CN112759475A - Environment-friendly slow-release compound fertilizer based on humic acid and preparation method thereof - Google Patents
Environment-friendly slow-release compound fertilizer based on humic acid and preparation method thereof Download PDFInfo
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- CN112759475A CN112759475A CN202110248435.8A CN202110248435A CN112759475A CN 112759475 A CN112759475 A CN 112759475A CN 202110248435 A CN202110248435 A CN 202110248435A CN 112759475 A CN112759475 A CN 112759475A
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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
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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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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Abstract
The application relates to the field of compound fertilizers, and particularly discloses an environment-friendly slow-release compound fertilizer based on humic acid and a preparation method thereof. The compound fertilizer comprises the following components in parts by weight: 45-55 parts of humic acid, 12-20 parts of biomass charcoal, 4-8 parts of urea, 2-4 parts of mineral substances, 2-5 parts of water-soluble potash fertilizer, 2-5 parts of water-soluble nitrogenous fertilizer and 1-3 parts of water-soluble phosphate fertilizer; the preparation method comprises the following steps: weighing biomass charcoal, urea and mineral substances, wet mixing and drying to constant weight; adding humic acid, a water-soluble potassium fertilizer, a water-soluble nitrogen fertilizer and a water-soluble phosphate fertilizer, and fully mixing to obtain the compound fertilizer. The compound fertilizer can be used for soil fertilization with poor self-cleaning capability, and has the advantages of long fertilizer efficiency duration and sufficient fertilizer quantity; according to the preparation method, the urea, the mineral substances and the biomass charcoal are fully mixed, so that the porosity of the biomass charcoal is increased, and the nano-scale structure of the biomass charcoal is increased, so that the adsorption effect of the biomass charcoal on harmful substances is enhanced.
Description
Technical Field
The application relates to the field of compound fertilizers, in particular to an environment-friendly slow-release compound fertilizer based on humic acid and a preparation method thereof.
Background
The fertilizer can provide one or more nutrient elements necessary for crops, can improve the soil property and improve the soil fertility, and is one of material bases of agricultural production; the fertilizer has various types, and the compound fertilizer and urea are widely matched for use in the current agricultural production so as to play a role in promoting the growth of crops; after the urea is applied to soil, the urea is quickly dissolved in water during irrigation, is hydrolyzed into ammonium ions under the action of urease and exists in the soil in the form of ammonium nitrogen or nitrate nitrogen, and part of nitrogen is volatilized to the atmospheric environment in the form of ammonia gas; meanwhile, ammonium nitrogen and nitrate nitrogen in the soil flow into surface water or underground water along with irrigation, rainfall and runoff; both of these conditions result in not only loss of nitrogen, but also environmental damage.
The Chinese patent with the publication number of CN107011047B discloses an organic water-soluble carbon fertilizer and a preparation method thereof, wherein the carbon fertilizer is prepared from the following raw materials in parts by weight: 55-65 parts of humic acid, 3-5 parts of sodium oxide, 8-10 parts of potassium oxide, 5-6 parts of nitric acid, 5-7 parts of phosphorus pentoxide, 15-20 parts of urea, 1.5-2.5 parts of boric acid, 1.5-2.5 parts of zinc sulfate, 5-10 parts of a filtrate reducer and 1-2 parts of a suspending agent; in the raw materials, humic acid and urea are main components; the urea plays a role in providing a nitrogen source, the humic acid can promote the growth of nitrogen-fixing bacteria in soil, the loss of nitrogen elements is reduced, the growth of crops is promoted, and meanwhile, the damage of the applied urea to the environment is reduced.
With respect to the related art in the above, the inventors consider that: the humic acid has strong flocculation property, is easy to agglomerate harmful substances such as sulfide in soil, is not beneficial to the degradation of the harmful substances, and is easy to cause soil pollution when the fertilizer is used in the soil with poor self-cleaning capability for a long time.
Disclosure of Invention
In order to solve the technical problem of soil pollution caused by humic acid, the application provides an environment-friendly slow-release compound fertilizer based on humic acid and a preparation method thereof.
In a first aspect, the application provides an environment-friendly slow-release compound fertilizer based on humic acid, which adopts the following technical scheme:
an environment-friendly slow-release compound fertilizer based on humic acid comprises the following components in parts by weight:
45-55 parts of humic acid, 12-20 parts of biomass charcoal, 4-8 parts of urea, 2-4 parts of mineral substances, 2-5 parts of water-soluble potash fertilizer, 2-5 parts of water-soluble nitrogenous fertilizer and 1-3 parts of water-soluble phosphate fertilizer.
