CN113477238B - 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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- CN113477238B CN113477238B CN202110678196.XA CN202110678196A CN113477238B CN 113477238 B CN113477238 B CN 113477238B CN 202110678196 A CN202110678196 A CN 202110678196A CN 113477238 B CN113477238 B CN 113477238B
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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
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- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
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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 used for modifying the high-calcium solid waste based CaO, so that the surface modification can be carried out on the high-calcium solid waste, 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, and the active sites on the surface are richer, so that 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 ores such as limestone and dolomite 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 rich biomass resource reserves, develops and continuously optimizes a biomass conversion mode, is favorable for reasonably disposing biomass solid wastes and promoting resource utilization, and has important significance for relieving the current situation of energy resource shortage in China and realizing the aim of carbon peak carbon neutralization.
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 removed 2 The 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 process 2 Increasing H in the pyrolysis gas 2 、CH 4 The contents of the components are equal, the heat value of the pyrolysis gas is improved, 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 waste 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 can be generated, and the calcium-containing solid waste has 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 high-calcium solid waste with an organic acid solution, and drying to obtain a catalyst precursor;
and 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 waste 2+ The molar ratio of (a) to (b) is 0.5.
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.
More preferably, the pyrolysis temperature is 400 to 700 ℃ and the pyrolysis time is 20 to 40min.
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, 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 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 present 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 invention 2 -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 invention 2 -TPD characterization results;
FIG. 8 is a view showing a preferred embodiment H of the present invention + With Ca 2+ The organic acid modified CaO catalyst obtained at different calcination temperatures with the molar ratio of 1In the pyrolysis, a relative content comparison graph of various main substances in pyrolysis gas is prepared;
FIG. 9 is a drawing H of a preferred embodiment of the present invention + With Ca 2+ When the molar ratio is 1;
FIG. 10 is a view of the preferred embodiment of the present invention H + With Ca 2+ CO of the organic acid modified CaO catalyst obtained at different calcination temperatures with the molar ratio of 1 2 -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 further described in 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 high-calcium solid waste into an organic acid solution, stirring at room temperature to obtain thick mixed slurry, and then placing the mixed slurry into a drying oven at 100-105 ℃ to dry for 12-24 h to obtain a catalyst precursor;
and S2, heating the mixture to a preset temperature in a muffle furnace at a heating rate of 10 ℃/min, and calcining the catalyst precursor at the preset temperature to obtain 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 waste 2+ The molar ratio of (1) to (3) is 0.5, and the range can realize full modification of the high-calcium solid waste, and simultaneously avoid the reduction of the alkaline strength and the surface alkaline site number of the modified catalyst so as to reduce the catalytic reforming efficiency of the catalyst.
Further, in the step S2, the calcining temperature is 700-850 ℃, the calcining time is 3-5 h, so as to completely convert the calcium into the CaO catalyst and remove impurities, prevent the calcium in the CaO catalyst from existing in the form of organic acid calcium and being incapable of playing a role of catalytic deoxidation, and simultaneously prevent the CaO catalyst from agglomerating due to high-temperature melting phenomenon, so that the size of crystal grains 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 CaO catalyst before modification, 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 CO 2 A 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 1.5-1. 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 slag 2+ The molar ratio of the carbide slag powder to the organic acid modified CaO catalyst is 3;
(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;
(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 slag 2+ Is 0.5.
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 the carbide slag 2+ 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 slag 2+ In a molar ratio of 2.
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 ℃, wherein the drying time is 12-24 h;
(b) Preparing formic acid solution with a certain concentration, and H in the formic acid solution + With Ca in the eggshell 2+ Slowly adding eggshell powder into the eggshell powder at a molar ratio of 3;
(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 straw pyrolysis 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;
(d) And (d) 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 then drying in an oven at 100-105 ℃, wherein the drying time is 12-24 h;
(b) Preparing acetic acid solution with a certain concentration, and H in the acetic acid solution + With Ca in the shell 2+ The molar ratio of the organic acid modified CaO catalyst to the shell powder is 2;
(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;
(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 30min;
(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;
(d) And (d) 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 graphs comparing the relative contents of various main substances in the pyrolysis gas and the bio-oil obtained 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 catalyst 2 、CH 4 The content is increased to some extent, CO 2 The content is obviously reduced, and the gas heat value is increased to 16.17MJ/m 3 However, 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 FIG. 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 effect.
