CN107597108B - A kind of naphthane adds hydrogen to prepare catalyst of decahydronaphthalene and its preparation method and application - Google Patents
A kind of naphthane adds hydrogen to prepare catalyst of decahydronaphthalene and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of naphthanes, and hydrogen to be added to prepare the catalyst and its preparation method and application of decahydronaphthalene.The catalyst is made of active component, auxiliary agent and carrier, is more evenly distributed in active component and auxiliary agent on carrier using equi-volume impregnating, is improved the dispersion degree of active component and auxiliary agent, is reduced the dosage of active component, improve decahydronaphthalene instead along than.Active component is Pt, Pd etc., the oxide of auxiliary agent Zn, Ni, Mg, Ce, Zr, La, Fe, Cu, Co, carrier Al2O3、SiO2、TiO2With one of ZSM-5 molecular sieve etc. or several combinations.The preparation-obtained catalyst of the present invention can be used as the secondary hydrogenation catalyst of two-step method, and bullion content is low, and catalytic activity is high, and reaction condition is moderate, and preparation method simple possible, economic benefit is good, have preferable prospects for commercial application.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of naphthane adds hydrogen to prepare the catalyst of decahydronaphthalene
And its preparation method and application.
Background technique
Decahydronaphthalene is a kind of high-performance solvent, be mainly used for dry spinning polyethylene fibre, as aviation kerosine and
Battery hydrogen storage material etc..The thermal stability of trans-decalin is higher, is to improve the essential substance of aviation kerosine thermal stability,
It is also used as the raw material of preparation high quality liquid crystal material；Cis-decaline mainly for the production of decanedioic acid so that produce nylon 6,
Nylon 10 and plasticizer.The sold decahydronaphthalene of existing market is instead along than between 2-4, decahydronaphthalene is instead along more than its higher stability
Height, price is also higher, but prepares also more difficult.It there is no mature decahydronaphthalene instead along than the production technology and catalysis higher than 4 at present
Agent.
Crude naphthalene catalytic hydrogenation is the main technique of current production decahydronaphthalene, but in crude naphthalene containing a large amount of sulphur, nitrogen and
Beavy metal impurity, it is serious to catalyst poisoning effect, cause catalyst reduced service life.China's crude naphthalene is mainly derived from coal
Tar, it is resourceful, therefore add hydrogen to prepare decahydronaphthalene by crude naphthalene will to greatly improve its added value, while can also alleviate certain
Environmental protection pressure.
The prior art adds hydrogen to prepare decahydronaphthalene there are two types of method with crude naphthalene, and one is one step Deep catalytics of crude naphthalene to add hydrogen
Method.
Such as Chinese patent application CN102838439A discloses a kind of method that naphthalene adds hydrogen to produce decahydronaphthalene, this method is adopted
With fixed bed continuously hydrogen adding technique, naphthalene carries out hydrogenation reaction, used hydroconversion condition are as follows: hydrogen under reduction-state nickel-base catalyst
Gas divides 0.2MPa-10MPa, and 120 DEG C -320 DEG C of reaction temperature, liquid volume air speed is 0.5h-1-4.0h-1, hydrogen-oil ratio is
300-500.The process flow is shorter and catalyst cost is relatively low, but its poor catalyst stability, by-product is more in product.
CN104645976A discloses a kind of catalyst and preparation method thereof for adding hydrogen production decahydronaphthalene for one step of naphthalene, should
Catalyst is loaded catalyst, is made of active component and carrier, and active component is platinum, carrier Al2O3、ZrO2Or TiO2,
It can be normal pressure~3.0MPa in pressure, temperature is 200~300 DEG C, and air speed is 1000~3000h using the catalyst-1Under mention
High naphthalene adds the selectivity and conversion ratio of hydrogen decahydronaphthalene.
Patent application CN102320913A discloses " a method of synthesis decahydronaphthalene ", and this method is with loading type Pd/γ-
Al2O3As catalyst, using fixed bed continuously hydrogen adding technique, used hydroconversion condition are as follows: reaction temperature is 100-280 DEG C,
Reaction pressure is 1.5-4.0MPa, and mass space velocity is 0.5-2.0h when liquid-1, hydrogen-oil ratio 80-1000.Although naphthalene turns in experiment
Rate is up to 99.92%, and decahydronaphthalene yield reaches 99.36%, but Pd content is up to 1% in the catalyst, catalyst at
This valuableness.Sulphur nitrogen content is higher in crude naphthalene simultaneously, will cause serious murder by poisoning to noble metal, reduces its service life.
