CN104607232B - A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation - Google Patents
A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation Download PDFInfo
- Publication number
- CN104607232B CN104607232B CN201510014117.XA CN201510014117A CN104607232B CN 104607232 B CN104607232 B CN 104607232B CN 201510014117 A CN201510014117 A CN 201510014117A CN 104607232 B CN104607232 B CN 104607232B
- Authority
- CN
- China
- Prior art keywords
- cyclo
- catalyst
- octadiene
- octene
- selectivity
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation of a kind of Pd/S C catalyst and its select the application being hydrogenated in cyclo-octene in 1,5 cyclo-octadiene.This material is with carbonitride mesoporous silicon complex chemical compound as carrier, by controlling heat treatment temperature, obtain the Pt-supported catalyst with different-grain diameter, under uniform temperature and pressure condition, the Pd/S C catalyst being obtained using different heat treatment temperature or different catalytic reaction temperatures, the selectivity generating cyclo-octene or cyclooctane can be controlled, keep 1,5 cyclo-octadiene conversion ratios to be more than 99% simultaneously；Under normal temperature and pressure, with the carrier loaded Pd/S C that 300 C are processed, 95% is up to the conversion ratio of 1,5 cyclo-octadiene hydrogenation reaction, keeps selectivity to be more than 99% simultaneously；Even if under 0 C, the conversion ratio being hydrogenated to cyclo-octene to 1,5 cyclo-octadiene also reaches 60%, and selectivity is more than 98% simultaneously.
Description
Technical field
The invention belongs to the preparation of new material and applied technical field are and in particular to a kind of preparation side of Pd/S-C catalyst
Method and its application in catalysis 1,5- cyclo-octadiene hydrogenation reaction, especially in catalysis 1,5- cyclo-octadiene selective hydrogenation system
Application in standby cyclo-octene.
Background technology
Because sustainable development and environmental conservation etc. need, the production standard in chemical process was by originally reacting
The conversion ratio of thing is gradually changed to the selectivity of product, that is, the atom utilization of reactant to be improved.This requires to react
Used in the process of catalyst not only to have higher activity, also to have preferable selectivity simultaneously.How to improve turning of catalyst
Rate and selectivity thus to be that urgently to be resolved hurrily in current Chemical Manufacture one is great study a question
(Angew.Chem.Int.Ed.2008,47,9212-9228).The solution of this problem can be carried out from the design aspect of catalyst.Example
Size as controlled catalyst aperture can prevent macromole access hole internal active sites so that small molecule can enter and instead
Should；And control the size of granule, shape, nano-particle contact surface then so that catalyst substrate is had different activity and
Selectivity, thus obtain different products (J.Am.Chem.Soc.2011,133,2362-2365).
Hydrogenation reaction is the important organic reaction of a class, is also an important route of synthesis fine-chemical intermediate.With
The enhancing to environmental consciousness for the recent years, this technology receives much concern.Cyclo-octene is a kind of important centre in commercial production
1,5- cyclo-octadiene selection Hydrogenation therefore, has been obtained extensive concern for cyclo-octene with green route by body.Additionally, 1,5-
Cyclo-octadiene has two identical C=C double bonds, thus also will be to evaluate the selective mould of catalyst for hydrogenation
Type reacts.Really, the catalyst of document report is (such as：Pd/C、Pd/Al2O3) 1,5- cyclo-octadiene deep hydrogenation can be made to generate ring
Octane, reduces to the selectivity of cyclo-octene (AICHE J.2008,54,258-268).Therefore, find and there is high activity, high selection
Property and reusable selective hydrocatalyst be current one great challenge and captivation problem.
In the application, with carbonitride-porous silicon compound (S-C) as carrier, palladium nano-particles are activearm to inventor
Point, by carrier is carried out with the process of different temperatures, obtain the palladium nanocatalyst (Pd/S-C) with different-grain diameter.Result
Display, this catalyst selects to be hydrogenated in cyclo-octene reaction show good activity and selectivity in 1,5- cyclo-octadiene.
With United States Patent (USP) 5525211 disclosed with magnesium aluminate spinel as carrier, compared with the catalyst as active component for the molybdenum cobalt, in the present invention
The preparation method of Pd/S-C catalyst is simple and has higher activity and stability.Additionally, this catalyst separates easy, regeneration
Functional, thus will be the industrial applications catalysis that a class is potentially used for that 1,5- cyclo-octadiene selects to be hydrogenated to cyclo-octene
Agent.
