CN104056639A - Preparation method of magnetic precious metal heterogeneous catalyst - Google Patents
Preparation method of magnetic precious metal heterogeneous catalyst Download PDFInfo
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- CN104056639A CN104056639A CN201410269353.1A CN201410269353A CN104056639A CN 104056639 A CN104056639 A CN 104056639A CN 201410269353 A CN201410269353 A CN 201410269353A CN 104056639 A CN104056639 A CN 104056639A
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a magnetic precious metal heterogeneous catalyst. The preparation method comprises the following steps: firstly, introducing iron, cobalt and nickel into a carrier, endowing the carrier with magnetic properties, and further loading precious metals of platinum, palladium, ruthenium, gold, silver, iridium or osmium in the magnetic carrier through a reducing reaction to prepare the magnetic precious metal heterogeneous catalyst. The magnetic precious metal heterogeneous catalyst prepared by adopting the preparation method has excellent catalysis activity, and can be rapidly recycled through magnetic separation. In addition, the magnetic property of the magnetic precious metal heterogeneous catalyst is easily adjusted, and the magnetic separation time can be adjusted and controlled; catalyst structures such as specific surface area and duct structure are adjustable; precious particles are uniformly distributed, and loading amount and particles are controllable in sizes. The preparation method provided by the invention has the advantages of simplicity in operation, low cost, and the like, and can be produced in large scale. The prepared magnetic precious metal heterogeneous catalyst can be applied to recycling of conventional and special reaction system catalysts.
Description
Technical field
The invention belongs to technical field of material, be specifically related to a kind of preparation method of magnetic noble metal heterogeneous catalysis.
Background technology
In modern chemistry industry, catalyst occupies extremely important status, almost has chemical products more than half in production process, all to adopt catalyst.Noble metal catalyst is as most important catalyst material, with its good activity, selective and stability, increasing attention and application have been won, hydrogenation, dehydrogenation, oxidation, reduction, isomerization, aromatisation, cracking, the reaction such as synthetic have been widely used at present, in fields such as chemical industry, petroleum refinement, petrochemistry, medicine, environmental protection, and the field such as new forms of energy, sensing plays very important effect.By catalytic reaction classification, noble metal catalyst can be divided into homogeneous catalysis use and two large class catalyst for heterogeneous catalysis.Homogeneous catalysis is generally soluble compound with catalyst.The heterogeneous catalysis that heterogeneous catalysis is used is insoluble solid thing, and its Main Morphology is woven wire state and carried metal state.In whole catalytic reaction processes, heterogeneous catalytic reaction accounts for 80%～90%, and in heterogeneous precious metal catalyst, loaded noble metal catalyst is occupied an leading position, and in nearly all present catalyst application, has application, and its development is most important.
Yet because Precious Metals Resources is rare, expensive, the recovery of noble metal catalyst resource has significant economy and society and is worth, and has been subject to the general attention in countries in the world.Catalyst solid in heterogeneous reaction solution system, owing to being subject to different reaction conditions as the stress influence that High Temperature And Velocity stirs, has formed tiny particle and has been dispersed in solution.Use early stage gravity settling separation method efficiency low, length consuming time.Modern Application more widely separation and recovery of catalyst method is multiple mechanical phonograph recorder separation, and this separation method mainly contains following four kinds:
(1) centrifugal sedimentation partition method.Be divided into spinning liquid partition method and centrifugal sedimentation partition method, two kinds of methods, respectively by high-speed screw and circular motion, utilize centrifugal force to carry out separated to solution with solid.
(2) electrostatic separation method.This method is applicable to that solid content is relatively low, particle diameter is in micron order and the larger system of liquid resistance rate.Cardinal principle is, when solution system is flowed through filler under high voltage electric field effect, thereby catalyst is adsorbed on after polarized and on filler, completes separation.
(3) isolated by filtration method.For slurry oil system, when high temperature low viscosity, adopt special filter to carry out filter operation, but for the having relatively high expectations of instrument, preferably filtering material can guarantee filter process continue carry out.
(4) chemical assistant partition method.The especially low-molecular-weight polymer of some chemical assistant, can with system in catalyst granules form stronger affinity, stop the diffusion of particle in solution, promote cohesion, and then can accelerate sedimentation.
In above-mentioned several method, when procatalyst adopt centrifugal or filter methods separated with reaction system more, clean again afterwards, regenerate and the processing such as oven dry.These two kinds of methods can effectively realize the separated of catalyst and most of reaction system, yet reaction solutions a large amount of in industrial production is carried out centrifugal and filtered, and need to expend the longer time, relate to more complicated operation.Meanwhile, for the system that needs special operational condition, as relate to toxic compounds, volatile, inflammable, explosive material, need to completely cut off the system of air-operated etc., and it is comparatively complicated that centrifugal and filtered and recycled method will become.Moreover, use two kinds of methods for catalyst granules small system to carry out separative efficiency also more limited.
