CN116675873A - Method for efficiently extracting humic acid from lignite - Google Patents
Method for efficiently extracting humic acid from lignite Download PDFInfo
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- CN116675873A CN116675873A CN202310593115.5A CN202310593115A CN116675873A CN 116675873 A CN116675873 A CN 116675873A CN 202310593115 A CN202310593115 A CN 202310593115A CN 116675873 A CN116675873 A CN 116675873A
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- 239000004021 humic acid Substances 0.000 title claims abstract description 79
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003077 lignite Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 46
- 239000007790 solid phase Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007791 liquid phase Substances 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 13
- 238000012216 screening Methods 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 26
- 238000000605 extraction Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000005406 washing Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The application relates to a method for efficiently extracting humic acid from lignite, which comprises the following steps: crushing and screening lignite to 60-80 meshes, and putting the lignite into a baking oven for drying for 24 hours; weighing a certain amount of lignite, fully mixing with alkali liquor, dropwise adding a certain amount of hydrogen peroxide solution, continuously stirring under the water bath condition until the reaction is finished, separating the reaction mixture by suction filtration to obtain a liquid phase and a solid phase, forming a mixed solution by a cleaning solution of the solid phase and the liquid phase, and performing rotary evaporation and drying treatment on the mixed solution to obtain humic acid. According to the application, the humic acid is extracted from the lignite by mixing alkali liquor and hydrogen peroxide, so that the lignite can be fully decomposed, the yield of the humic acid is improved, and the obtained humic acid has lower aromaticity, molecular weight and more oxygen-containing functional groups; the method for extracting humic acid from lignite is simple, the yield of humic acid is high, the extraction period is short, and the method is suitable for large-scale application.
Description
Technical Field
The application belongs to the technical field of humic acid extraction, and particularly relates to the technical field of a method for efficiently extracting humic acid from lignite.
Background
Lignite is the lowest grade of coal and is a rich natural resource. However, because lignite has the characteristics of high moisture content, high volatile matter content, low heat value, high ash content and the like, the lignite is high in combustion control difficulty, meanwhile, air pollution is caused, the released pollutant gas can cause greenhouse effect and acid rain generation, global climate abnormality and sea level rise are caused, and huge threat is presented to human living environment, which is contrary to 'carbon neutralization and carbon reaching peak'. Therefore, efficient utilization of lignite resources is a hot topic of current research. The lignite contains rich humic acid, and the humic acid has high water solubility and strong activity and is important to be applied in the fields of agriculture, industry, medicine and the like.
Therefore, the humic acid is extracted from the lignite, the defects of high moisture content, low heat value and easy air pollution caused by combustion of the lignite are overcome, the high value-added utilization of lignite resources is effectively improved, and the method has important significance for the production of humic acid products, the development and utilization of lignite resources and the protection of ecological environment. Humic acid has the characteristics of low molecular weight, dense functional groups, more acidic groups, good solubility, strong permeability, high activity and the like, is a scarce resource, and has unique efficacy in the fields of modern agriculture, ecological restoration, life sciences and the like. Currently, aqueous extraction is one of the main technologies for extracting humic acid from lignite.
Some common oxidants (e.g. HNO 3 ) Because oxidation-reduction reaction occurs in the system, a large amount of polluted gas is discharged in the air, which is unfavorable for protecting the environment, so that the use of pollution-free oxidant instead is an environment-friendly strategy. In addition, the yield of humic acid is still one of the important problems of current concern, and the yield of humic acid which is currently studied is low and cannot meet the requirements of industrial development. H 2 O 2 As an environment-friendly oxidant, the lignite is oxidized to have more oxygen-containing functional groups, and has positive effect on improving the yield of humic acid. However, due to the complexity and variety of coal raw materials, H is used alone 2 O 2 The yield of humic acid is not significantly improved. In addition, KOH and NaOH can effectively reduce the molecular weight and the aromaticity of HA and effectively improve the yield of humic acid. Thus, H is 2 O 2 The combination of KOH or NaOH is beneficial to improving the yield of humic acid, and has important significance for systematically analyzing the influence of the activator on the extraction of humic acid.
Disclosure of Invention
The application aims to solve the defects, and provides a method for efficiently extracting humic acid from lignite.
