CN114574879B - Method for improving yield of humic acid prepared by coal electrolysis through coal particle surface coating - Google Patents
Method for improving yield of humic acid prepared by coal electrolysis through coal particle surface coating Download PDFInfo
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- CN114574879B CN114574879B CN202210203049.1A CN202210203049A CN114574879B CN 114574879 B CN114574879 B CN 114574879B CN 202210203049 A CN202210203049 A CN 202210203049A CN 114574879 B CN114574879 B CN 114574879B
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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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
Abstract
The invention belongs to the technical field of coal chemical industry, and provides a method for improving the yield of humic acid prepared by coal electrolysis by using a coal particle surface coating film, which solves the problem of low yield of humic acid prepared by coal electrochemical oxidation. The surface of the coal particles is covered by the surface active agent 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 surface hydrophilicity of the coal particles is improved, the current intensity is effectively improved, and the product humic acid is more easily separated from the coal particles, so that the yield of the humic acid prepared by the electrochemical oxidation of the coal 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 coating technology and preparing humic acid by electrolytic oxidation of coal slurry.
Background
Humic acid is a macromolecular organic acid composed of aromatic and various functional groups, accounts for 50% -80% of the total organic matters in soil and water ring ecology systems, is regarded as a green and friendly macromolecular organic matter, and is widely applied to various fields of agriculture, forestry, chemical industry, building materials, medicine and health, environmental protection and the like, and is widely paid attention to and applied to.
The coal resource is ascertained in China, the low-rank coal accounts for 59%, and more than 90% of the low-rank coal is used for power generation, industrial boilers and civil fuel direct combustion. In recent years, there is an urgent need for developing low-rank coal utilization technologies with high efficiency, low consumption and economy in countries and enterprises. The method takes coal oxidation as a means, utilizes oxidizing groups to cut off coal macromolecules, directly prepares chemicals with high added value, and is an effective way for clean, efficient and quality-divided utilization of coal.
Coal oxidation can be classified into chemical oxidation and electrochemical oxidation, and due to the large amount of wastewater generated in the chemical oxidation process, people's line of sight is gradually faded out under the increasingly strict environmental protection requirements. The electrochemical oxidation of coal has the advantages of mild operation conditions, simple equipment requirements, energy consumption saving, simple process flow and the like, accords with the green production concept, and is one of the most potential coal oxidation technologies. At present, the problem of low oxidation efficiency and low yield of humic acid exists 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 film coating technology which is applied to electrolytic coal slurry to solve the problem of low yield of humic acid in the 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 is that the surface of the coal particle can be coated with surface active agent iron dodecyl sulfonate [ Fe (DDS) 3 ]The hydrophilic film layer is formed by covering and suspending in the anolyte (potassium hydroxide) solution, and the existence of the hydrophilic film layer can effectively improve the current intensity and make the humic acid product easier to separate from coal particles, thereby improving the yield of humic acid prepared by electrochemical oxidation of coal.
The technical scheme of the invention is as follows:
the method for improving the yield of humic acid prepared by coal electrolysis by using the coal particle surface coating comprises the following steps:
(1) Preparing iron dodecyl sulfonate: molar ratio 3:1, adding sodium dodecyl benzene sulfonate and ferric nitrate into water for mixing, and controlling the concentration of the ferric nitrate to be 0.013g/mL; stirring at a constant temperature of 70 ℃, carrying out suction filtration and repeated water washing on the generated precipitate, recrystallizing, and drying to obtain the iron dodecyl sulfate;
(2) Crushing the coal sample to below 200 meshes; dissolving the iron dodecyl sulfate obtained in the step 1 by cyclohexane to obtain a film forming solution, wherein the concentration of the iron dodecyl sulfate in the film forming solution is 0.002-0.01 g/ml; soaking the coal sample in a film forming solution for 1-3 hours, 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 pool after ultrasonic treatment; the cathode pool is added with potassium hydroxide solution with the same concentration as the anode, then the electrode is assembled, and simultaneously, a magnetic stirrer is turned on to stir the coal slurry, and the temperature of the electrolytic pool is kept by a circulating water pump.