By adopting the technical scheme, the biomass charcoal has a loose porous structure, the surface of the biomass charcoal is rich in polar functional groups, the biomass charcoal has an effective adsorption effect on harmful substances such as sulfides, and the damage of the coagulation property of humic acid to soil is reduced; however, the biomass charcoal has small porosity, is easily interfered by other substances in soil when being used alone and practically, and has poor adsorption effect on harmful substances; the application adds urea in the components to solve the problems; the urea is attached to the biomass charcoal, ammonia gas is easily decomposed when the biomass charcoal is heated, and the porosity of the biomass charcoal is convenient to increase, so that the adsorption effect of the biomass charcoal on harmful substances in soil is improved; when the porosity of the biomass charcoal is higher, the self nano-scale structure is less, and the adhesion of harmful substances on the biomass charcoal is not high; in order to solve the problems, the components are added with mineral substances which are rich in trace elements, so that the nanoscale mechanism of the biomass charcoal can be increased, and the adhesive force of the biomass charcoal to harmful substances is increased.
Preferably, the preparation method of the biomass charcoal comprises the following steps:
weighing biomass such as wood, manure or dead leaves, removing impurities, crushing, and sieving to obtain a mixture 1;
weighing 50% by volume of phosphoric acid according to the weight ratio of the biomass to the phosphoric acid of 25:1, and fully mixing the phosphoric acid and the biomass to obtain a mixture 2;
fully pyrolyzing the mixture 2 at the temperature of 300-700 ℃ to obtain a mixture 3;
and fully performing ultrasonic treatment on the mixture 3 at room temperature to obtain the biomass charcoal.
By adopting the technical scheme, after high-temperature pyrolysis, the biomass charcoal contains a large number of groups such as hydroxyl, carboxyl, carbon-carbon double bond and the like on the surface, exists in an anion form, has strong polarity and is convenient for adsorbing harmful substances such as sulfide and the like;
according to the preparation method, before pyrolysis, phosphoric acid is selected to impregnate the biomass, part of organic matters on the surface of the biomass are subjected to low molecular weight degradation by utilizing the catalytic degradation effect of the phosphoric acid, and in the subsequent pyrolysis process, the low molecular weight organic matters are heated to volatilize gas, so that pores are left on the surface of the biomass charcoal, and the adsorption of the biomass charcoal on harmful substances is increased; in addition, the biomass charcoal is subjected to ultrasonic treatment after pyrolysis, so that the number of active groups and the types of functional groups on the surface of the biomass charcoal are increased, the specific surface area of the biomass charcoal is also increased, and the adsorption performance of the biomass charcoal is further improved.
Preferably, in the above production method, the heating temperature at the time of pyrolysis is 520 ℃.
By adopting the technical scheme, during pyrolysis, the biomass is heated to volatilize water vapor, carbon dioxide, carbon monoxide and the like; when the temperature reaches 520 ℃, the pore structure of the biomass charcoal becomes compact, the specific surface area is larger, and the biomass charcoal has stronger adsorption capacity on harmful substances such as sulfide.
When the heating temperature is higher than 520 ℃, the rate of the carboxylic acid groups in the biomass charcoal being removed by heating is obviously increased, and the reduction of the carboxylic acid groups is not beneficial to the biomass charcoal adsorbing harmful substances in soil.
Preferably, the biomass charcoal is metal modified biomass charcoal.
By adopting the technical scheme, phosphorus is an essential element for the growth and development of crops and mainly exists in the form of phosphate radical in the fertilizer; however, phosphate radicals easily flow into rivers, lake water or underground water in modes of irrigation, runoff and the like, so that environmental problems such as water eutrophication and the like are caused, and a great negative effect is generated on an aquatic ecosystem;
when the biomass carbon is selected from the metal modified biomass carbon, the metal cations are attached to the biomass carbon, so that the adsorption effect of the biomass carbon on anions such as phosphate radicals is increased, the possibility of phosphate radical loss is reduced, and the positive effect on the prevention and treatment of water eutrophication is achieved.
Preferably, the metal modified biomass charcoal is calcium modified biomass charcoal, magnesium modified biomass charcoal or iron modified biomass charcoal.
