CN113477254A - Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof - Google Patents
Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst and preparation method thereof Download PDFInfo
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000008188 pellet Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910007928 ZrCl2 Inorganic materials 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 29
- 229960002446 octanoic acid Drugs 0.000 description 25
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000700 radioactive tracer Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
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- 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
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Abstract
The invention discloses a three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2A catalyst and a preparation method thereof relate to the field of catalyst design. The Ni/ZrO2The Ni content of the catalyst load is 1-7 wt.%, and the Ni/ZrO ratio is2The micro-morphology of the catalyst with the macropores distributed is in a honeycomb-shaped ordered distribution, and the framework is also provided with micropores, wherein the pore diameter of the macropores is 650-750 nm, the pore diameter of the micropores is 5-10 nm, and the density is 1.1g/cm3. The preparation method comprises the following steps: the method comprises the following steps: (1) By using
Method for preparing SiO2A pellet template; (2) preparation of ZrCl2·8H2Taking the O solution as a precursor solution of Zr; (3) under the vacuum condition, SiO2Adding a pellet template to ZrCl2·8H2Soaking in O solution water solution, drying and calcining; (4) putting the calcined substance obtained in the step (3) into NaOH solution, heating in water bath to obtain white solid, and adding Ni (NO)3)2Loading the white solid on the obtained solid by an impregnation method, and reducing the white solid after calcining to obtain the Ni/ZrO with the three-dimensional ordered macroporous structure2A catalyst.
Description
Technical Field
The invention relates to the field of catalyst design, in particular to a three-dimensional ordered macroporous Ni/ZrO for catalytic hydrogenation upgrading of octanoic acid2A catalyst and a preparation method thereof.
Background
The excessive consumption of fossil fuels raises concerns about environmental issues and national energy safety, and thus, the demand for environmentally friendly and renewable alternative fuels is increasing. At present, biomass plays an increasingly important role in the chemical industry as an alternative renewable carbon source, and is one of promising renewable energy sources. However, direct utilization of biomass as a liquid fuel is not feasible because biomass has a high oxygen content, a low combustion heat value, poor chemical stability and strong corrosiveness, which all hinder practical use of the product as a renewable energy source. Therefore, the production of liquid fuel with high combustion heat value by catalytic hydrogenation upgrading of biomass will provide significant environmental, economic and strategic advantages for the future. The main biomass product obtained by co-pyrolysis of the wood chips and the plastics at the early stage is the octanoic acid, and the octanoic acid is subjected to catalytic hydrogenation to prepare fuels with high combustion heat values such as gasoline and the like, so that the method has extremely high economic value.
At present, the octanoic acid is catalyzed and hydrogenated to prepare the fuel with high combustion heat value such as gasoline, and the used catalyst is mostly Ni/HS-ZrO2Catalyst (spherical Ni/ZrO)2Catalyst), we found that the conversion of octanoic acid is only 70% at the highest during the actual useThe product yield is not more than 60% at most, and the problems of low reaction conversion rate and low product yield exist, so that the maximum economic value cannot be realized.
Disclosure of Invention
The invention aims to provide a three-dimensional ordered macroporous Ni/ZrO2 catalyst for catalytic hydrogenation upgrading of octanoic acid and a preparation method thereof, and aims to solve the technical problems of low reaction conversion rate and low product yield in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Catalyst of said Ni/ZrO2The Ni content of the catalyst load is 1-7 wt.%, and the Ni/ZrO ratio is2The micro-morphology of the catalyst with the macropores distributed is in a honeycomb-shaped ordered distribution, and the framework is also provided with micropores, wherein the pore diameter of the macropores is 650-750 nm, the pore diameter of the micropores is 5-10 nm, and the density is 1.1g/cm3。
Three-dimensional ordered macroporous structure Ni/ZrO2The preparation method of the catalyst comprises the following steps:
(1) by using
Method for preparing SiO2A pellet template;
(2) preparation of ZrCl2·8H2Taking the O solution as a precursor solution of Zr;
(3) under the vacuum condition, SiO2Adding a pellet template to ZrCl2·8H2Soaking in an O solution water solution, drying after soaking, and then calcining to obtain a calcined substance;
(4) putting the calcined substance obtained in the step (3) into NaOH solution, heating in water bath to obtain white solid, and adding Ni (NO)3)2Loading the white solid on the obtained solid by an impregnation method, and reducing the white solid after calcining to obtain the Ni/ZrO with the three-dimensional ordered macroporous structure2A catalyst.
