CN106432752A - Preparing method of coal fulvic acid with high purity - Google Patents
Preparing method of coal fulvic acid with high purity Download PDFInfo
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- CN106432752A CN106432752A CN201610833887.1A CN201610833887A CN106432752A CN 106432752 A CN106432752 A CN 106432752A CN 201610833887 A CN201610833887 A CN 201610833887A CN 106432752 A CN106432752 A CN 106432752A
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- fulvic acid
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- purity mineral
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
Abstract
The invention provides a preparing method of coal fulvic acid with high purity. The preparing method comprises the steps of using aqueous alkali to extract peat or brown coal, conducting centrifugation and microfiltration to remove undissolved substances and macromolecular colloid, then using an ultrafiltration membrane to cut out a fulvic acid salt fraction with molecular weight being 300-2500 da, then removing residual inorganic salt through an ion exchange membrane, transforming the fulvic acid salt fraction into a fulvic acid solution, and conducting drying to obtain a pharmaceutical grade fulvic acid with purity being 98% or above. The preparing method is simple in process, low in energy consumption and high in extraction ratio and purity of the fulvic acid, and obviously reduces environmental pollution.
Description
Technical field
Product of the present invention belongs to fine chemistry formulation art and in particular to a kind of preparation side of high-purity mineral fulvic acid
Method.
Technical background
Fulvic acid（Code name FA）It is low-grade coal（Including peat, brown coal and weathered coal）In extract a kind of fat-
The mixture of aromatic series complexity organic carboxyl acid.Because the collective effect of wherein distinctive multiple functional groups is so that FA has extensively
Chemism and biologically active, not only in agricultural, have been widely used in animal husbandry, and in food, health care and medical treatment neck
Be identified in domain have anti-oxidant, anti-aging, antiviral, anti-inflammatory invigorates blood circulation, suppression tumour, strengthen immunity, promote microcirculation,
Prevent and treat the effect such as cardiovascular and cerebrovascular diseases.The extractive technique of FA still rests essentially within traditional acid extraction or the water of alkali soluble-acid out at present
Flat, purify and refined means also no quantum jump, market mostly is the rough FA product of low-purity, seriously govern the high-end of FA should
With（It is mainly the application of field of medicaments）.
Chinese invention patent application discloses a kind of preparation method extracting fulvic acid in peat（Application number
201210445089.3）With peat as raw material, extracted by dilute alkaline soln, cationic surfactant purifies for precipitating reagent, tree
Fat adsorbing metal ions are purified.This preparation process includes four steps altogether：（1）Extract peat with dilute alkaline soln, add in extract
Enter sulfuric acid solution, acid out precipitates, collect filtrate, obtain the extract containing fulvic acid；（2）Extract is adjusted pH value to neutrality, plus
Enter cationic surfactant, flocculation sediment, stand 24 hours, sediment is collected by filtration, with acid flux material dissolution precipitation material,
Then extracted with organic solvent, collect aqueous phase solution；（3）Use cationic ion-exchange resin desalination；（4）Drying concentrated in vacuo, obtains
Fulvic acid.The method process is numerous and diverse, recovery rate is not also high.
Content of the invention
The present invention is to solve the above problems, and provides a kind of preparation method of high-purity mineral fulvic acid, its technique is advanced, warp
Ji practicality, low production cost, product yield and purity height, process non-environmental-pollution.
The technical solution adopted in the present invention is as follows：
A kind of preparation method of high-purity mineral fulvic acid, it includes following operating procedure：
（1）Extract：In the reactor in mass ratio 6～12:1 adds extractant and feed coal, ultrasonic in supersonic generator
React 0.5～2 hour after stirring and be heated to 60～100 DEG C, obtain suspension；Described feed coal is meadow peat or the Tertiary Period
Young brown coal is it is desirable to ash content≤30%, humic acid >=60%, fulvic acid >=5%（It is butt）；Described supersonic generator ginseng
Number is：Power 300～1000W, frequency 28～100KHz；Described extractant is the NaOH of concentration 0.1～0.5mol/L, KOH,
Na2CO3、K2CO3One or more of the aqueous solution or ammoniacal liquor.
（2）Centrifugation：With centrifuge, gained suspension is centrifuged, obtains the thick liquid of humate；Described centrifuge
Rotating speed >=10000r/min.
（3）Micro-filtration：Thick for humate liquid is passed through microfiltration membranes, collects filtrate；Described micro-filtration membrane aperture is 50 μm, behaviour
Make flow >=10L/min, pressure 0.2～0.4MPa.
