CN103804076A - Method for separating humic acid in pH mode and application thereof - Google Patents

Method for separating humic acid in pH mode and application thereof Download PDF

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CN103804076A
CN103804076A CN201410026137.4A CN201410026137A CN103804076A CN 103804076 A CN103804076 A CN 103804076A CN 201410026137 A CN201410026137 A CN 201410026137A CN 103804076 A CN103804076 A CN 103804076A
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humic acids
precipitation
water
acid
supernatant liquor
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CN103804076B (en
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袁亮
赵秉强
李燕婷
李伟
王薇
林治安
温延臣
杨相东
李娟�
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Institute of Agricultural Resources and Regional Planning of CAAS
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Abstract

The invention relates to a method for separating humic acid in a pH mode and application thereof. The method comprises the following steps: extracting water-soluble humic acid, separating the water-soluble humic acid in a pH mode, and separating a precipitate L of the humic acid in the pH mode. According to the method, the distribution of the humic acid in different pH ranges can be determined, the method is an activation method for researching the structural characteristics and extraction rate of the humic acid, and method support can be provided for influence on the crop growth and fertilizer release and conversion and depth development and high-efficiency utilization of the humic acid according to the humic acid in various pH ranges.

Description

A kind of method and purposes that separates humic acids in pH mode
[technical field]
The invention belongs to chemical fertilizer auxiliary agent technical field.More specifically, the present invention relates to a kind of method that separates humic acids in pH mode, also relate to the purposes of described method.
[background technology]
The chemical fertilizer utilization ratio of China is generally lower, nitrogenous fertilizer average utilization approximately 30%, phosphate fertilizer this season utilization ratio approximately 25%, potassium utilization rate approximately 50%.Fertilizer scientific worker has carried out large quantity research to improving the methods of utilization rate of fertilizer, has obtained certain effect, but still there is production technique for fertilizer complexity, the problem such as cost is high, use is inconvenient, be difficult to apply on field crop.In recent years, under the condition how dropping in low cost, the fertilizer industry of China is carried out to technology upgrading and be transformed into study hotspot.In the past few decades, China is to fertilizer, and particularly the research of nitrogen fertilizer potentiating agent is more.These researchs mostly concentrate on the research of the chemicals such as urease inhibitor and nitrification inhibitor and apply above, less for crude substance and the applied research of modified natural material on fertile auxiliary agent, and humic acids is the important source material of exploitation Natural fertilizers auxiliary agent.
Humic acids not only can be improved soil, or good urease inhibitor and nitrification inhibitor, adds this material can obviously improve fertilizer efficiency in urea, extends the retention time of blood urea nitrogen in soil, can yet be regarded as a kind of effectively slow releasing agent of urea and synergistic agent.Humic acids can also activate by the phosphorus of soil fixing, potassium and middle trace element, improves the validity of these plant-growth essential nutrient elements.Meanwhile, the active group in humic acids, as carboxyl, phenolic hydroxyl group etc. can promote crop root growth, improves improving activity of root system, strengthens the ability of Crop nutrient.
Up to the present, the structure of the not yet clearly each humic acids component of scientific research personnel and impact, the impact on plant growth etc. that fertilizer is discharged and transformed, this has seriously hindered deep development and efficient utilization of humic acids.At present, researchist utilizes alkali-soluble acid analysis, acetone (ethanol) to extract the traditional method of classification more, the constitutional features of research humic acids etc., also there is researchist by humic acids separation, classification, obtain total humic acid, pyrotomalenic acid, yellow humic acid and 4 kinds of fractions of hymatomalenic acid (Zhao Hongyan, Zhang Zeyou, Zhao Xia, " application of humic acid in peat class material in clean coal technology ", " humic acids ", (4), 15-21(2006)).But the method for these classifications is all more extensive, be difficult to launch the further investigation to humic acids.Also have researchist to utilize the method for ultrafiltration that humic acids is divided into 8 fraction (LiL, ZhaoZ Y, Huang W L, et al. " Characterization of humic acids fraetionated by ultrafi1tration ", " Organic Geochemistry ", 35 (9), 1025-1037.(2004)), but because the difference of ultrafiltration apparatus causes the unstable result of this research method.The extensive present situation of humic acids investigative technique is directly caused to the extensive of resource of humic acid utilization, the degree of depth developing is inadequate, although the resource of humic acid of China is very abundant, but humic acids is also Nonrenewable resources, need to save and utilize, deep development, improves its utilising efficiency, gives full play to the effect of humic acids in industrial and agricultural production.
