CN110437467A - Soluble humus suitable for soil, peat and lignite extracts and purification process - Google Patents
Soluble humus suitable for soil, peat and lignite extracts and purification process Download PDFInfo
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- CN110437467A CN110437467A CN201910674324.6A CN201910674324A CN110437467A CN 110437467 A CN110437467 A CN 110437467A CN 201910674324 A CN201910674324 A CN 201910674324A CN 110437467 A CN110437467 A CN 110437467A
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- 239000003864 humus Substances 0.000 title claims abstract description 47
- 239000002689 soil Substances 0.000 title claims abstract description 22
- 239000003077 lignite Substances 0.000 title claims abstract description 18
- 239000003415 peat Substances 0.000 title claims abstract description 18
- 238000000746 purification Methods 0.000 title claims abstract description 18
- 239000000284 extract Substances 0.000 title claims abstract description 17
- 239000004021 humic acid Substances 0.000 claims abstract description 81
- 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 claims abstract description 75
- 239000002509 fulvic acid Substances 0.000 claims abstract description 58
- 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 claims abstract description 52
- 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 claims abstract description 52
- 229940095100 fulvic acid Drugs 0.000 claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 238000000502 dialysis Methods 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 14
- 230000020477 pH reduction Effects 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000002663 humin Substances 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000002085 persistent effect Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000012479 in-house spinning solution Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 16
- 230000002572 peristaltic effect Effects 0.000 description 8
- 239000002956 ash Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BVPWJMCABCPUQY-UHFFFAOYSA-N 4-amino-5-chloro-2-methoxy-N-[1-(phenylmethyl)-4-piperidinyl]benzamide Chemical compound COC1=CC(N)=C(Cl)C=C1C(=O)NC1CCN(CC=2C=CC=CC=2)CC1 BVPWJMCABCPUQY-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The soluble humus that the invention discloses a kind of suitable for soil, peat and lignite extracts and purification process, the described method comprises the following steps with: (I) solubility humus extracts；(II) slightly mentions Humic acids and fulvic acids；The purifying of (III) humic acid；The purifying of (IV) fulvic acid.The present invention provides a kind of soluble humus extraction suitable for soil, peat and lignite and purification process, the extracting method of the humic acid (HA) and fulvic acid (FA) that propose to national humus association (IHSS) improves and optimizes, it is made to be more suitable for domestic humus material resource characteristic.
Description
Technical field
The invention belongs to a kind of humic acid-extractions, and in particular to a kind of suitable for the solvable of soil, peat and lignite
Property humus extract and purification process.
Background technique
Humus is animals and plants remains by the decomposition and conversion of microorganism and a series of geochemical process shapes
At with a kind of colloidal substance for accumulating, it is widely distributed in Soil sediment, be not only to ensure the important of plant growth
Fertility index is also important ecological environment regulatory factor.Last century end gos deep into humus research with people, discovery
Humus has organo-functional group abundant and surface-active site, can generate absorption, network to heavy metal and organic pollutant
The effects of conjunction, hydrophobic decomposition and photochemistry, significantly reduces dirty to effectively restrict the diffusion mobility of pollutant in the soil
The enrichment of object (especially heavy metal contaminants) in crops is contaminated, and the pollutant in water body can be efficiently removed.This
Outside, humus belongs to natural organic matter, will not generate secondary pollution to ecological environment, so humus is in environmental pollution control
System and reparation aspect have immeasurable potential value, become the hot research problem in environment remediation field in recent years.
Humus has very strong chemical heterogeneity, is to have different molecular weight and different functional groups group by a series of
Organic complex composed by larger molecular organics at feature, the chemical property difference of component according to contained by it are international at present
It is upper to be generally acknowledged that humus includes three main components, i.e. fulvic acid (FA), humic acid (HA) and humin (HM).For corruption
Grow the extraction of matter each component, international humic acid association (IHSS) proposed in the nineties in last century it is a set of with reference to method, at present its
The humus standard substance of sale is exactly to extract referring to the set method.And there are some problems in this method:
First is that existing all kinds of extracting methods and will extract a variety of objects substantially all just for a humic-like substance material resource at present
Different agent prescription and extraction process are just needed when the extractions of humic substance in source, this does not utilize humus each component to extract very much
Industrialization, can greatly increase and extract difficulty and cost.