Content of the invention
For the deficiencies in the prior art, object of the present invention is to provide one kind is with carbonitride-porous silicon
(S-C) be carrier the preparation method of Pt-supported catalyst (i.e. Pd/S-C) and its catalysis 1,5- cyclo-octadiene selective hydrogenation
Application in reaction.By changing the heat treatment temperature of carrier, the structure of carrier and chemical property can be controlled to bear thus controlling
The granular size of carried palladium catalyst, the size finally according to nano-particle controls the activity and selectivity to reaction for the catalyst.
The technical scheme is that：
A kind of Pd/S-C catalyst preparation and its catalysis 1,5- cyclo-octadiene be hydrogenated to cyclo-octene reaction in should
With comprising the following steps that：
1st, the preparation method of Pd/S-C catalyst, its step is as follows：
(1) cyanamid dimerization is dissolved in the mixed solvent being made up of distilled water and dehydrated alcohol, is heated to 80 DEG C, after dissolving
Add the SBA-15 with quality such as cyanamid dimerizations, keep 80 DEG C of solvents with stirring to system to volatilize completely；
Described mixed solvent is distilled water and dehydrated alcohol according to 1：4 volume ratio mixes；
Described cyanamid dimerization and mixed solvent solid-to-liquid ratio are 3g：(40-50)mL；
The inventive method does not have particular/special requirement to SBA-15, and SBA-15 used herein is inventor's laboratory according to routine
Prepared by method, concrete preparation method is shown in specific embodiment；
(2) product drying obtaining step (1) overnight, from room temperature to 300-500 DEG C in nitrogen atmosphere, is protected
Warm processes 4h, and then cooling, taking-up, obtain catalyst carrier；
The speed of described intensification is 2 DEG C/min；
(3) catalyst carrier is pressed solid-to-liquid ratio 0.5g：50mL is added to the PdCl of 0.001M2In solution, ultrasonic 5 minutes,
Then dipping absorption 4h, sucking filtration, washing, vacuum drying, the sample obtaining is then at H2It is incubated from room temperature to 300 DEG C under atmosphere
Heat treatment 3h (heating rate is 1 DEG C/min), hydrogen flow rate is 50mL/min.
2nd, the application of cyclo-octene is prepared in the selective hydrogenation of catalyst 1,5- cyclo-octadiene：
(1) under uniform temperature and pressure condition：Experimental provision is autoclave and the heat-collecting magnetic stirring device of 50mL.
Add 50mg catalyst, 0.25mL1,5- cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane in reactor, Hydrogen Vapor Pressure is
2MPa, 80 DEG C are reacted 90 minutes, sample is centrifuged, filter after be analyzed with gas chromatograph.
(2) under normal temperature and pressure：Experimental provision is 50mL three-neck flask.Left neck connects a hydrogen balloon, and middle neck connects one
Rubber tube is used for discharging hydrogen, and right neck connects a sampler.50mg catalyst, 0.25mL1,5- ring is added in three-neck flask
Octadiene, 0.2mL dodecane, 30mL normal heptane, seal reactor, are passed through hydrogen exclusion air, sample, sample after certain time
Separated, filter after, use gas chromatographic analysiss.
Compared with prior art, advantages of the present invention and having the beneficial effect that：
(1) catalyst preparation is simple, without special material and condition, and can be recycled.
(2) high conversion rate of raw material, the selectivity of target product is good.Prior art is hydrogenated with to 1,5- cyclo-octadiene list and selects
Property low, and need carry out under uniform temperature and pressure condition.The present invention under normal temperature and pressure conditionses, reported first Pd/S-C
Catalyst 1, the selectivity that 5- cyclo-octadiene generates cyclo-octene, the high conversion rate of raw material, and target product is high.
(3) response time is short, efficiency high.Under the conditions of the present invention, catalysis 1,5- cyclo-octadiene generates the reaction of cyclo-octene
Time is 90min.Compared with other catalyst, have the advantages that the response time is short, reaction efficiency is high.
