CN101691387B - Hydrolysis process for preparing humic acid (HA) from corn straw - Google Patents
Hydrolysis process for preparing humic acid (HA) from corn straw Download PDFInfo
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Abstract
The invention relates to a hydrolysis process for preparing humic acid (HA) from corn straw. The HA is prepared from the raw material of the corn straw with the chemical oxidation and hydrolysis technology by taking less than 0.1 percent sulfuric acid at catalyst to regulate the solid-liquid ratio, the reaction temperature, the reaction time and the reactor stirring speed at different steps during the hydrolysis reaction of 50-60 min with the segmented temperature control method and then taking sodium hydroxide as solvent and hydrochloric acid as precipitate to regulate the concentration, the solid-liquid ratio, the reaction time and the like so as to purify the HA. The HA for agricultural production has characteristics of high content and good quality and can stimulate the growth of the crops and improve the soil nutrient utilization ratio. The HA has such technical index as the concentration of 50-85 percent, the pH value of 4.5-6.5 and the dry ash of 10-18 percent.
Description
Technical field
The present invention relates to the hydrolysis process that a kind of cornstalk prepares humic acids.
Background technology
The agricultural humic acids of China mostly is in peat, weathered coal, brown coal and extracts at present, and its preparation needs the exploitation natural resources, easily causes environmental pollution and ecological damage.Produce humic acids by stalk and mostly be fermentation method, by extracting humic acids after the microflora degradation stalk, the cycle is long, and condition is harsh, and unstable products.Existing prepare by oxidation in stalk the shortcoming that the technique of humic acids exists and have: reaction time is long, and the catalysis acid concentration is high, and productive rate is low, and heat-up time is long, the problems such as energy dissipation.
Summary of the invention
The objective of the invention is the hydrolysis process that cornstalk prepares humic acids, greatly reduce the corrosion to production unit, also effectively reduce the environmental pollution of discharging, humic acids content is high, biological activity is strong.The present invention realizes by following preparation technology:
(1) raw material adopts the maize straw of content of cellulose 32-40%, (2) raw material through air-dry, pulverizing, is crossed 20 mesh sieves, (3) hydrolysis: in high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 0.8～1: 12, take the sulfuric acid of percentage concentration 0.05～0.1% as catalyzer, 215～220 ℃ of temperature of reaction, in 20～30 minutes reaction times, carry out under agitator speed 300r/ minute condition, then rapid cooling, make the interior temperature of kettle be down to 70 ℃, and stirring velocity is adjusted into 200～500rpm, reacts under condition of normal pressure 30 minutes again, (4) extract: collect 60 ℃ of oven dry pulverizing of residue in reactor, all cross 2.5 mm sieve, under room temperature condition, sodium hydroxide solution take mass percent as 1～2% is as extraction agent, solid-to-liquid ratio 1: 10～1: 12.5, vibration lixiviate 30～60 minutes, whizzer 2500～3500rpm got supernatant liquor in centrifugal 20～30 minutes, was Sodium salts humic acids stoste, (5) purify: transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid the Sodium salts humic acids stoste that obtains, shook 0.5～1 hour, there is flocculent precipitate to occur, stoste is all filtered, get to filter and obtain solid sample and add the 1mol/L sodium hydroxide solution at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 20～30 minutes of vat liquor 2000～3000rpm, get supernatant liquor, add the 6mol/L hydrochloric acid soln to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 2000～3000rpm is centrifugal 20～30 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, (6) concentrated: under the 50 ℃ of conditions of humic acid solution after purifying, oven dry is concentrated into humic acids content 50-60%, (7) the yellowish brown solid that obtains after cooling drying is agricultural humic acids HA (humic acids) 50-85%, pH4.5-6.5, dry basis ash content 10-18%.
The present technique characteristic feature of an invention:
(1) raw material screening: take maize straw as raw material, because the Heilongjiang Province is big agricultural province, what in agricultural waste material, waste was maximum is exactly rice straw, rice husk, corn stalk, so raw material sources are extensive and with low cost; The agricultural humic acids of preparation is carried out biological organic fertilizer processing, again be applied to farm crop and realized resource circulation utilization.
(2) the extremely low acids hydrolysis technology is adopted in the humic acids preparation, hydrolyzed solution is mass percent concentration less than 0.1% sulphuric acid soln, its low acid hydrolysis technology of commonly using at present requires acid concentration 0.5-5% much lower, this not only reduces the corrosion to production unit greatly, also effectively reduces the environmental pollution of discharging.
