CN114574879A - Method for improving yield of humic acid prepared by coal electrolysis by coating film on surface of coal particles - Google Patents
Method for improving yield of humic acid prepared by coal electrolysis by coating film on surface of coal particles Download PDFInfo
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- CN114574879A CN114574879A CN202210203049.1A CN202210203049A CN114574879A CN 114574879 A CN114574879 A CN 114574879A CN 202210203049 A CN202210203049 A CN 202210203049A CN 114574879 A CN114574879 A CN 114574879A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
The invention belongs to the technical field of coal chemical industry, provides a method for improving the yield of humic acid prepared by coal electrolysis by coating a film on the surface of coal particles, and solves the problem of low yield of humic acid prepared by coal electrochemical oxidation. The surface of the coal particles is covered by the surfactant of the iron dodecyl sulfonate to form a hydrophilic film layer which is suspended in the potassium hydroxide solution, and due to the existence of the hydrophilic film layer, the hydrophilicity of the surface of the coal particles is improved, the current intensity is effectively improved, and the product humic acid is easier to separate from the coal particles, so that the yield of humic acid prepared by coal electrochemical oxidation is improved.
Description
Technical Field
The invention belongs to the technical field of coal chemical industry, and particularly relates to the technical field of designing a coal particle surface film coating technology and preparing humic acid by coal slurry electrolytic oxidation.
Background
Humic acid is a high molecular organic acid composed of aromatic and various functional groups thereof, accounts for 50% -80% of total organic matters in soil and water ring ecosystems, is regarded as a green and friendly macromolecular organic matter, is widely applied to various fields of agriculture, forestry, chemical industry, building materials, medical health, environmental protection and the like, and is widely concerned and applied.
China is a big coal country, and in China, over 90 percent of low-rank coal accounts for 59 percent of coal resources, and is directly combusted as power generation, industrial boilers and civil fuels. In recent years, the development of low-rank coal utilization technology with high efficiency, low consumption and economy is urgently required by countries and enterprises. The method is characterized in that coal oxidation is used as a means, oxidizing radicals are used for cutting off coal macromolecules, chemicals with high added values are directly prepared, and the method is an effective way for clean, efficient and quality-divided utilization of coal.
Coal oxidation can be divided into chemical oxidation and electrochemical oxidation, and because a large amount of wastewater is generated in the chemical oxidation process, the vision of people is gradually faded out under increasingly strict environmental protection requirements. The electrochemical oxidation of coal has the advantages of mild operation conditions, simple equipment requirements, energy conservation, simple process flow and the like, conforms to the green production concept, and is one of the most potential coal oxidation technologies. At present, the problems of low oxidation efficiency and low humic acid yield generally exist in the preparation of humic acid by coal oxidation.
Aiming at the defects of the existing coal electrochemical oxidation technology, the invention provides a coal particle surface coating technology applied to electrolytic coal slurry to solve the problem of low yield of humic acid generated by coal electrochemical oxidation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for improving the yield of humic acid prepared from coal by coating a film on the surface of coal particles. The method comprises that the surface of coal particles can be coated with surfactant ferric dodecyl sulfonate (Fe (DDS))3]The hydrophilic film layer formed by covering is suspended in the anode electrolyte (potassium hydroxide) solution, and the existence of the hydrophilic film layer can effectively improve the current intensity and enable the product humic acid to be more easily separated from coal particles, thereby improving the yield of humic acid prepared by coal electrochemical oxidation.
