CN107857606A - A kind of ureaformaldehyde modifying agent and its preparation method and application - Google Patents
A kind of ureaformaldehyde modifying agent and its preparation method and application Download PDFInfo
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- CN107857606A CN107857606A CN201711092088.4A CN201711092088A CN107857606A CN 107857606 A CN107857606 A CN 107857606A CN 201711092088 A CN201711092088 A CN 201711092088A CN 107857606 A CN107857606 A CN 107857606A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/02—Fertilisers containing urea or urea compounds containing urea-formaldehyde condensates
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- C—CHEMISTRY; METALLURGY
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- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P39/00—Processes involving microorganisms of different genera in the same process, simultaneously
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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Abstract
The present invention relates to slow-release fertilizer ureaformaldehyde modification treatment technology field, especially a kind of ureaformaldehyde modifying agent and its preparation method and application, using amylofermentation organic acid as ureaformaldehyde modifying agent, carried out the modification of ureaformaldehyde, it not only causes the characteristics of nitrogen release of ureaformaldehyde to obtain quickly, so that it is adaptive to the making of slow-release fertilizer, improve the quality of slow-release fertilizer, and the organic acid added is obtained by components of biomass fermentation, wherein it is compounded with a variety of components of biomass, it is after entering in soil, being capable of effective improved soil, nutrient is provided for crop.
Description
Technical field
The present invention relates to slow-release fertilizer ureaformaldehyde modification treatment technology field, especially a kind of ureaformaldehyde modifying agent and its system
Preparation Method and application.
Background technology
Also gradually embodied with the continuous development of ureaformaldehyde slow-release fertilizer, the defects of ureaformaldehyde slow-release fertilizer so that urea
Formaldehyde slow-release fertilizer is longer due to the sustained release cycle of ureaformaldehyde so that nutrient is difficult in most of plant growing process, release
Completely, cause that ureaformaldehyde slow-release fertilizer nutrients release and most of crop growth cycle are uncoordinated, and especially growth cycle is at 6
Crops within month.Its reason is：By being monitored to nutrient slowly-released situation in existing ureaformaldehyde slow-release fertilizer, draw,
For existing ureaformaldehyde during nutrient is sustained, it is sustained the cycle after six months, also has the nutrient (nitrogen) of the overwhelming majority not
It is released, after this has resulted in crop growth end cycle, and the nutrient in the fertilizer being manured into soil is not by sufficient profit
With, this not only causes environment and is contaminated, and it is higher to also results in proportion of crop planting cost, fertilizer application amount increase, or even also
The yield of crops can be influenceed.
But for slow-release fertilizer, it can reduce labor intensity, traditional agriculture can be compared, planting cost is reduced, with fertilizer
Cost has been unquestionable, and raw material of the ureaformaldehyde as slow-release fertilizer, its have effect be also it is considerable, it is still, right
In the continuous improvement of agricultural fertilizer quality, the direction that art technology researcher constantly pursues is still；Therefore, it is directed to urea first
The drawbacks described above that aldehyde highlights, then be necessary to be modified ureaformaldehyde processing so that its deenergized period is rationalized,
Ensure the reduction of agricultural fertilizer cost, avoid environmental pollution.
Also this is based on, this researcher to the modifying agent needed to use in ureaformaldehyde modifying process by grinding
Study carefully so that ureaformaldehyde does not lose the effect of slow-release fertilizer, and is only merely the nutrient slowly-released cycle for changing ureaformaldehyde slow-release fertilizer, pole
The nitrogen utilization efficiency improved in ureaformaldehyde slow-release fertilizer of big degree, reduces the fertile cost of agricultural planting.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of ureaformaldehyde modifying agent and its system
Preparation Method and application.
It is achieved particular by following technical scheme：
A kind of ureaformaldehyde modifying agent, material composition are starch, the organic acidfast bacilli of production；Starch is configured to solution, adds 1-
The 5% organic acidfast bacilli of production, fermentation are prepared.In the fermentation process, it is referred in the prior art, by amylofermentation system
The standby method into organic acid, such as using yellow ginger as raw material, by digesting, being saccharified, being inoculated with and produce organic acidfast bacilli, by it certain
Fermentation is prepared under the conditions of temperature etc.；Such as the disclosure of Patent No. 201010152619.6；For another example sweet potato waste is fermented
Composite organic acid is produced, by using compound strain so that compound strain has the function of production organic acid, has instead of above-mentioned production
The addition of machine acidfast bacilli so that its organic acid prepared has preferably quality, such as the disclosure of Patent No. 201410327470.9
Content.
