CN103084170B - A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application - Google Patents
A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN103084170B CN103084170B CN201110332379.2A CN201110332379A CN103084170B CN 103084170 B CN103084170 B CN 103084170B CN 201110332379 A CN201110332379 A CN 201110332379A CN 103084170 B CN103084170 B CN 103084170B
- Authority
- CN
- China
- Prior art keywords
- microemulsion
- carrier
- selective hydrogenation
- hydrogenation catalyst
- active component
- 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.)
- Active
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides one and prepare C 3 fraction selective hydrogenation catalyst and its preparation method and application.The active component of described catalyst prepares through microemulsion method and loads on carrier, and the particle diameter of the main active component Pd of prepared catalyst is little, size tunable, good dispersion degree, and its grain diameter is for being less than 10nm; Preparation method of the present invention is simple, easy to operate, and preparation condition is gentle; Catalyst application had in pyrolysis product C3 fraction higher activity and selective preferably when propine and allene selective hydrogenation reaction.
Description
Technical field
The invention belongs to a kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application, relate in particular to a kind of microemulsion method that utilizes and generate supported selective hydrogenation catalyst of propylene and its preparation method and application for the preparation of propine in pyrolysis product C3 fraction and allene selec-tive hydrogenation.
Background technology
Petroleum hydrocarbon is after cracking is separated, and containing propylene, propane, and a small amount of propine and allene (being called for short MAPD), propine and allene are about 1% ~ 5% (volume content) in C3 fraction.Because impurity MAPD can reduce the activity of polypropylene catalyst, affect the quality of polymerization product, therefore need the content of MAPD to be removed to certain level.Current industrial widely used acetylene removal method is catalysis selective hydrogenation method.
Patent CN 100512955C discloses a kind of alkynes and diolefin hydrogenate Catalysts and its preparation method, inert carrier outer surface is coated on by aluminum oxide coating layer, the main active component of catalyst and help active component to be only distributed on the aluminum oxide coating layer of catalyst surface, improves the hydrogenation efficiency of catalyst activity component.But the activity and selectivity of catalyst is still unsatisfactory.
Patent CN 101875009A discloses a kind of Catalysts and its preparation method preparing propylene for propylene in C3 fraction and allene selec-tive hydrogenation, catalyst activity component precursor passes through the load of impregnating method on carrier, by ionising radiation process, metal active constituent is by direct-reduction, directly can put into production, not need to use hydrogen reducing.But the activity and selectivity of catalyst is still unsatisfactory.
Show the characteristics such as quantum size effect, bulk effect, surface and interface effect, quantum size tunnel-effect due to nano particle, make nano-particle catalyst show excellent characteristic.The method preparing nano particle mainly comprises steam condensing method, mechanochemical reaction, sol-gel process, the precipitation method, hydro-thermal method, irradiation method, microemulsion method etc.Wherein microemulsion method is as a kind of effective ways preparing nano particle, and the interfacial film consisted of surfactant and cosurfactant is wrapped to form the drop of microemulsion, by adjusting the consumption of aqueous phase and surfactant, can control the particle diameter of nano particle.Microemulsion method has experiment condition gentleness, and equipment is simple, the advantages such as size tunable.
Summary of the invention
For the problems of the prior art, the object of this invention is to provide and a kind ofly generate supported selective hydrogenation catalyst of propylene and its preparation method and application for propine in pyrolysis product C3 fraction and allene selec-tive hydrogenation, the catalyst that the method obtains has higher activity and selective preferably.
One of the object of the invention is to provide a kind of C 3 fraction selective hydrogenation catalyst, this catalyst is used for propine and allene selec-tive hydrogenation in pyrolysis product C3 fraction and generates the reaction of propylene, comprise carrier and be carried on the active component on carrier, the active component of described catalyst utilizes microemulsion method prepare and obtain.
Described carrier is Al
2o
3, SiO
2, ZnO, TiO
2, V
2o
5, SnO
2in one or both and two or more mixtures.Preferred vector shape be granular, spherical, profile of tooth, annular, tooth are spherical, sheet shape, the bar shaped such as bar shaped or clover.
