CN1260008C - Method for preparing novel Raney Ni catalyzer and its application - Google Patents
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Abstract
The present invention provides a new method for preparing a Raney Ni catalyst, the nickel content of the prepared catalyst is from 70 to 90 wt%, the specific surface area is from 70 to 100m<2>/g, the pore volume is from 0.054 to 0.084cm<3>/g, the pore size distribution is within the range of 2.0 to 220 nm, and the average pore size is from 2.84 to 3.66 nm. The method comprises following steps: (i) nickel aluminum alloy is ground into particles of 80 to 100 meshes; (ii) the particles of the step (i) are added into NaOH solution, the mixture is stirring, the ratio of alloy weight (gram) to alkaline liquor volume (milliliter) is from 1:8 to 1:15, aluminum extraction is carried out on the solution by ultrasonic wave for 5 to 30 minutes, the ultrasonic frequency is from 28 to 48kHz, the water bath temperature is from 25 to 60 DEG C, after the ultrasonic wave extraction is finished, the solution is continuously stirred for 2 to 6 hours, the alkaline liquor of the upper layer is removed, and the whole process is carried out in an inert atmosphere; (iii) the particles of the step (ii) are washed to be neutral with deionized water, anhydrous alcohol is used for washing the particles to remove water, and the Raney Ni catalyst is prepared. The present invention also provides the purposes of the Raney Ni catalyst.
Description
Technical field
The present invention relates to a kind of method for preparing novel Raney Ni catalyst, be specifically related to use ultrasonic wave to carry out the method that extracting aluminium prepares novel Raney Ni catalyst.
Background technology
Raney Ni catalyst has used decades in industrial and laboratory, and it is widely used in reduction reaction, as the catalytic hydrogenation and the dehalogenation reaction of alkene, aromatic rings, aldehyde, ketone, nitro, itrile group etc., is one of most important catalyst of Chemical Manufacture.Raney Ni catalyst has higher activity and selectivity, and low price is so be the pith in catalyst research field to its research always.
The conventional method for preparing Raney Ni catalyst is the aluminium of using earlier in the NaOH solution extracting nickel alumin(i)um alloy, washing then, and residue is the spongy porous Raney Ni of a class particle, granular size is about 25～150 .Mainly contain Ni, Al (1～8 weight %) in the catalyst, small amount of N iO and Al
2O
3Hydrate (1～20 weight %), total surface area is 50～130 meters
2/ gram.It should be noted that the Ni surface area only accounts for 50～100% of total surface area.With similar method can also the cobalt aluminium alloy, alloy such as albronze prepares catalyst such as corresponding Raney Co and Raney Cu.
About the preparation of skeleton catalyst, nearly all patent documentation all concentrates on preparation method, pulverizing and the processing method of alloy.The difference of the various Raney Ni of the W1～W8 that has reported catalyst mainly is to add the condition of alloy, the concentration of alkali, the wash conditions of taking out aluminium time and temperature and gained catalyst.Relevant modification type Raney Ni catalyst also has more report as adding metals such as Mo, Ti, Cr, Fe, Co, B, Cu on document.
In recent years, the application of ultrasonic wave in Preparation of Catalyst causes people's attention just gradually, but its application in the RaneyNi catalyst only limit to last cleaning (the Japan Patent 03249946A that has announced be Raney Ni that extracting is good in deionized water for ultrasonic and modify optical active substance), its application in taking out the aluminium process does not appear in the newspapers so far.
Summary of the invention
The invention provides a kind of new method for preparing Raney Ni catalyst, the nickel content of the catalyst that makes is 70～90 weight %, and specific area is at 70～100 meters
2/ gram scope, 75～95 meters more fortunately
2/ gram scope, pore volume are 0.054～0.085 centimetre
3/ gram, pore-size distribution is in 2.0～220nm scope, and average pore size is 2.84～3.66nm; Described method comprises the following steps:
(i) nickel alumin(i)um alloy is ground to form 80～100 purpose particles;
(ii) the particle of step (i) is added in the NaOH solution and stirs, weight alloy (gram) is 1: 8～1: 15 with the ratio of alkali lye volume (milliliter), this solution was carried out ultrasonic wave extracting aluminium 5～30 minutes, ultrasonic frequency is 28～48kHz, and bath temperature is 25～60 ℃, is preferably 30～50 ℃, the ultrasonic wave extracting finishes the back and continues to stir 2～6 hours, remove upper strata alkali lye afterwards, overall process is carried out in inert gas, more fortunately N
2Carry out under the protection;
(iii) step particle (ii) spends deionised water to neutral, removes with absolute ethanol washing and anhydrates, and makes described Raney Ni catalyst.
