CN102247856B - Eggshell nickel-based bifunctional hydrogenation catalyst and preparation method and application thereof - Google Patents
Eggshell nickel-based bifunctional hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an eggshell nickel-based bifunctional hydrogenation catalyst and a preparation method and application thereof, and belongs to the technical field of hydrogenation catalysts. In order to meet the requirement of developing an eggshell nickel-based catalyst at present, the invention provides a catalyst which comprises a carrier and a loaded ingredient loaded on the carrier, wherein the loaded ingredient comprises a nickel active ingredient, a first accelerator and a second accelerator; over 90 percent of active ingredient is distributed in an area between a half depth from the surface of the carrier to the center or a central shaft and the surface; and the preparation steps of the catalyst comprise ionization, irradiation and reduction. The invention also provides the preparation method of the eggshell bifunctional hydrogenation catalyst. The catalyst is prepared by performing ionization, irradiation and reduction on a metal active ingredient precursor or oxide obtained by roasting the metal active ingredient precursor. In addition, the invention provides the specific application of the catalyst. The utilization rate of the main active ingredient nickel is improved, and hydrogenation activity and selectivity are obviously improved.
Description
Technical field
The present invention relates to a kind of eggshell type dual-functional hydrogenation catalyst and its preparation method and application, further say to relate to and a kind ofly can carry out simultaneously eggshell type nickel-based catalyst of carbonyl and double-bond hydrogenation and its preparation method and application, particularly relate to eggshell type nickel-based catalyst of a kind of aldehyde hydrogenation synthol and its preparation method and application.
Background technology
For difunctional aldehyde hydrogenation, commercial catalyst uses copper base and Supported Nickel Catalyst usually, wherein copper-based catalysts (for example CuO-ZnO, CuO-ZnO/Al
2O
3) being applied to aldehyde gas phase hydrogenation technique, the product sulfuric acid colourity of this explained hereafter is high, and high-boiling components content is high in the accessory substance, and product purity is low.Supported Nickel Catalyst is applied in energy consumption is low, product purity the is high aldehyde liquid-phase hydrogenatin technique.At present, there are many companies that the patented technology of nickel-base catalyst is arranged both at home and abroad, such as BASF AG, Mitsubishi Kasei Corp, Zhuan Xin company, Czech Chemopetrol company, Germany HoechstAktiengesellschaft company, Russia KHVOROVALEKSANDR PETROVICH company, Salanis Co., Ltd, shell, the Sinopec Beijing Chemical Research Institute, Sinopec asphalt in Shenli Refinery etc., and the activity and selectivity that above-mentioned company catalyst adopts the auxiliary agent of change carrier or adding mostly or the mode of adding auxiliary agent is improved catalyst in liquid charging stock.For example, EP 394842 discloses a kind of liquid phase aldehyde hydrogenating catalyst, and its chief component is Ni-Cu, and this catalyst adds Cu as auxiliary agent, improves catalyst performance; CN 1478596 discloses a kind of catalyst, and this catalyst of this catalyst is take metallic nickel as active component, or/and aluminium oxide is promoter, siliceous compound is carrier take alkaline earth oxide, and silicon-containing compound is with SiO in the carrier
2Meter accounts for the 10%-70% of catalyst weight, and the oxide of alkaline-earth metal accounts for 0-50%, and aluminium oxide accounts for 0-50%, and active component nickel content accounts for 10%-90% in NiO, and the pore volume of catalyst is 0.35cm
3More than/the g, the form of active component nickel employing and carrier coprecipitation, kneading or a coprecipitated kneading loads on the carrier.JP61172838 discloses a kind of Ni-Cr/ diatomite catalyst, need to add tertiary amine when using this catalyst in liquid charging stock, and is selective to improve.The catalyst of mentioning in the above-mentioned document is traditional Active components distribution, does not also see at present in the disclosed document to be the report that eggshell distributes about the non-noble metal supported catalyst of the aldehyde field of hydrogenation especially active component of nickel-base catalyst.
