CN110396203A - The extraction of humus and purification process suitable for soil, peat and lignite - Google Patents
The extraction of humus and purification process suitable for soil, peat and lignite Download PDFInfo
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Abstract
The invention discloses a kind of extraction of humus suitable for soil, peat and lignite and purification process, the described method comprises the following steps and (I) alkali carries solubility humus；(II) the molten alkali carries Iron-linked humin of acid；(III) the molten alkali carries Clay-combined humin of acid；(IV) insoluble humin is isolated and purified.The extraction of the proposition humin of present system and purification process, and the Humic acids and fulvic acids extracting method proposed to national humus association improves and optimizes, it is set to be more suitable for domestic humus material resource characteristic, and both methods is combined, the extraction standard method of different material resource humus each components that form a whole set of system with independent intellectual property rights, globality.
Description
Technical field
The invention belongs to a kind of humic acid-extractions, and in particular to one kind humic suitable for soil, peat and lignite
The extraction of matter and purification process.
Background technique
Humus is that animals and plants remains are formed by the decomposition and conversion of microorganism and a series of geochemical processes
It is widely distributed in Soil sediment with a kind of colloidal substance accumulated, it is not only to ensure the important fertilizer of plant growth
Power index is also important ecological environment regulatory factor.Last century end gos deep into humus research with people, finds humic
Matter has organo-functional group abundant and surface-active site, can generate absorption to heavy metal and organic pollutant, be complexed, hydrophobic
The effects of decomposition and photochemistry, significantly reduces pollutant (especially to effectively restrict the diffusion mobility of pollutant in the soil
It is heavy metal contaminants) enrichment in crops, and the pollutant in water body can be efficiently removed.In addition, humus
Belong to natural organic matter, secondary pollution will not be generated to ecological environment, so humus is in environment pollution control and reparation side
There is immeasurable potential value in face, becomes the hot research problem in environment remediation field in recent years.
Humus has very strong chemical heterogeneity, by a series of there is different molecular weight and different functional groups to form
Organic complex composed by the larger molecular organics of feature, the chemical property difference of component according to contained by it, at present in the world
It is generally acknowledged that humus includes three main components, i.e. fulvic acid (FA), humic acid (HA) and humin (HM).For humus
The extraction of each component, international humic acid association (IHSS) propose a set of with reference to method, its sale at present in the nineties in last century
Humus standard substance be exactly referring to the set method extract.And there are some problems in this method:
First is that existing humus extracting method is primarily to extract Humic acids and fulvic acids at present, the two components
Soluble humus (DOM) is belonged to, they can be extracted using a certain proportion of alkaline solution, and humin is just deposited
It is after extracting in remaining residue, but also contains a large amount of impurity in these residues, there is presently no a kind of methods of maturation
It is purified out out of residue.
Second is that existing all kinds of extracting methods and will extract a variety of material resources substantially all just for a humic-like substance material resource at present
Extractions of humic substance when just need different agent prescription and extraction process, this do not utilize very much humus each component extract production
Industry can greatly increase and extract difficulty and cost.
Third 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, a kind of suitable for soil the purpose is to provide
The extraction of humus and purification process in earth, peat and lignite.
The technical scheme is that
A kind of extraction of the humus suitable for soil, peat and lignite and purification process, comprising the following steps:
(I) alkali carries solubility humus
(I) solubility humus extracts
Weigh a certain amount of pretreated Objective extraction object；Na is added into Objective extraction object4P2O7With the mixing of NaOH
Solution carries out alkali soluble and is then centrifuged for separating by solidliquid mixture oscillation treatment, collects upper layer dark solution；It is more to lower sediment
Secondary to repeat alkali soluble operation, after collecting centrifugation every time upper layer dark solution, as soluble humus extracting solution, residue precipitating are used
It is extracted in 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 Hu Min
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 daily
2 deionized waters then take 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
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, receives
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；Restore white with NaOH solution elution resin to resin again and eluent be colourless,
Collect fulvic acid eluent；By fulvic acid eluent by being rushed again with deionized water after the chromatographic column equipped with cation exchange resin
It washes, 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, carries out vacuum freeze drying,
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；
(II) the molten alkali carries Iron-linked humin of acid
(I) Iron-linked humin extracts
(a) acid is molten
Precipitating obtained in the soluble humus extraction of step (I-I) is used into H2SO4Supernatant acid is abandoned in dissolution, oscillation, centrifugation,
Retain lower sediment, is repeated several times operation；
(b) alkali carries
Step gained precipitating is dissolved with NaOH solution, oscillation, centrifugation collect supernatant liquid, and to lower sediment NaOH
