CN106701130A - Method for extracting fulvic acid through low-temperature carbonization - Google Patents
Method for extracting fulvic acid through low-temperature carbonization Download PDFInfo
- Publication number
- CN106701130A CN106701130A CN201710032570.2A CN201710032570A CN106701130A CN 106701130 A CN106701130 A CN 106701130A CN 201710032570 A CN201710032570 A CN 201710032570A CN 106701130 A CN106701130 A CN 106701130A
- Authority
- CN
- China
- Prior art keywords
- acid
- alkali
- extraction
- coal
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for extracting fulvic acid through low-temperature carbonization. The method comprises the following steps of 1, low temperature carbonization, decomposed coal is smashed into particles with the size not larger than 4 mm, and then placed into a closed container isolated from air, and low-temperature carbonization is performed on the condition of 500-650 DEG C for 30-40 min to collect coal tar; 2, alkaline extraction, wherein coal tar and a weak base solution are mixed, the pH of the mixed solution is adjusted to be 6.0-8.0 to obtain an alkaline extraction solution, the alkaline extraction solution is stirred for digestion for 0.5-1 h, and precipitates are removed after centrifuging is performed, and an alkaline extraction supernate is obtained; 3, acid extraction, wherein a 0.5 MHNO3 solution is used for adjusted the pH of the alkaline extraction solution to 1.0-2.0 to obtain an acid extraction solution, the acid extraction solution is stirred for digestion for 0.5-1 h, precipitates are removed after centrifuging is performed, and an acid extraction supernate is obtained; 4, freeze drying, wherein the acid extraction supernate is frozen and dried to obtain fulvic acid powder. Before alkali extraction and acid extraction, low-temperature carbonization is performed on decomposed coal, organic matter in the decomposed coal can be split to the maximum extent, and the fulvic acid extraction rate is increased; weak base is adopted for alkali extraction, and equipment corrosivity is small in the extraction process.
Description
Technical field
The present invention relates to fulvic acid extractive technique field, more particularly to a kind of method that fulvic acid is extracted in low temperature distillation.
Background technology
Background of related of the invention is illustrated below, but these explanation might not constitute it is of the invention existing
Technology.
Fulvic acid is an important component part of humus, and it can be dissolved in acid, alkali and neutral solution, be water body, soil
Organic matter important component.The structure of fulvic acid is extremely complex, and element composition and chemical constitution change with space-time and source.
Fulvic acid plays an important roll in environmental geochemistry and the world's ecosystems, and forefathers are various to Yu Haiyang, river, waste water etc.
The Geochemical Characteristics of source fulvic acid have carried out extensive research, have been achieved for a series of progress.It is generally acknowledged that：Fulvic acid
It is by moving the macromolecular organic mixture for planting that residuum passes through complicated physics, chemistry and bioprocess are formed.
Fulvic acid can be extracted from the low price coal such as weathered coal, lignite and obtained, and conventional extracting method is " alkali-soluble acid analysis ",
But the method recovery rate is relatively low, residue discharge capacity is big.
The content of the invention
It is an object of the invention to propose a kind of method that fulvic acid is extracted in low temperature distillation, can greatly improve from weathered coal
The middle recovery rate for extracting fulvic acid, and it is easy to operate, and the feature of environmental protection is good.
The method that fulvic acid is extracted in low temperature distillation of the present invention, comprises the following steps：
(1) low temperature distillation：Weathered coal is broken into the no more than particle of 4mm, the closed container of isolation air is subsequently placed in
In, the low temperature distillation 30min to 40min under the conditions of 500 DEG C -650 DEG C collects coal tar；
(2) alkali carries：Coal tar mixes with weak caustic solution, the pH of mixed liquor is adjusted to 6.0-8.0 and obtains alkali extract, stirring
Alkali extract extracts 0.5~1h, and precipitation is discarded after centrifugation, obtains alkali carries supernatant；
(3) acid is carried：Use 0.5MHNO3The pH to 1.0-2.0 of solution regulation alkali carries supernatant obtains sour extract, and stirring acid is carried
Immersion carries 0.5~1h, and precipitation is discarded after centrifugation, obtains acid and puts on clear liquid；
(4) freeze-drying：Clear liquid is put in acid described in freeze-drying, obtains fulvic acid powder.
