CN105536800A - Synthesis method of Ni/ZrO2 hydrogenation catalyst and application of catalyst in hydrogenation catalysis reaction - Google Patents

Synthesis method of Ni/ZrO2 hydrogenation catalyst and application of catalyst in hydrogenation catalysis reaction Download PDF

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CN105536800A
CN105536800A CN201510881545.2A CN201510881545A CN105536800A CN 105536800 A CN105536800 A CN 105536800A CN 201510881545 A CN201510881545 A CN 201510881545A CN 105536800 A CN105536800 A CN 105536800A
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catalyst
reaction
zro
hydrogenation
temperature
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CN105536800B (en
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陈超
王慧泽
彭艳
赵丹
张宁
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Nanchang University
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Nanchang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Abstract

The invention relates to a synthesis method of an Ni/ZrO2 hydrogenation catalyst and application of the catalyst in hydrogenation catalysis reaction. The synthesis method comprises the steps of: preparing a zirconium source into a 0.8mol/L solution, conducting room temperature stirring, adding reducing alcohol according to a mole ratio of the zirconium source to alcohol of 1:3, performing stirring for 15min, adding an alkali solution to adjust the pH to 11-13, conducting stirring for 15min, then adding a 0.5mM/ml nickel source solution with a zirconium-nickel mole ratio of 1:48-1:2, further performing stirring for 15min, then transferring the mixed solution into a high-pressure reaction kettle, carrying out reaction for 18h at a constant temperature of 160DEG C, subjecting the generated precipitate to pumping filtration, washing, drying and grinding, thus obtaining the catalyst. The catalyst provided by the invention has simple formula and simple and feasible synthesis process, can realize low temperature preparation of cyclohexane, and has high conversion rate. Also in addition to preparation of cyclohexane, the Ni/ZrO2 catalyst involved in the invention can be used for reduction of p-nitrophenol to prepare p-aminophenol, and the catalytic activity is far higher than that of raney nickel under the same reaction conditions.

Description

A kind of Ni/ZrO 2the synthetic method of hydrogenation catalyst and the application of this catalyst in hydrogenation catalyst reaction
Technical field
The invention belongs to the application of catalyst and catalyst.
Background technology
Nickel-base catalyst has wide range of applications, and in hydrogenation reaction, catalytic cracking, all there is applications well the aspects such as polymerizing olefin monomers.Such as, catalytic benzene hydrogenation preparing cyclohexane.Cyclohexane is a kind of important Organic Chemicals, it is one of important intermediate of producing polyamide-based fiber, for the production of products such as cyclohexanol, cyclohexanone, nylon 6 and nylon66 fiber, be again fine solvent and other industrial chemicals of resin, grease, pitch and rubber simultaneously.Industrial production cyclohexane is primarily of following two kinds of methods: benzene catalytic hydrogenation method and petroleum hydrocarbon fractionation method for refining, along with the development of petroleum refining industry, benzene catalytic hydrogenation produces the main stream approach that cyclohexane has become current, the catalyst of producing cyclohexane by benzene hydrogenation is generally loaded catalyst, and active component can be Pt, Ru, Ni, Mo, Co etc.The catalytic activity of precious metals pt and Ru is good, usually at room temperature can carry out hydrogenation reaction, but expensive.At present, what be widely used in industrial production is nickel catalyst, and main carriers used is generally Al 2o 3.But pure Al 2o 3to the Ni active specy on its surface, there is stronger active force, be easy to form the phases such as nickel aluminate, have impact on the Hydrogenation of Ni species on the contrary.Therefore, how to weaken the strong interaction of metal and carrier, improve the decentralization of active specy, become key prepared by high activity Ni hydrogenation catalyst.