(4) And opening an electrochemical workstation to perform a reaction, wherein a constant-voltage electrochemical test method is selected in the reaction process.
(5) And after the reaction is finished, carrying out suction filtration, centrifugation, acidification, filtration and drying on the coal slurry to obtain humic acid, weighing the weight of the humic acid, and calculating to obtain the yield of the humic acid.
The dosage of the surfactant for preparing the coal water slurry by the coal sample 1 in the step (2) is 0.1% of the mass of the coal sample, and the dosage of the surfactant for preparing the coal water slurry by the coal sample 2 is 0.5% 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 cathodic platinum electrodes and anodic nickel electrodes used in the examples of this patent; wherein the temperature is 40-60 ℃; the concentration of the coal slurry is 30g/L to 75g/L (based on dry ash-free base); the time is 2-6 h.
In the step (5), the humic acid yield is calculated according to the formula: (based on dry ashless basis)
Y i ＝(m i ÷m)×100％
Wherein: m represents the mass of the coal sample, and i represents the mass of humic acid.
The invention has the beneficial effects that:
(1) The surface film coating technology for the coal particles is provided, so that a hydrophilic film layer is formed on the surfaces of the coal particles, and the dispersing effect of the surfaces of the coal particles in potassium hydroxide solution is effectively improved.
(2) The hydrophilic membrane can improve the hydrophilicity of coal particles, greatly increases the oxidation current of coal after membrane coating compared with that before membrane coating under the same reaction condition, and improves the current efficiency.
(3) After the membrane is covered, the humic acid passes through the membrane layer to be separated from the surface of the coal particles more easily due to the hydrophilicity of the humic acid, and enters the anode liquid KOH to form potassium humate, so that the yield of the humic acid is finally improved. Humic acid is easier to separate, so that more coal particle surfaces are exposed, and coal oxidation is facilitated.
Drawings
FIG. 1 is a schematic diagram of an electrochemical reactor used in the present invention.
FIG. 2 is an i-t curve of coal sample 1 before and after film coating.
FIG. 3 is an i-t curve of coal sample 1 before and after film coating.
FIG. 4 is an i-t curve of coal sample 2 before and after film coating.
FIG. 5 is an i-t curve of coal sample 2 before and after film coating.
In the figure: 1-a data display system; 2-CHI760D electrochemical workstation; 3-CHI680 high current amplifier; 4-a water bath heater; 5-collecting bag; 6-working electrode; 7-a reference electrode; 8-a pair of electrodes; 9-liquid salt bridge; 10-an anode chamber; 11-cathode cell; 12-ion exchange membrane; 13-a magnetic stirrer; 14-a magnetic force stirrer; 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 using the coal particle surface coating film,
the properties of the coal samples used in the experiments are shown in Table 1. From the data in the table, coal sample 1 was a long flame coal, and coal sample 2 was brown coal.
Table 1 industrial analysis of coal samples
Note that: * Obtained by subtraction
Example 1
An H-type glass electrolytic cell is used as a reaction device, 150mL of 10wt.% potassium hydroxide solution is added into a cathode, 200mL of prepared 50g/L coal water slurry solution is added into an anode, the reaction temperature is controlled to be 60 ℃ through a water bath, and the electrolysis is performed at a constant voltage of 0.8V for 6H. The i-t curve obtained by constant voltage electrolysis before and after film coating is shown in FIG. 2.
The electrolysis results are shown in Table 1, and the yield of humic acid after film coating under the same reaction conditions is increased by 1.89% absolute and 113.85% relative compared with that before film coating.
