CN114644333A - Preparation method of sulfonated carbon for thermal cracking aromatization of biomass at constant temperature and temperature - Google Patents
Preparation method of sulfonated carbon for thermal cracking aromatization of biomass at constant temperature and temperature Download PDFInfo
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- CN114644333A CN114644333A CN202210264161.6A CN202210264161A CN114644333A CN 114644333 A CN114644333 A CN 114644333A CN 202210264161 A CN202210264161 A CN 202210264161A CN 114644333 A CN114644333 A CN 114644333A
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Abstract
A preparation method of sulfonated carbon by thermal cracking and aromatization of biomass at a constant temperature and controlling temperature relates to the technical field of sulfonated carbon preparation, and comprises the following steps: firstly, performing aromatization on carbon by taking biomass residues as a biomass carbon source to obtain an aromatization carbon precursor; secondly, mixing the aromatized carbon precursor with sulfuric acid for sulfonation, and carrying out ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain the sulfonated carbon. The method can improve the yield of the sulfonated carbon and prepare the sulfonated carbon with higher acid value and quality.
Description
Technical Field
The invention relates to the technical field of sulfonated carbon preparation, in particular to a method for preparing sulfonated carbon through thermal cracking and aromatization of biomass at a constant temperature and a controlled temperature.
Background
The wood-plastic composite (WPC) is a novel green material formed by compounding wood fibers or plant fibers and thermoplastic polymers or other materials, and has excellent corrosion resistance, waterproof performance, thermal insulation performance, easy processing performance and the like. The biomass charcoal modified wood-plastic composite material is beneficial to weight reduction, light weight and high reinforcement of the WPC, can improve the high temperature resistance of the WPC, and reduces heat release and smoke and toxic gas emission in the heating process of the WPC.
Sulfonated carbon is biomass carbon which is very suitable for modifying wood-plastic composite materials, but the existing sulfonated carbon preparation method is only obtained by simply reacting concentrated sulfuric acid with activated carbon, and then pumping, washing and drying, so that the yield of the obtained sulfonated carbon is low, the acid value of the sulfonated carbon is low, and the quality of the product is not ideal.
Disclosure of Invention
The invention aims to provide a method for preparing sulfonated carbon by thermal cracking and aromatization of biomass at a constant temperature and a temperature controlled to improve the yield of the sulfonated carbon and prepare the sulfonated carbon with higher acid value and quality.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps:
and firstly, performing aromatization carbon by taking the biomass residue as a biomass carbon source to obtain an aromatization carbon precursor.
Secondly, mixing the aromatized carbon precursor with sulfuric acid for sulfonation, and carrying out ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain the sulfonated carbon.
Wherein, in the step one, the aromatization is carried out for 2 hours at the constant temperature and the temperature is controlled at the temperature of 350 ℃ at the heating rate of 30 ℃/min.
Preferably, in the step one, the aromatization carbon formation process adopts a vacuum pumping mode for pressure reduction.
More preferably, in the second step, the sulfonation temperature is 60-120 ℃, and the sulfonation time is 2-8 hours.
More preferably, in the second step, 98% sulfuric acid is selected, and the mass ratio of the aromatization carbon precursor to sulfuric acid is 1: 6-1: 10.
the invention has the beneficial effects that: the biomass residue is subjected to thermal cracking, aromatization and carbonization at a certain temperature, and then the sulfonated carbon is prepared by concentrated sulfuric acid through constant-temperature-control sulfonation, so that the yield can reach 105.3-127.0%, the product quality is better, the sulfonated carbon has a higher acid value, and the method is more suitable for modification of wood-plastic composite materials.