At present, Chinese scholars mainly by Ni and other metal are formed amorphous alloy, add auxiliary agent and to Al 2o 3carrier carries out the methods such as modification to improve the Activity and stabill of Ni catalyst.But these methods being all by adding multiple species, regulating activity and the decentralization of active metal, and changing carrier A l 2o 3surface nature, the strong interaction reducing active metal and carrier improves the Hydrogenation of catalyst, in the process of these modifications, various metals active specy and carrier adds (usually more than ten kinds of elements), cause catalyst synthesizing formula complicated, treatment step is loaded down with trivial details, impact reaction can not to survey factor too much.Therefore, a kind of formula of synthesis is simple, and the simple efficient hydrogenation catalyst of synthesis technique for hydrogenation theoretical research and industrial production aspect all very important.For this situation, the present invention selects chemical stability good and surface has the ZrO of acid centre and basic center simultaneously 2as carrier, prepared a kind of novel Ni catalyst based, this catalyst all shows good activity in the probe catalytic reactions such as low-temperature catalytic benzene hydrogenation preparing cyclohexane, p-nitrophenol hydrogenating reduction.
Summary of the invention
The object of this invention is to provide a kind of Ni/ZrO 2the synthetic method of hydrogenation catalyst and the application of this catalyst in hydrogenation catalyst reaction.
The present invention selects chemical stability good and surperficial existing acid centre has again the ZrO of basic center 2as carrier, prepared a kind of novel Ni catalyst based, this catalyst all shows good activity in the probe catalytic reactions such as catalytic benzene hydrogenation preparing cyclohexane, p-nitrophenol hydrogenating reduction, provides new reference for synthesizing simple nickel-base catalyst efficiently.
The reaction temperature window of described catalytic reaction is 20 DEG C-200 DEG C.
Described Nickel Content In Catalyst is 1%-25%.
The present invention adopts one-step method directly to add Ni salt as precursor in advance containing the aqueous solution of Zr ion, and is aided with a certain amount of reproducibility alcohol, constant temperature 180 DEG C reaction 18h under suitable pH, by regulate Ni Zr than obtaining a series of hydrogenation catalyst.
The present invention is achieved by the following technical solutions.
A kind of Ni/ZrO of the present invention 2the synthetic method of hydrogenation catalyst, as follows:
Zirconium source is made into the solution of 0.8mol/L, stirring at normal temperature, add the reproducibility alcohol that zirconium source and alcohols mol ratio are 1:3, stir 15min, add aqueous slkali by pH modulation 11 ~ 13, stir and after 15 minutes, to add the 0.5mM/ml nickel source solution that zirconium and nickel mol ratio are 1:48-1:2, after continuing to stir 15min clock, mixed liquor is moved into autoclave, constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, washing, obtains catalyst after drying and grinding.
Zirconium source of the present invention is ZrCl 4, Zr (NO 3) 45H 2o, Zr (CH 3cOO) 4or ZrOCl 2.
Nickel source of the present invention is Ni (NO 3) 26H 2o, NiCl 26H 2o, NiSO 46H 2o or Ni (CH 3cOO) 24H 2o.
Reproducibility auxiliary agent of the present invention: ethylene glycol, glycerine or diethylene glycol.
Alkali of the present invention is NH 4oH, NaOH.
Another object of the present invention is the Ni/ZrO of described synthetic method synthesis 2the application of hydrogenation catalyst in hydrogenation catalyst reaction.
The Ni/ZrO synthesized in the present invention 2the effect that catalyst application reacts in catalytic benzene hydrogenation and current Ni system or this reacting phase ratio of Pt series catalyzer to catalyse, the present invention fills a prescription merely, and synthesis technique is simple, prepares cyclohexane under can realizing lower temperature, and has high conversion ratio.And except preparing cyclohexane, Ni/ZrO of the present invention 2catalyst may be used for p-nitrophenol reduction and prepares para-aminophenol, and its catalytic activity is under the same reaction conditions far away higher than Raney's nickel.
Accompanying drawing explanation
Fig. 1 is the XRD test result figure of catalyst of the present invention.
Fig. 2 is the TEM photo of catalyst of the present invention.
Fig. 3 is the high power electromicroscopic photograph of catalyst of the present invention after hydrogen pretreatment.
Detailed description of the invention
The present invention will be described further by following examples, but not thereby limiting the invention.
Catalyst of the present invention can carry out structural characterization by following means:
1, the composition of catalyst is measured by inductively coupled plasma spectrum (ICP).
2, the structure of catalyst is measured by X-ray powder diffraction (XRD).
