CN113477238A - Organic acid modified CaO catalyst, and preparation method and application thereof - Google Patents
Organic acid modified CaO catalyst, and preparation method and application thereof Download PDFInfo
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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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention belongs to the field of biomass utilization, and particularly relates to an organic acid modified CaO catalyst, and a preparation method and application thereof. The method comprises the following steps: mixing the high-calcium solid waste with an organic acid solution, and drying to obtain a catalyst precursor; and calcining the catalyst precursor to prepare the organic acid modified CaO catalyst. According to the invention, organic acid is utilized to modify the high-calcium solid waste based CaO, so that the surface modification of the high-calcium solid waste can be carried out, the surface appearance and the pore structure of the high-calcium solid waste are influenced, the calcined CaO has a richer pore structure and a larger specific surface area, the particles are dispersed more uniformly, the active sites on the surface are richer, the CaO with excellent performance can be obtained while the solid waste is recycled, the resource utilization of the high-calcium solid waste is favorably realized, the exploitation of limestone, dolomite and other ores is relieved, and the ecological environment is protected.
Description
Technical Field
The invention belongs to the field of biomass utilization, and particularly relates to an organic acid modified CaO catalyst, and a preparation method and application thereof.
Background
The development and progress of the current society are closely related to energy sources, and the traditional fossil energy sources have the defects of limited resources and easy environmental pollution, so that renewable and low-pollution alternative energy sources are urgently needed to be found. China has abundant biomass resource reserves, develops and continuously optimizes a biomass conversion mode, is beneficial to reasonably disposing biomass solid wastes and promotes resource utilization, and has important significance for relieving the current situation of energy resource shortage in China and realizing the aim of carbon neutralization by carbon peak.
Active sites or shape selectivity of the catalyst in the catalytic pyrolysis process of the biomass can change a secondary reaction path of volatile matters, so that the quality of a product is improved, CaO has the advantages of high chemical activity, environmental friendliness, high yield and the like, a prominent effect is achieved on modification and quality improvement of bio-oil and pyrolysis gas, and CO can be removed2The form of the biological oil removes oxygen in the biological oil, so that the biological oil has higher H/C ratio, and CaO can absorb CO in gas in the pyrolysis process2Increasing H in the pyrolysis gas2、CH4The content of the components is equal, the heat value of the pyrolysis gas is improved, the carbon emission is reduced, and the greenhouse effect is reduced.
The conventionally used CaO catalyst is generally prepared by calcining analytically pure reagents such as calcium carbonate and the like, and although a certain effect is achieved on the improvement of the product quality, the oxygen content in the pyrolysis oil is still kept at a high level, and the reaction cost is increased to a certain extent; the preparation of CaO catalysts from natural ores such as dolomite, limestone, etc. also causes environmental damage due to ore mining. In human production and life, a large amount of calcium-containing solid wastes such as eggshells, crab shells, oyster shells, animal bones and the like in agricultural production and papermaking white mud, steel slag, carbide slag, phosphogypsum and the like in industrial production are generated, and the calcium-containing solid wastes have great potential in the aspect of being applied to CaO-based catalysts. However, the problems of limited deoxidation efficiency and limited product quality improvement capability still exist in both the CaO obtained by calcining an analytical reagent and the CaO prepared by calcium-containing solid waste, and how to improve the deoxidation activity of the CaO becomes a bottleneck problem to be solved urgently in developing the application of the high-calcium solid waste-based CaO in the field of biomass catalytic pyrolysis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organic acid modified CaO catalyst, a preparation method and an application thereof, and aims to solve the problem of poor deoxidation activity of the existing high-calcium solid waste based CaO.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing an organic acid-modified CaO catalyst, the method comprising the steps of:
s1, mixing the high-calcium solid waste with an organic acid solution, and drying to obtain a catalyst precursor;
s2, calcining the catalyst precursor to obtain the organic acid modified CaO catalyst.
As a further preferred, in step S1, the high-calcium solid waste includes one or more of carbide slag, shells and eggshells, and is further preferably carbide slag.
