CN112919463A - Activated carbon prepared from tiamulin waste salt and preparation method thereof - Google Patents
Activated carbon prepared from tiamulin waste salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses activated carbon prepared by using tiamulin waste salt and a preparation method thereof, belonging to the technical field of activated carbon preparation and the field of industrial solid waste recycling. It comprises 1) providing an activated carbon with high pore volume, high specific surface area and graded pore diameter (micropore and mesopore); 2) provides a simple method for preparing activated carbon without adding an activating agent (such as potassium hydroxide, zinc chloride and the like). Has the advantages of simple structure, reasonable design and easy manufacture.
Description
Technical Field
The invention belongs to the technical field of activated carbon preparation and the field of industrial solid waste recycling, and particularly relates to activated carbon with high pore volume, high specific surface area and hierarchical pore diameter (micropores and mesopores) and a preparation method thereof.
Background
Activated carbon is used in a wide range of fields as an adsorbent, an electrode material for a capacitor, a catalyst, and the like. The size of the specific surface area, the size of the pore volume and the grading and distribution of the pore diameter are very important in the application process of the activated carbon, and the application effect is determined. For example, mesopores are important for the transport and storage of targets, and micropores are important for the increase of the specific surface area, surface adsorption energy and action sites of the material.
For example, in the first patent document, there is provided a method for producing activated carbon having a high specific surface area, in which activated carbon having a thickness of approximately 1500m is produced by using sludge as a raw material and a potassium hydroxide solution as an activator2Specific surface area in g. For example, patent document two provides a method for preparing activated carbon with a high specific surface area hierarchical pore structure, which includes mixing sucrose as a raw material with potassium hydroxide according to a mass ratio, heating the mixture to a viscous state, stirring the mixture at a high speed, performing high-temperature activation treatment on the stirred material under the protection of an inert atmosphere, performing acid washing, water washing and drying on the activated material to obtain activated carbon with a mesopore rate of more than 96% and a large specific surface area, wherein the specific surface area of the activated carbon reaches 1240-1580 m2/g。
Therefore, for the research of the activated carbon, the research on obtaining a high specific surface area, a high pore volume and the construction of a reasonable pore system is one of the mainstream research directions.
Patent document one: application No.: 201610592345. X; application date: 2016.07.25, respectively; name: a preparation method of activated carbon with a high specific surface area hierarchical pore structure;
patent document two: application No.: 201710273579.2, respectively; application date: 2017.04.24, respectively; name: a method for preparing sludge activated carbon.
Disclosure of Invention
1. Problems to be solved
In view of the above, an object of the present invention is to provide a fluffy activated carbon having a high specific surface area and a high pore volume;
meanwhile, it is another object of the present invention to provide a simple method for preparing activated carbon without adding an activator (such as potassium hydroxide, zinc chloride, etc.).
2. Technical scheme
The idea of the invention comes from the practical research process, the conventional treatment means is adopted aiming at the waste liquid in the tiamulin production process, namely the extraction work of the sodium p-toluenesulfonate is carried out, but in the practical research, the inventor finds that because the components contained in the waste liquid are too complex, even if the sodium p-toluenesulfonate can be recovered, the purification process which is time-consuming and labor-consuming is still needed in the later period, otherwise the recovered sodium p-toluenesulfonate basically belongs to a waste salt row, and the existing research does not have a mature purification process, so that the recovery of the sodium p-toluenesulfonate from the waste liquid in the tiamulin production process is actually impractical.
Based on the research on the resource utilization of the waste liquid in the production process of tiamulin, the invention obtains the following technical scheme:
[1]an activated carbon having a range of 1cm3G to 2.5cm3A total pore volume of/g, wherein 45% to 100% of the total pore volume is formed by micropores and mesopores; the micropores have a pore diameter of not less than 0.4nm and less than 2nm, and the mesopores have a pore diameter in a range of not less than 2nm and less than 50 nm; wherein the activated carbon has a BET specific surface area of 1000m2(ii)/g to 2300m2/g。
[1.1] further, the activated carbon has an iodine adsorption value of not less than 1000mg/g, wherein the iodine adsorption value is measured according to the method of GB/T12496.8-2015.
