CN103553847A - Method for preparing slow release fertilizer wrapping film by use of tanning waste cowhair - Google Patents
Method for preparing slow release fertilizer wrapping film by use of tanning waste cowhair Download PDFInfo
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Abstract
The invention discloses a method for preparing a slow release fertilizer wrapping film by use of tanning waste cowhair. The method consists of a series of scientific and ordered chemical reactions of tanning waste cowhair keratin hydrolysate with starch pasting liquid, polyvinyl alcohol, carboxymethylcellulose, a methanol crosslinking agent, glycerin and borax. By adopting the method disclosed by the invention, the production process of the prepared slow release fertilizer wrapping film is simple and environment-friendly, and the cost is low; the slow release fertilizer wrapping film has good slow release property in soil and is easily degraded without causing secondary pollution to the soil.
Description
Technical field
The present invention relates to a kind of preparation method of slow-release fertilizer peplos, be specifically related to a kind of method of utilizing leather-making waste ox hair to prepare slow-release fertilizer peplos.
Background technology
Vast territory and abundant resources in China, agricultural is one of development pillar of national economy, but in agriculture production, exist the low problem of chemical fertilizer utilization ratio always, understand according to investigations, conventional fertilizers utilization ratio is low, and a large amount of nutrient elements runs off, and not only bad for plant growth, has caused the waste of resource also environment to be caused to certain pollution, thereby producing type coated slow release fertilizer friendly to environment for use is one of main trend of current Growth of Chemical Fertilizer Industry.Although slowly/controlled releasing fertilizer can effectively address this problem, on the one hand the higher large-scale promotion that is not suitable for of cost cost is used, if slow-release fertilizer coating materials utilizes and improperly also can bring secondary pollution to environment on the other hand.In the situation that a current central file does one's utmost to encourage to reduce fertilizer application amount and greenhouse gas emissions with slow-release fertilizer, developing new release-controlled coated material will be conducive to promote China's agricultural long-term health, lasting development.
In leather industry, after technology is extensively promoted in leather industry, protect hair epilation and also become gradually the leading epilation in tanning production, this method has effectively reduced suspended substance and the organism in waste water, biological oxygen demand (BOD) and chemical oxygen demand (COD) (COD) have been reduced, both reduce pollution, also saved cost.But due in process hides depilation journey, ox hair emits after being normally hydrolyzed together with sewage, the hair that these reclaim again, because effect and its most of color through highly basic are darker, if be applied in high-end fine chemicals industry as medical, beauty industry, not too suitable, also be difficult in weaving, felt industry, be applied again, so how these discarded ox hairs of recycling treatment become when next problem that need be to be solved.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method of preparing slow-release fertilizer peplos with leather-making waste ox hair is provided, and to solve, current agricultural production slow-release fertilizer production cost is too high lacks the good problem of utilizing approach with the discarded ox hair in process hides field.
Technical scheme of the present invention is as follows:
Utilize leather-making waste ox hair to prepare a method for slow-release fertilizer peplos, it is characterized in that, carry out in accordance with the following steps successively:
1), prepare Keratin sulfate hydrolyzed solution:
1.1, get leather-making waste ox hair and rinse and soak with clear water, remove impurity; Then 25～45 ℃ are dried to constant weight;
1.2, get dried ox hair 5 ~ 10 weight parts, add wherein: 2 ~ 5 weight part mercaptoethanols, 5 ~ 10 weight part urea and 1 ~ 5 weight part Sodium dodecylbenzene sulfonate, under 45～95 ℃ of water-bath stirring at low speed conditions, react 5～24h, obtain ox hair hydrolyzed solution;
1.3, ox hair hydrolyzed solution is cooled to after room temperature with filter cloth suction filtering, discards filter residue, obtain Keratin sulfate hydrolyzed solution;
2), prepare slow-release fertilizer coating materials:
2.1, first 10 ~ 15 weight part starch and 50 ~ 100 weight parts waters are stirred to gelatinization 20 ~ 50min under 75 ℃ of conditions, obtain starch pasting liquid;
2.2, get starch pasting liquid 60 ~ 100 weight parts that step 2.1 obtains, add wherein: the cmc soln of the polyvinyl alcohol solution of 5 ~ 10 weight parts 10% and 5 weight parts 5%, the Keratin sulfate hydrolyzed solution that adds again 25 weight part steps 1.3 to obtain, 80 ~ 90 ℃ of stirring reaction 30 ~ 50min; Then the glycerol that slowly drips formaldehyde and 1.5 ~ 3.5 weight parts of 1 ~ 3 weight part, dropwises rear reaction 30 ~ 60min; The borax that adds again 0.1 ~ 0.5 weight part, reacts 15 ~ 30min, obtains release membranes feed liquid;
2.3, feed liquid step 2.2 being obtained is placed after deaeration, is poured on casting film-forming on sheet glass, takes off film after vacuum-drying, obtains finished product slow-release fertilizer peplos.