The technical scheme of the invention is as follows:
a method for improving the yield of humic acid prepared by coal electrolysis by coating a film on the surface of coal particles comprises the following steps:
(1) preparing ferric dodecyl sulfonate: mixing a molar ratio of 3: 1, adding sodium dodecyl benzene sulfonate and ferric nitrate into water for mixing, and controlling the concentration of the ferric nitrate to be 0.013 g/mL; stirring at a constant temperature of 70 ℃, carrying out suction filtration and multiple water washing on the generated precipitate, recrystallizing, and drying to obtain ferric dodecyl sulfonate;
(2) crushing a coal sample to below 200 meshes; dissolving the ferric dodecyl sulfonate obtained in the step 1 by using cyclohexane to obtain a film forming solution, wherein the concentration of the ferric dodecyl sulfonate in the film forming solution is 0.002-0.01 g/ml; soaking the coal sample in the film forming solution for 1-3 h, and then filtering and drying to obtain a treated coal sample;
(3) adding the treated coal sample prepared in the step (2) into a potassium hydroxide solution with the concentration of 5-15 wt.% to prepare a coal water slurry solution, wherein the concentration of the treated coal sample in the coal water slurry solution is 30-75 g/L, and adding the treated coal sample into an anode tank after ultrasonic treatment; adding potassium hydroxide solution with the same concentration as the anode into the cathode pool, then installing the electrodes, simultaneously turning on a magnetic stirrer to stir the coal slurry, and maintaining the temperature of the electrolytic cell by using a circulating water pump.
(4) And opening an electrochemical workstation for reaction, wherein a constant-voltage electrochemical test method is selected in the reaction process.
(5) After the reaction is finished, carrying out suction filtration, centrifugation, acidification, filtration and drying on the coal slurry to obtain humic acid, and weighing the humic acid by weight to calculate the humic acid yield.
In the step (2), the dosage of the surfactant for preparing the coal water slurry from the coal sample 1 is 0.1 percent of the mass of the coal sample, and the dosage of the surfactant for preparing the coal water slurry from the coal sample 2 is 0.5 percent of the mass of the coal sample.
The electrodes used in step (3) are electrodes of various materials and materials, including but not limited to the cathode platinum electrode and the anode nickel electrode used in the examples cited in this patent; wherein the temperature is 40-60 ℃; the coal slurry concentration is 30 g/L-75 g/L (based on dry ashless base); the time is 2-6 h.
In the step (5), the humic acid yield calculation formula is as follows: (based on a dry ashless base)
Yi＝(mi÷m)×100％
In the formula: m represents the mass of the coal sample, and i represents the mass of humic acid.
The invention has the beneficial effects that:
(1) provides a coal particle surface film coating technology, which enables the coal particle surface to form a hydrophilic film layer and effectively improves the dispersion effect of the coal particle surface in a potassium hydroxide solution.
(2) The hydrophilic membrane can improve the hydrophilicity of coal particles, under the same reaction condition, the oxidation current of the coal after membrane covering is greatly increased compared with that before membrane covering, and the current efficiency is improved.
(3) After film covering, due to the hydrophilicity of humic acid, the humic acid can more easily penetrate through the film layer to be separated from the surface of coal particles and enter into anolyte KOH to form potassium humate, and the yield of the humic acid is finally improved. Humic acid is easier to separate, so that more surfaces of coal particles are exposed, and the coal oxidation is facilitated.
Drawings
FIG. 1 is a schematic view of an electrochemical reactor used in the present invention.
FIG. 2 is an i-t curve before and after the coal sample 1 is coated.
FIG. 3 is an i-t curve before and after the coal sample 1 is coated.
FIG. 4 is an i-t curve before and after the coal sample 2 is coated.
FIG. 5 is an i-t curve before and after the coal sample 2 is coated.
In the figure: 1-a data display system; 2-CHI760D electrochemical workstation; 3-CHI680 high current amplifier; 4-water bath heater; 5-air collecting bag; 6-a working electrode; 7-a reference electrode; 8-a counter electrode; 9-liquid salt bridge; 10-an anode chamber; 11-a cathode cell; 12-an ion exchange membrane; 13-magnetic stirring; 14-magnetic stirring device; 15-an exhaust pipe; 16-circulating water pipe.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the specific examples.