And Na2SO4Mixed solution repeats alkali carries, and receipt whole upper liquid is Iron-linked humin extracting solution, and lower sediment is used for
Clay-combined humin extracts；
The purifying of (II) Iron-linked humin
It is pure to the progress of Iron-linked humin extracting solution obtained by upper step using identical method is purified with step (III) humic acid
Change to get Iron-linked humin powder；
(III) the molten alkali carries Clay-combined humin of acid
(I) Clay-combined humin extracts
(a) acid is molten
Acid is carried out with HCl and HF mixed solution to gained lower sediment in the molten alkali carries Iron-linked humin of step (II) acid
It is molten, vibrate, centrifugation takes supernatant liquor, and supernatant liquor bleeds off supernatant after standing 24 hours, bottom have the turbid of precipitating again from
The heart, centrifugation gained precipitating repeat aforesaid operations；
(b) alkali carries
With NaOH and Na2SO4Mixed solution alkali soluble on step gained precipitating, vibrate, centrifugation, collect upper layer iron combination Hu Min
Plain extracting solution, lower sediment is for isolating and purifying insoluble humin；
The purifying of (II) Clay-combined humin
It is pure to the progress of Iron-linked humin extracting solution obtained by upper step using identical method is purified with step (III) humic acid
Change to get Clay-combined humin powder；
(IV) insoluble humin is isolated and purified
(I) separatin non-soluble humin and inorganic ash content
Precipitating in the extraction of step (I) Clay-combined humin is subjected to centrifugal treating, obvious layering occurs, upper layer is black
The insoluble humin of color, lower layer are white inorganic ash content, give up lower layer's inorganic ash content；
The insoluble humin in the upper layer isolated is dispersed with stirring with HCl and HF mixed solution, upper layer is collected in artificial light rolling
The insoluble humin turbid of black staticly settles in the further insoluble humin of separation removal naturally in beaker and is deposited to burning
The inorganic ash content in bottom of a cup portion, is repeated several times；
(II) insoluble humin purifying
(a) initial gross separation grey matter
Insoluble humin turbid obtained by upper step is further diluted with HCl and HF mixed solution, then vibrates, is centrifuged,
Supernatant liquor is collected, after standing 24 hours, is centrifuged again after removing supernatant, takes lower sediment；
(b) alkali soluble
With NaOH and Na2SO4Mixed solution dispersion gained precipitating carries out subtracting extraction, and oscillation, centrifugation remove supernatant, remove
Layer precipitating；
(c) it is acidified
HCl and HF mixed solution is added into lower sediment to stir evenly, is acidified, centrifugation removes supernatant；
(d) dialysis
The precipitating in step is washed with water out, and stirs evenly, obtains insoluble humin and mixes liquid, insoluble humin is mixed
Liquid is fitted into dialysis bag, dialysis four days and changes 2 deionized waters sooner or later daily, then takes out the insoluble Hu Min in dialysis bag
Element, one night of pre-freeze；
(e) freeze-drying saves
The good insoluble humin of pre-freeze is put into freeze dryer, is freeze-dried, insoluble humin powder is obtained, is received
Collect vial, snarl bottle cap with sealed membrane, be 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: natural air drying, the sieve of ground 100 mesh are carried out to Objective extraction object
Son, drying are sealed.
The Na4P2O7Concentration with the mixed solution of NaOH is 0.1M, wherein Na4P2O7Molar ratio with NaOH is 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 is washed with deionized water 4~6 times after first boiling 10min with ethanol solution；NaHCO is used again3(2%) and EDTA-2Na
(1mmol/L) mixed solution, which boils dialysis bag, to be cleaned 4~6 times with deionized water after 10min；Finally boiled again with deionized water
10min 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 mainly sharp
The extraction of each component is carried out with 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 extracts Hu Min
The purity of element.
Insoluble humus, i.e. humin can be divided into two class of soluble humin (HMs) and insoluble humin (HMr).
Wherein, HMs includes Iron-linked humin (HMi) and Clay-combined humin (HMc), the two essence be regarded as respectively with iron aluminium
The humic acid that oxide and Clay Minerals And Clay Oxides are combined closely, therefore it is being utilized respectively H2SO4, HCl&HF dissolve corresponding iron alumina
In the case where object and Clay Minerals And Clay Oxides, the two can have alkali solubility again, to be able to separate from thick humin.And HMr due to
Its molecular size and molecular structure determine its essence insoluble in alkali or acid.Therefore, HMi and HMc can by " acid it is molten-
The mode of alkali carries " extracts, and HMr then can utilize the two based on the difference of itself and inorganic mineral components in density
Density variation is separated by way of centrifugation layering.
The beneficial effects of the present invention are:
The present invention provides a kind of extraction of humus suitable for soil, peat and lignite and purification process, systematicness
Proposition humin (HM) extraction and purification process, and to national humus association (IHSS) propose humic acid (HA) and richness
In the extracting method of sour (FA) improve and optimize, so that it is more suitable for domestic humus material resource characteristic, and by both sides
Method combines, and different material resource humus each components that form a whole set of system with independent intellectual property rights, globality mention
Take standard method；The standard substance of humus each component can be produced by standard method, and the standard substance is accomplished to mark
The level of quasi- industrialization preparation, breaks the external monopolization to humus standard substance, enabling studies in China, person easily obtains
First-class, price material benefit the humus each component standard substance to quality is that China's humus is respectively led in environmental protection, medicine, pesticide etc.
