CN109734752B - Method for extracting fulvic acid from lignite by catalytic oxidation method - Google Patents
Method for extracting fulvic acid from lignite by catalytic oxidation method Download PDFInfo
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- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 title claims abstract description 93
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002509 fulvic acid Substances 0.000 title claims abstract description 93
- 229940095100 fulvic acid Drugs 0.000 title claims abstract description 93
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 95
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 48
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000019253 formic acid Nutrition 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000003245 coal Substances 0.000 claims abstract description 43
- 239000011218 binary composite Substances 0.000 claims abstract description 33
- 239000003250 coal slurry Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000006864 oxidative decomposition reaction Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
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- 238000000605 extraction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
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- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a method for extracting fulvic acid from lignite by using a catalytic oxidation method, belongs to the technical field of fulvic acid extraction methods, and solves the technical problems of low fulvic acid extraction conversion effect and extraction rate, environmental pollution and limited purity in the prior art. The method comprises the following steps: s1, selecting lignite from the coal, and preparing a powder lignite coal sample; s2, selecting an iron oxide/cerium dioxide binary composite catalyst and adding the iron oxide/cerium dioxide binary composite catalyst into the pulverized lignite coal sample; s3, preparing a coal slurry mixture from hydrogen peroxide, formic acid and a catalyst-containing powder lignite coal sample according to a certain proportion; s4, heating in a water bath, magnetically stirring the coal slurry mixture prepared in the S3 step, and carrying out catalytic oxidative decomposition on the coal sample; and separating to obtain fulvic acid solid after the reaction is finished. The invention improves the yield of the fulvic acid and avoids environmental pollution by selecting the hydrogen peroxide and formic acid to oxidize and decompose the lignite coal sample and the ferric oxide/cerium dioxide binary composite catalyst for catalytic oxidation.
Description
Technical Field
The invention relates to the technical field of extraction of fulvic acid from lignite, in particular to extraction of fulvic acid from lignite.
Background
Fulvic acid is an organic acid with small molecular weight and high activity in humic acid, and plays an important role in the fields of modern agriculture, industry, medicine, livestock breeding and the like. In the aspect of agriculture, the fertilizer has the effects of improving soil, promoting plant growth, improving the utilization rate of fertilizer and the like; the method is mainly used for treating heavy metal-containing sewage and purifying water resources in industry; in the pharmaceutical industry, fulvic acid has important functions of stopping bleeding, resisting inflammation, inhibiting cancer cells, improving the immunity of the organism and the like; in the aspect of livestock breeding, the fulvic acid additive can enhance disease resistance, promote growth and development of livestock and poultry and the like.
The fulvic acid is extracted by mainly adopting methods such as an alkali dissolution method, a strong acid extraction method, an exchange resin method, an oxidative decomposition method and the like in the prior art, but the methods have certain defects, for example, the alkali dissolution method and the strong acid extraction method have certain corrosion and pollution to the operation environment and equipment due to large consumption of acid and alkali; the exchange resin method has high resin selection and operation technical requirements, is difficult to realize, and many components of fulvic acid can cause dissolution damage to exchange resin, so that the exchange resin is difficult to maintain and the cost of replacing materials is high; the common oxidant used in the oxidative decomposition method is hydrogen peroxide and nitric acid, and the nitric acid oxidation of the lignite to extract the fulvic acid can generate a large amount of nitrogen oxides, thereby bringing environmental pollution; although the hydrogen peroxide oxidized lignite is environment-friendly, the yield of the fulvic acid extracted by the hydrogen peroxide alone is not high.
Disclosure of Invention
In view of the above analysis, the embodiment of the present invention aims to provide a method for extracting fulvic acid from lignite, so as to solve the technical problems of low yield of fulvic acid extraction and environmental pollution in the prior art.
