CN100337752C - Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst - Google Patents
Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst Download PDFInfo
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Abstract
The present invention belongs to the technical field of a hydrogenation catalyst and particularly relates to a preparation method for a nanometer nickel catalyst, particularly to a method for preparing a supported nanometer nickel hydrogenation catalyst by a gas-phase permeation and deposition method in metal organic chemistry. The preparation method is characterized in that nickel carbonyl compounds are loaded into a stock tower by carrier gas firstly to carry out the permeation and adsorption of nickel carbonyl on carries, and then thermolysis deposition of the nickel carbonyl compounds are carried out on the carrier through heating and temperature rise further; finally, the supported nanometer nickel catalyst can be obtained through baking the carrier. Compared with the prior art, the method of the present invention has the advantages of simple process, easy control, high productive efficiency, low cost, no pollution and convenient application.
Description
Technical field
The invention belongs to the hydrogenation catalyst technical field, be specifically related to a kind of preparation method of nano nickel catalyst, particularly prepare the method for supported nanometer nickel catalyst by Organometallic Chemistry gas phase permeation precipitation method.
Background technology
In the prior art, nanocatalyst has very thin uniform outer surface layer and special crystal structure, electronic structure that it is unique and good surface characteristic help the carrying out of the absorption and the surface chemical reaction of reactant, thereby nanocatalyst shows light specific gravity, and specific area is big, the reactivity height, selectivity is strong, long service life, outstanding advantage such as good operation performance especially all has higher activity and selectivity to catalytic oxidation, reduction and cracking reaction.
The preparation method who is applied to the supported nanometer nickel catalyst of catalytic hydrogenation at present has infusion process, plasma method, mixes and pinch roasting method etc.Patent USP4490480 has introduced a kind of Ni/Al
2O
3Hydrogenization catalyst preparation method adopts the method for nickel amine complex dipping to make, and this catalyst nickel content is at 5-40wt%, and wherein 95% nickel crystal is dispersed in the inside of aluminium oxide.This catalyst nickel content higher (directly causing higher cost), active low, preparation process is complicated, and catalyst produces a large amount of environmental contaminants NO in roasting process
xIt is that raw material passes through the method that the arc plasma legal system is equipped with nanometer Ni-Pd alloy ultro-micro partical catalyst with two kinds of close refractory metal nickel and palladiums of fusing point that patent CN94115078 discloses a kind of.This method cost of material costliness, preparation efficiency is low, and this nanometer alloy catalyst do not have solid shape, can't use under many conditions.Patent CN1132685 has introduced a kind of catalyzer for hydrogenization of nano nickel, and method is to be carrier with the refractory inorganic matter, with mechanical vibration method nanometer nickel crystallite (10-90nm) is dispersed in carrier surface, again at 450-550 ℃ of roasting 0.5-4 hour.The catalyst nickel content of this method preparation is lower, and corresponding its catalytic efficiency is lower, and high-temperature roasting simultaneously easily causes the sintering inactivation of nanocrystal.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, easy to control, production efficiency is high, cost is low, the gas phase permeation precipitation method for preparation of pollution-free, the supported nanometer nickel hydrogenation catalyst being convenient to use.
According to above-mentioned purpose, technical scheme of the present invention is: obtain supported nanometer nickel catalyst by the gas phase permeation precipitation of carbonyl metal compound on carrier, it can make specific components be deposited on the matrix with atomic state (nanomorphic) structure by condition control, and prepared new material obtains on semiconductor photoelectric device and microwave device extensively and applications well.
According to above-mentioned purpose and technical scheme, this preparation method comprises following concrete steps:
A, the carbonyl nickel of in evaporimeter, packing into, the carrier of in gas-phase permeation and deposition material tower, packing into, whole system keeps air-tight state;
B, 30-60 ℃ of water-bath of employing or oil bath heating fumigators make carbonyl nickel form steam, and logical then carrier gas carrier band carbonyl nickel steam enters gas-phase permeation and deposition is expected tower; Volumetric mixture ratio with flowmeter control carbonyl nickel steam and carrier gas is 1: 2-20, and the temperature of control material tower is 40-60 ℃, the time is 0.25-2h, is adsorbed onto carrier inside so that the carbonyl nickel steam can fully permeate;
C. raise gas-phase permeation and deposition material tower to 100-250 ℃, the carbonyls that is diffused into this moment in the carrier hole begins to decompose deposition, and sedimentation time is controlled at 0.5-3h;
D. deposition finishes, and the carrier of loading with nanometer nickel is further heated baking burn, and removes a small amount of undecomposed carbonyls, and baking is burnt temperature and is controlled at 200-350 ℃, and the time is 0.5-3h;