The further investigation of domain application provides material guarantee, also mutually compares for each research work achievement and protects referring to uniformity is provided
Barrier；The preparation research of the humus each component standard substance (including soil, peat and lignite etc.) is realized in different material resources, for difference
The standard substance guarantee that material resource humic Quality Research provides.
Detailed description of the invention
Fig. 1 is humic qualitative classification situation map；
Fig. 2 is flow diagram of the invention；
Fig. 3 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
As shown in Fig. 2, extraction and the purification process of a kind of humus suitable for soil, peat and lignite, including it is following
Step:
(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), after extracting solution is cooled to room temperature every time
PH is surveyed, the variation of pH value before and after adding extracting solution is compared.
(2) 1:1 hydrochloric acid
12L concentrated hydrochloric acid (4 bottles × 3L/ bottles) constant volume is measured to 24L；
(B) it extracts
(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/L
Na4P2O7+ 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, twist
Tight 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 that DOM extracting solution surveys alkali in band valve 25L liquid storing barrel
The pH value of 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 0.1mol/L Na of the precipitating 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, cannot directly be carried out with NaOH solid with concentrated NaOH solution
PH is adjusted.
Acidification centrifugation carries out first time purifying on the day of DOM, separates HA and FA；If generated residual after the centrifugation of HA first time alkali soluble
Slag, 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 to return 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 dissolution 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 112.21gKOH 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) cut suitable length (about 50cm) dialysis bag first use large volume 50% ethanol solution (ethyl alcohol and deionized water,
V:v=1:1 it is washed with deionized water 4-6 times after) boiling 10min；
(2) 2%NaHCO of large volume (about 2.5L) is used3It will be seeped with 1mmol/L EDTA-2Na (pH=8.0) mixed solution
Analysis 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
Part, 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,
Give up upper solution.Then repeat above-mentioned 1~4 alkali soluble-souring operation 3 times, until alkali soluble HA centrifugation without precipitating and meanwhile be acidified from
Supernatant is clear, colorless.
(5) the 0.1mol/L HCl&0.3mol/L HF for the precipitating large volume that last HA acidification, centrifugation obtain is mixed
Acid solution is stirred at room temperature deashes for 24 hours, and centrifugation acquisition HA precipitating adds 0.1mol/L HCl&0.3mol/L HF and deashes, weight
Again twice.
(6) acid solution of the 0.1mol/L HCl&0.3mol/L HF containing HA is centrifuged, is that 3500r/min is centrifuged in revolving speed
30min, reduction of speed Dec=3, use up a small amount of deionized water and wash out HA, and HA liquid pH value is surveyed after stirring evenly and (adds deionized water after first removing again
It washes, 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 vial of 250mL, snarls bottle cap with sealed membrane, is put in shady place, sealing is protected from light guarantor
It deposits.
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,
Contain a large amount of FA in 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 is not when dialysis bagged liquid
It can exceed that the 70% of dialysis bag volume, influence dialysis effect to prevent swollen bag.Dialysis bag is reusable, but must re-start and boil
Boiling processing, and preferably dialysis same substance.PH value must be measured before and after HA dialysis.When collecting HA freeze-dried powder, gently to scrape
Tinfoil surface prevents from being mixed into tinfoil clast in HA.
The purifying of (IV) fulvic acid
(A) match liquid
(1) 0.1mol/L NaOH 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 resin
Then full water continues to rinse resin by peristaltic pump.
(2) it AmberliteIR-120 hydrogen type cation exchange resin (amount of 1 chromatographic column): is impregnated with 0.1mol/LHCl
Hydrogen type cation exchange resin for 24 hours, then rinses (6-8 times) with water purification, is dipped in deionized water and saves backup.Take quantity of resin
Fill out column, the water column that 3-5cm is retained on resin column makes resin satisfy water, then continues flushing resin by peristaltic pump.
The pretreatment of (3) 0.45 μm of filter membranes: deionized water cleans (6-8 times) after boiling 10min in deionized water, be dipped in from
It is saved backup in sub- 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
And eluent is colourless, collects eluent (about 3L).
(5) FA eluent with the flow velocity of 20mL/min by equipped with IR-120 hydrogen type cation exchange resin chromatographic column after
It is rinsed again with the deionized water of 1V, 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 shady place,
Sealing is 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, is lower than
Chromatograph capital 2-3cm.Resin must stand 2-4h after loading and voluntarily settle.Whether FA liquid first wants check device when crossing resin
Then leakage adjusts liquid inlet volume=seepage discharge, is constantly in resin and necessarily is in water-saturated state.If there is void column, to stop
Only absorption is 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.When chromatographic column temporarily ceases work, first outlet tube to be lifted
Height is fixed at the top of pillar, is then turned off peristaltic pump.Resin may be reused in the short time, must reactivate before.
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 with compacted
Dynamic pump control.