Described ox hair is in ox-hide process hides, to protect the waste that hair epilation produces.
The criterion of acceptability of the Keratin sulfate hydrolyzed solution that step 1.3 obtains is: adopt its dissolution rate of mercapto-ethanol reduction method to reach more than 60%, and bulk molecule amount can reach 20000～25000.
Positively effect of the present invention is:
1, the present invention adopts discarded ox hair to prepare slow-release fertilizer coating, ox hair is as natural biological protein material, not only there is good mechanics, thermal stability, also there is good biological degradability, under 25 ℃ of conditions, after burying in soil 60 days, the rate of weight loss of film approaches 50%, therefore use the material that the present invention makes not only to there is good water-absorbent, water-permeable and slow release effect as slow-release fertilizer coating, and use procedure can not cause secondary pollution to soil yet.
Efficiently solve the discarded ox hair in the too high and process hides field of current agricultural production slow-release fertilizer production cost and lack the good problem of utilizing approach.
2, in material preparation process, utilize wide material sources and reproducible starch as one of main raw material.And step 2.2 selects formaldehyde as linking agent, it can promote starch pasting, reacts and forms multidimensional network structure with the alcoholic extract hydroxyl group of starch with linking agent methyl alcohol.Also make product there is preservative activity simultaneously, can suppress the putrid and deteriorated of fertilizer and release membranes thereof, thereby weaken the hydrolysis of soil microorganisms to slow-release fertilizer, extend the fertilizer efficiency period of fertilizer.
3, the polyvinyl alcohol adding in step 2.2 contains a large amount of polar group hydroxyls, has the advantages such as unique cementability, film forming, water tolerance.
Step 2.2 also adds carboxymethyl cellulose to have thickening and increases the effect of film toughness, in addition, through chemically crosslinked or modification, the physical strength of film forming and chemical stability is all significantly improved.
4, those skilled in the art easily find out, technological process of the present invention is succinct, and low production cost, and preparation process environmental protection, can not cause environmental pollution substantially.
Accompanying drawing explanation
Fig. 1 is the Fourier transform infrared spectroscopy figure of the slow release fertilizer coating of example 1 preparation.
Embodiment
Below in conjunction with specific implementation method, further set forth the present invention.