The performance of difunctional aldehyde hydrogenating catalyst is not only relevant, also relevant with the distribution of nickel in the carrier duct with the effect power of the particle size of active component nickel and nickel and carrier.For example, if reactant molecule is difficult to enter depths, catalyst duct, the utilization rate that is distributed in so the nickel at hole depth place may be lower.The product molecule that generates in the reaction of depths, catalyst duct further reacts as can not in time spreading out, and affects on the one hand the selective of catalyst, will affect on the other hand the life-span of catalyst.Especially the aldehyde hydrogenation wishes that reaction occurs in the position that is beneficial to reactant and product diffusion, and general hope occurs in catalyst coating.Nickel is distributed in the eggshell type nickel-based catalyst in the very thin top layer.In addition, in the cost of nickel-base catalyst, the cost proportion of active component nickel is larger, if the nickel active component that is distributed in the depths, duct that utilization rate is not high moves in the zone near catalyst coating, can significantly improve undoubtedly the activity and selectivity of aldehyde hydrogenating catalyst.
The catalytically-active metals salt of common aldehyde hydrogenating catalyst or the described carrier of solution impregnation of organo-metallic compound, then fixing by precipitation, hydrolysis, heat treatment, roasting and/or reduction, with catalytically-active metals dipping or be applied to that this need to repeatedly be heated to impregnated catalyst 200 ℃～1200 ℃ usually on the porous carrier, make slaine or organo-metallic compound be decomposed into corresponding oxide, the catalyst after the roasting could be used for hydrogenation reaction after need leading to before use hydrogen reducing.The catalyst decentralization of tradition infusion process preparation is often lower, and nickel crystallite is large, has affected giving full play to of active component catalytic performance.Make in this way Kaolinite Preparation of Catalyst, the greatest problem of existence is that the high temperature of roasting process can cause the active component sintering, makes the degradation of catalyst.
Therefore, reduce the nickel crystallite size, increase activated centre quantity, reduce the impact of diffusion couple reaction, improve the utilization rate of nickel in the catalyst, thereby improve the activity and selectivity of catalyst, simplify the preparation method, reducing production costs remains the present technical issues that need to address.
Summary of the invention
The present invention is in order to satisfy at present to developing the demand of eggshell type nickel-based catalyst, carried out intensive research, find through research, by regulating the distribution situation of active component nickel on catalyst carrier, make the active component nickel major part concentrate on carrier surface in half the zone of the degree of depth of central shaft, get by the ionizing radiation reduction, can significantly improve the conversion ratio of catalyst with selective.
The present invention realizes that the technical scheme of above-mentioned purpose is:
Eggshell type nickel-based dual-functional hydrogenation catalyst of the present invention comprises carrier and the load component that loads on the carrier, described load group is divided and is comprised nickel active component, the first promoter and the second promoter, in half degree of depth and the zone between the surface of center or central shaft, the preparation process of described catalyst comprises the ionizing radiation reduction to Active components distribution more than 90% at carrier surface.
Preferably, described the first promoter is thulium, and described the second promoter is alkali metal, alkali earth metal and/or transition metal.
More preferably, described alkali metal is at least a among Li, Na, K and the Cs, and described alkali earth metal is at least a among Mg, Ca and the Ba, and described transition metal is at least a among Mn, Co, Cu, Zn, Mo, Pd and the Bi.
Preferably, the Active components distribution more than 95% at carrier surface in half degree of depth and the zone between the surface of center or central shaft.
Preferably, described catalyst contains the nickel active component of 5wt%～50wt%.More preferably, described catalyst contains the nickel active component of 10wt%～40wt%.
Catalyst of the present invention can use any suitable carrier.From the use generality of carrier and being easy to get property, preferred described carrier is aluminium oxide, silica, active carbon, titanium dioxide, molecular sieve or two or more mixture in them, also can be according to needs carrier granular shape and the size of different process.
From the feature of catalyst of the present invention, preferably, spray or infusion process are adopted in the load of the load component of described catalyst, and spray or dipping are that the pH value is 5～12 nickel salt solution with liquid.
The present invention also provides a kind of method for preparing eggshell type nickel-based catalyst, the method is simple to operation, and preparation process is few, and repeatability is reliable, and prepared Supported Nickel Catalyst is used for having higher activity and selectivity in two keys and the carbonyl hydrogen field, particularly aldehyde field of hydrogenation.
Particularly, the invention provides a kind of preparation method of eggshell type nickel-based dual-functional hydrogenation catalyst, adopt the reducing loaded carrier that oxide after load component precursor or the roasting of load component precursor is arranged of ionizing radiation, obtain described catalyst; Described load component precursor is compound corresponding to described load component.