Second is that previous most of humus extracting method is only applicable to the extraction of a small amount of extractions of humic substance in laboratory,
And it is unable to satisfy the production requirement of industrialization.
Summary of the invention
The present invention is proposed to overcome disadvantage existing in the prior art, and the purpose is to provide one kind to be suitable for
The soluble humus of soil, peat and lignite extracts and purification process.
The technical scheme is that
A kind of extraction of soluble humus and purification process suitable for soil, peat and lignite, comprising the following steps:
(I) solubility humus extracts
Weigh a certain amount of pretreated Objective extraction object；Na is added into Objective extraction object4P2O7With mixing for NaOH
It closes solution progress alkali soluble to be then centrifuged for separating by solidliquid mixture oscillation treatment, collects upper layer dark solution；To lower sediment
Alkali soluble is repeated several times to operate, the upper layer dark solution after collecting centrifugation every time, as soluble humus extracting solution is remaining heavy
It forms sediment and is extracted for Iron-linked humin；
(II) slightly mentions Humic acids and fulvic acids
Solubility humus extracting solution pH to 1 ± 0.05 is adjusted, after being stirred at room temperature, centrifugation, collecting lower sediment is thick produce
Product humic acid, supernatant liquor are the acid solution of crude product fulvic acid；
The purifying of (III) humic acid
(a) alkali soluble
Crude product humic acid precipitating is washed out with KOH and KCl mixed solution, is stirred evenly, adjusting suspension pH to 12.5~
13, obtain humic acid aqueous slkali；Centrifugal treating humic acid aqueous slkali collects upper layer black liquor, and lower sediment is returned and is walked
Suddenly in the lower sediment of (I)；
(b) it is acidified
Upper layer black liquor pH to 1.00 ± 0.05 is adjusted with HCl, stirring obtains humic acid acid solution；Centrifugal treating Hu Min
Sour acid solution retains lower sediment humic acid, gives up upper solution；
(c) alkali soluble is acidified repeatedly
Acidification gained lower sediment humic acid is repeated into alkali soluble souring operation, until after occurring when alkali soluble processing without precipitating,
Last time acidification obtains lower layer's humic acid precipitating；
(d) it deashes
The humic acid precipitating that acidification obtains is stirred at room temperature with HCl and HF mixed solution and is deashed for 24 hours, centrifugation obtains recklessly
Quick acid precipitating adds HCl and HF mixed solution and deashes, and is repeated twice；
(e) dialysis
Humic acid precipitating after deashing is washed with water out, stirs evenly, is fitted into dialysis bag, dialysis four days and daily morning and evening
2 deionized waters are changed, the humic acid in dialysis bag, one night of pre-freeze are then taken out；
(f) freeze-drying saves
The good humic acid of pre-freeze is put into freeze dryer, is freeze-dried, is obtained humic acid powder, be collected in vial
In, bottle cap is snarled with sealed membrane, is put in shady place, sealing is kept in dark place；
The purifying of (IV) fulvic acid
(a) it filters
The acid solution that step (II) is slightly mentioned to the resulting fulvic acid of Humic acids and fulvic acids carries out filtering water system filter membrane,
Collect fulvic acid filtrate；
(b) elution exudation
By fulvic acid filtrate by the chromatographic column equipped with macroreticular resin, after resin becomes dark-brown from white, deionization is used
Water elution resin drives salinity, gives up leacheate；Again with NaOH solution elute resin to resin restore white and eluent without
Color collects fulvic acid eluent；By fulvic acid eluent by using deionization again after the chromatographic column equipped with cation exchange resin
Water rinses, and collects fulvic acid diffusate；
(c) freeze-drying saves
By fulvic acid diffusate pre-freeze a whole night；The good fulvic acid of pre-freeze is put into freeze dryer, it is dry to carry out vacuum refrigeration
It is dry, the cotton-shaped powder of fulvic acid is obtained, vial is collected into, snarls bottle cap with sealed membrane, is put in shady place, sealing is kept in dark place；
The Objective extraction object is any one in soil, peat or lignite.
