CN113231058A - Preparation method of zinc-modified hydrophilic Ru-based catalyst and application of zinc-modified hydrophilic Ru-based catalyst in catalyzing selective hydrogenation reaction of benzene - Google Patents
Preparation method of zinc-modified hydrophilic Ru-based catalyst and application of zinc-modified hydrophilic Ru-based catalyst in catalyzing selective hydrogenation reaction of benzene Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 28
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 28
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 12
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 42
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004925 denaturation Methods 0.000 abstract description 2
- 230000036425 denaturation Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 36
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 206010016807 Fluid retention Diseases 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a zinc-modified hydrophilic Ru-based catalyst and application of the zinc-modified hydrophilic Ru-based catalyst in catalyzing selective hydrogenation reaction of benzene. The invention realizes the uniform introduction of Zn and other metal atoms in hydrotalcite laminates based on the adjustable denaturation of the element composition and proportion of the hydrotalcite laminates, constructs Zn-LDHs with different element compositions and proportions, and then prepares the zinc modified hydrophilic Ru-based catalyst by deposition precipitation and low-temperature hydrogen reduction. When the catalyst is applied to the catalytic benzene selective hydrogenation reaction, the benzene hydrogenation conversion rate can reach 30.3-100%, the cyclohexene selectivity can reach 10-87.2%, the yield can reach 35.2-41.5%, the cyclohexene yield can be maintained at 32.2-40.6% after the catalyst is repeatedly used for 4 times, and the catalyst has excellent cycle stability.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a zinc-modified hydrophilic Ru-based catalyst and application of the zinc-modified hydrophilic Ru-based catalyst in catalyzing selective hydrogenation reaction of benzene.
Background
Cyclohexene has an active C ═ C double bond and two active alpha-H bonds and is an important organic chemical raw material for the production of cyclohexanol, adipic acid, polyamide, polyester and other fine chemicals. At present, the preparation method of cyclohexene mainly comprises hexanol dehydration, cyclohexane dehydrogenation, dehalogenation reaction of halogenated cyclohexane and the like, but the method is often plagued by the problems of complex reaction path, high production cost, low efficiency, more byproducts and the like in the process of preparing cyclohexene, and can not meet the requirements of industrial production. Compared with the process, the process for preparing cyclohexene by selective hydrogenation of benzene has the advantages of cheap raw materials, simple reaction path, environmental friendliness, energy conservation, high efficiency and cyclic utilization of the byproduct cyclohexane, and is thus paid attention to by the industry. Benzene hydrogenation reaction is usually carried out in a four-phase coexistence system of solid phase, gas phase, water and organic phase, and the benzene hydrogenation is easier to generate cyclohexane from the reaction thermodynamics level or the molecular structure level, so benzene and H are easy to generate in the reaction process2The dispersion degree of cyclohexane and cyclohexene in a four-phase system, and the adsorption capacity and reaction capacity of raw materials and products on the surface of the catalyst have important influence on the yield of the cyclohexene.
Layered Double hydroxide (also called hydrotalcite (abbreviated as LDHs)) is a typical anionic Layered nanomaterial. The general structural formula of the LDHs is as follows: [ M ] A1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O, wherein M2+、M3+Respectively representing divalent and trivalent metal cations, A, located on the layern-Denotes an anion exchangeable between layers. Unique crystal structure of hydrotalciteThe metal ions on the laminate are affected by the lowest effect of lattice energy and the positioning effect of lattice and are uniformly distributed according to a specific mode, and the composition and proportion of metal elements of the laminate, the charge density of the laminate, the types of anions between layers and the like can be modified. The functional materials with excellent series of performances are obtained by modulating the composition of metal elements of the laminate, the types and the quantity of interlayer anions, controlling the morphology of the materials and the like, and the functional materials are widely applied to various fields, particularly the catalysis field. Meanwhile, the hydrotalcite has the structural characteristics that the surface of the hydrotalcite is rich in a large number of metal-hydroxyl (M-OH), so that the hydrotalcite has strong hydrophilicity.
Disclosure of Invention
The invention aims to provide a zinc-modified hydrophilic Ru-based catalyst and a preparation method thereof, the zinc-modified hydrophilic Ru-based catalyst is applied to the catalytic benzene selective hydrogenation reaction, the benzene hydrogenation conversion rate can reach 30.3-100%, the cyclohexene selectivity can reach 10-87.2%, the yield can reach 35.2-41.5%, the cyclohexene yield can be kept at 32.2-40.6% after the catalyst is repeatedly used for 4 times, and the zinc-modified hydrophilic Ru-based catalyst has excellent circulation stability. The preparation method of the catalyst is simple and universal, is convenient for realizing large-scale preparation, and is convenient to recover in use.