Preferably, described preparation method comprises one of following methods:
(1) load there is described load group divide the described carrier of precursor, uses the solution-wet that contains free radical scavenger, under wetting state, described carrier is carried out ionizing radiation; Carrier behind the ionizing radiation is carried out drying, make described catalyst;
(2) load there is described load group divide the described carrier of precursor, uses the solution submergence that contains free radical scavenger, under submerged state, described carrier is carried out ionizing radiation; Carrier behind the ionizing radiation is carried out drying, make described catalyst;
(3) be load component precursor solution with described load component precursor formulation, add free radical scavenger; Described carrier adding is contained in the mixed liquor of described free radical scavenger and described load component precursor, under the solution submerged state, carry out ionizing radiation; At last the carrier behind the ionizing radiation is carried out drying, make described catalyst.
In described preparation method, preferably, in the described load component precursor solution, solvent is selected from least a in deionized water, hydrochloric acid, nitric acid, organic acid and the alcohols.
Preferably, the pH of the mixed liquor of free radical scavenger and active component precursor is 1～7 in described active component precursor solution or the described method (3).
Preferably, described free radical scavenger is at least a in the derivative of alcohols, C1～C5 alcohols of C1～C5 and the organic acid, and the alcohols of described C1～C5 is preferably selected from ethanol, ethylene glycol, isopropyl alcohol and the tert-butyl alcohol; Described organic acid is preferably formic acid.
Preferably, the solvent of radicals scavenging agent solution is water in described method (1) and method (2), is used for load is had the wetting radicals scavenging agent solution of carrier of load component, and the volume ratio of its free radical scavenger and water is 20～80: 100; Be used for load is had the radicals scavenging agent solution of the carrier submergence of load component, wherein the volume ratio of free radical scavenger and water is 1～50: 100; In described method (3), the volume ratio of free radical scavenger and load component precursor solution is 1～50: 100.
Preferably, described ionizing radiation is gamma-rays, X ray or electron beam irradiation, and absorbed dose rate is 10～10000Gy/min, is preferably 20～100Gy/min, and absorbed dose of radiation is 0.01～1 * 10
5KGy.Radiographic source is optional
60Co (γ source),
137Cs (γ source), x-ray source or electron accelerator (electron beam), preferred
60Co, x-ray source or electron accelerator, more preferably
60Co.Described ionizing radiation reduction process does not have particular determination to temperature conditions, preferably carries out under room temperature or low temperature, does not affect the reduction process and gets final product.More preferably at room temperature carry out.
In addition, with weight and the weight percent meter of catalyst, described catalyst preferably contains 0%～10% rare earth metal, more preferably contains 0%～7% rare earth metal.
Preferably, with weight and the weight percent meter of catalyst, described catalyst contains 0%～15% alkali metal or alkaline-earth metal, more preferably contains 0%～10% alkali metal or alkaline-earth metal.
The nickel salt that catalyst of the present invention uses can be any soluble nickel salt, comprises for example nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel acetate, citric acid nickel and nickelous sulfate etc.
The rare earth that catalyst of the present invention uses can be its oxide, also can be any soluble-salt of rare earth metal.
The alkali metal that catalyst of the present invention uses is preferably sodium, potassium, and alkaline-earth metal is calcium, magnesium, barium.The alkali metal salt or the alkali salt that use can be its any soluble-salt.
The pH value scope of the mixed liquor of free radical scavenger and active component precursor is 1～10 also with above-described maceration extract in the described method (3), preferred 1～7.The pH value can use the solution such as common NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate or ethamine to regulate.
Described free radical scavenger can be selected from least a in the derivative, organic acid of alcohols, the C1～C5 alcohols of C1～C5.The alcohols of described C1～C5 is preferably from ethanol, ethylene glycol, isopropyl alcohol, the tert-butyl alcohol; Described organic acid is preferably from formic acid.Described free radical scavenger is isopropyl alcohol and ethylene glycol preferably.When concrete adding free radical scavenger, usually use its aqueous solution.Be used for load is had the wetting radicals scavenging agent solution of carrier of active component, the volume ratio of its free radical scavenger and water is 20～80%, preferred 30～60%; Be used for load is had the radicals scavenging agent solution of the carrier submergence of active component, wherein the volume ratio of free radical scavenger and water is 1～50%, preferred 5～20%.Free scavenger solution phase to load the consumption of carrier of active component precursor be 5～50%, preferred 15～30%.In the described method (3), the volume ratio of free radical scavenger and active component precursor solution is 1～50%.In using method (3) when flooding, can determine by the volume ratio of free radical scavenger-maceration extract the adding dosage of free radical scavenger, making the concentration of solution is 1～50% in the volume ratio of above-mentioned free radical scavenger and water, preferred 5～20% interior getting final product.
