阅读说明：本技术 一种用于催化乙醇转化为正丁醇的介孔炭负载型催化剂及其制备方法 (A kind of mesoporous carbon loaded catalyst and preparation method thereof being converted into n-butanol for catalysis ethanol ) 是由 刘钢 王海迪 于 2019-09-16 设计创作，主要内容包括：一种用于催化乙醇转化为正丁醇的介孔炭负载型催化剂及其制备方法,属于生物质催化转化技术领域。首先是制备介孔炭载体,然后将活性组分铜和铈分步浸渍到介孔炭载体,其中铜以金属态的形式存在,铈以氧化态的形式存在,铜的负载量为1wt％～20wt％,铜和铈的原子摩尔比为(2～5)：1。本发明制备方法简单,在制备过程中能够自还原为金属态铜,在使用时不需要额外的还原处理,催化剂原料没有使用任何贵金属,原料廉价易得,具有推广性。该催化剂在温和的反应条件下具有较高的催化活性,在反应过程中能够有效地抑制金属铜纳米颗粒的烧结。催化剂具有较好的催化稳定性,且容易回收,在一定的温度下简单处理就能够重复使用。(A kind of mesoporous carbon loaded catalyst and preparation method thereof being converted into n-butanol for catalysis ethanol, belongs to biomass catalyzing transformation technology field.It is to prepare mesoporous high-area carbon first, then by active ingredient copper and cerium step impregnation to mesoporous high-area carbon, wherein copper exists in the form of metallic state, and cerium exists in the form of oxidation state, the load capacity of copper is 1wt%~20wt%, and the atomic molar ratio of copper and cerium is (2~5): 1.Preparation method of the present invention is simple, during the preparation process can autoreduction be metallic state copper, do not need additional reduction treatment when in use, catalyst raw material does not use any noble metal, and raw material is cheap and easy to get, have generalization.Catalyst catalytic activity with higher under mild reaction conditions, can effectively inhibit the sintering of metal copper nano granules during the reaction.Catalyst has preferable catalytic stability, and is easy recycling, and simple process can be reused at a certain temperature.)

1. a kind of preparation method for the mesoporous carbon loaded catalyst for being converted into n-butanol for catalysis ethanol, its step are as follows:

A. the preparation of mesoporous high-area carbon

Aluminum nitrate, citric acid, sucrose are added in distilled water by a certain percentage, it is a certain amount of to be added dropwise after completely dissolution Phosphoric acid makes dosage molar ratio 0.5:(0.5~2.5 of citric acid in solution, sucrose, aluminum nitrate, phosphoric acid): 1.0:1.0, stirring With ammonium hydroxide adjusting pH value of solution to 4.8~5.5 after 0.5~1h, continues 2~5h of stirring, solution is evaporated under 70~90 DEG C of water-baths, Obtain gel presoma；Obtained presoma is handled into 8~15min at 280~350 DEG C, is then placed in argon atmosphere again In, 5~8h of processing obtains the combination product of aluminum phosphate and charcoal at 700~900 DEG C；By the combination product concentration be 3~ 6mol·L^-1Nitric acid solution in 5~8h is handled at 70~90 DEG C, remove aluminum phosphate hard template, obtained product filtered, water It is washed till neutrality, it is dry under the conditions of 80~100 DEG C, obtain mesoporous high-area carbon；

B. the preparation of mesoporous carbon loaded catalyst

(1) mesoporous high-area carbon and cerium precursor are weighed, cerium precursor is added in 30~50mL distilled water, cerium salt concentration is 1.0×10^-2~3.0 × 10^-2Mol/L, to which the mesoporous high-area carbon of 1~2g is added after completely dissolution；

(2) mixture obtained step (1) stirs after 3~6h the water bath method at 80~100 DEG C, then at 80~100 DEG C 8~12h of lower drying；

(3) product for obtaining step (2) roasts 2~6h in argon atmosphere at 400~600 DEG C, obtains being loaded with the mesoporous of cerium High-area carbon；

(4) it weighs copper presoma to be added in distilled water, the mesoporous carbon for being loaded with cerium obtained to which step (3) is added after completely dissolution Carrier；The mole dosage ratio of copper presoma and cerium precursor is (2~5): 1；

(5) in 80~100 DEG C of water bath methods after the 3~6h of mixture stirring obtained step (4), then at 80~100 DEG C Dry 8~12h；

(6) product for obtaining step (5) roasts 2~6h in argon atmosphere at 400~600 DEG C, to be loaded with simultaneously The mesoporous carbon loaded catalyst that n-butanol is converted into for catalysis ethanol of cerium and copper.