Peristaltic pump must calibrated before.Peristaltic pump feed liquor parameter is summarized as follows table 1:
1 peristaltic pump of table uses parameter setting
(II) the molten alkali carries Iron-linked humin of acid
(I) matches liquid
(1)1mol/L H2SO4Solution
Measure 1087.0mL H2SO4It is slowly poured into water along wall of cup, stirs and be diluted when pouring into, after being cooled to room temperature
Constant volume is to 20L；
(2)0.1mol/L NaOH+0.3mol/L Na2SO4(5:1) solution
66.67g NaOH and 142.04g anhydrous Na is weighed respectively2SO4Constant volume is dissolved to 20L；
(3) 0.4mol/L NaOH solution
It weighs 320gNaOH and dissolves constant volume to 20L；
(4) hydrochloric acid (1+1) solution
12L concentrated hydrochloric acid (4 bottles × 3L/ bottles) constant volume is measured to 24L.
(II) Iron-linked humin extracts
The extraction of HMi mainly includes two large divisions, first is that acid is molten: using 1mol/L H2SO4Dissolve the removal of ferrimanganic oxide mineral
The support carrier of Iron-linked humin HMi；Second is that alkali carries: using 0.1mol/L NaOH+0.3mol/L Na2SO4(5:1) by HMi from
Removing is on mineral to obtain HMi lye.Main operational steps are as follows:
(1) 1mol/L H is used2SO4Solution washes out the residue after the 6th alkali carries of step (I) in centrifugal bottle and puts into shaker flask
In, constant volume to nearly bottle mouth position surveys the pH value of acid before reaction.
(2) shaker flask is put into 50 DEG C, the turnover oscillator of 35r/min oscillation 18~for 24 hours.
(3) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), pH value after reaction is surveyed.Native water mixed liquid is respectively charged into 1L
Centrifugal bottle, 3500r/min are centrifuged 30min, reduction of speed Dec=3, abandon supernatant acid, retain lower sediment.Repeat above-mentioned 1~3 operation again
With 1mol/L H2SO4Acidleach processing.
(4) 0.5mol/L NaOH is used, residue in centrifugal bottle is washed out and is put into shaker flask, constant volume is to nearly bottle mouth position, then
The pH value of alkali before side reaction.
(5) shaker flask is put into 50 DEG C, the turnover oscillator of 35r/min oscillation 18~for 24 hours, the alkali carries for carrying out HMi take.
(6) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), pH value after reaction is surveyed.Native water mixed liquid is respectively charged into 1L
Centrifugal bottle, 3500r/min are centrifuged 30min, reduction of speed Dec=1, collect whole upper layers HMi extracting solution in 25L liquid storing barrel, and protect
Leaving layer precipitating.Repeat above-mentioned 4~6 operation 0.1mol/L NaOH+0.3mol/L Na2SO4(5:1) alkali carries.
(7) HMi extract lye it is more muddy, need the same day acidification centrifugation carry out first time purifying, alkali soluble centrifugation after if
Residue is generated, Yu Ci returns bottle.Subsequent purification work can suspend subsequent progress and store HMi with small size.(each alkali carries are all
So).
(8) it repeats above-mentioned acidic leaching with alkaline and mentions 3 circulations (+2 alkali carries of=2 acidleach of circulation) of operation, until acidleach
First time alkali extracting solution clear, colorless afterwards.
Due to H2SO4Concentration crosses ambassador's subsequent alkaline and mentions the alkaline environment that pH ≈ 12.70 is not achieved, and first time alkali carries need suitable
When increasing NaOH concentration, preliminary debugging is obtained: the first alkali carries of every circulation are directly using about 0.4mol/L NaOH solution (concentration
Need to correct, pH value reaches 12.5 or so), and second of normal use 0.1mol/L NaOH+0.3mol/L Na2SO4
(5:1).1mol/L H is added in lower sediment2SO4PH value is surveyed before heating oscillation after constant volume, is taken out after oscillation after being cooled to room temperature
Survey pH value.If acid pH is more than pH meter measurement range, the proportion of sulfuric acid is clearly recorded.Similarly, it also to measure and add lye
Vibrate the pH value of front and back.
The purifying of (III) Iron-linked humin
(A) match liquid
(1) 2%NaHCO3&1m mol/L EDTA-2Na solution
Weigh dissolution 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/L HF
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) cut suitable length (about 50cm) dialysis bag first use large volume 50% ethanol solution (ethyl alcohol and deionized water,
V:v=1:1 it is washed with deionized water 4-6 times after) boiling 10min；
(2) 2%NaHCO of large volume (about 2.5L) is used3It will be seeped with 1mmol/L EDTA-2Na (pH=8.0) mixed solution
Analysis 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 HMi is close with HA purifying, and preparation will also pre-process dialysis bag, and purification process is slightly
Difference operates as follows:
(1) by HMi alkali extract 1:1 hydrochloric acid tune pH=1 ± 0.05,30min is stirred at room temperature.
(2) HMi acid solution is attached in the centrifugal bottle of 1L, and 3500r/min is centrifuged 30min, reduction of speed Dec=3, abandons supernatant, is received
Integrate lower sediment as crude product 3 (Iron-linked humin, HMi).