By adopting the technical scheme, the three metal elements of calcium, magnesium and iron can be attached to the biomass charcoal, the adsorption capacity of the biomass charcoal on anions such as phosphate radicals can be effectively improved, the raw materials of the three elements are easy to obtain, and the preparation is convenient.
Preferably, the metal modified biomass charcoal is Fe-Zn composite modified biomass charcoal.
By adopting the technical scheme, the Fe-Zn composite modified biomass carbon has an effective adsorption effect on anions such as phosphate radical and the like, and is beneficial to preventing and treating soil eutrophication; in addition, Zn and Fe are indispensable trace elements for crop growth, Fe can promote crops to synthesize chlorophyll, and Zn can promote the synthesis of crop proteins; the Fe-Zn composite modified biomass charcoal can also slowly release iron and zinc, provide trace elements for crops for a long time, and is beneficial to absorption and utilization of the crops.
Preferably, the food also comprises 3-5 parts of pH regulator.
By adopting the technical scheme, the biomass charcoal is alkaline, and the yield is reduced after the biomass charcoal is used for some crops sensitive to high pH; the pH regulator can reduce the alkalinity of the biomass charcoal, so that the biomass charcoal is suitable for high-pH sensitive crops.
Preferably, the pH adjusting agent comprises ammonium sulfate, ammonium nitrate or ammonium acetate.
By adopting the technical scheme, the ammonium sulfate is strong acid and weak base salt, has certain acidity, and can effectively neutralize the alkalinity of the biomass charcoal, so that the biomass charcoal is suitable for high-pH sensitive crops; in addition, ammonium sulfate molecules also contain ammonium ions, so that the ammonium ions are easily absorbed by crops, and the nitrogen source of the crops is increased;
compared with ammonium sulfate, ammonium ions and nitrate ions in the molecules can provide nitrogen, so that the nitrogen source of crops is further increased, and the growth and development of the crops are promoted;
ammonium acetate is a weak acid and weak base salt, and is dissolved in water during irrigation to slowly ionize ammonium ions, so that the slow release of the fertility of the mixed material is improved, the mixed material is more beneficial to crop absorption, and the possibility of nitrogen loss is reduced.
In a second aspect, the application provides a preparation method of an environment-friendly slow-release compound fertilizer based on humic acid, which adopts the following technical scheme:
a preparation method of an environment-friendly slow-release compound fertilizer based on humic acid comprises the following steps:
weighing biomass carbon, urea and mineral substances according to the parts by weight, fully wet-mixing, and drying at the temperature of 150-;
and (3) weighing humic acid, a water-soluble potassium fertilizer, a water-soluble nitrogen fertilizer and a water-soluble phosphate fertilizer, adding into the mixture 1, and fully mixing to obtain the compound fertilizer.
By adopting the technical scheme, the preparation method of the biomass charcoal wet-mixes the biomass charcoal, the urea and the mineral substance and then heats and dries the mixture, so that the biomass charcoal has good porosity and more nano-scale structures, and the adsorption effect of the biomass charcoal on harmful substances is increased; in addition, the preparation method is simple to operate and convenient for large-scale production and manufacturing.
In summary, the present application has the following beneficial effects:
1. the biomass charcoal has a loose and porous structure, has an adsorption effect on harmful substances such as sulfides, and decomposes ammonia gas by heating urea, so that the porosity of the biomass charcoal is increased; the nano-scale structure of the biomass charcoal is increased by utilizing the trace elements in the mineral substances, so that the adhesive force of the biomass charcoal to harmful substances is increased.
2. According to the preparation method of the biomass charcoal, the biomass is soaked by phosphoric acid, organic matters on the surface of the biomass are catalytically degraded into more volatile micromolecular substances, and the porosity of the biomass charcoal is further increased; in addition, the preparation method carries out ultrasonic treatment on the biomass charcoal, increases the types of the surface active functional groups of the biomass charcoal, and thus increases the adsorption performance of the biomass charcoal.
3. The biomass carbon is preferably metal modified biomass carbon, so that the adsorption capacity of the biomass carbon on phosphate radicals is increased, the possibility that the phosphate radicals flow into rivers, lakes and the like is reduced, and the positive effect on preventing and treating the problems of water eutrophication and the like is achieved.
4. The metal modified biomass charcoal is preferably Fe-Zn composite modified biomass charcoal, and can slowly release Fe and Zn as nutrient elements of crops.
