CN105080571A

CN105080571A - Preparation method of acetophenone hydrodeoxygenation catalyst and application research thereof

Info

Publication number: CN105080571A
Application number: CN201410211159.8A
Authority: CN
Inventors: 张明慧; 张英
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2014-05-14
Filing date: 2014-05-14
Publication date: 2015-11-25

Abstract

The invention relates to a preparation method of an acetophenone hydrodeoxygenation catalyst and its application research. The catalyst is a novel supported solid acid catalyst obtained by preparation of a sulfonated carrier. The catalyst prepared by the method has characteristics of mild preparation condition, good dispersity and high catalyst activity, and is suitable for catalyzing a hydrodeoxygenation reaction.

Description

The preparation method of hydrogenation of acetophenone dehydrogenation catalyst and application study thereof

Technical field

The present invention relates to a kind of preparation method of hydrogenation deoxidation catalyst and the application in hydrogenation of acetophenone deoxygenation thereof, is a kind of method preparing the load-type solid acid catalyst with high catalytic activity in particular.

Background technology

Along with the exhaustion day by day of petroleum resources, people increase day by day to petroleum resources demand, the oxysulfide simultaneously produced along with sulphur-containing burning oil burning causes increasingly sharpening of the environmental pollutions such as acid rain acid mist, high flow rate amount can be substituted, the clean energy resource of high pollution arises at the historic moment, it is desirable substitute that coal transforms oil, shale oil and biomass fuel, but also there is its intrinsic defect in the primary product of these novel fungible energy source, as low in combustion heat value, poor stability and there is the shortcomings such as corrosivity.But all these defects are all too high relevant with its oxygen content, the mass fraction of some bio-oil oxygen content is up to 50%.In order to address this problem, need to carry out hydrogenation deoxidation refinement treatment to it further.Therefore, catalytic hydrodeoxygenation technique become exploitation this new forms of energy put technology into.But, hydrogenation deoxidation also exists self depression effect, traditional Hydrobon catalyst has certain hydrogenation deoxidation active, but such catalyst hydrogenation deoxy activity still can not meet the development requires of new forms of energy completely, therefore, in the urgent need to exploitation high activity and the wide hydrogenation deoxidation catalyst of range of application.Because bio-oil oxygenatedchemicals is mainly ketone, phenols and ester class etc., the research therefore for these organic hydrogenation deoxidations is subject to extensive concern.

Hydrogenation deoxidation is because operating condition is relatively gentle, production cost is lower, and cutting ketone compounds has higher hydrogenation deoxidation effect, becomes emerging technology.The principle of hydrogenation deoxidation is hydrogenation and hydrogenolysis, and obtain saturated hydrocarbons organic matter by hydrogenation, hydrogenolysis reaches deoxidation effect.

Summary of the invention

The object of this invention is to provide a kind of preparation method of hydrogenation deoxidation catalyst and be applied to correlative study, it is the method preparing load-type solid acid catalyst, this catalyst active center fully can disperse at carrier surface, activated centre is fully exposed, therefore it contains certain acid amount higher hydrogenation activity, for its deoxidation provides condition.

Feature of the present invention is that prepared solid acid catalyst is bifunctional catalyst, and its metal active centres and carrier all have different response functions, and the gentle efficiency of reaction condition improves greatly.

The preparation process of catalyst is as follows:

Activity carbon carrier fully mixes by a certain percentage with the concentrated sulfuric acid, the 120-200 DEG C of lower electromagnetic agitation of heating also passes into argon gas, reaction 2-10h, continuous suction filtration after being cooled to room temperature, wash and adopt 0.1M barium chloride to detect to the SO42-in filtrate to generate without precipitation, then add 80-110 DEG C of dry 2-5h in baking oven, it is mixed with RuCl3 certain proportion, stir dipping 2-8h, suction filtration, washing, drying, reductase 12-6h in H2 atmosphere, obtains described catalyst.

Catalyst can also adopt following steps to prepare:

Activity carbon carrier fully mixes by a certain percentage with the concentrated sulfuric acid, and 150 DEG C of lower electromagnetic agitation of heating also pass into argon gas, reaction 6h, continuous suction filtration after being cooled to room temperature, washs to SO ₄ ^2-clean, then add dry 2h in baking oven, by itself and RuCl ₃certain proportion mixes, and stirs dipping 4h, suction filtration, washing, drying.At H ₂4h is reduced in atmosphere.

The product temperature of described catalyst is 300-400 DEG C, preferably 350 DEG C.

Described catalyst loadings is 5%.

Accompanying drawing explanation

Fig. 1 is the X-ray diffractogram of catalyst prepared by the present invention.

Fig. 2 is the TEM figure of catalyst prepared by the present invention.

Fig. 3 is the TPD figure of Kaolinite Preparation of Catalyst of the present invention.

Detailed description of the invention

This example illustrates the preparation process of catalyst.

Embodiment 1-12

These embodiments illustrate the research process of solid acid catalyst.

