CN103084168B - A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application - Google Patents
A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application Download PDFInfo
- Publication number
- CN103084168B CN103084168B CN201110331911.9A CN201110331911A CN103084168B CN 103084168 B CN103084168 B CN 103084168B CN 201110331911 A CN201110331911 A CN 201110331911A CN 103084168 B CN103084168 B CN 103084168B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- microemulsion
- furfural
- carrier
- decarbonylation
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural 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, narrowly distributing, good dispersion degree, and its grain diameter is less than 10nm.The preparation method of catalyst of the present invention is simple, and operating condition is gentle, is easy to produce; Catalyst application of the present invention had higher furfural conversion ratio, higher activity and selectivity when the reaction of preparing furan through decarbonylation of furfural.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application, specifically a kind of loaded catalyst utilizing microemulsion technology to prepare with palladium to be active component, this catalyst is used for preparing furan through decarbonylation of furfural.
Background technology
Furfural is a kind of Organic Chemicals cheap and easy to get, is generally produced by wastes of crops.China is a large agricultural country, produces tens0000 tons, furfural per year, and decarbonylation of furfural method production furans productive rate is higher, therefore, has good prospect by preparing furan through decarbonylation of furfural.
Furfural gas phase decarbonylation furans is the method that current domestic production furans is conventional, and technique is comparatively ripe.Forefathers once used ZnO-Cr
2o
3, ZnO-Cr
2o
3-MnO
2, ZnO-CdO-MnO-Al
2o
3deng oxide catalyst.But due to the less poor stability of its production capacity, service condition is harsh, and can cause environmental pollution and be eliminated gradually.The sixties rise, and OuakerOats company proposes Pd catalyst application in this decarbonylation reaction.The patents such as SU1699601, SU1710125, RU2027714 also propose to use this decarbonylation reaction of Pd catalyst, its catalytic activity and selectively all reach more than 90%, but the load capacity of noble metal is generally greater than 1%.In recent years, the Pd catalyst making load capacity high due to the continuous rise of Pd price is applicable to large-scale industrial production.
CN1095397C discloses a kind of preparing furan by gas-phase decarbonylation of furaldehyde high efficiency load type noble metal catalyst, with AL
2o
3-TiO
2composite oxides are carrier, containing Pt0.4 ~ 0.7wt%, simultaneously containing K
2o or CS
2o or MgO or CaO or BaO, its content is 0.5 ~ 2.0wt%.At ambient pressure, 280 DEG C, furfural air speed is 0.9h to this catalyst
-1(volume space velocity), the mol ratio of furfural and hydrogen is under 0.5 ~ 2.0 condition, and conversion ratio can reach 80 ~ 97%, selectively reaches 85 ~ 92%.But the load capacity of Pd is higher, the activity and selectivity of catalyst is still unsatisfactory.
CN101422738A discloses a kind of preparation of high-efficiency furfural decarburization furans catalyst, and comprising in order to particle diameter is the active A l of 1-6mm
2o
3for carrier, being take Pd as main active, wherein containing 0.25% ~ 0.5%Pd, is be used as catalyst aid with Ni and K of 0.25% ~ 0.5%.Adopt traditional dipping method to carry out Kaolinite Preparation of Catalyst, prepared catalyst application is in furfural gas phase decarburizing reaction.Result shows catalyst prepared by the method and has good activity, makes the conversion ratio of furfural reach more than 98%, is selectively also increased to more than 90% by original about 70%, but the load capacity of Pd is higher.
Lee's equality is in Industrial Catalysis, 2009, a kind of preparation of high-efficiency furfural decarbonylation furans catalyst is provided in exploitation one literary composition of the preparing furan through decarbonylation of furfural catalyst in 17 (2), take active al2o3 as carrier, be main active component with Pd, prepare Pt-supported catalyst by infusion process, the particle diameter being wherein the Pd that 0.75%, SEM characterization result shows containing Pd is 2 ~ 4 microns.