The invention discloses a method for extracting fulvic acid from lignite by using a catalytic oxidation method, which comprises the following steps:
s1, selecting lignite from the coal, and preparing a powder lignite coal sample;
s2, selecting an iron oxide/cerium dioxide binary composite catalyst and adding the iron oxide/cerium dioxide binary composite catalyst into the pulverized lignite coal sample prepared in the step S1;
s3, mixing hydrogen peroxide, formic acid and the powdered lignite coal sample containing the iron oxide/cerium dioxide binary composite catalyst prepared in the step S2 according to the mass ratio of 1-10: 1-10: preparing a coal slurry mixture according to the proportion of 0.5-5, and performing inert gas protection on the coal slurry mixture;
s4, heating in a water bath, magnetically stirring, and carrying out catalytic oxidation decomposition on the coal slurry mixture prepared in the step S3; and separating the lignite residue and the catalyst mixture after the reaction is finished to prepare fulvic acid solid.
Further, in step S2, the program is executed by: 10000-1000000 of the mass ratio of the iron oxide/cerium dioxide binary composite catalyst to the powder lignite coal sample prepared in the step S1.
Further, in step S2, the program is executed by: adding an iron oxide/cerium dioxide binary composite catalyst into the pulverized lignite coal sample prepared in the step S1 according to the mass ratio of 100000-500000.
Further, in the step S2, the mass ratio of iron oxide to ceria in the iron oxide/ceria binary composite catalyst is 2: 1-6: 1.
further, in the step S3, the mass concentration of hydrogen peroxide is 15% to 45%.
Further, in the step S3, the mass concentration of the hydrogen peroxide is 15-25%.
Further, in the step S3, the formic acid has a mass concentration of 20% to 80%.
Further, in the step S3, the mass concentration of formic acid is 20-50%.
Further, in the step S3, the heating temperature for heating the coal slurry mixture in a water bath is 40 to 100 ℃.
Further, in the step S4, the catalytic oxidation decomposition time of the coal slurry mixture is 5-600 min.
Further, in the step S4, the catalytic oxidation decomposition time of the coal slurry mixture is 10-240 min.
Further, in step S1, the brown coal is pulverized into ultrafine powder particles of 500 mesh or less.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the invention adopts the iron oxide/cerium dioxide binary composite catalyst which has excellent targeted catalytic selectivity and high catalytic activity in the reaction system, ensures that the iron oxide/cerium dioxide has higher catalytic effect on specific contact specific surface sites by controlling the particle size range of the iron oxide/cerium dioxide, can fully and well contact with a lignite coal sample in the reaction, accelerates the extraction rate of fulvic acid, further ensures the yield of the fulvic acid by controlling the addition amount of the iron oxide/cerium dioxide, and can realize effective separation and recovery of the catalyst.
(2) According to the invention, through respective characteristic oxidation of hydrogen peroxide and formic acid and further under the deep catalytic oxidation action of an iron oxide/cerium dioxide composite catalyst, a characteristic catalytic reaction is carried out on a weak bond and an unstable bonding part of a target lignite molecule, oxidative decomposition and bond breaking oxidative conversion of lignite molecule side chains and branched chains and catalytic decomposition and oxidative conversion of functional groups are preferentially selected, and the fulvic acid micromolecule compound is generated by cutting and separation, so that a large amount of acidic groups and related cluster micromolecules are generated, and the fulvic acid is efficiently extracted.
(3) Hydrogen peroxide, formic acid, a catalyst and a lignite coal sample are prepared into a reaction mixing system according to a specific mass ratio of reaction and catalytic chemical composition, so that the efficient catalytic oxygenolysis reaction of lignite is realized; and inert gas is introduced into the mixture system for protection, excessive reaction is controlled, side reaction is prevented, and the effective yield of the fulvic acid can be ensured.
In the invention, the above technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description of the embodiments.
Detailed Description
The preferred embodiments of the present invention will be described in detail below.