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance palladium, and palladium content is the 0.01wt% ~ 2.0wt% of described carrier gross weight, is preferably the 0.05wt% ~ 0.5wt% of total weight of carrier;
The described active component that helps is one or more in La, Ag, Au, Bi, Cu, Sn, Cs, Ge, alkali metal, and content is the 0.0wt% ~ 10.0wt% of described carrier gross weight, is preferably the 0.0wt% ~ 5.0wt% of total weight of carrier.
The grain diameter of described main active component is less than 10nm;
In described catalyst of the present invention, active component adopts microemulsion method preparation and obtains, and be carried on carrier, comprises the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained C 3 fraction selective hydrogenation catalyst of the present invention.
Wherein said non-ionic surface active agent is at least one in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10; Described cosurfactant is C
3~ C
8alcohols, more preferably from normal propyl alcohol, isobutanol, n-amyl alcohol, the one in isooctanol; Described oil phase is selected from C
6~ C
12linear paraffin, cyclic alkane, at least one in branched paraffin, more preferably from cyclohexane, n-hexane, isooctane; Described salting liquid is selected from the one in described nitrate, sulfate, chloride, acetate.
Reduction reaction temperature in step (2) is 0 ~ 60 DEG C, and described reducing agent is at least one in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
The catalyst activity component above-mentioned reduction fully obtained loads on carrier by conventional methods such as dipping, sprayings, more preferably the catalyst activity component prepared of described microemulsion by a step dipping or step impregnation load on carrier.
Present invention employs microemulsion method to combine with catalyst preparation process and prepare loaded catalyst, the interfacial film consisted of the surfactant in microemulsion and cosurfactant mixing controls the size of water core, namely in microemulsion system, control the particle diameter of metal active constituent, then by the method for flooding or spray metal active constituent loaded on carrier and be prepared into loaded catalyst, the different metal nanoparticle of particle diameter can be obtained by adjustment water with the ratio of surfactant.By the method for microemulsion Kaolinite Preparation of Catalyst of the present invention, the particle diameter forming nano particle in microemulsion is shown by high resolution transmission electron microscopy (TEM) test result, the particle diameter < 10nm of the nano particle formed, can with reference to accompanying drawing 1.
Another object of the present invention is to provide a kind of method preparing C 3 fraction selective hydrogenation catalyst.In the method, the aqueous solution of activity component metal salt is dispersed in oil phase through non-ionic surface active agent and cosurfactant parcel, load on carrier by the mode of dipping, spraying after reducing agent reduction, the metal nanoparticle average diameter formed in microemulsion is less than 10nm.Specifically comprise the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained C 3 fraction selective hydrogenation catalyst of the present invention.
3rd object of the present invention is to provide this catalyst propine and allene selec-tive hydrogenation in pyrolysis product C3 fraction and generates the application in the reaction of propylene.
The present invention compared with prior art has the following advantages:
(1) preparation method of the present invention is simple, easy to operate, and experiment condition is gentle.
(2) C 3 fraction selective hydrogenation catalyst prepared of the present invention, because adopting microemulsion method to be prepared from, its size tunable, evenly, good dispersion, good stability, considerably improves catalyst activity and selectivity in the reaction.
Accompanying drawing explanation
Fig. 1 is the distribution of catalyst nanoparticles in microemulsion system
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited in following embodiment.
Embodiment 1
Take the Pd (NO of 100mg/ml
3)
2solution 2.17ml, use deionized water to be diluted to 5ml, 13.8mlTween80 and 17.73ml isopropyl alcohol mixes with 20ml cyclohexane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the Pd (NO of dilute with water
3)
2solution, magnetic agitation certain hour is until obtain transparent microemulsion; Pd (the NO that a certain amount of hydrazine hydrate makes in microemulsion is added in above-mentioned microemulsion
3)
2be reduced into simple substance Pd; Take 100g Al
2o
3carrier, is impregnated into the microemulsion after reduction on carrier.Then dry, roasting is prepared into described catalyst A, and wherein Pd content is 0.1wt%.
Embodiment 2
Take the PdCl of 200mg/ml
2solution 1.23ml, deionized water is used to be diluted to 5ml, 14.2ml TX-100 and 18.23ml n-butanol mix with 25ml normal octane under magnetic stirring, and then add the metal salt solution of dilute with water by 25 DEG C in water bath with thermostatic control, and magnetic agitation certain hour is until obtain transparent microemulsion; The PdCl that a certain amount of hydrazine hydrate makes in microemulsion is added in above-mentioned microemulsion
2be reduced into simple substance Pd; Take 100gTiO
2carrier, is impregnated into the microemulsion after reduction on carrier.Then dry, roasting is prepared into described catalyst B, and wherein Pd content is 0.15wt%.