The catalyst with magnetic separation function by development of new can address the above problem well, thereby can carry out separated this solution thinking of magnetic existing many achievements in research at home and abroad, research ferrite, the i.e. Fe of using by making catalyst carrier have magnetic more
2o
3or Fe
3o
4as magnetic component, with the coated core-shell type structure that forms of the common vector such as porous carbon, aluminium oxide, silica, then reload active component.The present invention adopts iron, cobalt, nickel as magnetic component, by iron, cobalt, nickel metal are introduced to carrier, give its magnetic property, further by reduction reaction carried noble metal, preparation magnetic noble metal catalyst, this catalyst not only has good catalytic performance, can use easily magnetic separation effectively to reclaim simultaneously.
Summary of the invention
The object of the invention is to provide a kind of preparation method of magnetic noble metal heterogeneous catalysis.
The preparation method of the magnetic noble metal heterogeneous catalysis that the present invention proposes is as follows:
(1) carrier is scattered in the solution that contains iron, cobalt, nickel ion, then in solution, adds reducing agent, make iron, cobalt, nickel ion be reduced to metal, make magnetic carrier, the 1-40% that Metal Supported weight is carrier;
(2) precursor liquid of platinum, palladium, ruthenium, rhodium, gold, silver, iridium or osmium is splashed in the solution that contains magnetic carrier, pass through reduction, noble metal granule is loaded on magnetic carrier, magnetic is separated, after washing is dry, obtain magnetic noble metal heterogeneous catalysis, the 1-30% that noble-metal-supported amount is magnetic carrier.
In the present invention, catalyst carrier can be selected multiple inorganic or macromolecular material, as Woelm Alumina, the compound of one or more of porous carbon, porous silica, kaolin, diatomite, zeolite, cellular glass, molecular sieve, porous polymer materials etc., carrier can be through suitable surface treatment to improve load effect.
In the present invention, catalyst magnetic mainly comes from the alloy of one or more materials of iron, cobalt, nickel metal, and this magnetic component is carried on carrier surface with particle or stratiform, the 1-40% that Metal Supported weight is original vector; The inorganic matters such as sulphate, nitrate compound, chloride, phosphate cpd and hydroxide that catalyst magnetisable material iron, cobalt, nickel metal precursor are this metal, or relevant organic compound is as oxalate compound, acetic acid compound etc.
In the present invention, iron, cobalt, nickel Metal Supported are dipping-reducing process, absorption-reducing process or hydro-thermal method-reducing process to the method for carrier.Wherein, iron, cobalt, nickel precursor solution concentration are 0.01-3 mol/L, be controlled at-10-95 of temperature when dipping or absorption
oC, during hydro-thermal-reducing process, temperature is controlled at 100-180
oc; Solvent is selected from water, ethanol, methyl alcohol, ethylene glycol, ether, oxolane, toluene and varsol; Reducing agent is selected from boron hydride, hydrazine, alanate, citrate, vitamin C, alcohols material, ascorbate, oxalic acid, hydrogen.
In the present invention, noble metal catalyst mainly refers to the catalyst of platiniferous, palladium, ruthenium, rhodium, gold, silver, iridium or osmium, the DDGS that the presoma of this catalyst is such material, as chloride, nitrate compound, organic compound etc., its precursor solution concentration is 0.01-2mol/L.
In the present invention, the method that noble metal catalyst is loaded to magnetic catalyst is for entering to contain reaction load in the solution of magnetic carrier by noble metal precursor drop, and reaction temperature is-10
oc-95
oC, when solution drips, stir or ultrasonic dispersion; The noble metal that reaction generates is dispersed in magnetic carrier, and granular size is mainly between 2-100nm;
In the present invention, prepared magnetic noble metal catalyst product specific area and aperture can be selected and load capacity is controlled by carrier; Final products specific area is at 150-1200 m
2/ g; In addition, prepared magnetic noble metal catalyst magnetic disengaging time can regulate and control at tens seconds in dozens of minutes.
Beneficial effect of the present invention is: magnetic noble metal heterogeneous catalysis of the present invention not only has the catalytic performance of traditional noble metal heterogeneous catalysis, there is magnetic separation function simultaneously, can be by separated simple, efficient, quick separated recovery of magnetic after reaction finishes.This separation method is not only applicable to popular response system, and can be used for the reaction system of the special protection of needs, for it provides simple, safe catalyst separation method.In addition, magnetic noble metal heterogeneous catalysis agent carrier of the present invention is selected wide, and specific area, pore-size distribution, noble-metal-supported amount, magnetic disengaging time etc. can regulate and control.Preparation method of the present invention is simple, low for equipment requirements, output is high, cost is low, be produced on a large scale.