CN102941093A is disclosed " naphthalene adds hydrogen to prepare decahydronaphthalene and preparation method and application ", catalyst composition are as follows:
On the basis of the weight of catalyst, the active component of 10%-50%, the promoter metal of 0.1%-25%, remaining is carrier.China
Patent CN102836737A discloses " a kind of naphthalene hydrogenation catalyst and preparation method thereof ", the composition of catalyst are as follows: with catalysis
On the basis of the weight of agent, the content of ZSM-5 molecular sieve is 10%-80%, and the content of alkali metal is 1%-10%, group VIII gold
The content of category is 0.1%-3.0%, the silica of the content of auxiliary agent 0.1%-5% and surplus based on the element, and the auxiliary agent is
One or more of tin, lead, rhenium composition.Above-mentioned two patent prepares decahydronaphthalene by naphthalene direct hydrogenation, although catalyst system
The simple use cost of Preparation Method is low, but catalysis reaction in side reaction it is more, it is obtained that product purity is low, cannot selectivity system
It is standby anti-along decahydronaphthalene, limit the purposes of decahydronaphthalene.
The method of above-mentioned step decahydronaphthalene, universal impurity in products is more, simultaneously as technique limits, catalyst is easily poisoned
Inactivation, service life are shorter.
The method that another kind prepares decahydronaphthalene is two-step method, first hydrogenates naphthalene and generates the higher naphthane of purity, then with four
Hydrogen naphthalene prepares decahydronaphthalene, and this method product purity is relatively high, but second step reaction is more difficult, and need to improve catalyst adds hydrogen
Performance.
The present inventor passes through early-stage study, and a kind of two-step method work is disclosed in patent application CN106565398A
Industry naphthalene adds the method for hydrogen production decahydronaphthalene, using Ni-Mo series catalysts as one-stage hydrogenation catalyst, to add using crude naphthalene as raw material
Sulphur nitrogen impurity in hydrogen removing raw material is tentatively hydrogenated to naphthane and decahydronaphthalene simultaneously, then will through zinc oxide adsorption fine de-sulfur
Sulfur content takes off to 1ppm hereinafter, obtained product is then carried out secondary hydrogenation, the catalyst which uses
For nickel catalyst, catalyst shows stronger hydrogenation activity, is finally obtained with low cost, high conversion and high yield high
The decahydronaphthalene of purity.
But the prior art whether uses one-step method or two-step method, in addition to respectively having catalyst to be easily poisoned, use
The deficiencies such as the service life is short, purity is low are outer, also there are problems that decahydronaphthalene instead along than low (nearly all lower than 4), is unable to satisfy market
Demand to high stability decahydronaphthalene product.Therefore, be based on existing two-step method, develop it is a kind of have it is higher it is anti-along than, high turn
Rate and highly selective decahydronaphthalene catalyst are of great significance.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of naphthanes, and hydrogen to be added to prepare decahydronaphthalene
Catalyst and its preparation method and application.The catalyst is used for the step that naphthane adds hydrogen to prepare decahydronaphthalene in two-step method decahydronaphthalene
Suddenly, the anti-along than making product obtain higher stability, at low cost, high conversion rate, selection of product decahydronaphthalene can be effectively improved
Property is good.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of naphthane adds hydrogen to prepare the catalyst of decahydronaphthalene, containing active component, catalyst promoter and catalyst carrier,
On the basis of the weight of catalyst, wherein the active component is the noble metals such as Pt, Pd that mass content is 0.05%-0.3%
The combination of middle one or more；The catalyst promoter be mass content be Zn, Ni of 1%-6%, Mg, Ce, Zr, La, Fe,
One of oxide of Cu, Co etc. or several combinations；The catalyst carrier is that mass content is 93.7%-
98.95% Al2O3、SiO2、TiO2With combination one or more of in ZSM-5 molecular sieve.
Some specific embodiments according to the present invention, above-mentioned naphthane add hydrogen to prepare the catalyst of decahydronaphthalene, the activity
Component is Pd the Pt-Pd metallic combination that mass content is 0.15%-0.3%, and the mass content of Pd is not less than 0.15%.
It was found by the inventors of the present invention that the content of Pd is higher, institute using the catalyst of preparation method preparation two-step method of the invention
Catalyst is obtained more to be conducive to improve the anti-along than when the mass content of Pd is not less than 0.15%, energy is effectively of decahydronaphthalene product
Guarantee the anti-along than being higher than 4 of decahydronaphthalene product.