3, pattern and the particle diameter of catalyst activity component is observed by transmission electron microscope (TEM).
Embodiments result is as follows.
(1) ICP of catalyst tests test result
。
(2) the XRD test result of catalyst is shown in accompanying drawing 1.
Can find out that from the XRD spectra of accompanying drawing 1 catalyst crystal degree of the present invention is better, ZrO 2for tetragonal phase zirconium oxide, Ni is with Ni (OH) 20.75H 2o and NiO 2(OH) 4two kinds of form existence.
(3) the TEM photo of catalyst.
Accompanying drawing 2 for Ni content be the TEM photo of the catalyst of 15%, accompanying drawing 3 is the high power electromicroscopic photograph of catalyst after hydrogen pretreatment, corresponding with the spacing of lattice in zirconia (011) face and nickel (111) face respectively through measuring the spacing of lattice found in photo, in the catalyst after measuring and drawing reduction, the particle of zirconic and nickel is all at about 5nm.
Experimental technique in following embodiment, if no special instructions, is conventional method.
Embodiment 1.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrCl 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add glycerine 8.48ml(ZrCl 4be 1:3 with glycerine mol ratio), stir 15min, add appropriate ammoniacal liquor and pH is adjusted to 12, stir the amount adding 25.2mL(25.2ml after 15 minutes and add needed for the catalyst of 15% for preparing Ni content in theory) 0.5mM/mlNiCl 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 20 ~ 110 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 10% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 1 embodiment 1
。
Embodiment 2.Ni/ZrO 2the preparation of catalyst and prepare para-aminophenol for p-nitrophenol reduction.
(1) Ni/ZrO 2the preparation method of catalyst.
With embodiment 1 step (1).
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 10mgNi/ZrO 2catalyst (nickel content is 10%) loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
B para-aminophenol is prepared in the reduction of () p-nitrophenol.
50mL concentration is 3*10 -4the p-NPh (p-nitrophenol) of mol/L and the NaBH of 50mL0.03mol/L 4the aqueous solution (p-NPh:NaBH 4mol ratio=1:100) introduce step (1) process after 10mg catalyst react, control reaction temperature be 25 DEG C.According to the inverted signal of passage of time sampling by p-nitrophenol in ultraviolet spectrometer assaying reaction system.
Equally for Ni content in the catalyst of synthesis be 10% catalyst and Raney's nickel expression activitiy under the same reaction conditions as following table 2:
Obtained catalyst and the test result of Raney's nickel in p-nitrophenol reduction reaction in table 2 embodiment 2
。
Embodiment 3.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
Experimental technique in following embodiment, if no special instructions, is conventional method.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (CH 3cOO) 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add diethylene glycol 11.39ml(Zr (CH 3cOO) 4be 1:3 with diethylene glycol mol ratio), stir 15min, add appropriate NaOH solution by pH modulation 12, stir after 15 minutes and add 25.2mL (amount that 25.2ml adds for preparing Ni content in theory needed for the catalyst of 15%) 0.5mM/mlNi (CH 3cOO) 24H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 20 ~ 110 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 10% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 3 embodiment 3
。
Embodiment 4.Ni/ZrO 2the preparation of catalyst and prepare para-aminophenol for p-nitrophenol reduction.
(1) Ni/ZrO 2the preparation method of catalyst.
With embodiment 3 step (1).
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 10mgNi/ZrO 2catalyst (nickel content is 10%) loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
B para-aminophenol is prepared in the reduction of () p-nitrophenol.
50mL concentration is 3*10 -4the p-NPh (p-nitrophenol) of mol/L and the NaBH of 50mL0.03mol/L 4the aqueous solution (p-NPh:NaBH 4mol ratio=1:100) introduce step (1) process after 10mg catalyst react, control reaction temperature be 25 DEG C.According to the inverted signal of passage of time sampling by p-nitrophenol in UV-vis spectrophotometer reaction system.