As a further preferred, in step S1, the organic acid solution includes one or more of oxalic acid, citric acid, formic acid and acetic acid.
Further preferably, in step S1, H in the organic acid solution+With Ca in high-calcium solid waste2+The molar ratio of (a) to (b) is 0.5:1 to 3: 1.
More preferably, in step S2, the calcination temperature is 700 to 850 ℃ and the calcination time is 3 to 5 hours.
According to another aspect of the present invention, there is provided an organic acid modified CaO catalyst prepared by the above method.
According to another aspect of the present invention, there is provided a use of the organic acid modified CaO catalyst in biomass pyrolysis, the method specifically comprises: in the biomass pyrolysis process, carrying out catalytic reforming on volatile components generated by pyrolysis by using the organic acid modified CaO catalyst; and then cooling the reformed volatile components, and collecting liquid products and non-condensable products to obtain the biomass oil and pyrolysis gas.
It is further preferred that the biomass is one or more of cotton stalk, rice stalk, corn stalk, peanut shell, and the biomass feedstock is crushed to 60-100 mesh prior to pyrolysis.
More preferably, the mass ratio of the biomass to the organic acid modified CaO catalyst is 1: 0.5-1: 1.5.
More preferably, the pyrolysis temperature is 400 to 700 ℃ and the pyrolysis time is 20 to 40 min.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. the invention provides a preparation method of an organic acid modified CaO catalyst, which utilizes organic acid to modify high-calcium solid waste based CaO, can modify the surface of the high-calcium solid waste to influence the surface appearance and the pore structure of the high-calcium solid waste, so that the calcined CaO has richer pore structure and larger specific surface area, the particles are dispersed more uniformly, the active sites on the surface are richer, and further the solid waste can be recycled while the CaO with excellent performance can be obtained, the resource utilization of the high-calcium solid waste is facilitated, the exploitation of ores such as limestone and dolomite is relieved, and the ecological environment is protected;
2. particularly, the invention optimizes the types of the high-calcium solid waste and the organic acid, and optimizes the mixing ratio of the high-calcium solid waste and the organic acid and the calcining temperature, so that the physical and chemical properties of the modified CaO catalyst can be improved to the greatest extent, the crystal grain size is smaller, the alkaline strength and the alkaline figure are higher, and the deoxidation capability is stronger;
3. meanwhile, the invention provides the application of the organic acid modified CaO catalyst in biomass pyrolysis, and volatile components generated by biomass pyrolysis are deoxidized and modified by using the organic acid modified CaO catalyst, so that the content of oxygen-containing components in the pyrolysis volatile components can be reduced, the calorific value of pyrolysis gas and the quality of biomass oil are improved, and the carbon emission is reduced;
4. in addition, the invention optimizes the mass ratio of the biomass to the organic acid modified CaO catalyst, so that the quality of biomass pyrolysis products can be improved, the carbon deposition yield can be reduced, and the inactivation of the modified CaO catalyst can be delayed.