In the zinc-modified hydrophilic Ru-based catalyst, Ru nanoparticles are uniformly dispersed on the surface of a flaky zinc-aluminum hydrotalcite carrier, the particle size of the Ru nanoparticles is 1.1-2.5nm, the mass percentage content of active center Ru is 2-5%, and the specific surface area of the catalyst is 40-150m2(ii)/g; the laminate of the zinc-aluminum hydrotalcite also contains a metal element Li+、Mg2 +、Ni2+、Co2+、Fe2+One or more of them.
The preparation method of the zinc modified hydrophilic Ru-based catalyst comprises the following steps:
A. preparing a zinc-aluminum hydrotalcite carrier, wherein a laminate of the zinc-aluminum hydrotalcite also contains a metal element Li+、Mg2+、Ni2+、Co2+、Fe2+One or more of the above;
B. weighing 0.5-1g of the zinc-aluminum hydrotalcite carrier prepared in the step A, and adding the zinc-aluminum hydrotalcite carrier into a four-neck flask filled with 50-100mL of deionized waterUltrasonic dispersion; 2-4mL of RuCl with the concentration of 50mmol/L3Diluting the solution with 40-80mL of deionized water; diluting RuCl under stirring3Simultaneously dripping the solution and a sodium hydroxide solution with the concentration of 0.02mol/L into a four-neck flask, and controlling the pH of a reaction solution in the four-neck flask to be 9-10; continuously stirring and crystallizing for 5-48h at the temperature of 40-60 ℃ after the dropwise addition is finished; after the reaction is finished, centrifugally washing the mixture to be neutral, and drying the mixture to obtain a catalyst precursor;
C. and D, carrying out reduction reaction on the catalyst precursor prepared in the step B for 1-5h at the temperature of 200-350 ℃ in the mixed atmosphere of hydrogen and nitrogen, thus obtaining the zinc-modified hydrophilic Ru-based catalyst.
The prepared zinc-modified hydrophilic Ru-based catalyst is applied to catalyzing selective hydrogenation reaction of benzene. The conditions for catalyzing the selective hydrogenation reaction of benzene are as follows: adding 5-10mL of benzene, 20-40mL of deionized water and 0.1-0.4g of zinc modified hydrophilic Ru-based catalyst into a high-pressure reaction kettle at the same time, and introducing 2.5-5.5MPa of H2The reaction is stirred for 10-60min at the temperature of 120-180 ℃.
The invention has the following remarkable advantages:
(1) the invention realizes the uniform introduction of Zn and other metal atoms in hydrotalcite laminates based on the adjustable denaturation of the element composition and proportion of the hydrotalcite laminates, constructs Zn-LDHs with different element compositions and proportions, and then prepares the zinc modified hydrophilic Ru-based catalyst by deposition precipitation and low-temperature hydrogen reduction. Solves the problems of equipment corrosion, dirt, difficult separation and the like caused by the traditional homogeneous zinc auxiliary agent, and improves the yield of cyclohexene prepared by benzene hydrogenation.
(2) According to the method, based on the lattice positioning effect of each metal element in the hydrotalcite layer plate, the atomic-level uniform dispersion of Zn components in the hydrotalcite layer plate is realized, the electrostatic adsorption effect of metal-hydroxyl on the hydrotalcite layer plate is utilized, the highly uniform loading of Ru active components on the surface of a hydrotalcite carrier is realized, rich Ru-Zn active sites are constructed, the electron transfer between Ru and Zn is enhanced, a large number of Ru species lacking electrons are generated, the adsorption capacity on cyclohexene is weakened, and the desorption of cyclohexene from the surface of a catalyst and the improvement of the yield of cyclohexene are facilitated.
(3) The low-temperature hydrogen reduction keeps rich metal-hydroxyl (M-OH) on the hydrotalcite laminate, so that the prepared Ru-Zn-LDHs catalyst has stronger hydrophilicity, is favorable for constructing a proper 'retention water layer' on the surface of the catalyst, further weakens the adsorption capacity of cyclohexene on an Ru-Zn active center, and is favorable for improving the activity and selectivity of cyclohexene prepared by benzene hydrogenation.