Some specific embodiments according to the present invention, above-mentioned naphthane add hydrogen to prepare the catalyst of decahydronaphthalene, the catalysis
Agent aid is CuO, MgO, ZnO, NiO, CeO, ZrO or Co that mass content is 1%-6%2O3One or more of.Catalyst
The type of auxiliary agent is to the anti-suitable than also having an impact of decahydronaphthalene product, when active component is identical, Co2O3> NiO > CuO > MgO >
ZnO > CeO, ZrO.Preferred catalyst promoter is the Co that mass content is 1%-6%2O3, one of NiO, CuO, MgO or
A combination thereof.It is not less than 0.15%, Co in the mass content of Pd2O3, NiO, CuO, MgO make auxiliary agent, according to the method for the present invention be made urge
Agent, decahydronaphthalene product it is anti-along than be higher than 5.
Some specific embodiments according to the present invention, above-mentioned naphthane add hydrogen to prepare the catalyst of decahydronaphthalene, the activity
Component is the Pd that mass content is 0.3%, and the catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO group
It closes.The preferred technical solution guarantee in 1000h long period test naphthane conversion ratio and decahydronaphthalene selectivity it is higher
While (being maintained at 99% or more for a long time), the anti-along than being up to 7 or more of decahydronaphthalene can be made for a long time, keep product with higher steady
It is qualitative.And the anti-of the decahydronaphthalene that other catalysts obtain declines, substantially less than 7 along than that can increase with the reaction time.
Some specific embodiments according to the present invention, above-mentioned naphthane add hydrogen to prepare the catalyst of decahydronaphthalene, the activity
Component is the Pd that mass content is 0.3%, and the catalyst promoter is mass content 6%Co2O3.The preferred technical solution can
The selectivity of the conversion ratio and decahydronaphthalene that make naphthane reaches 100%, and decahydronaphthalene is anti-along than reaching 12.7, and effect is made us
It is pleasantly surprised.
The present invention also provides a kind of method for preparing the catalyst that above-mentioned naphthane adds hydrogen to prepare decahydronaphthalene, including it is following
Step:
(1) by the catalyst carrier ball milling 5h, 200 meshes are crossed, then in 400~500 DEG C of air atmospheres roasting 4~
6h obtains carrier A；
(2) formulation aid precursor solution, adjusting its pH value with acid solution is 1~5, according to needed for incipient impregnation
Amount, takes the maceration extract of corresponding amount；Carrier A is weighed again pour into and stir and evenly mix 20~40min in maceration extract, then stand at room temperature
It is aged 10~14h, drying takes out and roasts 1~10h in 400~500 DEG C of air atmospheres, obtains carrier B；
(3) noble metal precursor liquid solution is prepared, adjusting its pH value with acid solution is 1~5, by needed for incipient impregnation
Amount, takes the maceration extract of corresponding amount；Obtained carrier B in step (2) is fallen and stirs and evenly mixs 20~40min in maceration extract, then
Still aging 10~14h at room temperature, drying, is added suitable quantity of water and binder and its kneading is squeezed into item, the molding column of institute
Particle diameter is 3~5mm, and particle length is 6~15mm, then by obtained cylindrical particle in 400~500 DEG C of air atmospheres
1~10h is roasted, sample C is obtained；
(4) reducing agent solution is prepared, sample C is immersed in reducing agent solution, stands 2-24h, takes out sample C distilled water
Washing 1-5 times, drying obtains the catalyst in 90~120 DEG C of baking ovens.
Some specific embodiments according to the present invention, in above-mentioned preparation method, step (2) adjuvant used precursor solution is
Zn(NO3)2、Ni(NO3)2、Ce(NO3)3、Mg(NO3)2、Zr(NO3)4、La(NO3)3、Fe(NO3)3、Cu(NO3)2、Co(NO3)3In
Any one or several mixed solutions；Step (3) the noble metal precursor liquid solution is chloroplatinic acid, in palladium chloride
The mixed solution of any one or two kinds.
Some specific embodiments according to the present invention, in above-mentioned preparation method, step (2) and (3) described acid solution are
Dilute hydrochloric acid, dust technology, any one or several mixing in spirit of vinegar.
Some specific embodiments according to the present invention, in above-mentioned preparation method, step (3) binder is that activity is white
Soil, kaolin, mixing one or two kinds of in sesbania powder.
In above-mentioned preparation method, step (4) reducing agent is one in formaldehyde, hydrazine hydrate, sodium borohydride and potassium borohydride
Kind or two kinds of mixing.Some specific embodiments according to the present invention, selection is sodium borohydride.
