CN106432368A - Method of efficiently extracting fulvic acid from papermaking black liquid - Google Patents
Method of efficiently extracting fulvic acid from papermaking black liquid Download PDFInfo
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- CN106432368A CN106432368A CN201610847821.8A CN201610847821A CN106432368A CN 106432368 A CN106432368 A CN 106432368A CN 201610847821 A CN201610847821 A CN 201610847821A CN 106432368 A CN106432368 A CN 106432368A
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- black liquid
- fulvic acid
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- acid substance
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- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to a method of efficiently extracting fulvic acid from papermaking black liquid. The method includes: sequentially adding a protective agent, an oxidant and a catalyst into the papermaking black liquid, rising temperature to 60-90 DEG C while stirring, allowing reaction for 30-90 min, and using an acidizing solution to adjust pH of mixed liquid to 2-3; centrifuging the mixed liquid at a high speed of 6000r/min for 30 min; standing, performing vacuum suction filtering, and removing precipitation impurities to obtain a fulvic acid solution of 37-40% in concentration (calculated according to mass percentage). By the method, the black liquid which is the most major pollutant in papermaking industry can be fully recycled, environment pollution caused by the black liquid and pollution treatment cost are lowered, and good environment benefit is acquired; the fulvic acid prepared at the same time has wide application prospect in agriculture.
Description
First, technical field
The present invention relates to the use of black liquid and extract fulvic acid substance, belong to agricultural resource and fertilizer synergist application neck
Domain.
2nd, background technology
Fulvic acid is a kind of small-molecule substance containing multiclass heterocycles such as phenyl ring, thick phenyl ring, and its ring and side chain include
The various active such as phenolic hydroxyl group, COOH, cyclohexyl methoxy, ketone group functional group, has obvious stimulation growth promoting function to plant, thus its
Agriculturally there is application widely.The primary raw material preparing fulvic acid at present both at home and abroad is peat, weathered coal and brown coal
The subject matter existing Deng, these raw materials and its extracting method is that fulvic acid content is low, extracts high with preparation cost；Extraction used
Agent is substantially concentrated acid or concentrated base, and the molecular structure to fulvic acid or active group can cause over oxidation or destruction, thus dropping
The low biologically active of extract, thus be difficult to agriculturally extensively applying.In order to overcome these shortcomings researcher to open
Open up substantial amounts of research work, begun attempt to be extracted from agricultural wastes and the technology being prepared fulvic acid.
China is production of paper products and consumption big country, and paper mill is produced using wheat straw waste and produces substantial amounts of papermaking after paper
Black liquor, processes or purifies the relatively costly of black liquid input, has had a strong impact on or has limited paper industry health, persistently sent out
Exhibition.The process of black liquid is one and had not only consumed energy but also the engineering of cost, and research finds to contain substantial amounts of fulvic acid in black liquid
Class material.If a kind of cost-efficiently extracting method can be developed, both can reach the purpose of recycling waste, solution
Certainly the difficult point in paper industry, can play its effect again, promote Agriculture Production.
The method preparing fulvic acid at present on the market mainly has：
1st, alkali-soluble acid analysis.The principle that alkali-soluble acid analysis method prepares fulvic acid is that humic acid is dissolved in alkali insoluble in acid, and fulvic acid was both
It is dissolved in alkali and is dissolved in acid again, and ulmic acid had not both dissolved in acid insoluble and alkali yet.So with alkali lye by fulvic acid and humic acid from raw material
In separate, then mixed liquor is acidified, humic acid can be made to precipitate, be finally centrifuged at a high speed solid-liquid, then pass through vacuum
Suction filtration goes the removal of impurity, you can obtain the solution of fulvic acid.
Alkali-soluble acid analysis method is mainly used in extracting fulvic acid from weathered coal, peat, and the method extraction fulvic acid content is low, effect
Rate is poor, and soda acid consumption is big, easily produces over oxidation to the fulvic acid of small molecule, leads to the biologically active of product poor.
2nd, fermentation method.Early in early 1990s, China can be mainly used in by fermentation to produce fulvic acid
Foliage fertilizer.Conventional method is to obtain humic acid using agricultural residue such as straw dust etc. by microbial fermentation technology, then passes through
Isolate and purify and obtain fulvic acid.Dariellys Martinez-Balmori et al. utilizes cow dung, bagasse, sunflower oil cake etc.
With earthworm mixed fermentation.