Drawings
FIG. 1 is a flow chart of the application of an organic acid modified CaO catalyst in biomass pyrolysis according to a preferred embodiment of the invention;
FIG. 2 is a graph showing the comparison of the relative contents of various main substances in pyrolysis gas obtained by applying an unmodified calcium carbide slag-based CaO catalyst and CaO catalysts modified by different organic acids to cotton stalk pyrolysis in the preferred embodiment of the present invention;
FIG. 3 is a graph showing the comparison of the relative contents of various main substances in biomass oil obtained by applying an unmodified calcium carbide slag-based CaO catalyst and CaO catalysts modified by different organic acids to cotton stalk pyrolysis in accordance with a preferred embodiment of the present invention;
FIG. 4 shows CO of an unmodified calcium carbide slag-based CaO catalyst and CaO catalysts modified with different organic acids according to a preferred embodiment of the present invention2-TPD characterization results;
FIG. 5 is a graph showing the comparison of the relative contents of various main substances in the pyrolysis gas obtained by applying CaO catalysts modified by oxalic acid with different concentrations to cotton stalk pyrolysis in the preferred embodiment of the present invention;
FIG. 6 is a graph showing the comparison of the relative contents of various main substances in liquid oil obtained by applying CaO catalysts modified by oxalic acid with different concentrations to cotton stalk pyrolysis according to a preferred embodiment of the present invention;
FIG. 7 shows the CO of CaO catalysts modified by oxalic acid of different concentrations according to preferred embodiments of the present invention2-TPD characterization results;
FIG. 8 is a view showing a preferred embodiment H of the present invention+With Ca2+When the molar ratio is 1:1, the organic acid modified CaO catalyst obtained at different calcination temperatures is applied to cotton stalk pyrolysis to prepare a relative content comparison graph of various main substances in pyrolysis gas;
FIG. 9 is a view of the preferred embodiment of the present invention H+With Ca2+When the molar ratio is 1:1, the organic acid modified CaO catalyst obtained at different calcination temperatures is applied to cotton stalk pyrolysis to prepare a relative content comparison graph of various main substances in the biomass oil;
FIG. 10 is a view of the preferred embodiment of the present invention H+With Ca2+CO of organic acid modified CaO catalyst obtained at different calcination temperatures with a molar ratio of 1:12-TPD characterization results.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of an organic acid modified CaO catalyst, which comprises the following steps:
s1, slowly adding the high-calcium solid waste into an organic acid solution, stirring at room temperature to obtain thick mixed slurry, and then placing the mixed slurry in an oven at 100-105 ℃ for drying for 12-24 h to obtain a catalyst precursor;
s2 is heated to a preset temperature in a muffle furnace at a heating rate of 10 ℃/min, and the catalyst precursor is calcined at the temperature to prepare the organic acid modified CaO catalyst.
Further, in step S1, the high-calcium solid waste includes one or more of carbide slag, shells and eggshells, and is further preferably carbide slag; the organic acid solution includes one or more of oxalic acid, citric acid, formic acid, and acetic acid. H in organic acid solution+With Ca in high-calcium solid waste2+The molar ratio of (a) is 0.5: 1-3: 1, the high-calcium solid waste can be fully modified in the range, and meanwhile, the reduction of the alkaline strength and the surface alkaline site number of the modified catalyst is avoided, so that the catalytic reforming efficiency is reduced.
Further, in step S2, the calcination temperature is 700-850 ℃ and the calcination time is 3-5 h, so as to completely convert the CaO catalyst and remove impurities, thereby preventing calcium in the CaO catalyst from existing in the form of organic acid calcium and failing to play a role in catalytic deoxidation, and simultaneously preventing the CaO catalyst from agglomerating due to a high-temperature melting phenomenon, so that the grain size of the CaO catalyst is increased, and the number of surface active sites is reduced.
According to another aspect of the present invention, there is provided an organic acid modified CaO catalyst prepared by the above method. The organic acid modified CaO catalyst has optimized physical and chemical properties, enriches the number of surface active sites and has higher catalytic activity.
According to another aspect of the present invention, there is provided an application of the organic acid modified CaO catalyst in biomass pyrolysis, the method specifically comprises: respectively placing a biomass raw material and an organic acid modified CaO catalyst in a two-section fixed bed reactor, carrying out pyrolysis in an inert atmosphere, and reforming generated volatile components through an organic acid modified CaO catalyst bed layer at the same temperature, so that the volatile components generated by pyrolysis are catalytically reformed by using the organic acid modified CaO catalyst; and then, cooling the reformed volatile component by adopting an ice-water mixture, and collecting a liquid product and a non-condensable product to obtain the biomass oil and pyrolysis gas. Compared with the prior art, the modified CaO catalyst has more abundant active sites, is beneficial to improving the deoxidation effect, can improve the product quality, reduce the oxygen content in the product, relieve the carbon deposition condition on the surface of the catalyst, delay the inactivation of the catalyst and is beneficial to the cyclic regeneration of the organic acid modified CaO catalyst while obtaining a high-yield biomass-based product.
CaO obtained by calcining high-calcium solid waste is directly applied to biomass pyrolysis, and the problems of limited deoxidation activity, relatively weak product quality improvement effect and the like exist. According to the invention, organic acid is utilized for pretreatment, so that the surface modification effect on the high-calcium solid waste can be achieved, the surface appearance and the pore structure of the high-calcium solid waste are further influenced, the modified CaO catalyst has a richer pore structure and a larger specific surface area, particles are dispersed more uniformly, meanwhile, the active sites on the surface are richer, and CO in pyrolysis gas can be converted into CO2A large amount of the biomass oil is fixed, the gas heat value is greatly improved, meanwhile, the oxygen in the biomass oil is removed in a dehydration mode, a decarboxylation mode and the like, the quality is effectively improved, and compared with the biomass oil before being modified, the biomass oil has a better deoxidation and upgrading effect.
Further, the biomass raw material is one or more of cotton stalks, rice stalks, corn stalks and peanut shells, the biomass raw material is crushed into particles of 60 meshes to 100 meshes before pyrolysis, the heating area of the biomass particles is increased, the reaction rate is increased, the reaction is ensured to be fully carried out, and then the biomass raw material is dried at 100 ℃ to 105 ℃ for 12h to 24h, so that the moisture in the biomass raw material is fully removed, the reaction rate is increased, the reaction equipment is protected, and the oxygen content in the product can be reduced.
Further, the mass ratio of the biomass raw material to the organic acid modified CaO catalyst is 1: 0.5-1: 1.5. Meanwhile, the pyrolysis temperature is preferably 400-700 ℃, and the pyrolysis time is 20-40 min. When the pyrolysis temperature is too low and the time is too short, the biomass raw material cannot be fully converted into pyrolysis gas and bio-oil products, and excessive coke products with low added values can be generated; and the pyrolysis temperature is too high, and when the pyrolysis time is too long, the improvement to the product composition is not obvious, and simultaneously the pyrolysis oil yield can reduce by a wide margin, is unfavorable for subsequent refining and utilization, and too long pyrolysis time can cause heat waste, increases reaction cost.
The technical solution provided by the present invention is further explained below according to specific embodiments.
Example 1
(a) Crushing cotton stalks into particles of 60-100 meshes, and drying in an oven at 100-105 ℃ for 12-24 h;
(b) preparing oxalic acid solution with a certain concentration, and H in the oxalic acid solution+With Ca in carbide slag2+The molar ratio of the carbide slag powder to the organic acid modified CaO catalyst is 3:1, the carbide slag powder is slowly added into the carbide slag powder and stirred for 2 hours by a magnetic stirring device at room temperature to obtain thick slurry, the stirred slurry is dried for 24 hours in a 105 ℃ oven until the water is completely volatilized, the obtained catalyst precursor is ground and crushed to 60-100 meshes of particles, the temperature is raised to 850 ℃ in a muffle furnace at the speed of 10 ℃/min, and the particles are calcined for 4 hours to obtain the organic acid modified CaO catalyst;
(c) performing catalytic cracking by using a two-section fixed bed reactor, respectively placing a cotton stalk and an organic acid modified CaO catalyst in the upper section and the lower section of the two-section fixed bed reactor, performing pyrolysis reaction in an inert atmosphere, and reforming volatile components generated by pyrolysis of the cotton stalk by using an organic acid modified CaO catalyst bed layer at the same temperature, wherein the pyrolysis reaction temperature is 600 ℃, the reaction time is 30min, and the mass ratio of the cotton stalk to the organic acid modified CaO catalyst is 1: 1;
(d) and (c) cooling the volatile component obtained in the step (c) by using an ice water mixture to obtain a high-quality biomass-based product, wherein the liquid product is a high-quality bio-oil product, and the non-condensable product is a high-quality pyrolysis gas product.
Example 2
The main difference between this example and example 1 is that the organic acid solution in step (b) is formulated from citric acid.
Example 3
The main difference between this example and example 1 is that the organic acid solution in step (b) is prepared from formic acid.
Example 4
The main difference between this example and example 1 is that the organic acid solution in step (b) is prepared from acetic acid.
Example 5
The main difference between this example and example 1 is the presence of H in the oxalic acid solution of step (b)+With Ca in carbide slag2+Is 0.5: 1.
Example 6
The main difference between this example and example 1 is the presence of H in the oxalic acid solution of step (b)+With Ca in carbide slag2+Is 1:1.
Example 7
The main difference between this example and example 1 is the presence of H in the oxalic acid solution of step (b)+With Ca in carbide slag2+In a molar ratio of 2: 1.
Example 8
This example is compared with example 6, the main difference being that the calcination temperature in step (b) is 700 ℃.
Example 9
This example is compared with example 6, the main difference being that the calcination temperature in step (b) is 750 ℃.
Example 10
This example is compared with example 6, the main difference being that the calcination temperature in step (b) is 800 ℃.
Example 11
(a) Crushing the rice straw into particles of 60-100 meshes, and then drying in a drying oven at 100-105 ℃ for 12-24 h;
(b) preparing a formic acid solution with a certain concentration, and H in the formic acid solution+With Ca in the eggshell2+Slowly adding eggshell powder into the eggshell powder at a molar ratio of 3:1, stirring the eggshell powder for 2 hours at room temperature by using a magnetic stirring device to obtain thick slurry, drying the stirred slurry in a 105 ℃ oven for 24 hours until the water is completely volatilized, grinding the obtained catalyst precursor into particles of 60-100 meshes, heating the particles to 800 ℃ at a speed of 10 ℃/min in a muffle furnace, and calcining the particles for 3 hours to obtain the organic acid modified CaO catalyst;
(c) performing catalytic cracking by using a two-section fixed bed reactor, respectively placing straw and an organic acid modified CaO catalyst in the upper section and the lower section of the two-section fixed bed reactor, performing pyrolysis reaction in an inert atmosphere, and reforming volatile components generated by the pyrolysis of the straw by using an organic acid modified CaO catalyst bed layer at the same temperature, wherein the pyrolysis reaction temperature is 400 ℃, the reaction time is 40min, and the mass ratio of the straw to the organic acid modified CaO catalyst is 1: 0.5;
(d) and (c) cooling the volatile component obtained in the step (c) by using an ice water mixture to obtain a high-quality biomass-based product, wherein the liquid product is a high-quality bio-oil product, and the non-condensable product is a high-quality pyrolysis gas product.
Example 12
(a) Crushing cornstalks into particles of 60-100 meshes, and drying in an oven at 100-105 ℃ for 12-24 h;
(b) preparing acetic acid solution with a certain concentration, and H in the acetic acid solution+With Ca in the shell2+Slowly adding shell powder into the mixture, stirring the mixture for 2 hours at room temperature by using a magnetic stirring device to obtain thick slurry, drying the stirred slurry in a 105 ℃ oven for 24 hours until the water is completely volatilized, grinding the obtained catalyst precursor into particles of 60-100 meshes, heating the particles to 750 ℃ at a speed of 10 ℃/min in a muffle furnace, and calcining the particles for 5 hours to obtain the organic acid modified CaO catalyst;
(c) performing catalytic cracking by using a two-section fixed bed reactor, respectively placing corn stalks and an organic acid modified CaO catalyst in the upper section and the lower section of the two-section fixed bed reactor, performing pyrolysis reaction in an inert atmosphere, and reforming volatile components generated by pyrolysis of the corn stalks by using an organic acid modified CaO catalyst bed layer at the same temperature, wherein the pyrolysis reaction temperature is 700 ℃, the reaction time is 20min, and the mass ratio of the corn stalks to the organic acid modified CaO catalyst is 1: 1.5;
(d) and (c) cooling the volatile component obtained in the step (c) by using an ice water mixture to obtain a high-quality biomass-based product, wherein the liquid product is a high-quality bio-oil product, and the non-condensable product is a high-quality pyrolysis gas product.
Comparative example 1
(a) Crushing cotton stalks into particles of 60-100 meshes, and drying in an oven at 100-105 ℃ for 12-24 h;
(b) carrying out cotton stalk pyrolysis reaction under inert atmosphere, wherein the pyrolysis reaction temperature is 600 ℃, and the reaction time is 30 min;
(d) and (c) cooling the volatile component obtained in the step (c) by using an ice water mixture to obtain a high-quality biomass-based product, wherein the liquid product is a high-quality bio-oil product, and the non-condensable product is a high-quality pyrolysis gas product.