The catalyst of the inventive method preparation, its nickel content reaches 70～90 weight %, and specific area is at 70～100 meters
2/ gram scope, 75～95 meters more fortunately
2/ gram scope, pore volume are 0.054～0.085 centimetre
3/ gram, pore-size distribution is in 2.0～220nm scope, and average pore size is 2.84～3.66nm.
The catalyst of method preparation of the present invention can be used for hydrogenation reaction, can improve conversion ratio and selectivity.Especially the reaction that benzene hydrogenation is prepared cyclohexane is compared with the catalyst that does not adopt the preparation of ultrasonic wave extraction steps, and hydrogen-absorption speed and conversion ratio are the highest can to improve 54% and 82.4% respectively.
In the said method, nickel alumin(i)um alloy is commercially available, and its nickel content is about 40～50 weight %, and the granularity of grinding the back particle is about 80～100 orders.Be to get a certain amount of above-mentioned sample under 5～20 ℃ the environment in room temperature, in ice-water bath, slowly be added in the NaOH solution, the concentration of NaOH solution is 4～10 mol, and weight alloy (gram) is 1: 8～1: 15 with the ratio of alkali lye volume (milliliter), preferably 1: 10; The frequency that ultrasonic wave is handled is 28～48kHz.The temperature of ultrasound bath is 25～60 ℃, is preferably 30～50 ℃.The ultrasonic wave extracting time is about 5～30 minutes, is preferably 10～20 minutes, preferably 15 minutes.Weight alloy (gram) is 1: 10 with the ratio of alkali lye volume (milliliter).The ultrasonic wave extracting finishes the back and continued the backflow stir about 2～6 hours, is preferably 4 hours, and the entire process process is at inert atmosphere, as N
2In carry out, preventing the sample oxidation, and adopt reflux to prevent the variation of NaOH concentration.Reaction is removed supernatant liquor after finishing, and catalyst granules is extremely neutral with the deionized water cyclic washing earlier, and then anhydrates to remove with absolute ethanol washing.The Raney Ni catalyst that makes should be stored in absolute ethyl alcohol.
The Raney Ni catalyst that makes thus determines that by icp analysis its Ni content range is about 70～90 weight %, and total specific area that the BET method is measured is about 70～100 meters
2/ gram, pore volume is 0.054～0.085 centimetre
3/ gram, pore-size distribution is in 2.0～220nm scope, and mainly is distributed in the scope of 3.4～4.0nm.
In embodiment preferred of the present invention, NaOH concentration is 6.0 mol, and Ni-Al weight alloy (gram) is 1: 10 with the ratio of alkali lye volume (milliliter), and the frequency that ultrasonic wave is handled is 28kHz, and the temperature of ultrasonic water bath is 25 ℃.The Ni content range of the Raney Ni catalyst that makes thus is about 72.5～85.8 weight %, and specific area is about 88～96 meters
2/ gram, pore-size distribution is in 2.0～220.8nm scope, and mainly is distributed in the scope of 3.4～4.0nm.
Hyperacoustic facilitation is mainly owing to its peptizaiton, cleaning action and the microwave energy that provided.Hyperacoustic peptizaiton helps increasing specific area, aperture and pore volume, and it is more even that the activity of such catalysts position is distributed; Hyperacoustic cleaning action can make catalyst surface brighter and cleaner; And the energy activated metal Ni atom as the activated centre that ultrasonic wave provides (bunch), make the hydrogen that is stored in the Raney Ni catalyst more active simultaneously.