Accompanying drawing explanation
The SEM photo of Fig. 1 magnetic carbon carrier.
The SEM photo of Fig. 2 magnetic palladium carbon.
The BET result of Fig. 3 magnetic palladium carbon.
Fig. 4 magnetic noble metal heterogeneous catalysis magnetic separating effect, (a) starts sedimentation and (b) the sample photo after sedimentation completely.Wherein, same width figure left side sample natural subsidence, right side magnetic sample is separated.
Fig. 5 magnetic noble metal heterogeneous catalysis hysteresis curve.
Fig. 6 magnetic palladium-carbon catalyst and business palladium-carbon catalyst are for the conversion ratio result of hydrogenation of chloronitrobenzene.
The specific embodiment
Below by embodiment, further illustrate the present invention.
Embodiment 1:
The preparation method of magnetic carrier
Under room temperature, in 500mL there-necked flask, add 1.0 g activated carbon, 0.5 g FeSO
47H
2o, 0.25g NiSO
46H
2o, 250mL deionized water, makes it to dissolve with the speed mechanical agitation of 220r/min, passes into N simultaneously
2air in emptying system, then dropwise adds 10mL to be dissolved with 0.12 g NaBH while stirring
4deionized water solution.React after 30 minutes, by the separated black suspension of magnetic, the solution that inclines, uses deionized water wash solution, and above-mentioned product vacuum drying is obtained to magnetic carbon carrier for 2 hours, and Fig. 1 is the SEM photo of magnetic carbon carrier.
Replacing activated carbon is that aluminium oxide, kaolin, diatomite etc. can obtain corresponding carbon carrier.
Embodiment 2:
The preparation method of magnetic palladium carbon (palladium content 5%)
In 250mL there-necked flask, add 0.2g activated carbon, 0.1g FeSO
47H
2o, 0.05g NiSO
46H
2o, 20mL methyl alcohol and 30mL deoxidized water, make it to dissolve with the speed mechanical agitation of 220r/min, passes into N simultaneously
2air in emptying system, then dropwise adds 10mL to be dissolved with 0.04g NaBH while stirring
4deoxidized water solution.Obtain black suspension, strengthen N
2flow, places 1 hour.Afterwards, improve rotating speed to 500r/min, dropwise add while stirring and be dissolved with 0.03g Na
2pdCl
4the aqueous solution, dropwise rear continuation reaction 30min and stop.Product is carried out to magnetic separation, and with after deoxidized water and ethanol washing, vacuum drying 2h obtains magnetic palladium-carbon catalyst.
Fig. 2 is the SEM photo of magnetic palladium-carbon catalyst, by figure, can be seen, has generated the palladium particle of a few nanometer to tens nanometers on carrier.Fig. 3 is its BET result, can see that this catalyst has larger specific area (>1000m
2/ g).Fig. 4 is the magnetic separating effect figure of this product, compares natural subsidence and uses magnetic separating effect obvious, has obvious separating effect in 20s, can be completely separated in 2 minutes.Fig. 5 is product hysteresis curve, can see, this material has good soft magnet performance.Fig. 6, for this material and commercial magnetic C catalyst (being 5% palladium content) catalysis hydrogenation of chloronitrobenzene experimental result under the same conditions, can see that magnetic palladium-carbon catalyst and commercial catalyst have suitable catalytic activity.
Embodiment 3:
The preparation method of magnetic platinum carbon
Adopt the process of example 2, by Na
2pdCl
4be replaced by Na
2ptCl
4can make magnetic platinum C catalyst.
Claims (10)
1. a magnetic noble metal heterogeneous catalysis preparation method, concrete steps are as follows:
(1) carrier is scattered in the solution that contains magnetisable material iron, cobalt, nickel ion, then in solution, adds reducing agent, make iron, cobalt, nickel ion be reduced to metal, make magnetic carrier, the 1-40% that Metal Supported weight is carrier;
(2) precursor liquid of platinum, palladium, ruthenium, rhodium, gold, silver, iridium or osmium is splashed in the solution that contains magnetic carrier, pass through reduction, noble metal granule is loaded on magnetic carrier, magnetic is separated, after washing is dry, obtain magnetic noble metal heterogeneous catalysis, the 1-30% that noble-metal-supported amount is magnetic carrier.