[1.2]Further, the activated carbon has a range of 2cm3G to 2.5cm3(ii) a total pore volume in g,
wherein the mesoporous volume accounts for 40-90% of the total pore volume, and the microporous volume accounts for 5-10% of the total pore volume;
furthermore, the activated carbon has a BET specific surface area of 2000m2(ii)/g to 2300m2/g；
Further, the activated carbon has an iodine adsorption value of not less than 1500mg/g, wherein the iodine adsorption value is tested according to the method of GB/T12496.8-2015.
[1.3] the activated carbon is prepared by using waste salt recovered from tiamulin production waste liquid as a raw material:
the waste salt contains Na2SO4、NaCl、KH2PO4Inorganic salts within, and organic carbons; wherein the content of the first and second substances,
the content of the organic carbon is 275 +/-25 mg/g;
the inorganic salt content is 45 + -5% by weight.
[2] A preparation method of activated carbon is characterized in that: the method comprises the following steps:
s1, recovering an active carbon production raw material (namely tiamulin waste salt) from tiamulin production waste liquid:
concentrating the waste liquid, and separating to obtain a solid raw material and a water material flow; the concentration treatment is carried out within the range of 95-115 ℃;
s2, carbonizing treatment:
carbonizing the solid raw material; the carbonization treatment comprises a temperature rising stage and a heat preservation stage, wherein the temperature rising speed is 4-10 ℃/min, the heat preservation temperature is 400-500 ℃, and the heat preservation time is 1-3 h;
s3, pyrolysis treatment:
carrying out pyrolysis treatment on the carbonized material; the pyrolysis treatment comprises a heating stage and a heat preservation stage, wherein the heating speed is 4-10 ℃/min, the heat preservation temperature is 700-900 ℃, and the heat preservation time is 1-3 h;
s4, cooling treatment:
and cooling the material subjected to pyrolysis treatment to obtain the activated carbon.
In one embodiment, the water stream in S1 refers to a process of concentrating waste liquid, and the rest of the materials are separated from solid raw materials in a liquid form or a gas form; in addition, the concentration treatment mode can be high-temperature evaporation, reduced pressure distillation or filtration and evaporation, etc.;
secondly, the heating temperature selected in the concentration treatment is different, so that the types and components of elements and compounds contained in the obtained solid raw material are not greatly different, but the content of the elements and the compounds, particularly the moisture (Mad) in the solid raw material is influenced.
[2.1] further, the solid raw material contains metal elements including Na and K and non-metal elements including C, H, O, N, S, P, Cl and Br.
[2.2]Further, the solid raw material contains Na2SO4、NaCl、KH2PO4Inorganic salts within, and organic carbons; wherein the content of the organic carbon is 275 +/-25 mg/g; the content of the inorganic salt is 45 +/-5 percent by weight;
in addition, the organic carbon is mainly carbon-containing organic matters including pleuromutilin and sodium p-toluenesulfonate.
The element is Na in the solid raw material2SO4、NaCl、KH2PO4And the like, and organic substances such as pleuromutilin, tiamulin impurities and the like (the total content of the organic substances is expressed by TOC) are also contained in the solid raw material. Inorganic salt KH in the solid raw material2PO4And organic matters mainly play a role in pore formation. KH (Perkin Elmer)2PO4The medium potassium ions can be converted into gas state to leave waste salt after 762 ℃, when the pyrolysis temperature is higher than the boiling point of potassium, potassium vapor can permeate into carbon lattices and can migrate to a distorted carbon layer among carbon microcrystals, and the pore structure of the activated carbon is further enriched; KH (Perkin Elmer)2PO4Middle H2PO4 -Can be used as activator for preparing active carbon H2PO4 -In the waste salt, the catalyst is firstly used to catalyze the functional groups and long chain breakage of macromolecular organic matters in the waste salt, such as promoting CO and CO2、CH4Generated at a lower temperature; at the same time, H2PO4 -The derivative metaphosphoric acid generated by heated dehydration can generate esterification reaction with the hydroxyl of the organic matters in the waste salt, and is embedded into the organic matter structure to prepare for subsequent pore-forming. With further temperature rise, the phosphate ester bonds are almost completely broken, the phosphoric acid is separated from the organic matter structure main body, the condensation polymerization and thermal contraction effects are dominant, and H2A large amount is generated and pores are gradually reduced, so that micropores are formed.
