CN105665033A - Ni catalyst for hydrodeoxygenation of ethyl acetate and preparation method of Ni catalyst - Google Patents
Ni catalyst for hydrodeoxygenation of ethyl acetate and preparation method of Ni catalyst Download PDFInfo
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- CN105665033A CN105665033A CN201610124805.6A CN201610124805A CN105665033A CN 105665033 A CN105665033 A CN 105665033A CN 201610124805 A CN201610124805 A CN 201610124805A CN 105665033 A CN105665033 A CN 105665033A
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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Abstract
The invention discloses a method for preparing a Ni catalyst for hydrodeoxygenation of ethyl acetate by adopting a hard template method. The method comprises the following steps: (1) impregnating a mesoporous KIT-6 template agent in an absolute ethyl alcohol solution of Ni(NO3)2.6H2O, continuously stirring, steam-drying the absolute ethyl alcohol solvent at the temperature of 40 to 50 DEG C to obtain a raw material I, drying the raw material I for 24 h at a constant temperature of 100 DEG C to obtain a dry material I, placing the dry material I into a muffle furnace, and roasting for 2-3 h at the temperature of 400 DEG C; (2) repeating the process of the step (1) for the product roasted in the step (1); and (3) washing the product roasted in the step (2) by virtue of a template agent, and drying the product to obtain the catalyst. The Ni catalyst is prepared by adopting the hard template method and has good catalytic hydrogenation activity for hydrogenating the ethyl acetate to prepare ethane. The invention also discloses a preparation method for preparing the Ni catalyst by adopting a precipitation method.
Description
Technical field
The present invention relates to the catalyzer that a kind of ethyl acetate hydrogenation deoxidation prepares alkane, it is specifically related to a kind of Ni Catalysts and its preparation method preparing ethane for ethyl acetate hydrogenation deoxidation.
Background technology
Ethane, as the hydrocarbon the most simply containing carbon-carbon single bond, is widely used in chemical industry, has broad application prospects. first-selected ethane can be used as unstripped gas, ethene is produced by steam splitting process, and ethene is the important symbol weighing a national petrochemical complex developmental level, for comparing, relative to other, the starting material planted, ethane sizable part in steam-cracking process becomes ethene, compound heavier than it then can produce many mixtures, so in the production process of ethene, ethane plays an important role, secondly ethane can use as cooling agent in refrigeration, the sample transparence that liquid ethane makes water content high, and it just can well protect the structure of soft material in liquid water like this, certain ethane is also added in Sweet natural gas, increase the calorific value of Sweet natural gas, burning produces more heat completely, last ethane can also as unstripped gas, produce monochloroethane, oxyethane, nitroethane, even a series of product such as diesel oil, so ethane is more and more subject to the attention of common people, the demand of ethane is also being increased by countries in the world year by year, and ethane is mainly derived from shale oil gas at present, energy dilemma is arrived, the development of chemical industry also will be transitioned into renewable energy source from fossil oil gradually, therefore, searching out a kind of cheapness should row biological substitution raw material be the task of top priority. ethyl acetate, a kind of at the chemicals of China's annual production more than 2,000,000 tons, production technology is ripe, product purity height, and commercially, the general layout that supply exceed demand occurs, so how solving problem of excess production capacity to be worth thinking. at present, hydrogen producing technology development is swift and violent, substantially, industrialization is realized by technology such as water electrolysis hydrogen production, photolysis water hydrogen and biomass hydrogen preparations, so when hydrogen source is so enriched, prepared by ethyl acetate catalytic hydrodeoxygenation other Functional Chemicals attract wide attention, and have not been reported by the technology of ethane being prepared by ethyl acetate hydrogenation deoxidation. in traditional hydrogenation reaction, mostly adopt precious metal, as Pt, Pd, Ru and Au etc. are used as catalyzer, because their d electronic orbits are not filled, it is easy to absorption reaction thing, hydrogen storage ability is strong, and have high catalytic hydrogenation activity, high reaction-ure conversion-age, but they also have a series of shortcoming simultaneously, such as expensive price, target product selectivity difference etc. limits its application in hydrogenation reaction.Therefore, metal catalyst excessively cheap in recent years causes the interest of people, by changing the shape looks form of catalyzer, thus show the superior activity of catalyzer and stability, it is even possible that reach the catalytic effect of precious metal, there is again huge advantage in them, so causing the great attention of current researcher in price and output etc.