The invention relates to a method for extracting fulvic acid from lignite by using a catalytic oxidation method, which comprises the following steps:
s1, selecting lignite from the coal, and preparing a powder lignite coal sample;
s2, selecting an iron oxide/cerium dioxide binary composite catalyst with the particle size range of 10-500 nm and adding the iron oxide/cerium dioxide binary composite catalyst into the powdery lignite coal sample prepared in the step S1;
s3, mixing hydrogen peroxide, formic acid and the catalyst-containing powder lignite coal sample prepared in the step S2 according to the mass ratio of 1-10: 1-10: preparing a coal slurry mixture according to the proportion of 0.5-5, and performing inert gas protection on the coal slurry mixture;
s4, heating in a water bath, magnetically stirring, and carrying out catalytic oxidation decomposition on the coal slurry mixture prepared in the step S3;
s5, separating the lignite residues and the catalyst mixture after the reaction is finished to obtain the fulvic acid solid.
Compared with the prior art, the method adopts hydrogen peroxide and formic acid to carry out oxidative decomposition on the lignite coal sample, the hydrogen peroxide and the formic acid can generate peroxyformic acid in the reaction process, and the peroxyformic acid has stronger oxidizability, can carry out deep decomposition on the lignite coal sample, and further improves the yield of the fulvic acid. The characteristic catalytic reaction of weak bonds and unstable bonding parts of target lignite molecules is selected through the respective characteristic oxidation of hydrogen peroxide and formic acid and the further characteristic catalytic oxidation of peroxyformic acid generated by the reaction of hydrogen peroxide and formic acid under the deep catalytic oxidation action of an iron oxide/cerium dioxide composite catalyst, the oxidative decomposition and bond breaking oxidative conversion of side chains and branched chains of lignite molecules and the catalytic decomposition and oxidative conversion of functional groups are preferentially selected, the fulvic acid micromolecule compounds are generated through cutting and separation, and then a large amount of acid groups and related cluster micromolecules are generated, so that the fulvic acid is efficiently extracted.
The iron oxide/cerium dioxide composite catalyst adopted by the invention can not only directly promote the reaction of hydrogen peroxide and coal, but also promote the reaction of the hydrogen peroxide and formic acid to generate peroxyformic acid and promote the oxidation reaction of the peroxyformic acid and lignite coal samples to generate fulvic acid.
In order to further improve the catalytic oxidation effect, in the step of S2, the ratio of 1: 10000-1000000 parts by mass of an iron oxide/cerium dioxide binary composite catalyst is added into the powder brown coal sample prepared in the step S1, and the weight ratio is 1: 100000-500000. Considering the high efficiency of the catalytic oxidation of the lignite coal sample, the mass ratio of the iron oxide/cerium dioxide binary composite catalyst to the lignite coal sample is 1: 100000-500000; this is because when the mass ratio of the iron oxide/cerium oxide binary composite catalyst to the lignite coal sample is less than 1: 500000, the binary composite catalyst has poor catalytic effect on hydrogen peroxide, formic acid and peroxyformic acid, and cannot fully improve the yield of fulvic acid; when the mass ratio of the ferric oxide/cerium dioxide binary composite catalyst to the lignite coal sample is more than 1: 100000; on one hand, the waste of the catalyst is caused, and the cost for extracting the fulvic acid is further increased; on the other hand, if the amount of the catalyst to be added is too large, the yield of fulvic acid decreases, and the cost is wasted.
In order to fully exert the catalytic characteristics of the iron oxide/cerium oxide dual composite catalyst, in one aspect of the present invention, in the step S2, the mass ratio of iron oxide to cerium dioxide in the iron oxide/cerium oxide dual composite catalyst is 2: 1-6: 1, the particle size range of the ferric oxide and the cerium dioxide is controlled between 10 nm and 500 nm. Because the iron oxide plays a main catalytic role, a certain amount of cerium dioxide is added on the basis of the main catalytic role, the auxiliary catalytic role can be played, but the yield of the fulvic acid is not obviously improved due to excessive cerium dioxide, and the price of the iron oxide is lower than that of the cerium dioxide, and considering the catalytic effect of the catalyst on the lignite oxidative decomposition reaction and the extraction cost of the fulvic acid, the mass ratio of the iron oxide to the cerium dioxide is controlled to be 2: 1-6: 1.