2. a kind of preparation for the mesoporous carbon loaded catalyst for being converted into n-butanol for catalysis ethanol as described in claim 1 Method, it is characterised in that: in step (1) and (4), cerium precursor and copper presoma are nitrate or acetate.

3. a kind of preparation for the mesoporous carbon loaded catalyst for being converted into n-butanol for catalysis ethanol as described in claim 1 Method, it is characterised in that: in step (3) and step (6), maturing temperature is 400~550 DEG C.

4. a kind of mesoporous carbon loaded catalyst for being converted into n-butanol for catalysis ethanol, it is characterised in that: by claim 1 Method described in~3 any one is prepared.

5. a kind of mesoporous carbon loaded catalyst for being converted into n-butanol for catalysis ethanol as claimed in claim 4, special Sign is: copper exists in the form of metallic state, and cerium exists in the form of oxidation state, and the load capacity of copper is 1wt%~20wt%, copper Atomic molar ratio with cerium is (2~5): 1.

Technical field

The invention belongs to biomass catalyzing transformation technology fields, and in particular to one kind autoreduction and can effectively inhibit The mesoporous carbon loaded catalyst that n-butanol is converted into for catalysis ethanol that metal copper nano granules are sintered during the reaction And preparation method thereof.

Background technique

Our used chemicals in production and living and fuel are mainly transformed using fossil resource, and this Consuming excessively for non-regeneration energy will certainly bring energy crisis.Compared with traditional fossil resource, biomass energy has Reproducibility, cleaning, it is resourceful the advantages that, therefore the development and utilization of biomass energy receives global concern.Second Alcohol is translated into the higher chemicals of added value by global concern as a kind of biomass energy.

N-butanol is usually as a kind of highly important organic solvent and industrial chemicals, mainly for the manufacture of O-phthalic The N-butyl class plasticizer of acid, aliphatic dibasic acid and phosphoric acid, it is also widely used in various plastics and rubber product, and has The raw material of butyraldehyde, butyric acid, butylamine and butyl lactate etc. is prepared in machine synthesis.It or grease, drug (such as antibiotic, vitamin) With the extractant of fragrance, the additive etc. of phthalic resin coating, and can be used as organic dyestuff and print ink solvent, dewaxing Agent.N-butanol development and utilization the whole world is caused as a kind of novel motor vehicle fuel at present widely to pay close attention to.As gasoline Substitute, n-butanol is a kind of compared with alcohol performance more preferably engine fuel, the physicochemical property and gasoline more adjunction of n-butanol Closely, it can arbitrarily dissolve each other with gasoline, available engine and pipeline are not corroded.Energy density (the 29MJL of n-butanol^-1) with Gasoline is close to (32MJL^-1), and the energy density (19.6MJL of now widely used ethyl alcohol^-1) it is the 61% of gasoline. In addition, heat of vaporization (the 0.43MJL of n-butanol^-1) there was only ethyl alcohol (0.92MJL^-1) half, with gasoline (0.36MJL^-1) It is close, therefore there is better engine cold-starting performance, and existing vehicle is not required to carry out any repacking can to use The gasoline of n-butanol is mixed with as fuel.N-butanol can reduce SO as bio-fuel_X、NO_X, CO, hydrocarbon and temperature The discharge of room gas has good environmental benefit, has biggish application using n-butanol substitution ethyl alcohol as renewable energy Prospect, therefore the important directions that n-butanol has become energy development are converted by ethyl alcohol.