The present invention mainly passes through preparation method, change the shape looks form of Ni catalyzer, thus prepare the high performance catalyst that ethane is prepared by ethyl acetate hydrogenation deoxidation, make the conversion completely that it realizes ethyl acetate at a lower temperature, selectivity reaches more than 90% simultaneously, and this technique that ethyl acetate hydrogenation deoxidation is prepared ethane has extremely important scientific meaning.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of Ni Catalysts and its preparation method preparing ethane for ethyl acetate hydrogenation deoxidation, this catalyzer is with low cost and has good catalytic hydrogenation activity.
For achieving the above object, the present invention provides following technical scheme:
1, preparing the preparation method of the Ni catalyzer of ethane for ethyl acetate hydrogenation deoxidation, adopt hard template method preparation, concrete steps are as follows:
1) Jie hole KIT-6 template is flooded in Ni (NO3)2·6H2In the ethanol solution of O, constantly stir and under 40-50 DEG C of temperature condition, steam dry anhydrous ethanol solvent obtain raw material Ι, by raw material Ι dry 24h under 100 DEG C of constant temperature, obtained siccative Ι, siccative Ι is placed in retort furnace, and under 400 DEG C of temperature condition roasting 2-3h;
2) by through step 1) product after roasting floods again in Ni (NO3)2·6H2In the ethanol solution of O, constantly stir and under 40-50 DEG C of temperature condition, steam dry anhydrous ethanol solvent obtain raw material II, by raw material II dry 24h under 100 DEG C of constant temperature, obtained siccative II, siccative II is placed in retort furnace, and under 500 DEG C of temperature condition roasting 2-3h;
3) spend template to wash through step 2) product of roasting, during washing at 40-50 DEG C stir process, centrifugation after washing, and then add template, so repeat 3-4 time, until template is removed, wash with water to product in neutral, the obtained described catalyzer of oven dry.
Preferably, described step 1) intermediary hole KIT-6 template and Ni (NO3)2·6H2O mass ratio is 1:1～2.
Preferably, described step 2) in through step 1) product after roasting and Ni (NO3)2·6H2O mass ratio is 1:1～2.
Preferably, step 3) described in go template to be the NaOH solution of concentration 1-2mol/L.
2, the Ni catalyzer prepared and obtain by described method.
3, described catalyzer prepares ethane for ethyl acetate hydrogenation deoxidation.
4, preparing the preparation method of the Ni catalyzer of ethane for ethyl acetate hydrogenation deoxidation, adopt precipitator method preparation, concrete steps are as follows: take Ni (NO3)2·6H2O is in distilled water, stir into homogeneous solution, solution ph is regulated to be 8-10 with NaOH, after the throw out of formation at room temperature being settled into 24h, fall supernatant liquor and with distilled water wash throw out to neutral, throw out is put into the dry 20-24h of 80-100 DEG C of constant temperature oven, the solid sample obtained after drying is placed in retort furnace, lower roasting 4.0-5.0h under 550 DEG C of temperature condition.
The useful effect of the present invention is: the present invention adopts hard template method to prepare Ni catalyzer, ethyl acetate hydrogenation is prepared ethane there is good catalytic hydrogenation activity, it it is efficient ethyl acetate hydrogenation catalyst, this catalyzer achieves the conversion completely of ethyl acetate when 300 DEG C, ethane selectivity reaches 97.8%, the selectivity of other compound only has 2.2%, and after 240 DEG C, the selectivity of ethanol is 0.Catalyzer prepared by the employing precipitator method is when 340 DEG C, and ethyl acetate has transformed substantially, and ethane selectivity reaches 95.7%, and other compound selective is that after 4.3%, 300 DEG C, ethanol selectivity is 0. Preparation method disclosed in this invention is simple, and old low.
Accompanying drawing explanation
In order to make the object of the present invention, technical scheme and useful effect clearly, the present invention provides following accompanying drawing:
Fig. 1 represents that the XRD of Ni catalyzer characterizes;
Fig. 2 represents that the BET of Ni catalyzer characterizes and pore size distribution;
Fig. 3 represents the TPR research figure of Ni catalyzer.
Embodiment
Below with reference to accompanying drawings the preferred embodiments of the present invention are described in detail. The experimental technique of unreceipted concrete condition in embodiment, usually conveniently condition or the condition advised according to manufacturer.
Embodiment 1
Different preparation methods is adopted to prepare Ni catalyzer: the Ni catalyzer employing precipitator method prepared in following examples is referred to as " Ni-PC ", Ni catalyzer employing complexometry prepared is referred to as " Ni-CA ", the Ni catalyzer prepared by employing soft template method is referred to as " Ni-ST ", and Ni catalyzer employing die version method prepared is referred to as " Ni-HT ".