Pretreatment in the step (I) specifically: carry out natural wind again after removing grass cuttings impurity to Objective extraction object
Dry, the sieve of ground 100 mesh, drying is sealed.
The Na4P2O7Concentration with the mixed solution of NaOH is 0.1mol/L, wherein Na4P2O7With the molar ratio of NaOH
For 1:1；Objective extraction object and Na4P2O7Solid-liquid mass ratio with the mixed solution of NaOH is 1:5.
The mode of solidliquid mixture oscillation treatment in the step (I) are as follows: by Objective extraction object and Na4P2O7With NaOH's
Mixed solution is placed in shaker flask, and shaker flask is fixed on 50 DEG C, in the constant temperature oscillator of 35r/min, and persistent oscillation 18~
For 24 hours, shaker flask is taken out after the completion of oscillation to be cooled to room temperature.
Dialysis bag used in the dialysis is using preceding being pre-processed, pretreated method are as follows: cut the infiltration of suitable length
Analysis bag first boils 10min with the ethanol solution that volume fraction is 50%, then is washed with deionized water 4~6 times；Again with quality point
The NaHCO that number is 2%3Dialysis bag is boiled into 10min with the mixed solution of 1mmol/L EDTA-2Na, then clear with deionized water
It washes 4~6 times；10min finally is boiled with deionized water again, can be used after cooling.
The principle of the present invention is:
Humus situation of specifically classifying is as shown in Figure 1.Humus is mainly made of three parts, respectively humic acid
(HA), fulvic acid (FA) and humin (HM), their own chemical constituent and physical property have difference, and this project is main
The extraction of each component is carried out using solubility of each component in different pH, different chemical reagent.
Soluble humus (DOM) is directly extracted with alkaline solution.Wherein humic acid (product 1) is dissolved only in alkali, but
Insoluble in acid；And fulvic acid (product 2) had both been dissolved in alkali, also was soluble in acid.Therefore, the two can by acidification DOM alkali extracting solution into
Row separation.Carrying out residue remaining after extracting repeatedly using lye is inorganic mineral components and insoluble humus (Hu Min
Element) mixture.The stage takes SEE continuous extraction to be eliminated as much as DOM component, so that it is guaranteed that follow-up phase is extracted recklessly
The purity of quick element.
The beneficial effects of the present invention are:
It is right the present invention provides a kind of soluble humus extraction suitable for soil, peat and lignite and purification process
The extracting method of humic acid (HA) and fulvic acid (FA) that national humus association (IHSS) proposes improves and optimizes, and makes
It is more suitable for domestic humus material resource characteristic, and both methods is combined, and forms a whole set of with independent intellectual property right
System, the extraction standard methods of the different material resource humus each components of globality；Corruption can be produced by standard method
The standard substance of matter each component is grown, and the standard substance is accomplished to the level of standard industrialization preparation, breaks foreign countries to humus
The monopolization of standard substance, the person that enables studies in China easily get that quality is first-class, humus each component of price material benefit
Standard substance, the further investigation for China's humus in the application of each field such as environmental protection, medicine, pesticide provide material guarantee, also for
Each research work achievement mutually compares and reference provides uniformity guarantee；Realize in different material resources (including soil, peat and
Lignite etc.) humus each component standard substance preparation research, the reference substance quality guarantee provided for different material resource humic Quality Research
Barrier.
Detailed description of the invention
Fig. 1 is humic qualitative classification situation map；
Fig. 2 is to be applied to the resulting different humic acid constituents infrared spectrums of the method for the present invention.