Drawings
FIG. 1 is an XRD spectrum of the Ru-Zn-LDHs catalyst prepared in example 1 before and after reduction.
FIG. 2 is a TEM image of the Ru-Zn-LDHs catalyst prepared in example 1.
FIG. 3 is N of the Ru-Zn-LDHs catalyst prepared in example 12Adsorption and desorption curve chart.
FIGS. 4-5 are XPS spectra of Ru-Zn-LDHs catalysts prepared in example 1.
FIG. 6 is a water vapor adsorption in situ IR spectrum of the Ru-Zn-LDHs catalyst prepared in example 2.
FIG. 7 is the static contact angle of the Ru-Zn-LDHs catalyst prepared in example 2.
FIG. 8 is a graph of the benzene selective hydroconversion and selectivity to cyclohexene and cyclohexane for the Ru-Zn-LDHs catalyst prepared in example 1 as a function of time.
Detailed Description
Example 1
A. 2.6g of a soluble metal salt LiNO was added30.89g of Zn (NO)3)2·6H2O, 7.5g of Al (NO)3)2·9H2Preparing a mixed salt solution by using O and 80mL of deionized water;
B. dissolving soluble 6.3g of anhydrous sodium carbonate and 5.8g of sodium hydroxide in 80-100mL of deionized water to prepare a mixed alkali solution;
C. and (3) slowly dripping the prepared solutions in the step A and the step B into a four-neck flask filled with 50mL of deionized water at the same time under the condition of room temperature, continuously stirring at the rotating speed of 800 rpm, and controlling the pH value of the reaction solution in the four-neck flask to be 9.5. After the dropwise addition, the mixture is transferred to a water bath kettle at 70 ℃ for crystallization for 24 hours. After the reaction is finished, cooling to room temperature, centrifuging, washing to be neutral, and drying in an oven at 80 ℃ for 12h to obtain a Zn-LDHs carrier;
D. weighing 1g of Zn-LDHs carrier prepared in the step C, adding the Zn-LDHs carrier into a four-neck flask filled with 100mL of deionized water, ultrasonically dispersing the Zn-LDHs carrier into the deionized water, and weighing 4mL of RuCl with the concentration of 50mmol/L3Dissolving the solution in 40mL of deionized water, taking 100mL of 0.02mol/L sodium hydroxide solution, and diluting RuCl3The solution and the sodium hydroxide solution were simultaneously added dropwise to a four-necked flask at a rotation speed of 800 rpm, and the pH of the reaction solution in the four-necked flask was controlled to 10. After the dropwise addition, the mixture is transferred to a water bath kettle at 40 ℃ for crystallization for 6 hours. After the reaction is finished, cooling to room temperature, centrifuging, washing to be neutral, and drying in an oven at 80 ℃ for 12h to obtain a Ru-Zn-LDHs catalyst precursor;
E. and D, reducing the catalyst precursor prepared in the step D for 3 hours at 200 ℃ under a hydrogen-nitrogen mixed atmosphere with the flow rate of 50mL/min and the volume ratio of 1:9 to obtain the zinc modified hydrophilic Ru-based catalyst Ru-Zn-LDHs catalyst.
Fig. 1 is XRD spectra before and after reduction of the zinc-modified hydrophilic Ru-based catalyst Ru-Zn-LDHs of example 1, from which it can be seen that characteristic diffraction peaks (JCPDS No.35-0965) corresponding to crystal planes of hydrotalcite (003), (006), (009), (110) and (113) appear at 2 θ of 11.8 °, 23.6 °, 36.1 °, 63.6 ° and 64.9 ° before and after hydrogen reduction of the sample, indicating that the synthesized product has a higher crystal structure of hydrotalcite, and that low-temperature reduction does not destroy the layered structure of hydrotalcite, and that characteristic diffraction peaks of Ru are not seen, possibly due to lower loading and higher dispersion of Ru.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the zinc-modified hydrophilic Ru-based catalyst Ru-Zn-LDHs in example 1. It can be seen that the Ru nanoparticles are uniformly highly dispersed on the surface of the support, and have a uniform particle size with an average particle diameter of about 1.2 nm.