The particle size range of the iron oxide/cerium dioxide is controlled to be between 10 and 500nm, and the iron oxide/cerium dioxide binary composite catalyst in the particle size range can ensure that the binary composite catalyst has a high catalytic effect on specific contact specific surface sites of lignite, so that the binary composite catalyst can be in full and good contact with lignite coal-like reactants in a reaction, and the extraction rate of fulvic acid is increased.
In order to ensure that lignite is sufficiently oxidized and decomposed and the oxidative decomposition process is carried out stably, the mass concentration of hydrogen peroxide is controlled to be 15-45% under the condition of adding the catalyst; on one hand, under the catalytic action of the catalyst, the hydrogen peroxide in the concentration range can accelerate the oxidative decomposition of lignite and improve the generation rate of fulvic acid; on the other hand, hydrogen peroxide and formic acid react under the catalytic action of the catalyst to generate peroxyformic acid, and the peroxyformic acid can sufficiently oxidize and decompose lignite, so that the generation rate of fulvic acid can be further increased; it should be noted that, when the mass concentration of the hydrogen peroxide is controlled to be between 25% and 25%, the hydrogen peroxide in the concentration range can ensure the yield of the fulvic acid, can also ensure the reaction to be carried out stably, and is easy to control; if the concentration of the hydrogen peroxide exceeds 45 percent, the lignite oxidative decomposition reaction is difficult to control due to violent reaction; if the concentration of the hydrogen peroxide is lower than 15%, the reaction of directly oxidizing and decomposing the lignite by the hydrogen peroxide is insufficient, the amount of generated performic acid is reduced, the reaction of oxidizing and decomposing the lignite by the performic acid is influenced, and finally the yield of the fulvic acid is influenced.
In order to improve the yield of fulvic acid, the mass concentration of formic acid in the step S3 is 20-80%. When the mass concentration of the formic acid is lower than 20%, the amount of the hydroperoxyl generated by the hydrogen peroxide and the formic acid is small, and the catalytic effect of the formic acid on the reaction is not obvious; when the mass concentration of the formic acid is more than 80%, the catalytic oxidation effect of the peroxyformic acid is too strong, so that the rate of oxidative decomposition of the fulvic acid is greater than the rate of generation of the fulvic acid, and the yield of the fulvic acid is reduced; in order to improve the yield of fulvic acid, the mass concentration of formic acid adopted by the invention is 20-80%.
In order to further improve the yield of fulvic acid, the mass concentration of formic acid in the step of S3 is 20% to 50%. When the mass concentration of the formic acid is between 20 and 50 percent, the generation rate of the fulvic acid is far greater than the rate of the fulvic acid oxidized and decomposed by the peroxyformic acid, so the mass concentration of the formic acid is further controlled to be between 20 and 50 percent.
In the step S4, the coal slurry mixture is heated in a water bath and magnetically stirred, and the heating temperature is 40 to 100 ℃. Through carrying out water bath heating and carrying out magnetic stirring to the lignite oxidative decomposition reaction, can realize the high dispersion of lignite coal sample, and then make lignite coal sample and oxidant carry out high even contact, improved the area of contact of lignite coal sample with formic acid, hydrogen peroxide and peroxyformic acid, effectively pull open the little mesoscale space of lignite molecule three-dimensional structure, highly expose oxidative decomposition active site, promote the high-efficient contact of oxidant and lignite oxidative decomposition active site, realize that catalytic oxidation decomposes high-efficiently and go on.
The oxidative decomposition time of the coal slurry mixture is 5-600 min. Side reactions and impurities are easy to generate even if the reaction time is too long; too short reaction time easily causes insufficient reaction, low conversion rate of fulvic acid and the like.
In order to ensure that hydrogen peroxide, formic acid and the lignite coal sample are fully reacted and further fully oxygenolyze and decompose the lignite coal sample, in the step S4, the reaction time is controlled within the range of 5-600 min, particularly 10-240 min; if the reaction time is too short, the contact time of the lignite and the peroxide hydroxyl is insufficient, little oxidative decomposition is caused, and the generated fulvic acid is little; with the increase of time, the lignite and the hydroperoxyl react fully and gradually, and the yield of the fulvic acid is increased; if the time is too long, the oxidation decomposition reaction rate of the lignite is greatly reduced, and meanwhile, a large amount of generated fulvic acid is oxidized, so that the yield of the fulvic acid is reduced, and therefore, the reaction time is controlled within the range of 10-240 min. And after the lignite is oxidized and decomposed, carrying out solid-liquid separation on the reaction mixture, separating liquid, evaporating and drying to obtain fulvic acid solid.
In order to ensure high efficiency conversion and extraction of fulvic acid, in step S1, lignite is crushed into particles of 50 mesh or less to prepare a pulverized lignite coal sample. After the lignite is crushed into small particles, the specific surface area of the lignite is increased, and when the lignite is subjected to oxidative decomposition reaction, the lignite with high specific surface area can be fully contacted with an oxidant, so that complete oxidative decomposition reaction is ensured.
In conclusion, the invention creatively adopts the iron oxide/cerium dioxide binary composite catalyst, through targeted selective catalysis, and the lignite is subjected to oxidative decomposition by means of hydrogen peroxide, formic acid and reaction product peroxyformic acid, so that the yield of fulvic acid is improved; in addition, the method provided by the invention solves the problems of low purity, low yield, pollution and poor catalyst recovery effect of conventional lignite fulvic acid extraction, and meanwhile, the method has the advantages of simple steps, easiness in operation, economy, high efficiency and environmental friendliness.
Example 1
S1, crushing the lignite to 50 meshes, and weighing 10g of the pulverized lignite sample.
S2, selecting an iron oxide/cerium dioxide binary composite catalyst with the particle size of 10-50 nm and mixing the two components according to the mass ratio of 1: 50000 the mass ratio of ferric oxide to cerium dioxide is 2: 1.
s3, weighing 5g of hydrogen peroxide with a mass concentration of 15% and 20g of formic acid with a mass concentration of 20%, sequentially adding the hydrogen peroxide with the mass concentration of 15% and the formic acid with the mass concentration of 20% into the mixture of the lignite and the catalyst to prepare a coal slurry mixture containing hydrogen peroxide, formic acid and the catalyst, and introducing inert gas nitrogen into the mixture for protection.
S4, placing the coal slurry mixture in a water bath for heating and stirring, heating to 5 ℃, and maintaining for 5 min.
S5, separating lignite and catalyst residues, evaporating and drying the liquid to obtain fulvic acid solid, weighing 2.923g of fulvic acid, and obtaining the yield of 29.2%.
Example 2
S1, crushing the lignite to 50 meshes, and weighing 10g of the pulverized lignite sample.
S2, selecting an iron oxide/cerium dioxide binary composite catalyst with the particle size of 10-50 nm and mixing the two components according to the mass ratio of 1: 200000, adding into the pulverized lignite coal sample prepared in the step S1, wherein the mass ratio of ferric oxide to cerium dioxide is 6: 1.
s3, weighing 8g of hydrogen peroxide with a mass concentration of 15% and 10g of formic acid with a mass concentration of 30%, sequentially adding the hydrogen peroxide with the mass concentration of 15% and the formic acid with the mass concentration of 30% into the mixture of the lignite and the catalyst to prepare a coal slurry mixture containing hydrogen peroxide, formic acid and the catalyst, and introducing inert gas nitrogen into the mixture for protection.
And S4, heating the coal slurry mixture in a water bath, stirring, heating to 80 ℃, and maintaining for 100 min.
S5, separating lignite and catalyst residues, evaporating and drying the liquid to obtain fulvic acid solid, weighing fulvic acid, wherein the mass of the fulvic acid is 3.014g, and the yield is 30.1%.
Example 3
S1, crushing the lignite to 50 meshes, and weighing 10g of the pulverized lignite sample.