Specific embodiment
With reference to the accompanying drawings of the specification and embodiment the present invention is described in detail:
Embodiment 1
A kind of extraction of the humus suitable for soil, peat and lignite and purification process, comprising the following steps:
(I) alkali carries DOM
(I) DOM is extracted
(A) match liquid
(1) alkali extracting solution (0.1mol/L): Na4P2O7+ NaOH (molar ratio 1:1) solution
Weigh 265.90g anhydrous Na4P2O7Constant volume is dissolved to 20L solution with 40.00gNaOH；
Configuration Na every time4P2O7PH value determination is needed when+NaOH (molar ratio 1:1), and extracting solution is cooled to room temperature every time
After survey pH, compare plus extracting solution before and after pH value variation.
(2) hydrochloric acid (1+1)
12L concentrated hydrochloric acid (4 bottles × 3L/ bottles) constant volume is measured to 24L；
(B) (by taking black earth as an example) is extracted
(1) black earth of the 400g by air-drying and sieving with 100 mesh sieve is weighed in the polytetrafluoro bottle of 2L, adds 0.1mol/
LNa4P2O7+ NaOH (molar ratio 1:1) solution is stirred evenly to bottleneck about 1.8L (solid-to-liquid ratio 1:5), vibration measuring swing before pH value,
Tighten bottle cap；
(2) bottle is fixed on 50 DEG C, in the constant temperature oscillator of 35r/min, persistent oscillation 18~for 24 hours, it carries out DOM and mentions
It takes；
(3) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), native water mixed liquid is respectively charged into 1L centrifugal bottle,
3500r/min is centrifuged 30min, reduction of speed Dec=1, and collecting upper layer dark solution is DOM extracting solution in band valve 25L liquid storing barrel
In, survey the pH value of alkali extracting solution；
Shaker flask taking-up be cooled to room temperature, can with natural cooling, can also be put into refrigerator but want the strict control time and
Temperature (15 ± 5 DEG C), the too low solubility that can reduce HA and FA of temperature, to reduce extraction efficiency.
(4) by the precipitating 0.1mol/LNa in centrifugal bottle4P2O7+ NaOH (molar ratio 1:1), which mixes liquid and washes out to be packed into, to be vibrated
Bottle, and constant volume repeats above-mentioned 2,3,4, operation 6 DOM alkali carries of progress to nearly bottleneck.Since black earth organic content is high, pH buffering
Property it is strong, for the first time plus lye be not achieved pH value requirement, be adjusted with concentrated NaOH solution, cannot directly with NaOH solid into
Row pH is adjusted.
Acidification centrifugation carries out first time purifying on the day of DOM, separates HA and FA；If generated after the centrifugation of HA first time alkali soluble
Residue, Yu Ci return bottle.Subsequent purification work can suspend subsequent progress.
(II) slightly mentions Humic acids and fulvic acids
Retain whole DOM alkali extracting solution.1:1 hydrochloric acid tune pH=1 ± 0.05 is used on the day of the DOM extracting solution of reservation, room temperature is stirred
3500r/min is centrifuged 30min, reduction of speed Dec=3 after mixing 30min, and collection lower sediment is crude product 1 (humic acid, HA), upper layer
Clear liquid is the acid solution of crude product 2 (fulvic acid, FA) and carries out FA filtering during the extraction process.Theoretically, it takes and is cooled to room
The method being centrifuged after temperature, residue can seldom after alkali soluble, if centrifugation generates residue after HA first time alkali soluble, residue needs are returned
Bottle.If above-mentioned HA and FA liquid wouldn't be handled, 4 DEG C of low temperature seals is needed to save.
The purifying of (III) humic acid
(A) match liquid
(1) 2%NaHCO3&1mmol/L EDTA-2Na solution
Weigh 50.00g NaHCO3Constant volume is dissolved to 2.5L with 0.85g EDTA-2Na；
(2) 0.1mol/L KOH&0.2mol/L KCl solution
It weighs 112.21g KOH and 298.20g KCl dissolution and is settled to 20L；
(3) hydrochloric acid (1+1) solution
12L concentrated hydrochloric acid (4 bottles × 3L/ bottles) constant volume is measured to 24L；
(4)0.1mol/L HCl&0.3mol/LHF
The concentrated hydrochloric acid and 180.2mL HF of measurement 166.67mL is poured into water dilution, rear constant volume to 20L along wall of cup.