Equally for Ni content in the catalyst of synthesis be 10% catalyst and Raney's nickel expression activitiy under the same reaction conditions as following table 2:
Obtained catalyst and the test result of Raney's nickel in p-nitrophenol reduction reaction in table 4 embodiment 4
。
Embodiment 5.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
Experimental technique in following embodiment, if no special instructions, is conventional method.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (NO 3) 45H 2o is made into the solution 50ml of 0.8mol/L, stirring at normal temperature, adds ethylene glycol 6.68ml(Zr (NO 3) 45H 2o and ethylene glycol mol ratio are 1:3), stir 15min, add appropriate NaOH solution by pH modulation 13, stir after 15 minutes and add 13.44mL (amount that 13.44ml adds for preparing Ni content in theory needed for the catalyst of 8%) 0.5mM/mlNi (NO 3) 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(3) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 50 ~ 170 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 10% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 5 embodiment 5
。
Embodiment 6.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrOCl 2be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add glycerine 8.48ml(ZrOCl 2be 1:3 with glycerine mol ratio), stir 15min, add appropriate NH 4oH, by pH modulation 11, stirs after 15 minutes and adds 16.8mL (amount that 16.8ml adds for preparing Ni content in theory needed for the catalyst of 10%) 0.5mM/mlNiSO 46H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 35 ~ 170 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 10% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 6 embodiment 6
。
Embodiment 7.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrCl 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add diethylene glycol 8.48ml(ZrCl 4be 1:3 with diethylene glycol mol ratio), stir 15min, add appropriate NH 4oH, by pH modulation 11, stirs after 15 minutes and adds 1.68mL (amount that 1.68ml adds for preparing Ni content in theory needed for the catalyst of 1%) 0.5mM/mlNi (NO 3) 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 40 ~ 200 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 7 embodiment 7
。
Embodiment 8.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrCl 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add ethylene glycol 8.48ml(ZrCl 4be 1:3 with ethylene glycol mol ratio), stir 15min, add appropriate NaOH by pH modulation 12, stir after 15 minutes and add 8.4mL (amount that 8.4ml adds for preparing Ni content in theory needed for the catalyst of 5%) 0.5mM/mlNi (CH 3cOO) 24H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 50 ~ 200 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 8 embodiment 8
。
Embodiment 9.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (NO 3) 45H 2o is made into the solution 50ml of 0.8mol/L, stirring at normal temperature, adds glycerine 8.48ml(Zr (NO 3) 45H 2o and glycerine mol ratio are 1:3), stir 15min, add appropriate NaOH by pH modulation 12, stir after 15 minutes and add 16.8mL (amount that 8.4ml adds for preparing Ni content in theory needed for the catalyst of 5%) 0.5mM/mlNi (CH 3cOO) 24H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 35 ~ 170 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 9 embodiment 9
。
Embodiment 10.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (NO 3) 45H 2o is made into the solution 50ml of 0.8mol/L, stirring at normal temperature, adds diethylene glycol 8.48ml(Zr (NO 3) 45H 2o and diethylene glycol mol ratio are 1:3), stir 15min, add appropriate NaOH by pH modulation 12, stir after 15 minutes and add 33.6mL (amount that 33.6ml adds for preparing Ni content in theory needed for the catalyst of 20%) 0.5mM/mlNiSO 46H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 20 ~ 155 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 10 embodiment 10
。
Embodiment 11.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (CH 3cOO) 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add glycerine 8.48ml(Zr (CH 3cOO) 4be 1:3 with glycerine mol ratio), stir 15min, add appropriate NaOH by pH modulation 12, stir after 15 minutes and add 8.4mL (amount that 8.4ml adds for preparing Ni content in theory needed for the catalyst of 5%) 0.5mM/mlNi (NO 3) 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 50 ~ 200 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 11 embodiment 11
。
Embodiment 12.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By Zr (CH 3cOO) 4be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add ethylene glycol 8.48ml(Zr (CH 3cOO) 4be 1:3 with ethylene glycol mol ratio), stir 15min, add appropriate NaOH by pH modulation 11, stir after 15 minutes and add 42mL (amount that 42ml adds for preparing Ni content in theory needed for the catalyst of 25%) 0.5mM/mlNiCl 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 35 ~ 170 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 12 embodiment 12
。
Embodiment 13.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrOCl 2be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add ethylene glycol 8.48ml(ZrOCl 2be 1:3 with ethylene glycol mol ratio), stir 15min, add appropriate NH 4oH, by pH modulation 11, stirs after 15 minutes and adds 16.8mL (amount that 16.8ml adds for preparing Ni content in theory needed for the catalyst of 10%) 0.5mM/mlNi (NO 3) 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 35 ~ 170 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 13 embodiment 13
。
Embodiment 14.Ni/ZrO 2the preparation of catalyst and for benzene hydrogenation.