The first step: prepare leather-making waste ox hair hydrolyzed solution:
Get clear water a large amount of for leather-making waste ox hair and rinse and soak, remove the impurity such as mould, material, then put into the dry 4h constant weight of 30 ℃ of electric heating constant-temperature blowing drying boxes.Get the dried ox hair of 5g and move in 250 ml there-necked flasks, take 3g mercaptoethanol, 6g urea, 2g Sodium dodecylbenzene sulfonate and be placed in there-necked flask, the warm water bath stirring at low speed reaction 10h of 85 ℃;
Remove agitator and warm water bath, ox hair hydrolyzed solution is cooled to room temperature and with 400 object filter cloth suction filterings, makes Keratin sulfate hydrolyzed solution, standby;
Second step: prepare slow-release fertilizer coating materials:
First 10g starch and 80ml water are added in there-necked flask, in 75 ℃ of water-baths, stir gelatinization, the time is 30min.Get the starch pasting liquid of 80g gained and react 40min, the cmc soln of the polyvinyl alcohol solution of 6g 10% and 5 g 5% is poured in 85 ℃ of there-necked flasks with agitator together with 25g keratin solution.Then slowly drip the linking agent formaldehyde of 2g and the glycerol of 2.5g, then react 40min.And then add the borax of 0.3g, after reaction 20min, obtain release membranes feed liquid.
Feed liquid is placed after deaeration, feed liquid is poured on to casting film-forming on sheet glass, vacuum-drying, takes off film and preserves.
After testing, in 25 ℃ of fixed temperature and humidity incubators, carry out biological degradation experiment in soil, after result is buried 60 days in soil, the rate of weight loss of this film is 48.6%.
The slow release fertilizer coating that example 1 is made carries out Fourier transform infrared spectroscopy detection, and result as shown in Figure 1.
As seen from Figure 1 wherein obvious several peak respectively at 3355cm-1, 2923cm-1, 1662cm-1 place, with the infrared spectrogram of independent polyvinyl alcohol as a reference, can find out, in the absorption peak at 3355cm-1 place and the infrared spectrogram of polyvinyl alcohol, compare and narrowed down, it is the hydroxyl peak correspondence position of polyvinyl alcohol herein, and the carbonyl peak that wave number 1700cm-1 place is present in polyvinyl alcohol ester bond originally becomes 1662cm-1, at the C-H at 2922cm-1 place stretching vibration peak, but died down, under the existence of formaldehyde, in system, each has intermolecularly formed interactional cross-link bond in explanation, the existence of these cross-link bonds effectively raises the consistency of film.
embodiment 2
The first step: prepare leather-making waste ox hair hydrolyzed solution:
Get clear water a large amount of for leather-making waste ox hair and rinse and soak, remove the impurity such as mould, material, then put into the dry 6h constant weight of 45 ℃ of electric heating constant-temperature blowing drying boxes.Get the dried ox hair of 8g and move in 250 ml there-necked flasks, take 5g mercaptoethanol, 10g urine, 5g Sodium dodecylbenzene sulfonate is placed in there-necked flask, the warm water bath stirring at low speed reaction 5h of 95 ℃; Remove agitator and warm water bath, ox hair hydrolyzed solution is cooled to room temperature condition and with 300 object filter cloth suction filterings, makes Keratin sulfate hydrolyzed solution, standby;
Second step: prepare slow-release fertilizer coating materials:
First 15g starch and 100ml water are added in there-necked flask, in 75 ℃ of water-baths, stir gelatinization, the time is 50min.Get starch pasting liquid, the polyvinyl alcohol solution of 10g 10% and the cmc soln of 5g 5% that 100g obtains pours in 90 ℃ of there-necked flasks with agitator and reacts 50min together with keratin solution 25g.Then slowly drip the linking agent formaldehyde of 3g and the glycerol of 3.5g, reaction 60min.Then the borax that adds 0.5g, obtains release membranes feed liquid after reaction 30min.The feed liquid that the 4th step is obtained is placed after deaeration, and feed liquid is poured on to casting film-forming on sheet glass, and vacuum-drying is taken off film and preserved.