Fermentation method prepares that fulvic acid speed is slow, time length, recovery rate are low, and the fulvic acid impurity being obtained is many, and concentration is impure.
3rd, ion-exchange-resin process.It is critical only that of ion-exchange selects suitable ion-exchanger and absorption, drip washing
Condition.In exchanger, the size of the property of cation exchange groups, the degree of cross linking, granularity and exchange capacity has important shadow to exchange process
Ring.Add complexing agent can improve the selectivity of ion-exchange, to obtain better separating effect toward in solution.In raw material
Fulvic acid inorganic salts ash content and fulvic acid metal ion can occur migrate and with acid-type ion-exchange resin in hydrogen ion
Ion exchange is occurred to discharge fulvic acid.
But ion exchange prepare fulvic acid complex process, high cost, recovery rate are low, be difficult to technology produce it is impossible to
Agriculturally extensively apply.
3rd, content of the invention
In order to solve the above problems, the invention provides a kind of side of high efficiency extraction fulvic acid substance from black liquid
Method；It is that a kind of method of addition protective agent, oxidant and catalyst etc. in black liquid prepares fulvic acid；The present invention is first
It is initially charged protective agent, the small molecule fulvic acid substance that former black liquid contains can be protected, prevent over oxidation from making
Become to destroy；Then, add oxidant and catalyst, the material oxidation of macromolecular becomes small molecule by macromolecular, increases simultaneously
Add active group；Then extract again, realize the technology breakthrough that high efficiency, low cost extracts fulvic acid substance.
A kind of method of high efficiency extraction fulvic acid substance from black liquid, its step is as follows：
Black liquid is concentrated into the concentrated black liquid that solid content is 40%-60% (mass percent)；Concentrated black liquid first adds
Enter protective agent to be quickly uniformly mixed, protective agent addition is the 1 ‰ -5 ‰ of concentrated black liquid weight ratio；Again in above-mentioned mixed liquor
Add oxidant, add oxidant 1g in every 200-500ml concentrated black liquid, be sufficiently mixed；Add catalyst to stir and evenly mix immediately,
Catalyst 1g is added in every 20000-50000ml concentrated black liquid；It is warming up to 60 DEG C -90 DEG C, after reaction 30-90 minute in whipping process
Adjusting pH of mixed with souring soln is 2-3；By mixed liquor 6000r/min high speed centrifugation 30 minutes；Carry out vacuum after standing to take out
Filter, removes precipitated impurities, obtains the fulvic acid substance solution that concentration is 37%-40% (calculating according to mass percent).
Described black liquid is the black liquor being obtained for raw material through neutral ammonium sulfite process with various agricultural crop straws.Make
Solid content in paper black liquor, organic matter accounts for 65%-70%, mainly lignin and hemicellulose, pectin, polysaccharide and its difference
The degradation material of degree.
Described protective agent is sodium sulfite, ferrous sulfate, iron ammonium sulfate, Tea Polyphenols, butylated hydroxy anisole, dibutyl
The mixture of one or more of hydroxy-methylbenzene, TBHQ；
Described oxidant is potassium peroxydisulfate, ammonium persulfate, two or more the mixture in potassium permanganate；
Described catalyst is two or more the mixture such as manganese dioxide, potassium nitrate, platinum, copper；
Described souring soln is the dilute sulfuric acid of 2mol/L or watery hydrochloric acid for concentration.
In the present invention, protective agent is antioxidant, can be with bases such as the hydroxyl in small-molecule substance, carboxyl, sulfonic groups
Group combines, and prevents excessively oxidated；It is to use strong oxidizer oxygen that chemical oxidization method (catalyst is combined with oxidant) prepares fulvic acid
The macromolecular substances such as the lignin in change black liquor and cellulose, are changed into small-molecule substance by macromolecular, increased little point simultaneously
Active group number in sub- material.
It is an advantage of the current invention that：
1. extract, for raw material, the pollution that fulvic acid can reduce paper technology using black liquid, promote agricultural resource circulation
Using.
2. adopt black liquid to replace the materials such as common weathered coal, brown coal, both can increase the yield of fulvic acid, may be used again
To reduce production cost.
3. the transform mode of black liquor is the first method with protective agent oxidizer oxidation again, have that recovery rate is high, the time is short,
Energy consumption is low, preparation process is simple, the feature more than prepared fulvic acid substance active function groups.
The present invention can allow the maximum pollutant black liquor of paper industry obtain sufficient recycling, reduces it to environment
Pollution and process pollution cost, there is good environmental benefit；The fulvic acid substance simultaneously prepared agriculturally has
Wide application prospect.