（4）Ultrafiltration：Successively filtrate is passed through milipore filter, collect the trapped fluid of 1500da～500da；Described milipore filter is two
Layer milipore filter；Two-layer milipore filter molecular weight respectively 1500～2500da and 300～500da, operation flow >=5L/min,
Pressure is 0.5～1.0MPa.
（5）Ion exchange：Trapped fluid is passed through negative ions exchange membrane, obtains true yellow corruption acid solution；Described positive and negative from
Proton exchange is macromolecule homogeneous membrane, exchange capacity >=2mol/kg, surface resistance≤12 Ω cm2, operate flow >=3L/
Min, pressure 0.5～1.0MPa.
（6）It is dried：By step（5）Middle gained true yellow corruption acid solution is dried, and obtains fulvic acid pulvis or fulvic acid
Grain；Described fulvic acid pulvis is gained to be dried with spray dryer, and described fulvic acid particle is to be made with bed spray
Grain machine processes gained.
The present invention is with respect to the advantage of prior art and technique effect：
（1）The present invention adopts ultrasonic extraction technology, to reduce fulvic acid（FA）Molecular weight, raising recovery rate；Using industry
The supercentrifuge changed and membrane separation technique（Micro-filtration, ultrafiltration and amberplex）To fulvic acid（FA）It is classified and purified.
Ultrasonic wave has larger energy density and " cavitation ", the enormous impact ripple that it is launched, and not only can strengthen corruption
The extraction reaction of phytic acid, and humic acid macromolecular structure can be destroyed, improve fulvic acid ratio.Therefore, take with traditional alkali carries
Compare, after additional ultrasonic, fulvic acid content can improve 50% to 400%.
（2）Using supercentrifuge and micro-filtration, can be by water-insoluble organic and inorganic impurity from more than 5% original fall
To less than 0.5%.
（3）Replace traditional sour intermediate processing removing macromolecular ulmic acid and humic acid and inorganic salts with hyperfiltration technique, and
So that the Xanthohumate solution of retention is concentrated, replace with physical method Chemical Decomposition and evaporimeter to concentrate, enormously simplify
Operation, saves the energy, reduces cost, prevented the pollution to environment for the acid waste liquid.Compared with macroporous absorbent resin, equally
Possesses this advantage.
（4）Replace usual granular cationic ion-exchange resin with amberplex, can remove simultaneously remnants anion and
Cation, substantially increases fulvic acid purity, has abandoned loaded down with trivial details resin treatment process, has been more beneficial for environmental protection.
Reach more than 98% using preparation method gained fulvic acid purity of the present invention.
Brief description
Accompanying drawing 1 is the embodiment of the present invention 1 process chart.
Specific embodiment
Embodiment 1：
The Yunnan stone screen peat 100g weighing pulverizing for granularity 200 mesh, in stainless steel reactor, adds 800ml0.5mol/L's
KOH, using can the supersonic generator that produces of Li Xin ultrasonic wave Co., Ltd be passed through power be 500W, frequency be the super of 80KHz
Sound wave, reacts 1 hour at 80 DEG C；With injury Ba Jiu Industrial Co., Ltd. produce model 2-16KL/2-16P high speed from
Scheming is centrifuged gained suspension, and centrifuge speed is 10000r/min, discards residue, obtains the thick liquid of potassium humate；In 0.4MPa
Under conditions of pressure, operation flow are 10L/min, thick for humic acid potassium liquid are passed through the microfiltration membranes in 50 μm of aperture, collect filtrate, abandon
Go to retain residue；Under the pressure of 1.0MPa, filtrate is pumped into successively the milipore filter that molecular weight is 1500da and 500da, collect
Trapped fluid after ultrafiltration（Potassium fulvate solution）, passing through exchange capacity in the case of pressure 0.8MPa again is 2.5mol/kg
Negative ions exchange membrane, wherein surface resistance be 10 Ω cm2, operation flow is 3L/min, pressure 0.8MPa, obtains fulvic acid
Solution；By fulvic acid solution under the conditions of≤60 DEG C, using model LW- of Shanghai Li Wen scientific instrument Co., Ltd production
015 spray dryer carries out drying under reduced pressure, obtains fulvic acid pulvis.Through flocculation gravimetric method inspection, gained pressed powder FA contains
Measure as 98.7%（Butt）.