[2.3] further, the solid feedstock has 46 + -2% ash (Aad), 50 + -2% volatiles (Vad), 2 + -2% moisture (Mad), and 0.02 + -0.02% fixed carbon (FCad) by weight;
wherein the sum of Aad, Vad, Mad and FCad is 100%.
It should be noted that, when the coal is measured by the industrial analysis method GB/T212-2008, Mad is used as a main volatile component and Vad is used as a component capable of cracking to generate gas in the preparation process of activated carbon, which plays an important role in the formation of activated carbon pores.
[2.4] further, the solid starting material had approximately the same thermogravimetric analysis TG curve and DTG curve as sodium p-toluenesulfonate.
[2.5] further, the solid raw material itself is a uniform powdery solid having a low water content. The uniform powder is beneficial to fully releasing pyrolysis gas in the subsequent firing process, and further promotes the formation of a porous structure rich in materials.
[2.6] further, the tiamulin production waste liquid is obtained by the following method: p-toluenesulfonyl and pleuromutilin are used for reaction, then the reaction is carried out with 2-diethylaminoethanethiol, and then tiamulin production waste liquid is obtained through separation.
Specifically, in the tiamulin production process, pleuromutilin obtained by microbial fermentation and p-toluenesulfonyl chloride are subjected to sulfonation reaction in an alkaline environment to generate sulfonated pleuromutilin, and the sulfonated pleuromutilin and excessive 2-diethylaminoethanethiol are subjected to amination reaction under the catalysis of trace tetrabutylammonium bromide to generate tiamulin precursor of tiamulin (the flow is shown in fig. 8). In the process flow, metabolites generated by microbial fermentation, sodium p-toluenesulfonate as a byproduct generated by sulfonation reaction and ammoniation reaction and corresponding raw material reagents which do not completely react enter waste liquid to form tiamulin production waste liquid.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the range of the active carbon provided by the invention is 1cm3G to 2.5m3A total pore volume per gram, the total pore volume being formed primarily of micropores and mesopores; and the activated carbon has a BET specific surface area of 1000m2(ii)/g to 2300m2(ii)/g; the most preferred activated carbon has a range of 2cm3G to 2.5cm3A total pore volume in g, a BET specific surface area of 2000m2(ii)/g to 2300m2/g；
Further, the activated carbon has an iodine adsorption value of not less than 1500mg/g, wherein the iodine adsorption value is tested according to the method of GB/T12496.8-2015.
(2) According to the preparation method of the activated carbon, the raw material (namely tiamulin waste salt) is taken from the waste liquid generated in the tiamulin production process, so that a new idea is provided for resource utilization of the tiamulin waste salt; on the other hand, the specific surface area can be prepared up to 2268m without additional activator2The iodine adsorption value (GB/T12496.8-2015) of the high-quality activated carbon reaches 1603mg/g, and the obtained activated carbon has excellent adsorption performance.
It should be noted that, at present, most activated carbons are prepared by using coal and common biomass materials such as pericarp, sawdust, straw, corncob and the like as raw materials, adding an activating agent, and activating at high temperature. But the added activating agent greatly increases the preparation cost of the activated carbon, and limits the large-scale production of the activated carbon to a certain extent.
(3) The main reasons for calcining tiamulin waste salt as a raw material to obtain the high-quality active carbon are as follows:
firstly, tiamulin waste salt is obtained by concentrating tiamulin waste liquid, compared with a traditional method for mixing and calcining a carbon source and an activating agent, each component in the tiamulin waste salt has the advantage of natural high mixing uniformity, and particularly, each component with a boiling point higher than the concentration treatment temperature in the waste liquid is uniformly distributed in the waste salt after the treatment process, so that pores are uniformly distributed during subsequent pore forming;
secondly, the tiamulin waste salt is a uniform powdery solid, the particles are fine and loose, and the prepared active carbon is loose;
thirdly, the tiamulin waste salt has high organic matter content (namely high carbon content) and high pH value (the pH value is measured to be 10-11 according to a solid waste corrosivity measurement-glass electrode method GB/T15555.12-1995) and has the potential for preparing the activated carbon, and a proper alkaline condition is provided for the preparation precursor of the activated carbon;
fourthly, the tiamulin waste salt contains KH2PO4Can act as an activator to activate the carbon precursor.