Preferably, in the step (1), SiO2The preparation process of the pellet template comprises the following steps: 28 wt.% ammonia water, deionized water and ethyl acetateMixing alcohol at a volume ratio of 1:2:7, dissolving ethyl orthosilicate with the same volume as ammonia water in ethanol with more than 9 times of volume, mixing the two mixed solutions, stirring vigorously at 40 deg.C for 2.5h, centrifuging to obtain white suspension, washing with ethanol for four times, drying in air, and centrifuging for more than 10 hr to obtain SiO2And (4) a small ball template.
Preferably, in the step (3), the SiO2Template of pellet in ZrCl2·8H2Soaking in the O solution for at least 10 hr.
Preferably, the SiO2The pellet template was impregnated and dried at a temperature of 110 ℃.
Preferably, in the step (3), the SiO2Drying the pellet template, then sending the pellet template into an oven, heating the oven from room temperature to 450 ℃ at a heating rate of 10 ℃/min, and calcining for 4h at the temperature of 450 ℃.
Preferably, in step (4), the water bath temperature of the calcine suspension is 80 ℃.
Preferably, in step (4), Ni (NO) is impregnated3)2The calcination temperature of the white solid of (2) was 450 ℃ and the calcination time was 2 hours.
Preferably, in the step (4), the reduction environment is a hydrogen atmosphere at 450 ℃ and the reduction time is 2 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the three-dimensional ordered macroporous catalyst provided by the invention has the advantages that the dead zone or the recirculation zone is smaller, the effective area of the catalyst is large, and the activity of the catalyst is favorably improved;
2. the three-dimensional ordered macroporous catalyst provided by the invention has high activity and selectivity, and can show that the activity is not lower than that of the existing Ni/HS-ZrO at lower temperature2The catalyst has higher catalytic reaction activity at higher temperature, and can be used for development and application of green and environment-friendly new energy; shows higher activity and yield, the highest conversion rate can reach 89 percent, the selectivity of heptane can reach 79.9 percent at the highest, and the yield of heptane can directly reach 71.6 percent and is far higher than that of Ni/HS-ZrO2Catalyst assemblyThe yield of the product is high;
3. the three-dimensional ordered macroporous structure catalyst provided by the invention has the advantages of low cost, safe and easily obtained raw material medicament, convenient process flow, simple operation, energy conservation and contribution to engineering popularization.
Drawings
FIG. 1 is a three-dimensional ordered macroporous Ni/ZrO structure2A microscopic topography of the catalyst;
FIG. 2 shows the trace gas in Ni/3DOM-ZrO2(three-dimensionally ordered macroporous Ni/ZrO)2) And residence time distribution in Ni/HS-ZrO 2;
FIG. 3 is Ni/3DOM-ZrO2With Ni/HS-ZrO2Comparative graph of octanoic acid hydrogenation catalysis in gas phase system;
FIG. 4 shows Ni/HS-ZrO2Histogram of the effect of different Ni loadings on catalytic activity (reaction conditions: reaction temperature 280 ℃; 1g catalyst; 10% H)2；90％Ar)；
FIG. 5 shows Ni/3DOM-ZrO2Histogram of the effect of different Ni loadings on catalytic activity (reaction conditions: reaction temperature 280 ℃; 1g catalyst; 10% H)2；90％Ar)；
FIG. 6 shows 5Ni/HS-ZrO at different reaction temperatures2Line drawing for catalytic hydrogenation of octanoic acid (reaction conditions: 1g catalyst; 10% H)2；90％Ar)；
FIG. 7 shows 5Ni/3DOM-ZrO at different reaction temperatures2Line drawing for catalytic hydrogenation of octanoic acid (reaction conditions: 1g catalyst; 10% H)2；90％Ar)。
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