The present invention carried out low temperature distillation before alkali carries and acid are carried to weathered coal, can farthest by weathered coal
Organic cracking out, improves the recovery rate of fulvic acid；Alkali carries are carried out using weak base, extraction process is small to equipment corrosion.
Specific embodiment
Illustrative embodiments of the invention are described in detail below.Description to illustrative embodiments is only
For illustration purposes, it is definitely not to the present invention and its application or the limitation of usage.
A kind of method that fulvic acid is extracted in low temperature distillation, it is characterised in that comprise the following steps：
(1) low temperature distillation：Weathered coal is broken into the no more than particle of 4mm, the closed container of isolation air is subsequently placed in
In, the low temperature distillation 30min to 40min under the conditions of 500 DEG C -650 DEG C collects coal tar；
(2) alkali carries：Coal tar mixes with weak caustic solution, the pH of mixed liquor is adjusted to 6.0-8.0 and obtains alkali extract, stirring
Alkali extract extracts 0.5~1h, and precipitation is discarded after centrifugation, obtains alkali carries supernatant；
(3) acid is carried：Use 0.5MHNO3The pH to 1.0-2.0 of solution regulation alkali carries supernatant obtains sour extract, and stirring acid is carried
Immersion carries 0.5~1h, and precipitation is discarded after centrifugation, obtains acid and puts on clear liquid；
(4) freeze-drying：Clear liquid is put in acid described in freeze-drying, obtains fulvic acid powder.
Weathered coal is broken into the no more than particle of 4mm in step (1), the purpose is to make weathered coal in low temperature distillation process
Can fully crack.The particle of weathered coal is excessive, is unfavorable for the weathered coal cracking inside particle；But, weathered coal
Grain can not be too small, and the coal tar produced otherwise in low temperature distillation process easily wraps up weathering coal particle so that wrapped
The weathering coal particle wrapped up in cannot fully occur cracking reaction.Preferably, in step (1) by weathered coal be broken into 1.5~3mm
Grain.
In low temperature distillation process, it is impossible to steam or gas containing oxygen is passed through in closed container, can otherwise reduce
The recovery rate of fulvic acid in weathered coal, concrete reason is unclear, it may be possible to due to the bar that weathered coal exists in steam or oxygen
The organic matter produced under part is different and use follow-up processing step of the invention effectively cannot extract richness from this organic matter
In acid.Heretofore described fulvic acid recovery rate, refers to that the quality of the fulvic acid powder for extracting accounts for weathered coal gross mass
Percentage.
Prior art typically uses " alkali-soluble acid analysis " method when fulvic acid is extracted, and extracts the Hu Min in coal by alkali carries first
Acid and fulvic acid mixed liquor, are then carried by acid and fulvic acid are extracted from mixed liquor.The molecular weight of coal is larger, in order to the greatest extent
Amount improves the recovery rate of Humic acids and fulvic acids, general to carry out alkali carries using strong base solution, acid is carried out using strong acid solution carry.By force
Not only operational danger is high for alkali and strong acid, and the corrosivity to extraction equipment is also strong.Additionally, this " alkali-soluble acid analysis " method is to fulvic acid
Recovery rate it is relatively low.The present invention carried out low temperature distillation before alkali carries to weathered coal, can farthest by weathered coal
Organic cracking out, on the one hand, be conducive to improve from weathered coal extract fulvic acid recovery rate, on the other hand, due to
Organic matter in weathered coal cracks out to greatest extent, thus need not using highly basic and denseer acid just can fully by
Humic acids and fulvic acids in weathered coal are extracted, it is to avoid because using highly basic to the corrosion caused by extraction equipment.Preferably, walk
Suddenly the weak caustic solution in (2) is ammoniacal liquor.