It (3), can be by the HMi of three circulations after alkali soluble precipitating is returned bottle by each HMi alkali extracting solution completion purifying for the first time
Acid precipitation is collected into together, is purified together.Solution overall control is in 1L or so before dialysis.
It is identical as HA purifying, also to measure the pH value before and after HMi dialysis.
(III) the molten alkali carries Clay-combined humin of acid
(I) Clay-combined humin extracts
(A) match liquid
(1) 2mol/L HCl+HF (1:1) solution
It measures 1666.67mL HCl and 600.60Ml HF to be slowly poured into water along wall of cup, it is dilute that progress is stirred when pouring into
It releases, is cooled to after room temperature constant volume to 20L；
(2)0.5mol/L NaOH+0.3mol/L Na2SO4(5:1) solution
333.33g NaOH and 142.04g anhydrous Na is weighed respectively2SO4Constant volume is dissolved to 20L；
(3)0.1mol/L NaOH+0.3mol/L Na2SO4(5:1) solution
66.67g NaOH and 142.04g anhydrous Na is weighed respectively2SO4Constant volume is dissolved to 20L；
(4) hydrochloric acid (1+1) solution
12L concentrated hydrochloric acid (4 bottles × 3L/ bottles) constant volume is measured to 24L.
(B) it extracts
The extraction of HMc mainly includes two large divisions, first is that acid is molten: being gone with 2mol/L HCl+HF (1:1) dissolution clay mineral
Except the support carrier of Clay-combined humin HMc；Second is that alkali carries 0.1mol/L NaOH+0.3mol/L Na2SO4(5:1) will
HMc removes to obtain HMc lye from mineral.Main operational steps are as follows:
(1) simultaneously with the residue in centrifugal bottle after second stage 3 circulation alkali carries of 2mol/L HCl+HF (1:1) solution wash-off
It puts into shaker flask, constant volume to nearly bottle mouth position, surveys the pH value of acid before reaction.
(2) shaker flask is put into 50 DEG C, the turnover oscillator of 35r/min oscillation 18~for 24 hours.
(3) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), pH value sour after reacting is surveyed.Native water mixed liquid fills respectively
Enter 1L centrifugal bottle, 3500r/min stands 10~15min after being centrifuged 15min Dec=9+15min Dec=1, collect supernatant in
In bucket of the 25L with valve, standing bleeds off supernatant afterwards for 24 hours, and the turbid centrifugation 15min Dec=9+15min of precipitating is arranged at bottom
10~15min is stood after Dec=1, deposit returns to shaker flask.Repeat it is above-mentioned 1~3 operation again with 2mol/L HCl+HF (1:
1) acidleach is handled.
(4) 0.5mol/L NaOH&0.3mol/L Na is used2SO4(5:1) washes out residue in centrifugal bottle and puts into shaker flask
In, constant volume to nearly bottle mouth position, the then pH value of the alkali before side reaction.
(5) shaker flask is put into 50 DEG C, the turnover oscillator of 35r/min oscillation 18~for 24 hours, the alkali carries for carrying out HMc take.
(6) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), the pH value of alkali after reaction is surveyed.Native water mixed liquid fills respectively
Enter 1L centrifugal bottle, 3500r/min stands 10~15min after being centrifuged 15min Dec=9+15min Dec=1, collects whole upper layers
HMi extracting solution retains lower sediment in 25L liquid storing barrel.Repeat above-mentioned 4~6 operation 0.1mol/L NaOH+0.3mol/
L Na2SO4(5:1) alkali carries.HMc extracts that lye is more muddy, and anti-bottle (each) is wanted in lye centrifugation when purifying.
(7) HMc extract lye it is more muddy, need the same day acidification centrifugation carry out first time purifying, alkali soluble centrifugation after if
Residue is generated, Yu Ci returns bottle.Subsequent purification work can suspend subsequent progress, and store HMc with small size.(each alkali carries
All so).
It repeats above-mentioned acidic leaching with alkaline and mentions 6 circulation left and right (+2 alkali carries of=2 acidleach of circulation) of operation, until acidleach
First time alkali extracting solution clear, colorless afterwards, and occur two layers of obvious black and white precipitating in precipitating.
It crosses ambassador's subsequent alkaline due to 2mol/L HCl+HF (1:1) concentration and mentions and the alkaline environment of pH ≈ 12.70 is not achieved,
Alkali carries need appropriate increasing NaOH concentration, and preliminary debugging obtains: the first alkali carries of every circulation use about 0.5mol/L NaOH
+0.3mol/L Na2SO4(5:1) solution, and second of normal use 0.1mol/L NaOH+0.3mol/L Na2SO4(5:1)。
In acid dissolution, upper layer acid solution is toppled over after the molten centrifugation of the first hypo acid can stay a small amount of liquid, retain residual substance；Second hypo acid
When toppling over after molten centrifugation, liquid is stayed less as far as possible or is not stayed, in order to avoid influence next step alkali carries.During alkali soluble, first time alkali carries
Upper layer acid solution is toppled over after centrifugation can stay a small amount of liquid, all topple over after second of alkali carries centrifugation.It is residual that HMc purifies alkali soluble centrifugation
Bottle is returned on the day of slag.PH value is surveyed before heating oscillation after soil sample addition 2mol/L HCl+HF (1:1) constant volume, takes out and is cooled to after oscillation
Also pH value is surveyed after room temperature.If acid pH is more than pH meter measurement range, the proportion of sulfuric acid is clearly recorded.Similarly, it also to survey
Amount plus the pH value of lye oscillation front and back.