Drawings
FIG. 1 is a schematic diagram of TG and DTG curves of a solid raw material (also referred to as tiamulin waste salt) of activated carbon (N2，5℃/min，50ml/min)；
FIG. 2A schematic representation of TG and DTG curves for sodium p-toluenesulfonate (N)2，5℃/min，50ml/min)；
Nitrogen adsorption-desorption curves of activated carbon of fig. 3 a) J57, b) J58, c) J59;
FIG. 4 SEM photograph of the activated carbon prepared in example 2;
FIG. 5 iodine adsorption values of different activated carbons;
FIG. 6 methylene blue adsorption values of different activated carbons;
FIG. 7 SEM of the activated carbon prepared with potassium hydroxide as the activating agent;
FIG. 8 is a production flow chart of tiamulin waste salt.
In the figure: j57 represents an activated carbon prepared via the following parameters: the carbonization treatment temperature is 500 ℃, the carbonization treatment time is 2 hours, the pyrolysis treatment temperature is 700 ℃, and the pyrolysis treatment time is 2 hours;
j58 represents an activated carbon prepared via the following parameters: the carbonization treatment temperature is 500 ℃, the carbonization treatment time is 2 hours, the pyrolysis treatment temperature is 800 ℃, and the pyrolysis treatment time is 2 hours;
j59 represents an activated carbon prepared via the following parameters: the carbonization treatment temperature is 500 ℃, the carbonization treatment time is 2h, the pyrolysis treatment temperature is 900 ℃, and the pyrolysis treatment time is 2 h.
Detailed Description
The tiamulin waste salt is solid waste salt formed by concentrating wastewater generated in a tiamulin production process at 95-115 ℃, and is complex in components, the main component is p-toluenesulfonate, and the organic matter content is high (expressed by TOC, about 300mg/L of TOC). In recent years, the production amount of tiamulin is high, and the production amount of waste salt is huge. Common waste salt comprehensive utilization and resource utilization methods include a salt washing method, a soda ash preparation method, a membrane separation method and the like. The salt washing method is only suitable for waste salt with single component and low organic matter content, the solvent consumption is large, and the risk of secondary pollution of eluent exists; the application range of the soda ash preparation method is narrow and the market is saturated; the membrane separation method has narrow application range and high operation cost. Therefore, the existing common method is not suitable for comprehensive utilization and resource utilization of tiamulin waste salt.
Schematically, the solid raw material for producing the activated carbon in the following embodiment is obtained by selecting waste liquid generated in a production process of certain tiamulin and evaporating the waste liquid at a high temperature of 95-115 ℃. And the solid raw material obtained by detection and analysis has the basic characteristics of elements, components and the like as shown in the following tables 1-4:
TABLE 1 basic Material information
| Components | Content (wt.) |
| TOC | 294.22±1.08mg/g |
| NaCl | ～22.91％(wt) |
| Na2SO4 | ～17.75％(wt) |
| KH2PO4 | ～6.29％(wt) |
TABLE 2 element information
| Components | Absolute content (wt%) |
| C | 32.92 |
| H | 3.47 |
| N | 0.19 |
| S | 5.78 |
| O | 28.13 |
TABLE 3 basic Components information
| Components | Absolute content (wt%) |
| Mad | 2.27±1.23 |
| Aad | 46.95±0.10 |
| Vad | 51.69±0.04 |
| FCad | 0.02±0.02 |
TABLE 4 XRF analysis
| Components | Relative content (wt%) |
| Na2O | 56.29 |
| P2O5 | 0.75 |
| SO3 | 38.26 |
| K2O | 0.04 |
| Cl | 1.38 |
| Br | 0.27 |
In addition, the above solid raw material for producing activated carbon has a weight loss curve (TG) and a weight loss rate curve (DTG) as shown in fig. 1. Obviously, the curve is similar to the curve of TG and DTG of pure sodium p-toluenesulfonate (as shown in figure 2), the maximum weight loss rate appears before 500 ℃ from the weight loss rate curve, and the main component of the tiamulin waste salt is sodium p-toluenesulfonate which is basically decomposed after 500 ℃.
The invention is further described with reference to specific examples.