By adopting the method for improving the yield of humic acid prepared by coal electrolysis by coating the film on the surface of the coal particles,
the properties of the coal samples used in the experiment are shown in table 1. The data in the table show that the coal sample 1 is long flame coal, and the coal sample 2 belongs to lignite.
TABLE 1 Industrial analysis of coal samples
Note: is obtained by differential subtraction
Example 1
An H-type glass electrolytic cell is taken as a reaction device, 150mL of 10 wt.% potassium hydroxide solution is added to a cathode, 200mL of prepared 50g/L water-coal-slurry solution is added to an anode, the reaction temperature is controlled at 60 ℃ through a water bath, constant-voltage electrolysis is carried out at 0.8V, and the electrolysis time is 6H. FIG. 2 shows the i-t curve obtained by constant-voltage electrolysis before and after coating.
The electrolysis results are shown in table 1, and the yield of humic acid after film coating is increased by 1.89% in absolute percentage and 113.85% in relative percentage compared with that before film coating under the same reaction conditions.
Table 1: yield of humic acid obtained by electrolysis before and after coating of coal sample 1
| Serial number | Anode coal sample | Humic acid yield (%) |
| 1 | Before 50g/ |
1.66 |
| 2 | After 50g/ |
3.55 |
Example 2
An H-type glass electrolytic cell is taken as a reaction device, 150mL of 10 wt.% potassium hydroxide solution is added to a cathode, 200mL of prepared 75g/L water-coal-slurry solution is added to an anode, the reaction temperature is controlled at 40 ℃ through a water bath, constant-voltage electrolysis is carried out at 0.8V, and the electrolysis time is 2H. FIG. 3 shows the i-t curve obtained by constant-voltage electrolysis before and after coating.
The electrolysis results are shown in table 2, and the yield of humic acid after film coating is increased by 0.57% in absolute percentage and 58.76% in relative percentage compared with that before film coating under the same reaction conditions.
Table 2: yield of humic acid obtained by electrolysis before and after coating of coal sample 1
| Serial number | Anode coal sample | Humic acid yield (%) |
| 1 | Before the film covering of 75g/ |
0.97 |
| 2 | After 1 film coating of 75g/L coal sample | 1.54 |
Example 3
An H-type glass electrolytic cell is taken as a reaction device, 150mL of 10 wt.% potassium hydroxide solution is added to a cathode, 200mL of prepared 30g/L water-coal-slurry solution is added to an anode, the reaction temperature is controlled at 60 ℃ through a water bath, constant-voltage electrolysis is carried out at 0.8V, and the electrolysis time is 6H. FIG. 4 shows the i-t curve obtained by constant-voltage electrolysis before and after coating.
The electrolysis result is shown in table 3, and the yield of humic acid after film coating under the same reaction condition is increased by 56.07 percent in absolute percentage and 317.14 percent in relative percentage compared with that before film coating.
Table 3: yield of humic acid obtained by electrolysis before and after coating of coal sample 2
| Serial number | Anode coal sample | Humic acid yield (%) |
| 1 | Before the film covering of a coal sample 2 of 30g/L | 17.68 |
| 2 | After the coal sample 2 of 30g/L is coated with a film | 73.75 |
Example 4
An H-type glass electrolytic cell is taken as a reaction device, 150mL of 10 wt.% potassium hydroxide solution is added to a cathode, 200mL of prepared 50g/L water-coal-slurry solution is added to an anode, the reaction temperature is controlled at 40 ℃ through a water bath, constant-voltage electrolysis is carried out at 0.8V, and the electrolysis time is 4H. FIG. 5 shows the i-t curve obtained by constant-voltage electrolysis before and after coating.
The electrolysis results are shown in table 4, and the yield of humic acid after film coating is increased by 21.6% in absolute percentage and 142.29% in relative percentage compared with that before film coating under the same reaction conditions.