The catalyst for adding hydrogen to prepare decahydronaphthalene invention further provides above-mentioned naphthane is preparing answering in decahydronaphthalene
With, first by the catalyst 150-400 DEG C, hydrogen partial pressure be 0.5-5MPa condition restore 1-20h.
Further, in above-mentioned application, the reaction temperature of the catalyst is 150-400 DEG C, pressure 0.5-10MPa,
Volume space velocity is 0.5-8h when liquid-1, hydrogen-oil ratio 100-2000.
The positive effect of the present invention is:
1. the present invention uses equi-volume impregnating, it is more evenly distributed in active component and auxiliary agent on carrier, improves
The dispersion degree of active component and auxiliary agent, reduces the dosage of active component, and catalyst obtained is highly suitable for naphthane and adds hydrogen system
Standby decahydronaphthalene can effectively improve the anti-along than increasing the stabilization of product of the yield and purity of decahydronaphthalene, especially raising decahydronaphthalene
Property, some preferred embodiments especially of the invention, decahydronaphthalene more preferably reaches 5 or more, more instead along than that can reach 4 or more
Reach 12.7 excellently, provides preferable technical foundation to prepare the decahydronaphthalene product of high-quality.
2. adding hydrogen to prepare the crude naphthalene of the patent application CN106565398A of catalyst combination early-stage study of the invention
The method use in conjunction of naphthane is more advantageous to the service life for extending catalyst, reduces the use cost of catalyst.
3. the present invention also obtains the technological parameter of suitable catalyst application of the present invention through numerous studies, prepared for naphthane
Decahydronaphthalene provides preferable operating condition.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the catalysis detection device that the embodiment of the present invention is used；
Wherein, 1-mass flowmenter (gas and liquid), 2-three-way ball valves, 3-ball valves, 4-gasification furnaces, 5-catalysis
Agent reactor, 6-temperature indicators, 7-condensers, 8-plunger pumps, 9-fluid reservoirs, 10-counterbalance valves, 11-vent gas treatments
Tank.
Fig. 2 is that naphthane conversion ratio and decahydronaphthalene of the catalyst D7 and D11 in 1000h life experiment selectively change
Figure, wherein 1 is D7,2 be D11；
Fig. 3 is that catalyst D7 and D11 is catalyzed the anti-suitable than variation diagram of decahydronaphthalene in 1000h life experiment, wherein 1 is
D7,2 be D11.
Specific embodiment
Naphthane provided by the invention adds hydrogen to prepare the catalyst of decahydronaphthalene, containing active component, catalyst promoter and urges
Agent carrier, wherein the active component is one or more of in the noble metals such as Pt, Pd that mass content is 0.05%-0.3%
Combination；The catalyst promoter is the oxidation of Zn, Ni, Mg, Ce, Zr, La, Fe, Cu, Co that mass content is 1%-6% etc.
One or more of combination in object；The catalyst carrier is the Al that mass content is 93.7%-98.95%2O3Powder, SiO2
Powder, TiO2One or more of combination in powder and ZSM-5 molecular sieve powder etc..
In some preferred embodiments, the active component is the Pd noble metal that mass content is 0.3%；The catalysis
Agent aid is the Co that mass content is 6%2O3Combination；More preferably, the active component is the Pd that mass content is 0.3%, described
Catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO combination.The inventors found that the active group
It point is the Pd that mass content is 0.3%, the catalyst promoter is that mass content is 2%Co2O3The combination of+2%NiO+2%MgO
When the catalyst that is prepared into, the selectivity of conversion ratio and decahydronaphthalene that naphthane can be made in the experiment of 1000h long period reaches
99% or more, and decahydronaphthalene is anti-along reaching 7 or more than for a long time.
Catalyst of the invention is prepared by following preparation method:
(1) by the catalyst carrier ball milling 5h, 200 meshes are crossed, then in 400~500 DEG C of air atmospheres roasting 4~
6h obtains carrier A；
(2) formulation aid precursor solution, adjusting its pH value with acid solution is 1~5, according to needed for incipient impregnation
Amount, takes the maceration extract of corresponding amount；Carrier A is weighed again pour into and stir and evenly mix 20~40min in maceration extract, then stand at room temperature
It is aged 10~14h, drying takes out and roasts 1~10h in 400~500 DEG C of air atmospheres, obtains carrier B；
(3) noble metal precursor liquid solution is prepared, adjusting its pH value with acid solution is 1~5, by needed for incipient impregnation
Amount, takes the maceration extract of corresponding amount；Obtained carrier B in step (2) is fallen and stirs and evenly mixs 20~40min in maceration extract, then
Still aging 10~14h at room temperature, drying, is added suitable quantity of water and binder and its kneading is squeezed into item, the molding column of institute
Particle diameter is 3~5mm, and particle length is 6~15mm, then by obtained cylindrical particle in 400~500 DEG C of air atmospheres
1~10h is roasted, sample C is obtained；
(4) reducing agent solution is prepared, sample C is immersed in reducing agent solution, stands 2-24h, takes out sample C distilled water
Washing 1-5 times, drying obtains the catalyst in 90~120 DEG C of baking ovens.