The present invention, according to humic acids different characteristic of solvability under different pH, take pH as index, separates the humic acids in weathered coal or brown coal according to different pH scopes, therefore be also referred to as " pH cutting method ".The inventor has carried out lot of experiments research work on the basis of summing up prior art, has finally completed the present invention.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of method that separates humic acids in pH mode.
Another object of the present invention is to provide the described purposes that separates humic acids method in pH mode.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of method that separates humic acids in pH mode.
The step of the method is as follows:
A, extraction fulvo acid
More than raw material weathered coal or brown coal powder are broken to 80 orders, then in reactor, according to coal dust and water weight ratio 1:4~5, described coal dust is added in water, under the condition of 40 ℃~50 ℃ of temperature, extract 5~10 minutes, then be cooled to room temperature, obtain the supernatant liquor Q that contains fulvo acid through centrifugation, its pH is W, with precipitation L.
Described weathered coal is that one is subject to weathering, and its chemistry and physical properties have all occurred very significantly to change, and have occurred that oxygen level increases, thermal value reduction and the coal that contains the considerable changes such as regeneration humic acids; Described brown coal are coals that degree of coalification is low, and its outward appearance is brown more, and gloss dimness contains higher inherent moisture and the soil ulmin of different quantities.
In the present invention, raw material weathered coal or brown coal use normally used disintegrating apparatus in coal processing technique field to pulverize, and described disintegrating apparatus is for example the pulverizer sold with trade(brand)name energy-saving ball mill of the pulverizer sold with trade(brand)name JHM elite mill of Weifang Jinghua Powder Engineering Equipment Co.Ltd, upper hamming work heavy equipment company limited, the pulverizer that Henan Zheng Ya mechanical means Manufacturing Co., Ltd sells with the energy-efficient ball milling agent of trade(brand)name.
B, with pH mode separating water-soluble humic acids
(i) under the condition stirring, contain toward described in the supernatant liquor Q of fulvo acid and drip concentration 20% inorganic acid aqueous solution by weight, by the pH regulator to 1 of the described supernatant liquor Q that contains fulvo acid, obtain containing the 1 solubilized humic acids HA at pH < through centrifugation 1supernatant liquor Q 1with precipitation L 1;
(ii) under the condition stirring, according to precipitation L 1with weight ratio 1:4~5 of water, will precipitate L 1soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 2, obtain containing at pH1~2 solubilized humic acids HA through centrifugation 2supernatant liquor Q 2with precipitation L 2;
(iii) under the condition stirring, according to precipitation L 2with weight ratio 1:4~5 of water, will precipitate L 2soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to pH value for W, obtain containing solubilized humic acids HA under pH2~W 3humic acid liquid Q 3;
C, separate humic acids precipitation L in pH mode
(i) under the condition stirring, according to weight ratio 1:4~5 of precipitation L and water, will precipitate L soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 4, obtain containing time solubilized humic acids HA in pH W~4 through centrifugation 4supernatant liquor HA 4with precipitation L 4;
(ii) under the condition stirring, according to precipitation L 4with weight ratio 1:4~5 of water, will precipitate L 4soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 4.5, obtain containing time solubilized humic acids HA in pH4~4.5 through centrifugation 4.5supernatant liquor HA 4.5with precipitation L 4.5;
According to above-mentioned steps (ii) same mode implement, from pH5.0, according to 0.5 pH unit sequence repeat implementation step (ii) n time, so obtain respectively containing solubilized humic acids HA 5+0.5nsupernatant liquor HA 5+0.5nwith precipitation L 5+0.5n, wherein n=0~16.