The purifying of (II) Clay-combined humin
(a) match liquid
(1) 2%NaHCO3&1mmol/L EDTA-2Na solution
Weigh dissolution 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) 2mol/L HCl+HF (1:1) solution
It measures 1666.67mL HCl and 600.60mL HF to be slowly poured into water along wall of cup, it is dilute that progress is stirred when pouring into
It releases, is cooled to after room temperature constant volume to 20L.
(B) it purifies
The purification work of HMc is close with HA purifying, and preparation will also pre-process dialysis bag, purification process operation
It is as follows:
1. 30min is stirred at room temperature in HMc alkali extract 1:1 hydrochloric acid tune pH=1 ± 0.05.
2.HMc acid solution is attached in the centrifugal bottle of 1L, and 3500r/min is centrifuged 30min, reduction of speed Dec=3, abandons supernatant, is collected
Lower sediment is crude product 4 (Clay-combined humin, HMc).
3. three can be recycled after alkali soluble centrifugation is returned bottle by each HMc alkali extracting solution completion first time purifying
HMc acid precipitation is collected into together, is purified together.HMc purification process is identical as HA, can use for reference chapters and sections 3.1.2 product 1
(HA) purifying is operated.But it deashes and is carried out using 2mol/L HCl+HF (1:1) room temperature, liquid measure is controlled in 3~4L.Dialysis
Preceding solution overall control is in 1L or so.
It is identical as HA purifying, also to measure the pH value before and after HMc dialysis.
(IV) insoluble humin is isolated and purified
(I) separatin non-soluble humin and inorganic ash content
(a) match liquid
2mol/L HCl+HF (1:1) solution:
It measures 1666.67mL HCl and 600.60mL HF to be slowly poured into water along wall of cup, it is dilute that progress is stirred when pouring into
It releases, is cooled to after room temperature constant volume to 20L.
(b) it separates
(1) residue of step (III) is centrifuged 30min with the small centrifuge tube 3500r/min of 50mL, obvious layering: upper layer occurs
For the HMr of black, lower layer is white SiO2Equal inorganic minerals, give up lower layer's inorganic ash content.Or it is not centrifuged directly separation by hand.
(2) it is manually gently shaken using 2mol/L HCl+HF (1:1) solution and separates black and white substance, collection upper layer as far as possible is black
Color HMr turbid in beaker, iterated through after stirring evenly nature staticly settle further separation removal HMr in be deposited to beaker bottom
Inorganic ash content.Separation completely, may be stood liquid separation 10 times or more, until following without obvious white ash content.
Artificial settle and separate inorganic ash content and when HMr, repeatedly carry out.If had around discovery walls of beaker during standing
Canescence floating material, which gently stirs a circle along walls of beaker with glass bar, makes inorganic ash content fall within beaker bottom.
(II) insoluble humin purifying
(A) match liquid
(1) 2mol/L HCl+HF (1:1) solution
It measures 1666.67mL HCl and 600.60mL HF to be slowly poured into water along wall of cup, it is dilute that progress is stirred when pouring into
It releases, is cooled to after room temperature constant volume to 20L；
(2)0.5mol/L NaOH+0.3mol/L Na2SO4(5:1) solution: weigh respectively 333.33g NaOH and
142.04g anhydrous Na2SO4Constant volume is dissolved to 20L.
(B) it purifies
Dialysis bag is pre-processed, and the main purpose of HMr purifying is exactly to be eliminated as much as ash content.Concrete operations are such as
Under:
(1) its HMr turbid is poured into shaker flask and (can synthesizes 4 bottles), with 2mol/L HCl+HF (1:1) solution constant volume
To nearly bottleneck.
(2) shaker flask is put into 50 DEG C, the overturning vibrating machine of 35r/min concussion 18~for 24 hours, further removes ash content.
(3) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), 3500r/min is centrifuged 15min Dec=9+15min
10~15min is stood after Dec=1, collects supernatant in bucket of the 25L with valve, standing bleeds off supernatant afterwards for 24 hours, and sinking has
10~15min is stood after the liquid centrifugation 15min Dec=9+15min Dec=1 of deposit, deposit returns to shaker flask.
It repeats aforesaid operations 3 times.
(4) 0.5mol/L NaOH&0.3mol/L Na is used2SO4(5:1) washes out residue in centrifugal bottle and puts into shaker flask,
Constant volume is to nearly bottle mouth position, the then pH value of the alkali before side reaction.