Embodiment 3
Take the Pd (NO of 200mg/ml
3)
2the AgNO of solution 1.62ml, 300mg/ml
3solution 1.57ml uses deionized water to be diluted to 5ml.10mlNP-10 and 5ml n-amyl alcohol mixes with 30ml cyclohexane under magnetic stirring by 20 DEG C in water bath with thermostatic control, and then add the metal salt solution of dilute with water, magnetic agitation certain hour, until obtain transparent microemulsion, adds a certain amount of potassium borohydride and makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage in above-mentioned microemulsion.Take 100gAl
2o
3carrier, sprays on carrier by the microemulsion after reduction, and then dry, roasting is prepared into described catalyst C.Wherein Pd content is 0.15wt%.Wherein Ag content is 0.3wt%.
Embodiment 4
Take the Pd (NO of 100mg/ml
3)
2solution 2.17ml, adds the Cu (NO of 100mg/ml
3)
2solution 3.77ml, adds the La (NO of 200mg/ml
3)
3solution 1.56ml, deionized water is used to be diluted to 10ml, 10ml OP-10 and 5ml normal propyl alcohol mix with 25ml normal heptane under magnetic stirring, and then add the metal salt solution of dilute with water by 25 DEG C in water bath with thermostatic control, and magnetic agitation certain hour is until obtain transparent microemulsion; In above-mentioned microemulsion, add a certain amount of hydrazine hydrate makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage; Take 100g Al
2o
3carrier, sprays to the microemulsion after reduction on carrier.Then dry, roasting is prepared into described catalyst D, and wherein Pd content is 0.1wt%, and wherein Cu content is 0.1wt%, and wherein La content is 0.1wt%.
Embodiment 5
Take the Pd (NO of 200mg/ml
3)
2solution 1.62ml, adds the HAuCl of 200mg/ml
4solution 2.09ml, deionized water is used to be diluted to 5ml, 10mlTween60 and 10ml n-hexyl alcohol mixes with 25ml normal octane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the metal salt solution of dilute with water, and magnetic agitation certain hour is until obtain transparent microemulsion; In above-mentioned microemulsion, add a certain amount of hydrazine hydrate makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage.Take 100g Al
2o
3carrier, sprays on carrier by the microemulsion after reduction, and then dry, roasting is prepared into described catalyst E, and wherein Pd content is 0.1wt%, and wherein Au content is 0.1wt%.
Embodiment 6
Take the Pd (NO of 200mg/ml
3)
2the AgNO of solution 2.17ml, 100mg/ml
3solution 1.57ml, adds the Bi (NO containing 100mg/ml
3)
35H
2o solution 2.32ml, uses deionized water to be diluted to 10ml; 10mlTween80 and 5ml n-hexyl alcohol mixes with 25ml cyclohexane under magnetic stirring by 25 DEG C in water bath with thermostatic control, and then adds the metal salt solution of dilute with water, and magnetic agitation certain hour is until obtain transparent microemulsion; In above-mentioned microemulsion, add a certain amount of hydrazine hydrate makes the reducing metal ions in the metal salt solution in microemulsion become elemental stage.Take 100g Al
2o
3carrier, sprays on carrier by the microemulsion after reduction, and then dry, roasting is prepared into described catalyst F, and wherein Pd content is 0.2wt%, and wherein Ag content is 0.1wt%, and wherein Bi content is 0.1wt%.
Comparative example
Take the Pd (NO of 100mg/ml
3)
2the AgNO of solution 6.5ml, 100mg/ml
3solution 1.57ml, uses deionized water dilution 50ml, takes 100gAl
2o
3the metal salt solution that carrier adds dilution leaves standstill 30min, and dry, roasting, obtains catalyst G.Wherein Pd content is 0.3wt%, and wherein Ag content is 0.3wt%.