S2, selecting an iron oxide/cerium dioxide binary composite catalyst with the particle size of 10-50 nm and mixing the two components according to the mass ratio of 1: 100000 the weight ratio of iron oxide to cerium dioxide is 5: 1.
s3, weighing 15g of hydrogen peroxide with the mass concentration of 20% and 20g of formic acid with the mass concentration of 40%, sequentially adding the hydrogen peroxide with the mass concentration of 20% and the formic acid with the mass concentration of 40% into the mixture of the lignite and the catalyst to prepare a coal slurry mixture containing hydrogen peroxide, formic acid and the catalyst, and introducing inert gas nitrogen into the mixture for protection.
And S4, heating the coal slurry mixture in a water bath, stirring, heating to 100 ℃, and maintaining for 180 min.
S5, separating lignite and catalyst residues, evaporating and drying the liquid to obtain fulvic acid solid, weighing fulvic acid with the mass of 3.178g and the yield of 31.8%.
Example 4
S1, crushing the lignite to 50 meshes, and weighing 10g of the pulverized lignite sample.
S2, selecting an iron oxide/cerium dioxide binary composite catalyst with the particle size of 10-50 nm and mixing the two components according to the mass ratio of 1: 100000 the weight ratio of iron oxide to cerium dioxide is 4: 1.
s3, weighing 10g of hydrogen peroxide with the mass concentration of 25% and 15g of formic acid with the mass concentration of 5%, sequentially adding the hydrogen peroxide with the mass concentration of 25% and the formic acid into the mixture of the lignite and the catalyst to prepare a coal slurry mixture containing hydrogen peroxide, formic acid and the catalyst, and introducing inert gas nitrogen into the mixture for protection.
S4, placing the coal slurry mixture in a water bath for heating and stirring, heating to 100 ℃, and maintaining for 240 min.
5. Lignite and catalyst residues are separated, and the liquid is evaporated and dried to obtain fulvic acid solid, wherein the weighed mass of fulvic acid is 3.311g, and the yield is 33.1%.
Comparative example 1
The oxidant of the comparative example selects hydrogen peroxide to carry out oxidative decomposition on the lignite coal sample to extract the lignite fulvic acid:
s1, crushing brown coal powder into 600-mesh particles, and weighing 10g of brown coal powder.
S2, weighing 30g of hydrogen peroxide with the mass concentration of 25%, adding brown coal powder to prepare a coal slurry mixture containing hydrogen peroxide, and introducing nitrogen for protection.
S3, carrying out ultrasonic treatment on the coal slurry mixture for 120min, selecting the ultrasonic frequency to be 40KHz and the ultrasonic power to be 0.5w/cm2While simultaneously heating the coal slurry mixture to maintain a temperature of 40 ℃.
S4, carrying out solid-liquid separation on the reaction mixture after ultrasonic treatment, separating liquid, evaporating and drying to obtain fulvic acid solid, wherein the mass of the fulvic acid obtained by weighing is 1.584g, and the yield is 15.8%.
Comparative example 2
The oxidant of the comparative example selects hydrogen peroxide to carry out oxidative decomposition on the lignite coal sample to extract the lignite fulvic acid:
s1, crushing brown coal powder into 600-mesh particles, and weighing 10g of brown coal powder.
S2, weighing 25g of 30% hydrogen peroxide by mass concentration, adding lignite powder to prepare a coal slurry mixture containing hydrogen peroxide, and introducing nitrogen for protection.
S3, carrying out ultrasonic treatment on the coal slurry mixture for 300min, selecting the ultrasonic frequency of 80KHz and the ultrasonic power of 0.8w/cm2While simultaneously heating the coal slurry mixture to maintain a temperature of 60 ℃.
S4, carrying out solid-liquid separation on the reaction mixture after ultrasonic treatment, separating liquid, evaporating and drying to obtain fulvic acid solid, wherein the mass of the fulvic acid obtained by weighing is 1.672g, and the yield is 16.7%.
In order to more intuitively embody the superiority of the method for extracting fulvic acid provided by the present invention, table 1 lists the yields of fulvic acid of examples 1-4 and comparative examples 1-2 of the present invention, specifically as follows:
TABLE 1 yield of fulvic acid in examples 1-4 and comparative examples 1-2
In conclusion, compared with the fulvic acid yield of comparative example 1 and comparative example 2, the yield of fulvic acid extracted from oxidized lignite provided by the invention is sufficiently improved by more than ten percent, because the invention not only selects the combination of oxidants of hydrogen peroxide and formic acid, but also adopts an iron oxide/cerium dioxide binary composite catalyst to catalyze and oxidize lignite coal samples; the hydrogen peroxide is an environment-friendly oxidant, and the oxidative decomposition product is green and pollution-free; the formic acid is organic weak acid, has mild property, can react with the hydrogen peroxide to generate oxidant peroxyformic acid with stronger oxidability, and reacts with the lignite macromolecular organic matter; the iron oxide/cerium dioxide binary composite catalyst can be used for decomposing low-deterioration lignite through targeted selective catalysis and stepwise graded oxidation by means of hydrogen peroxide, formic acid and reaction product peroxyformic acid, and simultaneously, the yield of fulvic acid is improved by means of heating in a water bath, magnetic stirring and catalytic oxidation. The method provided by the invention solves the problems of low purity, low yield, pollution and poor catalyst recovery effect of conventional lignite fulvic acid extraction, and meanwhile, the method has the advantages of simple steps, easiness in operation, economy, high efficiency and environmental friendliness.
Note: the fulvic acid yield calculation formula is as follows:
Myield of＝m2/m1*100％
Wherein, the M yield is the fulvic acid yield; m is2The unit is gram (g) for the mass of the fulvic acid product obtained; m is1The unit is the mass of the raw material powder lignite coal sample used and is gram (g).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention.
Claims (7)
1. A method for extracting fulvic acid from lignite by using a catalytic oxidation method is characterized by comprising the following steps:
s1, selecting lignite from the coal, and preparing a powder lignite coal sample;
s2, selecting an iron oxide/cerium dioxide binary composite catalyst and adding the iron oxide/cerium dioxide binary composite catalyst into the pulverized lignite coal sample prepared in the step S1;
s3, mixing hydrogen peroxide, formic acid and the powdered lignite coal sample containing the iron oxide/cerium dioxide binary composite catalyst prepared in the step S2 according to the weight ratio of 1-10: 1-10: preparing a coal slurry mixture according to the mass ratio of 0.5-5, and performing inert gas protection on the coal slurry mixture;
s4, heating in a water bath, magnetically stirring the coal slurry mixture prepared in the S3, and carrying out catalytic oxidative decomposition on the lignite coal sample;
s5, separating the lignite residues and the catalyst mixture after the reaction is finished to prepare fulvic acid solid;
in the step S2, the mass ratio of the iron oxide to the cerium dioxide in the iron oxide/cerium dioxide binary composite catalyst is 2: 1-6: 1; the particle size of the iron oxide/cerium dioxide binary composite catalyst is 10-50 nm;
in the step S3, the mass concentration of the formic acid is 20-80%;
in the step S4, the heating temperature for heating the coal slurry mixture in the water bath is 40-100 ℃.
2. The method for extracting fulvic acid from lignite according to claim 1, wherein in the step of S2, the ratio of fulvic acid to fulvic acid is 1: 10000-1000000 of the mass ratio of the iron oxide/cerium dioxide binary composite catalyst to the powder lignite coal sample prepared in the step S1.
3. The method for extracting fulvic acid from lignite by catalytic oxidation according to claim 2, wherein the mass concentration of hydrogen peroxide in the step S3 is 15% -45%.
4. The method for extracting fulvic acid from lignite by using the catalytic oxidation method according to claim 3, wherein in the step S3, the mass concentration of hydrogen peroxide is 15-25%.
5. The method for extracting fulvic acid from lignite according to claim 4, wherein the concentration of formic acid in S3 is 20-50% by mass.
6. The method for extracting fulvic acid from lignite by catalytic oxidation according to claim 5, wherein in the step S4, the catalytic oxidation time of the coal slurry mixture is 5-600 min.
7. The method for extracting fulvic acid from lignite according to claim 6, wherein lignite is crushed into ultrafine powder particles of 500 mesh or less in step S1.
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