FIG. 3 is a low-temperature nitrogen adsorption-desorption curve of the hydrophilic Ru-based catalyst Ru-Zn-LDHs modified by Zn in example 1, and it can be seen from the figure that the isothermal adsorption curves of the series of catalysts are similar, and all show IV-type adsorption-desorption curves and H3Type hysteresis loopAt a higher relative pressure P/P0No adsorption platform appears, which is mainly caused by the slit-shaped pore structure formed after the aggregation of the flaky nano particles. The specific surface area of the support was calculated to be 126.9m2/g。
FIGS. 4-5 show XPS spectra of Ru-Zn-LDHs, hydrophilic Ru-based catalysts modified with zinc, according to example 1. It can be seen in FIG. 4 that the samples show the presence of Ru3d at 279.9eV and 281.2eV5/2Indicating that Ru is present in the metallic form in the sample. The low temperature reduction process can reduce the Ru species to the elemental metal state. The peak in fig. 5 at 530.5eV, which O1s can be assigned to hydroxyl oxygen, indicates that the catalyst contains a large amount of hydroxyl oxygen and has a high hydrophilicity.
The prepared zinc-modified hydrophilic Ru-based catalyst is applied to the selective hydrogenation reaction of catalytic benzene: 5mL of benzene, 10mL of deionized water and 0.1g of catalyst are added into a high-pressure reaction kettle at the same time, and 5MPa of H is introduced2When the temperature is raised to 150 ℃, stirring is started, the benzene hydrogenation conversion rate can reach 45.3 percent after the reaction is carried out for 15min under the condition of 800 revolutions per minute, and the cyclohexene selectivity reaches 79.1 percent.
Example 2
A. Adding 4.7g of soluble metal salt Mg (NO)3)2·6H2O, 0.69g Zn (NO)3)2·6H2O, 7.5g of Al (NO)3)2·9H2Preparing a mixed salt solution by using O and 80mL of deionized water;
B. dissolving soluble 6.3g of anhydrous sodium carbonate and 5.8g of sodium hydroxide in 80-100mL of deionized water to prepare a mixed alkali solution;
C. and (3) slowly dripping the prepared solutions in the step A and the step B into a four-neck flask filled with 50mL of deionized water at the same time at room temperature, continuously stirring at the rotating speed of 800 r/min, and controlling the pH of the reaction solution in the four-neck flask to be 9.5. After the dropwise addition, the mixture is transferred to a water bath kettle at 70 ℃ for crystallization for 24 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging, washing to be neutral, and drying in an oven at 80 ℃ for 12h to obtain the Zn-LDHs carrier;
D. weighing 1g of Zn-LDHs carrier prepared in the step C, adding the carrier into the containerIn a four-neck flask of 100mL deionized water, ultrasonically dispersing in the deionized water, and measuring 4mL RuCl with the concentration of 50mmol/L3Dissolving the solution in 40mL of deionized water, taking 100mL of 0.02mol/L sodium hydroxide solution, and diluting RuCl3The solution and the sodium hydroxide solution were simultaneously added dropwise to a four-necked flask at a rotation speed of 800 rpm, and the pH of the reaction solution in the four-necked flask was controlled to 10. After the dropwise addition, the mixture is transferred to a water bath kettle at 40 ℃ for crystallization for 6 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging and washing the mixture to be neutral, and drying the mixture in an oven at the temperature of 80 ℃ for 12 hours to obtain a Ru-Zn-LDHs catalyst precursor;
E. and D, reducing the catalyst precursor prepared in the step D for 3 hours at 200 ℃ under a hydrogen-nitrogen mixed atmosphere with the flow rate of 100mL/min and the volume ratio of 1:9 to obtain the zinc-modified hydrophilic Ru-based catalyst Ru-Zn-LDHs catalyst.
FIG. 6 is a water vapor adsorption in situ infrared image of the hydrophilic Ru-Zn-LDHs based catalyst modified with Zn according to example 2, which is clearly seen at a wave number of 3465cm-1Has a metal-hydroxyl (M-OH) stretching vibration peak at 1659cm-1The bending vibration peak of water appears, which shows that the material has abundant surface hydroxyl groups.
FIG. 7 is the static contact angle of water on the surface of the hydrophilic Ru-Zn-LDHs catalyst modified by zinc in example 2, and it can be seen that the contact angle is only 25.8 degrees, further illustrating that the material has higher hydrophilicity.