Evaluation test
Above-mentioned catalyst A, B, C, D, E, F, G are carried out C3 fraction propine and allene selective hydrogenation reaction, and reaction condition is as follows:
1ml catalyst is loaded in stainless steel tube reactor, after using nitrogen displacement, individual hour of hydrogen 180 DEG C of reductase 12s, then pass in reactor by unstripped gas, the composition (molar fraction) of reaction raw materials is: the mol ratio of propane 4.99%, propylene 92.3%, allene 1.19%, propine 1.39%, hydrogen and propine and allene (MAPD) is 1.4 ~ 1.6.Experiment air speed is 10000h
-1.By each catalyst reaction to the conversion ratio (Conversion) of (MAPD) and the computational methods of selective (Selectivity) be:
The reactivity worth of table 1 catalyst
Experimental result shows, the load capacity of catalyst metals active component Pd of the present invention is low, but MAPD is hydrogenated into the reaction of propylene, and compared with comparative example, catalyst of the present invention has higher activity and selective.
Claims (8)
1. prepare a C 3 fraction selective hydrogenation catalyst, comprise carrier and be carried on the active component on carrier, it is characterized in that:
Described carrier is Al
2o
3, SiO
2, ZnO, TiO
2, V
2o
5, SnO
2, SiC, at least one in kaolin, the specific area of described carrier is 1 ~ 200m
2/ g, its face shaping be spherical, profile of tooth, annular, tooth are spherical, granular, sheet, strip, clover or bunge bedstraw herb;
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance palladium, and palladium content is the 0.01wt% ~ 2.0wt% of described carrier gross weight;
The described active component that helps is at least one in La, Ag, Au, Bi, Cu, Sn, Ge, alkali metal, helps the content of active component to be the 0.0wt% ~ 10.0wt% of total weight of carrier;
The grain diameter of described main active component is for being less than 10nm;
Active component in described catalyst adopts microemulsion method preparation and obtains, and be carried on carrier through dipping, spraying, and concrete steps are:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1:x:y:z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier through dipping, spraying;
(4) dry for microemulsion obtained for step (3), roasting are obtained C 3 fraction selective hydrogenation catalyst.
2. C 3 fraction selective hydrogenation catalyst according to claim 1, is characterized in that described palladium content is the 0.05wt% ~ 0.5wt% of described carrier gross weight.
3. C 3 fraction selective hydrogenation catalyst according to claim 1, is characterized in that the described active component content that helps is the 0.0wt% ~ 5.0wt% of described carrier gross weight.
4. C 3 fraction selective hydrogenation catalyst according to claim 1, it is characterized in that described non-ionic surface active agent is at least one in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10, described cosurfactant is C
3~ C
8alcohols, described oil phase is C
6~ C
12linear paraffin, cyclic alkane, at least one in branched paraffin, described salting liquid is at least one in the nitrate of noble metal, sulfate, chloride, acetate.
5. C 3 fraction selective hydrogenation catalyst according to claim 1, it is characterized in that described cosurfactant is normal propyl alcohol, isobutanol, n-amyl alcohol, isooctanol, described oil phase is cyclohexane, n-hexane, isooctane.
6. C 3 fraction selective hydrogenation catalyst according to claim 1, the reduction reaction temperature that it is characterized in that described step (2) is 0 ~ 60 DEG C, and described reducing agent is at least one in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
7. the preparation method of the C 3 fraction selective hydrogenation catalyst that one of claim 1-6 is described, comprises the following steps:
(1) microemulsion is prepared: in water bath with thermostatic control, the aqueous phase be made up of the salting liquid of non-ionic surface active agent, catalyst activity component, cosurfactant, oil phase mix in proportion, stir the w/o type microemulsion system that preparation is stable, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1:x:y:z, wherein x is 0.1 ~ 5, y is 0.1 ~ 10, z is 0.1 ~ 4;
(2) reduce: joined by reducing agent in the obtained microemulsion of step (1), the mol ratio of reducing agent and salt is (1 ~ 10): 1;
(3) load: the catalyst activity component fully obtained of step (2) being reduced loads on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained selective hydrogenation catalyst.