The suitable ultrasonic time of control in the suction filtration process of Ni-Al alloy, can significantly improve the hydrogenation activity of Raney Ni catalysis, for example, in embodiment of the present invention, to be used for benzene hydrogenation by the catalyst that ultrasonic wave extracting processing obtains and prepare cyclohexane, the highest hydrogen-absorption speed reaches 43.0 mMs/hour gram, react that conversion ratio reaches more than 20% after 3 hours, compare with the catalyst that does not use ultrasonic wave to carry out alkali extracting Processing of Preparation, hydrogen-absorption speed and conversion ratio are the highest can to improve 54% and 82.4% respectively.Ultrasonic wave to the facilitation of catalytic activity mainly owing to following factor: (1) hyperacoustic peptizaiton attenuates Raney Ni catalyst granules, and decentralization increases, thereby specific area increases; (2) hyperacoustic cleaning action reduces the alumina layer of catalyst surface and other impurity, and the surface is clean, smooth more, makes more active sites be exposed to the surface of catalyst, help its with reactant contact and interaction the raising catalytic activity; (3) hyperacoustic cleaning action helps removing the impurity of Raney Ni skeleton inside, and the duct is increased, and pore volume increases, and helps reactant in the absorption of catalyst inner surface, improves catalytic activity; (4) in the Ni-Al alloy, metal A l provides portions of electronics to metal Ni, and the category-B in this situation and the Ni-B amorphous alloy studies show that in a large number that seemingly the Ni active sites of electron rich attitude helps improving its catalytic hydrogenation activity to phenyl ring.Ultrasonic wave is handled and is made Al content increase in the Raney Ni catalyst, and the ultrasonic processing of what is more important increases the content of Raney Ni surface metal attitude Al, causes metal Ni electron rich more thus, and hydrogenation activity is increased; (5) the microwave energy part that provides of ultrasonic wave is absorbed by the RaneyNi catalyst, makes as the Ni atom of active sites and the hydrogen that is stored in the catalyst more vivaciously, helps improving catalytic hydrogenation activity.But, when ultrasonic time is long, on the one hand particle is reunited, some pore passage structure can be destroyed simultaneously, and the storage of " active hydrogen " among the Raney Ni can be reduced, cause catalytic activity to descend.
The present invention is applied to ultrasonic technology the extracting aluminium process of Raney Ni catalyst first, with the ultrasonic cleaning of the Raney Ni catalyst of having reported exist essential distinction (the Japan Patent 03249946A that has announced be Raney Ni that suction filtration is good in deionized water for ultrasonic and modify optical active substance).This law is easy and simple to handle, cost is low, a kind of novel Raney Ni catalyst (LM Raney Ni not only is provided, be different from W1～W8 type Raney Ni catalyst of having reported), but also provide a kind of new method for the further modification for preparing other matrix type metallic catalysts and Raney Ni catalyst.Prepared LM Raney Ni has bigger aperture and the pore volume of Geng Gao than the Raney Ni (traditional Raney Ni) that handles without ultrasonic wave under the same terms, and specific area also slightly increases; And impurity content significantly reduces in surface and the body.
LM Raney Ni catalyst of the present invention not only has high activity to benzene hydrogenation, and in many catalytic hydrogenation reactions such as hydrogenation of acetonitrile, glucose hydrogenation and hydrogenation of chloronitrobenzene, all shown excellent catalytic activity and selectivity, be expected to substitute traditional Raney Ni catalyst and be used for suitability for industrialized production.
To further describe the present invention by specific embodiment below, enumerating these embodiment only is in order to set forth rather than limit by any way the present invention.
Specific embodiments
Embodiment 1
With nickel alumin(i)um alloy (available from Shanghai chemical reagents corporation of Chinese Medicine group (experiment reagent LR); its nickel content is about 40～50 weight %) grind to form 80～100 purpose particles; get a certain amount of above-mentioned sample; in ice bath and under stirring; it slowly is added in the NaOH solution of 6.0 mol; weight alloy (gram) is 1: 10 with the ratio of alkali lye volume (milliliter); after treating that the Ni-Al alloy all adds; above-mentioned solution is carried out the ultrasonic wave extracting to be handled; the frequency that ultrasonic wave is handled is 28kHz; the bath temperature that ultrasonic wave is handled is 25 ℃, and ultrasonic time is respectively 0; 5; 10; 15; 20 and 25 minutes.After the ultrasonic wave extracting finished, temperature rose to 70 ℃, and stir about is 4 hours under continuation refluxes.Remove upper strata alkali lye afterwards, use the deionized water cyclic washing, and then anhydrate to remove, make Raney Ni catalyst thus with absolute ethanol washing to neutral.Whole process is at N
2Carry out in the atmosphere, and adopt reflux to prevent the NaOH change in concentration.The Raney Ni catalyst that makes is stored in absolute ethyl alcohol under 5～20 ℃ of environment.
The Ni content of the Raney Ni catalyst that is made by said method by icp analysis is about 72.5～85.8 weight %, and the specific area that the BET method is measured is about 88～96 meters
2/ gram, pore-size distribution is at 2.0～220.8nm, and mainly is distributed in the scope of 3.4～4.0nm.The part-structure parameter of each Raney Ni catalyst that different ultrasonic times obtain is down listed in table 1.
