CN115869952B - Catalyst for hydrogen production by plastic degradation and preparation method and application thereof - Google Patents
Catalyst for hydrogen production by plastic degradation and preparation method and application thereof Download PDFInfo
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- CN115869952B CN115869952B CN202310146242.0A CN202310146242A CN115869952B CN 115869952 B CN115869952 B CN 115869952B CN 202310146242 A CN202310146242 A CN 202310146242A CN 115869952 B CN115869952 B CN 115869952B
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Abstract
The invention discloses a catalyst for hydrogen production by plastic degradation, a preparation method and application thereof, and relates to the field of waste treatment. The method comprises the following steps: respectively preparing an alcohol solution A containing aluminum oxide and an alcohol solution B containing ferric salt and alkali, mixing, performing solvothermal reaction, filtering, drying, calcining in an oxygen-containing gas atmosphere, quenching, filtering and washing to obtain the catalyst. The catalyst is an alumina/ferric oxide composite material containing hydroxyl and oxygen defects and having a heterojunction structure, has high specific surface area, is favorable for catalyzing the exposure of self surface active sites in the plastic degradation process, can generate active hydrogen in situ, optimizes hydrogenolysis and chain scission of long-chain alkane, has the capability of cracking polyethylene plastic by alumina, and also has the catalytic activity of aromatization reaction of iron element in the plastic pyrolysis process, and meanwhile, the oxygen defect structure of ferric oxide brings more Lewis acid sites, so that the catalyst has high catalytic activity and low cost.
Description
Technical Field
The invention relates to the field of waste material treatment, in particular to a catalyst for hydrogen production by plastic degradation, a preparation method and application thereof.
Background
The global plastic raw material yield would reach 11 million tons in 2050, as estimated by the united nations environmental planning agency (UNEP). The plastic is taken as an important component in the field of carbon circulation, and the plastic is effectively recycled in resource so as to be beneficial to simultaneously realizing carbon and pollutant emission reduction.
To date, the most common methods for treating waste plastics are landfill, incineration, pyrolysis and the like, wherein the two methods have low decomposition efficiency on plastics and are easy to cause great pressure on environmental resources; pyrolysis technology can convert waste plastics into high added value energy sources such as fuel oil, hydrogen, solid fuel and the like, but generally requires noble metal catalysts such as ruthenium, platinum and the like, so that the technology is high in implementation cost and difficult to land.
Disclosure of Invention
The invention provides a catalyst for hydrogen production by plastic degradation, and a preparation method and application thereof, and aims to provide a catalyst with low cost and high catalytic activity for hydrogen production by plastic degradation.
In order to solve the technical problems, one of the purposes of the invention is to provide a preparation method of a catalyst for hydrogen production by plastic degradation, which comprises the following steps:
(1) Respectively preparing an alcohol solution A containing aluminum oxide and an alcohol solution B containing ferric salt and alkali, pouring the alcohol solution B into the alcohol solution A which is continuously stirred for solvothermal reaction, filtering after the reaction, and drying in an atmosphere containing oxygen to obtain an aluminum-iron-containing precursor;
(2) Calcining precursor containing aluminum and iron in oxygen-containing gas atmosphere, quenching after the end, filtering and washing to obtain the catalyst containing heterojunction structure, wherein the structure also contains hydroxyl and oxygen defects.
According to the scheme, the aluminum-containing and iron-containing precursor is prepared by the solvothermal method, the spinel type iron aluminate generated by the product can be avoided by adopting the aluminum oxide, and the aluminum oxide/iron oxide composite material containing hydroxyl and oxygen defects and having a heterojunction structure is obtained after calcination and quenching. The heterojunction structure of the aluminum oxide and the ferric oxide has the cracking capability of the aluminum oxide on polyethylene plastics, and also has the catalytic activity of aromatization reaction of iron element in the plastic pyrolysis process, and meanwhile, the oxygen defect structure of the ferric oxide brings more Lewis acid sites, so that the surface acidity of the catalyst is further improved, and the gas component generated by plastic degradation catalysis is increased.
Preferably, in step (1), the molar ratio of the iron salt to the alumina is 1: (0.1-20).
Preferably, in step (1), the molar ratio of the iron salt to the alumina is 1: (0.4-4).
Preferably, in step (1), the iron salt is one or more of nitrate of iron, sulfate of iron, acetate of iron, chloride of iron or hydrate of the above.
Preferably, the particle size of the alumina is 10-50nm.
Preferably, in step (1), the alcohol in the alcohol solution a and the alcohol solution B is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and sec-butanol.
In the step (1), the alkali in the alcohol solution B is one or more of ammonia water, ethylenediamine and triethylamine, and the pH value of the alcohol solution B is adjusted to be 10.5-12.5 by adopting the alkali.
By adopting the scheme, as the surface of the alumina has rich Lewis acidic sites, the crystal phase of the catalyst product prepared without adding alkali is relatively impurity and unstable, and possibly contains oxides, oxyhydroxide, hydrate containing ferric salt and the like.
In the step (1), the solvothermal reaction temperature is 60-120 ℃ and the reaction time is 15-30 h; the drying temperature is 50-120 ℃.
Preferably, in the step (2), the calcination temperature is 150-600 ℃ and the calcination time is 0.1-4 h.
Preferably, in the step (2), the calcination temperature is 300-500 ℃ and the calcination time is 1-3 h.
Preferably, in the step (2), quenching is performed in an aqueous solution containing iron, wherein the iron in the aqueous solution containing iron is one or more of ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric triacetate, ferrous chloride and ferric chloride.
By adopting the scheme, the quenching medium has influence on the quenching effect, and compared with a pure water solution, the ferric salt water solution has higher cooling speed during quenching, and can bring more oxygen defect structures to the material and improve the activity of the catalyst.
Preferably, the concentration of iron in the aqueous solution containing iron is 0.01 mol-1 mol.
Preferably, in the steps (1) and (2), the oxygen-containing gas atmosphere is one or more of air, oxygen/nitrogen mixed gas with any proportion and oxygen/inert gas mixed gas with any proportion.
By adopting the scheme, the iron-containing base precursor on the surface of the aluminum oxide can be completely converted into the ferric oxide active species after solvothermal reaction in the oxygen-containing gas atmosphere, and the product is ensured to form aluminum oxide/ferric oxide with a heterojunction structure.
In order to solve the technical problems, the second object of the invention is to provide a catalyst for producing hydrogen by plastic degradation.
In order to solve the technical problems, the invention provides an application of the catalyst in the field of plastic degradation.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst is an alumina/ferric oxide composite material containing hydroxyl and oxygen defects and having a heterojunction structure, the specific surface area of the material is high, the exposure of the surface active sites of the material in the process of catalyzing plastic degradation is facilitated, the exposed hydroxyl can generate active hydrogen in situ, the hydrogenolysis is optimized, and long-chain alkane chain scission is realized.
Drawings
Fig. 1: a scanning electron microscope image of a catalyst for hydrogen production by plastic degradation in 200nm resolution in the embodiment 3 of the invention;
fig. 2: a scanning electron microscope image of a catalyst for hydrogen production by plastic degradation in the resolution of 50nm in the embodiment 3 of the invention;
FIG. 3; a nitrogen isothermal adsorption and desorption curve chart of a catalyst for hydrogen production by plastic degradation in the embodiment 3 of the invention;
fig. 4: the Fourier transform infrared spectrogram of the catalyst for producing hydrogen by plastic degradation in the embodiment 3 of the invention;
fig. 5: the Fourier transform infrared spectrogram of the catalyst for producing hydrogen by plastic degradation in the embodiment 5 of the invention;
fig. 6: a Fourier transform infrared spectrogram of a catalyst for producing hydrogen by plastic degradation in comparative example 1;
fig. 7: a high-resolution transmission electron microscope image of a catalyst for hydrogen production by plastic degradation in the embodiment 3 of the invention;
fig. 8: an XPS diagram of a catalyst for hydrogen production by plastic degradation in example 3 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A catalyst for producing hydrogen by plastic degradation, comprising the following preparation steps:
(1) Preparation of aluminum-containing and iron-containing precursors: 5mmol of alumina with the particle size of 20 nm is dispersed in 100 mL absolute ethyl alcohol in an ultrasonic way to form a dispersion liquid A, and the dispersion liquid A is transferred into an oil bath kettle to be stirred; dispersing 0.5 mmol of anhydrous ferric chloride in 100 mL absolute ethyl alcohol by ultrasonic, adding 2 mL ammonia water (the concentration is 28 wt%), continuing ultrasonic to obtain a solution B, regulating the pH value of the alcohol solution B to be within 10.5-12.5 by ammonia water, pouring the solution B into a continuously stirred dispersion liquid A to perform solvothermal reaction with the reaction temperature of 80 ℃ and the reaction time of 24 h, performing reduced pressure filtration after the reaction is finished, and drying overnight in a forced air drying oven in an air atmosphere at 105 ℃ to obtain an aluminum-iron-containing precursor;
(2) Preparation of catalyst for hydrogen production by plastic degradation: placing the aluminum-containing and iron-containing precursor powder obtained in the step (1) into a corundum porcelain boat, and transferring the porcelain boat to a muffleFurnace at 50deg.C for min in air atmosphere -1 And (2) heating to 350 ℃ and preserving heat for 2 h for calcining, immediately transferring the catalyst into 0.3 mol ferric chloride aqueous solution for quenching after the reaction is finished, filtering and washing with deionized water to obtain the catalyst for preparing hydrogen by plastic degradation.
Example two
The catalyst for producing hydrogen by degrading plastics is prepared by the same steps as the first embodiment, and the reagents and process parameters used in the steps are the same as those in the first embodiment except that in the step (1), the content of alumina is 2mmol.
Example III
The catalyst for producing hydrogen by plastic degradation is prepared by the same steps as the first embodiment, and the reagents and technological parameters used in the steps are the same as those in the first embodiment, except that in the step (1), the contents of alumina and anhydrous ferric chloride are 2mmol.
Characterization results show that the morphology structure of the third embodiment is shown in fig. 1-2, and after the aluminum-containing and iron-containing precursor obtained through solvothermal reaction is calcined and extracted, as shown in fig. 8, peaks at positions of binding energies 530.4 eV, 531.1 eV, 531.8eV and 532.5 eV respectively represent an Fe-O bond, an Al-O bond, a hydroxyl group and an oxygen defect structure (oxygen vany), which indicates that iron oxide particles with oxygen defect structures are interpenetrated and grown on the alumina film substrate. And as shown in fig. 7, the catalyst prepared in example 3 can obviously observe crystal planes belonging to the alumina (220) and the crystal plane of the iron oxide (110), and a heterojunction structure is formed at the junction of the two crystal planes, which indicates that the obtained alumina/iron oxide composite material has a heterojunction structure. As shown in the test of the isothermal adsorption and desorption curve of the nitrogen in FIG. 3, the specific surface area of the catalyst prepared in the third embodiment is as high as 142.53 m 2 g -1 The catalyst is beneficial to the exposure of the active site of the catalyst surface in the process of catalyzing the degradation of the plastic; the results of the Fourier IR spectrum in FIG. 4 show that the catalyst of example three, after qualitative analysis, was found to be a catalyst other than at 560cm -1 Containing Fe-O bonds and at 552 cm -1 And at 821 cm -1 Contains Al-O bond, and contains a large amount of hydroxyl groups in the structure, hydrogen in the hydroxyl structureMolecular hydrogen bonds are formed between the catalyst and carbon atoms on hydrocarbon obtained by pyrolysis of plastics in situ, so that the activation energy of dehydrogenation is reduced, the hydrogenolysis in the process of catalyzing plastic degradation is optimized, and more hydrogen gas is obtained from the product.
Example IV
The catalyst for producing hydrogen by plastic degradation is characterized in that the preparation method comprises the steps, reagents used in the steps and process parameters the same as those in the first embodiment, and the difference is that in the step (1), the content of alumina is 2mmol, and the content of anhydrous ferric chloride is 5mmol.
Example five
The catalyst for producing hydrogen by plastic degradation is characterized in that in the step (2), 0.3. 0.3M of ferric chloride aqueous solution for quenching is replaced by deionized water.
Characterization results are shown in FIG. 5, which shows the Fourier infrared spectrum results at 552 cm in the catalyst structure of this example -1 And at 821 cm -1 The position contains Al-O bond at 560cm -1 The catalyst contains Fe-O bond and part of adsorbed water molecules, and also contains a large amount of hydroxyl groups.
Comparative example one
The preparation method of the catalyst for hydrogen production by plastic degradation comprises the following steps: 5mmol of alumina having a particle size of 20. 20 nm was placed in a corundum porcelain boat and the boat was transferred to a muffle furnace at 50℃for a minute in an air atmosphere -1 And (2) heating to 350 ℃ and preserving heat for 2 h to calcine, thus obtaining the catalyst.
Comparative example one without added iron oxide component, therefore, no quenching step was performed, and the characterization result was shown as the result of the Fourier IR spectrum of FIG. 6, after qualitative analysis, the comparative example one showed only 552 cm in the catalyst structure -1 Sum 821 cm -1 The water molecules which are partially adsorbed and contain Al-O bonds and also contain a large number of hydroxyl groups, and the water molecules do not contain Fe-O bonds.
Performance test
1. Generating device and detecting device for rapid pyrolysis degradation of plasticsA combined system for separation detection (8890, agilent, USA) was performed with a vertical microreactor (Rx-3050 TR, front end laboratories, japan) and gas chromatography, respectively. The system adopts helium as carrier gas, and the flow is 156 mL min -1 The plastics were high density polyethylene powder, 100 μg feed, catalyst examples 1-5 or comparative example 1, feed 2 mg. In the reaction, the pyrolysis reaction temperature of the upper layer of the vertical microreactor is 600 ℃, and the catalysis temperature of the lower layer is 800 ℃. In detection, the gas product of the reaction is separated by chromatographic column (113-4362, agilent) and detected by thermal conductivity detector, with reference flow rate of 20 mL min -1 . The initial temperature of the column box of the gas chromatograph is 40 ℃ and the temperature is 6 ℃ for min -1 The temperature rise rate of (2) was increased to 280℃and maintained for 6 min. The hydrogen production of the catalytic degradation high-density polyethylene powder of different examples and comparative examples is quantified by an external standard method, and the hydrogen production of the catalytic degradation high-density polyethylene powder of different examples and comparative examples is shown in the table 1 below.
TABLE 1 catalytic degradation of hydrogen production by catalysts of examples and comparative examples herein
| Detecting items | Hydrogen production (mul) |
| Example 1 | 20.63 |
| Example two | 32.19 |
| Example III | 78.04 |
| Example IV | 39.39 |
| Example five | 66.16 |
| Comparative example one | 3.14 |
As can be seen from the performance detection results of the embodiment 1 and the comparative example 1 in the table 1, the catalyst is an alumina/ferric oxide composite material containing hydroxyl and oxygen defects and having a heterojunction structure, has a high specific surface area, is favorable for catalyzing the exposure of self surface active sites in the plastic degradation process, has the capability of cracking polyethylene plastic by using alumina, has the catalytic activity of aromatization reaction of iron element in the plastic pyrolysis process, and has more Lewis acid sites brought by the oxygen defect structure of ferric oxide, and the catalytic activity is obviously higher than that of the alumina of the comparative example 1.
As can be seen from the performance test results of examples 1 and 5 in table 1, the present application uses the aqueous solution containing iron as the quenching medium, and compared with the pure aqueous solution, the aqueous solution containing salt has a higher cooling rate, and can bring more oxygen defect structures to the material, thereby improving the activity of the catalyst.
As can be seen from a combination of the performance measurements of examples 1-4 in table 1, the present application defines the molar ratio of iron oxide to aluminum oxide, which allows control of the catalytic activity of the catalyst when the molar ratio of iron oxide to aluminum oxide is 1:1, the hydrogen production capacity of the catalyst is the highest.
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present invention, and are not to be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit and principles of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the catalyst for producing hydrogen by plastic degradation is characterized by comprising the following steps:
(1) Respectively preparing an alcohol solution A containing aluminum oxide and an alcohol solution B containing ferric salt and alkali, pouring the alcohol solution B into the alcohol solution A which is continuously stirred for solvothermal reaction, wherein the solvothermal reaction temperature is 60-120 ℃, the reaction time is 15-30 h, filtering after the reaction, and drying in an oxygen-containing gas atmosphere to obtain an aluminum-iron-containing precursor;
(2) Calcining precursor containing aluminum and iron in an oxygen-containing gas atmosphere, quenching after the end, filtering and washing to obtain a catalyst containing a heterojunction structure, wherein the structure also contains hydroxyl and oxygen defects;
in step (1), the molar ratio of iron salt to alumina is 1:1, the alkali in the alcohol solution B is one or more of ammonia water, ethylenediamine and triethylamine, and the pH value of the alcohol solution B is regulated to be 10.5-12.5 by adopting the alkali; in the step (2), the calcination temperature is 150-600 ℃ and the calcination time is 0.1-4 h; quenching in an aqueous solution containing iron.
2. The method of preparing a catalyst for hydrogen production by plastic degradation as claimed in claim 1, wherein in the step (1), the iron salt is one or more of nitrate of iron, sulfate of iron, acetate of iron, chloride of iron, or hydrate of the above.
3. The method for preparing a catalyst for hydrogen production by plastic degradation according to claim 1, wherein in the step (1), the alcohol in the alcohol solution a and the alcohol solution B is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and sec-butanol.
4. The method for preparing a catalyst for hydrogen production by plastic degradation as claimed in claim 1, wherein in the step (1), the drying temperature is 50 to 120 ℃.
5. The method for preparing a catalyst for hydrogen production by plastic degradation as claimed in claim 1, wherein in the step (2), the iron in the aqueous solution containing iron is one or more of ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric triacetate, ferrous chloride, and ferric chloride, and the concentration of the iron in the aqueous solution containing iron is 0.01 mol L -1 -1 mol L -1 。
6. The method for preparing a catalyst for hydrogen production by plastic degradation as claimed in claim 1, wherein in the steps (1) and (2), the atmosphere of the oxygen-containing gas is one or more of air, oxygen/nitrogen mixture of any proportion, and oxygen/inert gas mixture of any proportion.
7. Use of the catalyst prepared in the preparation method based on the catalyst for hydrogen production by plastic degradation according to any one of claims 1-6 in the field of plastic degradation.
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