(5) shaker flask is put into 50 DEG C, the turnover oscillator of 35r/min oscillation 18~for 24 hours, the alkali carries for carrying out HMc take.
(6) after taking-up shaker flask is cooled to room temperature (10~20 DEG C), the pH value of alkali after reaction is surveyed.Native water mixed liquid fills respectively
Enter 1L centrifugal bottle, 3500r/min stands 10~15min after being centrifuged 15min Dec=9+15min Dec=1, gives up HMc supernatant
Liquid.
(7) lower sediment directly into centrifugal bottle is added 500ml 2mol/L HCl+HF (1:1) and stirs and evenly mixs, and is acidified
After 1h, after standing 10~15min after direct 3500r/min centrifugation 15min Dec=9+15min Dec=1, give up supernatant.
(8) go out HMr precipitating with the washing of small size and stir evenly (after first removing again plus deionization washing, total liquid measure control
In 1L or so), survey pH value determination before dialysis.
(9) HMr is mixed liquid to be fitted into dialysis bag, dialysis 4d and changes 2 deionized waters sooner or later daily and (survey and seep when changing water every time
The pH and record of bleed).Then pH value was taken out and surveyed to the 4th day afternoon, is fitted into plug-in bottle and is surrounded by the disk of the double-deck tinfoil, when
Its evening pre-freeze.
(10) the good HMr of pre-freeze is put into freeze dryer, is freeze-dried, about 3 days.Freeze-drying situation is watched daily.
(11) HMr powder is collected into the vial of 250mL, snarls bottle cap with sealed membrane, is put in shady place, sealing is protected from light
It saves.
With a small amount of HMr turbid washed out it has been found that when excessive volume, HMr can be kept heavy by the method for standing 2-4h
Behind shallow lake, supernatant is outwelled, then stirs evenly again and pours into dialysis in dialysis bag.Specific gravity is larger, and dialysis is shaken during dialysis
Band, to prevent deposit clumps.
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 extractions of humic substance
Quality 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, aqueous
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 not
Corresponding absorption peak can be generated at co-wavelength, so that it is determined that the relative amount of humus different functional groups.Fig. 3 is different humus
Infrared comparison figure, wherein ordinate be absorption intensity, abscissa is wave number, unit cm-1。
Through infrared analysis, original soil sample does not have apparent difference with a bottle HMi and HMc for residue extraction is returned, but HMr otherness is very
Greatly, mainly original is because having a large amount of ash content, such as SiO in the HMr of soil extract2。
Claims (6)
1. extraction and the purification process of a kind of humus suitable for soil, peat and lignite, it is characterised in that: including following step
It is rapid:
(I) alkali carries solubility humus
(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；
(II) the molten alkali carries Iron-linked humin of acid
(I) Iron-linked humin extracts
(a) acid is molten
Precipitating obtained in the soluble humus extraction of step (I-I) is used into H2SO4Dissolution, oscillation, centrifugation are abandoned supernatant acid, are retained
Lower sediment is repeated several times operation,
(b) alkali carries
Dissolve step gained precipitating with NaOH solution, supernatant liquid is collected in oscillation, centrifugation, and to lower sediment with NaOH and
Na2SO4Mixed solution repeats alkali carries, and receipt whole upper liquid is Iron-linked humin extracting solution, and lower sediment is for gluing
Burl closes humin and extracts；
The purifying of (II) Iron-linked humin
Iron-linked humin extracting solution obtained by upper step is purified using identical method is purified with step (III) humic acid, i.e.,
Obtain Iron-linked humin powder；
(III) the molten alkali carries Clay-combined humin of acid
(I) Clay-combined humin extracts
(a) acid is molten
Sour molten, vibration is carried out with HCl and HF mixed solution to gained lower sediment in the molten alkali carries Iron-linked humin of step (II) acid
It swings, is centrifuged, bleed off supernatant after taking supernatant liquor, supernatant liquor to stand 24 hours, bottom has the turbid of precipitating to be centrifuged again, from
Precipitating obtained by the heart repeats aforesaid operations；
(b) alkali carries
With NaOH and Na2SO4Mixed solution alkali soluble on step gained precipitating, vibrate, centrifugation, collect upper layer Iron-linked humin mention
Liquid is taken, lower sediment is for isolating and purifying insoluble humin；
The purifying of (II) Clay-combined humin
Iron-linked humin extracting solution obtained by upper step is purified using identical method is purified with step (III) humic acid, i.e.,
Obtain Clay-combined humin powder；
(IV) insoluble humin is isolated and purified
(I) separatin non-soluble humin and inorganic ash content
Precipitating in the extraction of step (I) Clay-combined humin is subjected to centrifugal treating, obvious layering occurs, upper layer is black
Insoluble humin, lower layer are white inorganic ash content, give up lower layer's inorganic ash content；
The insoluble humin in the upper layer isolated is dispersed with stirring with HCl and HF mixed solution, upper layer black is collected in artificial light rolling
Insoluble humin turbid staticly settles in the further insoluble humin of separation removal naturally in beaker and is deposited to bottom of the beaker
The inorganic ash content in portion, is repeated several times；
(II) insoluble humin purifying
(a) initial gross separation grey matter
Insoluble humin turbid obtained by upper step is further diluted with HCl and HF mixed solution, then vibrates, is centrifuged, collect
Supernatant liquor after standing 24 hours, is centrifuged again after removing supernatant, takes lower sediment；
(b) alkali soluble
With NaOH and Na2SO4Mixed solution dispersion gained precipitating carries out subtracting extraction, and oscillation, centrifugation remove supernatant, take lower layer
Precipitating；
(c) it is acidified
HCl and HF mixed solution is added into lower sediment to stir evenly, is acidified, centrifugation removes supernatant；
(d) dialysis
The precipitating in step is washed with water out, and stirs evenly, obtains insoluble humin and mixes liquid, insoluble humin is mixed into liquid dress
Enter in dialysis bag, dialysis four days and change 2 deionized waters sooner or later daily, then takes out the insoluble humin in dialysis bag, in advance
Freeze a night；
(e) freeze-drying saves
The good insoluble humin of pre-freeze is put into freeze dryer, is freeze-dried, is obtained insoluble humin powder, be collected into
Vial snarls bottle cap with sealed membrane, is put in shady place, and sealing is kept in dark place.