What (3) hydrolysis process adopted is sectional temperature-controlled technology: 215～220 ℃ of temperature, 20～30 minutes reaction times; Make the interior temperature of kettle be down to 70 ℃, then reacted 30 minutes; This has shortened approximately 60 minutes reaction times than similar hydrolysis reaction.Hydrolysis reaction is more thorough, and the cellulose conversion rate reaches 100%, is better than similar research 90%; Humic Acid Production Rate is up to 38.45%, also apparently higher than 27.4% of other similar research.
(4) product extraction room temperature is carried out, and mild condition is easy and simple to handle.
(5) humic acids of the present invention's preparation is compared with primary humic acids and is had the characteristics such as content is high, biological activity is strong, and the humic acids average content of preparation is more than 50%, and primary humic acids average is in 33% left and right; Show that by solution culture agricultural humic acids is remarkable to the long growth stimulation of root, seedling of rice seedlings, handle well more than 10% than primary humic acids.Humic acids is the polymeric organic acid mixture that a class is made of aromatic series and multiple functional group thereof, so it does not have the fixed member structure, but its structure can be carried out qualitative identification by infrared spectra.
The technical indicator that the humic acids of the technology of the present invention preparation reaches is humic acids 82.4%, pH5.1, ash content 15.2%.Technical target of the product of the present invention with at present domestic publish take straw-like materials as raw material, the humic acids of producing by oxidation style is compared humic acids content and is improved 15%, ash oontent reduces by 49%.The humic acids that adopts the present invention to make can be used as agricultural humic acid fertilizer.
Description of drawings:
Fig. 1 is the infared spectrum of regeneration humic acids
Embodiment:
(1) raw material adopts the maize straw of content of cellulose 32-40%, (2) raw material through air-dry, pulverizing, is crossed 20 mesh sieves, (3) hydrolysis: in high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 0.8～1: 12, take the sulfuric acid of percentage concentration 0.05～0.1% as catalyzer, 215～220 ℃ of temperature of reaction, in 20～30 minutes reaction times, carry out under agitator speed 300r/ minute condition, then rapid cooling, make the interior temperature of kettle be down to 70 ℃, and stirring velocity is adjusted into 200～500rpm, reacts under condition of normal pressure 30 minutes again, (4) extract: collect 60 ℃ of oven dry pulverizing of residue in reactor, all cross 2.5 mm sieve, under room temperature condition, sodium hydroxide solution take mass percent as 1～2% is as extraction agent, solid-to-liquid ratio 1: 10～1: 12.5, vibration lixiviate 30～60 minutes, whizzer 2500～3500rpm got supernatant liquor in centrifugal 20～30 minutes, was Sodium salts humic acids stoste, (5) purify: transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid the Sodium salts humic acids stoste that obtains, shook 0.5～1 hour, there is flocculent precipitate to occur, stoste is all filtered, get to filter and obtain solid sample and add the 1mol/L sodium hydroxide solution at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 20～30 minutes of vat liquor 2000～3000rpm, get supernatant liquor, add the 6mol/L hydrochloric acid soln to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 2000～3000rpm is centrifugal 20～30 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, (6) concentrated: under the 50 ℃ of conditions of humic acid solution after purifying, oven dry is concentrated into humic acids content 50-60%, (7) the yellowish brown solid that obtains after cooling drying is agricultural humic acids HA (humic acids) 50-85%, pH4.5-6.5, dry basis ash content 10-18%.
As shown in Figure 1, infared spectrum shows that its primary structure is included in and presents saw shape frequency multiplication peak between absorption peak 466-899, and its structure is aromatic hydrocarbon substance; Present the alcoholic extract hydroxyl group feature between absorption peak 1100-1250; Between 1350-1436, saw shape frequency multiplication peak belongs to COO-base and fragrant C=C; 1511 places belong to C=C base on the aromatic ring of C=O and COO-conjugation; 1588 places belong to-NO
2With fragrant C=C base; 1701 places are contained C=O carbonyl in aldehyde, ketone or carbonyl; 2911 places are CH in the aliphatics alkane structure
2And CH
3C-H base, be the characteristic peak band that alkane structure exists; The 3300-3500 place is association-OH base in carboxylic acid, the characteristic peak band that hydroxyl structure exists.This shows, the regeneration humic acids is the material of the class formation complexity that obtains by oxydrolysis technique.