It is illustrated below by way of specific embodiment is further to summary of the invention of the invention, but should not be construed as the present invention
Range be only limitted to example below, invention thinking according to the present invention and entire contents, can will be each in following instance
Technical characteristic makes combination/replacement/adjustment/modification appropriate etc., this is will be obvious to those skilled in the art that still
Belong to the scope that the present invention protects.
Embodiment 1:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A1；
(2) it weighs 11.5g magnesium nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A1 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 1；
(3) it weighs 2g palladium chloride to be dissolved in 200ml deionized water, it is 4 that hydrochloric acid solution, which is added dropwise, and adjusts its pH value, is obtained
(a) solution.It measures 15ml (a) solution to be added in 2.5L plastic beaker, then adds 35ml deionized water and stir and evenly mix；It will
(2) carrier B 1 being prepared in, which is poured into rapidly, stirs and evenly mixs 30min in plastic beaker, then still aging 12h at room temperature,
12h is dried under the conditions of 120 DEG C.It weighs 1g sesbania powder to be dissolved in 5g deionized water, by itself and the sample blending after drying, then
Pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then by obtained cylindrical particle 120
12h is dried under the conditions of DEG C, taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C1.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C1 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C1 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D1.
Embodiment 2:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A2；
(2) it weighs 4.5g cerium nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A2 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 2；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 2 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C2.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C2 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C2 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D2.
Embodiment 3:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A3；
(2) five water zirconium nitrate of 6.3g, which is dissolved in 50ml deionized water, obtains compounding agent solution, adjusts its pH value with nitric acid solution
It is 4, places it in 2.5L plastic beaker；It weighs 28.11g carrier A3 and pours into rapidly and stir and evenly mix 30min in plastic beaker, so
Still aging 12h at room temperature afterwards, dries 12h in 100 DEG C of baking ovens, and taking-up roasts 5h in 450 DEG C of air atmospheres, carried
Body B3；
(3) measure and make (a) solution 25ml in case 1 and be added in 2.5L plastic beaker, then add 25ml go from
Sub- water stirs and evenly mixs；The carrier B 3 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then in room
Still aging 12h under temperature dries 12h under the conditions of 120 DEG C.It weighs 1g sesbania powder to be dissolved in 5g deionized water, by itself and drying
Sample blending afterwards, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then by gained
To cylindrical particle dry 12h under the conditions of 120 DEG C, taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C3.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C3 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C3 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D3.
Embodiment 4:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A4；
(2) it weighs 5.44g nitrate trihydrate copper and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A4 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 4；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 4 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C4.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C4 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C4 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D4.
Embodiment 5:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A5；
(2) it weighs six water nickel nitrate of 7.0g and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A5 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 5；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 5 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C5.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C3 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C3 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D5.
Embodiment 6:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A6；
(2) it weighs 6.61g zinc nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A6 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 6；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 6 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C6.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C6 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C6 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D6.
Embodiment 7:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A7；
(2) it weighs 6.3g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A7 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 7；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 7 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C7.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C7 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C7 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D7.
Embodiment 8:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A8；
(2) it weighs 1.05g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 29.61g carrier A8 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 8；
(3) it measures configured (a) solution 15ml in case 1 to be added in 2.5L plastic beaker, then adds 35ml
Deionized water stirs and evenly mixs；The carrier B 8 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C8.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C8 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C8 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D8.
Embodiment 9:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier A9；
(2) it weighs 6.3g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A9 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 9；
(3) it measures configured (a) solution 10ml in case 1 to be added in 2.5L plastic beaker, then adds 40ml
Deionized water stirs and evenly mixs；The carrier B 9 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then
Still aging 12h at room temperature dries 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with
Sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then is incited somebody to action
Obtained cylindrical particle dries 12h under the conditions of 120 DEG C, and taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C9.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C9 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C9 and is washed with distilled water 4 times, dries 12h in 120 DEG C of baking ovens
Obtain catalyst D9.