(B) dialysis bag pre-processes
(1) 50% ethanol solution (ethyl alcohol and deionization that suitable length (about 50cm) dialysis bag first uses large volume are cut
Water, v:v=1:1) boil 10min after be washed with deionized water 4-6 times；
(2) 2%NaHCO of large volume (about 2.5L) is used3It will with 1mmol/L EDTA-2Na (pH=8.0) mixed solution
Dialysis bag is cleaned 4-6 times after boiling 10min with deionized water；
(3) last to boil 10min with deionized water again, it can be used after cooling.
If dialysis bag needs the short time to save, it is fully immersed in deionized water and is protected in 4 DEG C of low temperature seals
It deposits.
(C) it purifies
The purification work of HA mainly include HA KOH&KCl-HCl repeatedly alkali soluble acidification, HCl&HF deashes and dialysis
Three parts, concrete operations are as follows:
(1) the HA precipitating that DOM acidification is isolated is washed out with suitable 0.1mol/L KOH&0.2mol/L KCl, uses cantilever
Formula blender stirring 30min (surveys pH value and guarantees pH=12.5~13.0, realize HA alkali soluble)；
(2) by HA aqueous slkali loaded in 1L centrifugal bottle, 3500r/min is centrifuged 30min, reduction of speed Dec=1, and it is black to collect upper layer
Lower sediment is simultaneously returned to shaker flask by color liquid, that is, HA aqueous slkali.
(3) HA lye in upper layer is added 1:1HCl and adjusts pH=1.00 ± 0.05 overhead stirrer stirring 30min；
(4) HA acid solution is fitted into 1L centrifugal bottle, and 3500r/min is centrifuged 30min, reduction of speed Dec=3, retains lower sediment
HA gives up upper solution.Then above-mentioned 1~4 alkali soluble-souring operation is repeated 3 times, until alkali soluble HA centrifugation is sour simultaneously without precipitating
Change centrifuged supernatant is clear, colorless.
(5) the 0.1mol/L HCl&0.3 mol/L HF for the precipitating large volume that last HA acidification, centrifugation obtain is mixed
Acid solution is stirred at room temperature and removes ash content for 24 hours, and centrifugation obtains HA precipitating and adds 0.1 mol/L HCl&0.3mol/L HF dedusting
Point, it is repeated twice.
(6) acid solution of the 0.1mol/L HCl&0.3mol/L HF containing HA is centrifuged, in revolving speed be 3500r/min from
Heart 30min, reduction of speed Dec=3, use up a small amount of deionized water and wash out HA, surveyed after stirring evenly HA liquid pH value (after first removing again plus go from
Son washing, within 6L, HA liquor ratio is more sticky for all overall controls).
(7) HA liquid is fitted into dialysis bag, dialysis 4d and changes 2 deionized waters sooner or later daily and (survey dialysis when changing water every time
The pH and record of water).Then the HA that the 4th day afternoon took out dialysis bag kind in beaker and surveys pH value, is packed into plug-in bottle and is surrounded by
In the disk of the double-deck tinfoil, one night of evening on same day pre-freeze.
(8) the good HA of pre-freeze is put into freeze dryer, is freeze-dried, about 3 days.Freeze-drying situation is watched daily.
(9) HA powder is collected into the band spiral cover vial of 250mL, bottle cap is snarled with sealed membrane, is put in shady place, it is close
Envelope is kept in dark place.
HA amount is big, and purifying to be conducted batch-wise during the extraction process.Retain the supernatant of acidification centrifugation for the first time when HA is purified
A large amount of FA is contained in liquid, inside.When 0.1mol/L KOH&0.2mol/L KCl dissolves HA, 0.1mol/L KOH&0.2mol/L
KCl lye volume is unsuitable very few, guarantees alkaline environment (survey pH value and guarantee pH=12.5~13.0).Liquid when dialysis bagged liquid
70% of body no more than dialysis bag volume influences dialysis effect to prevent swollen bag.Dialysis bag is reusable, but must be again
It carries out boiling processing, and preferably dialysis same substance.PH value must be measured before and after HA dialysis.When collecting HA freeze-dried powder,
Tinfoil surface is gently scraped, prevents from being mixed into tinfoil clast in HA.