Table 1
The Raney Ni catalyst that different ultrasonic times obtain down
Performance such as nickel content, specific area, pore-size distribution
| Sample number into spectrum | Ultrasonic time (minute) | Ni content (weight %) | Specific area (rice 2/ gram) | Pore volume (centimetre 3/ gram) | Pore-size distribution (nm) | Average pore size (nm) |
| 1# | 0 | 79.1 | 94.247 | 0.0779 | 2.1～178.7 | 3.3085 |
| 2# | 5 | 72.5 | 94.614 | 0.0793 | 2.1～213.9 | 3.3539 |
| 3# | 10 | 83.7 | 96.035 | 0.0798 | 2.1～220.8 | 3.3247 |
| 4# | 15 | 81.0 | 93.595 | 0.0846 | 2.0～110.8 | 3.6137 |
| 5# | 20 | 85.8 | 87.986 | 0.0745 | 2.1～157.9 | 3.3873 |
| 6# | 25 | 84.5 | 89.675 | 0.0821 | 2.0～143.8 | 3.6624 |
Above-mentioned catalyst is used for the prepared from benzene and hydrogen cyclohexane, and the initial pressure of hydrogenation reaction is
Reaction temperature is controlled at 90 ℃, is reflected in 200 milliliters of stainless steel autoclaves to carry out, and initially adds 0.5 gram Raney Ni catalyst, 10 milliliters of benzene and 30 milliliters of ethanol, and the reaction time is 3 hours, result such as table 2:
Table 2
The hydrogenation activity of the Raney Ni catalyst that different ultrasonic times obtain down relatively
| Raney Ni sample | 1# | 2# | 3# | 4# | 5# | 6# |
| Hydrogen-absorption speed (mM/hour. gram) | 27.9 | 33.3 | 35.5 | 43.0 | 35.5 | 34.4 |
| Conversion ratio (%) | 12.5 | 17.2 | 19.6 | 22.8 | 19.9 | 17.0 |
By table 2 as seen, through the Raney Ni catalyst after the ultrasonic wave extracting processing, prepare in the cyclohexane process at benzene hydrogenation, hydrogen-absorption speed and conversion ratio obviously raise, and the catalyst of preparation prepares in the cyclohexane process at benzene hydrogenation when using ultrasonic time to be 15 minutes, and hydrogen-absorption speed and conversion ratio reach maximum 43.0 mMs/hour gram and 22.8%.Compare with the Raney Ni catalyst that does not adopt the preparation of ultrasonic wave extraction steps, hydrogen-absorption speed and conversion ratio improve 54% and 82.4% respectively.
Embodiment 2
Adopt method similarly to Example 1 to prepare Raney Ni catalyst, difference is that used NaOH solution concentration is 10 mol, and weight alloy (gram) is 1: 8 with the ratio of alkali lye volume (milliliter), ultrasonic frequency is 48kHz, and the ultrasonic water bath temperature is 30 ℃ or 50 ℃.The part-structure parameter of Zhi Bei catalyst is listed in table 3 with this understanding.
Table 3
The Raney Ni catalyst that different ultrasonic times and bath temperature obtain down
Performance such as nickel content, specific area, pore-size distribution
| Sample number into spectrum | The extracting time (minute) | Bath temperature (℃) | Ni content (weight %) | Specific area (rice 2/ gram) | Pore volume (centimetre 3/ gram) | Pore-size distribution (nm) | Average pore size (nm) | Atom is formed (%) |
| 7# | 0 | 84.7 | 91.213 | 0.0671 | 2.1-173.3 | 2.9415 | Al 20.9Ni 79.1 | |
| 8# | 15 | 30 | 83.3 | 87.826 | 0.0726 | 2.2-154.2 | 3.3047 | Al 18.2Ni 81.8 |
| 9# | 5 | 50 | 85.0 | 93.937 | 0.0667 | 2.1-167.3 | 2.8414 | Al 18.5Ni 81.5 |
| 10# | 10 | 50 | Do not survey | Do not survey | Do not survey | Do not survey | Do not survey | Do not survey |
| 11# | 15 | 50 | Do not survey | Do not survey | Do not survey | Do not survey | Do not survey | Do not survey |
These catalyst are used for the prepared from benzene and hydrogen cyclohexane, and the initial pressure of hydrogenation reaction is
Reaction temperature is controlled at 90 ℃, is reflected in 200 milliliters of stainless steel autoclaves to carry out, and initially adds 0.5 gram Raney Ni catalyst, 10 milliliters of benzene and 30 milliliters of ethanol, and the reaction time is 3 hours.Gained the results are shown in table 4:
Table 4
The hydrogenation activity of the Raney Ni catalyst that different ultrasonic times obtain down relatively
| Raney Ni sample | 7# | 8# | 9# | 10# | 11# |
| Hydrogen-absorption speed (mM/hour gram) | 31.2 | 39.8 | 41.9 | 35.5 | 30.1 |
| Conversion ratio (%) | 16.1 | 21.7 | 21.5 | 21.2 | 14.9 |
By table 4 as seen, the Raney Ni catalyst that under the effect of 48kHz ultrasonic wave, adopts the high activity of Raney Ni catalyst that the NaOH solution extracting Ni-Al alloy of 10 mol obtained to be obtained not as the NaOH solution extracting Ni-Al that under the effect of 28kHz ultrasonic wave, adopts 10 mol, simultaneously, the too high catalytic activity that is unfavorable for Raney Ni catalyst of ultrasonic processing bath temperature.