USSR342857 discloses a kind of Pd catalyst producing methylfuran, improves the selective of reaction by adding alkali metal K, but result 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.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, the particle diameter of nano particle can be controlled.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 a kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application.The catalyst that the method obtains, when main active component content is lower, has higher activity and selective preferably.
One of the object of the invention is to provide a kind of catalyst for preparing furan through decarbonylation of furfural, and this catalyst comprises carrier and is carried on the active component on carrier, and the active component of described catalyst utilizes microemulsion method prepare and obtain.
Described carrier is active carbon, Al
2o
3, SiO
2, ZnO, TiO
2, V
2o
5, SnO
2in one or both and two or more mixtures; More preferably the shape of described carrier be spherical, profile of tooth, annular, tooth are spherical, granular, sheet, strip, clover or bunge bedstraw herb, the specific area of carrier is 1 ~ 400m
2/ g.
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% ~ 5.0wt% of described carrier gross weight, is preferably the 0.01wt% ~ 1.0wt% of total weight of carrier;
The described active component that helps is one or more in Ni, Co, Mg, Ca, Ba, Sn, Ge, Cr, rare earth element, alkali metal, and its content is the 0.0wt% ~ 20.0wt% of total catalyst weight, is preferably the 0wt%-10wt% of total weight of carrier;
The grain diameter of described main active component is less than 10nm.
In 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 the catalyst for preparing furan through decarbonylation of furfural 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 be 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 of the catalyst for the preparation of preparing furan through decarbonylation of furfural.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 the catalyst for preparing furan through decarbonylation of furfural of the present invention.
3rd object of the present invention is to provide the application of this catalyst in preparing furan through decarbonylation of furfural.
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) the preparing furan through decarbonylation of furfural 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 100mgPd/ml
3)
2solution 1.5ml, 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 100gAl
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 0.15wt%.
Embodiment 2
Take the PdCl of 200mgPd/ml
2solution 1.0ml, deionized water is used to be diluted to 5ml, 14.2mlTX-100 and 18.23ml n-butanol 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; 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 0.2wt%.
Embodiment 3
Take the Pd (NO of 200mgPd/ml
3)
2ni (the NO of solution 1.5ml, 300mgNi/ml
3)
2solution 1.0ml 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 Ni content is 0.3wt%.
Embodiment 4
Take the Pd (NO of 100mgPd/ml
3)
2solution 1.0ml, adds the Co (NO of 100mgCo/ml
3)
2solution 1.0ml, adds the La (NO of 200mgLa/ml
3)
3solution 0.5ml, deionized water is used to be diluted to 10ml, 10mlOP-10 and 5ml normal propyl alcohol mixes with 25ml normal heptane 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 100gAl
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 Co content is 0.1wt%, and wherein La content is 0.1wt%.
Embodiment 5
Take the Pd (NO of 200mgPd/ml
3)
2solution 0.5ml, adds the KNO of 200mgK/ml
3solution 0.5ml, 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, is then adding 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 100gAl
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%, K content 0.1wt%.
Embodiment 6
Take the Pd (NO of 200mgPd/ml
3)
2mg (the NO of solution 1.0ml, 100mgMg/ml
3)
2solution 1.0ml, 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 100gAl
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%, Mg content is 0.1wt%.
Comparative example
Take the Pd (NO of 100mgPd/ml
3)
2the KNO of solution 3.0ml, 200mgK/ml
3solution 1.5ml, 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%, k content is 0.3wt%.
The above-mentioned catalyst of preparation is carried out furfural and faces hydrogen decarbonylation reaction, reaction condition is as follows: loaded by 1ml catalyst in stainless steel tube reactor, after using nitrogen displacement, and individual hour of hydrogen 180 DEG C of reductase 12s, then will pass in reactor after feed vaporization, the mol ratio of hydrogen and furfural be 1 ~ 2.Experiment air speed is 0.9h
-1.By each catalyst reaction to the conversion ratio of furfural and optionally computational methods be:
Conversion ratio=[(C
enter-C
go out)/C
0] × 100%
Selective=[C
furans/ (C
enter-C
go out)] × 100%
Wherein: C
enterfor furfural content in entrance raw material, C
go outfor (reactor outlet) furfural content in product, C
furansfor the concentration of furans in product.
