CN108982393A - A kind of fast and convenient humic acid molecular-weight gradation method - Google Patents
A kind of fast and convenient humic acid molecular-weight gradation method Download PDFInfo
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- CN108982393A CN108982393A CN201810535519.8A CN201810535519A CN108982393A CN 108982393 A CN108982393 A CN 108982393A CN 201810535519 A CN201810535519 A CN 201810535519A CN 108982393 A CN108982393 A CN 108982393A
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- 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 106
- 239000004021 humic acid Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 230000001174 ascending effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 238000002798 spectrophotometry method Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000002242 deionisation method Methods 0.000 description 6
- 239000003864 humus Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 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 description 2
- 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 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002509 fulvic acid Substances 0.000 description 2
- 229940095100 fulvic acid Drugs 0.000 description 2
- 239000002663 humin Substances 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of fast and convenient humic acid molecular-weight gradation methods, the molecular-weight gradation of humic acid is realized using the suction-operated of nano ferriferrous oxide and the permeability of regenerated cellulose film, the nano ferriferrous oxide prepared is specially placed in formation film packet in regenerated cellulose film, power is provided using adsorptivity of the nano ferriferrous oxide for humic acid, so that the humic acid for being less than regenerated cellulose film molecular weight penetrates film, humic acid and nano ferriferrous oxide greater than regenerated cellulose film molecular weight are trapped in outside film, achieve the purpose that humic acid by the film packet of sequence addition different molecular weight from small to large and passes through molecular-weight gradation.The beneficial effects of the invention are as follows easy to operate, fast and easys, and the material non-toxic used is harmless, environmental-friendly, and structure, composition and the property for further research humic acid provide technical support.
Description
Technical field
The invention belongs to polluted-water comprehensive treatments and water ecology recovery technique, and in particular to a kind of fast and convenient corruption
Grow acid molecule amount stage division.
Background technique
Humus is that most wide organic matter is distributed in nature, is widely present in soil, deposit, river, lake and sea
Midocean is the product that plant and animal residues are formed by chemistry and bioprocess.Humus largely participates in global carbon
Process accounts for the 50%-90% of dissolved organic carbon in fresh water.Since humus can occur instead with multiple compounds in environment
It answers, therefore it plays an important role in water body and soil.
Humus is the mixture with the larger molecular organics of a variety of functional groups, according to its dissolubility in aqueous solution
Can be divided into three classes substance: fulvic acid (Fulvic Acid), it is water-soluble in any pH value；Humic acid (Humic Acid): only
It is dissolved in alkalinity and does not dissolve in acid solution；Humin (Humin): any pH value not soluble in water.
Molecular weight is one of the formation of research humus, chemical structure and important parameter of physicochemical characteristic.For humic
For this mixing macromolecular substances being made of natural complicated organic matter of matter, the molecular weight not determined, only molecular weight
Distribution, therefore, the effective molecular weight for measuring humus is not a nothing the matter.
Currently, the measuring method of molecular weight mostly uses greatly size exclusion chromatography, ultrafiltration, supercentrifugation, viscosimetry, small
Angle X-ray scanning, field separation and colligative property method.But the generally existing classification of these methods takes a long time, required instrument and equipment
It is required that it is high and be not easy to obtain, different calibration object result difference are big, molecular weight calculates complicated, classification process can be right using chemical reagent
Environment causes the drawbacks such as secondary pollution, complicated for operation, higher cost.
