CN118122343A - Preparation method and application of high-activity persulphate oxide type solid super acidic catalyst - Google Patents
Preparation method and application of high-activity persulphate oxide type solid super acidic catalyst Download PDFInfo
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
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- 239000003930 superacid Substances 0.000 claims abstract description 21
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 9
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- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- 238000011068 loading method Methods 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
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- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
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Abstract
The invention discloses a high-activity persulphate oxide type solid super acidic catalyst, and a preparation method and application thereof, and belongs to the field of catalysis. The preparation method of the solid superacid catalyst comprises the steps of immersing commercial ZrO 2 in ammonium persulfate solution, drying and roasting to obtain single-component S 2O8/ZrO2 solid superacid; and then taking S 2O8/ZrO2 as a carrier, and dipping in a nickel precursor solution to obtain the Ni-S 2O8/ZrO2 solid super acidic catalyst. Ni-S 2O8/ZrO2 shows excellent catalytic activity in the hydrocracking reaction of diphenyl ether, and when the reaction condition is 180 ℃ and 1MPa H 2 and 120min, the conversion rate of catalyzing the hydrogenation conversion of the diphenyl ether reaches 100 percent, and the activity of hydrogenolysis of a C-O bond is also high, and the main products are benzene, cyclohexane and cyclohexanol. The Ni-S 2O8/ZrO2 catalyst provides a new path for the application of the solid super acidic catalyst in the aspect of hydrocracking, and compared with some noble metal hydrogenation catalysts, the Ni-S 2O8/ZrO2 catalyst has the advantages of greatly reducing cost and having good application prospect.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a high-activity persulphate oxide type solid super acidic catalyst.
Background
Compared with a liquid acid catalyst, the solid super acidic catalyst has the advantages of stronger acidity, stability, reusability, no pollution to the environment and the like, and is an environment-friendly catalyst. But is mainly applied to reactions such as esterification, isomerization, alkylation and the like at present, and has less application in the field of hydrocracking.
Lignin is one of the three major components of lignocellulosic biomass, a major renewable aromatic biopolymer on earth, and can replace fossil fuels and serve as a feedstock for the production of alternative chemicals, materials and biofuels. The structure of lignin contains a plurality of C-O bonds, mainly comprises alpha-O-4, beta-O-4 and 4-O-5 bonds, wherein the bond energy of the 4-O-5 bond is highest, and the bond breaking is most difficult, so that the selection of diphenyl ether with the 4-O-5 bond as a lignin model compound for depolymerization has important significance. At present, many researches on hydrocracking catalysts of lignin and model compounds thereof have been developed, particularly metal hydrogenation catalysts are the most, however, the catalytic effect of transition metal catalysts is poor, and the activity is low; while noble metal catalysts, although having high hydrogenation activity, have low yields and are expensive and disadvantageous for large-scale industrial applications. The catalyst prepared by using the solid super acid as the carrier loaded metal has less research on hydrocracking, but the unique acid characteristic and the synergistic effect between the acid site and the metal active center also show very high catalytic activity and selectivity on hydrocracking, and a new idea is provided for the application of the solid super acid catalyst in the hydrogenation direction.
Disclosure of Invention
The invention aims to provide a preparation method of a high-activity persulphate oxide type solid super acidic catalyst, which is simple in preparation and safe in operation.
The second purpose of the invention is to provide the persulphate oxide type solid super acidic catalyst prepared by the preparation method, noble metals are not needed, and the catalytic activity is high.