E. the further logical carrier gas of system is cooled to the room temperature discharging, weighs and assay.
Carrier is any or any two the mixed thing of pinching in high-ratio surface material one zeolite, aluminium oxide, zirconia, silica, diatomite, molecular sieve, active carbon of porous.
The shape of carrier is any in spherical, graininess or the strip.
Carrier gas is any in purity 99.9% above carbon monoxide, nitrogen or the argon gas.
For improve quality and the uniformity that nanometer nickel deposits in the carrier inside hole, carrier is in vibrating state with the material tower all the time in the preparation process.
The carrier that to load with nanometer nickel simultaneously carries out the step of batch turning mixing infiltration deposition more repeatedly.
Nickel content weight % is at 5-22% in the supported nanometer nickel catalyst of preparation, and the size of nanometer nickel is at 10-80nm.
The present invention has compared with prior art that technology is simple, easy to control, production efficiency is high, cost is low, pollution-free, be convenient to advantages of application.Specific as follows:
1. technology is simple, and condition is easily controlled;
2. nickel content is low than infusion process, kneading method, save cost, and production efficiency is higher;
3. the harmful tail gas that produces in the deposition process becomes metallic nickel and C0 through the processing of tail gas destructor
2, do not have environmental pollution;
4. be convenient to use, can be directly used on the hydrogenation plant of various ways such as fixed bed.
5, the catalyst activity selectivity is good.
The specific embodiment
Embodiment 1
From storage tank, put 5L carbonyl nickel liquid and go into evaporimeter, take by weighing 800g γ type aluminium oxide bar shaped carrier (Φ 1mm) pack into gas-phase permeation and deposition material tower, operate by above-mentioned B-E step then.Operating parameter is: 35 ℃ of evaporator water bath temperatures; The volumetric mixture ratio of carbonyl nickel steam and carrier gas is 1: 6, and carrier gas is 99.9% nitrogen; During gas-phase permeation, the temperature of material tower is 40 ℃, and the time is 0.5h; During pyrolytic deposition, the temperature of material tower is 90 ℃, and the time is 0.5h; Baking burning temperature was controlled at 330 ℃ after deposition finished, and the time is 1h.
Experiment finishes, and the nickel content of analysis of catalyst is 5.6wt%, and use emission scan electronic microscope photos nanometer nickel is of a size of 25-45nm.
Embodiment 2-5, experimental technique is with embodiment 1, and experiment parameter sees Table 1.
Table 1
Embodiment 6
Carry out catalyst hydrogenation performance evaluation by continuous micro counter-chromatography system.The hydrogenation oil sample is the mixture of decahydronaphthalene (60%) and toluene (40%), catalyst amount 0.1g.Before the hydrogenation catalyst being carried out 200 ℃ of 3h reduction handles.Hydrogenation reaction is carried out under normal pressure, hydrogen flowing quantity 180ml/min, and hydrogen-oil ratio 1800: 1, hydrogenation temperature are 130 ℃, the chromatogram sample analysis all carried out later at logical oil sample in 3 hours.The hydrogenation evaluation result of embodiment 1-5 catalyst sees Table 2.