Embodiment 3
Adopt method similarly to Example 1 to prepare Raney Ni catalyst, difference is that used NaOH solution concentration is 4 mol, and Ni-Al weight alloy (gram) is 1: 15 with the ratio of alkali lye volume (milliliter), ultrasonic frequency is 48kHz, and the bath temperature of ultrasonic processing is 30 ℃ or 50 ℃.The part-structure parameter of Zhi Bei each Raney Ni catalyst is listed in table 5 with this understanding.
Table 5
The Raney Ni catalyst that different ultrasonic times and bath temperature obtain down
Performance such as nickel content, specific area, pore-size distribution
| Sample number into spectrum | Ultrasonic time (minute) | Bath temperature (℃) | Ni content (weight %) | Specific area (rice 2/ gram) | Pore volume (centimetre 3/ gram) | Pore-size distribution (nm) | Average pore size (nm) | Atom is formed (%) |
| 12# | 0 | 89.2 | 70.761 | 0.0541 | 2.1-132.1 | 2.875 | Al 16.2Ni 83.8 | |
| 13# | 15 | 30 | 88.2 | 74.885 | 0.0590 | 2.2-155.5 | 3.1497 | Al 15.5Ni 54.5 |
| 14# | 10 | 50 | 88.0 | 81.437 | 0.0701 | 2.1-145.3 | 3.2567 | Al 14.6Ni 85.4 |
| 15# | 15 | 50 | 88.3 | 89.328 | 0.0763 | 2.1-151.7 | 3.4158 | Al 14.0Ni 86.0 |
Above-mentioned catalyst is used for the prepared from benzene and hydrogen cyclohexane, and the initial pressure of hydrogenation reaction is
Reaction temperature is controlled at 90 ℃, is reflected in 200 milliliters of stainless steel autoclaves to carry out, and initially adds 0.5 gram Raney Ni catalyst, 10 milliliters of benzene and 30 milliliters of ethanol, and the reaction time is 3 hours, result such as table 6:
Table 6
The hydrogenation activity of the Raney Ni catalyst that different ultrasonic times and bath temperature obtain down relatively
| Raney Ni sample | 12# | 13# | 14# | 15# |
| Hydrogen-absorption speed (mM/hour gram) | 32.3 | 46.2 | 35.5 | 39.8 |
| Conversion ratio (%) | 15.1 | 20.2 | 17.4 | 20.0 |
By table 6 as seen, reduce the concentration of the used NaOH of suction filtration and increase the ratio of Ni-Al weight alloy (gram) and alkali lye volume (milliliter), help improving the hydrogenation activity of Raney Ni catalyst, same, the too high catalytic activity that is unfavorable for Raney Ni catalyst of ultrasonic processing bath temperature.
Listed specific embodiments of the present invention above, under the situation of the spirit and scope that do not deviate from appended claims of the present invention, those skilled in the art can modify and revise it.
Claims (7)
1. the method for preparing Raney Ni catalyst, described method comprises the following steps:
(i) nickel alumin(i)um alloy is ground to form 80～100 purpose particles;
(ii) the particle of step (i) is added in the NaOH solution and stirs, weight alloy gram number is 1: 8～1: 15 with the ratio of alkali lye volume milliliter number, this solution was carried out ultrasonic wave extracting aluminium 5～30 minutes, ultrasonic frequency is 28～48kHz, bath temperature is 25～60 ℃, the ultrasonic wave extracting finishes the back and continues to stir 2～6 hours, removes upper strata alkali lye afterwards, and overall process is carried out in inert gas;
(iii) step particle (ii) spends deionised water to neutral, removes with absolute ethanol washing and anhydrates, and makes Raney Ni catalyst.