Embodiment 10:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier
A10；
(2) it weighs 6.3g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A10 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 10；
(3) measure in case study on implementation 1 that each 3ml of (b) solution is added to 2.5L plastic beaker in (a) solution and case study on implementation 5
In, it then adds 47ml deionized water and stirs and evenly mixs；The carrier B 10 being prepared in (2) is poured into plastic beaker rapidly
30min is stirred and evenly mixed, then still aging 12h at room temperature, dries 12h under the conditions of 120 DEG C.It weighs 1g sesbania powder and is dissolved in 5g
In deionized water, by itself and the sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm,
Grain length is 8mm, then obtained cylindrical particle is dried 12h under the conditions of 120 DEG C, and taking-up roasts in 450 DEG C of air atmospheres
5h is burnt, sample C10 is obtained.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C10 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C10 and is washed with distilled water 4 times, dries in 120 DEG C of baking ovens
12h obtains catalyst D10.
Embodiment 11:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier
A11；
(2) 3.83g nitrate trihydrate magnesium, six water nickel nitrate of 2.33g and 2.1g cobalt nitrate hexahydrate are weighed and is dissolved in 50ml deionization
Compounding agent solution is obtained in water, adjusting its pH value with nitric acid solution is 4, is placed it in 2.5L plastic beaker；Weigh 29.67g load
Body A11, which is poured into rapidly, stirs and evenly mixs 30min in plastic beaker, then still aging 12h at room temperature, dries in 100 DEG C of baking ovens
Dry 12h, taking-up roast 5h in 450 DEG C of air atmospheres, obtain carrier B 11；
(3) measure in case study on implementation 1 that each 15ml of (b) solution is added to 2.5L plastic beaker in (a) solution and case study on implementation 5
In, it then adds 35ml deionized water and stirs and evenly mixs；The carrier B 10 being prepared in (2) is poured into plastic beaker rapidly
30min is stirred and evenly mixed, then still aging 12h at room temperature, dries 12h under the conditions of 120 DEG C.It weighs 1g sesbania powder and is dissolved in 5g
In deionized water, by itself and the sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm,
Grain length is 8mm, then obtained cylindrical particle is dried 12h under the conditions of 120 DEG C, and taking-up roasts in 450 DEG C of air atmospheres
5h is burnt, sample C10 is obtained.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C11 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C11 and is washed with distilled water 4 times, dries in 120 DEG C of baking ovens
12h obtains catalyst D11.
Embodiment 12:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier
A12；
(2) it weighs 6.3g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A12 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 12；
(3) it weighs 1.66g chloroplatinic acid (platinum content 38%) to be dissolved in 100ml deionized water, hydrochloric acid solution is added dropwise and adjusts it
PH value is 4, obtains (b) solution.It measures 15ml (b) solution to be added in 2.5L plastic beaker, then adds 35ml deionization
Water stirs and evenly mixs；The carrier B 12 being prepared in (2) is poured into rapidly and stirs and evenly mixs 30min in plastic beaker, then in room temperature
Under still aging 12h, dry 12h under the conditions of 120 DEG C.1g sesbania powder is weighed to be dissolved in 5g deionized water, by its with after drying
Sample blending, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is 4mm, particle length 8mm, then will obtained by
Cylindrical particle dry 12h under the conditions of 120 DEG C, taking-up roasts 5h in 450 DEG C of air atmospheres, obtains sample C12.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C12 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C12 and is washed with distilled water 4 times, dries in 120 DEG C of baking ovens
12h obtains catalyst D12.
Embodiment 13:
(1) by Al2O3Carrier ball milling 5h crosses 200 meshes, then roasts 5h in 450 DEG C of air atmospheres, obtain carrier
A13；
(2) it weighs 6.3g cobalt nitrate hexahydrate and is dissolved in 50ml deionized water and obtain compounding agent solution, adjust it with nitric acid solution
PH value is 4, is placed it in 2.5L plastic beaker；It weighs 28.11g carrier A13 and pours into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, and taking-up roasts in 450 DEG C of air atmospheres
5h obtains carrier B 13；
(3) measure in case study on implementation 1 that (c) solution 7.5ml is added to 2.5L modeling in (a) solution 7.5ml and case study on implementation 12
Expect then to add 35ml deionized water in beaker and stir and evenly mix；The carrier B 13 being prepared in (2) is poured into rapidly plastics
30min is stirred and evenly mixed in beaker, then still aging 12h at room temperature, dry 12h under the conditions of 120 DEG C.Weigh 1g sesbania powder
It is dissolved in 5g deionized water, by itself and the sample blending after drying, then pinching is pressed into item, and the molding cylindrical particle diameter of institute is
4mm, particle length 8mm, then obtained cylindrical particle is dried into 12h under the conditions of 120 DEG C, it takes out in 450 DEG C of air atmospheres
Middle roasting 5h is enclosed, sample C13 is obtained.