Example 1
S1, taking the schematic solid raw materials for producing the activated carbon in the section of [ embodiment mode ];
s2, carbonizing treatment;
in N2Carbonizing the solid raw material under the atmosphere; the carbonization treatment comprises a temperature rise stage and a heat preservation stage, wherein the temperature rise speed is 4 ℃/min, the heat preservation temperature is 500 ℃, and the heat preservation time is 2 h;
then, naturally cooling, taking out and grinding to obtain a first material;
s3, carrying out pyrolysis treatment;
in N2Carrying out pyrolysis treatment on the first material under the atmosphere; the pyrolysis treatment comprises a heating stage and a heat preservation stage, wherein the heating speed is 4 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 2 h;
then, naturally cooling and taking out to obtain a material II;
s4, putting the second material in a proper amount for deionizationAdjusting pH to neutral with 0.1M dilute hydrochloric acid in water, and washing with deionized water until no NaCl or Na is present2SO4Obtaining the activated carbon J57.
S5, drying the activated carbon at 105 ℃ to constant weight, and sieving the dried activated carbon with a 200-mesh sieve.
The activated carbon prepared in this example was found to have a BET specific surface area of 1099m as shown in FIG. 3a2The iodine adsorption value measured according to GB/T12496.8-2015 was 987 mg/g.
Example 2
S1, taking the schematic solid raw materials for producing the activated carbon in the section of [ embodiment mode ];
s2, carbonizing treatment;
in N2Carbonizing the solid raw material under the atmosphere; the carbonization treatment comprises a temperature rise stage and a heat preservation stage, wherein the temperature rise speed is 4 ℃/min, the heat preservation temperature is 500 ℃, and the heat preservation time is 2 h;
then, naturally cooling, taking out and grinding to obtain a first material;
s3, carrying out pyrolysis treatment;
in N2Carrying out pyrolysis treatment on the first material under the atmosphere; the pyrolysis treatment comprises a heating stage and a heat preservation stage, wherein the heating speed is 4 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 2 h;
then, naturally cooling and taking out to obtain a material II;
s4, placing the second material in a proper amount of deionized water, adjusting the pH value to be neutral by using 0.1M dilute hydrochloric acid, and then cleaning the second material by using the deionized water until no NaCl or Na exists2SO4Obtaining the activated carbon J58.
S5, drying the activated carbon at 105 ℃ to constant weight, and sieving the dried activated carbon with a 200-mesh sieve.
The activated carbon prepared in this example was tested to have a BET specific surface area of 2268m as shown in FIG. 3b2/g。
Meanwhile, the prepared activated carbon has a microstructure shown in fig. 4, the surface of the activated carbon has rich and uniformly distributed pore structures, and the activated carbon has an obvious layered structure and is loose in texture.
Comparative example 1
This comparative example is substantially the same as example 2 except that the solid raw material used for producing activated carbon, specifically sodium p-toluenesulfonate, was different and activated carbon was obtained under optimum activation conditions (2mol/L KOH, 800 ℃ C., 2 hours) by adding potassium hydroxide as an activator.
The activated carbon prepared in the example has a BET specific surface area of 1200m2/g。
Meanwhile, the prepared activated carbon has a microstructure shown in fig. 7, and the surface of the activated carbon has a rich typical open bubble pore structure. Basically has no laminated structure and compact texture.
Example 3
S1, taking the schematic solid raw materials for producing the activated carbon in the section of [ embodiment mode ];
s2, carbonizing treatment;
in N2Carbonizing the solid raw material under the atmosphere; the carbonization treatment comprises a temperature rise stage and a heat preservation stage, wherein the temperature rise speed is 4 ℃/min, the heat preservation temperature is 500 ℃, and the heat preservation time is 2 h;
then, naturally cooling, taking out and grinding to obtain a first material;
s3, carrying out pyrolysis treatment;
in N2Carrying out pyrolysis treatment on the first material under the atmosphere; the pyrolysis treatment comprises a heating stage and a heat preservation stage, wherein the heating speed is 4 ℃/min, the heat preservation temperature is 900 ℃, and the heat preservation time is 2 h;
then, naturally cooling and taking out to obtain a material II;
s4, placing the second material in a proper amount of deionized water, adjusting the pH value to be neutral by using 0.1M dilute hydrochloric acid, and then cleaning the second material by using the deionized water until no NaCl or Na exists2SO4Obtaining the activated carbon J59.
S5, drying the activated carbon at 105 ℃ to constant weight, and sieving the dried activated carbon with a 200-mesh sieve.