4th, brief description
Fig. 1 is the flow chart of the present invention；
In figure 1 is black liquid；Black liquid is concentrated by 2；3 add protective agent, oxidant and catalyst successively；4 heating
And stirring reaction；5 acidifyings；6 carry out high speed centrifugation, vacuum filtration separation solid-liquid；7 obtain product；8 impurity；9 packagings, storage.
5th, specific embodiment
Embodiment 1：
The black liquor that paper mill is produced concentrates as the material 40%-60% (percent mass such as containing cellulose, hemicellulose
Number calculate) concentrated black liquor, be firstly added sodium sulfite, ferrous sulfate, iron ammonium sulfate, Tea Polyphenols, butylated hydroxy anisole
According to weight than for 1:1:1:1:1 mixture (protective agent), addition be described concentrate after black liquid weight 1 ‰, soon
Speed is uniformly mixed；It is subsequently adding potassium peroxydisulfate and potassium permanganate weight than for 1:2 mixture (oxidant), addition with
Black liquor ratio after concentration is 1g：200-500ml, is sufficiently mixed.The mixing of manganese dioxide, potassium nitrate and platinum is added after mixing
Catalyst, in this mixed catalyst, the mass ratio of manganese dioxide, potassium nitrate and platinum is 1:1:1 mixture, stirs and evenly mixs immediately,
This mixed catalyst and concentrated black liquor ratio are 1g：20000-50000ml.During being stirred continuously, it is warming up to 50 DEG C, react 90
Minute, adjusting pH value of solution with dilute sulfuric acid after question response is complete is 2-3, high speed centrifugation 30 minutes；Carry out vacuum filtration after standing, go
Fall precipitated impurities, obtain the fulvic acid substance solution that concentration is about 37%-40% (calculating according to mass percent), this solution
The molecular weight of middle fulvic acid is concentrated mainly on 30-60kDa, and total acidic group is about 12mmol/g.Prove through lot of experiments, utilize
The fulvic acid substance solution of this method preparation carries out fertigation on cotton and is not added with this fulvic acid substance solution control
Relatively about 15% can be increased production；This fulvic acid substance is carried out on Chinese cabbage foliage-spray and compares with clear water can increasing production about
30%.
Embodiment 2：
The material 40%-60% such as pulp concentrating black liquor containing cellulose that paper mill is produced, hemicellulose are (by percent mass
Number calculates) concentrated black liquid, be firstly added protective agent, this protective agent by sodium sulfite, ferrous sulfate according to weight ratio for 1:1 is carried out
Mixing, after addition about concentration, the 5 ‰ of black liquid weight, are quickly uniformly mixed；It is subsequently adding potassium peroxydisulfate and height
The weight of potassium manganate is than for 1:2 mixtures (oxidant), after adding weight and concentrating, the ratio of black liquid is 1g：200-
500ml, is sufficiently mixed.Add mixed catalyst, this mixed catalyst by manganese dioxide, potassium nitrate and copper according to weight ratio is
1:1:1 mixing, stirs and evenly mixs immediately, and catalyst and concentrated black liquid ratio are 1g：20000-50000ml.During being stirred continuously,
Need to be warming up to 90 DEG C, react 30 minutes, adjusting pH value of solution with dilute sulfuric acid after question response is complete is 2-3, high speed centrifugation 30 minutes；
Carry out vacuum filtration after standing, remove precipitated impurities, obtain the Huang that concentration is about 37%-40% (calculating according to mass percent)
Rotten acid solution, in this solution, the molecular weight of fulvic acid is concentrated mainly on 30-60kDa, and total acidic group is about 12mmol/
g.Prove through lot of experiments, the fulvic acid substance solution using this method preparation carries out fertigation on cotton and is not added with this
Fulvic acid substance solution control relatively can increase production about 15%；This fulvic acid substance carry out on Chinese cabbage foliage-spray with clear
Water comparison can increase production about 30%.