The invention provides a three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of octanoic acid2Catalyst of said Ni/ZrO2The Ni content of the catalyst load is 1-7 wt.%, and the Ni/ZrO ratio is2The micro-morphology of the catalyst with large pores is in honeycomb-shaped ordered distribution, and the bone is formedSmall holes are also distributed on the frame, wherein the aperture of the large hole is 650-750 nm, the aperture of the small hole is 5-10 nm, and the density is 1.1g/cm3。
Example 1
The three-dimensional ordered macroporous structure Ni/ZrO2 catalyst for catalytic hydrogenation upgrading of octanoic acid is prepared by the following steps:
a) by using
Method for preparing SiO2And (4) a small ball template. First, 10mL of aqueous ammonia (28 wt.%), 20mL of deionized water and 70mL of ethanol were mixed and transferred to a three-necked flask. Then, 10mL of tetraethyl orthosilicate (TEOS) was dissolved in 90mL of ethanol, the solution was added to the pre-mixed solution, vigorously stirred at 40 ℃ for 2.5h, and the resulting white suspension was centrifuged. Washed four times with ethanol, then dried in air, and the SiO2Centrifuging the pellet at 3000rpm for 10 hours to obtain SiO2And (5) template.
b) Preparing 2mol/L ZrCl2·8H2And taking the O solution as a precursor solution of Zr.
c) Adding SiO2 template into ZrOCl2·8H2Soaking in O water solution. Dipping for 10 hours under vacuum condition until ZrOCl is ready2·8H2Complete impregnation of aqueous O solution into SiO2After the gap of the template, SiO2The template was removed, dried at 110 ℃ for 3h, and then calcined in an oven at a ramp rate of 10 ℃/min from room temperature to 450 ℃ for 4 h.
d) The sample was placed in 35mL of a 2.0mol/LNaOH solution and the resulting suspension was transferred to a 50mL hydrothermal autoclave maintained at 80 ℃ for 4h to give a white solid. Finally, a certain amount of Ni (NO) is added3)2Loading the obtained white solid by dipping, calcining the precursor in air at 450 ℃ for 2h, finally reducing the precursor in hydrogen atmosphere at 450 ℃ for 2h to obtain the three-dimensional ordered macroporous Ni/ZrO2The catalyst has the microscopic morphology shown in FIG. 1.
By using tracer gas introduced into both catalyst models, as can be seen in FIG. 2, the cumulative concentration of tracer gas in both catalyst models is the same as the reaction beginsIt increases rapidly. In particular in Ni/HS-ZrO2In the model, the trace gas concentration increase rate ratio detected at the outlet before 0.0022s is Ni/3DOM-ZrO2The speed in the model is fast. However, with increasing reaction time, Ni/3DOM-ZrO2The cumulative trace gas concentration at the model outlet will exceed the Ni/HS-ZrO after 0.0022s2Cumulative trace gas concentration at the model outlet. Over time, its cumulative gas concentration becomes higher. Ni/3DOM-ZrO2The cumulative trace gas concentration at the model outlet reached about 60% rapidly over a short period of time and then increased slightly. By contrast, through Ni/HS-ZrO2The cumulative trace gas concentration at the exit of the model reached 18% quickly and then rose slowly. As shown in FIG. 3, the reason is that the trace gas enters Ni/3DOM-ZrO2And Ni/HS-ZrO2After the model, a part of the trace gas is trapped in the dead zone of the model flow field, and is difficult to come out for a short time. Ni/HS-ZrO2Porous structure ratio of Ni/3DOM-ZrO2Narrow and tortuous, so that more tracer gas is trapped in the Ni/HS-ZrO2In the model. For Ni/HS-ZrO2Model, only about 18% of the trace gas passed through the model rapidly, the remainder being in the Ni/HS-ZrO2Stagnation in the dead zone or recirculation zone of the model is difficult to pass through the model. The presence of dead or recycle zones can reduce the effective volume in the catalyst, affecting the extent of the catalytic reaction. Ni/3DOM-ZrO2The dead zone or the recirculation zone in the model is smaller, the effective area of the catalyst is large, and the activity of the catalyst is favorably improved.