In 25 ℃ of fixed temperature and humidity incubators, carry out biological degradation experiment in soil, after result is buried 60 days in soil, the rate of weight loss of this film is 49.2%.
embodiment 3
The first step: prepare leather-making waste ox hair hydrolyzed solution:
Get clear water a large amount of for leather-making waste ox hair and rinse and soak, remove the impurity such as mould, material, then put into the dry 4h constant weight of 25 ℃ of electric heating constant-temperature blowing drying boxes.Get the dried ox hair of 10g and move in 250 ml there-necked flasks, take 2g mercaptoethanol, 5g urea, 1g Sodium dodecylbenzene sulfonate is placed in there-necked flask, the warm water bath stirring at low speed reaction 24h of 45 ℃;
Remove agitator and warm water bath, ox hair hydrolyzed solution is cooled to room temperature and with 400 object filter cloth suction filterings, makes Keratin sulfate hydrolyzed solution, standby;
Second step: prepare slow-release fertilizer coating materials:
First 12g starch and 50ml water are added in there-necked flask, in 75 ℃ of water-baths, stir gelatinization, the time is 20min.Get the starch pasting liquid of 60g gained and react 30min, the cmc soln of the polyvinyl alcohol solution of 5g 10% and 5 g 5% is poured in 80 ℃ of there-necked flasks with agitator together with 25g keratin solution.Then slowly drip the linking agent formaldehyde of 1g and the glycerol of 1.5g, then react 30min.And then add the borax of 0.1g, after reaction 15min, obtain release membranes feed liquid.
Feed liquid is placed after deaeration, feed liquid is poured on to casting film-forming on sheet glass, vacuum-drying, takes off film and preserves.
After testing, in 25 ℃ of fixed temperature and humidity incubators, carry out in soil biological degradation experiment, after result is buried 60 days in soil, the rate of weight loss of this film is for being 46.8%.
Claims (3)
1. utilize leather-making waste ox hair to prepare a method for slow-release fertilizer peplos, it is characterized in that, carry out in accordance with the following steps successively:
1), prepare Keratin sulfate hydrolyzed solution:
1.1, get leather-making waste ox hair and rinse and soak with clear water, remove impurity; Then 25～45 ℃ are dried to constant weight;
1.2, get dried ox hair 5 ~ 10 weight parts, add wherein: 2 ~ 5 weight part mercaptoethanols, 5 ~ 10 weight part urea and 1 ~ 5 weight part Sodium dodecylbenzene sulfonate, under 45～95 ℃ of water-bath stirring at low speed conditions, react 5～24h, obtain ox hair hydrolyzed solution;
1.3, ox hair hydrolyzed solution is cooled to after room temperature with filter cloth suction filtering, discards filter residue, obtain Keratin sulfate hydrolyzed solution;
2), prepare slow-release fertilizer coating materials:
2.1, first 10 ~ 15 weight part starch and 50 ~ 100 weight parts waters are stirred to gelatinization 20 ~ 50min under 75 ℃ of conditions, obtain starch pasting liquid;
2.2, get starch pasting liquid 60 ~ 100 weight parts that step 2.1 obtains, add wherein: the cmc soln of the polyvinyl alcohol solution of 5 ~ 10 weight parts 10% and 5 weight parts 5%, the Keratin sulfate hydrolyzed solution that adds again 25 weight part steps 1.3 to obtain, 80 ~ 90 ℃ of stirring reaction 30 ~ 50min; Then the glycerol that slowly drips formaldehyde and 1.5 ~ 3.5 weight parts of 1 ~ 3 weight part, dropwises rear reaction 30 ~ 60min; The borax that adds again 0.1 ~ 0.5 weight part, reacts 15 ~ 30min, obtains release membranes feed liquid;
2.3, feed liquid step 2.2 being obtained is placed after deaeration, is poured on casting film-forming on sheet glass, takes off film after vacuum-drying, obtains finished product slow-release fertilizer peplos.
2. a kind of method of utilizing leather-making waste ox hair to prepare slow-release fertilizer peplos according to claim 1, is characterized in that: described ox hair is in ox-hide process hides, to protect the waste that hair epilation produces.