Experimental result shows, uses catalyst prepared by microemulsion method of the present invention, generates the conversion ratio of furans and selectively list in table 1 for decarbonylation of furfural
Table 1 catalyst performance
Experimental result shows, the load capacity of catalyst metals active component Pd prepared by microemulsion method of the present invention is low, but for the reaction of preparing furan through decarbonylation of furfural, compared with comparative example, have higher furfural conversion ratio, this catalyst has higher activity and selective.
Claims (6)
1., for a catalyst for preparing furan through decarbonylation of furfural, comprise carrier and be carried on the active component on carrier, it is characterized in that:
Described carrier is active carbon, Al
2o
3, SiO
2, ZnO, TiO
2, V
2o
5, SnO
2in at least one, the specific area of carrier is 1 ~ 400m
2/ g, its face shaping be spherical, tooth is spherical, granular, profile of tooth, annular, sheet, strip, clover or bunge bedstraw herb;
Described active component comprises main active component and helps active component;
Described main active component is simple substance palladium, and palladium content is the 0.01wt% ~ 1.0wt% of described carrier gross weight;
The described active component that helps is at least one in Mg, Ba, Sn, Ge, Cr, rare earth element, alkali metal, and content is the 0.0wt% ~ 20.0wt% of described carrier gross weight;
The grain diameter of described main active component is less than 10nm;
In described catalyst, active component adopts microemulsion method preparation and obtains, and flood, be sprayed on carrier and obtain catalyst, concrete steps comprise: (1) prepares microemulsion: in water bath with thermostatic control, by non-ionic surface active agent, the aqueous phase of the salting liquid composition of catalyst activity component, cosurfactant, oil phase mixes 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: step (2) is reduced fully obtain catalyst activity component dipping, spraying load on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained the catalyst for preparing furan through decarbonylation of furfural;
Wherein, 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, and 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.
2. the catalyst for preparing furan through decarbonylation of furfural according to claim 1, helps the content of active component to be the 0wt%-10.0wt% of total weight of carrier described in it is characterized in that.
3. the catalyst for preparing furan through decarbonylation of furfural 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.
4. the catalyst for preparing furan through decarbonylation of furfural 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.
5. the preparation method of the catalyst for preparing furan through decarbonylation of furfural that one of claim 1-4 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: step (2) is reduced fully obtain catalyst activity component dipping, spraying load on carrier;
(4) dry for microemulsion obtained for step (3), roasting are obtained selective hydrogenation catalyst.