The precipitator method (Ni-PC): accurately take 2.5gNi (NO3)2·6H2O, in 10-20mL distilled water, is placed on magnetic stirring apparatus and stirs after evenly, slowly drip the NaOH solution adding 1-2mol/L in beaker, and maintenance solution ph is: 8-10, after the throw out of formation at room temperature being settled into 24h, and its supernatant liquor. With distilled water wash throw out to neutral, put into the dry 24h of 80-100 DEG C of constant temperature oven. Again the solid sample obtained after drying is placed in retort furnace, roasting 4.0-5.0h at 550 DEG C, obtained described Ni-PC catalyzer.
Complexometry (Ni-CA): accurately take 12.89g citric acid, 9.910gNi (NO3)2·6H2O is in beaker, add 80-100mL distilled water, it is placed on magnetic stirring apparatus and stirs after evenly, it is warming up to 60-80 DEG C, the dry 24h of 80-90 DEG C of baking oven is put into after steaming do completely, again the solid sample obtained after drying is placed in retort furnace, roasting 3.0h at 450 DEG C, obtained described Ni-CA catalyzer.
Soft template method (Ni-ST): take 2-3gP123 (PEO-PPO-PEO) and be dissolved in the ethanolic soln of 60-70ml50%, add 1-2gNaOH, stirred at ambient temperature 3h simultaneously, then accurately add NH4F (0.028g:0.81mmol), stirs 20-30min, adds HCl solution (1.07mol, about 25cm3), stir 20-30min, add n-hexyl alcohol (74mmol), stir 20-30min, finally add Ni (NO3)2·6H2O solution (Ni (NO3)2·6H2O:0.82g ethanol: 6ml), and it is placed in 35-45 DEG C of water-bath, stirs 20h, take out and be placed on crystallization 48h in 80-90 DEG C of baking oven, get solid product after taking out filter in 80-100 DEG C of vacuum-drying, last 400 DEG C (2 DEG C/min) roasting 5h. Obtained described Ni-ST catalyzer.
Hard template method (Ni-HT): Jie hole KIT-6 template is flooded in Ni (NO3)2·6H2(consumption of template and Ni (NO in the ethanol solution of O3)2·6H2The gross weight of O is than being 1:1-2), steam dry anhydrous ethanol solvent in 40-50 DEG C under continuous agitation condition, obtain raw material, gained raw material freeze-day with constant temperature 24h at 100 DEG C, obtained siccative. Obtained siccative 400 DEG C of roasting 3h in room temperature retort furnace; Product after roasting is flooded again in Ni (NO3)2·6H2In the ethanol solution of O (consumption of nitrate floods identical with first time), steaming dry anhydrous ethanol solvent in 40-50 DEG C, obtain raw material under continuous agitation condition, gained raw material is freeze-day with constant temperature 24h at 100 DEG C, obtained siccative.Obtained siccative 500 DEG C of roasting 2-3h in room temperature retort furnace. Be the product after the NaOH solution washing re-baking of 2mol/L by concentration, during washing at 40-50 DEG C stir process, centrifugation after washing, and then adds template, so repeats 3-4 time, the template in product is removed; Washing removes the product after template to neutral, then dries, obtained described Ni-HT catalyzer.
The Ni catalyzer that above-mentioned 4 kinds of methods will be adopted to prepare, prepares ethane for ethyl acetate hydrogenation deoxidation, carries out activity rating of catalyst; Activity rating of catalyst in internal diameter be at ambient pressure 12mm miniature tubular fixed-bed reactor in carry out, thermopair is built in reactor, and temperature of reaction is controlled by temperature programming controller, and microreactor is placed in folding formula process furnace; Ethyl acetate by volume per-cent comprise: ethyl acetate 3.33801% and hydrogen 96.66199%; Concrete operation steps is as follows:
Measure in the reaction tubes that 50mg catalyzer loads miniature tubular fixed-bed reactor, it is warmed up to temperature of reaction, lead to the ethyl acetate into described composition, at this temperature of reaction and 12,000mL h-1·g-1Constant temperature shortening (hydrogen flowing quantity is by under meter control) when reaction gas air speed, by residual mixture content in the SC-3000B type gas-chromatography on-line checkingi tail gas of band fid detector, testing conditions is: detector temperature 210 DEG C, temperature of vaporization chamber 150 DEG C, post case temperature 170 DEG C.
