6. the system of the PtO@MFI encapsulating structure catalyst according to claim 4 for methane portion oxidation synthesis gas
Preparation Method, which is characterized in that the Nano-meter SiO_22For the single crystalline Si O of 15~50 nm of crystallite dimension2。
7. a kind of PtO@MFI encapsulating structure catalyst for methane portion oxidation synthesis gas, which is characterized in that the PtO@
The composition of MFI encapsulating structure catalyst are as follows: the content wt% of 1 wt%~5 of activity component metal Pt, 95 wt%~99 of vector contg
wt%。
8. a kind of PtO@MFI encapsulating structure catalyst as claimed in claim 7 for methane portion oxidation synthesis gas is solid
Application in fixed bed reactor, which is characterized in that 300~700 DEG C of the temperature of oxidized portion, 2~3 h of oxidization time, the oxygen
Change process carries out in pure oxygen atmosphere；The reaction velocity of methanation portion is 10800~14400 mlh-1·g-1, methane/oxygen
Gas charge ratio 2/1,600~800 DEG C of reaction temperature.
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Cited By (1)
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| CN115555044A (en) * | 2022-10-10 | 2023-01-03 | 无锡威孚环保催化剂有限公司 | Preparation method of catalyst for NOx pollutants of hydrogen internal combustion engine |
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