Handled by above-mentioned method so that the organic acid of preparation is as ureaformaldehyde modifying agent so that ureaformaldehyde is in conduct
When slow-release fertilizer raw material is applied, it can effectively ensure that the sustained release cycle of ureaformaldehyde is reasonable, enabling adapt to most of crops
Growth cycle, it is ensured that in plant growing process, the wherein nutrient such as nitrogen obtains whole releases, and these nutrients are released
Put and be not concentrated in a period of time release, but in a kind of the effect of being sustained, effectively meet caused by slow-release fertilizer
Effect, it also ensure that the nitrogen effective rate of utilization in ureaformaldehyde is significantly improved.
And the organic-acid complex prepared by above-mentioned amylofermentation is used as modifying agent, its realization is modified to ureaformaldehyde
Principle be：Contain substantial amounts of zymophyte in organic-acid complex, these zymophytes are during modified urea formaldehyde is added, energy
Enough and ureaformaldehyde molecule mutually winds combination so that organic acid molecule, zymophyte, ureaformaldehyde molecule etc. are combined closely, and are made
Obtain and be applied to prepare in slow-release fertilizer by modified ureaformaldehyde so that the tight structure of formation enters in slow-release fertilizer, and is entering
After entering in soil, zymophyte utilizes the resource effect in soil at this, shortens the cycle of ureaformaldehyde nutrients release, improves soil knot
Structure performance, strengthen fertilizer efficiency.
It is preferred that the described organic acidfast bacilli of production is bacillus, one or two kinds of any ratio mixing in Actinobacillus.
It is preferred that described starch is configured to solution, it is to use protolysate that it is dense to be configured to starch quality for raw material
Spend the solution for 30-50%；Wherein protolysate is that water, potassium hydroxide, albumen according to mass ratio are 100-150:1:35-45
Obtained after mixing.
In the addition of protein hydrolysate so that the organic acid that it can be prepared with amylofermentation is compound so that
The organic acid that protein hydrolysate can be prepared with fermentation acts synergistically, and effectively changes ureaformaldehyde slow-release fertilizer molecule
Structure, and the optimization of the structure is realized, improve Nitrogen releasing in ureaformaldehyde slow-release fertilizer.
Above-mentioned ureaformaldehyde preparation method for modifier, comprises the following steps：
(1) starch is configured to solution, obtains starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added 12-27U with every gram of starch, be stirred using saccharification ferment treatment, carbohydrase addition
It is 45-53 DEG C of stir process 5-8h in temperature after uniformly, obtains saccharified liquid；
(4) 5-10g nitric acid, 1-2g potassium dihydrogen phosphates, 5-8g dusty yeasts are added according to 1L into saccharified liquid, stirred,
It is transferred in fermentation tank, is inoculated with seed liquor so that organic acidfast bacilli accounts for the 1-5% of starch solution quality in seed liquor, adjusts pH value
For 5-7, fermented under the conditions of 30-55 DEG C of temperature, and during the fermentation, stirred by 30-50r/min of speed of agitator, wait to ferment
Sugared constituent concentration in tank is less than 1.1g/L, terminates fermentation, adjustment moisture content is 8-15%, is produced.
Ureaformaldehyde modifying agent is being applied to the modification of slow-release fertilizer ureaformaldehyde, it enables to the carboxylic in organic acid
Base enters in ureaformaldehyde molecular structure, and contains substantial amounts of zymophyte in organic acid prepared by fermentation so that in zymophyte
After entering with carboxyl, it can effectively make it that the degradation rate of the agroform of difficult degradation is optimized, promote nitrogen
Release, efficiently solve and be used for slow-release fertilizer preparation process, it is necessary to be controlled to the degree of polymerization of ureaformaldehyde in ureaformaldehyde, come real
The speed problem of its existing nutrients release, reduce the difficulty of ureaformaldehyde slow-release fertilizer preparation.The organic acid prepared using amylofermentation
As modifier modification processing so that the molecular structure of ureaformaldehyde is optimized and improved, and is introducing having for fermentation preparation
In machine acid, containing substantial amounts of zymophyte, in its soil that applies fertilizer after, these floras can provide scission of link for ureaformaldehyde molecular degradation
Energy, promoting the ureaformaldehyde fragmentation of macromolecular so that ureaformaldehyde Nitrogen releasing speed disclosure satisfy that fertilizer requirement for crop growth rule,
So that ureaformaldehyde slow-release fertilizer nutrient releasing speed matches with crops regulation of fertilizer requirement, having for ureaformaldehyde nitrogen is effectively raised
Utilization rate is imitated, reduces proportion of crop planting with fertile cost.