Ni-HT, Ni-PC, Ni-ST, NI-CA catalyst activity evaluation result is as shown in the table:
Ethyl acetate hydrogenation deoxidation is prepared ethane performance evaluation by table 1Ni-HT, Ni-PC, Ni-ST, NI-CA catalyzer
As shown in Table 1, Ni-HT catalyzer achieves the conversion completely of ethyl acetate when 300 DEG C, and ethane selectivity reaches 97.8%, and other compound selective only has 2.2%, and after 240 DEG C, the selectivity of ethanol is 0; Ni-PC catalyzer is when 340 DEG C, and ethyl acetate has transformed substantially, and ethane selectivity reaches 95.7%, and other compound selective is that after 4.3%, 300 DEG C, ethanol selectivity is 0; Ni-ST catalyzer ethyl acetate transformation efficiency when 360 DEG C is 94%, and now the selectivity of ethane, other compound and ethanol is respectively: 83.4%, 14.5%, 1.7%. Ni-CA catalyzer ethyl acetate transformation efficiency when 380 DEG C reaches 100%, and the selectivity of ethane, other compound and ethanol is respectively: 93.46%, 6.2%, 0.4%. As can be seen from the above data, the catalyzer adopting hard template method to prepare obviously has good catalytic activity, ethyl acetate hydrogenation is prepared ethane and is shown different performances by four kinds of catalyzer, different preparation methods causes catalyzer to have very big difference in shape looks, and the catalytic hydrogenation activity that this species diversity result in them is not quite similar.
By the Ni catalyzer of embodiment in 450 DEG C, carrying out X-ray diffraction analysis when hydrogen flowing quantity 25mL/min after reductase 12 h, X-ray diffraction analysis adopts and carries out on Japan's Co., Ltd. RigakuD/Max-2500/PC type X-ray diffractometer of science; CuKαFor gamma ray source,Ni filtering, pipe pressure is 40kV, Guan Liuwei 200mA, and scanning speed is 3 °/min, and sweep interval is 20-80 °, and scanning step is 0.02 °.
As shown in Figure 1,4 kinds of catalyzer all detect out the diffraction peak of simple substance Ni, in Ni-CA, Ni-PC and Ni-HT catalyzer, mainly based on simple substance Ni diffraction peak, NiO, Ni do not occur2O3Characteristic peak, and in Ni-ST catalyzer, except the diffraction peak of simple substance Ni, also detect out the characteristic peak of other Ni species.Contrast 4 kinds of catalyzer, we can see that the diffraction peak intensity of simple substance Ni has fine distinction, it is followed successively by from weak to strong: Ni-HT < Ni-ST < Ni-PC < Ni-CA, illustrate that their degree of crystallinity strengthens gradually, and in the Ni-HT catalyzer that degree of crystallinity is worst, its diffraction peak is weak and wide in range, illustrates that Ni is present in catalyzer with highly dispersed state or non-crystal form.
By the Ni catalyzer of embodiment in 450 DEG C, when hydrogen flowing quantity 25mL/min, after reductase 12 h, carry out N2Adsorption-desorption is analyzed, N2Adsorption-desorption isothermal curve is measured at-196 DEG C by ASAP2020 type (Merck & Co., Inc, the U.S.) fully-automatic analyzer. Before test, sample is vacuum outgas 4h at 300 DEG C all, with relative pressure p/p on adsorption curve0Data by the specific surface area of BET Equation for Calculating sample.
As shown in Figure 2, the specific surface area of Ni-HT, Ni-ST, Ni-PC and Ni-CA catalyzer is respectively: 90.1780m2/g、45.3940m2/g、11.2431m2/ g and 2.4411m2/ g, the Ni catalyzer prepared by different methods has the specific surface area of different sizes, Ni-HT and Ni-ST catalyzer all forms bigger hysteresis loop, illustrates that they have cavernous structure, and the catalytic activity existing for catalyzer high of this kind of cavernous structure is laid a good foundation.
The Ni catalyzer fresh sample of embodiment is carried out H2-temperature programmed reduction(TPR) is tested, H2-temperature programmed reduction(TPR) is tested at a self-built H2-TPR device carries out, it may also be useful to thermal conductivity cell detector (TCD) detects hydrogen-consuming volume. Gas, first by the reference arm of thermal conductivity cell detector, then enters the crystal reaction tube that external diameter is 6mm, and gas enters the working arm of thermal conductivity cell detector after sample. With H2Content is the H of 5%2-Ar gas mixture is reducing gas. At the 5vol%H of 25mL/min2In/Ar atmosphere, with the speed of 10 DEG C/min by room temperature to design temperature, record the hydrogen-consuming volume of sample.