Comparative example 2
(a) Crushing cotton stalks into particles of 60-100 meshes, and drying in an oven at 100-105 ℃ for 12-24 h;
(b) grinding and crushing the carbide slag into particles of 60-100 meshes, heating to 850 ℃ at a speed of 10 ℃/min in a muffle furnace, and calcining for 4 hours to obtain a CaO catalyst;
(c) performing catalytic cracking by using a two-section fixed bed reactor, respectively placing a cotton stalk and a CaO catalyst in the upper section and the lower section of the two-section fixed bed reactor, performing pyrolysis reaction in an inert atmosphere, and reforming volatile components generated by pyrolysis of the cotton stalk through a CaO catalyst bed layer at the same temperature, wherein the pyrolysis reaction temperature is 600 ℃, the reaction time is 30min, and the mass ratio of the cotton stalk to the CaO catalyst is 1: 1;
(d) and (c) cooling the volatile component obtained in the step (c) by using an ice water mixture to obtain a high-quality biomass-based product, wherein the liquid product is a high-quality bio-oil product, and the non-condensable product is a high-quality pyrolysis gas product.
FIGS. 2 and 3 are comparative graphs of relative contents of various main substances in the pyrolysis gas and the biomass oil prepared in examples 1 to 4 and comparative examples 1 and 2. As shown in figure 2, compared with the single pyrolysis of cotton stalks, H in the pyrolysis gas is generated under the action of organic acid modified CaO catalyst2、CH4The content is increased to some extent, CO2The content is obviously reduced, and the gas heat value is increased to 16.17MJ/m3However, the deoxidation and upgrading effects of the modified catalyst are inferior to that of the unmodified CaO catalyst for gas products, and the performance of the modified catalyst can be further optimized. As shown in figure 3, compared with the single cotton stalk pyrolysis and catalytic reforming by using an unmodified CaO catalyst, the content of acid and furan substances in the biomass oil is further reduced and the content of hydrocarbon substances is obviously increased under the action of the organic acid modified CaO catalyst, which is beneficial to reducing the oxygen content of the pyrolysis oil, wherein the CaO catalyst modified by oxalic acid has the best deoxidation effectIt is preferred.
FIG. 4 is a graph showing CO of different organic acid-modified CaO catalysts and unmodified calcium carbide slag-based CaO catalysts in examples 1 to 4 and comparative example 22TPD characterization results in CO2In the TPD graph, the temperature corresponding to the desorption peak can show the alkalinity of the catalyst, and the higher the temperature, the stronger the alkalinity, and the higher the catalytic activity; the desorption peak area size can show the number of the basic sites on the surface of the catalyst, and the larger the peak area is, the higher the number of the basic sites on the surface is, and the higher the catalytic activity is. The desorption temperature of the catalyst modified by the organic acid is similar to that of unmodified CaO, which proves that the alkalinity of the catalyst is equivalent, but the desorption peak areas of the modified catalyst are higher than those of the unmodified CaO, namely the modified catalyst has richer alkaline sites, wherein the desorption peak area of the CaO catalyst modified by the oxalic acid is the highest, so that the CaO modified by the oxalic acid has the best deoxidation effect.
FIGS. 5 and 6 are comparative graphs of the relative contents of various main substances in the pyrolysis gas and the biomass oil prepared in examples 1 and 5 to 7, respectively. H in the modification+With Ca2+Is increased so that CO in the pyrolysis gas is generated2The content is reduced and then increased, and the lower calorific value is accompanied by H+With Ca2+The increase of the molar ratio of (A) is first increased and then decreased; meanwhile, acids and furans in the biomass oil are in H+With Ca2+Is reduced significantly in the range of 0.5:1 to 1:1, and therefore, H is contained in the organic acid solution+With Ca in high-calcium solid waste2+The molar ratio of (a) to (b) is more preferably 1:1 to 2: 1.