It is preferred that when being used for slow-release fertilizer with ureaformaldehyde modification using ureaformaldehyde modifying agent, urea, formalin are pressed
It is 1.5-2.5 according to weight ratio:After 1 mixing, use alkali to adjust pH value as 9-10, be warming up to 40-45 DEG C, stirring reaction 30min, then
Ureaformaldehyde modifying agent is added, regulation pH value is 7, you can.
It is preferred that described formalin, quality percentage meter, content 39-41%.
It is controlled by the proportioning of PARA FORMALDEHYDE PRILLS(91,95), urea so that processing ureaformaldehyde is being modified using fermentation organic acid,
Its effect specific aim is stronger, and improvement is more preferably notable.
For the invention ureaformaldehyde modifying agent after modified urea formaldehyde processing, the ureaformaldehyde of acquisition is applied to slow
Release in fertile preparation process, the crops Kiwi berry of its preferred pin pair, Rosa roxburghii, corn, vegetables.
Starch source in the invention is extensive, as long as contain starch component, can be mutual with the organic acidfast bacilli of production
The raw material of effect, can as the source of starch, or directly using the starch that extract as raw material, such as from sweet potato,
Starch is obtained in potato, corn, wheat, paddy etc., then by after starch preparation solution, by its fermentation process, prepares organic acid；Obtain
Must be that fermentation prepares organic acid after directly above-mentioned raw materials material is beaten.
The present invention carries out the modification of ureaformaldehyde using organic acid, and it not only causes the characteristics of nitrogen release of ureaformaldehyde to obtain
To quick so that it is adaptive to the making of slow-release fertilizer, improves the quality of slow-release fertilizer, and the organic acid added is to pass through life
Material composition ferments and obtained, wherein being compounded with a variety of components of biomass, it, being capable of effective conditioned soil after entering in soil
Earth, nutrient is provided for crop.
Embodiment
Limited with reference to specific embodiment technical scheme is further, but claimed
Scope is not only limited to made description.
Embodiment 1
A kind of ureaformaldehyde preparation method for modifier, comprises the following steps：
(1) starch and water are configured to solution, obtain starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added into 12U with every gram of starch using saccharification ferment treatment, carbohydrase addition, be stirred
It is 45 DEG C of stir process 5h in temperature after even, obtains saccharified liquid；
(4) 5g nitric acid, 1g potassium dihydrogen phosphates, 5g dusty yeasts are added according to 1L into saccharified liquid, stirs, be transferred to fermentation
In tank, seed liquor is inoculated with so that organic acidfast bacilli accounts for the 1% of starch solution quality in seed liquor, and adjustment pH value is 5, temperature 30
Fermented under the conditions of DEG C, and during the fermentation, stirred by 30r/min of speed of agitator, treat that the sugared constituent concentration in fermentation tank is low
In 1.1g/L, terminate fermentation, adjustment moisture content is 8%, is produced.The organic acidfast bacilli of described production is bacillus.
Embodiment 2
A kind of ureaformaldehyde preparation method for modifier, comprises the following steps：
(1) starch is configured to solution, obtains starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added into 27U with every gram of starch using saccharification ferment treatment, carbohydrase addition, be stirred
It is 53 DEG C of stir process 8h in temperature after even, obtains saccharified liquid；
(4) 10g nitric acid, 2g potassium dihydrogen phosphates, 8g dusty yeasts are added according to 1L into saccharified liquid, stirs, be transferred to hair
In fermentation tank, seed liquor is inoculated with so that organic acidfast bacilli accounts for the 5% of starch solution quality in seed liquor, and adjustment pH value is 7, temperature
Fermented under the conditions of 55 DEG C, and during the fermentation, stirred by 50r/min of speed of agitator, treat the sugared constituent concentration in fermentation tank
Less than 1.1g/L, terminate fermentation, adjustment moisture content is 15%, is produced.The organic acidfast bacilli of described production is Actinobacillus.
Described starch is configured to solution, is to use protolysate as raw material, and being configured to starch quality concentration is
30% solution；Wherein protolysate be water, potassium hydroxide, albumen according to mass ratio be 100:1:Obtained after 35 mixing.