Embodiment 3：
It is 40%-60% (according to matter that the black liquor that paper mill is produced concentrates as materials such as containing cellulose, hemicelluloses
Amount percentage calculate) concentrated black liquor, be firstly added by sodium sulfite, ferrous sulfate, iron ammonium sulfate, TBHQ
According to weight than for 1:1:1:1 protective agent being mixed with, after addition about concentration, the 2 ‰ of black liquid weight, quickly stir
Mix and mix；It is subsequently adding by potassium peroxydisulfate, ammonium persulfate and potassium permanganate according to weight than for 1:1:2 mixed oxidization
Agent, after adding weight and concentrating, the ratio of black liquid is 1g：200-500ml, is sufficiently mixed.Add by manganese dioxide, nitre
Sour potassium is according to weight than for 1:1 mixed catalyst, stirs and evenly mixs immediately, and catalyst and concentrated black liquid ratio are 1g：20000-
50000ml.During being stirred continuously, need to be warming up to 70 DEG C, react 50 minutes, after question response is complete, adjust solution with dilute sulfuric acid
PH is 2-3, high speed centrifugation 30 minutes；Carry out vacuum filtration after standing, remove precipitated impurities, obtain concentration and be about 37%-40%
The fulvic acid substance solution of (calculating according to mass percent), in this solution, the molecular weight of fulvic acid is concentrated mainly on 30-
60kDa, total acidic group is about 12mmol/g.Prove through lot of experiments, will be molten for the fulvic acid substance prepared using this method
Liquid carries out fertigation on cotton and is not added with this fulvic acid substance solution ratio and can increase production about 15%；This xanthohumic acid kind thing
Matter carries out foliage-spray and compares with clear water increasing production about 30% on Chinese cabbage.
Embodiment 4：
The black liquor that paper mill is produced concentrates as the material 40%-60% such as containing cellulose, hemicellulose (according to weight
Percentage calculates) concentrated black liquor, be firstly added by sodium sulfite, ferrous sulfate according to weight ratio as 1:1 hybrid protection agent,
After addition about concentration, the 3 ‰ of black liquid weight, are quickly uniformly mixed；It is subsequently adding by potassium peroxydisulfate and persulfuric acid
Ammonium is according to weight than for 1:1 hybrid oxidant, adds weight and the ratio of concentrated black liquid to be about 1g：200-500ml, fully mixed
Close.Add by manganese dioxide and potassium nitrate according to weight than for 1:1 mixed catalyst stirs and evenly mixs immediately, catalyst with dense
Black liquor ratio is 1g：20000-50000ml.During being stirred continuously, need to be warming up to 60 DEG C, react 40 minutes, question response is complete
Adjusting pH value of solution with dilute sulfuric acid after complete is 2-3, high speed centrifugation 30 minutes；Carry out vacuum filtration after standing, remove precipitated impurities, obtain
It is about the fulvic acid substance solution of 37%-40% (calculating according to mass percent) to concentration, in this solution, fulvic acid divides
Son amount is concentrated mainly on 30-60kDa, and total acidic group is about 12mmol/g.Prove through lot of experiments, using this xanthohumic acid kind thing
Matter is prepared solution and is carried out fertigation on cotton and be not added with fulvic acid and compare increasing production about 15%；This fulvic acid substance exists
Foliage-spray carried out on Chinese cabbage compare with clear water increasing production about 30%.
Claims (5)
1. a kind of method of high efficiency extraction fulvic acid substance from black liquid is it is characterised in that step is as follows：
Black liquid is concentrated into the concentrated black liquid that solid content is mass percent 40%-60%；It is initially charged protection in concentrated black liquid
Agent is quickly uniformly mixed, and protective agent addition is the 1 ‰ -5 ‰ of concentrated black liquid weight ratio；Oxygen is added again in above-mentioned mixed liquor
Agent, adds oxidant 1g in every 200-500ml concentrated black liquid, is sufficiently mixed；Add catalyst to stir and evenly mix immediately, often
Catalyst 1g is added in 20000-50000ml concentrated black liquid；It is warming up to 60 DEG C -90 DEG C in whipping process, use after reaction 30-90 minute
It is 2-3 that souring soln adjusts pH of mixed；By mixed liquor 6000r/min high speed centrifugation 30 minutes；Carry out vacuum filtration after standing,
Remove precipitated impurities, obtain the fulvic acid substance solution that concentration is 37%-40%.
2. as claimed in claim 1 a kind of method of high efficiency extraction fulvic acid substance from black liquid it is characterised in that
Described protective agent is sodium sulfite, ferrous sulfate, iron ammonium sulfate, Tea Polyphenols, butylated hydroxy anisole, butylated hydroxy-a
The mixture of one or more of benzene and TBHQ.
3. as claimed in claim 1 a kind of method of high efficiency extraction fulvic acid substance from black liquid it is characterised in that
Described oxidant is two or more the mixture in potassium peroxydisulfate, ammonium persulfate and potassium permanganate.