2. extraction and the purification process of the humus according to claim 1 suitable for soil, peat and lignite, feature
Be: the Objective extraction object is any one in soil, peat or lignite.
3. extraction and the purification process of the humus according to claim 1 suitable for soil, peat and lignite, feature
It is: the pretreatment in the step (I) specifically: grass cuttings impurity is removed to Objective extraction object, then natural air drying again,
The sieve of ground 100 mesh, drying are sealed.
4. extraction and the purification process of the humus according to claim 1 suitable for soil, peat and lignite, feature
It is: the Na4P2O7Concentration with the mixed solution of NaOH is 0.1mol/L, wherein Na4P2O7Molar ratio with NaOH is 1:
1；Objective extraction object and Na4P2O7Solid-liquid mass ratio with the mixed solution of NaOH is 1:5.
5. extraction and the purification process of the humus according to claim 1 suitable for soil, peat and lignite, feature
It is: the mode of solidliquid mixture oscillation treatment in the step (I) are as follows: by Objective extraction object and Na4P2O7With the mixing of NaOH
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, oscillation
Shaker flask is taken out after the completion to be cooled to room temperature.
6. extraction and the purification process of the humus according to claim 1 suitable for soil, peat and lignite, feature
Be: dialysis bag used in the dialysis is using preceding being pre-processed, pretreated method are as follows: cut the dialysis bag of suitable length
10min first is boiled with the ethanol solution that volume fraction is 50%, then is washed with deionized water 4 ~ 6 times；It is again 2% with mass fraction
NaHCO3Dialysis bag is boiled into 10min with the mixed solution of 1mmol/L EDTA-2Na, then is cleaned 4 ~ 6 times with deionized water；Most
10min is boiled with deionized water again afterwards, can be used after cooling.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112546667A (en) * | 2020-12-03 | 2021-03-26 | 浙江大学温州研究院 | Hemin extraction device and restoration method for restoring heavy metal contaminated soil |
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| CN110951492A (en) * | 2019-11-19 | 2020-04-03 | 西北农林科技大学 | Preparation method and application of soil remediation medicament humin based on modified peat |
| CN110951492B (en) * | 2019-11-19 | 2021-04-27 | 西北农林科技大学 | Preparation method and application of soil remediation medicament humin based on modified peat |
| CN111748103A (en) * | 2020-06-29 | 2020-10-09 | 中国环境科学研究院 | Method for purifying humin in soil |
| CN111748103B (en) * | 2020-06-29 | 2021-02-23 | 中国环境科学研究院 | Method for purifying humin in soil |
| CN112546667A (en) * | 2020-12-03 | 2021-03-26 | 浙江大学温州研究院 | Hemin extraction device and restoration method for restoring heavy metal contaminated soil |
| CN112546667B (en) * | 2020-12-03 | 2022-03-18 | 浙江大学温州研究院 | Hemin extraction device and restoration method for restoring heavy metal contaminated soil |
| CN112504746A (en) * | 2020-12-24 | 2021-03-16 | 山东微谱检测技术有限公司 | Water sample extraction method |
| CN113959812A (en) * | 2021-11-09 | 2022-01-21 | 西南林业大学 | Method for extracting fulvic acid and humic acid from soil |
| CN114409920A (en) * | 2022-01-17 | 2022-04-29 | 黑龙江大学 | Method for separating and extracting soil humus |
| CN115991881A (en) * | 2022-05-05 | 2023-04-21 | 山东金科力电源科技有限公司 | Humic acid iron removing method |
| CN115991881B (en) * | 2022-05-05 | 2024-02-27 | 山东金科力电源科技有限公司 | Humic acid iron removing method |
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