The prepared zinc-modified hydrophilic Ru-based catalyst is applied to the selective hydrogenation reaction of catalytic benzene: 5mL of benzene, 10mL of deionized water and 0.1g of catalyst are added into a high-pressure reaction kettle at the same time, and 5MPa of H is introduced2When the temperature is raised to 150 ℃, stirring is started, the benzene hydrogenation conversion rate can reach 68.9 percent after the reaction is carried out for 15min under the condition of 800 revolutions per minute, and the cyclohexene selectivity reaches 59.1 percent.
Example 3
A. Adding soluble metal salt 7.5g of Fe (NO)3)2·9H2O, 0.69g Zn (NO)3)2·6H2O, 7.5g of Al (NO)3)2·9H2Preparing a mixed salt solution by using O and 80mL of deionized water;
B. dissolving soluble 6.3g of anhydrous sodium carbonate and 5.8g of sodium hydroxide in 80-100mL of deionized water to prepare a mixed alkali solution;
C. and (3) slowly dripping the prepared solutions in the step A and the step B into a four-neck flask filled with 50mL of deionized water at the same time at room temperature, continuously stirring at the rotating speed of 800 r/min, and controlling the pH of the reaction solution in the four-neck flask to be 9.5. After the dropwise addition, the mixture is transferred to a water bath kettle at 70 ℃ for crystallization for 24 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging, washing to be neutral, and drying in an oven at 80 ℃ for 12h to obtain the Zn-LDHs carrier;
D. weighing 1g of Zn-LDHs carrier prepared in the step C, adding the Zn-LDHs carrier into a four-neck flask filled with 100mL of deionized water, ultrasonically dispersing the Zn-LDHs carrier into the deionized water, and weighing 4mL of RuCl with the concentration of 50mmol/L3Dissolving the solution in 40mL of deionized water, taking 100mL of 0.02mol/L sodium hydroxide solution, and diluting RuCl3The solution and the sodium hydroxide solution were simultaneously added dropwise to a four-necked flask at a rotation speed of 800 rpm, and the pH of the reaction solution in the four-necked flask was controlled to 10. After the dropwise addition, the mixture is transferred to a water bath kettle at 40 ℃ for crystallization for 6 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging and washing the mixture to be neutral, and drying the mixture in an oven at the temperature of 80 ℃ for 12 hours to obtain a Ru-Zn-LDHs catalyst precursor;
E. and D, reducing the catalyst precursor prepared in the step D for 3 hours at 200 ℃ in a hydrogen-nitrogen mixed atmosphere with the flow rate of 80mL/min and the volume ratio of 1:9 to obtain the zinc-modified hydrophilic Ru-based catalyst Ru-Zn-LDHs catalyst.
The prepared zinc-modified hydrophilic Ru-based catalyst is applied to the selective hydrogenation reaction of catalytic benzene: 5mL of benzene, 10mL of deionized water and 0.1g of catalyst are added into a high-pressure reaction kettle at the same time, and 5MPa of H is introduced2When the temperature is raised to 150 ℃, stirring is started, the benzene hydrogenation conversion rate can reach 57.3 percent after the reaction is carried out for 15min under the condition of 800 revolutions per minute, and the cyclohexene selectivity reaches 68.4 percent.
Example 4
A. 2.8g of soluble metal salt LiNO30.69g of Zn (NO)3)2·6H2O, 7.5g of Al (NO)3)2·9H2Preparing a mixed salt solution by using O and 80mL of deionized water;
B. dissolving soluble 6.3g of anhydrous sodium carbonate and 5.8g of sodium hydroxide in 80-100mL of deionized water to prepare a mixed alkali solution;
C. and (3) slowly dripping the prepared solutions in the step A and the step B into a four-neck flask filled with 50mL of deionized water at the same time under the condition of room temperature, continuously stirring at the rotating speed of 800 r/min, and controlling the pH of the reaction solution in the four-neck flask to be 9.5. After the dropwise addition, the mixture is transferred to a water bath kettle at 70 ℃ for crystallization for 24 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging, washing to be neutral, and drying in an oven at 80 ℃ for 12h to obtain the Zn-LDHs carrier;
D. weighing 1g of the Zn-LDHs catalyst carrier prepared in the step C, adding the Zn-LDHs catalyst carrier into a four-neck flask filled with 100mL of deionized water, ultrasonically dispersing the Zn-LDHs catalyst carrier into the deionized water, and weighing 4mL of RuCl with the concentration of 50mmol/L3Dissolving the solution in 40mL of deionized water, taking 100mL of 0.02mol/L sodium hydroxide solution, and diluting RuCl3The solution and the sodium hydroxide solution were simultaneously added dropwise to a four-necked flask at a rotation speed of 800 rpm, and the pH of the reaction solution in the four-necked flask was controlled to 10. After the dropwise addition, the mixture is transferred to a water bath kettle at 40 ℃ for crystallization for 6 hours. After the reaction is finished and the temperature is cooled to room temperature, centrifuging and washing the mixture to be neutral, and drying the mixture in an oven at the temperature of 80 ℃ for 12 hours to obtain a Ru-Zn-LDHs catalyst precursor;
E. and D, reducing the catalyst precursor prepared in the step D for 3 hours at 200 ℃ under a hydrogen-nitrogen mixed atmosphere with the flow rate of 100mL/min and the volume ratio of 1:9 to obtain the zinc-modified hydrophilic Ru-based catalyst Ru-Zn-LDHs catalyst.