The invention also provides application of the persulphate oxide type solid super acidic catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the present invention provides a method for preparing a high activity persulfate oxide type solid superacid catalyst, comprising the steps of:
(1) Immersing zirconia powder in 0.01-0.015mol/L ammonium persulfate methanol solution, performing ultrasonic treatment for 10-15min, and then mixing and stirring for 5-7h; the mass volume ratio of the zirconia to the ammonium persulfate methanol solution is 1g:50mL;
(2) Carrying out suction filtration on the mixture obtained in the step (1), drying a filter cake, and grinding to obtain solid powder;
(3) Calcining the solid powder obtained in the step (2) in a muffle furnace, cooling and grinding to obtain S 2O8/ZrO2 solid;
(4) Soaking the S 2O8/ZrO2 solid obtained in the step (3) in a nickel precursor aqueous solution, and carrying out ultrasonic treatment for 10-15min;
(5) Adding sodium borohydride into the mixed solution in the step (4) for reduction, and then stirring for 5-7h;
(6) And (5) carrying out suction filtration, drying a filter cake, and grinding to obtain the Ni-S 2O8/ZrO2 solid super acidic catalyst.
Preferably, the drying temperature in the step (2) is 100-120 ℃ and the drying time is 16-20h.
Preferably, in the step (3), the calcination temperature is 550 ℃, the calcination time is 3 hours, and the temperature rising rate is 10 ℃/min.
Preferably, the nickel precursor in step (4) is selected from nickel nitrate hexahydrate with a Ni loading of 10%.
Preferably, the drying mode in the step (6) is vacuum drying, the drying temperature is 110 ℃, and the drying time is 16-20h.
In a second aspect, the present invention provides a high activity persulfate oxide type solid superacid catalyst prepared by the above-described preparation method. The catalyst has small metal particle size, high dispersivity and strong acidity. Through the synergistic effect between the metal site and the acid site, hydrogen can be well adsorbed, activated and dissociated to form hydrogen free radicals which overflow to Lewis acid sites and attack O in diphenyl ether, so that C-O bond is broken, the reaction is carried out for 2 hours under the pressure of 1MPa H 2 at 180 ℃, and the conversion rate of the diphenyl ether can reach 100%.
In a third aspect, the invention provides the use of the high activity persulfate oxide type solid superacid catalyst in a diphenyl ether hydrocracking reaction.
The specific application steps comprise: putting substrate diphenyl ether, ni-S 2O8/ZrO2 solid super acidic catalyst and isopropanol into a reaction kettle, sealing, and replacing 3-4 times of air with hydrogen; pressurizing the reactor with hydrogen at room temperature at 1-2MPa; then the temperature is raised to 160 ℃ to 200 ℃ and is vigorously stirred for 60 to 120min at 800 rpm; after the experiment is finished, naturally cooling the reaction system to room temperature and releasing pressure; the organic phase obtained was filtered and analyzed by gas chromatography-mass spectrometry and gas phase.
Preferably, the catalyst is a 10% Ni-S 2O8/ZrO2 catalyst.
Preferably, the catalyst comprises 50% of the substrate mass.
Preferably, the reaction conditions for the hydrogenation reaction are: 180 ℃,1MPa,120min.
Compared with the prior art, the invention has the following beneficial effects:
1. The Ni-based solid superacid catalyst prepared by the invention can well control the direct cracking of the diphenyl ether C-O bond and inhibit the hydrogenation reaction of the aromatic ring by utilizing the synergistic catalysis of the metal active center and the acidic component, thereby generating more single-ring target products.
2. The metal Ni in the catalyst is highly dispersed on a solid super acidic carrier, and has better catalytic performance.
Drawings
FIG. 1 is an XRD spectrum of a catalyst prepared in example 1 of the present invention;
FIG. 2 is an SEM image of the catalyst of example 1 of the present invention;
FIG. 3 is an XPS graph of the catalyst prepared in example 1 of the present invention;
FIG. 4 is the effect of reaction temperature on diphenyl ether hydroconversion;
FIG. 5 is the effect of hydrogen pressure on diphenyl ether hydroconversion.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Example 1: preparation of 10% Ni-S 2O8/ZrO2 catalyst by NaBH 4 reduction
Weighing 0.12g of ammonium persulfate (NH 4)2S2O8 in a beaker, adding 50mL of methanol, carrying out ultrasonic treatment for 10-15min, weighing 1g of commercial ZrO 2 powder (with the particle size of about 200 nm) and adding the powder into the beaker, carrying out ultrasonic treatment for 10-15min, then carrying out magnetic stirring for 5-7h, carrying out suction filtration, drying a filter cake in a baking oven at 110 ℃ overnight, grinding to obtain solid powder, placing the solid powder in a muffle furnace for roasting at 550 ℃ for 3h, heating at a rate of 3 ℃/min to obtain single-component solid superacid S 2O8/ZrO2, weighing 0.2753g of nickel nitrate hexahydrate in the beaker according to Ni loading amount of 10%, adding 15mL of deionized water, carrying out ultrasonic treatment for 10min, weighing 0.5g S 2O8/ZrO2, adding the excessive sodium borohydride NaBH 4 powder into the beaker, carrying out reduction, carrying out magnetic stirring for 5-7h, placing the filter cake in a vacuum drying oven at 110 ℃ for drying overnight, and grinding to obtain the 10% Ni-S 2O8/ZrO2 catalyst.
As shown in fig. 1, XRD characterization showed diffraction peaks of metallic nickel at positions of 45.5 ℃, 53.04 ℃ and 78.3 ℃ to be present, the intensities of the diffraction peaks being very low, almost invisible, corresponding to the crystal planes (111), (200), (220) of Ni, respectively, indicating that the nickel metal is highly dispersed. Particularly pronounced diffraction peaks at 28.2 ℃, 31.5 ℃, 34.1 ℃ and 50.1 ℃ appear, respectively, ascribed to (-111), (002), (220) crystal planes of ZrO 2.
As shown in fig. 2, SEM characterization shows that the metallic Ni is uniformly coated on the single-component solid super acid carrier, so that the dispersion is uniform, and the surface morphology of the carrier is rough.
As shown in fig. 3, the XPS characterization showed that Ni 2p3/2 in the 10% Ni-S 2O8/ZrO2 solid super acid catalyst exhibited corresponding peak intensities at binding energies 852.4eV and 856.7eV, belonging to the metallic and oxidized states of nickel, respectively.
Comparative example 1: preparation of 10% Ni-S 2O8/ZrO2 catalyst by H 2 reduction
S 2O8/ZrO2 is substantially the same as the preparation method of example 1, except for the reduction method: after Ni is loaded to S 2O8/ZrO2 for drying, solid powder is calcined at 450 ℃ for 2 hours under the flow of 70mL/min argon, then reduced at the same flow of 450 ℃ for 2 hours under the hydrogen with the temperature rising rate of 15 ℃/min, and then cooled to room temperature under the argon atmosphere after calcination and reduction, so as to obtain the 10% Ni-S 2O8/ZrO2 catalyst.
Example 2: hydrogenation application of 10% Ni-S 2O8/ZrO2 solid super acidic catalyst
Taking the catalytic reaction of diphenyl ether as an example:
All catalytic reactions were performed in a 100mL stainless steel autoclave. In a typical experiment, 0.1g of reaction substrate (diphenyl ether), catalyst (50 mg) and isopropyl alcohol (20 mL) were placed in a reactor. After sealing, residual air was removed by passing hydrogen 3 times. Subsequently, the reactor was pressurized to the desired pressure (2 MPa) with hydrogen at room temperature and then the temperature was raised to the desired temperature (180 ℃) and maintained at a vigorous stirring speed of 800rpm for a certain period of time (2 h). After the experiment was completed, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst and the obtained organic phase was analyzed by gas chromatography-mass spectrometry (GC-MS) and gas phase (GC).
TABLE 1 hydrogenation catalytic conversion Performance of catalysts to diphenyl ethers under different reduction methods
Reaction conditions: 0.1g of diphenyl ether, 50mg of catalyst, 20mL of isopropanol, 180 ℃ and 2MPa of H 2 for 2 hours.
Table 1 summarizes the results of the hydroconversion reactions of 10% Ni-S 2O8/ZrO2 solid superacid catalysts prepared by the different reduction methods on diphenyl ether. Obviously, when no catalyst is added, the diphenyl ether is not hydroconverted under the reaction conditions studied; when the single-component S 2O8/ZrO2 catalyst without the load metal is added, the diphenyl ether undergoes weak conversion and has poor catalytic activity. However, when the 10% Ni-S 2O8/ZrO2 catalyst of the supported metallic nickel prepared by different reduction methods is added, the catalytic activity is greatly improved, and the catalytic activities are different from one another. The catalyst prepared by hydrogen reduction has a conversion rate of 30% for diphenyl ether under the reaction condition of 180 ℃ and 2MPa H 2 and 2H; under the same reaction conditions, the conversion rate of diphenyl ether can reach 100% by using the catalyst prepared by reducing sodium borohydride, the obtained product mainly comprises cyclohexane, cyclohexanol and dicyclohexyl ether, and more aromatic ring hydrogenation products dicyclohexyl ether exist at the same time of cracking the diphenyl ether. It can be seen that when the metal is loaded, the catalytic activity of the catalyst is greatly improved, because the added metal sites promote the adsorption and activation of hydrogen, so that the hydrogen is dissociated to generate more active hydrogen, and the hydrocracking reaction of the diphenyl ether is promoted.
Comparative example 2: the solid super acid catalyst loaded with different transition metals is applied to the catalytic hydrogenation of diphenyl ether.
The three solid superacid catalysts, namely 10 percent of Ni-S 2O8/ZrO2、10％Co-S2O8/ZrO2 and 10 percent of Cu-S, are prepared by adopting different metal sources, including nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate through an impregnation method 2O8/ZrO2
To screen out which transition metal has the best hydrogenation performance, all catalytic reactions were performed in a 100mL stainless steel autoclave. In a typical experiment, 0.1g of reaction substrate (diphenyl ether), catalyst (50 mg) and isopropyl alcohol (20 mL) were placed in a reactor. After sealing, residual air was removed by passing hydrogen 3 times. Subsequently, the reactor was pressurized to the desired pressure (2 MPa) with hydrogen at room temperature and then the temperature was raised to the desired temperature (180 ℃) and maintained at a vigorous stirring speed of 800rpm for a certain period of time (2 h). After the experiment was completed, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst and the obtained organic phase was analyzed by gas chromatography-mass spectrometry (GC-MS) and gas phase (GC).
TABLE 2 catalytic Performance of different transition metal solid superacid catalysts for hydrogenation of diphenyl ether
Reaction conditions: 0.1g of diphenyl ether, 50mg of catalyst, 20mL of isopropanol, 180 ℃,2MPa of H 2, 2H.
The experimental results show that: under the same reaction conditions, compared with a solid super acid catalyst which is not loaded with metal and is loaded with metal copper and metal cobalt, the catalytic activity of the 10% Ni-S 2O8/ZrO2 catalyst prepared by loading metal nickel is obviously improved, the conversion rate of diphenyl ether can be improved from less than 20% to 100%, and the obtained product is mainly cyclohexane, cyclohexanol and dicyclohexyl ether which is a hydrogenation product of various aromatic rings. In this catalyst system, the catalytic activity of the transition metal nickel is higher.
Example 3: effect of reaction temperature on diphenyl ether hydroconversion
Reaction conditions: 0.1g of diphenyl ether, 50mg of catalyst, 20mL of isopropanol, 1MPa of H 2, 2H.
As can be seen from FIG. 4, the conversion rate of diphenyl ether by 10% Ni-S 2O8/ZrO2 catalyst is gradually increased along with the increase of the reaction temperature, the conversion rate is only about 30% at 140 ℃, the conversion rate is increased to 100% when the temperature reaches 180 ℃, the temperature is increased continuously, and the products are mainly cyclohexane and cyclohexanol. At temperatures exceeding 160 ℃ the cyclohexylphenyl ether in the product disappears, the c—o bond breaks, and the cleaved product continues to undergo hydrogenation reactions to produce more cyclohexane and cyclohexanol.
Example 4: influence of Hydrogen pressure on the hydroconversion of diphenyl ether
Reaction conditions: 0.1g of diphenyl ether, 50mg of catalyst, 20mL of isopropanol, 180℃for 2h.
As can be seen from FIG. 5, the conversion of diphenyl ether by the 10% Ni-S 2O8/ZrO2 catalyst increased with increasing hydrogen pressure, reaching a maximum of 100% at 1MPa H 2, and then remained unchanged, with the products being predominantly cyclohexane, cyclohexanol and some dicyclohexyl ether. When the hydrogen pressure is increased from 0.5Mpa to 1Mpa, benzene is firstly hydrogenated to form cyclohexane, then C-O bonds are cracked to form more benzene and phenol, and the cracked products are further hydrogenated to form cyclohexane and cyclohexanol.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the high-activity persulphate oxide type solid super acidic catalyst is characterized by comprising the following steps of:
(1) Immersing zirconia powder in 0.01-0.015mol/L ammonium persulfate methanol solution, performing ultrasonic treatment for 10-15min, and then mixing and stirring for 5-7h; the mass volume ratio of the zirconia to the ammonium persulfate methanol solution is 1g:50mL;
(2) Carrying out suction filtration on the mixture obtained in the step (1), drying a filter cake, and grinding to obtain solid powder;
(3) Calcining the solid powder obtained in the step (2) in a muffle furnace, cooling and grinding to obtain S 2O8/ZrO2 solid;
(4) Soaking the S 2O8/ZrO2 solid obtained in the step (3) in a nickel precursor aqueous solution, and carrying out ultrasonic treatment for 10-15min;
(5) Adding sodium borohydride into the mixed solution in the step (4) for reduction, and then stirring for 5-7h;
(6) And (5) carrying out suction filtration, drying a filter cake, and grinding to obtain the Ni-S 2O8/ZrO2 solid super acidic catalyst.
2. The method for preparing a high activity persulfate oxide type solid superacid catalyst according to claim 1, wherein the drying temperature in the step (2) is 100-120 ℃ and the drying time is 16-20h.
3. The method for preparing a high activity persulfate oxide type solid superacid catalyst according to claim 1, wherein the calcination temperature in the step (3) is 550 ℃, the calcination time is 3 hours, and the temperature rising rate is 10 ℃/min.
4. The method for preparing a high activity persulfate oxide type solid super acidic catalyst according to claim 1, wherein the nickel precursor in the step (4) is selected from nickel nitrate hexahydrate, and the Ni loading is 10%.
5. The method for preparing a high-activity persulphate oxide type solid superacid catalyst according to claim 1, wherein the drying mode in the step (6) is vacuum drying, the drying temperature is 110 ℃, and the drying time is 16-20h.
6. A high activity persulfate oxide type solid superacid catalyst characterized by being produced by the production method as set forth in any one of claims 1 to 5.
7. The use of a high activity persulfate oxide type solid superacid catalyst as set forth in claim 6 in a diphenyl ether hydrocracking reaction.
8. The use according to claim 7, characterized in that the specific steps comprise: putting substrate diphenyl ether, ni-S 2O8/ZrO2 solid super acidic catalyst and isopropanol into a reaction kettle, sealing, and replacing 3-4 times of air with hydrogen; pressurizing the reactor with hydrogen at room temperature at 1-2MPa; then the temperature is raised to 160 ℃ to 200 ℃ and is vigorously stirred for 60 to 120min at 800 rpm; after the experiment is finished, naturally cooling the reaction system to room temperature and releasing pressure; the organic phase obtained was filtered and analyzed by gas chromatography-mass spectrometry and gas phase.
9. The use according to claim 8, wherein the catalyst comprises 50% of the substrate mass.
10. The use according to claim 8, wherein the reaction conditions of the hydrogenation reaction are: 180 ℃,1MPa,120min.
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