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
air-dry maize straw 300 grams were pulverized 20 mesh sieves, put into high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 0.8, adding mass percent concentration is 0.1% sulphuric acid soln, agitator speed 300rpm, reaction is 30 minutes under 215 ℃ of conditions, condensation is cooled to temperature 70 C, agitator speed is 300rpm, reacted 30 minutes, collect 60 ℃ of oven dry pulverizing of residue in still, all cross 2.5 mm sieve, under room temperature condition, take mass percent concentration as 1% sodium hydroxide solution as extraction agent, solid-to-liquid ratio 1: 12.5, concussion lixiviate 30 minutes, centrifugal 20 minutes of whizzer 2500rpm, get supernatant liquor, transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid, shook 0.5 hour, cross the leaching solid sample, add again the sodium hydroxide solution of 1mol/L at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 30 minutes of vat liquor 2000rpm, add the 6mol/L hydrochloric acid soln to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 2000rpm is centrifugal 30 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, obtain agricultural humic acids solid after under 50 ℃ of conditions, oven dry concentrates.
Embodiment 2
air-dry maize straw 300 grams were pulverized 20 mesh sieves, put into high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 10, adding mass percent is 0.05% sulphuric acid soln, agitator speed 300rpm, reaction is 30 minutes under 220 ℃ of conditions, condensation is cooled to temperature 70 C, agitator speed is 200rpm, reacted 30 minutes, collect 60 ℃ of oven dry pulverizing of residue in still, all cross 2.5 mm sieve, under room temperature condition, sodium hydroxide solution take mass percent as 2% is as extraction agent, solid-to-liquid ratio 1: 10, concussion lixiviate 40 minutes, whizzer 3500rpm got supernatant liquor in centrifugal 30 minutes, transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid, shook 0.5 hour, cross the leaching solid sample, add again the sodium hydroxide solution of 1mol/L at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 20 minutes of vat liquor 3000rpm, add the hydrochloric acid soln of 6mol/L to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 3000rpm is centrifugal 20 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, obtain agricultural humic acids solid after under 50 ℃ of conditions, oven dry concentrates.
Embodiment 3
air-dry maize straw 300 grams were pulverized 20 mesh sieves, put into high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 12, adding mass percent is 0.1% sulphuric acid soln, agitator speed 300rpm, reaction is 20 minutes under 220 ℃ of conditions, condensation is cooled to temperature 70 C, agitator speed is 300rpm, reacted 30 minutes, collect 60 ℃ of oven dry pulverizing of residue in still, all cross 2.5 mm sieve, under room temperature condition, sodium hydroxide solution take mass percent as 2% is as extraction agent, solid-to-liquid ratio 1: 12.5, concussion lixiviate 30 minutes, whizzer 3500rpm got supernatant liquor in centrifugal 30 minutes, transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid, shook 0.5 hour, cross the leaching solid sample, add again the sodium hydroxide solution of 1mol/L at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 20 minutes of vat liquor 3000rpm, add the hydrochloric acid soln of 6mol/L to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 3000rpm is centrifugal 20 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, obtain agricultural humic acids solid after under 50 ℃ of conditions, oven dry concentrates.