(4) it weighs 2g sodium borohydride to be dissolved in 100ml deionized water, then place it in ice-water bath, by sample
C12 is added in sodium borohydride solution, is stood for 24 hours, is taken out sample C13 and is washed with distilled water 4 times, dries in 120 DEG C of baking ovens
12h obtains catalyst D13.
Comparative example
Pd/ γ-the Al that load capacity according to the preparation of 2 method of patent application CN102320913A embodiment is 0.3%2O3It urges
Agent.
Active testing:
The performance evaluation that carries out catalyst, catalysis detection are led directly in reaction tube in the tempering of diameter 20mm and a length of 700mm
Device is as shown in Figure 1, the amount of fill of catalyst is 20ml.First 200 DEG C, hydrogen partial pressure be 0.5MPa under the conditions of by embodiment
1~13 catalyst reduction 2h.Catalyst reaction temperatures are 230 DEG C, pressure 3MPa, liquid when volume space velocity be 2h-1, hydrogen-oil ratio
It is 600.Comparative example carries out a step catalytic hydrogenation to crude naphthalene according to literature method, detect be made decahydronaphthalene it is anti-it is suitable than.Use D7
1000h life experiment is carried out with D11, the naphthane conversion ratio and decahydronaphthalene for detecting each catalyst selectively change with time,
Fig. 2 is made.The decahydronaphthalene of each catalyst is detected instead along than changing with time, Fig. 3 is made.
1 catalyst activity parameter of table
According to testing result, compared with prior art, when active component is identical, the catalyst of the method for the present invention preparation is urged
The decahydronaphthalene of change is instead along than with significant advantage.Especially when active component is 0.3%Pd metal, the Co that adjuvant component is 6%2O3,
The decahydronaphthalene that the catalyst made from method of the invention is catalyzed is anti-suitable than being up to 12.7, the sold decahydro of existing market
Naphthalene is instead along than between 2-4, decahydronaphthalene is anti-suitable higher than its higher stability, and price is higher, and the method for the present invention is prepared
Catalyst performance it is excellent, be able to satisfy and require the higher market demand.
Shown in catalytic process by 1000h life experiment, the naphthane conversion ratio and decahydronaphthalene of D7 and D11 catalyst
Selectivity is maintained at 99% or more for a long time, and the anti-of the decahydronaphthalene being catalyzed becomes along than whole in what is fallen before and then tend to be steady
Gesture, when steady, catalyst D7's is anti-along than being maintained at 5.8 or so, and catalyst D11's is anti-suitable than being maintained at 7.5 or so, advantage compared with
It is obvious.
Claims (7)
1. a kind of naphthane adds hydrogen to prepare the catalyst of decahydronaphthalene, containing active component, catalyst promoter and catalyst carrier,
It is characterized in that, on the basis of the weight of catalyst, the active component is the Pd that mass content is 0.3%；The catalyst helps
Agent is that mass content is 2%Co2 O3 + 2%NiO+2%MgO combination；The catalyst carrier is that mass content is 93.7%-
98.95% Al2 O3 、SiO2 、TiO2 With combination one or more of in ZSM-5 molecular sieve, and the catalyst is by including
It is prepared by the method for following steps:
(1) by the catalyst carrier ball milling 5h, 200 meshes are crossed, 4~6h is then roasted in 400~500 DEG C of air atmospheres,
Obtain carrier A；
(2) formulation aid precursor solution, adjusting its pH value with acid solution is 1~5, according to incipient impregnation aequum, is taken
The maceration extract of corresponding amount；Carrier A is weighed again pouring into, 20~40min is stirred and evenly mixed in maceration extract, it is then still aging at room temperature
10~14h, drying take out and roast 1~10h in 400~500 DEG C of air atmospheres, obtain carrier B；
(3) noble metal precursor liquid solution is prepared, adjusting its pH value with acid solution is 1~5, by incipient impregnation aequum, is taken
The maceration extract of corresponding amount；Obtained carrier B in step (2) is poured into and stirs and evenly mixs 20~40min in maceration extract, then in room
Still aging 10~14h under temperature, drying, is added suitable quantity of water and binder and its kneading is squeezed into item, the molding cylindrical particle of institute
Diameter is 3~5mm, and particle length is 6~15mm, then obtained cylindrical particle is roasted in 400~500 DEG C of air atmospheres
1~10h obtains sample C；
(4) reducing agent solution is prepared, sample C is immersed in reducing agent solution, stands 2-24h, sample C is taken out and is washed with distilled water
1-5 times, drying obtains the catalyst in 90~120 DEG C of baking ovens.