Table 1: yield of humic acid obtained by electrolysis before and after coal sample 1 film coating
| Sequence number | Anode coal sample | Humic acid yield (%) |
| 1 | 50g/L coal sample 1 before film coating | 1.66 |
| 2 | After the film is coated on 50g/L coal sample 1 | 3.55 |
Example 2
An H-type glass electrolytic cell is used as a reaction device, 150mL of 10wt.% potassium hydroxide solution is added into a cathode, 200mL of prepared 75g/L coal water slurry solution is added into an anode, the reaction temperature is controlled to be 40 ℃ through a water bath, and the electrolysis is carried out at a constant voltage of 0.8V for 2H. The i-t curve obtained by constant voltage electrolysis before and after film coating is shown in FIG. 3.
The electrolysis results are shown in Table 2, and the yield of humic acid after film coating under the same reaction conditions is increased by 0.57% absolute and 58.76% relative compared with that before film coating.
Table 2: yield of humic acid obtained by electrolysis before and after coal sample 1 film coating
| Sequence number | Anode coal sample | Humic acid yield (%) |
| 1 | 75g/L coal sample 1 before film coating | 0.97 |
| 2 | After 75g/L of coal sample 1 is coated | 1.54 |
Example 3
An H-type glass electrolytic cell is used as a reaction device, 150mL of 10wt.% potassium hydroxide solution is added into a cathode, 200mL of prepared 30g/L coal water slurry solution is added into an anode, the reaction temperature is controlled to be 60 ℃ through a water bath, and the electrolysis is performed at a constant voltage of 0.8V for 6H. The i-t curve obtained by constant voltage electrolysis before and after film coating is shown in FIG. 4.
The electrolysis results are shown in Table 3, and the yield of humic acid after film coating under the same reaction conditions is increased by 56.07% compared with that before film coating, and the relative percentage is increased by 317.14%.
Table 3: yield of humic acid obtained by electrolysis before and after coal sample 2 film coating
| Sequence number | Anode coal sample | Humic acid yield (%) |
| 1 | 30g/L coal sample 2 before film coating | 17.68 |
| 2 | After the coal sample 2 with the concentration of 30g/L is coated | 73.75 |
Example 4
An H-type glass electrolytic cell is used as a reaction device, 150mL of 10wt.% potassium hydroxide solution is added into a cathode, 200mL of prepared 50g/L coal water slurry solution is added into an anode, the reaction temperature is controlled to be 40 ℃ through a water bath, and the electrolysis is performed at a constant voltage of 0.8V for 4H. The i-t curve obtained by constant voltage electrolysis before and after film coating is shown in FIG. 5.
The electrolysis results are shown in Table 4, and the yield of humic acid after film coating under the same reaction conditions is increased by 21.6% absolute and 142.29% relative to that before film coating.
Table 4: yield of humic acid obtained by electrolysis before and after coal sample 2 film coating
| Sequence number | Anode coal sample | Humic acid yield (%) |
| 1 | 50g/L coal sample 2 before film coating | 15.18 |
| 2 | After 50g/L coal sample 2 is coated | 36.78 |
Claims (1)
1. The method for improving the yield of humic acid prepared by coal electrolysis by using the coal particle surface coating is characterized by comprising the following steps:
(1) Preparing iron dodecyl sulfonate: molar ratio 3:1, adding sodium dodecyl benzene sulfonate and ferric nitrate into water for mixing, and controlling the concentration of the ferric nitrate to be 0.013g/mL; stirring at a constant temperature of 70 ℃, carrying out suction filtration and repeated water washing on the generated precipitate, recrystallizing, and drying to obtain the iron dodecyl sulfate;
(2) Crushing the coal sample to below 200 meshes; dissolving the iron dodecyl sulfate obtained in the step 1 by cyclohexane to obtain a film forming solution, wherein the concentration of the iron dodecyl sulfate in the film forming solution is 0.002-0.01 g/ml; soaking the coal sample in a film forming solution for 1-3 hours, 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 pool; the cathode cell is added with potassium hydroxide solution with the same concentration as the anode, and then electrolytic reaction is carried out.
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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 |
|---|
| 煤中腐植酸的研究;吴奇虎, 唐运千, 孙淑和, 钱秉钧, 申葆;燃料化学学报(02);第122-132页 * |
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