Step (2) before the pH of mixed liquor is adjusted carries out alkali carries to 6.0-8.0, first by coal tar and weak caustic solution
Mixing, its purpose is mainly dilution coal tar.The concentration of coal tar is very big, if directly adjusting to 6.0- the pH of coal tar
8.0 carry out alkali carries, do not simply fail to effectively extract Humic acids and fulvic acids therein, have dissolved in the humic acid and richness in alkali extract
In sour mixed liquor also cannot be with the magazine precipitate and separate of other in coal tar.When coal tar is too small with the mass ratio of alkali extract, coal
Tar cannot effectively be diluted.When coal tar is excessive with the mass ratio of alkali extract, the content of coal tar is relatively low in alkali extract, institute
The recovery rate for obtaining fulvic acid is low, in addition, the coal tar reagent consumption that can also increase subsequent step excessive with the mass ratio of alkali extract
With the dry energy ezpenditure of purification, the wasting of resources is caused.Preferably, coal tar and the mass ratio of alkali extract are 1 in step (2)：2
~3.
In some preferred embodiments, before step (2) stirring and leaching, to adding CuCl in coal tar2Powder, to urge
Wind transmission coal oxygenolysis produce fulvic acid.With addition CuCl2Solution ratio, powdered catalyst will not substantially increase alkali carries
The quality of liquid, so as to ensure the mass ratio stabilization of coal tar and alkali extract.In addition, powdered catalyst can also reduce follow-up step
Rapid reagent consumes and purifies dry energy ezpenditure, save resources.Weathered coal low temperature distillation produces coal tar, coal gas and pyrolysis
Water etc., the yield of various products is relevant with the Parameter Conditions of the quality of weathered coal and low temperature distillation, thus weathered coal quality
The quantitative relationship not being to determine and the quality of the coal tar of generation between.During fulvic acid being extracted from weathered coal, each
The addition of component to be obtained fulvic acid recovery rate there is material impact, in order to accurately determine every kind of component addition,
And then fulvic acid recovery rate is improved, the present invention determines CuCl using the quality of coal tar as benchmark2The addition of powder.It is preferred that
Ground, CuCl2Powder is with the mass ratio of coal tar：0.02~0.05：1.
In some preferred embodiments, MnO is added in the forward direction alkali carries supernatant that step (3) stirring acid is carried2Powder.One side
Face, MnO2Powder can adsorb the humic acid in alkali carries supernatant, on the other hand, MnO2Powder is water insoluble, after absorption humic acid
MnO2Powder exists in the form of precipitating, and is easy to be separated with the liquid containing fulvic acid.Preferably, MnO2On powder and alkali carries
The mass ratio of clear liquid is：0.05:0.25:100.But MnO2The addition of powder should not be excessive, otherwise in absorption humic acid
Simultaneously can absorbed portion fulvic acid, the recovery rate of reduction fulvic acid.
The present invention will be further detailed by way of embodiment below.
Embodiment 1
The method that fulvic acid is extracted in low temperature distillation, comprises the following steps：
(1) low temperature distillation：Weathered coal is broken into the no more than particle of 0.5mm, the closed appearance of isolation air is subsequently placed in
In device, the low temperature distillation 30min to 40min under the conditions of 500 DEG C -650 DEG C collects coal tar；
(2) alkali carries：Coal tar mixes with weak caustic solution, the pH of mixed liquor is adjusted to 6.0-8.0 and obtains alkali extract, to alkali
CuCl is added in extract2Powder, CuCl2Powder is 0.03 with the mass ratio of coal tar:1；Stirring alkali extract extracts 0.5~1h, from
Precipitation is discarded after the heart, alkali carries supernatant is obtained；
(3) acid is carried：Use 0.5MHNO3The pH to 1.0-2.0 of solution regulation alkali carries supernatant obtains sour extract, to sour extract
Middle addition MnO2Powder, MnO2Powder is 0.20 with the mass ratio of alkali carries supernatant:100；The sour extract of stirring extracts 0.5~1h, from
Precipitation is discarded after the heart, acid is obtained and is put on clear liquid；
(4) freeze-drying：Clear liquid is put in acid described in freeze-drying, obtains fulvic acid powder.
The calculating of fulvic acid recovery rate：
Quality × 100/ weathered coal the quality of fulvic acid recovery rate %=fulvic acid powder.