2. preparation method according to claim 1, it is characterized in that, described catalyst carrier is selected from Woelm Alumina, a kind of in porous carbon, porous silica, kaolin, diatomite, zeolite, cellular glass, molecular sieve, porous polymer materials, or wherein several.
3. preparation method according to claim 1 and 2, it is characterized in that, sulphate, nitrate compound, chloride, phosphate cpd or hydroxide that magnetisable material iron, cobalt, nickel metal precursor are this metal, or oxalate compound, acetic acid compound.
4. preparation method according to claim 1 and 2, is characterized in that, iron, cobalt, nickel Metal Supported are dipping-reducing process to the method for carrier, absorption-reducing process or hydro-thermal method-reducing process; Wherein, iron, cobalt, nickel precursor solution concentration are 0.01-3 mol/L, and when dipping or absorption, temperature is-10-95
oC, temperature 100-180 during hydro-thermal method
oc; Selecting solvent is one or more mixture of water, ethanol, methyl alcohol, ethylene glycol, ether, oxolane, toluene, varsol.
5. preparation method according to claim 4, it is characterized in that, the reducing agent of iron, cobalt, nickel compound is selected from one or more of following material: boron hydride, hydrazine, alanate, citrate, vitamin C, alcohols material, ascorbate, oxalic acid, hydrogen.
6. preparation method according to claim 1, it is characterized in that, the presoma of noble metal catalyst platinum, palladium, ruthenium, rhodium, gold, silver, iridium or osmium is the DDGS of such material, comprises chloride, nitrate compound or organic compound, and its precursor solution concentration is 0.01-2mol/L.
7. preparation method according to claim 1, is characterized in that, the described reduction of passing through, loads on magnetic carrier noble metal granule, and reaction temperature is-10
oc-95
oC, solution is aided with and stirs or ultrasonic dispersion while dripping.
8. preparation method according to claim 1, is characterized in that, noble metal is dispersed in catalyst, and granular size is between 2-100nm.
9. preparation method according to claim 1, is characterized in that, prepared magnetic noble metal catalyst product specific area and aperture can be selected and load capacity is controlled by carrier, and wherein specific area is at 150-1200m
2/ g, aperture is between 5-500nm.
10. preparation method according to claim 1, is characterized in that, prepared magnetic noble metal catalyst magnetic disengaging time is by regulating magnetic material composition and load capacity to regulate and control, and the catalyst saturation magnetization making is 0.5-100emu/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754792A (en) * | 2017-10-30 | 2018-03-06 | 上海泰坦科技股份有限公司 | A kind of preparation method of spherical mesoporous charcoal supported precious metal catalyst |
| CN111111689A (en) * | 2019-12-26 | 2020-05-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN114920659A (en) * | 2022-07-08 | 2022-08-19 | 绍兴众昌化工股份有限公司 | Catalytic synthesis method of aminobutanol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671672A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-supported nickel-based catalyst |
| CN103418342A (en) * | 2013-08-03 | 2013-12-04 | 彭晓领 | Preparation method of magnetically-separable active carbon material |
| CN103623824A (en) * | 2012-08-23 | 2014-03-12 | 华东师范大学 | Magnetic iron-carbon composite material, preparation method and application thereof |
| CN103691490A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Treatment method of porous carbon carrier for noble metal catalysts |
-
2014
- 2014-06-17 CN CN201410269353.1A patent/CN104056639A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671672A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院大连化学物理研究所 | Preparation method and application of carbon-supported nickel-based catalyst |
| CN103623824A (en) * | 2012-08-23 | 2014-03-12 | 华东师范大学 | Magnetic iron-carbon composite material, preparation method and application thereof |
| CN103418342A (en) * | 2013-08-03 | 2013-12-04 | 彭晓领 | Preparation method of magnetically-separable active carbon material |
| CN103691490A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Treatment method of porous carbon carrier for noble metal catalysts |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754792A (en) * | 2017-10-30 | 2018-03-06 | 上海泰坦科技股份有限公司 | A kind of preparation method of spherical mesoporous charcoal supported precious metal catalyst |
| CN111111689A (en) * | 2019-12-26 | 2020-05-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN111111689B (en) * | 2019-12-26 | 2022-07-08 | 中国科学院广州能源研究所 | Preparation method and application of bimetallic catalyst for preparing alanine by lactic acid amination |
| CN114920659A (en) * | 2022-07-08 | 2022-08-19 | 绍兴众昌化工股份有限公司 | Catalytic synthesis method of aminobutanol |
| CN114920659B (en) * | 2022-07-08 | 2023-11-24 | 绍兴众昌化工股份有限公司 | Catalytic synthesis method of amino butanol |
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Application publication date: 20140924 |