Example 2
Reaction process of reaction using catalyst: catalytic hydrogenation of octanoic acid was carried out in a 150mL autoclave. The catalyst is soaked in water in a vacuum pump until the hollow sphere is saturated with water. The catalyst and octanoic acid were then dispersed by sonication into 50mL decane solution and the compound was transferred to the autoclave. The reactor is firstly used with H2Purging three times, then with H2The pressure was increased to 3MPa and the stirring rate was constant (300 rpm). Then the reactor was heated to the desired reaction temperature and held for 12h, after cooling the autoclave to room temperature, the gas phase was developed with a GsBP Inowax (30 m.times.0.32 mm.times.0.25 m) capillary columnThe reaction product was subjected to FID composition analysis by a spectrometer (AgEnter GC 6820).
Investigating the influence of the catalyst on the actual reaction, with Ni/HS-ZrO2As a control.
Preparation of Ni/3DOM-ZrO with different Ni loading amounts2And Ni/HS-ZrO2Respectively used for the catalytic reaction, and the reaction conditions are as follows: the reaction temperature is 280 ℃; the amount of the catalyst is 1 g; reaction atmosphere 10% H290% Ar. FIG. 4 shows the conversion and yield of product for catalytic hydrogenation of octanoic acid for two different structures, Ni/3DOM-ZrO2 catalyst and Ni/HS-ZrO2 catalyst. As shown in FIGS. 4 and 5, the conversion of octanoic acid was varied depending on Ni/3DOM-ZrO2And Ni/HS-ZrO2Increases in the Ni content of (a). 5Ni/3DOM-ZrO with Ni loading of 5 wt%2The catalyst shows the best activity for catalytic hydrogenation of caprylic acid, the conversion rate of the caprylic acid reaches 88.1%, and the selectivity to heptane is 79.9%; in addition, when the amount of Ni is the same, Ni/3DOM-ZrO2The conversion rate of the caprylic acid is higher than that of Ni/HS-ZrO2(ii) a Octanoic acid in 5Ni/HS-ZrO2The conversion on the catalyst was only 60.2%, well below 5Ni/3DOM-ZrO2The catalytic effect of (3).
At a Ni loading of 5 wt.%, in 3DOM-ZrO2And HS-ZrO2The maximum conversion of octanoic acid was achieved on the support, so we chose Ni/3DOM-ZrO with a Ni loading of 5 wt.%2And 5Ni/HS-ZrO2The catalysts were studied for different catalytic temperatures.
Ni loading of 5 wt.% Ni/3DOM-ZrO at different temperatures2And 5Ni/HS-ZrO2The catalyst is used for the catalytic reaction, and the using amount of the catalyst is 1 g; reaction atmosphere 10% H290% Ar, as shown in fig. 6, 7, shows the octanoic acid conversion and product yield line plots in the octanoic acid catalytic hydrogenation reaction at different temperatures. For 5Ni/3DOM-ZrO2And 5Ni/HS-ZrO2The major product after hydrogenation of octanoic acid was heptane for both catalysts. In FIG. 6, at 5Ni/HS-ZrO2Catalytically, the conversion of octanoic acid and the product yield increased with increasing temperature. The octanoic acid conversion at 280 ℃ was 70.2%, the main products were heptane and octane, with yields of 43.9% and 12.3%, respectively. In the figure7 in, 5Ni/3DOM-ZrO2Has a catalytic activity higher than 5Ni/HS-ZrO2The conversion of octanoic acid and the yield of heptane at 280 ℃ were 89% and 71.6%, respectively. The comparison of the two can find that 5Ni/3DOM-ZrO2The three-dimensional ordered macroporous structure of the catalyst is beneficial to the catalytic hydrogenation of the octanoic acid gas phase.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (9)
1. Three-dimensional ordered macroporous structure Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2A catalyst, characterized by: the Ni/ZrO2The Ni content of the catalyst load is 1-7 wt.%, and the Ni/ZrO ratio is2The micro-morphology of the catalyst with the macropores distributed is in a honeycomb-shaped ordered distribution, and the framework is also provided with micropores, wherein the pore diameter of the macropores is 650-750 nm, the pore diameter of the micropores is 5-10 nm, and the density is 1.1g/cm3。
2. The three-dimensionally ordered macroporous Ni/ZrO of claim 12The preparation method of the catalyst is characterized by comprising the following steps:
(1) by using
Method for preparing SiO2A pellet template;
(2) preparation of ZrCl2·8H2Taking the O solution as a precursor solution of Zr;
(3) under the vacuum condition, SiO2Adding a pellet template to ZrCl2·8H2Soaking in an O solution water solution, drying after soaking, and then calcining to obtain a calcined substance;
(4) putting the calcined substance obtained in the step (3) into NaOH solution, heating in water bath to obtain white solid, and adding Ni (NO)3)2Loading the white solid on the obtained solid by an impregnation method, and reducing the white solid after calcining to obtain the Ni/ZrO with the three-dimensional ordered macroporous structure2A catalyst.