Embodiment 1:

Adopt Ru/AC-SO3H catalyst, this catalyst is solid acid catalyst prepared by method of sulfonating, and the use amount of catalyst is 0.1g, uses autoclave reactor.Reaction pressure is 3.0MPa, and reaction temperature is 423K, and the reaction time is 3h.By prepared catalyst 0.1g, reactant acetophenone and solvent according to 1: 20 ratio reaction.

The analysis of raw material and product adopts gas-chromatography Agilent7970, thermal conductivity detector (TCD) and hydrogen flame detector, detects the content of product.The analysis result A of product: the conversion ratio of reactant reaches more than 99%, and DNA vaccine reaches more than 90%.

Embodiment 2:

Carry out the preparation of catalyst by embodiment 1 reactions steps, the use of Ru/AC-SO3H catalyst is 0.1g, and use autoclave reactor, reaction pressure is 3MPa, and the reaction time is 3h, changes reaction temperature and changes 373K into, 393K, 453K.Obtain reaction result B, C, D.

Embodiment 3:

Carry out the preparation of catalyst by the reactions steps of embodiment 2, the amount using catalyst Ru/AC-SO3H is 0.1g, and use autoclave reactor, reaction temperature is 423K, and the reaction time is 3h, changes reaction pressure and changes 1MPa into, 2MPa, 4MPa.By prepared catalyst 0.1g, reactant acetophenone and solvent are according to 1; The ratio of 20 is obtained by reacting reaction result E, F, G.

Embodiment 4:

Carry out the preparation of catalyst by the reactions steps of embodiment 3, the use amount of Ru/AC-SO3H catalyst is 0.1g, and use autoclave reactor, reaction temperature is 423K, reaction time is 3h, and reaction pressure is 3MPa, and the change reaction time is respectively 30min, 60min, 90min, 120min.Obtain reaction result H-K.

Embodiment 5:

The preparation of catalyst is carried out according to the reactions steps of embodiment 4; the carrier of catalyst is absorbent charcoal carrier; need inert gas shielding, use concentrated nitric acid solution acidifying 6h at 60 DEG C, obtain the absorbent charcoal carrier of nitric acid acidifying; carrier after Ru/Cl3 and process is passed through infusion process; stir 4h, filtration, drying, at tube furnace reduction 4h; reduction temperature is 350 DEG C, prepares catalyst.

By prepared catalyst 0.1g, reactant acetophenone and solvent react according to the ratio of 1: 20, and reaction kit is autoclave reactor, and reaction temperature is 423K, and the reaction time is 3h, and reaction pressure is 4MPa.

The analysis of raw material and product adopts gas-chromatography Agilent7970, thermal conductivity detector (TCD) and hydrogen flame detector, detects the content of product.The analysis result L of product.

This example is for illustration of the catalytic performance of load-type solid acid catalyst in the reaction of simulation oil product hydrogenation deoxidation, and it has been obtained by reacting higher conversion ratio and selective, satisfactory for result.

Acquired results is in table 1.

Catalyst	The DNA vaccine of acetophenone
		A	93.2％
B	59.5％
		C	89.5％
D	96.7％
		E	51.5％
F	75.6％
		G	95.8％
H	40.8％
		I	55.6％
J	62.2％
		K	70.1％
L	86.2％

Claims

1. the preparation method of a hydrogenation deoxidation catalyst, it is characterized in that, described catalyst is load-type solid acid catalyst, this catalyst active center fully can disperse at carrier surface, activated centre is fully exposed, and it contains certain acid amount, for deoxidation provides condition, this solid acid catalyst is bifunctional catalyst, and its metal active centres and carrier all have different response functions:

The preparation process of catalyst is as follows:

Activity carbon carrier fully mixes by a certain percentage with the concentrated sulfuric acid, the 120-200 DEG C of lower electromagnetic agitation of heating also passes into argon gas, reaction 2-10h, continuous suction filtration after being cooled to room temperature, wash and adopt 0.1M barium chloride to detect to the SO42-in filtrate to generate without precipitation, then 80-110 DEG C of dry 2-5h in baking oven is added, by itself and RuCl ₃certain proportion mixes, and stir dipping 2-8h, suction filtration, washing, drying, at H ₂reductase 12-6h in atmosphere, obtains described catalyst.

2. according to the preparation method of hydrogenation deoxidation catalyst according to claim 1, it is characterized in that, H ₂the optimum temperature of reduction is 350 DEG C.

3. according to the preparation method of hydrogenation deoxidation catalyst described in claim 1, it is characterized in that, Ru accounts for 5% of total catalyst weight.

4. the application of catalyst in hydrogenation of acetophenone deoxygenation that prepare of any one of claim 1-3 preparation method, it is characterized in that, the optimal reaction temperature of hydrogenation deoxidation catalytic reaction is 423K.

5. according to application according to claim 4, it is characterized in that, the optimum response pressure of hydrogenation deoxidation catalytic reaction is 3MPa.

6. according to the application described in claim 4 or 5, it is characterized in that, the optimum reacting time of hydrogenation deoxidation catalytic reaction is 3h.