FIG. 7 shows CO of CaO catalysts obtained by modification of oxalic acid with different concentrations in examples 1 and 5 to 72-TPD characterization results. Similarly, very low acid concentrations (H) can be seen+:Ca2+0.5), the desorption peak temperature of the modified CaO catalyst is lowest and the peak area is smallest, which indicates that the modified CaO catalyst is weakest in alkalinity; h+:Ca2+When the ratio of the desorption peak temperature to the peak area is 1:1, the desorption peak temperature and the peak area are both obviously improved, the corresponding desorption temperature is the highest, and when the concentration of oxalic acid is further increased, the alkaline strength and the number of surface alkaline sites of the modified CaO catalyst are gradually reduced.
FIGS. 8 and 9 are comparative graphs of the relative contents of various main substances in the pyrolysis gas and the biomass oil prepared in examples 6 and 8 to 10, respectively. CO in the pyrolysis gas along with the increase of the calcining temperature2The content is increased, the lower calorific value is reduced, meanwhile, acid and furan substances in the biomass oil are obviously increased, the quality of the biomass oil is reduced, and therefore, the calcination temperature of the CaO catalyst prepared from the carbide slag is preferably 700 ℃.
FIG. 10 shows H in examples 6 and 8 to 10+With Ca2+CO of organic acid modified CaO catalyst obtained at different calcination temperatures with a molar ratio of 1:12-TPD characterization results. Similarly, it can be seen that the desorption temperature and desorption peak area corresponding to the modified catalyst gradually decrease with the increase of the calcination temperature, and the modified CaO catalyst obtained by calcination at 700 ℃ has the highest desorption peak temperature and the highest peak area, i.e. the modified CaO obtained by calcination at 700 ℃ has the strongest basicity and the richest basic sites on the surface of the catalyst.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
Claims (10)
1. The preparation method of the organic acid modified CaO catalyst is characterized by comprising the following steps:
s1, mixing the high-calcium solid waste with an organic acid solution, and drying to obtain a catalyst precursor;
s2, calcining the catalyst precursor to obtain the organic acid modified CaO catalyst.
2. The method for preparing an organic acid modified CaO catalyst according to claim 1, wherein the high calcium solid waste comprises one or more of carbide slag, shells and eggshells, and is further preferably carbide slag in step S1.
3. The method for preparing an organic acid modified CaO catalyst according to claim 1, wherein the organic acid solution comprises one or more of oxalic acid, citric acid, formic acid and acetic acid in step S1.
4. The method for preparing organic acid modified CaO catalyst according to claim 1, wherein in step S1, H in the organic acid solution+With Ca in high-calcium solid waste2+The molar ratio of (a) to (b) is 0.5:1 to 3: 1.
5. The method for preparing an organic acid modified CaO catalyst according to any one of claims 1 to 4, wherein in the step S2, the calcination temperature is 700 ℃ to 850 ℃ and the calcination time is 3h to 5 h.
6. An organic acid modified CaO catalyst prepared by the method according to any one of claims 1 to 5.
7. The use of the organic acid modified CaO catalyst according to claim 6 in biomass pyrolysis, wherein the method is specifically: in the biomass pyrolysis process, carrying out catalytic reforming on volatile components generated by pyrolysis by using the organic acid modified CaO catalyst; and then cooling the reformed volatile components, and collecting liquid products and non-condensable products to obtain the biomass oil and pyrolysis gas.
8. The use of the organic acid modified CaO catalyst according to claim 6 in biomass pyrolysis wherein the biomass is one or more of cotton stalks, rice stalks, corn stalks, peanut shells and the biomass feedstock is crushed to 60 to 100 mesh prior to pyrolysis.
9. The application of the organic acid modified CaO catalyst in biomass pyrolysis according to claim 6, wherein the mass ratio of the biomass to the organic acid modified CaO catalyst is 1: 0.5-1: 1.5.
10. The application of the organic acid modified CaO catalyst in biomass pyrolysis according to any one of claims 6 to 9, wherein the pyrolysis temperature is 400 ℃ to 700 ℃ and the pyrolysis time is 20min to 40 min.
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