At present in the research by alcohol catalysis conversion n-butanol, the response path approved is according to the path Guerbet It carries out, i.e., the dehydrogenation of ethyl alcohol produces acetaldehyde first, and then two molecules of acetaldehyde are dehydrated production crotonaldehyde by aldol condensation, finally Crotonaldehyde adds hydrogen to obtain n-butanol.The reaction reports that used homogeneous catalyst system is mainly concentrated on ruthenium at present (Ru), the noble metal catalyst based on iridium (Ir), although showing excellent catalytic activity, since noble metal is rare, valence Lattice are expensive, preparation cost is higher, preparation method is more complicated and difficult separation and recycling, and which greatly limits the catalysis The large-scale application and industrialized production of agent.It is prepared in the reaction of n-butanol by ethyl alcohol at present, it is heterogeneous for studying more Catalyst system, the presently used heterogeneous catalyst systems of the reaction mainly include solid acid alkali catalytic agent and supported catalyst Agent, but most solid acid base catalysator must can just show certain catalysis under the harsh conditions such as higher temperature and live Property, the practical application of this kind of catalyst is limited, uses a kind of solid base as catalysis as disclosed on patent CN106955690A Agent, (> 400 DEG C) show excellent catalytic activity at a higher temperature, but the catalyst is urged within a short period of time Agent significantly inactivates.According to Guerbet response path, catalyst needs to have a certain amount of metal active centres and soda acid is living Property center for dehydrogenation, plus hydrogen and aldol condensation, develop a series of loaded catalysts for this feature, but report at present Generally existing catalytic activity is low in road loaded catalyst, and the metal nanoparticle of load, which is easy sintering during the reaction, to be caused Catalyst serious inactivation, is published in Journal of Catalysis (2016) 344, in 184-193 paper, it was recently reported that use neatly A kind of loaded catalyst Ni/MgAlO simultaneously with soda acid activated centre and metal active centres of stone precursor preparation, should The catalytic activity of catalyst is lower, and n-butanol one-way yield is only 10%.It is published in Chemical communications In (2016) 52,13749-13752 paper, it was recently reported that use a kind of commercial activated carbons as the catalysis of support dispersion metallic Agent, the one-way yield of the n-butanol of the catalyst is close to 20%, but the catalyst needs certain density hydrogen before use Reduction a period of time is carried out at a certain temperature, it has not been convenient to be used, process is cumbersome, and there are some potential safety problemss, and the catalysis Agent metal nanoparticle in 12 hours rear catalysts of successive reaction is sintered, and catalytic activity gradually decreases, and stability is poor.Cause This, how to prepare efficient, stable loaded catalyst by cheap, simple, green, the means of safety is realization by biology Ethyl alcohol is converted into a key technology of the industrialized production of n-butanol.

Summary of the invention

It can under mild conditions efficiently and stably the purpose of the present invention is overcoming the deficiencies of the prior art and provide one kind Catalysis ethanol is converted into mesoporous carbon loaded catalyst of n-butanol and preparation method thereof, can efficiently solve the above problem.

A kind of mesoporous carbon loaded catalyst being converted into n-butanol for catalysis ethanol of the present invention, feature exist In: by active ingredient copper and cerium step impregnation to mesoporous high-area carbon (MC), copper exists in the form of metallic state, and cerium is with oxidation state Form exist, the load capacity of copper is 1wt%~20wt%, and the atomic molar ratio of copper and cerium is (2~5): 1.

A kind of preparation side of mesoporous carbon loaded catalyst being converted into n-butanol for catalysis ethanol of the present invention Method, its step are as follows:

1. the preparation of mesoporous high-area carbon (MC)

Aluminum nitrate, citric acid, sucrose are added in distilled water by a certain percentage, it is certain to be added dropwise after completely dissolution The phosphoric acid of amount makes dosage molar ratio 0.5:(0.5~2.5 of citric acid in solution, sucrose, aluminum nitrate, phosphoric acid): 1.0:1.0, PH value of solution is adjusted to 4.8~5.5 with ammonium hydroxide after 0.5~1h of stirring, continues 2~5h of stirring, by solution under 70~90 DEG C of water-baths It is evaporated, obtains gel presoma；Obtained presoma is handled into 8~15min at 280~350 DEG C, is then placed in argon gas again 5~8h, which is handled, in atmosphere, at 700~900 DEG C obtains the combination product of aluminum phosphate and charcoal；By the combination product concentration be 3~ 6mol·L^-1Nitric acid solution in 5~8h is handled at 70~90 DEG C, remove aluminum phosphate hard template, obtained product filtered, water It is washed till neutrality, it is dry under the conditions of 80~100 DEG C, obtain mesoporous high-area carbon (MC)；