The present invention further provides the application of eggshell type nickel-based dual-functional hydrogenation catalyst of the present invention, specifically can be used in the technique by carbonyl and double-bond hydrogenation, more particularly, can be applicable in the technique of aldehyde hydrogenation synthol.
Eggshell type nickel-based catalyst of the present invention is not limited to the aldehyde hydrogenation, for example can be used for the organic acid hydrogenation, also can be used for maleic anhydride hydrogenation etc.In various hydrogenation processes, can select suitable hydrogenation technique condition according to technical conditions and the experience of this area.Catalyst of the present invention does not have specific (special) requirements.
Eggshell type nickel-based catalyst of the present invention is used for the maleic anhydride hydrogenation reaction, and reaction bed adopts two sections and adds thermal control.120～150 ℃ of first paragraph (double-bond hydrogenation reaction zone) temperature, 220～260 ℃ of second segment (carbonyl hydrogen reaction zone) temperature, reaction pressure 9.0～10.0Mpa.Liquid air speed 1.0～1.5h
-1, during the reaction process condition of H2/ cis-butenedioic anhydride molecular proportion 13～15, cis-butenedioic anhydride conversion ratio 100%, the overall selectivity of gamma-butyrolacton and oxolane is greater than 85%.
Difunctional eggshell type nickel-based catalyst of the present invention and preparation method thereof has the following advantages:
1. the nickel Active components distribution of existing aldehyde hydrogenation nickel-base catalyst is on whole carrier, and in catalyst of the present invention, most of nickel component is distributed in the housing of carrier, the centronucleus part does not have the nickel component substantially, reactant easily arrives active sites, the product that reaction generates can leave active sites quickly, thereby is conducive to improve the activity of catalyst, also is conducive to improve the selective of catalyst.
2. the dual-functional hydrogenation catalyst of the present invention preparation, because the method through ionizing radiation is processed, the metallic nickel crystalline substance degree that loads on the carrier is better, particle diameter is easily controlled, particle diameter is little, make catalyst activity higher, compare with the commercial Application catalyst of conventional method preparation, can reduce the content of active metal nickel.
3. the present invention uses the load of ionising radiation irradiation that the carrier of active component precursor is arranged, and can operate under normal temperature and pressure or low temperature, has simplified preparation technology and has shortened manufacturing cycle, has lowered the discharging of energy consumption and gas pollutant, energy-conserving and environment-protective.
4. method for preparing catalyst of the present invention is simple to operation, and repeatability is high.
Description of drawings
Fig. 1 is the TEM photo of the catalyst of the embodiment of the invention 1 preparation.
The specific embodiment
The below further explains Catalysts and its preparation method of the present invention in the mode of embodiment, but the present invention is not limited to this.
Embodiment 1
The boehmite powder is mixed with water and binding agent, through kneading, extruded moulding, in 105 ℃ of oven dry 10 hours, then 900 ℃ of roastings, making specific surface is 170m
2/ g, the ball-type carrier of pore volume 0.8ml/g.
With nickel nitrate [Ni (NO
3)
26H
2O], lanthanum nitrate [La (NO
3)
36H
2O], potassium nitrate (KNO
3) be dissolved in and make the aqueous solution in the water, then the pH value with the ammoniacal liquor regulator solution is 10, adopts the equivalent impregnation method to flood above-mentioned alumina support, 80 ℃ of oven dry 2 hours, makes a.Get the mixed solution 50ml of 1: 1 deionized water of volume ratio and isopropyl alcohol preparation, pour among a, the Uniform Dispersion hypsokinesis goes out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation obtains catalyst A at 120 ℃ of lower dry 6h, in catalyst weight (wt), contains the nickel of 14wt%, lanthanum and the 1.7wt%K of 0.5wt%.Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules.Size and the uniformity of nickel crystallite have been tested with transmission electron microscope (TEM), as shown in Figure 1.
Embodiment 2
With nickel nitrate [Ni (NO
3)
26H
2O], magnesium nitrate [Mg (NO
3)
26H
2O] be dissolved in and make the aqueous solution in the water, the pH value of potassium hydroxide (KOH) regulator solution is 10.8, adopts the equivalent impregnation method to flood above-mentioned alumina support, 60 ℃ of oven dry 4 hours, makes b.Get the mixed solution 50ml of 1: 1 deionized water of volume ratio and isopropyl alcohol preparation, pour among the b, the Uniform Dispersion hypsokinesis goes out excess solution.Product is used under vacuum
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation makes catalyst B at 120 ℃ of lower dry 6h.B contains the nickel of 14wt%, magnesium and the 1.7wt%K of 2.0wt% in catalyst weight (wt).Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules.