The BET of the activated carbon J59 prepared in this example was determined to have a specific surface area of 1345cm as shown in FIG. 3c3/g。
Example 4
TABLE 1 information on the specific surface area and pore size of the activated carbons prepared in examples 1-3 (see FIGS. 3a-c)
First, iodine adsorption values were measured according to the GB/T12496.8-2015 method for each of the following activated carbons, as shown in fig. 5:
j57, 500 ℃, 2h, 700 ℃ and 2 h; iodine adsorption value of 987 mg/g;
j58, 500 ℃, 2h, 800 ℃ and 2 h; iodine adsorption value is 1603 mg/g;
j59, 500 ℃, 2h, 900 ℃ and 2 h; iodine adsorption value of 1409 mg/g;
comparative example 1: iodine adsorption value is 1350 mg/g;
CAC, commercial activated carbon (Nanjing Juyou scientific instruments Co., Ltd., G80545E, 200 mesh sieve); the iodine adsorption value was 700 mg/g.
Secondly, measuring the adsorption value of the activated carbon (0.005g) to methylene blue (50ml, 125mg/L) by using an ultraviolet spectrophotometry (GB/T9721-2006 chemical reagent molecular absorption spectrophotometry general rule (ultraviolet and visible light parts) standard), wherein the specific test steps are as follows:
1) adding 0.005g of adsorbent into a conical flask containing 50ml of methylene blue solution with the concentration of 125mg/g, sealing the conical flask, and placing the conical flask in a constant-temperature (the temperature is set to be 25 ℃) shaking table for 4 hours to ensure that the methylene blue is completely adsorbed;
2) after the oscillation is finished, the solution is taken out and passed through a membrane, and the concentration of methylene blue is measured by dilution (ultraviolet spectrophotometry), and the adsorption quantity is calculated.
The results are shown in FIG. 6:
j57, 500 ℃, 2h, 700 ℃ and 2 h; the adsorption value is 558 mg/g;
j58, 500 ℃, 2h, 800 ℃ and 2 h; the adsorption value is 742 mg/g;
j59, 500 ℃, 2h, 900 ℃ and 2 h; an adsorption value of 694 mg/g;
comparative example 1: the adsorption value is 658 mg/g;
CAC, commercial activated carbon (Nanjing Juyou scientific instruments Co., Ltd., G80545E, 200 mesh sieve); the adsorption value was 378 mg/g.
Claims (10)
1. An activated carbon characterized by: the activated carbon has a BET specific surface area of 1000m2(ii)/g to 2300m2/g；
The activated carbon has a range of 1cm3G to 2.5cm3A total pore volume of/g, wherein 45% to 100% of the total pore volume is formed by micropores and mesopores;
the micropores have a pore diameter of not less than 0.4nm and less than 2 nm;
the mesopores have a pore diameter of not less than 2nm and less than 50 nm;
wherein the activated carbon has a BET specific surface area of 1000m2(ii)/g to 2300m2/g。
2. The activated carbon of claim 1, wherein: the activated carbon has an iodine adsorption value of not less than 1000mg/g,
wherein the iodine adsorption value is obtained by testing according to the method of GB/T12496.8-2015.
3. The activated carbon of claim 1, wherein: the activated carbon has a range of 2cm3G to 2.5cm3(ii) a total pore volume in g,
wherein the mesoporous volume accounts for 40-90% of the total pore volume, and the microporous volume accounts for 5-10% of the total pore volume;
furthermore, the activated carbon has a BET specific surface area of 2000m2(ii)/g to 2300m2/g；
Further, the activated carbon has an iodine adsorption value of not less than 1500mg/g, wherein the iodine adsorption value is tested according to the method of GB/T12496.8-2015.
4. The activated carbon according to any one of claims 1 to 3, characterized in that: the activated carbon is prepared by using waste salt recovered from tiamulin production waste liquid as a raw material:
the waste salt contains Na2SO4、NaCl、KH2PO4Inorganic salts within, and organic carbons; wherein the content of the first and second substances,
the content of the organic carbon is 275 +/-25 mg/g;
the inorganic salt content is 45 + -5% by weight.