Embodiment 3
A kind of ureaformaldehyde preparation method for modifier, comprises the following steps：
(1) starch is configured to solution, obtains starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added into 17U with every gram of starch using saccharification ferment treatment, carbohydrase addition, be stirred
It is 49 DEG C of stir process 7h in temperature after even, obtains saccharified liquid；
(4) 9g nitric acid, 1.5g potassium dihydrogen phosphates, 7g dusty yeasts are added according to 1L into saccharified liquid, stirs, be transferred to hair
In fermentation tank, seed liquor is inoculated with so that organic acidfast bacilli accounts for the 3% of starch solution quality in seed liquor, and adjustment pH value is 6, temperature
Fermented under the conditions of 45 DEG C, and during the fermentation, stirred by 40r/min of speed of agitator, treat the sugared constituent concentration in fermentation tank
Less than 1.1g/L, terminate fermentation, adjustment moisture content is 11%, is produced.The organic acidfast bacilli of described production is bacillus, unwrapping wire bar
Bacterium is arbitrarily than mixing.
Described starch is configured to solution, is to use protolysate as raw material, and being configured to starch quality concentration is
50% solution；Wherein protolysate be water, potassium hydroxide, albumen according to mass ratio be 150:1:Obtained after 45 mixing.
Embodiment 4
A kind of ureaformaldehyde preparation method for modifier, comprises the following steps：
(1) starch is configured to solution, obtains starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added into 12U with every gram of starch using saccharification ferment treatment, carbohydrase addition, be stirred
It is 53 DEG C of stir process 5h in temperature after even, obtains saccharified liquid；
(4) 10g nitric acid, 1g potassium dihydrogen phosphates, 5g dusty yeasts are added according to 1L into saccharified liquid, stirs, be transferred to hair
In fermentation tank, seed liquor is inoculated with so that organic acidfast bacilli accounts for the 1% of starch solution quality in seed liquor, and adjustment pH value is 7, temperature
Fermented under the conditions of 30 DEG C, and during the fermentation, stirred by 30r/min of speed of agitator, treat the sugared constituent concentration in fermentation tank
Less than 1.1g/L, terminate fermentation, adjustment moisture content is 15%, is produced.The organic acidfast bacilli of described production is bacillus, unwrapping wire bar
It is one or two kinds of any than mixing in bacterium.
Described starch is configured to solution, is to use protolysate as raw material, and being configured to starch quality concentration is
40% solution；Wherein protolysate be water, potassium hydroxide, albumen according to mass ratio be 130:1:Obtained after 40 mixing.
Embodiment 5
A kind of ureaformaldehyde method of modifying, using the ureaformaldehyde modifying agent prepared in embodiment 1, urea, formalin are pressed
It is 1.5 according to weight ratio:After 1 mixing, use alkali to adjust pH value as 9-10, be warming up to 40 DEG C, stirring reaction 30min, then by urea first
Aldehyde modifying agent adds, and regulation pH value is 7, you can.
Embodiment 6
A kind of ureaformaldehyde method of modifying, using the ureaformaldehyde modifying agent prepared in embodiment 1, urea, formalin are pressed
It is 2.5 according to weight ratio:After 1 mixing, use alkali to adjust pH value as 9-10, be warming up to 45 DEG C, stirring reaction 30min, then by urea first
Aldehyde modifying agent adds, and regulation pH value is 7, you can.
Embodiment 7
A kind of ureaformaldehyde method of modifying, using the ureaformaldehyde modifying agent prepared in embodiment 1, urea, formalin are pressed
It is 2 according to weight ratio:After 1 mixing, use alkali to adjust pH value as 9-10, be warming up to 43 DEG C, stirring reaction 30min, then by ureaformaldehyde
Modifying agent adds, and regulation pH value is 7, you can.
Embodiment 8
A kind of Kiwi berry slow-release fertilizer, potassium sulfate 3kg, charcoal powder 0.8kg, bentonite 1.1kg, well-rotted farmyard manure 50kg, reality
The modified urea formaldehyde 30kg of the preparation of example 6 is applied, after being mixed evenly, is granulated, dries, obtain.
Embodiment 9
A kind of Rosa roxburghii slow-release fertilizer, potassium dihydrogen phosphate 4kg, potassium sulfate 1.5kg, saleratus 0.5kg, wormcast 20kg are real
The modified urea formaldehyde 13kg of the preparation of example 5 is applied, after being mixed evenly, is granulated, dries, obtain.