Drawings
FIG. 1 is a schematic diagram showing the influence of the pyrolysis carbonization temperature on the carbon yield and the amount of sulfonated carbon acid in the present invention;
FIG. 2 is a schematic diagram showing the influence of the pyrolysis carbonization time on the carbon yield and the amount of sulfonated carbon acid in the present invention;
FIG. 3 is a schematic diagram illustrating the effect of the pyrolysis temperature increase rate on the amount of sulfonated carbonic acid in the present invention;
FIG. 4 is an infrared spectrum of a poplar charcoal (a) and a sulfonated charcoal (b) according to the present invention;
FIG. 5 is an XPS plot of the inventive poplar charcoal (a) and sulfonated charcoal (b).
Detailed Description
The invention relates to a preparation method of sulfonated carbon by biomass thermal cracking aromatization at a constant temperature and temperature controlled by the invention, which mainly comprises the steps of aromatizing the biomass residues into carbon by using a biomass carbon source to obtain an aromatized carbon precursor, then mixing the aromatized carbon precursor with sulfuric acid for sulfonation, and carrying out ultrasonic washing, drying and ball milling nano-crystallization on the obtained sulfonated product to obtain the sulfonated carbon. In order to realize better aromatization carbon forming effect, the three aspects of pyrolysis carbonization temperature, pyrolysis carbonization time and pyrolysis temperature rise rate in the aromatization process are respectively tested to obtain better aromatization conditions.
Specifically, a proper amount of biomass charcoal source is divided into 5 groups in equal amount, thermal cracking is carried out respectively according to the conditions of 200 ℃, 250 ℃, 300 ℃, 350 ℃ and 400 ℃, the thermal cracking time and the temperature rising speed of each group are consistent, then the thermal cracking is mixed with sulfuric acid for sulfonation under the same conditions, the charcoal yield and the sulfonated charcoal acid amount of the product are detected, and the obtained structure is shown in figure 1, and as can be seen from the figure, the sulfonated carbonic acid amount of the product is the highest under the condition of 350 ℃.
Secondly, taking a proper amount of biomass charcoal source, dividing into 6 groups in equal amount, respectively carrying out thermal cracking according to the time conditions of 1.5h, 2h, 2.5h, 3h, 3.5h and 4h, wherein the thermal cracking temperature and the temperature rise speed of each group are consistent, then mixing with sulfuric acid under the same conditions for sulfonation, and then detecting the charcoal yield and the sulfonated charcoal acid amount of the product to obtain the structure shown in figure 2, wherein the sulfonated carbonic acid amount of the product is the highest under the thermal cracking time condition of 2 h.
Finally, a proper amount of biomass charcoal source is divided into 5 groups in equal amount, thermal cracking is carried out according to the conditions of the heating rates of 5 ℃/min, 10 ℃/min, 20 ℃/min, 30 ℃/min and 40 ℃/min, the final constant temperature and time of thermal cracking of each group are consistent, then the thermal cracking is mixed with sulfuric acid under the same conditions for sulfonation, and the sulfonated charcoal acid content of the product is detected, so that the obtained structure is shown in figure 3, and the sulfonated carbonic acid content of the product is the highest under the condition of the heating rate of thermal cracking of 0 ℃/min.
The test results are combined, and the optimal thermal cracking conditions are preferably selected, namely, the thermal cracking conditions are increased to 350 ℃ at the temperature rising rate of 30 ℃/min, and aromatization is carried out for 2 hours at constant temperature to complete the preparation of the sulfonated carbon in each embodiment and the corresponding proportion.
In order to facilitate understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps: firstly, using biomass residues as a biomass charcoal source, carrying out aromatization for 2 hours at a constant temperature control speed of 30 ℃/min to 350 ℃ to obtain an aromatization charcoal precursor, and carrying out pressure reduction in an aromatization process by adopting a vacuumizing mode; secondly, mixing the aromatized carbon precursor with sulfuric acid with the concentration of 98% according to the mass ratio of 1:8 for sulfonation, wherein the sulfonation temperature is 80 ℃, the sulfonation time is 2 hours, and performing ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain sulfonated carbon.