Claims (1)
1. a cornstalk prepares the hydrolysis process of humic acids, it is characterized in that: (1) raw material adopts the maize straw of content of cellulose 32-40%, (2) raw material through air-dry, pulverizing, is crossed 20 mesh sieves, (3) hydrolysis: in high-temperature high-pressure reaction kettle, according to solid-to-liquid ratio 1: 0.8～1: 12, take the sulfuric acid of percentage concentration 0.05～0.1% as catalyzer, 215～220 ℃ of temperature of reaction, in 20～30 minutes reaction times, carry out under agitator speed 300r/ minute condition, then rapid cooling, make the interior temperature of kettle be down to 70 ℃, and stirring velocity is adjusted into 200～500rpm, reacts under condition of normal pressure 30 minutes again, (4) extract: collect 60 ℃ of oven dry pulverizing of residue in reactor, all cross 2.5 mm sieve, under room temperature condition, sodium hydroxide solution take mass percent as 1～2% is as extraction agent, solid-to-liquid ratio 1: 10～1: 12.5, vibration lixiviate 30～60 minutes, whizzer 2500～3500rpm got supernatant liquor in centrifugal 20～30 minutes, was Sodium salts humic acids stoste, (5) purify: transfer its pH value to 2 to carry out acidifying with concentrated hydrochloric acid the Sodium salts humic acids stoste that obtains, shook 0.5～1 hour, there is flocculent precipitate to occur, stoste is all filtered, get to filter and obtain solid sample and add the 1mol/L sodium hydroxide solution at 1: 10 by solid-to-liquid ratio, vibrated 30 minutes, standing 8-10 hour, centrifugal 20～30 minutes of vat liquor 2000～3000rpm, get supernatant liquor, add the 6mol/L hydrochloric acid soln to regulate pH value to 2 in the supernatant liquor of collecting, after static 12 hours, 2000～3000rpm is centrifugal 20～30 minutes, collect the yellowish brown solid, repeatedly add distilled water in the yellowish brown solid, shake centrifugal, till can not detecting Cl-to the supernatant liquor, (6) concentrated: under the 50 ℃ of conditions of humic acid solution after purifying, oven dry is concentrated into humic acids content 50-60%, (7) the yellowish brown solid that obtains after cooling drying is agricultural humic acids: humic acids 50-85%, pH4.5-6.5, dry basis ash content 10-18%.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553898B (en) * | 2012-02-03 | 2014-03-05 | 刘文治 | Method for realizing resource utilization and zero emission by carrying out chemical catalytic hydrolysis processing on straws |
| CN105367141A (en) * | 2014-11-15 | 2016-03-02 | 深圳市芭田生态工程股份有限公司 | Method for preparing organic carbon fertilizer from agricultural wastes as raw materials |
| CN105037747A (en) * | 2015-07-29 | 2015-11-11 | 奥为（天津）环保科技有限公司 | Method for extracting fulvic acid from fermented products of kitchen waste |
| CN105218596A (en) * | 2015-10-14 | 2016-01-06 | 奥为（天津）环保科技有限公司 | The extraction element of xanthohumic acid in a kind of rubbish from cooking tunning |
| CN106317419A (en) * | 2016-08-22 | 2017-01-11 | 河北美即可酿科技有限公司 | Method for quickly preparing humic acid by polymerizing biomass material |
| CN111470887A (en) * | 2019-01-22 | 2020-07-31 | 吴东霖 | Method for producing organic fertilizer by rapid reaction of agricultural and forestry waste and plant straw |
| CN112011066B (en) * | 2019-05-29 | 2022-04-01 | 三通生物工程（潍坊）有限公司 | Production process of high-purity humic acid |
| CN114959263B (en) * | 2022-04-28 | 2023-02-07 | 北京科技大学 | Device and method for strengthening bioleaching by using acid to treat straws |
| CN114956873A (en) * | 2022-06-15 | 2022-08-30 | 上田环境修复有限公司 | Co-production process of rice straw-based potassium humate and activated carbon |
| CN115353639B (en) * | 2022-07-12 | 2023-08-08 | 昆明理工大学 | Method for preparing potassium humate by using corn straw and application |
| CN115007625B (en) * | 2022-08-09 | 2022-10-28 | 长春欣瑞德新材料科技开发有限公司 | Straw humus treatment method |
| CN116063695B (en) * | 2023-03-06 | 2024-02-09 | 中国科学院青岛生物能源与过程研究所 | Method for preparing humic acid from straw |
Citations (3)
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| CN1456539A (en) * | 2003-04-01 | 2003-11-19 | 刘泉 | Prepartion of xanthonumic acid for agriculture |
| CN1596661A (en) * | 2004-07-27 | 2005-03-23 | 郝锁振 | Method for preparing preparation for preventing and treating plant diseases by using crop straws |
| CN101040622A (en) * | 2007-04-24 | 2007-09-26 | 郝锁振 | Preparation method for producing composite humic acid plant growth regulator by using plant straws |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456539A (en) * | 2003-04-01 | 2003-11-19 | 刘泉 | Prepartion of xanthonumic acid for agriculture |
| CN1596661A (en) * | 2004-07-27 | 2005-03-23 | 郝锁振 | Method for preparing preparation for preventing and treating plant diseases by using crop straws |
| CN101040622A (en) * | 2007-04-24 | 2007-09-26 | 郝锁振 | Preparation method for producing composite humic acid plant growth regulator by using plant straws |
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