5. A preparation method of activated carbon is characterized in that: the method comprises the following steps:
s1, recovering active carbon production raw materials from tiamulin production waste liquid:
concentrating the waste liquid, and separating to obtain a solid raw material and a water material flow; the concentration treatment is carried out within the range of 95-115 ℃;
s2, carbonizing treatment;
carbonizing the solid raw material; the carbonization treatment comprises a temperature rising stage and a heat preservation stage, wherein the temperature rising speed is 4-10 ℃/min, the heat preservation temperature is 400-500 ℃, and the heat preservation time is 1-3 h;
s3, carrying out pyrolysis treatment;
carrying out pyrolysis treatment on the carbonized material; the pyrolysis treatment comprises a heating stage and a heat preservation stage, wherein the heating speed is 4-10 ℃/min, the heat preservation temperature is 700-900 ℃, and the heat preservation time is 1-3 h;
s4, cooling;
and cooling the material subjected to pyrolysis treatment to obtain the activated carbon.
6. The method for producing activated carbon according to claim 5, characterized in that: the solid raw material contains metal elements and non-metal elements, wherein the metal elements comprise Na and K, and the non-metal elements comprise C, H, O, N, S, P, Cl and Br.
7. The method for producing activated carbon according to claim 5, characterized in that: the solid raw material comprises 50 +/-2% of volatile components and 2 +/-2% of moisture by weight.
8. The process for producing activated carbon according to any one of claims 5 to 7, characterized in that: the solid feedstock had approximately the same thermogravimetric analysis TG curve as sodium p-toluenesulfonate and DTG curve.
9. The method for producing activated carbon according to claim 8, characterized in that: the solid raw material contains Na2SO4、NaCl、KH2PO4Inorganic salts within, and organic carbons; wherein the content of the first and second substances,
the content of the organic carbon is 275 +/-25 mg/g;
the inorganic salt content is 45 + -5% by weight.
10. The method for producing activated carbon according to claim 9, characterized in that: the tiamulin production waste liquid is obtained in the following mode: p-toluenesulfonyl and pleuromutilin are used for reaction, then the reaction is carried out with 2-diethylaminoethanethiol, and then tiamulin production waste liquid is obtained through separation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247433A (en) * | 2021-12-20 | 2022-03-29 | 中新国际联合研究院 | Method for treating organic waste salt and agricultural and forestry wastes and preparing biochar by molten salt method |
| CN116712980A (en) * | 2023-06-14 | 2023-09-08 | 南京理工大学 | Chitosan modified tiamulin waste salt activated carbon as well as preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB664436A (en) * | 1949-02-10 | 1952-01-09 | Distillers Co Yeast Ltd | Improvements in or relating to the recovery of antibiotic materials |
| JP2001521033A (en) * | 1997-10-29 | 2001-11-06 | スミスクライン・ビーチャム・パブリック・リミテッド・カンパニー | Pleuromutilin derivatives as antibacterial substances |
| WO2004015122A1 (en) * | 2002-08-09 | 2004-02-19 | Glaxo Group Limited | Method for reproducing pleuromutilins |
| CN101838199A (en) * | 2010-05-21 | 2010-09-22 | 西南大学 | Pleuromutilin solvent extraction process |
| CN102351368A (en) * | 2011-07-01 | 2012-02-15 | 石家庄开发区德赛化工有限公司 | Loading flocculation pretreatment method of antibiotic fermentation wastewater |
| CN104262210A (en) * | 2014-08-29 | 2015-01-07 | 宁夏泰瑞制药股份有限公司 | Method for extracting sodium p-toluenesulfonate from tiamulin synthesis wastewater |
| CN106672963A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Active carbon and preparation method thereof |
| US20170304791A1 (en) * | 2014-10-01 | 2017-10-26 | Cool Planet Energy Systems, Inc. | Biochar extracts and method for capturing material extracted from biochar |
| CN108455599A (en) * | 2018-02-11 | 2018-08-28 | 北京科技大学 | A kind of method that antibiotic bacterium dregs dry powder prepares the high performance active carbon rich in micropore |