Embodiment 2：
The Yunnan stone screen peat 100g weighing pulverizing for granularity 200 mesh, in stainless steel reactor, adds 600ml0.5mol/L's
KOH, remaining step, with embodiment 1, obtains fulvic acid pulvis, and through inspection, powder FA content is 98.3%（Butt）.
Embodiment 3：
The Yunnan stone screen peat 100g weighing pulverizing for granularity 200 mesh, in stainless steel reactor, adds 1200ml0.5mol/L
KOH, remaining step, with embodiment 1, obtains fulvic acid pulvis, and through inspection, powder FA content is 98.5%（Butt）.
Embodiment 4：
Weigh the Xinjiang Nao Maohu brown coal 200g pulverizing 150 mesh in stainless steel reactor, add 1200ml0.5mol/L's
NH3•H2O, be passed through power be 800W, frequency be 100KHz ultrasonic wave, at 90 DEG C react 2 hours.Remaining operates with embodiment 1,
Gained pressed powder FA content is 99.2%（Butt）.
Embodiment 5：
Weigh the Xinjiang Nao Maohu brown coal 200g pulverizing 150 mesh in stainless steel reactor, add 1500ml0.5mol/L's
NH3•H2O, with embodiment 4, gained pressed powder FA content is 98.6% for remaining operation（Butt）.
Embodiment 6：
Weigh the Xinjiang Nao Maohu brown coal 200g pulverizing 150 mesh in stainless steel reactor, add 2400ml0.5mol/L's
NH3•H2O, with embodiment 4, obtaining pressed powder FA content through inspection institute is 99.0% for remaining operation（Butt）.
Comparative example：
Yunnan stone screen peat 100g and 800g mass fraction 1.5% sodium pyrophosphate and mass fraction 0.7% for 80 mesh will be pulverized
The alkaline extract that NaOH mixed aqueous solution is prepared from adds in reactor, after shaken well, then extracts in boiling water bath
2h, extracts to be cooled to after terminating and filters after room temperature, collect filtrate, with water washing filter residue 3 times, merging filtrate and cleaning solution, uses
2mol/l sulfuric acid adjusts after pH=0 ~ 1 mixes and stands 2h, then filters, and collects filtrate, with water washing filter residue 3 times, merging filtrate and
Cleaning solution, obtains fulvic acid extract A；
Adjust extract A with NaOH, be then filled into pH=6 ~ 7, after mixing, stand 2h, collect filtrate, with water washing filter residue
3 times, merging filtrate and cleaning solution, obtain fulvic acid extract B.
Then add Domiphen bromide as cationic surfactant in B liquid, addition is Yunnan stone screen peat quality
25%, concussion 30min fully mixes, and so that fulvic acid is precipitated with cationic surfactant Xu Nin, then prevents standing at backlight
24h.Solution after flocculation sediment is filtered, collects deposit, the volume ratio of the HCI solution of deposit sample and 0.1M
For 1:20, obtain extract C.
Then with chloroform, extract C is extracted, chloroform is 1 with the volume ratio of extract C sample:1, point
Three extractions, merge aqueous phase solution, obtain extract D；732 type strong acid ion exchange resins are loaded in glass column, according to
Air speed S=0.2 ~ 0.3（L/L*h）Flow extract D is passed through resin column, then wash pillar with water it is known that efflux is no
Till color, merging filtrate and cleaning solution, obtain extract E；
Extract E is carried out rotary evaporation in vacuo drying, 45 DEG C ~ 60 DEG C of evaporating temperature, evaporation is closely dry, then vacuum drier again
In be dried to obtain powdery fulvic acid product.
With flocculation gravimetric method inspection, in gained powdery fulvic acid product, A content is 91.5%（Butt）.
Found by contrast, a kind of preparation method of high-purity mineral fulvic acid of the present invention, preparation process is simple,
Easy to operate, and the pressed powder FA purity obtaining is higher.
In the present invention, the method for inspection-flocculation gravimetric method of pressed powder FA content, centrifugation, micro-filtration, ultrafiltration, ion exchange
And the concrete grammar of dry run and operating procedure are the common knowledge that those of ordinary skill in the art should generally learn,
Will not be described here.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or using invention.Right
Multiple modifications of these embodiments will be apparent from for those skilled in the art, and as defined herein one
As principle can without departing from invention spirit or scope in the case of, realize in other embodiments.Therefore, invention will not
Be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Wide scope.
Claims (10)
1. a kind of preparation method of high-purity mineral fulvic acid is it is characterised in that comprise the steps：
（1）Extract：In the reactor in mass ratio 6～12:1 adds extractant and feed coal, ultrasonic in supersonic generator
React 0.5～2 hour after stirring and be heated to 60～100 DEG C, obtain suspension；
（2）Centrifugation：With centrifuge, gained suspension is centrifuged, obtains the thick liquid of humate；
（3）Micro-filtration：Thick for humate liquid is passed through microfiltration membranes, collects filtrate；
（4）Ultrafiltration：Successively filtrate is passed through milipore filter, collect the trapped fluid of 1500da～500da；
（5）Ion exchange：Trapped fluid is passed through negative ions exchange membrane, obtains true yellow corruption acid solution；
（6）It is dried：By step（5）Middle gained true yellow corruption acid solution is dried, and obtains fulvic acid pulvis or fulvic acid particle.
2. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described feed coal
It is meadow peat or Tertiary Period young brown coal, wherein butt mass fraction：Ash content≤30%, humic acid >=60%, fulvic acid >=5%.
3. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described ultrasonic wave
Generator parameter is：Power 300～1000W, frequency 28～100KHz.
4. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described extractant
NaOH, KOH, Na for concentration 0.1～0.5mol/L2CO3、K2CO3One or more of the aqueous solution or ammoniacal liquor.
5. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described centrifuge
Rotating speed >=10000r/min.
6. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described microfiltration membranes
Aperture is 50 μm, operation flow >=10L/min, pressure 0.2～0.4MPa.
7. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described step（4）
Milipore filter be two-layer milipore filter.
8. as claimed in claim 7 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Ultrafiltration described in two-layer
Membrane molecule amount is respectively 1500～2500da and 300～500da, and operation flow >=5L/min, pressure are 0.5～1.0MPa.
9. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Described positive and negative from
Proton exchange is macromolecule homogeneous membrane, exchange capacity >=2mol/kg, surface resistance≤12 Ω cm2, operation flow >=3L/min, pressure
Power 0.5～1.0MPa.
10. as claimed in claim 1 a kind of preparation method of high-purity mineral fulvic acid it is characterised in that：Step（6）Described
Fulvic acid pulvis be gained to be dried with spray dryer, described fulvic acid particle is to process institute with fluidized bed spray granulation machine
?.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866089A (en) * | 2017-12-26 | 2018-04-03 | 山东恒力新能源工程有限公司 | Weathered coal extracts the device and its extraction process of pharmaceutical grade fulvic acid |
| CN109180743A (en) * | 2018-11-13 | 2019-01-11 | 安徽富里馨生物科技有限公司 | A kind of food-grade fulvic acid and preparation method thereof |
| CN109942834A (en) * | 2019-03-07 | 2019-06-28 | 陕西艾顿腐植酸科技集团有限公司 | A kind of preparation method of medical xanthonumic acid |
| CN112504746A (en) * | 2020-12-24 | 2021-03-16 | 山东微谱检测技术有限公司 | Water sample extraction method |
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| US4918059A (en) * | 1987-03-12 | 1990-04-17 | Rutgerswerke Ag | Low molecular weight alkali metal huminates, method for their preparation and applications thereof |
| CN103073732A (en) * | 2012-11-09 | 2013-05-01 | 沈阳农业大学 | Preparation method of fulvic acid in peat |
| CN105733596A (en) * | 2016-03-21 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Soil conditioner for passivation of heavy metals and preparation method of soil conditioner |
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| US4918059A (en) * | 1987-03-12 | 1990-04-17 | Rutgerswerke Ag | Low molecular weight alkali metal huminates, method for their preparation and applications thereof |
| CN103073732A (en) * | 2012-11-09 | 2013-05-01 | 沈阳农业大学 | Preparation method of fulvic acid in peat |
| CN105733596A (en) * | 2016-03-21 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Soil conditioner for passivation of heavy metals and preparation method of soil conditioner |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866089A (en) * | 2017-12-26 | 2018-04-03 | 山东恒力新能源工程有限公司 | Weathered coal extracts the device and its extraction process of pharmaceutical grade fulvic acid |
| CN109180743A (en) * | 2018-11-13 | 2019-01-11 | 安徽富里馨生物科技有限公司 | A kind of food-grade fulvic acid and preparation method thereof |
| CN109942834A (en) * | 2019-03-07 | 2019-06-28 | 陕西艾顿腐植酸科技集团有限公司 | A kind of preparation method of medical xanthonumic acid |
| CN112504746A (en) * | 2020-12-24 | 2021-03-16 | 山东微谱检测技术有限公司 | Water sample extraction method |
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Application publication date: 20170222 |