3. The method according to claim 2, wherein in the step (1), SiO is used2The preparation process of the pellet template comprises the following steps: mixing 28 wt.% ammonia water, deionized water and ethanol according to a volume ratio of 1:2:7, dissolving tetraethoxysilane with the same volume as that of the ammonia water in ethanol with the volume of more than 9 times of that of the ammonia water, mixing the two mixed solutions, violently stirring the mixed solutions at 40 ℃ for 2.5 hours, centrifugally separating the mixed solutions to obtain white suspension, washing the white suspension with ethanol for four times, drying the white suspension in air, and finally centrifuging the white suspension for more than 10 hours to obtain SiO2And (4) a small ball template.
4. The method according to claim 2, wherein in the step (3), the SiO is2Template of pellet in ZrCl2·8H2Soaking in the O solution for at least 10 hr.
5. The method according to claim 2, wherein in the step (3), the SiO is2The pellet template was impregnated and dried at a temperature of 110 ℃.
6. The method according to claim 2, wherein in the step (3), the SiO is2Drying the pellet template, then sending the pellet template into an oven, heating the oven from room temperature to 450 ℃ at a heating rate of 10 ℃/min, and calcining for 4h at the temperature of 450 ℃.
7. The method according to claim 2, wherein in the step (4), the water bath temperature of the calcine suspension is 80 ℃.
8. The method according to claim 2, wherein in the step (4), Ni (NO) is impregnated3)2The calcination temperature of the white solid of (2) was 450 ℃ and the calcination time was 2 hours.
9. The method according to claim 2, wherein in the step (4), the reducing atmosphere is a hydrogen atmosphere at 450 ℃ and the reducing time is 2 hours.
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| CN101892047A (en) * | 2010-07-02 | 2010-11-24 | 北京交通大学 | Core-shell fluorescent material and preparation method thereof |
| CN104815635A (en) * | 2015-04-30 | 2015-08-05 | 中国石油大学(北京) | Catalyst for combustion of carbon smoke particles, preparation method and application thereof |
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| CN112717939A (en) * | 2021-01-06 | 2021-04-30 | 中国船舶重工集团公司第七一九研究所 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Process for preparing catalyst |
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- 2021-06-10 CN CN202110646930.4A patent/CN113477254A/en active Pending
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|---|---|---|---|---|
| CN101892047A (en) * | 2010-07-02 | 2010-11-24 | 北京交通大学 | Core-shell fluorescent material and preparation method thereof |
| CN104815635A (en) * | 2015-04-30 | 2015-08-05 | 中国石油大学(北京) | Catalyst for combustion of carbon smoke particles, preparation method and application thereof |
| CN107185567A (en) * | 2017-06-02 | 2017-09-22 | 钦州学院 | A kind of nickel system selective hydrocatalyst and preparation method thereof |
| CN112717939A (en) * | 2021-01-06 | 2021-04-30 | 中国船舶重工集团公司第七一九研究所 | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Process for preparing catalyst |
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