Example 2
A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps: firstly, using biomass residues as a biomass charcoal source, carrying out aromatization for 2 hours at a constant temperature control speed of 30 ℃/min to 350 ℃ to obtain an aromatization charcoal precursor, and carrying out pressure reduction in an aromatization process by adopting a vacuumizing mode; secondly, mixing the aromatized carbon precursor with sulfuric acid with the concentration of 98% according to the mass ratio of 1:6 for sulfonation, wherein the sulfonation temperature is 80 ℃, the sulfonation time is 2 hours, and performing ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain sulfonated carbon.
Example 3
A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps: firstly, using biomass residues as a biomass charcoal source, carrying out aromatization for 2 hours at a constant temperature control speed of 30 ℃/min to 350 ℃ to obtain an aromatization charcoal precursor, and carrying out pressure reduction in an aromatization process by adopting a vacuumizing mode; secondly, mixing the aromatized carbon precursor with sulfuric acid with the concentration of 98% according to the mass ratio of 1:10 for sulfonation, wherein the sulfonation temperature is 80 ℃, the sulfonation time is 2 hours, and performing ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain sulfonated carbon.
Example 4
A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps: firstly, using biomass residues as a biomass charcoal source, carrying out aromatization for 2 hours at a constant temperature control speed of 30 ℃/min to 350 ℃ to obtain an aromatization charcoal precursor, and carrying out pressure reduction in an aromatization process by adopting a vacuumizing mode; secondly, mixing the aromatized carbon precursor with sulfuric acid with the concentration of 90% according to the mass ratio of 1:8 for sulfonation, wherein the sulfonation temperature is 80 ℃, the sulfonation time is 2 hours, and performing ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain sulfonated carbon.
Comparative example 1
A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature with controlled temperature comprises the following steps: firstly, using biomass residues as a biomass charcoal source, carrying out aromatization for 2 hours at a constant temperature control speed of 30 ℃/min to 350 ℃ to obtain an aromatization charcoal precursor, and carrying out pressure reduction in an aromatization process by adopting a vacuumizing mode; secondly, mixing the aromatized carbon precursor with sodium bisulfite according to the mass ratio of 1:8 for sulfonation, wherein the sulfonation temperature is 80 ℃, the sulfonation time is 2 hours, and performing ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonation product to obtain sulfonated carbon.
In order to more fully show the performance difference of the sulfonated carbons prepared by the pyrolysis carbonization-sulfonation method under the influence of different factors, the above examples and comparative examples are selected as a few typical examples, and corresponding orthogonal experiments can be performed, and the specific factor levels of the orthogonal experiments can be listed as shown in table 1 below.
TABLE 1 sulfonation experiment orthogonal experiment factor level table
The results and analysis of the orthogonal experiments performed by the above-mentioned factors are shown in tables 2 and 3 below.
TABLE 2 sulfonation experiments orthogonal Experimental results
TABLE 3 sulfonation experiments orthogonal experimental results analysis
Through the analysis of the orthogonal experiment results of the sulfonation experiments, the importance sequence of the influencing factors on the yield of the sulfonated carbon is that the type of the sulfonating agent is more than the temperature, the feeding ratio and the sulfonation time in turn. In addition, as can be seen from the results in table 2, the sulfonated carbon prepared by the sulfonated carbon preparation method provided by the present invention has a sulfonation yield of 105.3-127.0%, and a relatively high sulfonation yield.
According to the results of the orthogonality experiment, in A2B2C2D2Continuously optimizing the sulfonated carbon preparation method on the basis of combination, firstly ensuring other conditions to be consistent in the sulfonation process, only changing the sulfonation temperature condition, sulfonating 4 groups of equivalent samples, and obtaining the results shown in Table 4Shown in the figure.