Embodiment 3
With nickel nitrate [Ni (NO
3)
26H
2O], lanthanum nitrate [La (NO
3)
36H
2O], palladium nitrate Pd (NO
3)
2, potassium nitrate (KNO
3) be dissolved in and make the aqueous solution in the water, then the pH value with the ammoniacal liquor regulator solution is 6, adopts the equivalent impregnation method to flood above-mentioned alumina support, all the other steps make catalyst C with embodiment 1.In catalyst weight (wt), contain the nickel of 14wt%, the lanthanum of 1.0wt%, the potassium of 0.8wt% and the palladium of 0.1wt%.Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules, does not substantially have the load component to exist in radius is half spherical nucleus of catalyst granules radius.
Embodiment 4
With nickel nitrate [Ni (NO
3)
26H
2O], lanthanum nitrate [La (NO
3)
36H
2O], potassium nitrate (K NO
3) be dissolved in and make the aqueous solution in the water, then the pH value with the ammoniacal liquor regulator solution is 6.4, adopts the equivalent impregnation method to flood above-mentioned alumina support, all the other steps are with embodiment 1, make catalyst D, in catalyst weight (wt), contain the nickel of 20wt%, lanthanum and the 2.0wt%K of 0.5wt%.Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules, does not substantially have the load component to exist in radius is half spherical nucleus of catalyst granules radius.
With nickel nitrate [Ni (NO
3)
26H
2O], copper nitrate [Cu (NO
3)
26H
2O], manganese nitrate [Mn (NO
3)
2], potassium nitrate (KNO
3) be dissolved in and make the aqueous solution in the water, then the pH value with the ammoniacal liquor regulator solution is 6, adopt the equivalent impregnation method to flood above-mentioned alumina support, all the other steps are with embodiment 1, make catalyst E, in catalyst weight (wt), contain the nickel of 20wt%, the copper of 0.8wt%, the potassium of 1.8wt% and the manganese of 2.0wt%.Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules, does not substantially have the load component to exist in radius is half spherical nucleus of catalyst granules radius.
Embodiment 6
With nickel nitrate [Ni (NO
3)
26H
2O], lanthanum nitrate [La (NO
3)
36H
2O], magnesium nitrate [Mg (NO
3)
26H
2O], manganese nitrate Mn (NO
3)
2Be dissolved in and make the aqueous solution in the water, then the pH value with ammoniacal liquor and the common regulator solution of potassium hydroxide is 11, adopt the equivalent impregnation method to flood above-mentioned alumina support, all the other steps are with embodiment 1, make catalyst F, in catalyst weight (wt), contain the nickel of 11wt%, the lanthanum of 0.5wt%, the magnesium of 1.6wt%K, 1.0wt% and the manganese of 1.0wt%.Catalyst granules is cut in half, can be clear that, the load component is distributed in the perimeter of catalyst granules, does not substantially have the load component to exist in radius is half spherical nucleus of catalyst granules radius.
Comparative example 1
With nickel nitrate [Ni (NO
3)
26H
2O], lanthanum nitrate [La (NO
3)
36H
2O], manganese nitrate Mn (NO
3)
2Be dissolved in and make the aqueous solution in the water, adopt the equivalent impregnation method to flood above-mentioned alumina support, 110 ℃ of oven dry 4 hours, 350 ℃ of roastings 3 hours, then reduced 8 hours at 420 ℃ with hydrogen.Make catalyst G, in catalyst weight (wt), contain the nickel of 20wt%, lanthanum and the 2.0wt%K of 0.5wt%.Catalyst granules is cut in half, can be clear that, the load component is evenly distributed in the whole particle of catalyst substantially.
Embodiment 7
Respectively 200 milliliters of catalyst A～G are loaded in the stainless steel single tube reactor, behind the nitrogen replacement, logical hydrogen also boosts to reaction pressure, is warmed up to reaction temperature, heat-insulation pressure keeping 24 hours, then charging.The volume ratio of raw material octenal and sec-n-octyl alcohol is 1: 5, and concrete reaction condition is listed in the table 1.