6. the catalyst application for preparing furan through decarbonylation of furfural according to claim 1 is in the reaction of preparing furan through decarbonylation of furfural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110331911.9A CN103084168B (en) | 2011-10-28 | 2011-10-28 | A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110331911.9A CN103084168B (en) | 2011-10-28 | 2011-10-28 | A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103084168A CN103084168A (en) | 2013-05-08 |
| CN103084168B true CN103084168B (en) | 2016-01-20 |
Family
ID=48197597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110331911.9A Active CN103084168B (en) | 2011-10-28 | 2011-10-28 | A kind of Catalysts and its preparation method for preparing furan through decarbonylation of furfural and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103084168B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3126342B1 (en) * | 2014-03-31 | 2018-11-14 | Shell International Research Maatschappij B.V. | Process for the production of furan from furfural |
| CN104941634B (en) * | 2015-06-03 | 2018-05-15 | 江苏清泉化学股份有限公司 | A kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof |
| CN105771982A (en) * | 2016-04-25 | 2016-07-20 | 张玲 | Method for preparing 5-hydroxymethyl furfural decarbonylation catalyst |
| CN107970928B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparing furan through decarbonylation of furfural catalyst, preparation method and application |
| CN107983343B (en) * | 2017-11-24 | 2020-12-11 | 上海化工研究院有限公司 | Decarbonylation chlorination catalyst and preparation method and application thereof |
| CN110339839A (en) * | 2018-04-03 | 2019-10-18 | 北京旭阳科技有限公司 | A kind of method preparing microspherical catalyst, by this method preparation microspherical catalyst and use the method for the catalyst preparation cyclopentanone |
| CN108607598A (en) * | 2018-06-12 | 2018-10-02 | 中科合成油技术有限公司 | A kind of Pd bases catalyst and the preparation method and application thereof |
| CN111298818B (en) * | 2019-11-14 | 2023-07-25 | 天津大学 | Palladium and platinum catalyst, preparation thereof and application thereof in furfuraldehyde preparation reaction |
| CN114433128A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Furfural hydrogenation catalyst, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural gas-phase hydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009003881A1 (en) * | 2007-07-02 | 2009-01-08 | Basf Se | Process for one-stage preparation of 2-methyltetrahydrofuran from furfural over two catalysts in a structured bed |
| CN101422738A (en) * | 2007-11-02 | 2009-05-06 | 刘金廷 | Efficient furan preparation catalyst by furfural decarbonylation |
| 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 |
-
2011
- 2011-10-28 CN CN201110331911.9A patent/CN103084168B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009003881A1 (en) * | 2007-07-02 | 2009-01-08 | Basf Se | Process for one-stage preparation of 2-methyltetrahydrofuran from furfural over two catalysts in a structured bed |
| CN101422738A (en) * | 2007-11-02 | 2009-05-06 | 刘金廷 | Efficient furan preparation catalyst by furfural decarbonylation |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103084168A (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 | |
| CN102527377B (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
| CN102350358B (en) | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| CN101851160B (en) | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst | |
| CN103084173B (en) | C4 fraction selective hydrogenation catalyst, preparation method and applications thereof | |
| CN103084172A (en) | C2 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 | |
| CN107096529A (en) | A kind of graphene aerogel of minimum particle size of nanometer silver load and its preparation method and application | |
| CN102513101A (en) | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method | |
| CN106345469A (en) | Dendritic Cu/C-CuSiO3 hydrogenation catalyst and preparation method thereof | |
| CN102632247A (en) | Preparation method of load-type silver nano-composite material | |
| CN102728359A (en) | Cobalt-base catalyst adopting silicon oxide mesoporous foam as carrier, and application thereof | |
| CN103084174B (en) | A kind of methanation catalyst removing oxycarbide and its preparation method and application | |
| CN106902826B (en) | A kind of cladding Ni-Al2O3@Al2O3-SiO2Catalyst and preparation method and application | |
| CN109590012A (en) | A kind of nitrogen-doped carbon cladding double nano metallic catalyst and its preparation method and application | |
| CN101371986A (en) | Method for preparing Cu-Cr metallic oxide with high specific surface area and application | |
| CN113634256B (en) | Multi-dimensional micro-nano non-noble metal composite catalyst and preparation and application thereof | |
| CN106807366B (en) | Core-shell catalyst for preparing lactic acid and pyruvic acid from glycerol, and preparation and application thereof | |
| CN105251509A (en) | Preparing method for Pt-Co flower-type nano-catalyst | |
| CN103084170B (en) | A kind of C 3 fraction selective hydrogenation catalyst and its preparation method and application | |
| CN117443428A (en) | Composite catalyst and preparation method and application thereof | |
| CN103586480A (en) | One-step microwave preparation method for bimetal/carbon layered composite sphere | |
| CN101862627B (en) | Preparation method of titanium dioxide microcapsule coating noble metal nano particles | |
| CN106040246A (en) | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol |
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 |