8. C 3 fraction selective hydrogenation catalyst according to claim 1 is applied to propine and allene selec-tive hydrogenation in C3 fraction and generates the reaction of propylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110332379.2A CN103084170B (en) | 2011-10-28 | 2011-10-28 | A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110332379.2A CN103084170B (en) | 2011-10-28 | 2011-10-28 | A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103084170A CN103084170A (en) | 2013-05-08 |
| CN103084170B true CN103084170B (en) | 2015-10-07 |
Family
ID=48197599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110332379.2A Active CN103084170B (en) | 2011-10-28 | 2011-10-28 | A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103084170B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928004B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | Carbon three-fraction selective hydrogenation method |
| CN112934232B (en) * | 2019-11-26 | 2023-10-31 | 中国石油天然气股份有限公司 | Catalyst for selective hydrogenation of carbon three fractions |
| CN112844407B (en) * | 2019-11-26 | 2024-06-28 | 中国石油天然气股份有限公司 | Preparation method of carbon three-fraction selective hydrogenation catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314020B1 (en) * | 1987-10-28 | 1990-08-08 | Süd-Chemie Ag | Catalyst for the selective hydrogenation of multiple unsaturated hydrocarbons |
| CN101757954A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Method for preparing supported selective hydrogenation catalyst by using microemulsion technology |
| CN101875009A (en) * | 2009-04-29 | 2010-11-03 | 中国石油化工股份有限公司 | C3 fraction selective hydrogenation catalyst and preparation method thereof |
| CN102220168A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for selective hydrogenation of pyrolysis gas |
-
2011
- 2011-10-28 CN CN201110332379.2A patent/CN103084170B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314020B1 (en) * | 1987-10-28 | 1990-08-08 | Süd-Chemie Ag | Catalyst for the selective hydrogenation of multiple unsaturated hydrocarbons |
| CN101757954A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Method for preparing supported selective hydrogenation catalyst by using microemulsion technology |
| CN101875009A (en) * | 2009-04-29 | 2010-11-03 | 中国石油化工股份有限公司 | C3 fraction selective hydrogenation catalyst and preparation method thereof |
| CN102220168A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for selective hydrogenation of pyrolysis gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103084170A (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103084168B (en) | A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application | |
| CN104415751B (en) | A kind of C-2-fraction gas phase selective hydrogenation catalyst and its preparation method and application | |
| CN103084172A (en) | C2 fraction selective hydrogenation catalyst, preparation method and applications thereof | |
| CN103084173B (en) | C4 fraction selective hydrogenation catalyst, preparation method and applications thereof | |
| CN103084169B (en) | A kind of hydrogenation of unsaturated hydrocarbons Catalysts and its preparation method and application | |
| US10913052B1 (en) | Supported bimetallic core-shell structure catalyst and its preparation method | |
| Liu et al. | K-modified Sn-containing dendritic mesoporous silica nanoparticles with tunable size and SnOx-silica interaction for the dehydrogenation of propane to propylene | |
| CN103084171B (en) | A kind of drippolene one section of selective hydrogenation catalyst and its preparation method and application | |
| CN101862653B (en) | Acetylene selective hydrogenation catalyst and preparation method and application thereof | |
| WO2013086691A1 (en) | Nano pd catalyst for preparation of oxalate by gas phase co oxidative coupling, and preparation process thereof | |
| CN107020147A (en) | A kind of MFI structure sheet molecular sieve catalyst, the preparation method and the usage of package metals oxide or metal nanoparticle | |
| CN103084174B (en) | A kind of methanation catalyst removing oxycarbide and its preparation method and application | |
| CN103084170B (en) | A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application | |
| Long et al. | Construction of trace silver modified core@ shell structured Pt-Ni nanoframe@ CeO 2 for semihydrogenation of phenylacetylene | |
| CN102513101A (en) | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method | |
| CN104415797B (en) | A kind of pyrolysis gasoline selective hydrogenation catalyst and its preparation method and application | |
| Yang et al. | Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir | |
| CN107262112A (en) | New structural catalyst | |
| CN101875009B (en) | C3 fraction selective hydrogenation catalyst and preparation method thereof | |
| CN103623874A (en) | Preparation method of C2 selective hydrogenation catalyst | |
| Taniya et al. | Preparation of SiO2-encapsulated SnPt nanoparticle catalysts for selective hydrogenation of unsaturated aldehyde | |
| CN103071495A (en) | Palladium metal catalyst comprising silica auxiliary agent, and application thereof | |
| CN104415752B (en) | A kind of liquid phase selective hydrogenation of C 3 hydrocarbons catalyst and its preparation method and application | |
| CN102451748A (en) | Hydrodewaxing catalyst and its preparation method | |
| CN107876054A (en) | A kind of supported cobalt catalysts and its preparation method and application |
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 |