3. a kind of method of utilizing leather-making waste ox hair to prepare slow-release fertilizer peplos according to claim 1, it is characterized in that: the criterion of acceptability of the Keratin sulfate hydrolyzed solution that step 1.3 obtains is: adopt its dissolution rate of mercapto-ethanol reduction method to reach more than 60%, and bulk molecule amount can reach 20000～25000.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058867A (en) * | 2014-07-08 | 2014-09-24 | 江苏天宁农木科技园有限公司 | Special fertilizer for apple tree as well as preparation method and application thereof |
| CN105924297A (en) * | 2016-05-17 | 2016-09-07 | 安徽永冠农业科技有限公司 | Bactericidal ox hair keratin-coated slow-release fertilizer and preparation method thereof |
| CN105948998A (en) * | 2016-05-17 | 2016-09-21 | 安徽永冠农业科技有限公司 | Ox hair keratin coated slow-release fertilizer capable of improving saline and alkaline land and preparation method of slow-release fertilizer |
| CN105967880A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Efficient cow hair keratin coated slow-release fertilizer and preparation method thereof |
| CN105967876A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cow-hair-keratin-coated slow-release fertilizer capable of enhancing fertility and preparation method thereof |
| CN105967879A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cowhair keratin membrane controlled-release fertilizer for reducing heavy metals and preparation method thereof |
| CN105967877A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cow-hair-keratin-coated slow-release fertilizer capable of promoting plant growth and preparation method thereof |
| CN105967878A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Disease-resistant cow hair keratin coated slow-release fertilizer and preparation method thereof |
| CN106007922A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Mire containing cowhair keratin coated slow-released fertilizer and preparation method thereof |
| CN106007925A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Cattle hair keratin coated slow-release fertilizer capable of preventing soil hardening and preparing method of cattle hair keratin coated slow-release fertilizer |
| CN106007919A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Ox hair keratin coated slow release fertilizer capable of increasing organic matter of soil and preparation method thereof |
| CN106007923A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Rare earth containing cowhair keratin coated slow-released fertilizer and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058867A (en) * | 2014-07-08 | 2014-09-24 | 江苏天宁农木科技园有限公司 | Special fertilizer for apple tree as well as preparation method and application thereof |
| CN104058867B (en) * | 2014-07-08 | 2016-08-24 | 江苏天宁农木科技园有限公司 | A kind of apple tree dedicated fertilizer and its preparation method and application |
| CN105924297A (en) * | 2016-05-17 | 2016-09-07 | 安徽永冠农业科技有限公司 | Bactericidal ox hair keratin-coated slow-release fertilizer and preparation method thereof |
| CN105948998A (en) * | 2016-05-17 | 2016-09-21 | 安徽永冠农业科技有限公司 | Ox hair keratin coated slow-release fertilizer capable of improving saline and alkaline land and preparation method of slow-release fertilizer |
| CN105967880A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Efficient cow hair keratin coated slow-release fertilizer and preparation method thereof |
| CN105967876A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cow-hair-keratin-coated slow-release fertilizer capable of enhancing fertility and preparation method thereof |
| CN105967879A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cowhair keratin membrane controlled-release fertilizer for reducing heavy metals and preparation method thereof |
| CN105967877A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Cow-hair-keratin-coated slow-release fertilizer capable of promoting plant growth and preparation method thereof |
| CN105967878A (en) * | 2016-05-17 | 2016-09-28 | 安徽永冠农业科技有限公司 | Disease-resistant cow hair keratin coated slow-release fertilizer and preparation method thereof |
| CN106007922A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Mire containing cowhair keratin coated slow-released fertilizer and preparation method thereof |
| CN106007925A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Cattle hair keratin coated slow-release fertilizer capable of preventing soil hardening and preparing method of cattle hair keratin coated slow-release fertilizer |
| CN106007919A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Ox hair keratin coated slow release fertilizer capable of increasing organic matter of soil and preparation method thereof |
| CN106007923A (en) * | 2016-05-17 | 2016-10-12 | 安徽永冠农业科技有限公司 | Rare earth containing cowhair keratin coated slow-released fertilizer and preparation method thereof |
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Application publication date: 20140205 |