The purifying of (IV) fulvic acid
(A) match liquid
(1) 0.1mol/LNaOH solution
It weighs 20.00gNaOH and dissolves constant volume to 5L；
(2) 0.1mol/L HCl solution
It measures 25mL concentrated hydrochloric acid and is poured into water constant volume to 3L along wall of cup；
(B) pretreatment
(1) XAD-8 type macroporous absorbent resin (amount of 3 chromatographic columns):
Sufficiently activation in 2 hours is impregnated and stirred with ethyl alcohol, is then washed with deionized water without obvious ethyl alcohol smell (6-8
It is secondary), it is dipped in deionized water and saves backup.Quantity of resin potting resin column is taken, the water column that 3-5cm is retained on resin column makes to set
Rouge is satisfied water, then continues to rinse resin by peristaltic pump.
(2) it AmberliteIR-120 hydrogen type cation exchange resin (amount of 1 chromatographic column): is soaked with 0.1 mol/L HCl
It steeps hydrogen type cation exchange resin for 24 hours, then rinses (6-8 times) with water purification, be dipped in deionized water and save backup.It takes appropriate
Resin fills out column, and the water column that 3-5cm is retained on resin column makes resin satisfy water, then continues flushing resin by peristaltic pump.
(3) 0.45 μm of filter membrane pretreatments: it is washed with deionized water (6-8 times) after boiling 10min in deionized water, is dipped in
It is saved backup in deionized water.
(4) chromatographic column: it is formal to carry out connecting peristaltic pump, pillar and corresponding hose before FA absorption, carry out leakage detection work
Make.
(c) it purifies
(1) when the supernatant FA of separation DOM acidification centrifugation, the gauze covering after being washed with water when toppling over is centrifuged bottleneck, removal
A large amount of floating clasts
(2) the FA solution being collected into is carried out filtering again 0.45 μm of water system filter membrane, collects FA filtrate.
(3) flow velocity with 40mL/min of FA filtrate by be equipped with XAD-8 type macroreticular resin 3 chromatographic columns, resin by
After white becomes dark-brown, tree is eluted with the speed of 20mL/min with the deionized water of 1V (i.e. every pillar volume about 500ml)
Rouge drives salinity, gives up leacheate.
(4) XAD-8 resin to resin is eluted with the speed of 20mL/min with the NaOH solution of 5L 0.1mol/L and restores white
Color and eluent is colourless is collected eluent (about 3L).
(5) FA eluent passes through the chromatographic column equipped with IR-120 hydrogen type cation exchange resin with the flow velocity of 20mL/min
It is rinsed again with the deionized water of 1V afterwards, collects diffusate (the FA liquid after crossing IR-120 is acidity, pH=2~3).
(6) FA liquid is fitted into and the plug-in bottle of freeze dryer and is surrounded by the disk of the double-deck tinfoil, pre-freeze a whole night.
(7) the good FA of pre-freeze is put into freeze dryer, carries out vacuum freeze drying, about 3 days.Freeze-drying feelings are watched daily
Condition.
(8) the cotton-shaped powder of FA is collected into the band spiral cover vial of 250mL, bottle cap is snarled with sealed membrane, is put in cool place
Place, sealing are kept in dark place.
Bubble cannot be contained inside when chromatographic column potting resin, liquid level is higher than interface 3-5cm on resin in chromatographic column, low
In chromatography capital 2-3cm.Resin must stand 2-4h after loading and voluntarily settle.FA liquid first wants check device when crossing resin
Whether leakage, then adjust liquid inlet volume be equal to seepage discharge, be constantly in resin and necessarily be in water-saturated state.If there is sky
Column will stop absorption to catch up with the bubble in resin.Resin must use at room temperature, and FA solution temperature is too low to weaken resin
Adsorption capacity.Therefore, the FA solution of storage is being adsorbed after must reaching room temperature.It, be first when chromatographic column temporarily ceases work
Outlet tube is raised and is fixed at the top of pillar, peristaltic pump is then turned off.Resin may be reused in the short time, must before
It must reactivate.Because our extracting cycles are 2.5~3 months, resin is wanted low temperature drying (lower than 45 DEG C) or is directly given up.