CN105549091A discloses a kind of method for measuring dissolubility humic acid molecular weight distribution in water, including walks as follows
It is rapid: 1) with the total organic carbon value of dissolubility humic acid in total organic carbon analyzer measurement dissolubility humic aqueous acid；Take dissolution
Property humic aqueous acid, being diluted to dissolubility humic acid concentration respectively with deionized water is 10mg/L-20mg/L；2) sample injector is used
The injection of 10ml step 1) acquired solution is taken to be in series with the non-right of multi-angle laser light scattering instrument and ultraviolet-visible detector below
Claim to be detected in field flow analyzer；3) software is carried using asymmetric field flow point analyzer to examine multi-angle laser light scattering instrument
The ultraviolet-visible signal peak that the light scattering signal peak and ultraviolet-visible detector measured detects is integrated, and is obtained rotten
Grow acid molecule amount distribution map；CN107436332A discloses a kind of separation and measures humic acid opposed polarity and molecular weight component
Method realizes humic acid opposed polarity and molecule by way of C19 column-detector-exclusion chromatography column-detector of connecting
The orderly of amount component separates and identifies simultaneously.The classification of humic acid molecular weight may be implemented in the above invention, but there are still required
The problems such as instrument and equipment requires high and is not easy to obtain, and complicated for operation, higher cost, classification take a long time.
In recent years, nano material receives the concern of people in the application that water environment pollution object removes, and nano material has
High specific surface area and brilliant absorption property, adsorption capacity is big and adsorption time is short, becomes water treatment field and preferably inhales
Attached dose.Starting point of the invention is to provide classification power to the suction-operated of humic acid with nano ferriferrous oxide, utilizes difference
The regenerated cellulose film of molecular weight forms the molecular-weight gradation that physical barriers realize humic acid, advances humic acid structure composition
Analysis research, structure, composition and property for further research humic acid provide technical support.
Summary of the invention
The object of the present invention is to provide a kind of humic acid molecular weight easy to operate, at low cost, rapidly and efficiently, environmental-friendly
Stage division.
In order to solve the above technical problems, the humic acid molecular-weight gradation method that one kind provided by the invention is fast and convenient,
The molecular-weight gradation of humic acid is realized using the suction-operated of nano ferriferrous oxide and the permeability of regenerated cellulose film, including
Following steps:
S1. nano ferriferrous oxide is respectively put into the regenerated cellulose film of at least nine different molecular weight grade, by film
Both ends are clamped with film, and the film packet of at least nine different molecular weight grade is made；
S2. humic acid is dissolved in the alkaline solution of 1.0M and forms humic acid solution；
S3. the film packet that step S1 is obtained is added in the humic acid solution obtained to step S2, adjusts humic acid solution to pH
Value is 5.0, and adsorption reaction is carried out under electromagnetic agitation；
S4. after the completion of the adsorption reaction of film packet, film packet is taken out, the concentration of the outer humic acid solution of measurement film packet utilizes minusing
Determine the concentration of humic acid in film packet, humic acid is then narrow molecular-weight humic acid in film packet；
S5. step S3 and S4 are repeated, after the completion of all film packet adsorption reactions, i.e., the classification of humic acid molecular weight is completed.
Preferably, the preparation method of nano ferriferrous oxide described in step S1, comprising the following steps:
(1) by FeCl2·4H2O and FeCl3·6H2O is dissolved in the deionized water of preparatory nitrogen deoxidation；
(2) concentrated hydrochloric acid that mass fraction is 36-39%, dissolution are added in the solution prepared to step (1)；
(3) solution prepared by step (2) is added dropwise in the NaOH solution of 1.5M, nitrogen guarantor is led in electromagnetic agitation
Shield, i.e. generation black nano ferroso-ferric oxide；
(4) nano ferriferrous oxide granule of generation is washed with deionized water 5 times, suspension saves in deionized water.
Preferably, the partial size of nano ferriferrous oxide described in step S1 is 10-20nm, and molecular weight is in 100000-
200000Da, the pH of isoelectric point position are 6.2.
Preferably, regenerated cellulose film described in step S1 is U.S. Spectrum regenerated cellulose film, is less than regeneration
The molecule of cellulose membrane molecular weight can pass through, and the molecule greater than regenerated cellulose film molecular weight is trapped, and the oxidation of nanometer four three
Iron particle cannot penetrate regenerated cellulose film.