(4) catalytic reaction condition is gentle, easily operated, can reach under normal temperature and pressure conditionses conversion ratio higher than 93% and
99% selectivity.Due to the high activity of Pd/S-C_300, or even under conditions of 0 DEG C, also reaction can be shown higher than 60%
Activity and 98% cyclo-octene selectivity.
(5) whole catalytic process is environmentally friendly, and atom utilization is high.The raw material 1,5- cyclo-octadiene consuming substantially can be complete
The single cyclo-octene of full generation, flow process is simple, is suitable for industrial applications.
Brief description
The nitrogen physisorption of SBA-15 and S-C_T (T=300, the 400,500) carrier for embodiment 1 preparation for the Fig. 1-de-
Attached isothermal curve and graph of pore diameter distribution.
Fig. 2 is the big angle XRD spectra of Pd/S-C_T (T=300, the 400,500) catalyst of embodiment 1 preparation.
Fig. 3 is the XPS spectrum figure of Pd/S-C_T (T=300, the 400,500) catalyst of embodiment 1 preparation.
Fig. 4 is the transmission electron microscope picture of Pd/S-C_T (T=300,400,500) catalyst of embodiment 1 preparation and corresponding
Pd grain diameter.
Fig. 5 A is for Pd/S-C_T (T=300,400,500) catalyst in embodiment 2 in H2Pressure is 2MPa, when 80 DEG C pair
The activity and selectivity (t=90min) of cyclo-octadiene catalytic hydrogenation reaction；Fig. 5 B is Pd/S-C_300 catalyst in embodiment 3
In H2Pressure is 2MPa, and temperature is 50, the activity and selectivity (t=to cyclo-octadiene catalytic hydrogenation reaction under the conditions of 60,80 DEG C
90min).
In Fig. 5 A and B, blank post represents the selectivity of cyclo-octene, and column with slant lines represents the selectivity of cyclooctane.
Fig. 6 is that in embodiment 4, Pd/S-C_T (T=300,400,500) catalyst is urged to cyclo-octadiene at normal temperatures and pressures
The activity that change is hydrogenated to cyclo-octene reaction changes over figure.
Fig. 7 is that in embodiment 5, Pd/S-C_300 catalyst generates to cyclo-octadiene catalytic hydrogenation under 0 DEG C, condition of normal pressure
The activity of cyclo-octene reaction changes over figure.
Fig. 8 is that in embodiment 6, Pd/S-C_300 catalyst is pungent to cyclo-octadiene catalytic hydrogenation generation ring at normal temperatures and pressures
The stability test figure of alkene reaction.
Specific embodiment
Applicant is by conjunction with specific embodiments to the preparation method and application of catalyst of the present invention in addition specifically below
Bright, so that those skilled in the art are further understood by the present invention.But following examples should not be solved by any way
It is interpreted as claims of the present invention is claimed with the restriction of scope.
Embodiment 1：A kind of preparation method of Pd/S-C catalyst, step is as follows：
(1) 3g cyanamid dimerization is dissolved in the mixed solvent being made up of 10mL distilled water and 40mL dehydrated alcohol, is heated to
It is incubated after 80 DEG C, after cyanamid dimerization is completely dissolved, adds 3g SBA-15, continue to be incubated and stir until solvent volatilizees completely.
The preparation method of the SBA-15 being related in the present embodiment is as follows：
5g P123 is taken to be dissolved in the mixed solvent being made up of 75g distilled water and 150g HCl (concentration 2M).Acute at 35 DEG C
Strong stir be completely dissolved to P123 after, after being slowly added dropwise 10.5g tetraethyl orthosilicate, at 35 DEG C continue stirring 24h.Then exist
100 DEG C of crystallization 24h in crystallization tank, cooling, washing, sucking filtration, obtain white powder.Then 24h is dried at 100 DEG C again, in Muffle furnace
Cool down after 550 DEG C of calcining 6h, obtain final product.
(2) product drying that step (1) is obtained overnight, from room temperature with the speed liter of 2 DEG C/min in nitrogen atmosphere
Temperature carries out heat treatment to T DEG C (T=300-500) insulation 4h, then cooling, take out, gained sample is labeled as S-C_T, as urging
Agent carrier is standby, and T corresponds to the actual temp numerical value (unit be DEG C) of aforementioned heat treatment, and the present embodiment is parallel to have set three not
Synthermal：300 DEG C, 400 DEG C, 500 DEG C, then T respectively 300,400,500, respectively obtain carrier S-C_300, S-C_400, S-
C_500.
(3) the S-C_T carrier obtaining 0.5g step (2) is added separately to the PdCl of 50mL 0.001mol/L2Solution
In, ultrasonic 5 minutes, then dipping absorption 4h, sucking filtration, washing, vacuum drying, the sample obtaining is then at H2From room temperature liter under atmosphere
To 300 DEG C of insulation 3h heat treatments (heating rate is 1 DEG C/min), hydrogen flow rate is 50mL/min to temperature.Gained catalyst is labeled as
Pd/S-C_T (T=300,400,500), the load capacity of Pd is 1%.
The instrumental characterizing of product：
(1) nitrogen physisorption of carrier S-C_T-desorption isothermal curve is shown in accompanying drawing 1A.All samples (include embodiment 1
Homemade SBA-15) all there is typical IV type adsorption-desorption isothermal curve, and have for 0.6-0.75 scope in relative pressure
There is H1 type hysteresis loop, the meso-hole structure with SBA-15 is described.The pore-size distribution of carrier S-C_T is shown in accompanying drawing 1B it is known that in sample
Define multi-stage porous, and also increase therewith with the aperture of the rising multi-stage porous of temperature.
(2) accompanying drawing 2 is the big angle XRD spectra of catalyst.By contrast standard PDF card, find sample 2 θ=
The diffraction maximum of 40.1 °, 46.4 ° and 67.9 ° is corresponding with the crystallographic plane diffraction peak of Metal Palladium (111), (200) and (220) respectively, says
There is Pd nano-particle in bright sample.And the reduction with vehicle treated temperature, the diffraction peak intensity reduction of Pd granule and half-peak
The wide palladium nano-particles particle diameter reduction increasing, formation being described.
(3) accompanying drawing 3 is the XPS spectrum figure of catalyst.Result shows that the existence form of palladium is mainly the Pd of metallic state0, have few
Amount is presented in PdO.
(4) transmission electron microscope picture of Pd/S-C_T catalyst is shown in accompanying drawing 4.Pd particle height be dispersed in the surface of SBA-15 and its
Particle diameter changes with the difference of vehicle treated temperature, and size order is Pd/S-C_300<Pd/S-C_400<Pd/S-C_
500, illustrate that carrier has good dispersibility to Pd granule, and its treatment temperature has very big shadow to the particle diameter of Pd granule
Ring.Additionally, in figure still can see the pore passage structure of SBA-15 rule, the structure that SBA-15 is described is in catalyst preparation process
In be not destroyed.
The following is the Application Example of embodiment 1 prepared catalyst.
Embodiment 2：
Pd/S-C_T catalyst 1,5- cyclo-octadiene selective hydrogenation under uniform temperature and pressure condition：
Experimental provision is autoclave and the heat-collecting magnetic stirring device of 50mL.50mg catalysis is added in reactor
Agent, 0.25mL 1,5- cyclo-octadiene, 0.2mL dodecane, 30mL normal heptane, Hydrogen Vapor Pressure is 2MPa, and 80 DEG C are reacted 90 minutes,
Sample is centrifuged, filter after be analyzed with gas chromatograph.
Accompanying drawing 5A compares Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 catalyst under these conditions to reaction
Activity and selectivity.It can be seen that all there is higher work to reaction after the carrier loaded Pd catalyst crossed for the treatment of of different temperature
Property, and selectivity is then closely related with the size of Pd granule：Small particle Pd catalyst is (i.e.：Pd/S-C_300) the choosing to cyclooctane
Selecting property is very high, and big particle diameter Pd catalyst is (i.e.：Pd/S-C_500) very high to cyclo-octene selectivity, the precondition of this result is height
Warm high pressure.That is Pd catalyst can be controlled to 1,5- ring by changing the treatment temperature of carrier under high-temperature and high-pressure conditions
The selectivity of octadiene hydrogenation reaction.Due to the high activity of Pd/S-C_300 catalyst, it will make reaction deep under this condition
Degree is hydrogenated to cyclooctane.For this reason, in subsequent reactions we with it as catalyst, by reduce reaction condition, by reaction controlling
In the cyclo-octene stage.High yield can be obtained, and can save energy.