Embodiment 10
A kind of corn slow-release fertilizer, calcium monohydrogen phosphate 3kg, activated carbon 8kg, boric acid 1kg, zinc sulfate 1kg, manganese carbonate 1.3kg, sulphur
Modified urea formaldehyde 9kg prepared by sour potassium 10kg, soybean stalks 20kg, soya bean root nodule 3kg, embodiment 7, is mixed evenly, makes
Grain, dry, obtain.
Claims (8)
1. a kind of ureaformaldehyde modifying agent, it is characterised in that material composition is starch, the organic acidfast bacilli of production；Starch is configured to molten
Liquid, adds the 1-5% organic acidfast bacilli of production, and fermentation is prepared.
2. ureaformaldehyde modifying agent as claimed in claim 1, it is characterised in that the organic acidfast bacilli of described production be bacillus,
It is one or two kinds of any than mixing in Actinobacillus.
3. ureaformaldehyde modifying agent as claimed in claim 1, it is characterised in that described starch is configured to solution, is to use egg
White hydrolysate is raw material, is configured to the solution that starch quality concentration is 30-50%；Wherein protolysate is water, hydrogen-oxygen
It is 100-150 to change potassium, albumen according to mass ratio:1:Obtained after 35-45 mixing.
4. the ureaformaldehyde preparation method for modifier as described in claim any one of 1-3, it is characterised in that comprise the following steps：
(1) starch is configured to solution, obtains starch solution；
(2) organic acidfast bacilli is produced in screening, and is carried out conventional liq fermentation, makes fermentation seed liquid；
(3) starch solution is added 12-27U with every gram of starch, be uniformly mixed using saccharification ferment treatment, carbohydrase addition
Afterwards, it is 45-53 DEG C of stir process 5-8h in temperature, obtains saccharified liquid；
(4) 5-10g nitric acid, 1-2g potassium dihydrogen phosphates, 5-8g dusty yeasts are added according to 1L into saccharified liquid, stirs, be transferred to
In fermentation tank, seed liquor is inoculated with so that organic acidfast bacilli accounts for the 1-5% of starch solution quality in seed liquor, and adjustment pH value is 5-
7, ferment under the conditions of 30-55 DEG C of temperature, and during the fermentation, stir, treated in fermentation tank by 30-50r/min of speed of agitator
Sugared constituent concentration be less than 1.1g/L, terminate fermentation, adjustment moisture content is 8-15%, is produced.
5. urea first prepared by the ureaformaldehyde modifying agent or method as claimed in claim 4 as described in claim any one of 1-3
Aldehyde modifying agent is applied to the modification of slow-release fertilizer ureaformaldehyde.
6. application as claimed in claim 5, it is characterised in that by urea, formalin according to weight ratio be 1.5-2.5:1 is mixed
After conjunction, use alkali to adjust pH value as 9-10, be warming up to 40-45 DEG C, stirring reaction 30min, then ureaformaldehyde modifying agent is added, adjust
It is 7 to save pH value, you can.
7. application as claimed in claim 6, it is characterised in that described formalin, quality percentage meter, content 39-
41%.
8. application as claimed in claim 5, it is characterised in that described slow-release fertilizer is for Kiwi berry, Rosa roxburghii, corn, vegetable
Fertilizer during colza plant.
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| CN110256144A (en) * | 2019-06-19 | 2019-09-20 | 中北大学 | Biodegradable high molecular containing various nutrient elements delays the preparation of controlled release organic nano fertilizer |
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| CN116640020A (en) * | 2023-05-31 | 2023-08-25 | 施可丰化工股份有限公司 | Efficient urea formaldehyde sustained and controlled release fertilizer and preparation method thereof |
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| CN110256144A (en) * | 2019-06-19 | 2019-09-20 | 中北大学 | Biodegradable high molecular containing various nutrient elements delays the preparation of controlled release organic nano fertilizer |
| CN115849959A (en) * | 2023-02-22 | 2023-03-28 | 中北大学 | Organic acid modified urea formaldehyde slow-release nitrogen fertilizer and reactive extrusion low-cost preparation process thereof |
| CN116640020A (en) * | 2023-05-31 | 2023-08-25 | 施可丰化工股份有限公司 | Efficient urea formaldehyde sustained and controlled release fertilizer and preparation method thereof |
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