Feed speed is controlled with peristaltic pump.
Peristaltic pump must calibrated before.Peristaltic pump feed liquor parameter is summarized as follows table 1:
1 peristaltic pump of table uses parameter setting
Product quality inspection is carried out to the embodiment of the present invention 1, as a result as follows:
One, yield
Continuous extraction stage by stage is carried out to 4.8kg black earth (opposite organic content 11.64%), obtains different humus groups
Sub-prime amount and yield such as the following table 2:
Table 2: different extractions of humic substance productivity and yields
Two, organic and content of ashes
Organic matter and ash determination determine calcination sample using of poor quality before and after setting different temperatures calcination experimental material
The content of moisture and organic matter in product.2% is not to be exceeded using organic and content of ashes is measured after 750 DEG C of calcination 4h of Muffle furnace
(except HMr).Specific steps are as follows:
1. weighing quality is m by clean crucible as 105 DEG C of drying 2h of Muffle furnace1；
2. the sample of 0.5g or so is added into crucible, weighs crucible and obtain gross mass quality to calcination material and be
m2；
3. crucible and calcination material are put into togerther Muffle furnace, 105 DEG C of burning 12h weigh quality m after natural cooling3, contain
Water rate calculates:
4. crucible and calcination material are put into togerther Muffle furnace, 750 DEG C of burning 4h weigh quality m after natural cooling4, organic
The absolute percentage composition of matter calculates:
Organic matter percentage contents calculate:
The absolute percentage composition of ash content calculates:
Ash content percentage contents calculate:
Three, the infrared functional group's characterization of different product
Infrared spectrum analysis can be used for studying the structure and chemical bond of molecule, and different functional groups are due to vibrating and rotating
Corresponding absorption peak can be generated at different wave length, so that it is determined that the relative amount of humus different functional groups.Fig. 2 is different corruption
The infrared comparison figure of matter is grown, wherein ordinate is absorption intensity, and abscissa is wave number, unit cm-1。
Through infrared analysis, original soil sample does not have apparent difference, but HMr otherness with a bottle HMi and HMc for residue extraction is returned
Very big, mainly original is because having a large amount of ash content, such as SiO in the HMr of soil extract2。
Claims (6)
1. a kind of soluble humus suitable for soil, peat and lignite extracts and purification process, it is characterised in that: including
Following steps:
(I) solubility humus extracts
Weigh a certain amount of pretreated Objective extraction object；Na is added into Objective extraction object4P2O7With the mixed solution of NaOH
It carries out alkali soluble to be then centrifuged for separating by solidliquid mixture oscillation treatment, collects upper layer dark solution；Lower sediment is repeatedly weighed
Multiple alkali soluble operation, the upper layer dark solution after collecting centrifugation every time, as soluble humus extracting solution, residue precipitating are used for iron
It is extracted in conjunction with humin；
(II) slightly mentions Humic acids and fulvic acids
Solubility humus extracting solution pH to 1 ± 0.05 is adjusted, after being stirred at room temperature, centrifugation, collecting lower sediment is crude product Hu
Quick acid, supernatant liquor are the acid solution of crude product fulvic acid；
The purifying of (III) humic acid
(a) alkali soluble
Crude product humic acid precipitating is washed out with KOH and KCl mixed solution, is stirred evenly, is adjusted suspension pH to 12.5 ~ 13, obtain
To humic acid aqueous slkali；Centrifugal treating humic acid aqueous slkali collects upper layer black liquor, and by lower sediment return step (I)
Lower sediment in；
(b) it is acidified
Upper layer black liquor pH to 1.00 ± 0.05 is adjusted with HCl, stirring obtains humic acid acid solution；Centrifugal treating humic acid acid
Solution retains lower sediment humic acid, gives up upper solution；
(c) alkali soluble is acidified repeatedly