Embodiment 3：
With Pd/S-C_300 as catalyst, reaction temperature is 50,60 and 80 DEG C, and other conditions are with embodiment 2.Experimental result
As shown in fig. 5b.It can be seen that temperature is very big on selective impact, when 80 drop to 50 DEG C, catalyst Pd/S-C_300 is pungent to ring
The selectivity of alkane is changed into 8% from 94%, and rises to 90% to the selectivity of cyclo-octene by 4%.Temperature pungent to 1,5 rings two is described
The selectivity of alkene hydrogenation has large effect.Low temperature can suppress the deep hydrogenation reacting, and is conducive to the generation of cyclo-octene.
Embodiment 4：
Pd/S-C_T catalyst 1,5- cyclo-octadiene selective hydrogenation under normal temperature and pressure：
Experimental provision is that the left neck of 50mL three-neck flask connects a hydrogen balloon, and middle neck connects a rubber tube and discharges hydrogen,
Right neck connects a sampler.Experimentation is as follows：50mg catalyst, 0.25mL 1,5- ring pungent two is added in three-neck flask
Alkene, 0.2mL dodecane, 30mL normal heptane, seal reactor, are passed through hydrogen exclusion air, normal-temperature reaction certain time, sample enters
Row centrifugation, filters and gas chromatographic analysiss.Accompanying drawing 6 compares Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 and urges
Agent changes over figure to the activity of reaction under these conditions.
It is pungent to ring that result is shown in Pd/S-C_300, Pd/S-C_400 and Pd/S-C_500 catalyst under normal temperature and pressure conditionses
Alkene there is over 98% selectivity, and Pd/S-C_300 shows higher activity at normal temperatures and pressures.
Embodiment 5：
Course of reaction with embodiment 4, but now with mixture of ice and water control system temperature in zero degrees celsius.Accompanying drawing 7 is should
Under the conditions of reactivity and selectivity.Even if result shows anti-to 1,5- cyclo-octadiene catalytic hydrogenation in zero degrees celsius catalyst
Higher catalysis activity (more than 60%) should be also showed that and keep the selectivity to cyclo-octene to be more than 98%.Pd/S-C_ is described
300 catalyst have preferable activity and selectivity to this hydrogenation reaction.
Embodiment 6：
In order to detect the repeatable usability of Pd/S-C_300, stability test is carried out to this catalyst.By embodiment 4
Middle reaction terminate after catalyst through filter, 100 DEG C dry 6 hours, carry out active testing again.Process is with embodiment 4.Result
As shown in Figure 8：Catalyst circulation five times afterwards conversion ratio only relatively for the first time (fresh catalyst) reduce 13%, period protects
Hold selectivity constant.Illustrate that catalyst does not only have preferable activity and selectivity, also there is higher stability simultaneously.
Embodiment 7：
Test the impact to Pd/S-C_300 catalyst reaction activity for the different solvents in catalytic reaction, experimentation is with real
Apply example 4, only convert solvent, result is as shown in table 1.Relatively understand, oxolane and normal heptane are all appropriate molten of this reaction
Agent, but the initial activity in view of catalyst, with normal heptane as optimum solvent.
Table 1：In embodiment 7, the impact to Pd/S-C_300 catalyst activity for the different solvents is compared.