In aforesaid operations of the present invention, the mineral alkali of use is sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood.
In aforesaid operations of the present invention, the mineral acid of use is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
In the present invention, the equipment that heating is used is heating installation normally used in the art, that sell in the market, the reactor that for example Wuxi City Hai Da chemical machinery company limited sells with trade(brand)name electrically heated stainless steel cauldron, the reactor that Henan Wanda Chemical Equipment Co., Ltd. sells with trade(brand)name electrically heated stainless steel cauldron and steam heating stainless steel cauldron, the reactor that Zibo Tai Ji glass-lined equipment company limited sells with trade(brand)name KF type glassed steel reaction vessels.
In the present invention; centrifugal used equipment is whizzer normally used in the art, that sell in the market, the whizzer that the whizzer that for example chemical machinery Co., Ltd., Factory in Shanghai sells with trade(brand)name horizontal scraper discharging centrifuge, whizzer, the Bengbu grand pharmaceutical machine equipment company limited that You Feng mechanical means Manufacturing Co., Ltd of Zhangjagang City sells with trade(brand)name 3-foot unloading under scraper whizzer sell with trade(brand)name 3-foot unloading under scraper whizzer.
In the present invention, measuring the equipment that uses of pH value of solution is pH meter normally used in the art, that sell in the market, and pH meter that for example the desk-top pH meter 6173 of Shanghai Yi Bo Instrument Ltd. trade(brand)name is sold, Shanghai Ai Ce Electronic Science and Technology Co., Ltd. be the pH meter in trade(brand)name MP511pH sale in right Instrument Ltd. in pH meter, Shanghai of trade(brand)name A331919pH sale.
The humic acids infrared spectra obtaining under condition of different pH that adopted conventional infrared spectroscopic determination, it the results are shown in attached Fig. 1 and 2.
Can find out from Fig. 1 and Fig. 2, the humic acids in pH6.5~7 and pH12.5~13 scope is at wave number 1000cm -1~3500cm -1there is the difference of highly significant in interior spectrogram, method of the present invention can be used for studying the relation between different pH scope humic acids unit structure differences and its activity.
The invention still further relates to the method that separates humic acids in pH mode such as, at research humic acids constitutional features and molecular weight thereof, humic acids activation method methods such as () microorganism fermentation, oxidations to the purposes in humic acids extraction yield and structure influence thereof within the scope of different pH.
The invention still further relates to the purposes of the method that separates humic acids in pH mode in farming research.
Described farming research comprises the impact that the humic acids within the scope of humic acids within the scope of different pH impact, the different pH on plant growth discharges and transforms fertilizer.The impact of different pH scope humic acidss on plant growth, the impact that different pH scope humic acids discharges and transforms fertilizer, these results of study are the research and development of novel humic acid fertilizer auxiliary agent and the deep development supplying method deposit of resource of humic acid.
[beneficial effect]
The invention has the beneficial effects as follows: adopt method of the present invention can determine the distribution of humic acids in different pH scopes, for studying its constitutional features, extraction yield, the activation method of humic acids, each pH scope humic acids is on plant growth, discharge and the impact and the deep development of humic acids that transform and efficiently utilize supplying method to support fertilizer.
[accompanying drawing explanation]
Fig. 1 is the infared spectrum of humic acids in the scope of pH6.5~7.0.
Fig. 2 is the infared spectrum of humic acids in the scope of pH12.5~13.0.
[embodiment]
Can understand better the present invention by following embodiment.
Embodiment 1: separate humic acids in pH mode
The implementation step of this embodiment is as follows:
A, extraction fulvo acid
More than the raw material weathered coal that Inner Mongol Wuhai is produced is crushed to 80 orders, then in reactor, according to coal dust and water weight ratio 1:4, described coal dust is added in water, under the condition of 40 ℃ of temperature, extract 5 minutes, then be cooled to room temperature, the whizzer that uses Shanghai chemical machinery Co., Ltd., Factory to sell with trade(brand)name horizontal scraper discharging centrifuge carries out centrifugation, and the pH meter that the supernatant liquor Q(that obtains containing fulvo acid uses Shanghai Yi Bo Instrument Ltd. to sell take the desk-top pH meter 6173 of trade(brand)name is measured its pH value as 3.87) with precipitate L;
B, with pH mode separating water-soluble humic acids
(i) under the condition stirring, contain toward described in the supernatant liquor Q of fulvo acid and drip concentration 20% aqueous sulfuric acid by weight, by the pH regulator to 1 of the described supernatant liquor Q that contains fulvo acid, use above-mentioned whizzer to carry out centrifugation, obtain containing the 1 solubilized humic acids HA at pH < 1supernatant liquor Q 1with precipitation L 1;
(ii) under the condition stirring, according to precipitation L 1with the weight ratio 1:4 of water, will precipitate L 1soluble in water, re-use concentration by weight 20% aqueous sodium hydroxide solution by its pH regulator to 2, use above-mentioned whizzer to carry out centrifugation, obtain containing at pH1~2 solubilized humic acids HA 2supernatant liquor Q 2with precipitation L 2;
(iii) under the condition stirring, according to precipitation L 2with the weight ratio 1:4 of water, will precipitate L 2soluble in water, re-use concentration by weight 20% aqueous sodium hydroxide solution be 3.87 by its pH regulator to pH value, obtain containing time solubilized humic acids HA in pH2~3.87 3humic acid liquid Q 3;
C, separate humic acids precipitation L in pH mode
(i) under the condition stirring, according to the weight ratio 1:4 of precipitation L and water, will precipitate L soluble in water, re-use concentration by weight 20% aqueous sodium hydroxide solution by its pH regulator to 4, use above-mentioned whizzer to carry out centrifugation, obtain containing time solubilized humic acids HA in pH3.87~4 4supernatant liquor HA 4with precipitation L 4;
(ii) under the condition stirring, according to precipitation L 4with the weight ratio 1:4 of water, will precipitate L 4soluble in water, re-use concentration by weight 20% aqueous sodium hydroxide solution by its pH regulator to 4.5, use above-mentioned whizzer to carry out centrifugation, contain time solubilized humic acids HA in pH4~4.5 4.5supernatant liquor HA 4.5with precipitation L 4.5;
According to above-mentioned steps (ii) same mode implement, from pH5.0, according to 0.5 pH unit sequence repeat implementation step (ii) n time, so obtain respectively containing solubilized humic acids HA 5+0.5nsupernatant liquor HA 5+0.5nwith precipitation L 5+0.5n, wherein n=0~16.
Embodiment 2: separate humic acids in pH mode
The implementation step of this embodiment is as follows:
A, extraction fulvo acid
More than the raw material brown coal powder of Xilin Hot, Inner Mongolia is broken to 80 orders, then in reactor, according to coal dust and water weight ratio 1:5, described coal dust is added in water, under the condition of temperature 50 C, extract 10 minutes, then be cooled to room temperature, use the carry out centrifugation of the You Feng of Zhangjagang City mechanical means Manufacturing Co., Ltd with the sale of trade(brand)name 3-foot unloading under scraper whizzer, obtain the supernatant liquor Q that contains fulvo acid, make Shanghai Ai Ce Electronic Science and Technology Co., Ltd. measure its pH value as 3.34 take the pH meter of trade(brand)name A331919pH sale, with precipitation L;
B, with pH mode separating water-soluble humic acids
(i) under the condition stirring, contain toward described in the supernatant liquor Q of fulvo acid and drip concentration 20% aqueous hydrochloric acid by weight, by the pH regulator to 1 of the described supernatant liquor Q that contains fulvo acid, use above-mentioned whizzer to carry out centrifugation, obtain containing the 1 solubilized humic acids HA at pH < 1supernatant liquor Q 1with precipitation L 1;
(ii) under the condition stirring, according to precipitation L 1with the weight ratio 1:5 of water, will precipitate L 1soluble in water, re-use concentration by weight 20% potassium hydroxide aqueous solution by its pH regulator to 2, use above-mentioned whizzer to carry out centrifugation, obtain containing at pH1~2 solubilized humic acids HA 2supernatant liquor Q 2with precipitation L 2;
(iii) under the condition stirring, according to precipitation L 2with the weight ratio 1:4 of water, will precipitate L 2soluble in water, re-use concentration by weight 20% potassium hydroxide aqueous solution be 3.34 by its pH regulator to pH value, obtain containing time solubilized humic acids HA in pH2~3.34 3humic acid liquid Q 3;
C, separate humic acids precipitation L in pH mode
(i) under the condition stirring, according to the weight ratio 1:4 of precipitation L and water, will precipitate L soluble in water, re-use concentration by weight 20% potassium hydroxide aqueous solution by its pH regulator to 4, use above-mentioned whizzer to carry out centrifugation, obtain containing time solubilized humic acids HA in pH....~4 4supernatant liquor HA 4with precipitation L 4;
(ii) under the condition stirring, according to precipitation L 4with the weight ratio 1:4 of water, will precipitate L 4soluble in water, re-use concentration by weight 20% potassium hydroxide aqueous solution by its pH regulator to 4.5, use above-mentioned whizzer to carry out centrifugation, contain time solubilized humic acids HA in pH4~4.5 4.5supernatant liquor HA 4.5with precipitation L 4.5;
According to above-mentioned steps (ii) same mode implement, from pH5.0, according to 0.5 pH unit sequence repeat implementation step (ii) n time, so obtain respectively containing solubilized humic acids HA 5+0.5nsupernatant liquor HA 5+0.5nwith precipitation L 5+0.5n, wherein n=0~16.
Embodiment 3: separate humic acids in pH mode
The implementation step of this embodiment is as follows:
A, extraction fulvo acid
More than the raw material weathered coal of Hami Yiwu County is crushed to 80 orders, then in reactor, according to coal dust and water weight ratio 1:4.5, described coal dust is added in water, under the condition of temperature 45 C, extract 8 minutes, then be cooled to room temperature, the whizzer that uses Bengbu grand pharmaceutical machine equipment company limited to sell with trade(brand)name 3-foot unloading under scraper whizzer carries out centrifugation, obtain the supernatant liquor Q that contains fulvo acid, use the right Instrument Ltd. in Shanghai to measure its pH value as 3.60 take the pH meter of trade(brand)name MP511pH sale, with precipitation L;
B, with pH mode separating water-soluble humic acids
(i) under the condition stirring, contain toward described in the supernatant liquor Q of fulvo acid and drip concentration 20% aqueous nitric acid by weight, by the pH regulator to 1 of the described supernatant liquor Q that contains fulvo acid, use above-mentioned whizzer to carry out centrifugation, obtain containing the 1 solubilized humic acids HA at pH < 1supernatant liquor Q 1with precipitation L 1;
(ii) under the condition stirring, according to precipitation L 1with the weight ratio 1:4 of water, will precipitate L 1soluble in water, re-use concentration by weight 20% aqueous sodium carbonate by its pH regulator to 2, use above-mentioned whizzer to carry out centrifugation, obtain containing at pH1~2 solubilized humic acids HA 2supernatant liquor Q 2with precipitation L 2;
(iii) under the condition stirring, according to precipitation L 2with the weight ratio 1:4 of water, will precipitate L 2soluble in water, re-use concentration by weight 20% aqueous sodium carbonate be 3.60 by its pH regulator to pH value, obtain containing time solubilized humic acids HA in pH2~3.60 3humic acid liquid Q 3;
C, separate humic acids precipitation L in pH mode
(i) under the condition stirring, according to the weight ratio 1:4 of precipitation L and water, will precipitate L soluble in water, re-use concentration by weight 20% aqueous sodium carbonate by its pH regulator to 4, use above-mentioned whizzer to carry out centrifugation, obtain containing time solubilized humic acids HA in pH3.60~4 4supernatant liquor HA 4with precipitation L 4;
(ii) under the condition stirring, according to precipitation L 4with the weight ratio 1:4 of water, will precipitate L 4soluble in water, re-use concentration by weight 20% aqueous sodium carbonate by its pH regulator to 4.5, use above-mentioned whizzer to carry out centrifugation, contain time solubilized humic acids HA in pH4~4.5 4.5supernatant liquor HA 4.5with precipitation L 4.5;
According to above-mentioned steps (ii) same mode implement, from pH5.0, according to 0.5 pH unit sequence repeat implementation step (ii) n time, so obtain respectively containing solubilized humic acids HA 5+0.5nsupernatant liquor HA 5+0.5nwith precipitation L 5+0.5n, wherein n=0~16.
Test example 1: the impact of the different pH scope of the present invention humic acids on Maize Seedling improving activity of root system
Utilize sand culture test to study the impact of different pH scope humic acidss on Seedling Root Systems In Maize vigor.
(HA4, HA7, HA12) 4 processing prepared by conventional contrast (CK) and the embodiment of the present invention 1 are established in test, repeat 6 times.First quartz sand is cleaned with clear water, put into stainless steel pallet, keep certain humidity, corn kernel is put into dish, cover on it with wet cloth, under the condition of 25 ℃ of temperature, grow seedlings.When corn sprouts while growing to 3-5cm, corn is taken out and puts into the cultivation cup that fills with quartz sand, watered the humic acid solution of 25mL concentration 0.1 % by weight every 2 days, CK is 25mL pure water.In the time that corn grows to 20cm left and right, take out root system, clean with clear water, adopt TTC method (reference: Zhang Xiong, " use " TTC " method (TCC) is measured vigor and the application thereof of wheat root and pollen ", " Plant Physiology Communications ", the 3rd phase of nineteen eighty-two) measure the improving activity of root system of corn.
Its test-results is listed in the table below in 1.
Table 1: Root Activity in Maize (mg/gh, TTC method)
Process Improving activity of root system
CK 0.980
HA4 1.732
HA7 1.471
HA12 1.105
Test-results shows, contrasts and compares with routine, and the humic acids of different pH scopes can improve the improving activity of root system of Maize Seedling, HA 4, HA 7, HA 12exceed 76.7%, 50.1% and 12.8% than contrast respectively.See thus, increase with the pH that dissolves humic acids, its increase rate to Root Activity in Maize reduces gradually, and this may be relevant from the component difference of different pH scope humic acidss.

Claims (6)

1. separate a method for humic acids in pH mode, it is characterized in that the step of the method is as follows:
A, extraction fulvo acid
More than raw material weathered coal or brown coal powder are broken to 80 orders, then in reactor, according to coal dust and water weight ratio 1:4~5, described coal dust is added in water, under the condition of 40 ℃~50 ℃ of temperature, extract 5~10 minutes, then be cooled to room temperature, obtain the supernatant liquor Q that contains fulvo acid through centrifugation, its pH is W, with precipitation L;
B, with pH mode separating water-soluble humic acids
(i) under the condition stirring, contain toward described in the supernatant liquor Q of fulvo acid and drip concentration 20% inorganic acid aqueous solution by weight, by the pH regulator to 1 of the described supernatant liquor Q that contains fulvo acid, obtain containing the 1 solubilized humic acids HA at pH < through centrifugation 1supernatant liquor Q 1with precipitation L 1;
(ii) under the condition stirring, according to precipitation L 1with weight ratio 1:4~5 of water, will precipitate L 1soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 2, obtain containing at pH1~2 solubilized humic acids HA through centrifugation 2supernatant liquor Q 2with precipitation L 2;
(iii) under the condition stirring, according to precipitation L 2with weight ratio 1:4~5 of water, will precipitate L 2soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to pH value for W, obtain containing solubilized humic acids HA under pH2~W 3humic acid liquid Q 3;
C, separate humic acids precipitation L in pH mode
(i) under the condition stirring, according to weight ratio 1:4~5 of precipitation L and water, will precipitate L soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 4, obtain containing time solubilized humic acids HA in pHW~4 through centrifugation 4supernatant liquor HA 4with precipitation L 4;
(ii) under the condition stirring, according to precipitation L 4with weight ratio 1:4~5 of water, will precipitate L 4soluble in water, re-use concentration by weight 20% inorganic base aqueous solution by its pH regulator to 4.5, obtain containing time solubilized humic acids HA in pH4~4.5 through centrifugation 4.5supernatant liquor HA 4.5with precipitation L 4.5;
(iii) implement according to the mode same with above-mentioned steps (ii), from pH5.0, according to 0.5 pH unit sequence repeat implementation step (ii) n time, so obtain respectively containing solubilized humic acids HA 5+0.5nsupernatant liquor HA 5+0.5nwith precipitation L 5+0.5n, wherein n=0~16.
2. method according to claim 1, is characterized in that described mineral alkali is sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood.
3. method according to claim 1, is characterized in that described mineral acid is sulfuric acid, hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
According to the method described in any one claim in claim 1-3 at research humic acids constitutional features and molecular weight thereof, humic acids activation method to the purposes in humic acids extraction yield and structure influence thereof.
5. the purposes in farming research according to the method described in any one claim in claim 1-3.
6. purposes according to claim 5, is characterized in that described farming research comprises the impact of humic acids on plant growth, the impact that fertilizer is discharged and transformed.
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CN105130535A (en) * 2015-08-10 2015-12-09 山西广宇通科技股份有限公司 Preparation method of humic acid solid water soluble fertilizer
CN105176536A (en) * 2015-09-15 2015-12-23 江苏锦宇环境工程有限公司 Preparation method of weathered coal humic acid water retention agent
CN107968233A (en) * 2017-11-27 2018-04-27 大同新成新材料股份有限公司 A kind of battery additive containing humic acid and preparation method thereof
CN109337726A (en) * 2018-08-24 2019-02-15 黑龙江科技大学 A kind of lignite process equipment
CN109912365A (en) * 2017-12-13 2019-06-21 赵月平 A kind of production method of fulvo acid
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CN102504277A (en) * 2011-11-04 2012-06-20 吕玉环 Innovative process technology for producing humate with weathered coal

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CN105130535A (en) * 2015-08-10 2015-12-09 山西广宇通科技股份有限公司 Preparation method of humic acid solid water soluble fertilizer
CN105061116A (en) * 2015-08-27 2015-11-18 山西广宇通科技股份有限公司 Liquid humic acid water-soluble fertilizer production method
CN105176536A (en) * 2015-09-15 2015-12-23 江苏锦宇环境工程有限公司 Preparation method of weathered coal humic acid water retention agent
CN107968233A (en) * 2017-11-27 2018-04-27 大同新成新材料股份有限公司 A kind of battery additive containing humic acid and preparation method thereof
CN109912365A (en) * 2017-12-13 2019-06-21 赵月平 A kind of production method of fulvo acid
CN110092683A (en) * 2018-01-27 2019-08-06 内蒙古际美生物技术有限公司 One kind is rich in sulphur humic acid liquid fertilizer and preparation method thereof
CN109337726A (en) * 2018-08-24 2019-02-15 黑龙江科技大学 A kind of lignite process equipment
CN109337726B (en) * 2018-08-24 2019-06-04 黑龙江科技大学 A kind of lignite process equipment

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