The prepared zinc-modified hydrophilic Ru-based catalyst is applied to the selective hydrogenation reaction of catalytic benzene: 5mL of benzene, 10mL of deionized water and 0.1g of catalyst are added into a high-pressure reaction kettle at the same time, and 5MPa of H is introduced2When the temperature is raised to 150 ℃, stirring is started, the benzene hydrogenation conversion rate can reach 57.2 percent and the cyclohexene selectivity reaches 63.4 percent after the reaction is carried out for 15min under the condition of 800 revolutions per minute.
Claims (4)
1. A zinc-modified hydrophilic Ru-based catalyst is characterized in thatThe catalyst has Ru nanoparticles dispersed homogeneously on the surface of flaky zinc-aluminum hydrotalcite carrier, Ru nanoparticles of 1.1-2.5nm size and active center Ru content of 2-5 wt%, and specific surface area of 40-150m2(ii)/g; the laminate of the zinc-aluminum hydrotalcite also contains a metal element Li+、Mg2+、Ni2+、Co2+、Fe2+One or more of them.
2. A preparation method of a zinc-modified hydrophilic Ru-based catalyst is characterized by comprising the following specific steps:
A. preparing a zinc-aluminum hydrotalcite carrier, wherein a laminate of the zinc-aluminum hydrotalcite also contains a metal element Li+、Mg2+、Ni2+、Co2+、Fe2+One or more of the above;
B. weighing 0.5-1g of the zinc-aluminum hydrotalcite carrier prepared in the step A, adding the zinc-aluminum hydrotalcite carrier into a four-neck flask filled with 50-100mL of deionized water, and performing ultrasonic dispersion; 2-4mL of RuCl with the concentration of 50mmol/L3Diluting the solution with 40-80mL of deionized water; diluting RuCl under stirring3Simultaneously dripping the solution and a sodium hydroxide solution with the concentration of 0.02mol/L into a four-neck flask, and controlling the pH of a reaction solution in the four-neck flask to be 9-10; continuously stirring and crystallizing for 5-48h at the temperature of 40-60 ℃ after the dropwise addition is finished; after the reaction is finished, centrifugally washing the mixture to be neutral, and drying the mixture to obtain a catalyst precursor;
C. and D, carrying out reduction reaction on the catalyst precursor prepared in the step B for 1-5h at the temperature of 200-350 ℃ in the mixed atmosphere of hydrogen and nitrogen, thus obtaining the zinc-modified hydrophilic Ru-based catalyst.
3. The use of the zinc-modified hydrophilic Ru-based catalyst prepared according to the method of claim 2 for catalyzing selective hydrogenation of benzene.
4. The use according to claim 3, wherein the conditions for catalyzing the selective hydrogenation of benzene are: 5-10mL of benzene, 20-40mL of deionized water and 0.1-0.4g of zinc modified hydrophilic Ru group are catalyzedAdding the agent into a high-pressure reaction kettle simultaneously, and introducing 2.5-5.5MPa of H2The reaction is stirred for 10-60min at the temperature of 120-180 ℃.
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| US4923837A (en) * | 1987-12-29 | 1990-05-08 | Mitsui Petrochemical Industries, Ltd. | Hydrogenation catalyst |
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| US4923837A (en) * | 1987-12-29 | 1990-05-08 | Mitsui Petrochemical Industries, Ltd. | Hydrogenation catalyst |
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