| CN109012599A (en) * | 2018-09-12 | 2018-12-18 | 北京观澜科技有限公司 | A kind of load Fe3+Antibiotic bacterium dregs active carbon and its preparation method and application |
| CN110697705A (en) * | 2019-10-18 | 2020-01-17 | 中国铝业股份有限公司 | Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure |
| CN110922320A (en) * | 2019-11-25 | 2020-03-27 | 河北威远动物药业有限公司 | Method for extracting methyl isobutyl ketone and sodium p-toluenesulfonate |
| CN110980731A (en) * | 2019-12-19 | 2020-04-10 | 中国科学院广州能源研究所 | Method for preparing vinasse activated carbon material with high specific surface area by using waste vinasse |
-
2021
- 2021-04-09 CN CN202110384516.0A patent/CN112919463B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB664436A (en) * | 1949-02-10 | 1952-01-09 | Distillers Co Yeast Ltd | Improvements in or relating to the recovery of antibiotic materials |
| JP2001521033A (en) * | 1997-10-29 | 2001-11-06 | スミスクライン・ビーチャム・パブリック・リミテッド・カンパニー | Pleuromutilin derivatives as antibacterial substances |
| WO2004015122A1 (en) * | 2002-08-09 | 2004-02-19 | Glaxo Group Limited | Method for reproducing pleuromutilins |
| CN101838199A (en) * | 2010-05-21 | 2010-09-22 | 西南大学 | Pleuromutilin solvent extraction process |
| CN102351368A (en) * | 2011-07-01 | 2012-02-15 | 石家庄开发区德赛化工有限公司 | Loading flocculation pretreatment method of antibiotic fermentation wastewater |
| CN104262210A (en) * | 2014-08-29 | 2015-01-07 | 宁夏泰瑞制药股份有限公司 | Method for extracting sodium p-toluenesulfonate from tiamulin synthesis wastewater |
| US20170304791A1 (en) * | 2014-10-01 | 2017-10-26 | Cool Planet Energy Systems, Inc. | Biochar extracts and method for capturing material extracted from biochar |
| CN106672963A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Active carbon and preparation method thereof |
| CN108455599A (en) * | 2018-02-11 | 2018-08-28 | 北京科技大学 | A kind of method that antibiotic bacterium dregs dry powder prepares the high performance active carbon rich in micropore |
| CN109012599A (en) * | 2018-09-12 | 2018-12-18 | 北京观澜科技有限公司 | A kind of load Fe3+Antibiotic bacterium dregs active carbon and its preparation method and application |
| CN110697705A (en) * | 2019-10-18 | 2020-01-17 | 中国铝业股份有限公司 | Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure |
| CN110922320A (en) * | 2019-11-25 | 2020-03-27 | 河北威远动物药业有限公司 | Method for extracting methyl isobutyl ketone and sodium p-toluenesulfonate |
| CN110980731A (en) * | 2019-12-19 | 2020-04-10 | 中国科学院广州能源研究所 | Method for preparing vinasse activated carbon material with high specific surface area by using waste vinasse |
Non-Patent Citations (4)
| Title |
|---|
| JI ZHENG ET AL: ""Antibiotic resistome promotion in drinking water during biological activated carbon treatment: Is it influenced by quorum sensing"", 《ECS TRANSACTIONS》 * |
| KAI ZHANG ET AL: ""Synergistic effects of combining ozonation, ceramic membrane filtration and biologically active carbon filtration for wastewater reclamation"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| XIAN-RUI LIANG ET AL: ""Solubility of tiamulin hydrogen fumarate in acetone,acetonitrile,ethyl acetate,ethyl formate,and butyl acetate from (288.2 to 318.2)K"", 《JOURNAL OF CHEMICAL AND ENGINEERING DATA》 * |
| 肖磊: ""生产泰妙菌素工业废水中难降解污染物的回收与处理"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247433A (en) * | 2021-12-20 | 2022-03-29 | 中新国际联合研究院 | Method for treating organic waste salt and agricultural and forestry wastes and preparing biochar by molten salt method |
| CN114247433B (en) * | 2021-12-20 | 2024-01-09 | 中新国际联合研究院 | Method for simultaneously preparing biochar by treating organic waste salt and agricultural and forestry waste through molten salt method |
| CN116712980A (en) * | 2023-06-14 | 2023-09-08 | 南京理工大学 | Chitosan modified tiamulin waste salt activated carbon as well as preparation method and application thereof |
| CN116712980B (en) * | 2023-06-14 | 2024-03-08 | 南京理工大学 | Chitosan modified tiamulin waste salt activated carbon as well as preparation method and application thereof |
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