2. the preparation of mesoporous carbon loaded catalyst

(1) mesoporous high-area carbon and cerium precursor are weighed, cerium precursor is added in 30~50mL distilled water, cerium salt concentration It is 1.0 × 10^-2~3.0 × 10^-2Mol/L, to which the mesoporous high-area carbon of 1~2g is added after completely dissolution；

(2) mixture obtained step (1) stirs after 3~6h the water bath method at 80~100 DEG C, then 80~ Dry 8~12h at 100 DEG C；

(3) product for obtaining step (2) roasts 2~6h in argon atmosphere at 400~600 DEG C, obtains being loaded with cerium Mesoporous high-area carbon；

(4) it weighs copper presoma to be added in distilled water, Jie for being loaded with cerium obtained to which step (3) is added after completely dissolution Hole high-area carbon；The mole dosage ratio of copper presoma and cerium precursor is (2~5): 1；

(5) in 80~100 DEG C of water bath methods after the 3~6h of mixture stirring obtained step (4), then 80~100 Dry 8~12h at DEG C；

(6) product for obtaining step (5) roasts 2~6h in argon atmosphere at 400~600 DEG C, to obtain this hair The mesoporous carbon loaded catalyst that n-butanol is converted into for catalysis ethanol of cerium and copper is loaded with while bright described.

Further, in step (1) and (4), cerium precursor and copper presoma are nitrate or acetate；

In step (3) and step (6), maturing temperature is 400~550 DEG C；

Cerium and copper are impregnated into carrier step by step using the mesoporous high-area carbon of high-specific surface area as carrier by catalyst of the invention On, compared with prior art, present invention has the advantage that

(1) mesoporous carbon loaded catalyst preparation method of the invention is simple, and catalyst raw material does not use your any gold Belong to, raw material is cheap and easy to get, has generalization.

(2) mesoporous carbon loaded catalyst of the invention during the preparation process can autoreduction be metallic state copper (metallic state Refer to that metal exists in the form of simple substance, valence state is zeroth order.Copper is existed in the form of metallic state, and cerium is in the form of oxidation state In the presence of), additional reduction treatment is not needed when in use, the application prospect with industrialization.

(3) mesoporous carbon loaded catalyst of the invention can live in catalysis with higher under mild reaction conditions Property, the sintering of metal copper nano granules can be effectively inhibited during the reaction, and catalyst has preferable catalytic stability.

(4) mesoporous carbon loaded catalyst of the invention is easy recycling, and simple process can weigh at a certain temperature It is multiple to use.

Detailed description of the invention

Fig. 1 is the nitrogen adsorption-desorption isotherm and pore size distribution curve of mesoporous high-area carbon provided by the invention；

The high-area carbon known to nitrogen adsorption-desorption isotherm is a kind of meso-hole structure, and mesoporous carbon (MC) is primarily present Two kinds of size ranges of 7.6nm and 3.9nm it is mesoporous.

Fig. 2 is sample X-ray powder diffraction figure provided by the invention；

The figure corresponding embodiment 3, the figure only have the diffraction maximum of metallic state copper, do not find the diffraction maximum of cerium oxide, explanation Copper has been reduced to metallic state copper in the preparation process of catalyst, and cerium oxide is highly dispersed at high-area carbon surface.

Fig. 3 is sample catalytic activity provided by the invention and stability curve；

Fig. 3 illustrates the progress with the reaction time, the conversion ratio of reactant, the selectivity and target product of target product Yield situation of change.The figure corresponding embodiment 3, the figure illustrate that the catalyst has preferable catalytic activity and stability.

Specific embodiment

In order to more clearly illustrate the present invention, following embodiment and comparative example are enumerated, specific skill of the invention is easy to understand Art scheme, but it is without any restrictions to protection scope of the present invention.