The application is realized by adopting the following technical scheme. A method for efficiently extracting humic acid from lignite comprises the following steps:
a method for efficiently extracting humic acid from lignite comprises the following steps:
(1) Crushing and screening lignite to a certain particle size, and putting the lignite into a drying oven to dry for 24 hours;
(2) Weighing a certain amount of lignite dried in the step (1), and fully mixing with alkali liquor;
(3) Dropwise adding a certain amount of hydrogen peroxide solution into the mixture in the step (2), and continuously stirring under the water bath condition until the reaction is finished;
(4) And (3) separating the reaction mixture in the step (3) by suction filtration to obtain a liquid phase and a solid phase, forming a mixed solution by the cleaning liquid of the solid phase and the liquid phase, and performing rotary evaporation and drying treatment on the mixed solution to obtain humic acid.
Further, the lignite obtained in the step (1) has the particle size of 60-80 meshes; the drying temperature of the oven is 80-110 ℃.
Further, the drying temperature of the drying oven in the step (1) is 105 ℃.
Further, the lignite obtained in the step (2) is 1-5 g in mass; the mass fraction of the alkali liquor is 0.5-3 mol/L; the mass volume ratio of the lignite to the alkali liquor in the step (2) is 1-5 g: 10-30 mL.
Further, the mass fraction of the hydrogen peroxide in the step (3) is 10-30%, and the adding volume of the hydrogen peroxide is 5-30 mL.
Further, the hydrogen peroxide added in the step (3) is 15mL.
Further, the water bath temperature in the step (3) is 30-90 ℃, the stirring rotation speed is 20-40 rpm, and the reaction time is 40-150 minutes.
Further, the water bath temperature in the step (3) is 50 ℃, the stirring rotation speed is 30 revolutions per minute, and the reaction time is 60 minutes or 150 minutes.
Further, the rotary steaming rotating speed in the step (4) is 60-100 revolutions per minute, the rotary steaming temperature is 40-60 ℃, the drying temperature is 85-110 ℃, and the drying time is 15-24 hours.
Further, in the step (4), the rotary steaming speed is 80 revolutions per minute, the rotary steaming temperature is 50 ℃, the drying temperature is 105 ℃, and the drying time is 24 hours.
Further, the alkali liquor is one or more of potassium hydroxide, sodium hydroxide and calcium hydroxide.
Further, the cleaning solution of the solid phase in the step (4) is a cleaning solution obtained by washing the solid phase with deionized water to be neutral.
The application has the beneficial effects that (1) the mixed use of the hydrogen peroxide and the alkali liquor can destroy the physical structure of the lignite, improve the yield of the humic acid, and the obtained humic acid has lower aromaticity, lower molecular weight and more oxygen-containing functional groups.
(2) The hydrogen peroxide and alkali solution in the application are used as the extracting solution of lignite, which can effectively promote the cracking of aromatic structures, so that the structural polarity of humic acid is increased, the humic acid is more soluble in water, and the yield of humic acid is increased.
(3) The method has the advantages of simple process, short production period and high extraction rate of humic acid, and is suitable for large-scale application.
The application is further explained below with reference to the drawings and the detailed description.
Drawings
FIG. 1 is a flow chart for extracting humic acid from lignite.
FIG. 2 is a FT-IR chart of humic acid of examples 1 to 4.
FIG. 3 is a UV-Vis diagram of humic acid of examples 1 to 4.
Detailed Description
Example 1:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1), fully mixing with 15mL of NaOH solution with the concentration of 3mol/L, and continuously stirring for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(3) And (3) carrying out suction filtration on the reaction mixture in the step (2) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 2:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1), fully mixing with 15mL of KOH solution with the concentration of 3mol/L, and continuously stirring for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(3) And (3) carrying out suction filtration on the reaction mixture in the step (2) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 3:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of NaOH solution with the concentration of 3mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 4:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of KOH solution with the concentration of 3mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 5:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of KOH solution with the concentration of 3mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 60 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 6:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of KOH solution with the concentration of 0.5 mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 7:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of KOH solution with the concentration of 1 mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 8:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1), fully mixing with 15mL of KOH solution with the concentration of 2mol/L, and continuously stirring for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(3) And (3) carrying out suction filtration on the reaction mixture in the step (2) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 9:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and fully mixing with 15mL of NaOH solution with the concentration of 1 mol/L;
(3) Dropwise adding 15mL of 30% by mass H to the mixture in step (2) 2 O 2 The solution is stirred for 150 minutes at the rotating speed of 30 revolutions per minute under the water bath condition of 50 ℃;
(4) And (3) carrying out suction filtration on the reaction mixture in the step (3) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
Example 10:
(1) Crushing and screening lignite to 60-80 meshes, and putting the lignite into a 105 ℃ oven for drying for 24 hours;
(2) Weighing 1g of lignite in the step (1) and 15mL of H with mass fraction of 30% 2 O 2 The solution was thoroughly mixed and stirred continuously at 30 rpm for 150 minutes in a 50 ℃ water bath;
(3) And (3) carrying out suction filtration on the reaction mixture in the step (2) at-0.06 Mpa to obtain a liquid phase and a solid phase, washing the solid phase by using deionized water, forming a mixed solution by the washing liquid of the solid phase and the liquid phase, carrying out rotary evaporation on the mixed solution at the temperature of 50 ℃ at the rotating speed of 80 rpm, and drying the mixed solution in a drying oven at the temperature of 105 ℃ for 24 hours to obtain humic acid.