Table 1 catalyst and appreciation condition thereof and evaluation result
Conversion ratio %=(1-product Raw aldehyde % ÷ 20%) * 100%
Octanol content %-80% in the selective %=[(product) ÷ (20%-product Raw aldehyde %)] * 100%
Show from the experimental result of table 1, use the egg-shell catalyst of ionizing radiation method preparation of the present invention, high for the octenal reactivity, selectively good.
Claims (11)
1. eggshell type nickel-based dual-functional hydrogenation catalyst, it is characterized in that, described catalyst comprises carrier and the load component that loads on the carrier, described load group is divided and is comprised that nickel active component, the first promoter and the second promoter, described load component precursor are compound corresponding to described load component; Described catalyst contains the nickel active component of 10wt%～40wt%, described the first promoter is thulium, described the second promoter is alkali metal, alkali earth metal and/or transition metal, Active components distribution more than 90% at carrier surface in half degree of depth and the zone between the surface of center or central shaft, the preparation process of described catalyst comprises: have described load group to divide the described carrier of precursor load, use contains the solution-wet of free radical scavenger, under wetting state described carrier is carried out ionizing radiation; Carrier behind the ionizing radiation is carried out drying, make described catalyst.
2. eggshell type nickel-based dual-functional hydrogenation catalyst as claimed in claim 1, it is characterized in that, described alkali metal is at least a among Li, Na, K and the Cs, described alkali earth metal is at least a among Mg, Ca and the Ba, and described transition metal is at least a among Mn, Co, Cu, Zn, Mo, Pd and the Bi.
3. eggshell type nickel-based dual-functional hydrogenation catalyst as claimed in claim 1 is characterized in that, the Active components distribution more than 95% at carrier surface in half degree of depth and the zone between the surface of center or central shaft.
4. eggshell type nickel-based dual-functional hydrogenation catalyst as claimed in claim 1 is characterized in that, described carrier is aluminium oxide, silica, active carbon, titanium dioxide, molecular sieve or two or more mixture in them.
5. eggshell type nickel-based dual-functional hydrogenation catalyst as claimed in claim 1 is characterized in that, spray or infusion process are adopted in the load of the load component of described catalyst, and spray or dipping are that the pH value is 5～12 nickel salt solution with liquid.
6. preparation method such as the described eggshell type nickel-based dual-functional hydrogenation catalyst of one of claim 1～5, it is characterized in that, there is described load group to divide the described carrier of precursor load, uses the solution-wet that contains free radical scavenger, under wetting state, described carrier is carried out ionizing radiation; Carrier behind the ionizing radiation is carried out drying, make described catalyst; Described load component precursor is compound corresponding to described load component.
7. preparation method as claimed in claim 6, it is characterized in that, described free radical scavenger is at least a in the derivative of alcohols, C1～C5 alcohols of C1～C5 and the organic acid, and the alcohols of described C1～C5 is preferably selected from ethanol, ethylene glycol, isopropyl alcohol and the tert-butyl alcohol; Described organic acid is preferably formic acid.
8. preparation method as claimed in claim 6 is characterized in that, the solvent of described radicals scavenging agent solution is water, is used for load is had the wetting radicals scavenging agent solution of carrier of load component, and the volume ratio of its free radical scavenger and water is 20～80:100; Be used for load is had the radicals scavenging agent solution of the carrier submergence of load component, wherein the volume ratio of free radical scavenger and water is 1～50:100.
9. preparation method as claimed in claim 6 is characterized in that, described ionizing radiation is gamma-rays, X ray or electron beam irradiation, and absorbed dose rate is 10～10000Gy/min, is preferably 20～100Gy/min, and absorbed dose of radiation is 0.01～1 * 10
5KGy.
10. be applied in the technique by carbonyl and double-bond hydrogenation such as the described eggshell type nickel-based dual-functional hydrogenation catalyst of one of claim 1～5.
11. be applied in the technique of aldehyde hydrogenation synthol such as the described eggshell type nickel-based dual-functional hydrogenation catalyst of one of claim 1～5.
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| US9670120B2 (en) | 2015-01-27 | 2017-06-06 | Celanese International Corporation | Process for producing ethanol using a solid catalyst |
| WO2016122465A1 (en) | 2015-01-27 | 2016-08-04 | Celanese International Corporation | Process for producing ethanol using solid catalysts |
| CN112756004B (en) * | 2019-11-04 | 2022-09-20 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and preparation method and application thereof |
| CN114345369B (en) * | 2022-01-12 | 2023-05-30 | 万华化学集团股份有限公司 | Acetyloxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
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