(1) Ni/ZrO 2the preparation method of catalyst.
By ZrOCl 2be made into the solution 50ml of 0.8mol/L, stirring at normal temperature, add diethylene glycol 8.48ml(ZrOCl 2be 1:3 with diethylene glycol mol ratio), stir 15min, add appropriate NH 4oH, by pH modulation 11, stirs after 15 minutes and adds 33.6mL (amount that 33.6ml adds for preparing Ni content in theory needed for the catalyst of 20%) 0.5mM/mlNiCl 26H 2o solution, moves into autoclave by mixed liquor after continuing to stir 15min clock, and constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, and washing, obtains catalyst after drying and grinding.
(2) benzene hydrogenation activity test and result.
The activation of (a) catalyst.
By 100mgNi/ZrO 2catalyst loads in U-shaped quartz ampoule, is to reduce two hours under the hydrogen atmosphere of 30mL/min at 400 DEG C at flow velocity.
(b) benzene hydrogenation.
The reaction of producing cyclohexane by benzene hydrogenation vapour phase reduction is in the enterprising horizontal pulse reaction of fixed-bed micro-reactor, temperature range 20 ~ 155 DEG C, sample size 1 μ l.Temperature of vaporization chamber: 105 DEG C, detector temperature: 120 DEG C, column temperature: 80 DEG C, bridge stream: 80mA, with high-purity hydrogen for carrying and reaction gas, flow value is 30mL/min.
For synthesis Ni content be the reaction result of the catalyst of 1% as following table:
Obtained catalyst differential responses temperature producing cyclohexane by benzene hydrogenation test result in table 14 embodiment 14

Claims (6)

1. a Ni/ZrO 2the synthetic method of hydrogenation catalyst, is characterized in that as follows:
Zirconium source is made into the solution of 0.8mol/L, stirring at normal temperature, add the reproducibility alcohol that zirconium source and alcohols mol ratio are 1:3, stir 15min, add aqueous slkali by pH modulation 11 ~ 13, stir and after 15 minutes, to add the 0.5mM/ml nickel source solution that zirconium and nickel mol ratio are 1:48-1:2, after continuing to stir 15min clock, mixed liquor is moved into autoclave, constant temperature 160 DEG C reaction 18h, the sediment that reaction generates is through suction filtration, washing, obtains catalyst after drying and grinding.
2. Ni/ZrO according to claim 1 2the synthetic method of hydrogenation catalyst, is characterized in that described zirconium source is ZrCl 4, Zr (NO 3) 45H 2o, Zr (CH 3cOO) 4or ZrOCl 2.
3. Ni/ZrO according to claim 1 2the synthetic method of hydrogenation catalyst, is characterized in that described nickel source is Ni (NO 3) 26H 2o, NiCl 26H 2o, NiSO 46H 2o or Ni (CH 3cOO) 24H 2o.
4. Ni/ZrO according to claim 1 2the synthetic method of hydrogenation catalyst, is characterized in that described reproducibility auxiliary agent is ethylene glycol, glycerine or diethylene glycol.
5. Ni/ZrO according to claim 1 2the synthetic method of hydrogenation catalyst, is characterized in that described alkali is NH 4oH or NaOH.
6. the Ni/ZrO in claim 1 to 5 described in arbitrary claim 2the Ni/ZrO of the synthetic method synthesis of hydrogenation catalyst 2the application of hydrogenation catalyst in hydrogenation catalyst reaction.
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CN113097511A (en) * 2021-03-30 2021-07-09 太原理工大学 Ni(OH)2ZrO2Preparation method of heterostructure fuel cell cathode oxygen reduction catalyst

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