The humic acid yield of lignite in examples 1 to 10 was measured by using the method for measuring the content of water-soluble humic acid-Capacity method, and the specific calculation formula is as follows:
Fe 2+ the concentration of the standard solution was calculated as follows:
wherein M represents Fe 2+ The concentration of the solution, V, indicates the consumption of Fe during titration 2+ Volume of solution.
Humic acid content HA in lignite ad The (analytical base) is expressed in mass percent (%), calculated as follows:
wherein V is 0 Indicating the consumption of Fe by titration blank 2+ Volume of solution, V 1 Indicating the consumption of Fe by titration of the sample 2+ The volume of the solution, 0.003 represents 1.00mL K 2 Cr 2 O 7 The mass of the consumed HA carbon, C represents the HA carbon coefficient of different samples, lignite is 0.58, a represents the total volume of the sample solution, and b represents the volume of the sample solution taken during measurement; g represents the mass of the sample, HA ad The analytical basis for HA is shown.
The humic acid content (dry basis) in lignite is expressed in mass percent (%), calculated as follows:
wherein, HA d Represents the dry basis of humic acid, HA ad Represents the analytical group of humic acid, M ad The moisture content of the sample is shown. The results of examples 1-9 are shown in Table 1.
TABLE 1 humic acid yield in lignite of examples 1-7
| Reaction conditions | Humic acid yield (%) | |
| Example 1 | 15mL 3mol/L NaOH; reaction for 150 min | 45.54 |
| Example 2 | 15mL 3mol/L KOH; reaction for 150 min | 49.68 |
| Example 3 | 15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 74.42 |
| Example 4 | 15mL 3mol/L KOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 82.08 |
| Example 5 | 15mL 3mol/L KOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The reaction was carried out for 60 minutes | 78.18 |
| Example 6 | 15mL 0.5mol/L KOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 68.34 |
| Example 7 | 15mL 1mol/L KOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 69.58 |
| Example 8 | 15mL 2mol/L KOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 75.66 |
| Example 9 | 15mL 1mol/L NaOH；15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 65.44 |
| Example 10 | 15mL 30％H 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Reaction for 150 min | 49.99 |
As can be seen from Table 1, the humic acid extraction rate was less than 50% in examples 1, 2 and 10, which showed that KOH, naOH and H were used alone 2 O 2 The extraction agent was weak in the decomposition ability to brown coal, the yield of humic acid was low, the extraction rates of humic acid of examples 3 to 9 were all 60% or more, H 2 O 2 The use of KOH or NaOH together can significantly improve the yield of humic acid, while KOH and H 2 O 2 The yield of humic acid used in a mixed way is superior to that of NaOH and H 2 O 2 When the mixture was used, the different concentrations of KOH in the mixture had different effects on the yield of humic acid, and in example 6, when the concentration of KON in the mixture was 0.5mol/L, the yield of humic acid was 68.34%, 15mL of KOH at a concentration of 3mol/L and 15mL of H at a mass fraction of 30% were used 2 O 2 The yield of humic acid was 82.08%.
FT-IR and UV-Vis pattern analysis was performed on the extracted humic acid of examples 1-4, and the results are shown in FIGS. 2-3.
As can be seen from FIG. 2, 3420cm -1 Absorption peak of O-H, KOH-H 2 O 2 The highest vibration intensity of humic acid O-H as extractant indicates that more humic acid existsAlcoholic hydroxyl groups and phenolic hydroxyl groups; 1645cm -1 Absorption peak for c=o bond, 1421cm -1 An absorption peak of c=c; 1320cm -1 An absorption peak of C-O-C; 870cm -1 And 780cm -1 The nearby absorption peak is the out-of-plane bending peak of aromatic hydrocarbon, KOH-H 2 O 2 The higher intensity of aromatic hydrocarbons in humic acid as extractant, demonstrated KOH-H 2 O 2 Can effectively break aromatic structure as extractant, 1320cm -1 、1260cm -1 And 1050cm -1 KOH-H caused by nearby C-O bond 2 O 2 The C-O bond of humic acid can be increased, and the water solubility of humic acid is increased. Thus, the yield of humic acid obtained is higher.
As can be seen from FIG. 3, the absorbance of humic acid extracted in examples 1-4 was monotonically decreased with the increase of the absorption wavelength, whereas the decrease was faster in the ultraviolet region and relatively gentle in the visible light range, and as a whole, all humic acid compositions had no significant peak. The slope of the absorption curve can be quantitatively described by the sum of the ratios of 280nm and 360nm (E2/E3), which is related to the aromaticity of humic acid, and the ratio of absorbance at 465nm and 665nm (E4/E6), which is inversely related to the molecular weight of humic acid, and these ratios are shown in Table 2, the results of which are that the reaction intensity is less than KOH-H with NaOH or KOH alone as extractant 2 O 2 And NaOH-H 2 O 2 This means H 2 O 2 Plays a main role in the humic acid extraction reaction process. KOH-H 2 O 2 The minimum aromatic degree and molecular weight of the extracted humic acid indicate KOH and H 2 O 2 The synergistic effect of the above can more effectively reduce the aromaticity, thereby improving the yield of humic acid.
TABLE 2E 2/E3 and E4/E6 ratios of the UV-Vis patterns of humic acids of examples 1-4
| E2/E3 | E4/E6 | |
| Example 1 | 1.95 | 2.44 |
| Example 2 | 1.99 | 2.72 |
| Example 3 | 2.46 | 4.52 |
| Example 4 | 3.41 | 4.67 |
The foregoing description is only a few specific embodiments of the present application (the embodiments are not intended to be exhaustive, and the scope of the application includes the scope of the application and other technical points), and the details or common sense of the present application are not described in any more detail herein (including but not limited to the shorthand, abbreviations, units commonly used in the art). It should be noted that the above embodiments do not limit the present application in any way, and it is within the scope of the present application for those skilled in the art to obtain the technical solution by equivalent substitution or equivalent transformation. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. The method for efficiently extracting humic acid from lignite is characterized by comprising the following steps of:
(1) Crushing and screening lignite to a certain particle size, and drying in an oven;
(2) Weighing a certain amount of lignite dried in the step (1), and fully mixing with alkali liquor;
(3) Dropwise adding a certain amount of hydrogen peroxide solution into the mixture in the step (2), and continuously stirring under the water bath condition until the reaction is finished;
(4) And (3) separating the reaction mixture in the step (3) by suction filtration to obtain a liquid phase and a solid phase, forming a mixed solution by the cleaning liquid of the solid phase and the liquid phase, and performing rotary evaporation and drying treatment on the mixed solution to obtain humic acid.
2. The method of claim 1, wherein the lignite of step (1) has a particle size of 60-80 mesh; the drying temperature of the oven is 80-110 ℃.
3. The method of claim 2, wherein the oven drying temperature of step (1) is 105 ℃.
4. The method according to claim 1, wherein the lignite of step (2) has a mass of 1-5 g; the mass fraction of the alkali liquor is 0.5-3 mol/L; the mass volume ratio of the lignite to the alkali liquor in the step (2) is 1-5 g: 10-30 mL.
5. The method according to claim 1, wherein the mass fraction of hydrogen peroxide in the step (3) is 10-30%, and the hydrogen peroxide addition volume is 5-30 mL.
6. The method of claim 5, wherein the hydrogen peroxide in step (3) is added in a volume of 15mL.
7. The method according to claim 1, wherein the water bath temperature in the step (3) is 30-90 ℃, the stirring speed is 20-40 rpm, and the reaction time is 40-150 minutes.
8. The method of claim 7, wherein the water bath temperature in step (3) is 50 ℃, the stirring speed is 30 rpm, and the reaction time is 60 minutes or 150 minutes.
9. The method according to claim 1, wherein the rotary steaming speed of the step (4) is 60-100 rpm, the rotary steaming temperature is 40-60 ℃, the drying temperature is 85-110 ℃, and the drying time is 15-24 h.
10. The method according to claim 1 or 4, wherein the lye is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide.
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