As shown in Figure 3, have all there is obvious consumption hydrogen peak in 4 samples, because the state of reduction species and kind are very complicated, so main consumption hydrogen peak is other all with takeing on peak on a small quantity, cause reduction peak more complicated. Ni-PC and Ni-CA catalyzer almost has identical initial peak temperature and reduces when 380 DEG C complete, and the initial peak temperature of Ni-HT and Ni-ST catalyzer obviously moves to high-temperature zone, Ni-HT catalyzer completes reduction in 450 DEG C, Ni-ST catalyzer just completes reduction in 560 DEG C, all there is flourishing pore structure and big surface-area due to these two kinds of catalyzer, cause the oxygenate kind being exposed to catalyzer outside surface and internal surface many, and the peak width of reduction peak and peak area are obviously increased.
What finally illustrate is, above embodiment is only in order to illustrate the technical scheme of the present invention and unrestricted, although by referring to the preferred embodiments of the present invention, invention has been described, but it will be understood by those within the art that, in the form and details it can be made various change, and do not deviate the scope of the present invention that appended claims limits.
Claims (7)
1. the preparation method of the Ni catalyzer of ethane is prepared for ethyl acetate hydrogenation deoxidation, it is characterised in that, adopt hard template method preparation, concrete steps are as follows:
1) Jie hole KIT-6 template is flooded in Ni (NO3)2·6H2In the ethanol solution of O, constantly stir and under 40-50 DEG C of temperature condition, steam dry anhydrous ethanol solvent obtain raw material Ι, by raw material Ι dry 24h under 100 DEG C of constant temperature, obtained siccative Ι, siccative Ι is placed in retort furnace, and under 400 DEG C of temperature condition roasting 2-3h;
2) by through step 1) product after roasting floods again in Ni (NO3)2·6H2In the ethanol solution of O, constantly stir and under 40-50 DEG C of temperature condition, steam dry anhydrous ethanol solvent obtain raw material II, by raw material II dry 24h under 100 DEG C of constant temperature, obtained siccative II, siccative II is placed in retort furnace, and under 500 DEG C of temperature condition roasting 2-3h;
3) spend template to wash through step 2) product of roasting, during washing at 40-50 DEG C stir process, centrifugation after washing, and then add template, so repeat 3-4 time, until template is removed, wash with water to product in neutral, the obtained described catalyzer of oven dry.
2. the preparation method of Ni catalyzer according to claim 1, it is characterised in that, described step 1) intermediary hole KIT-6 template and Ni (NO3)2·6H2O mass ratio is 1:1～2.
3. the preparation method of Ni catalyzer according to claim 1, it is characterised in that, described step 2) in through step 1) product after roasting and Ni (NO3)2·6H2O mass ratio is 1:1～2.
4. the preparation method of Ni catalyzer according to claim 1, it is characterised in that, step 3) described in go template to be the NaOH solution of concentration 1-2mol/L.
5. the Ni catalyzer obtained by the preparation of method described in Claims 1 to 4.
6. the application of ethane prepared by catalyzer described in claim 5 at ethyl acetate hydrogenation deoxidation.
7. the preparation method of the Ni catalyzer of ethane is prepared for ethyl acetate hydrogenation deoxidation, it is characterised in that, adopt precipitator method preparation, concrete steps are as follows: take Ni (NO3)2·6H2O is in distilled water, stir into homogeneous solution, solution ph is regulated to be 8-10 with NaOH, after the throw out of formation at room temperature being settled into 24h, fall supernatant liquor and with distilled water wash throw out to neutral, throw out is put into the dry 20-24h of 80-100 DEG C of constant temperature oven, the solid sample obtained after drying is placed in retort furnace, lower roasting 4.0-5.0h under 550 DEG C of temperature condition.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
| JP2009214077A (en) * | 2008-03-12 | 2009-09-24 | Nippon Steel Corp | Manufacturing method of catalyst for methanol synthesis and manufacturing method of methanol |
| CN102070206A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | Preparation method for nano nickel oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
| JP2009214077A (en) * | 2008-03-12 | 2009-09-24 | Nippon Steel Corp | Manufacturing method of catalyst for methanol synthesis and manufacturing method of methanol |
| CN102070206A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | Preparation method for nano nickel oxide |
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Application publication date: 20160615 |