2. a kind of method for preparing the catalyst that naphthane described in claim 1 adds hydrogen to prepare decahydronaphthalene, which is characterized in that packet
Include following steps:
(1) by the catalyst carrier ball milling 5h, 200 meshes are crossed, 4~6h is then roasted in 400~500 DEG C of air atmospheres,
Obtain carrier A；
(2) formulation aid precursor solution, adjusting its pH value with acid solution is 1~5, according to incipient impregnation aequum, is taken
The maceration extract of corresponding amount；Carrier A is weighed again pouring into, 20~40min is stirred and evenly mixed in maceration extract, it is then still aging at room temperature
10~14h, drying take out and roast 1~10h in 400~500 DEG C of air atmospheres, obtain carrier B；
(3) noble metal precursor liquid solution is prepared, adjusting its pH value with acid solution is 1~5, by incipient impregnation aequum, is taken
The maceration extract of corresponding amount；Obtained carrier B in step (2) is poured into and stirs and evenly mixs 20~40min in maceration extract, then in room
Still aging 10~14h under temperature, drying, is added suitable quantity of water and binder and its kneading is squeezed into item, the molding cylindrical particle of institute
Diameter is 3~5mm, and particle length is 6~15mm, then obtained cylindrical particle is roasted in 400~500 DEG C of air atmospheres
1~10h obtains sample C；
(4) reducing agent solution is prepared, sample C is immersed in reducing agent solution, stands 2-24h, sample C is taken out and is washed with distilled water
1-5 times, drying obtains the catalyst in 90~120 DEG C of baking ovens.
3. preparation method according to claim 2, which is characterized in that step (2) adjuvant used precursor solution is Ni
(NO3)2、Mg(NO3)2、Co(NO3)3, step (3) the noble metal precursor liquid solution is palladium dichloride solution.
4. preparation method according to claim 2, which is characterized in that step (2) and (3) described acid solution are dilute salt
Acid, dust technology, any one or several mixing, step (3) binder in spirit of vinegar are atlapulgite, kaolinite
One or two kinds of mixing in soil, sesbania powder.
5. preparation method according to claim 2, which is characterized in that step (4) reducing agent be formaldehyde, hydrazine hydrate,
One or two kinds of mixing in sodium borohydride and potassium borohydride.
6. the catalyst that naphthane described in claim 1 adds hydrogen to prepare decahydronaphthalene is preparing the application in decahydronaphthalene, feature
It is, is first that 0.5-5MPa condition restores 1-20h in 150-400 DEG C, hydrogen partial pressure by the catalyst.
7. application according to claim 6, which is characterized in that the reaction temperature of the catalyst is 150-400 DEG C, pressure
Volume space velocity is 0.5-8h when for 0.5-10MPa, liquid-1, hydrogen-oil ratio 100-2000.
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| CN109647457A (en) * | 2018-12-06 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene adds the catalyst and preparation method and application of hydrogen naphthane and decahydronaphthalene |
| CN109772311A (en) * | 2019-01-31 | 2019-05-21 | 郑州大学 | A kind of toluene complete hydrogenation hexahydrotoluene loaded catalyst and preparation method thereof, application method |
| CN110681398A (en) * | 2019-10-25 | 2020-01-14 | 西南化工研究设计院有限公司 | Noble metal catalyst for purifying carbon dioxide gas and preparation and application thereof |
| CN110975867A (en) * | 2019-12-12 | 2020-04-10 | 山西大学 | Pd-ZnO/Al2O3Catalyst, preparation method and application thereof |
| CN111569901B (en) * | 2020-05-14 | 2023-08-29 | 上海簇睿低碳能源技术有限公司 | Preparation method and application of non-noble metal and noble metal bimetallic catalyst for hydrogenation and dehydrogenation of organic hydrogen storage material |
| CN111545205B (en) * | 2020-05-29 | 2023-08-11 | 山东京博石油化工有限公司 | Catalyst for selective alkyne removal of catalytic cracking dry gas and preparation method and application thereof |
| CN117643897B (en) * | 2024-01-29 | 2024-05-03 | 成都岷山绿氢能源有限公司 | Selective semi-hydrogenation catalyst for N-heterocycle and preparation method thereof |
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