2. the method for claim 1 is characterized in that, ultrasonic frequency is 28kHz or 48kHz.
3. the method for claim 1 is characterized in that, the bath temperature during the ultrasonic wave extracting is 30～50 ℃.
4. the method for claim 1 is characterized in that, the ultrasonic wave extracting time is 10～20 minutes.
5. Raney Ni catalyst with the preparation of method according to claim 1, the nickel content that it is characterized in that described catalyst is 70～90 weight %, specific area is at 70～100 meters
2/ gram scope, pore volume are 0.054～0.085 centimetre
3/ gram, pore-size distribution is in 2.0～220nm scope, and average pore size is 2.84～3.66nm.
6. with the application of Raney Ni catalyst in hydrogenation reaction of method preparation according to claim 1.
7. application as claimed in claim 6 is characterized in that, described hydrogenation reaction is the prepared from benzene and hydrogen cyclohexane.
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| CN101537361B (en) * | 2008-03-21 | 2012-09-05 | 汉能科技有限公司 | Preparation method of Raney's nickel catalyst of fixed bed |
| CN101549297B (en) * | 2008-03-31 | 2012-09-05 | 汉能科技有限公司 | Preparation method of fixed bed raney nickel catalyst |
| CN102407152B (en) * | 2011-09-30 | 2013-05-29 | 上海师范大学 | Skeletal nickel phosphorus catalyst and preparation method and use thereof |
| CN102942971B (en) * | 2012-09-19 | 2014-01-15 | 太原理工大学 | Application of raney nickel as slurry reactor to synthesize methane catalyst |
| CN103055869B (en) * | 2012-11-29 | 2015-02-11 | 北京航空航天大学 | Porous metal nanometer granular catalyst and preparation method thereof |
| CN104084219B (en) * | 2014-07-08 | 2016-02-24 | 赛鼎工程有限公司 | A kind of preparation method and application being applicable to fixed bed methanation Raney's nickel catalyst |
| CN104069872B (en) * | 2014-07-08 | 2016-04-06 | 赛鼎工程有限公司 | A kind of preparation method and application being suitable for slurry bed system methanation catalyst |
| CN104056641B (en) * | 2014-07-08 | 2016-04-06 | 赛鼎工程有限公司 | A kind of preparation method and application of slurry bed system methanation in presence of sulfur Raney's nickel catalyst |
| CN104056640B (en) * | 2014-07-08 | 2016-08-17 | 赛鼎工程有限公司 | A kind of preparation method and application being suitable for slurry bed system methanation Raney's nickel catalyst |
| CN104084220B (en) * | 2014-07-08 | 2016-02-24 | 赛鼎工程有限公司 | A kind of preparation method and application of fixed bed methanation in presence of sulfur Raney's nickel catalyst |
| CN104056634B (en) * | 2014-07-08 | 2016-08-03 | 赛鼎工程有限公司 | A kind of preparation method and application being applicable to fixed bed methanation catalyst |
| CN104607207B (en) * | 2015-01-21 | 2017-02-22 | 江西创赢香精香料科技协同创新有限公司 | Method for synthesizing dihydroterpineol |
| TWI787215B (en) | 2016-11-22 | 2022-12-21 | 美商Ｗ Ｒ 康格雷氏公司 | Catalysts with reduced attrition and method for manufacturing the same |
| CN106938331B (en) * | 2017-03-01 | 2018-11-09 | 西南交通大学 | Mesoporous dusty materials of NiAl and preparation method thereof |
| CN107492633B (en) * | 2017-07-04 | 2019-12-03 | 上海空间电源研究所 | A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof |
| CN107585743B (en) * | 2017-09-20 | 2019-11-26 | 安徽工业大学 | A method of improving sodium alanate hydrogen storage property |
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Assignee: Shanghai Rongshi Biological Technology Co.,Ltd Assignor: Shanghai Normal University Contract fulfillment period: 2007.8.5 to 2013.8.5 contract change Contract record no.: 2008310000123 Denomination of invention: Method for preparing novel Raney Ni catalyzer and its application Granted publication date: 20060621 License type: Exclusive license Record date: 2008.10.6 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.8.5 TO 2013.8.5; CHANGE OF CONTRACT Name of requester: SHANGHAI RONGSHI BIOLOGICAL TECHNOLOGY CO., LTD. Effective date: 20081006 |
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