4. as claimed in claim 1 a kind of method of high efficiency extraction fulvic acid substance from black liquid it is characterised in that
Described catalyst is two or more the mixture in manganese dioxide, potassium nitrate, platinum and copper.
5. as claimed in claim 1 a kind of method of high efficiency extraction fulvic acid substance from black liquid it is characterised in that
Described souring soln is the dilute sulfuric acid of 2mol/L or watery hydrochloric acid for concentration.
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| CN106906261A (en) * | 2017-05-10 | 2017-06-30 | 山东农业大学 | A kind of method that utilization biofermentation extracts biochemical fulvic acid from black liquid |
| CN107987283A (en) * | 2017-12-05 | 2018-05-04 | 曲靖师范学院 | A kind of method of photochemical catalyst activation lignite extraction Xanthohumate |
| CN109183480A (en) * | 2018-09-06 | 2019-01-11 | 白博 | A kind of acid Ammonium Sulfite Method production technology preparing fulvic acid and high-strength corrugated paper slurry using non-wood fiber as raw material |
| CN110105407A (en) * | 2019-04-17 | 2019-08-09 | 上海应用技术大学 | A method of degradation humic acid and ulmic acid are to prepare fulvic acid |
| CN110495351A (en) * | 2019-09-20 | 2019-11-26 | 黔西南州丰宇农业发展有限公司 | A kind of cultivation of agaricus bisporus matrix and preparation method thereof |
| CN110575680A (en) * | 2019-09-19 | 2019-12-17 | 福建启元堂生物技术有限公司 | Method for double super-extraction of marine nutrients |
| CN111996827A (en) * | 2020-09-03 | 2020-11-27 | 大禾(上海)环保科技有限公司 | Fulvic acid activity improving method for co-producing high-strength corrugated paper pulp |
| TWI765137B (en) * | 2018-01-29 | 2022-05-21 | 日商Ｇ ８國際貿易股份有限公司 | The manufacture method of fulvic acid iron solution, fulvic acid ferric hydroxide solution and fulvic acid polyiron silicate solution |
| CN114702339A (en) * | 2022-02-11 | 2022-07-05 | 东华大学 | Method for preparing fulvic acid and active organic fertilizer by using lignin |
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| CN106906261A (en) * | 2017-05-10 | 2017-06-30 | 山东农业大学 | A kind of method that utilization biofermentation extracts biochemical fulvic acid from black liquid |
| CN107987283A (en) * | 2017-12-05 | 2018-05-04 | 曲靖师范学院 | A kind of method of photochemical catalyst activation lignite extraction Xanthohumate |
| CN107987283B (en) * | 2017-12-05 | 2020-05-26 | 曲靖师范学院 | Method for extracting fulvic acid salt by activating lignite with photocatalyst |
| TWI765137B (en) * | 2018-01-29 | 2022-05-21 | 日商Ｇ ８國際貿易股份有限公司 | The manufacture method of fulvic acid iron solution, fulvic acid ferric hydroxide solution and fulvic acid polyiron silicate solution |
| CN109183480A (en) * | 2018-09-06 | 2019-01-11 | 白博 | A kind of acid Ammonium Sulfite Method production technology preparing fulvic acid and high-strength corrugated paper slurry using non-wood fiber as raw material |
| CN110105407A (en) * | 2019-04-17 | 2019-08-09 | 上海应用技术大学 | A method of degradation humic acid and ulmic acid are to prepare fulvic acid |
| CN110105407B (en) * | 2019-04-17 | 2021-12-07 | 上海应用技术大学 | Method for preparing fulvic acid by degrading fulvic acid and ulmic acid |
| CN110575680A (en) * | 2019-09-19 | 2019-12-17 | 福建启元堂生物技术有限公司 | Method for double super-extraction of marine nutrients |
| CN110495351A (en) * | 2019-09-20 | 2019-11-26 | 黔西南州丰宇农业发展有限公司 | A kind of cultivation of agaricus bisporus matrix and preparation method thereof |
| CN111996827A (en) * | 2020-09-03 | 2020-11-27 | 大禾(上海)环保科技有限公司 | Fulvic acid activity improving method for co-producing high-strength corrugated paper pulp |
| CN114702339A (en) * | 2022-02-11 | 2022-07-05 | 东华大学 | Method for preparing fulvic acid and active organic fertilizer by using lignin |
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