Preferably, the molecular weight grade of regenerated cellulose film described in step S1 is 500-90000Da；Further preferably
Ground, the regenerated cellulose film include 500-1000Da, 3500Da, 9000Da, 10000Da, 15000Da, 25000Da,
9 molecular weight grades of 35000Da, 50000Da, 90000Da.
Preferably, alkaline solution described in step S2 is NaOH solution, and humic acid is completely dissolved in alkaline solution, and
Humic acid is greater than in the 4, water body environment less than 10 in pH to be precipitated.
Preferably, in the water body of no physical barriers, nano ferriferrous oxide is adsorbed on optimal pH to humic acid solution
Under conditions of=5, the reaction time reaches adsorption equilibrium when being 15min, and adsorbance can reach 82.3mg/g.
Preferably, film packet described in step S3 is put into humic according to the ascending sequence of regenerated cellulose film molecular weight
In acid solution.
Preferably, the condition of electromagnetic agitation described in step S3 are as follows: at 20-25 DEG C, carried out with the revolving speed of 120r/min
Stirring.
Preferably, after the completion of each film packet adsorption reaction of step S4, the outer humic acid solution of film packet is taken to utilize ultraviolet spectrometry light
Degree method measures the concentration of humic acid at UV254nm, determines the humic acid of different molecular weight magnitude in film packet using minusing
Concentration.
It is purchased from international humic acid association for verifying the humic acid of method provided by the invention in the present invention, by soil extract
2s101h type；All chemical reagent used in the present invention are that chemistry is pure.
Compared to the prior art, the medicine have the advantages that
(1) present invention provides classification power to the suction-operated of humic acid by nano ferriferrous oxide, utilizes difference point
The regenerated cellulose film of son amount forms the molecular-weight gradation that physical barriers realize humic acid.Nano ferriferrous oxide has larger ratio
Surface area and meso-hole structure, the electrically charged amount of unit area institute is bigger, has stronger adsorption capacity for humic acid, with humic
The absorption of acid is mainly codetermined by the effect of hydrophobic effect, electrostatic interaction and ligand exchange and mesoporous effect, in no physics screen
In the case where barrier, adsorption reaction generally reaches balance in 15min.Compared to traditional humic acid molecular-weight gradation method, utilize
Nano ferriferrous oxide is more quick to the suction-operated progress molecular-weight gradation of humic acid, and classification efficiency greatly improves.
(2) nano ferriferrous oxide can be made by laboratory, and manufacturing process is simple and convenient, nano ferriferrous oxide grain
The reproducibility of diameter is high, and regenerated cellulose film can be obtained by purchase, and entire classification process is compared to traditional stage division pair
Experimental facilities requires low, strong operability, simple and convenient, do not need to buy expensive instrument and equipment and to the operator of equipment into
Row training, and the material environment used in entire classification process is friendly, is easily handled, will not cause secondary pollution to environment.
(3) this method is to the humic being classified with conventional method reported in the humic acid and pertinent literature of soil extract
The percentage of acid, different fractions is close, and percentage differs 0.05-0.19%, therefore, the humic acid molecular weight that this method provides
Stage division, grading effect is good, can substitute traditional humic acid stage division.
(4) since ferroso-ferric oxide does not have fluorescence, ferroso-ferric oxide will not be to the fluorescence of different fractions humic acid
Interference is generated, and hydroxy functional group is only contained on ferroso-ferric oxide surface, the interference of this part can be by measuring unadsorbed humic acid
The functional group on nano ferriferrous oxide surface and exclude, therefore, the humic acid of different molecular weight that the present invention obtains classification, containing dry
It disturbs that ingredient is few, may be advantageously employed in the analysis and research of the fluorescence and functional group's property of humic acid, for further research humic
Structure, composition and the property of acid provide technical support.
(5) present invention selects the suction-operated of humic acid and the molecular weight of regenerated cellulose film using nano ferriferrous oxide
Selecting property, and the molecular-weight gradation of humic acid is realized, the classification efficiency of humic acid is significantly improved, greatly reduces and is classified into
This, easy to operate, to instrument and equipment and operator requires low, and the material non-toxic used is harmless, environmental-friendly.
Specific embodiment
Embodiment 1
A kind of stage division of humic acid molecular weight, includes the following steps:
S1. respectively by 40mg nano ferriferrous oxide be put into 500-1000Da, 3500Da, 9000Da, 10000Da,
It is made in the regenerated cellulose film of 9 molecular weight grades of 15000Da, 25000Da, 35000Da, 50000Da, 90000Da, it will
Film both ends are clamped with film, and the film packet of 9 different molecular weight grades is made；
S2. 50mg humic acid is added in 500ml volumetric flask, the NaOH solution of 1M is added dropwise thereto until humic acid
It is completely dissolved, with deionized water constant volume to 500ml, is with the pH that the concentrated hydrochloric acid of mass percent 39% adjusts humic acid solution
5.0, the smallest film packet of molecular weight grade is added thereto, at 20-25 DEG C, with 120rip/min, classification stirring 1h.
S3. after the completion of the adsorption reaction of film packet, film packet is taken out, and measures the concentration of the outer humic acid solution of film packet, according to film packet
The ascending sequence of molecular weight grade is put into the film packet of next molecular weight grade, repeats step S2 and S3, anti-to 9 film packets
After the completion of answering, then completion is classified.
Preferably, in step S1 nano ferriferrous oxide preparation process, comprising the following steps:
(1) by 2.0g FeCl2·4H2O and 5.2g FeCl3·6H2O is dissolved in the deionization of the preparatory nitrogen deoxidation of 25mL
In water, the concentrated hydrochloric acid that 0.95mL mass percent is 36% is added；
(2) solution made from step (1) is added dropwise in the NaOH solution of 250mL 1.5M, side edged electromagnetic agitation is simultaneously
Logical nitrogen protection；Produce black nano ferroso-ferric oxide.
(3) after the reaction was completed, it is washed 5 times with 200mL deionization, suspension is stored in the deionized water of 110mL, suspension
Middle nano ferriferrous oxide concentration is about 20mg/mL.
Preferably, prepared nano ferriferrous oxide granule partial size is 10-20nm, and molecular weight is in 100000-
200000Da, the pH of isoelectric point position are 6.2.
Preferably, after the completion of each film packet adsorption reaction, the outer humic acid solution of film packet is taken to exist using ultraviolet spectrophotometry
The concentration that humic acid is measured at UV254nm, the concentration of the humic acid of different molecular weight magnitude in film packet is determined using minusing.
Humic acid is classified as 10 components by this example, and the percentage composition distribution of different component is as shown in table 1.
The content distribution (wt%) of each fraction of table 1
Embodiment 2
A kind of humic acid molecular-weight gradation method, includes the following steps:
S1. respectively by 60mg nano ferriferrous oxide be put into 500-1000Da, 3500Da, 9000Da, 10000Da,
It is made in the regenerated cellulose film of 9 molecular weight grades of 15000Da, 25000Da, 35000Da, 50000Da, 90000Da, it will
Film both ends are clamped with film, and the film packet of 9 different molecular weight grades is made；
S2. 50mg humic acid is added in 500ml volumetric flask, the NaOH solution of 1M is added dropwise thereto until humic acid
It is completely dissolved, with deionized water constant volume to 500ml, is with the pH that the concentrated hydrochloric acid of mass percent 39% adjusts humic acid solution
5.0, the smallest film packet of molecular weight grade is added thereto, at 20-25 DEG C, with 120rip/min, classification stirring 0.5h；
S3. after the completion of the adsorption reaction of film packet, film packet is taken out, and measures the concentration of the outer humic acid solution of film packet, according to film packet
The ascending sequence of molecular weight grade is put into the film packet of next molecular weight grade, repeats step S2 and S3, anti-to 9 film packets
After the completion of answering, then completion is classified.