Acidification gained lower sediment humic acid is repeated into alkali soluble souring operation, until after occurring when alkali soluble processing without precipitating, finally
Primary acidification obtains lower layer's humic acid precipitating；
(d) it deashes
The humic acid precipitating that acidification obtains is stirred at room temperature with HCl and HF mixed solution and is deashed for 24 hours, centrifugation obtains humic acid
Precipitating adds HCl and HF mixed solution and deashes, and is repeated twice；
(e) dialysis
Humic acid precipitating after deashing is washed with water out, stirs evenly, is fitted into dialysis bag, dialysis four days and changes sooner or later 2 times daily
Deionized water then takes out the humic acid in dialysis bag, one night of pre-freeze；
(f) freeze-drying saves
The good humic acid of pre-freeze is put into freeze dryer, is freeze-dried, is obtained humic acid powder, be collected in vial, is used
Sealed membrane snarls bottle cap, is put in shady place, and sealing is kept in dark place；
The purifying of (IV) fulvic acid
(a) it filters
The acid solution that step (II) is slightly mentioned to the resulting fulvic acid of Humic acids and fulvic acids carries out filtering water system filter membrane, collects rich
In acidleach liquid；
(b) elution exudation
By fulvic acid filtrate by the chromatographic column equipped with macroreticular resin, after resin becomes dark-brown from white, drenched with deionized water
It washes resin and drives salinity, give up leacheate；Restore white with NaOH solution elution resin to resin again and eluent is colourless, collects
Fulvic acid eluent；By fulvic acid eluent by being rinsed again with deionized water after the chromatographic column equipped with cation exchange resin,
Collect fulvic acid diffusate；
(c) freeze-drying saves
By fulvic acid diffusate pre-freeze a whole night；The good fulvic acid of pre-freeze is put into freeze dryer, vacuum freeze drying is carried out, obtains
The cotton-shaped powder of fulvic acid, is collected into vial, snarls bottle cap with sealed membrane, is put in shady place, and sealing is kept in dark place.
2. the soluble humus according to claim 1 suitable for soil, peat and lignite extracts and purification process,
Be characterized in that: the Objective extraction object is any one in soil, peat or lignite.
3. the soluble humus according to claim 1 suitable for soil, peat and lignite extracts and purification process,
It is characterized in that: the pretreatment in the step (I) specifically: carry out natural wind again after removing grass cuttings impurity to Objective extraction object
Dry, the sieve of ground 100 mesh, drying is sealed.
4. the soluble humus according to claim 1 suitable for soil, peat and lignite extracts and purification process,
It is characterized in that: the Na4P2O7Concentration with the mixed solution of NaOH is 0.1mol/L, wherein Na4P2O7With the molar ratio of NaOH
For 1:1；Objective extraction object and Na4P2O7Solid-liquid mass ratio with the mixed solution of NaOH is 1:5.
5. the soluble humus according to claim 1 suitable for soil, peat and lignite extracts and purification process,
It is characterized in that: the mode of solidliquid mixture oscillation treatment in the step (I) are as follows: by Objective extraction object and Na4P2O7With NaOH's
Mixed solution is placed in shaker flask, and shaker flask is fixed on 50 DEG C, in the constant temperature oscillator of 35r/min, and persistent oscillation 18 ~ for 24 hours,
Shaker flask is taken out after the completion of oscillation to be cooled to room temperature.
6. the soluble humus according to claim 1 suitable for soil, peat and lignite extracts and purification process,
Be characterized in that: dialysis bag used in the dialysis is using preceding being pre-processed, pretreated method are as follows: cut the infiltration of suitable length
Analysis bag first boils 10min with the ethanol solution that volume fraction is 50%, then is washed with deionized water 4 ~ 6 times；It is with mass fraction again
2% NaHCO3Dialysis bag is boiled into 10min with the mixed solution of 1mmol/L EDTA-2Na, then cleans 4 ~ 6 with deionized water
It is secondary；10min finally is boiled with deionized water again, can be used after cooling.
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Application publication date: 20191112 |