Toluene level * 100% in the oil sample before toluene conversion %=(before the hydrogenation in the oil sample behind toluene level-hydrogenation in the oil sample toluene level)/hydrogenation
Table 2
Claims (6)
1, a kind of gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst is characterized in that this preparation method comprises following concrete steps:
A, the carbonyl nickel of in evaporimeter, packing into, the carrier material of the porous high-ratio surface of in gas-phase permeation and deposition material tower, packing into, whole system keeps air-tight state;
B, 30-60 ℃ of water-bath of employing or oil bath heating fumigators make carbonyl nickel form steam, and the carrier gas carrier band carbonyl nickel steam of any in logical then purity 99.9% above carbon monoxide, nitrogen or the argon gas enters gas-phase permeation and deposition material tower; Volumetric mixture ratio with flowmeter control carbonyl nickel steam and carrier gas is 1: 2-20, and the temperature of control material tower is 40-60 ℃, the time is 0.25-2h;
C. raise gas-phase permeation and deposition material tower to 100-250 ℃, the carbonyls that is diffused into this moment in the carrier hole begins to decompose deposition, and sedimentation time is controlled at 0.5-3h;
D. deposition finishes, and the carrier of loading with nanometer nickel is further heated baking burn, and baking is burnt temperature and is controlled at 200-350 ℃, and the time is 0.5-3h;
E. the further logical carrier gas of system is cooled to the room temperature discharging, weighs and assay.
2, the gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst according to claim 1, the carrier material that it is characterized in that the porous high-ratio surface are any or any two the mixed things of pinching in zeolite, aluminium oxide, zirconia, silica, diatomite, molecular sieve, the active carbon.
3, the gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst according to claim 2, the shape that it is characterized in that carrier are any in spherical, graininess or the strip.
4, the gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst according to claim 1 is characterized in that carrier is in vibrating state with the material tower all the time in the preparation process.
5, the gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst according to claim 1, the carrier that it is characterized in that will loading with simultaneously nanometer nickel carry out the step that repeatedly batch turning mixes infiltration deposition again.
6, the gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst according to claim 1, nickel content weight % is at 5-22% in the supported nanometer nickel catalyst that it is characterized in that preparing, and the size of nanometer nickel is at 10-80nm.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101822985B (en) * | 2009-03-04 | 2012-07-18 | 中国石油天然气股份有限公司 | Pre-treatment method of nickel hydrogenation catalyst |
| CN103084180B (en) * | 2013-02-28 | 2014-08-20 | 中国矿业大学 | Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring |
| CN103949256B (en) * | 2014-04-29 | 2015-07-29 | 中国石油大学(华东) | Nickel catalyst carried gas-phase deposition process for preparing |
| CN106082362A (en) * | 2016-06-22 | 2016-11-09 | 金川集团股份有限公司 | A kind of method improving light-weight carbonyl nickel powder granularity |
| CN109894157B (en) * | 2017-12-07 | 2021-09-07 | 中国科学院大连化学物理研究所 | Method for inhibiting nickel loss of nickel catalyst and application of method in methanation reaction |
| CN110261191B (en) * | 2019-05-23 | 2021-11-02 | 中国石油天然气股份有限公司 | Method for extracting bonded-state biomarker in hydrocarbon source rock |
| CN112973701B (en) * | 2021-03-08 | 2022-07-05 | 安徽理工大学 | Iron-sodium carbon material catalyst and preparation method and application thereof |
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| JPS6428309A (en) * | 1987-07-23 | 1989-01-30 | Sumitomo Metal Mining Co | Production of fine nickel powder |
| CN1049800A (en) * | 1989-08-28 | 1991-03-13 | 中国石油化工总公司石油化工科学研究院 | The preparation of nickel/aluminium oxide catalyst |
| EP0508757A1 (en) * | 1991-04-08 | 1992-10-14 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of fine powder |
| CN1213596A (en) * | 1998-03-27 | 1999-04-14 | 冶金工业部钢铁研究总院 | Nm gamma (iron, nickel) alloy powder and its making method and use |
| CN1240689A (en) * | 1998-07-08 | 2000-01-12 | 中国科学技术大学 | Process for preparing superfine powder by thermolyzing metal complex |
| CN1603037A (en) * | 2003-09-29 | 2005-04-06 | 中国科学院兰州化学物理研究所 | Method for preparing superfine nickel carbonyl powder by nickel carbonyl thermal decomposition |
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Patent Citations (6)
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| JPS6428309A (en) * | 1987-07-23 | 1989-01-30 | Sumitomo Metal Mining Co | Production of fine nickel powder |
| CN1049800A (en) * | 1989-08-28 | 1991-03-13 | 中国石油化工总公司石油化工科学研究院 | The preparation of nickel/aluminium oxide catalyst |
| EP0508757A1 (en) * | 1991-04-08 | 1992-10-14 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of fine powder |
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