Claims (1)
1. a kind of Pd/S-C catalyst prepares the application in cyclo-octene in catalysis 1,5- cyclo-octadiene selective hydrogenation；
The preparation method of described Pd/S-C catalyst, its step is as follows：
（1）Cyanamid dimerization is dissolved in the mixed solvent being made up of distilled water and dehydrated alcohol, is heated to 80 DEG C, add again after dissolving
Enter the SBA-15 with quality such as cyanamid dimerizations, keep 80 DEG C of solvents with stirring to system to volatilize completely；
Described mixed solvent is distilled water and dehydrated alcohol according to 1：4 volume ratio mixes；
Described cyanamid dimerization and mixed solvent solid-to-liquid ratio are 3g：（40-50）mL；
（2）By step（1）The product drying obtaining overnight, from room temperature to 300 DEG C in nitrogen atmosphere, is incubated heat treatment
4 h, then cooling, taking-up, obtain catalyst carrier；
（3）Catalyst carrier is pressed solid-to-liquid ratio 0.5g：50mL is added to the PdCl of 0.001M2In solution, ultrasonic 5 minutes, then soak
Stain adsorbs 4 h, sucking filtration, washing, vacuum drying, and the sample obtaining is then at H2Under atmosphere at room temperature to 300 DEG C of heat preservation hot
Manage 3 h；
The reaction that cyclo-octene is prepared in described catalysis 1,5- cyclo-octadiene selective hydrogenation is carried out in normal heptane solvent；
The reaction that cyclo-octene is prepared in described catalysis 1,5- cyclo-octadiene selective hydrogenation is carried out under normal temperature and pressure conditionses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510014117.XA CN104607232B (en) | 2015-01-12 | 2015-01-12 | A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510014117.XA CN104607232B (en) | 2015-01-12 | 2015-01-12 | A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104607232A CN104607232A (en) | 2015-05-13 |
| CN104607232B true CN104607232B (en) | 2017-03-08 |
Family
ID=53142035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510014117.XA Expired - Fee Related CN104607232B (en) | 2015-01-12 | 2015-01-12 | A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104607232B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN103641673B (en) * | 2013-12-12 | 2015-09-09 | 上海交通大学 | A kind of method of carbonitride load type metal nano particle catalysis reduction carbon-carbon double bond |
-
2015
- 2015-01-12 CN CN201510014117.XA patent/CN104607232B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104607232A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423251B (en) | A kind of preparation method of load type palladium catalyst | |
| CN108097255B (en) | Porous carbon frame nickel-based catalyst for carbon dioxide reforming reaction and preparation method and use method thereof | |
| Liu et al. | Highly efficient catalytic conversion of cellulose into acetol over Ni–Sn supported on nanosilica and the mechanism study | |
| US10399069B2 (en) | Hydroisomerization and cracking catalyst for preparing biological aviation kerosene from castor oil | |
| CN107185594B (en) | Preparation method of Ni-Zn-K-Ru/MOF catalyst | |
| CN105693659B (en) | A kind of preparation method of tetrahydrofurfuryl alcohol | |
| CN110252378A (en) | A kind of monatomic double activity center Co base ammonia synthetic catalyst and preparation method thereof | |
| CN111450843A (en) | High-efficiency Ru/Co limited-area ammonia synthesis catalyst and preparation method and application thereof | |
| CN107739297A (en) | It is a kind of to directly select the method that oxidation prepares methanol, formaldehyde, CO for methane | |
| CN113101941B (en) | Preparation method of cobalt-molybdenum catalyst and application of cobalt-molybdenum catalyst in catalyzing levulinic acid hydrogenation reaction | |
| CN108295849B (en) | My/LaxSr1-xTi1-yO3Catalyst, its preparation method and application | |
| CN104607232B (en) | A kind of preparation method of Pd/S C catalyst and its application in catalysis 1,5 cyclo-octadiene hydrogenation | |
| CN109999819B (en) | Preparation of porous perovskite LaFeO3In-situ carbon template method and application thereof | |
| CN113996303B (en) | Double-active interface supported catalyst, preparation method and application | |
| CN108940283B (en) | Supported high-efficiency hydrogenation catalyst and preparation method thereof | |
| CN105688891A (en) | High-initial-activity catalyst for propane dehydrogenation to prepare propylene and preparing method thereof | |
| CN113649010B (en) | Preparation and synthesis method and application of supported iron-based catalyst for preparing liquid fuel by carbon dioxide hydrogenation | |
| CN113351207B (en) | Multi-wall catalyst for preparing liquid fuel by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN112237931B (en) | Bulk phase nickel phosphide catalyst, preparation method and application in phenol hydrodeoxygenation | |
| CN108722409A (en) | Mesoporous copper-based aluminium oxide catalyst, preparation method and application | |
| CN113546631A (en) | La modified Ni/Al2O3Catalyst, preparation method and application | |
| CN110292947A (en) | A kind of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst and its preparation method and application | |
| CN105618132A (en) | Preparation method and application of aluminum phosphate molecular sieve loaded Ni catalyst | |
| Kucherov | Effect of the formation of secondary pores in zeolite ZSM-5 on the properties of molybdenum-zeolite catalysts for methane aromatization | |
| CN112237936B (en) | Liquid phase dehydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 Termination date: 20200112 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |