CN115254126B - Preparation method of biochar-based bifunctional catalyst - Google Patents
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a preparation method of a biochar-based bifunctional Fe-Ni-Ca catalyst, and belongs to the technical field of biomass thermal conversion resource utilization. The invention uses cheap Fe (NO) 3 ) 3 ·9H 2 O，Ni(NO 3 ) 2 ·6H 2 O，Ca(NO 3 ) 2 ·4H 2 O and the wheat straw after pickling pretreatment are used for preparing a difunctional biochar-based Fe-Ni-Ca catalyst and applied to the fixation of AAEM in biomass pyrolysis volatile matters. The catalyst has simple preparation process, the obtained catalyst not only can effectively fix the AAEM in biomass pyrolysis volatile matters, but also can be continuously used for catalytic pyrolysis of biomass after the activity of the catalyst fixed with the AAEM is recovered by simple method treatment. The method is not only suitable for fixing AAEM in biomass catalytic pyrolysis volatile matters, but also can be used for preparing hydrogen-rich gas by biomass catalytic pyrolysis by using the used catalyst.
Description
Technical Field
The invention belongs to the technical field of biomass thermal conversion resource utilization, and particularly relates to a preparation method of a bifunctional biochar-based catalyst.
Background
Energy is the basis and motive power for human society survival and development. The progress of human and the development of society are closely related to the development and utilization of energy, and the environmental pollution and ecological damage generated by the development of energy also influence the survival of human. The primary energy source that human beings rely on to survive and develop at present is mainly mineral energy (coal, petroleum, natural gas, etc.). There are two serious problems associated with the use of fossil energy. First, the reserves of mineral energy are limited. The current worldwide energy consumption and the well-established reserves of mineral energy indicate that the usable years of coal, petroleum and natural gas are 220, 40 and 60 years respectively, and human beings are inevitable to face energy crisis in long-term eye light. Secondly, the mineral energy source has serious damage to the environmentCombustion thereof produces a large amount of CO 2 、NO x And SO x Harmful gases such as the like cause not only global warming and ozone layer destruction but also direct harm to the environment and human health. Thus, thermochemical conversion techniques of biomass, particularly catalytic cracking/gasification, are widely recognized. Since this technology can accelerate conversion of biomass by reducing activation energy and promoting catalytic cracking and gasification reforming, it has proven to be the most promising method to convert biomass into clean fuels that are easy to use. However, biomass catalytic pyrolysis gasification technology is still under development. Currently, biomass refining is greatly emphasized by developed countries such as europe and america, and many countries, particularly developed countries, have already listed it as a strategic measure for economic and social development. In the near future, biomass will become an important source of energy, chemical raw materials, materials. The biomass hydrogen production comprises three methods of supercritical conversion hydrogen production, biomass gasification hydrogen production and biomass pyrolysis oil reforming hydrogen production. The technology for preparing the bio-oil by the rapid pyrolysis of the biomass has obviously advanced in the past 20 years, and provides a new method for the technology of preparing hydrogen by the biomass. The method has the advantage that the biological oil serving as the hydrogen production intermediate is easy to store and transport. At present, although biomass pyrolysis technology is mature, a few problems still exist.
A significant problem is that during long-term operation of the reactor, many ash-related problems (e.g., slagging, corrosion, fouling of heat exchange surfaces, etc.) occur, which are believed to be due to the high Alkali and Alkaline Earth Metal (AAEM) content of the ash. During pyrolysis of biomass, the refractory AAEM materials may react with several ash-based species including pyroxene ((Ca, mg, fe) Si) 2 O 6 ) Spodumene (NaCaMgAl (-Si) 2 O 6 ) 2 ) Anorthite (CaAl) 2 Si 2 O 8 ). On the one hand, the relatively low melting point of these varieties increases the risk of slagging. On the other hand, these species lower the melting temperature of the slag, which is characterized by a low temperature eutectic effect, of the order of 900-1000 ℃. Slagging potential in boilers is typically assessed by Ash Fusion Temperatures (AFTs), whereas mineralsThe composition and ratio determine the type of product under the specific reaction conditions; thus, AFTs are also affected. The problems cause serious problems of boiler scaling, slag bonding, high-temperature corrosion and the like, reduce the heat transfer coefficient of the boiler and even seriously threaten the production safety of a power plant. Aiming at a series of problems in the biomass pyrolysis process, the former makes a great deal of researches, and the proposed solution mainly comprises the steps of adding additives, treating a boiler heat exchange surface or leaching pretreatment and the like. The method for adding the additive is widely researched, but has the problems of low efficiency, high cost, low heat value and the like. At present, the boiler conversion surface treatment is also used for preventing ash from scaling and slagging. In order to reduce the extent of fouling and slagging, it is desirable to develop a new process to address this urgent problem. The invention develops a novel catalyst which can treat AAEM in biomass pyrolysis volatile matters, promote cracking of biomass pyrolysis tar, and maintain activity similar to that of a fresh catalyst. The catalyst has the characteristics of simple preparation method, low energy consumption, easy preparation and the like, and has great application prospect.
Disclosure of Invention
According to the invention, wheat straw is used as a raw material, a biochar-based catalyst is prepared firstly, then an ICP analysis technology is utilized to detect the AAEM fixing effect of the catalyst in biomass pyrolysis volatile matters, and finally the catalyst with the immobilized AAEM is used for biomass catalytic pyrolysis experiments. One of the purposes of the invention is to prepare a high-efficiency biochar-based Fe-Ni-Ca composite catalyst which can adsorb AAEM in biomass pyrolysis volatile matters and protect downstream pipelines, and has activity similar to that of a fresh catalyst after the AAEM in the volatile matters is immobilized.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the biochar-based bifunctional catalyst comprises the following steps:
(1) Carrying out acid washing pretreatment on the wheat straw: firstly, treating the wheat straw with a nitric acid pre-solution with a certain concentration, and then cleaning the wheat straw with deionized water to obtain an acid-washing pretreated wheat straw;
(2) Loading of iron-calcium-nickel catalyst: pretreating wheat straw and Fe (NO) with a certain concentration by pickling, wherein the wheat straw is obtained in the step (1) 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Ca(NO 3 ) 2 ·4H 2 Fully mixing the O aqueous solution, performing ultrasonic treatment in an ultrasonic instrument, then placing the mixture in a water bath kettle to evaporate redundant water, and then drying the mixture in a blast drying oven to obtain the wheat straw loaded with metal;
(3) Calcination of the catalyst-supporting biomass: calcining the wheat straw loaded with the metal obtained in the step (2) in a fixed bed reactor, wherein nitrogen is used as carrier gas in the calcining process, and calcining to obtain the biochar-based Fe-Ni-Ca catalyst;
(4) Fixing AAEM in wheat straw by using biochar-based Fe-Ni-Ca catalyst: in a two-stage fixed bed reactor, the wheat straw with the same amount of potassium, calcium, sodium and magnesium as the original wheat straw mineral substances is respectively added after the original wheat straw is filled in the upper stage and subjected to pickling pretreatment, and the catalyst obtained in the step (3) is filled in the lower stage to obtain the catalyst for fixing the AAEM in the biomass pyrolysis volatile matters;
(5) Recovery of activity after AAEM in immobilized biomass pyrolysis volatiles: and (3) calcining the catalyst with the AAEM immobilized in the biomass pyrolysis volatile component in the step (4) in a nitrogen atmosphere to remove carbon deposit on the surface.
Further; in the step (1), the concentration of the nitric acid pre-solution is 0.2mol/L, and the pretreatment stirring time is 24 hours.
Further; in the step (1), the wheat straw is selected to be 40 meshes.
Further; in the step (2), after one hour of ultrasonic treatment in an ultrasonic instrument, the excessive water is evaporated in a water bath at 80 ℃, and then dried in a blast drying oven at 80 ℃ for 24 hours.
Further; in the step (3), the calcination temperature in the fixed bed reactor is 900 ℃, the heat preservation time is 2 hours, nitrogen is used as carrier gas in the calcination process, and the flow rate is 200mL/min.
Further; in the step (4), the temperature of the lower section is 600 ℃, and the temperature of the upper section is 200 ℃,300 ℃,400 ℃,500 ℃,600 ℃,700 ℃ and 800 ℃ respectively; the incubation time at the different temperatures was one hour and the carrier gas flow rate was 40mL/min.
Further; in the step (5), the temperature is kept for 1h from the temperature rising rate of 10 ℃/min to 600 ℃ under the nitrogen atmosphere.
Further; in the step (4), the mass ratio of the wheat straw to the biochar-based Fe-Ni-Ca is 1-5:1.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The biochar-based Fe-Ni-Ca catalyst prepared by the method has better stability.
(2) The biochar-based Fe-Ni-Ca catalyst prepared by the invention can effectively fix the AAEM in biomass pyrolysis volatile matters, and can effectively prevent the problems of downstream pipeline blockage and reactor slagging.
(3) The biochar-based Fe-Ni-Ca catalyst prepared by the invention can be recycled, and experimental data and characterization analysis (SEM and TEM) show that the catalyst which is recycled maintains catalytic activity almost equal to that of a fresh catalyst.
Drawings
FIG. 1 is a catalyst flow diagram of the present invention;
FIG. 2 is a TEM image of the carbon-based Fe-Ni-Ca catalyst of the present invention, with the left image being a fresh carbon-based Fe-Ni-Ca catalyst; the right figure shows the catalyst after adsorbing AAEM in biomass pyrolysis volatiles.
FIG. 3 is an SEM image of a carbon-based Fe-Ni-Ca catalyst of the present invention; the upper two are fresh carbon-based Fe-Ni-Ca catalysts; the next two are catalysts after adsorbing AAEM in biomass pyrolysis volatiles.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
a preparation method of a biochar-based Fe-Ni-Ca catalyst comprises the following specific steps:
(1) Carrying out acid washing pretreatment on the wheat straw: the wheat straw which is dried in advance is ground, and the wheat straw with the grain diameter of 40 meshes is screened out. And weighing a certain amount of wheat straw for standby, preparing a nitric acid solution with the concentration of 0.2mol/L in a volumetric flask, pouring the weighed wheat straw into the nitric acid solution with the concentration of 0.2mol/L, pre-treating and stirring for 24 hours, and then washing with a large amount of deionized water until PH test paper does not change color, and removing the inherent AAEM in the raw materials.
(2) Loading of iron-calcium-nickel catalyst: 10.821g of Fe (NO) 3 ) 3 ·9H 2 O 1.2219g Ni(NO 3 ) 2 ·6H 2 O,2.6567g Ca(NO 3 ) 2 ·4H 2 Dissolving the catalyst precursor of O in 25mL of ionized water, and fully dissolving for later use; then weighing 30g of pretreated wheat straw, fully mixing with the prepared dissolution solution, carrying out ultrasonic treatment in an ultrasonic instrument for 1h, then placing in a water bath kettle at 80 ℃ to evaporate excessive moisture, and finally drying in an oven at 80 ℃ for 24h to obtain the wheat straw loaded with metal.
(3) Calcination of the catalyst-supporting biomass: calcining the catalyst in a fixed bed reactor by a one-step process; firstly, placing a wheat straw sample loaded with metal into a reaction tube, after the reaction tube is installed, purging a reactor with 200mL/min nitrogen for 20 minutes to replace air, then starting heating to 900 ℃ at a heating rate of 10 ℃/min for calcination, preserving heat for 2 hours at a target temperature, keeping the carrier gas flow rate of 200mL/min in the whole process, and stopping heating after preserving heat for two hours. And when the temperature of the reactor is reduced to room temperature, the reaction tube is taken down, the calcined sample is taken out, and the calcined sample is ground and then passes through a 120-mesh sieve, so that the obtained sample is the biochar-based Fe-Ni-Ca catalyst.
(4) Fixing AAEM in wheat straw by using biochar-based Fe-Ni-Ca catalyst: the method is characterized in that the effect of the catalyst on the immobilization of AAEM in pyrolysis volatile matters is studied in a two-stage fixed bed reactor, wheat loaded with potassium, calcium, sodium and magnesium is taken as raw materials and is placed at the upper section of a reaction tube, and the catalyst prepared in the step (3) is placed at the lower section of the reaction tube. After the reaction tube is installed, the reactor is purged by nitrogen with the flow rate of 200mL/min to replace air, then the flow rate of carrier gas is changed to 40mL/min, the lower section begins to heat the upper section at the rate of 10 ℃/min after rising to 600 ℃ at the heating rate of 20 ℃/min, and the temperature is preserved for 1h at the target temperature (200 ℃,300 ℃,400 ℃,500 ℃,600 ℃,700 ℃); experiments at different target temperatures are independent of each other, and the experiments are finished after the target temperatures are kept for one hour. A second target temperature experiment was started after the reactor temperature was reduced to room temperature. The carrier gas flow rate was 40mL/min for each experiment. After each reaction, the reactor is cooled to room temperature, the reaction tube is taken out, and the catalyst at the lower section is collected into a self-sealing bag for standby.
The performance of the catalyst in this example: the performance of the catalyst at different pyrolysis temperatures of the wheat straw was evaluated by using an ICP detection means, and table 1 shows ICP detection results of the catalyst obtained at different pyrolysis temperatures.
TABLE 1 content of carbon-based catalyst AAEM
From an examination of the data in table 1, it was found that AAEM in the feedstock was immobilized on the catalyst at different pyrolysis temperatures. And as the temperature increases, the immobilized AAEM increases as the high temperature favors volatilization of the AAEM.
Recovery of activity of AAEM immobilized catalyst: taking into account that part of carbon deposition exists in the pyrolysis process of the catalyst, the catalyst is calcined at 600 ℃, namely the catalyst is put into a tube furnace, and the catalyst is kept at 600 ℃ for one hour at a heating rate of 10 ℃/min in nitrogen atmosphere, so that the catalyst with carbon deposition removed is obtained.
Activity detection of AAEM immobilized catalyst: the process is carried out in a two-stage fixed bed reactor. The raw materials are wheat straw after acid washing, and the catalysts are two types, namely the catalyst with the activity recovered by the steps, and the catalyst is a fresh carbon-based Fe-Ni-Ca catalyst. After the reaction tube was installed, the reactor was purged with 200mL/min of nitrogen to displace air, then the carrier gas flow rate was changed to 40mL/min, the lower stage was started to be warmed to the target temperature at a rate of 10 ℃/min after being warmed to 600℃at a rate of 20 ℃/min, and the upper stage was incubated at the target temperature for 1 hour. The pickled wheat straw is used as a raw material, and is placed at the upper section of a reaction tube, and two types of catalysts in the implementation process are placed at the lower section of the reaction tube, so that a comparison experiment is carried out. The purpose of the upper section is to pyrolyze the wheat straw after acid washing at high temperature to generate pyrolysis volatile matters, and the lower section is to place different catalysts to compare the catalytic reforming effect of the two types of catalysts on the biomass pyrolysis volatile matters. Compared with a fresh Fe-Ni-Ca catalyst, the catalyst can show whether the AAEM immobilized in biomass pyrolysis volatile matters can be recycled or not. The pyrolysis gas generated in the reaction process is collected by using a gas bag, and the yield is analyzed by gas chromatography. The table shows the contents of the components in the gas phase.
Table 2 shows the distribution of biomass pyrolysis gas yields in this comparative example. It (mL/g) was determined as:
Y i : yield of each component in gas (unit: mL/g);
i: the percentage of each component detected in the gas chromatograph;
V total total volume of gas (mL);
m raw biomass mass (g);
A raw : the percentage of ash in the biomass.
Table 2: the contents of the components in the gas product in the examples
Class a catalysts: the catalyst absorbing the potassium element in the volatile matters is calcined to obtain the catalyst; class B catalysts: the catalyst absorbing calcium in volatile matters is calcined to obtain the catalyst; class C catalysts: the catalyst absorbing sodium element in volatile matters is calcined to obtain the catalyst; class D catalyst: the catalyst absorbing magnesium element in volatile matters is calcined to obtain the catalyst.
The comparison shows that the activity of the catalyst with the AAEM in the biomass pyrolysis volatile matters immobilized is fully utilized after calcination, and the catalytic activity of the catalyst is almost the same as that of a fresh catalyst.
FIG. 2 is a TEM image of the carbon-based Fe-Ni-Ca catalyst of the present invention, with the left image being a fresh carbon-based Fe-Ni-Ca catalyst; the right figure shows the catalyst after adsorbing AAEM in biomass pyrolysis volatile matters; from the figures it can be seen that the metal particles are uniformly distributed on the carbon support, however, by comparing the two figures it can be seen that the black particles in the right figure are slightly larger than the left figure, probably because the biochar-based Fe-Ni-Ca catalyst has a small part of carbon deposit on the catalyst surface in spite of the simple treatment volatilizing activity of AAEM in adsorbing biomass pyrolysis volatiles.