Embodiment 2-18
In addition to content shown in table 1 below, carry out in the same manner as in Example 1.
The factor level and experimental result of table 1 each embodiment
Note：In embodiment 17*, low temperature distillation is not carried out to weathered coal；In embodiment 6, CuCl2The addition of powder is 0；
In embodiment 11, MnO2The addition of powder is 0；In embodiment 18, CuCl2Powder and MnO2The addition of powder is 0.
Although with reference to illustrative embodiments, invention has been described, but it is to be understood that the present invention does not limit to
The specific embodiment that Yu Wenzhong is described in detail and shown, in the case of without departing from claims limited range, this
Art personnel can make various changes to the illustrative embodiments.
Claims (8)
1. a kind of method that fulvic acid is extracted in low temperature distillation, it is characterised in that comprise the following steps：
(1) low temperature distillation：Weathered coal is broken into the no more than particle of 4mm, is subsequently placed in the closed container of isolation air, in
Low temperature distillation 30min to 40min under the conditions of 500 DEG C -650 DEG C, collects coal tar；
(2) alkali carries：Coal tar mixes with weak caustic solution, the pH of mixed liquor is adjusted to 6.0-8.0 and obtains alkali extract, stirs alkali carries
Immersion carries 0.5~1h, and precipitation is discarded after centrifugation, obtains alkali carries supernatant；
(3) acid is carried：Use 0.5MHNO3The pH to 1.0-2.0 of solution regulation alkali carries supernatant obtains sour extract, the sour extract extraction of stirring
0.5~1h, discards precipitation after centrifugation, obtain acid and put on clear liquid；
(4) freeze-drying：Clear liquid is put in acid described in freeze-drying, obtains fulvic acid powder.
2. the method for claim 1, it is characterised in that weathered coal is broken into the particle of 1.5~3mm in step (1).
3. the method for claim 1, it is characterised in that the weak caustic solution in step (2) is ammoniacal liquor.
4. the method for claim 1, it is characterised in that coal tar and the mass ratio of alkali extract are 1 in step (2)：2~
3。
5. the method for claim 1, it is characterised in that before step (2) stirring and leaching, adds in coal tar
CuCl2Powder.
6. method as claimed in claim 5, it is characterised in that CuCl2Powder is with the mass ratio of coal tar：0.02~0.05：
1。
7. the method for claim 1, it is characterised in that added in the forward direction alkali carries supernatant that step (3) stirring acid is carried
MnO2Powder.
8. method as claimed in claim 7, it is characterised in that MnO2Powder is with the mass ratio of alkali carries supernatant：0.05:
0.25:100。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032570.2A CN106701130B (en) | 2017-01-16 | 2017-01-16 | A kind of method that fulvic acid is extracted in low temperature distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032570.2A CN106701130B (en) | 2017-01-16 | 2017-01-16 | A kind of method that fulvic acid is extracted in low temperature distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106701130A true CN106701130A (en) | 2017-05-24 |
| CN106701130B CN106701130B (en) | 2019-07-12 |
Family
ID=58907738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710032570.2A Active CN106701130B (en) | 2017-01-16 | 2017-01-16 | A kind of method that fulvic acid is extracted in low temperature distillation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106701130B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029114A (en) * | 2020-09-23 | 2020-12-04 | 山东奥淼科技发展有限公司 | Method and device for extracting medical fulvic acid from biomass pyrolysis liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120108816A (en) * | 2011-03-25 | 2012-10-05 | 허교 | Extacting method for humic acid and fulvic acid from humic substances |
| CN103352056A (en) * | 2013-07-18 | 2013-10-16 | 内蒙古科技大学 | Co-generation method for preparing methane, fulvic acid and organic fertilizer by taking peat as raw material |
| WO2014146206A1 (en) * | 2013-03-20 | 2014-09-25 | Diacarbon Technologies Inc. | Method & apparatus for producing biochar |
| CN104987873A (en) * | 2015-05-25 | 2015-10-21 | 昆明理工大学 | Cascade utilization method of inferior lignite |