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 2 2 TPD results, in CO 2 In a TPD diagram, the temperature corresponding to a desorption peak can show the alkalinity of the catalyst, and the higher the temperature is, the stronger the alkalinity is, and the higher the catalytic activity is; the desorption peak area 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 the unmodified CaO, which proves that the alkalinity of the catalyst is equivalent, but the desorption peak areas of the modified catalyst are higher than that of the unmodified CaO, namely the modified catalystThe catalyst has richer basic sites, wherein the desorption peak area of the CaO catalyst modified by oxalic acid is the highest, so that the CaO modified by oxalic acid has the best deoxidation effect.
FIGS. 5 and 6 are graphs comparing the relative contents of various main substances in the pyrolysis gas and the bio-oil obtained in example 1 and examples 5 to 7, respectively. H in the modification process + With Ca 2+ Is increased so that CO in the pyrolysis gas is generated 2 The content is reduced and then increased, and the lower calorific value is accompanied by H + With Ca 2+ The increase of the molar ratio of (a) is first increased but is reduced; meanwhile, acids and furans in the biomass oil are in H + With Ca 2+ In the range of 0.5 + With Ca in high-calcium solid waste 2+ The molar ratio of (c) is more preferably 1.
FIG. 7 shows CO values of CaO catalysts obtained in examples 1 and 5 to 7 under modification with oxalic acid of different concentrations 2 -TPD characterization results. Similarly, very low acid concentrations (H) can be seen + :Ca 2+ = 0.5), the desorption peak temperature of the modified CaO catalyst is lowest and the peak area is smallest, indicating that the modified CaO catalyst is the weakest in basicity; h + :Ca 2+ 1, the desorption peak temperature and the peak area are both significantly increased, the corresponding desorption temperature is the highest, and when the oxalic acid concentration 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 graphs comparing the relative contents of various main substances in the pyrolysis gas and the biomass oil obtained in example 6 and examples 8 to 10, respectively. CO in the pyrolysis gas along with the increase of the calcining temperature 2 The content is increased, the lower calorific value is reduced, meanwhile, the acid and furan substances in the biomass oil are obviously increased, and the quality of the biomass oil is reduced, so that the calcination temperature of the CaO catalyst prepared from carbide slag is preferably 700 ℃.
FIG. 10 shows H in examples 6 and 8 to 10 + With Ca 2+ CO of the organic acid modified CaO catalyst obtained at different calcination temperatures with the molar ratio of 1 2 -TPD characterization results. Similarly, it can be seen that the modified catalyst corresponds toThe desorption temperature and the desorption peak area are gradually reduced along with the rise of the calcination temperature, and the modified CaO catalyst obtained by calcination at 700 ℃ has the highest desorption peak temperature and the largest peak area, namely the modified CaO obtained by calcination at 700 ℃ has the strongest alkalinity 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 (6)
1. The application of the organic acid modified CaO catalyst in biomass pyrolysis is characterized by comprising the following steps:
s1, mixing carbide slag with an organic acid solution, and drying to obtain a catalyst precursor, wherein H in the organic acid solution + With Ca in the carbide slag 2+ 1;
s2, calcining the catalyst precursor at 700 ℃ to obtain an organic acid modified CaO catalyst;
s3, in the biomass pyrolysis process, carrying out catalytic reforming on volatile components generated by pyrolysis by using the organic acid modified CaO catalyst;
s4, cooling the reformed volatile component, and collecting a liquid product and a non-condensable product to obtain the biomass oil and pyrolysis gas.
2. The use of the organic acid modified CaO catalyst according to claim 1 in biomass pyrolysis, wherein in step S1, the organic acid solution comprises one or more of oxalic acid, citric acid, formic acid and acetic acid.
3. The use of the organic acid modified CaO catalyst in biomass pyrolysis according to claim 1 or 2, wherein in step S2, the calcination time is 3h to 5h.
4. The use of the organic acid modified CaO catalyst according to claim 1 in biomass pyrolysis wherein the biomass is one or more of cotton stalks, rice straw, corn stover, peanut shells and the biomass feedstock is crushed to 60 to 100 mesh prior to pyrolysis.
5. The use of the organic acid-modified CaO catalyst according to claim 1 in biomass pyrolysis, wherein the mass ratio of the biomass to the organic acid-modified CaO catalyst is 1.
6. The use of the organic acid modified CaO catalyst in biomass pyrolysis according to claim 1, wherein the pyrolysis temperature is 400 ℃ to 700 ℃ and the pyrolysis time is 20min to 40min.
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