FIG. 3 is an SEM image of a carbon-based Fe-Ni-Ca catalyst of the present invention; the upper two are fresh carbon-based Fe-Ni-Ca catalysts; the next two are catalysts after adsorbing AAEM in biomass pyrolysis volatiles. From the left two figures it can be seen that both types of catalyst supports retain the unique pore structure of the biomass, such surface properties providing active sites for catalytic reactions. As can be seen by comparing the two figures on the right, the metal particles are uniformly distributed on the biochar support, except that the particle sizes are not uniform, and the particle sizes in the lower right figure are slightly larger, which corresponds to the results of the TEM images.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure. More specifically, various variations and modifications may be made to the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, drawings and claims of this application. In addition to variations and modifications in the component parts and/or arrangements, other uses will be apparent to those skilled in the art.
Claims (4)
1. An application of a biochar-based bifunctional catalyst is characterized in that: the catalyst fixes alkali and alkaline earth metals in biomass pyrolysis volatile matters, and then the catalyst fixed with the alkali and alkaline earth metals is used for biomass catalytic pyrolysis reaction;
the method specifically comprises the following steps:
(1) Carrying out acid washing pretreatment on the wheat straw: firstly, treating the wheat straw with a nitric acid solution with a certain concentration, and then cleaning the wheat straw with deionized water to obtain the wheat straw pretreated by acid washing;
(2) Loading of iron-calcium-nickel catalyst: pretreating wheat straw and Fe (NO) with a certain concentration by pickling, wherein the wheat straw is obtained in the step (1) 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Ca(NO 3 ) 2 ·4H 2 Fully mixing the O aqueous solution, performing ultrasonic treatment in an ultrasonic instrument, then placing the mixture in a water bath kettle to evaporate redundant water, and then drying the mixture in a blast drying oven to obtain the wheat straw loaded with metal;
(3) Calcination of the catalyst-supporting biomass: calcining the wheat straw loaded with metal obtained in the step (2) in a fixed bed reactor, wherein nitrogen is used as carrier gas in the calcining process, and calcining to obtain the biochar-based Fe-Ni-Ca catalyst;
(4) Fixing alkali and alkaline earth metals in wheat straw by using a biochar-based Fe-Ni-Ca catalyst: carrying out the experiment in a two-stage fixed bed reactor, wherein the upper stage of the reactor is filled with the original wheat straw, and after the original wheat straw is subjected to acid washing pretreatment, the wheat straw with the same amount of potassium, calcium, sodium and magnesium as those in the mineral substances of the original wheat straw is respectively added, and the lower stage of the reactor is filled with the catalyst obtained in the step (3), so that the catalyst for fixing alkali and alkaline earth metals in the biomass pyrolysis volatile matters is obtained;
(5) And (3) activity recovery of the Fe-Ni-Ca catalyst after alkali and alkaline earth metals in the biomass pyrolysis volatile matters are fixed: calcining the catalyst fixed with alkali and alkaline earth metals in biomass pyrolysis volatile matters in the step (4) in a nitrogen atmosphere to remove carbon deposit on the surface;
(6) The catalyst with the recovered activity in the step 5 is used for catalytic reforming of biomass pyrolysis volatile matters;
in the step (3), the calcination temperature in the fixed bed reactor is 900 ℃, the heat preservation time is 2 hours, and the flow rate is 200mL/min;
in the step (4), the temperature of the lower section is 600 ℃, and the temperature of the upper section is 200 ℃,300 ℃,400 ℃,500 ℃,600 ℃,700 ℃ and 800 ℃ respectively; the heat preservation time at different temperatures is one hour, and the carrier gas flow rate is 40mL/min;
in the step (5), the temperature is kept for 1h from the temperature rising rate of 10 ℃/min to 600 ℃ in the nitrogen atmosphere;
in the step (4), the mass ratio of the wheat straw to the biochar-based Fe-Ni-Ca is 1-5:1.
2. The use according to claim 1, characterized in that: in the step (1), the concentration of the nitric acid solution is 0.2mol/L, and the pretreatment stirring time is 24 hours.
3. The use according to claim 1, characterized in that: in the step (1), the wheat straw is selected to be 40 meshes.
4. The use according to claim 1, characterized in that: in the step (2), after one hour of ultrasonic treatment in an ultrasonic instrument, the excessive water is evaporated in a water bath at 80 ℃, and then dried in a blast drying oven at 80 ℃ for 24 hours.
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