| CN105111463A (en) * | 2015-08-23 | 2015-12-02 | 唐山炬能节能科技有限公司 | Method for producing humic acid by treating biomass before steam explosion |
-
2017
- 2017-01-16 CN CN201710032570.2A patent/CN106701130B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120108816A (en) * | 2011-03-25 | 2012-10-05 | 허교 | Extacting method for humic acid and fulvic acid from humic substances |
| WO2014146206A1 (en) * | 2013-03-20 | 2014-09-25 | Diacarbon Technologies Inc. | Method & apparatus for producing biochar |
| CN103352056A (en) * | 2013-07-18 | 2013-10-16 | 内蒙古科技大学 | Co-generation method for preparing methane, fulvic acid and organic fertilizer by taking peat as raw material |
| CN104987873A (en) * | 2015-05-25 | 2015-10-21 | 昆明理工大学 | Cascade utilization method of inferior lignite |
| CN105111463A (en) * | 2015-08-23 | 2015-12-02 | 唐山炬能节能科技有限公司 | Method for producing humic acid by treating biomass before steam explosion |
Non-Patent Citations (1)
| Title |
|---|
| CRISTIANE PEREIRA DE ASSIS等: "Analytical pyrolysis of humic substances from a Latosol(Typic Hapludox) under different land uses in Minas Gerais,Brazil", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029114A (en) * | 2020-09-23 | 2020-12-04 | 山东奥淼科技发展有限公司 | Method and device for extracting medical fulvic acid from biomass pyrolysis liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106701130B (en) | 2019-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105944668A (en) | Modified biomass charcoal for treating arsenic pollution as well as preparation method and application of modified biomass charcoal | |
| Yue et al. | Improving salt leaching in a simulated saline soil column by three biochars derived from rice straw (Oryza sativa L.), sunflower straw (Helianthus annuus), and cow manure | |
| CN104258809B (en) | Modified biomass charcoal and the restorative procedure of heavy-metal contaminated soil | |
| CN103865552B (en) | A kind of method and charcoal preparing charcoal based on agriculture and forestry organic waste material | |
| CN104858229B (en) | A kind of soil-repairing agent and preparation method thereof | |
| Sardans et al. | Drought changes nutrient sources, content and stoichiometry in the bryophyte Hypnum cupressiforme Hedw. growing in a Mediterranean forest | |
| Sarrion et al. | Fate of nutrients during hydrothermal treatment of food waste | |
| CN106432368A (en) | Method of efficiently extracting fulvic acid from papermaking black liquid | |
| CN107254313A (en) | As polluted soil passivator and preparation method, the method for administering As polluted soil | |
| CN103543055A (en) | Pretreatment method for heavy metal element detection in solid sample and application of pretreatment method | |
| CN109336082B (en) | Straw treatment method, biochar and preparation method and application thereof | |
| CN108164358A (en) | A kind of preparation method of getting fat removing toxic substances type acid soil improving agent | |
| CN104841685A (en) | Method for stabilizing treatment of plants adsorbing or absorbing heavy metals | |
| CN110615437A (en) | Comprehensive utilization method of lignite | |
| CN108949188A (en) | A kind of preparation method of antibacterial passivator | |
| CN107617425A (en) | A kind of modified cocoanut shell and the method using vanadium in its reduction water body | |
| CN106701130A (en) | Method for extracting fulvic acid through low-temperature carbonization | |
| CN112980471B (en) | Method for improving content of sodium bicarbonate extracted phosphorus in animal manure biochar | |
| CN109535439A (en) | A kind of extracting method of humic acid | |
| Yuan et al. | Base cation‐enhancing role of corn straw biochar in an acidic soil | |
| CN107694519A (en) | The modified activated carbon of tetrabromobisphenol A biological effectiveness in a kind of reduction contaminated soil | |
| CN113854101A (en) | Method for utilizing waste bacterium rods to realize soil formation of copper tailings | |
| CN103585962B (en) | A kind of heavy metal ion biological adsorption agent and its preparation method and application | |
| CN113731357A (en) | Phosphorus recovery material based on biomass charcoal and preparation method thereof | |
| CN112500226A (en) | Composition for red mud modification and preparation method of composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |