CN104628792B - A kind of method that utilization wheat stalk prepares humic acidss - Google Patents
A kind of method that utilization wheat stalk prepares humic acidss Download PDFInfo
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- CN104628792B CN104628792B CN201310659335.XA CN201310659335A CN104628792B CN 104628792 B CN104628792 B CN 104628792B CN 201310659335 A CN201310659335 A CN 201310659335A CN 104628792 B CN104628792 B CN 104628792B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The present invention relates to method prepared by humic acidss, the method that specifically a kind of utilization wheat stalk prepares humic acidss.With wheat stalk be raw material first through high temperature cabonization, then nitric acid activation eventually passes alkali liquor and extracts sulfuric acid precipitation and prepare humic acidss.With wheat straw pavilion as raw material, China is large agricultural country to the present invention, and Semen Tritici aestivi is staple crops, so raw material sources are extensive and with low cost；The agricultural humic acidss for preparing are carried out biological organic fertilizer processing, are re-applied and resource circulation utilization are achieved in crops.The present invention prepares the extraction of humic acidss and carries out at ambient temperature, and mild condition is easy to operate.
Description
Technical field
The present invention relates to method prepared by humic acidss, specifically a kind of utilization wheat stalk prepares the side of humic acidss
Method.
Background technology
Shi Ge large agricultural countries of China, Semen Tritici aestivi are a kind of staple crops again, and annual stalk resource total amount reaches several hundred million tons.20 generation
Record before the middle period, wheat stalk is mainly used as life fuel, fertilizer and feedstuff.But with coal, oil liquefied gas fuel general
And and fertilizer application amount increase, cause to make a large amount of cumulatives of rural area wheat stalk.The utilization rate of straw from village is less than at present
2%, remaining is all dropped or on-site incineration, and many place dense smokes shroud and even result in road traffic accident or affect to take off.
The resource of preciousness is not only wasted, and causes environmental pollution.Therefore, the disposal of wheat stalk and effectively utilizes have become society
Problem demanding prompt solution and the focus of experts and scholars' research.
Humic acidss（Humic acid, abridge HA）Animals and plants remains, mainly remains of plant, through microorganism point
Solution and conversion, and a series of type organic matter that geochemical process are caused and accumulated.It mainly by aromatic series and
The polymeric organic acid that its multiple functional group is constituted, with functions such as good physiologically active and absorption, complexation, exchanges.Rotten plant
Acid is widely used in the every field such as Agriculture, forestry And Animal Husbandry, oil, chemical industry, building materials, medical and health, environmental protection as organic matter raw material.In recent years
To advocate ecological agriculture construction, pollution-less agriculture production, pollution-free food, pollution-free environment-friendly products etc., humic acidss are with its uniqueness
Characteristic, becomes a kind of indispensable organic fertilizer in agricultural production.
Due to the molecular structure of humic acidss sufficiently complex and unstable, so being still unable to synthetic so far.Current China
Agricultural humic acidss mostly are peat, weathered coal, extract in brown coal, but its preparations need to exploit natural resourcess, easily cause environmental pollution with
Ecological disruption.Existing oxidation from straw prepares the shortcoming of the technique presence of humic acidss to be had:Reaction uses the phase long, is catalyzed acid concentration
Height, low yield, heat time heating time are long, the problems such as energy waste.Humic acidss are produced by straw and mostly is fermentation method, by microflora degradation straw
Humic acidss are extracted behind pavilion, and the cycle is long, and condition is harsh, and unstable products.
Content of the invention
The purpose of the present invention is a kind of method that utilization wheat stalk prepares humic acidss.
For achieving the above object, the technical solution used in the present invention is：
A kind of method that utilization wheat stalk prepares humic acidss, is raw material first through high temperature cabonization with wheat stalk, then nitre
Acid activation, eventually passes alkali liquor and extracts sulfuric acid precipitation and prepare humic acidss.
Further, the wheat stalk of pulverization process is obtained black solid-Semen Tritici aestivi in the pyrolysis of tubular type carbide furnace biological
Charcoal, Semen Tritici aestivi charcoal carry out activation processing, sink through alkali carries acid and prepare humic acidss after process.
The wheat stalk of the pulverization process is by cleaned for wheat stalk, drying, crushes, and crosses 20 mesh sieves standby；Wherein
It is 35-45% wheat stalks that wheat stalk is content of cellulose.
The wheat stalk of the pulverization process is placed in tubular type carbide furnace, is led to in tube furnace with the flow velocity of 0.5-1L/min
N2With emptying furnace air；In-furnace temperature is warming up to 400-500 DEG C with the heating rate of 10-15 DEG C/min again then, then
Insulation is pyrolyzed 2-4 hours at this temperature；Room temperature is cooled to, black solid-Semen Tritici aestivi charcoal is obtained.
10-15% is added in the black solid-Semen Tritici aestivi charcoal（Mass percent）Nitric acid shake in 80 degree of water-baths
Swing oxidation 2-4h；Sample pH=5-7 is debugged with ammonia after oxidation, sucking filtration is carried out by 0.45 μm of filter paper then, post-drying is standby.
Wherein, black solid-Semen Tritici aestivi charcoal and nitric acid are according to mass volume ratio 1 (g):10-20（ml）Ratio mixing.
1-1.5% is added in charcoal after the oxidized activating process（Mass percent）NaOH solution, then in 80-
1-2h is shaken under conditions of 100 DEG C；The solution of humic acidss is obtained after concussion with 0.45 μm of filter membrane sucking filtration；By solution sulfur acid for adjusting pH
=1-2, stands overnight；Finally humic acidss solid sample is obtained with 0.45 μm of filter membrane sucking filtration.Wherein, charcoal after oxidized activating is processed
With NaOH solution according to mass volume ratio 1 (g):100-200（ml）Ratio mixing.
The sulfuric acid concentration is 1-2M.With wheat stalk be raw material first through high temperature cabonization, then nitric acid activation, eventually passes
Alkali liquor extracts sulfuric acid precipitation and prepares humic acidss, specially：
Advantage for present invention:
1. raw material low value is easy to get:With wheat straw pavilion as raw material, China is large agricultural country, and Semen Tritici aestivi is staple crops, so
Raw material sources are extensive and with low cost；The agricultural humic acidss for preparing are carried out biological organic fertilizer processing, is re-applied in crops
Achieve resource circulation utilization.
2. the yield of humic acidss greatly improved：2%, after the carbonization using the present invention is less than before the non-carbonization of Humic Acid Production Rate
Humic Acid Production Rate is up to more than 20%.And then using the high temperature carbonization technology of the present invention, it is achieved that raw material main body chemical constitution
From aliphatic category material to the conversion of fragrant same clan's material, and aromatic structure is the parent nucleus of humic acidss, therefore significantly can carry
The yield of high straw humic acidss.
3. humic acidss stability is prepared strong, fertilizer efficiency is permanent.High temperature carbonization of the present invention is achieved in raw material and is easily reduced fat
Same clan's material is converted into stable fragrant same clan's material（Fig. 2）, and fragrant same clan's material have than aliphatic category material higher
Stability, the humic acidss that therefore prepared by the technique are more stable, and fertilizer efficiency is more longlasting, it is achieved that the long-acting utilization of humic acidss.
4. the present invention prepares the extraction of humic acidss and carries out at ambient temperature, and mild condition is easy to operate.
Description of the drawings
Fig. 1 is the flow chart that utilization wheat stalk provided in an embodiment of the present invention prepares humic acidss.
Fig. 2 is the infrared spectrogram of the humic acidss for preparing gained using the present invention provided in an embodiment of the present invention.
Specific embodiment
Embodiment 1
The method for preparing humic acidss：
1）Raw material adopts content of cellulose for 32%, hemicellulose level 21%, the wheat straw of content of lignin 15%
Stalk；
2）By cleaned for above-mentioned wheat stalk, drying, crush, cross 20 mesh sieves standby；
3）Wheat stalk 100.0g after crushing is pyrolyzed in electron tubes type carbide furnace, with the flow velocity of 0.5L/min to tube furnace
In lead to N2With emptying furnace air；Stove is warming up to 400 DEG C with the heating rate of 10 DEG C/min again then, and keeping temperature pyrolysis
4 hours, and room temperature is cooled to, obtain black solid-Semen Tritici aestivi charcoal 33.0g；
4）The charcoal of preparation is activated：15% that the charcoal 10g of above-mentioned preparation is added 100ml（Quality hundred
Divide ratio）Nitric acid shakes oxidation 2h in 80 degree of water-baths；Oxidation debugs sample pH=7 with ammonia after terminating, then by 0.45 μm of filter
Paper carries out sucking filtration, and post-drying is standby；
5）Oxidative biological charcoal sinks through alkali carries acid and prepares humic acidss：Weigh 1.00g oxidation after charcoal in centrifuge tube, plus
Enter 100ml, 1%（Mass percent）NaOH solution, shakes 1h under conditions of 80 DEG C；Concussion is taken out with 0.45 μm of filter membrane after terminating
Filter humic acidss solution；Solution is adjusted pH=1 with the sulphuric acid of 1M, is stood overnight；Finally with 0.45 μm of filter membrane sucking filtration and spend
Ionized water fully washs to obtain humic acidss solid sample.
6）After lyophilization, black solid sample is Semen Tritici aestivi humic acidss 0.45g, and C content is 68%, and O content is 18%,
PH value is 4.8.Semen Tritici aestivi charcoal Humic Acid Production Rate is 45%, and comprehensive yied is 15%（Referring to Fig. 2）.
As shown in Figure 2, infared spectrum shows 3300-3500cm-1Associate-OH based structures, is the feature that hydroxyl structure is present
Peak band；2850-2950cm-1Locate as C-H key bands in alkane hydrogen structure；1700-1730cm-1Locate contained by aldehyde, ketone or carbonyl
C=O carbonyls;1600-1630cm-1And 1400-1440cm-1Between saw-like frequency multiplication peak belong to aromatic ring characteristic absorption peak；In absworption peak
1100-1250cm-1Between present alcoholic extract hydroxyl group feature；In absworption peak 493-771cm-1Between assume saw-like frequency multiplication peak, its structure is fragrance
Same clan's material.
Embodiment 2
The method for preparing humic acidss：
1）Raw material adopts content of cellulose for 32%, hemicellulose level 21%, the wheat straw of content of lignin 15%
Stalk；
2）Wheat stalk is cleaned, dry, crush, and crosses 20 mesh sieves standby；
3）Wheat stalk 100.0g after crushing is pyrolyzed in electron tubes type carbide furnace, with the flow velocity of 1L/min in tube furnace
Logical N2With emptying furnace air；Stove is warming up to 450 DEG C with the heating rate of 15 DEG C/min；And keep the temperature to be pyrolyzed 4 hours；
Room temperature is cooled to, black solid-Semen Tritici aestivi charcoal 28.5g is obtained；
4）The charcoal of preparation is activated：The charcoal 10g of above-mentioned preparation is added 10%（Mass percent）Nitre
Sour 200ml shakes oxidation in 80 degree of water-baths, and oxidization time is 2h；Oxidation debugs sample pH=7 with ammonia after terminating, and then passes through
The filter paper of 0.45um carries out sucking filtration, and post-drying is standby；
5）Oxidative biological charcoal sinks through alkali carries acid and prepares humic acidss：Weigh 1.00g oxidation after charcoal in centrifuge tube, plus
Enter 100ml, 1%（Mass percent）NaOH solution, shakes 2h under conditions of 80 DEG C；Concussion is taken out with 0.45 μm of filter membrane after terminating
Filter humic acidss solution；Solution is adjusted pH=2 with the sulphuric acid of 1M, is stood overnight；Finally with 0.45 μm of filter membrane sucking filtration and spend
Ionized water fully washs to obtain humic acidss solid sample 0.58g.
6）After lyophilization, black solid sample is Semen Tritici aestivi humic acidss, and C content is 71%, and O content is 14%, and pH value is
5.1.Semen Tritici aestivi charcoal Humic Acid Production Rate is 58%, and comprehensive yied is 17%.
Embodiment 3
The method for preparing humic acidss：
1）Raw material adopts content of cellulose for 32%, hemicellulose level 21%, the wheat straw of content of lignin 15%
Stalk；
2）Wheat stalk is cleaned, dry, crush, and crosses 20 mesh sieves standby；
3）Wheat stalk 100.0g after crushing is pyrolyzed in electron tubes type carbide furnace, with the flow velocity of 1L/min in tube furnace
Logical N2 is with emptying furnace air；Stove is made to be warming up to 500 DEG C with the heating rate of 15 DEG C/min；Keeping temperature is pyrolyzed 4 hours；Cooling
To room temperature, black solid-Semen Tritici aestivi charcoal 23.5g is obtained；
4）The charcoal of preparation is activated：The charcoal 10g of above-mentioned preparation is added 15%（Mass percent）Nitre
Sour 100ml shakes oxidation in 80 degree of water-baths, and oxidization time is 2h；Oxidation debugs sample pH=7 with ammonia after terminating, and then passes through
The filter paper of 0.45um carries out sucking filtration, and post-drying is standby；
5）Oxidative biological charcoal sinks through alkali carries acid and prepares humic acidss：Weigh 1.00g oxidation after charcoal in centrifuge tube, plus
Enter 100ml, 1.5%（Mass percent）NaOH solution, shakes 1h under conditions of 80 DEG C；Shake after terminating with 0.45 μm of filter membrane
Sucking filtration obtains the solution of humic acidss；Solution is adjusted pH=1 with the sulphuric acid of 1M, is stood overnight；Finally it is used in combination with 0.45 μm of filter membrane sucking filtration
Deionized water fully washs to obtain humic acidss solid sample 0.41g.
6）After lyophilization, black solid sample is Semen Tritici aestivi humic acidss, and C content is 75%, and O content is 15%, and pH value is
5.4.Semen Tritici aestivi charcoal Humic Acid Production Rate is 41%, and comprehensive yied is 9.6%.
Embodiment 4
Part unlike the embodiments above：
The black solid-Semen Tritici aestivi charcoal is with nitric acid according to mass volume ratio 1 (g):15（ml）Ratio mixing.
After the oxidized activating process, charcoal and NaOH solution are according to mass volume ratio 1 (g):150（ml）Ratio mix
Close.
Embodiment 5
Part unlike the embodiments above：
The black solid-Semen Tritici aestivi charcoal is with nitric acid according to mass volume ratio 1 (g):20（ml）Ratio mixing.
After the oxidized activating process, charcoal and NaOH solution are according to mass volume ratio 1 (g):200（ml）Ratio mix
Close.
Claims (3)
1. a kind of method that utilization wheat stalk prepares humic acidss, it is characterised in that：It is raw material first through pyrocarbon with wheat stalk
Change, then nitric acid activation, eventually pass alkali liquor and extract sulfuric acid precipitation and prepare humic acidss；
The wheat stalk of pulverization process is placed in tubular type carbide furnace, N is led to in tube furnace with the flow velocity of 0.5-1L/min2To arrange
Net furnace air；In-furnace temperature is warming up to 400-500 DEG C with the heating rate of 10-15 DEG C/min again then, then here temperature
The lower insulation pyrolysis 2-4 hours of degree；Room temperature is cooled to, black solid-Semen Tritici aestivi charcoal is obtained；
The nitric acid that mass percent is 10-15% is added to shake oxygen in 80 DEG C of water-baths in the black solid-Semen Tritici aestivi charcoal
Change 2-4h；Sample pH=5-7, then after 0.45 μm of filter paper carries out sucking filtration, dry for standby are debugged with ammonia after oxidation；Afterwards
Addition mass percent is 1-1.5%NaOH solution, then shakes 1-2h under conditions of 80-100 DEG C；With 0.45 μm after concussion
Filter membrane sucking filtration obtains the solution of humic acidss；Solution is adjusted pH=1-2 with sulphuric acid, is stood overnight；Finally with 0.45 μm of filter membrane sucking filtration
Obtain humic acidss solid sample.
2. the method that the utilization wheat stalk as described in claim 1 prepares humic acidss, it is characterised in that：The pulverization process
Wheat stalk is by cleaned for wheat stalk, drying, crushes, and crosses 20 mesh sieves standby；Wherein wheat stalk for content of cellulose is
35-45% wheat stalks.
3. the method that the utilization wheat stalk as described in claim 2 prepares humic acidss, it is characterised in that：The sulfuric acid concentration is
1-2M.
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| CN116178748A (en) * | 2023-01-17 | 2023-05-30 | 广西壮族自治区中国科学院广西植物研究所 | Preparation method and application of biomass humate prepared by low-temperature pyrolysis-oxidation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624302A (en) * | 2009-08-19 | 2010-01-13 | 河北师范大学 | Method for producing fertilizer by stewing mixture of stalk and sludge by alkaloid substance |
| CN102553898A (en) * | 2012-02-03 | 2012-07-11 | 刘文治 | Method for realizing resource utilization and zero emission by carrying out chemical catalytic hydrolysis processing on straws |
| CN103275333A (en) * | 2013-05-31 | 2013-09-04 | 苏州农业职业技术学院 | Like-humic acid substance extracted from crop straw and preparation method of compound fertilizer thereof |
-
2013
- 2013-12-09 CN CN201310659335.XA patent/CN104628792B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624302A (en) * | 2009-08-19 | 2010-01-13 | 河北师范大学 | Method for producing fertilizer by stewing mixture of stalk and sludge by alkaloid substance |
| CN102553898A (en) * | 2012-02-03 | 2012-07-11 | 刘文治 | Method for realizing resource utilization and zero emission by carrying out chemical catalytic hydrolysis processing on straws |
| CN103275333A (en) * | 2013-05-31 | 2013-09-04 | 苏州农业职业技术学院 | Like-humic acid substance extracted from crop straw and preparation method of compound fertilizer thereof |
Non-Patent Citations (1)
| Title |
|---|
| 稻草提取类腐植酸物质及其对水稻苗生长的影响;吕品等;《国土与自然资源研究》;20071231(第2期);92-93 * |
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