Preferably, in step S1 nano ferriferrous oxide preparation process, comprising the following steps:
(1) by 2.0g FeCl2·4H2O and 5.2g FeCl3·6H2O is dissolved in the deionization of the preparatory nitrogen deoxidation of 25mL
In water, the concentrated hydrochloric acid that 0.95mL mass percent is 39% is added；
(2) solution made from step (1) is added dropwise in the NaOH solution of 250mL 1.5M, side edged electromagnetic agitation is simultaneously
Logical nitrogen protection；Produce black nano ferroso-ferric oxide.
(3) after the completion of the adsorption reaction of film packet, film packet is taken out, is washed 5 times with 200mL deionization, suspension is stored in 110mL's
In deionized water, nano ferriferrous oxide concentration is about 20mg/mL in suspension.
Preferably, prepared nano ferriferrous oxide granule partial size is 10-20nm, and molecular weight is in 100000-
200000Da, the pH of isoelectric point position are 6.2.
Preferably, after the completion of each film packet response, the outer humic acid solution of film packet is taken to exist using ultraviolet spectrophotometry
The concentration that humic acid is measured at UV254nm, the concentration of the humic acid of different molecular weight magnitude in film packet is determined using minusing.
Humic acid is classified as 10 components by this example, and the percentage composition distribution of different component is as shown in table 2.
The content distribution (wt%) of each fraction of table 2
Embodiment 3
A kind of humic acid molecular-weight gradation method, includes the following steps:
S1. respectively by 60mg nano ferriferrous oxide be put into 500-1000Da, 3500Da, 9000Da, 10000Da,
It is made in the regenerated cellulose film of 9 molecular weight grades of 15000Da, 25000Da, 35000Da, 50000Da, 90000Da, it will
Film both ends are clamped with film, and the film packet of 9 different molecular weight grades is made；
S2. 80mg humic acid is added in 500ml volumetric flask, the NaOH solution of 1M is added dropwise thereto until humic acid
It is completely dissolved, with deionized water constant volume to 500ml, is with the pH that the concentrated hydrochloric acid of mass percent 39% adjusts humic acid solution
5.0, the smallest film packet of molecular weight grade is added thereto, at 20-25 DEG C, with 120rip/min, classification stirring 1h.
S3. after the completion of the adsorption reaction of film packet, film packet is taken out, and measures the concentration of the outer humic acid solution of film packet, according to film packet
The ascending sequence of molecular weight grade is put into the film packet of next molecular weight grade, repeats step S2 and S3, anti-to 9 film packets
After the completion of answering, then completion is classified.
Preferably, in step S1 nano ferriferrous oxide preparation process, comprising the following steps:
(1) by 2.0g FeCl2·4H2O and 5.2g FeCl3·6H2O is dissolved in the deionization of the preparatory nitrogen deoxidation of 25mL
In water, the concentrated hydrochloric acid that 0.95mL mass percent is 39% is added；
(2) solution made from step (1) is added dropwise in the NaOH solution of 250mL 1.5M, side edged electromagnetic agitation is simultaneously
Logical nitrogen protection；Produce black nano ferroso-ferric oxide.
(3) after the reaction was completed, it is washed 5 times with 200mL deionization, suspension is stored in the deionized water of 110mL, suspension
Middle nano ferriferrous oxide concentration is about 20mg/mL.
Preferably, prepared nano ferriferrous oxide granule partial size is 10-20nm, and molecular weight is in 100000-
200000Da, the pH of isoelectric point position are 6.2.
Preferably, after the completion of each film packet adsorption reaction, the outer humic acid solution of film packet is taken to exist using ultraviolet spectrophotometry
The concentration that humic acid is measured at UV254nm, the concentration of the humic acid of different molecular weight magnitude in film packet is determined using minusing.
Humic acid is classified as 10 components by this example, and the percentage composition distribution of different component is as shown in table 3.
The content distribution (wt%) of each fraction of table 3
Those skilled in the art should be understood that the above description is only an embodiment of the present invention, not be used to limit this
The practical range of invention；It is all to make equivalence changes and modification according to the present invention, all covered by the scope of the patents of the invention.
Claims (9)
1. a kind of humic acid molecular-weight gradation method, using nano ferriferrous oxide suction-operated and regenerated cellulose film it is saturating
The molecular-weight gradation of the property crossed realization humic acid, which comprises the following steps:
S1. nano ferriferrous oxide is respectively put into the regenerated cellulose film of at least nine different molecular weight grade, by film both ends
It is clamped with film, the film packet of at least nine different molecular weight grade is made；
The partial size of the nano ferriferrous oxide is 10-20nm, and molecular weight is in 100000-200000Da, the pH of isoelectric point position
It is 6.2；
S2. humic acid is dissolved in the alkaline solution of 1.0M and forms humic acid solution；
S3. the film packet that step S1 is obtained is added in the humic acid solution obtained to step S2, adjusting humic acid solution to pH value is
5.0, adsorption reaction is carried out under electromagnetic agitation；
S4. after the completion of the adsorption reaction of film packet, film packet is taken out, the concentration of the outer humic acid solution of measurement film packet is determined using minusing
The concentration of humic acid in film packet, humic acid is then narrow molecular-weight humic acid in film packet；
S5. step S3 and S4 are repeated, after the completion of all film packet adsorption reactions, i.e., the classification of humic acid molecular weight is completed.
2. humic acid molecular-weight gradation method according to claim 1, which is characterized in that nanometer four described in step S1
The preparation method of Fe 3 O, comprising the following steps:
(1) by FeCl2·4H2O and FeCl3·6H2O is dissolved in the deionized water of preparatory nitrogen deoxidation；
(2) concentrated hydrochloric acid that mass percent is 36-39%, dissolution are added in the solution prepared to step (1)；
(3) solution prepared by step (2) is added dropwise in the NaOH solution of 1.5M, nitrogen protection is led in electromagnetic agitation, i.e.,
Generate black nano ferroso-ferric oxide；
(4) nano ferriferrous oxide granule of generation is washed with deionized water 5 times, suspension saves in deionized water.
3. humic acid molecular-weight gradation method according to claim 1, which is characterized in that regeneration described in step S1 is fine
Tieing up plain film is U.S. Spectrum regenerated cellulose film, and the molecule less than regenerated cellulose film molecular weight can pass through, and is greater than regeneration
The molecule of cellulose membrane molecular weight is trapped, and nano ferriferrous oxide granule cannot penetrate regenerated cellulose film.
4. humic acid molecular-weight gradation method according to claim 1, which is characterized in that regeneration described in step S1 is fine
The molecular weight grade for tieing up plain film is 500-90000Da.
5. humic acid molecular-weight gradation method according to claim 4, which is characterized in that the regenerated cellulose film packet
Include 500-1000Da, 3500Da, 9000Da, 10000Da, 15000Da, 25000Da, 35000Da, 50000Da, 90000Da 9
A molecular weight grade.
6. humic acid molecular-weight gradation method according to claim 1, which is characterized in that alkalinity described in step S2 is molten
Liquid is NaOH solution.
7. humic acid molecular-weight gradation method according to claim 1, which is characterized in that film packet described in step S3 is pressed
It is put into humic acid solution according to the ascending sequence of regenerated cellulose film molecular weight.
8. humic acid molecular-weight gradation method according to claim 1, which is characterized in that electromagnetic agitation described in step S3
Condition are as follows: at 20-25 DEG C, be stirred with the revolving speed of 120r/min.
9. humic acid molecular-weight gradation method according to claim 1, which is characterized in that each film packet absorption of step S4 is anti-
After the completion of answering, takes the outer humic acid solution of film packet to measure the concentration of humic acid at UV254nm using ultraviolet spectrophotometry, use
Minusing determines the concentration of the humic acid of different molecular weight magnitude in film packet.
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