Table 4: yield of humic acid obtained by electrolysis before and after coating of coal sample 2
| Serial number | Anode coal sample | Humic acid yield (%) |
| 1 | Before 2 film-coating of 50g/L coal sample | 15.18 |
| 2 | After the membrane covering of a coal sample 2 of 50g/L | 36.78 |
Claims (1)
1. A method for improving the yield of humic acid prepared by coal electrolysis by coating a film on the surface of coal particles is characterized by comprising the following steps:
(1) preparing ferric dodecyl sulfonate: mixing a molar ratio of 3: 1, adding sodium dodecyl benzene sulfonate and ferric nitrate into water for mixing, and controlling the concentration of the ferric nitrate to be 0.013 g/mL; stirring at a constant temperature of 70 ℃, carrying out suction filtration and multiple water washing on the generated precipitate, recrystallizing, and drying to obtain ferric dodecyl sulfonate;
(2) crushing a coal sample to below 200 meshes; dissolving the ferric dodecyl sulfonate obtained in the step 1 by using cyclohexane to obtain a film forming solution, wherein the concentration of the ferric dodecyl sulfonate in the film forming solution is 0.002-0.01 g/ml; soaking the coal sample in the film forming solution for 1-3 h, and then filtering and drying to obtain a treated coal sample;
(3) adding the treated coal sample prepared in the step (2) into a potassium hydroxide solution with the concentration of 5-15 wt.% to prepare a coal water slurry solution, wherein the concentration of the treated coal sample in the coal water slurry solution is 30-75 g/L, and adding the coal water slurry solution into an anode pool; adding potassium hydroxide solution with the same concentration as the anode into the cathode cell, and then carrying out electrolytic reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430175A (en) * | 1981-12-22 | 1984-02-07 | Rutgerswerke Aktiengesellschaft | Process for the electrochemical conversion of coal and use of the reaction products |
| SU1713980A1 (en) * | 1989-12-19 | 1992-02-23 | Институт Органического Синтеза И Углехимии Ан Казсср | Method and electrolyzer for producing humic acids from hard-to-oxidize brown coals |
| CN102747381A (en) * | 2012-07-03 | 2012-10-24 | 大连理工大学 | Method for preparing humic acid through lignite electrochemical oxidation |
| CN103668304A (en) * | 2012-09-24 | 2014-03-26 | 淮南师范学院 | Method for electrolyzing coal slurry to make hydrogen employing Ti/nano TiO2-ZrO2 electrode |
| CN113831548A (en) * | 2021-09-29 | 2021-12-24 | 河南农业大学 | Application of penicillium MJ51 extracellular fluid in preparation of water-soluble humic acid by dissolving lignite |
-
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- 2022-03-02 CN CN202210203049.1A patent/CN114574879B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430175A (en) * | 1981-12-22 | 1984-02-07 | Rutgerswerke Aktiengesellschaft | Process for the electrochemical conversion of coal and use of the reaction products |
| SU1713980A1 (en) * | 1989-12-19 | 1992-02-23 | Институт Органического Синтеза И Углехимии Ан Казсср | Method and electrolyzer for producing humic acids from hard-to-oxidize brown coals |
| CN102747381A (en) * | 2012-07-03 | 2012-10-24 | 大连理工大学 | Method for preparing humic acid through lignite electrochemical oxidation |
| CN103668304A (en) * | 2012-09-24 | 2014-03-26 | 淮南师范学院 | Method for electrolyzing coal slurry to make hydrogen employing Ti/nano TiO2-ZrO2 electrode |
| CN113831548A (en) * | 2021-09-29 | 2021-12-24 | 河南农业大学 | Application of penicillium MJ51 extracellular fluid in preparation of water-soluble humic acid by dissolving lignite |
Non-Patent Citations (1)
| Title |
|---|
| 吴奇虎, 唐运千, 孙淑和, 钱秉钧, 申葆: "煤中腐植酸的研究", 燃料化学学报, no. 02, pages 122 - 132 * |
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