TABLE 4 Effect of sulfonation temperature on sulfonated Carbonic acid amount
TABLE 5 Effect of sulfonation time on sulfonated Carbonic acid amount
Influence of mass ratio of sulfuric acid at concentration of 698% to aromatized carbon precursor on sulfonated carbon acid amount
As can be seen from the above tables 4-6, when the mass ratio of the aromatized carbon precursor to the 98% sulfuric acid is 1:8, the sulfonation temperature is 80 ℃, and the temperature-controlled constant-temperature sulfonation time is 2 hours, the amount of the sulfonated carbon acid in the obtained product is relatively higher and can reach 2.28mmol-1. It can be seen that the sulfonated carbon with better product properties can be prepared by the preparation method provided in example 1.
Structural characterization
The sulfonated carbon prepared by the method provided in example 1 above using an appropriate amount of poplar charcoal as a raw material was subjected to elemental analysis, and the results of the specific surface area and pore volume measurement were compared with each other, and the results obtained are shown in table 7 below.
TABLE 7 Populus charcoal and sulfonated charcoal samples for elemental analysis, specific surface area, pore volume results
From the results in table 7, it can be seen that the percentage content of C, H element in the sulfonated charcoal product obtained after the poplar charcoal is sulfonated by the above preparation method is reduced, and the content of sulfur element is significantly increased, which indicates the success of sulfonation modification.
In addition, the poplar carbon and the prepared sulfonated carbon are respectively detected by infrared spectroscopy, and the obtained results are shown in figure 4; the poplar carbon and the prepared sulfonated carbon were respectively detected by X-ray photoelectron spectroscopy, and the obtained results are shown in fig. 5. It can be shown from the results of FIGS. 4-5 that sulfonic acid groups were successfully grafted to poplar wood charcoal in sulfonation experiments. It will be appreciated by those skilled in the art that the new peak appearing at 168.5eV in FIG. 5 is primarily R-SO3Characteristic peak of H.
The method for preparing the sulfonated carbon through thermal cracking and aromatization of biomass at the constant temperature and the controlled temperature realizes the breakthrough of the key technology for preparing the functional sulfonated carbon from the biomass resource residues, the prepared sulfonated carbon has high yield, and the product has higher acid value of the sulfonated carbon.
In order that those skilled in the art will readily understand the improvements made over the prior art, some of the figures and descriptions of the present invention have been simplified and the above-described embodiments are the preferred implementations of the present invention, and moreover, the present invention may be implemented in other ways, and any obvious substitutions are within the scope of the present invention without departing from the spirit of the present invention.
Claims (5)
1. A preparation method of sulfonated carbon for thermal cracking and aromatization of biomass at a constant temperature and temperature is characterized by comprising the following steps:
firstly, performing aromatization on carbon by taking biomass residues as a biomass carbon source to obtain an aromatization carbon precursor;
secondly, mixing the aromatized carbon precursor with sulfuric acid for sulfonation, and carrying out ultrasonic washing, drying and ball milling nanocrystallization on the obtained sulfonated product to obtain the sulfonated carbon.
2. The method for preparing sulfonated carbon through thermal cracking and aromatization of biomass at a constant temperature and a controlled temperature as claimed in claim 1, wherein the method comprises the following steps: in the first step, the aromatization is carried out for 2 hours at a constant temperature and temperature control with the temperature rising rate of 30 ℃/min to 350 ℃.
3. The method for preparing sulfonated carbon by thermal cracking and aromatization of biomass at a constant temperature and temperature controlled according to claim 1, which comprises the following steps: in the step one, the aromatization carbon formation process adopts a vacuum pumping mode for pressure reduction.
4. The method for preparing sulfonated carbon by thermal cracking and aromatization of biomass at a constant temperature and temperature controlled according to claim 1, which comprises the following steps: in the second step, the sulfonation temperature is 60-120 ℃, and the sulfonation time is 2-8 hours.
5. The method for preparing sulfonated carbon by thermal cracking and aromatization of biomass at a constant temperature and temperature controlled according to claim 1, which comprises the following steps: in the second step, 98% sulfuric acid is selected, and the mass ratio of the aromatization carbon precursor to the sulfuric acid is 1: 6-1: 10.
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