5. The components of the application also comprise a pH regulator, and the pH regulator can reduce the alkalinity of the biomass charcoal, so that the biomass charcoal is suitable for some high-pH sensitive crops.
6. According to the method, the mineral substances, the urea and the biomass charcoal are mixed firstly, so that the porosity of the biomass charcoal is increased, the nano-scale structure of the biomass charcoal is increased, and the adsorption effect of the biomass charcoal on harmful substances is increased.
Detailed Description
The present application will be described in further detail with reference to examples. It should be noted that, the biomass charcoal in the embodiment of the present application is straw biomass charcoal, but is not limited to straw biomass charcoal, and may also be biomass charcoal of pigs died of illness, corn stalk biomass charcoal, and mallotus japonicus branch biomass charcoal.
The straws of the embodiment are from Ningxiang county of Changsha city, and other raw materials can be obtained through market selling; wherein the humic acid is purchased from Shandong Yunzui biological science and technology Limited company, the content of the humic acid is more than or equal to 65 percent, and the grain diameter is 80-100 meshes; the mineral is purchased from Yingkou Fuxing mineral Co Ltd, and the main components are zinc sulfate, copper sulfate, ammonium sulfite and the like; the calcium oxide is purchased from Lin Yi quanlin chemical industry Co., Ltd, and has a granularity of 50-60 meshes; the magnesium oxide is purchased from Gaolining magnesium salt chemical Co., Ltd in Hebei province, and the granularity is 70-100 meshes; ferroferric oxide is purchased from Huixin mining processing factory in Lingshou county, and the granularity is 325 meshes; the zinc oxide is purchased from the research institute of zinc-magnesium nano materials in yellow river of Lanzhou, and has the granularity of 170-230 meshes.
Preparation examples of raw materials
Preparation example 1: preparation of straw biomass charcoal
S1, weighing 50kg of straws, removing impurities, putting into a straw crusher, crushing for 2 hours, and sieving with a 10-mesh sieve to obtain a mixture 1;
s2, weighing 2kg of phosphoric acid with the mass fraction of 50%, mixing the phosphoric acid with the mixture 1, and stirring for 1h at 100r/min to obtain a mixture 2;
s3, pyrolyzing at 520 ℃ until the weight of the mixture 2 is constant, so as to obtain a mixture 3;
s4, adding the mixture 3 into 80kg of distilled water, and performing ultrasonic treatment for 45min by using a KQ2200B ultrasonic instrument under the condition that the ultrasonic power is controlled to be 200w at room temperature to obtain a mixture 4;
s5, placing the mixture 4 in a constant-temperature blast oven, and drying at the temperature of 65 ℃ until the weight of the mixture 4 is constant to obtain the straw biomass charcoal.
Preparation example 2: preparation of straw biomass charcoal
This production example is different from production example 1 in that the pyrolysis temperature in the S3 step is 480 ℃.
Preparation example 3: preparation of straw biomass charcoal
The present production example was different from production example 1 in that the pyrolysis temperature in the S3 step was 550 ℃.
Preparation example 4: preparation of calcium-modified biomass charcoal
S1, weighing 30kg of straw biomass charcoal prepared in preparation example 1, mixing the straw biomass charcoal with 1.5kg of calcium oxide, and stirring for 40min at the speed of 120r/min to obtain a mixture 1;
s2, adding 60kg of distilled water into the mixture 1, placing the mixture in a KQ2200B ultrasonic instrument, controlling the ultrasonic power to be 250W, and carrying out ultrasonic treatment for 10min to obtain a mixture 2;
and S3, naturally drying the mixture 2 to constant weight to obtain the calcium modified biomass charcoal.
Preparation example 5: preparation of magnesium modified biomass charcoal
S1, weighing 30kg of straw biomass charcoal prepared in preparation example 1, mixing the straw biomass charcoal with 1.8kg of magnesium oxide, and stirring for 1h at 120r/min to obtain a mixture 1;
s2, adding 60kg of distilled water into the mixture 1, placing the mixture in a KQ2200B ultrasonic instrument, controlling the ultrasonic power to be 250W, and carrying out ultrasonic treatment for 30min to obtain a mixture 2;
and S3, naturally drying the mixture 2 to constant weight to obtain the magnesium modified biomass charcoal.
Preparation example 6: preparation of iron modified biomass charcoal
S1, weighing 30kg of straw biomass charcoal prepared in preparation example 1, mixing the straw biomass charcoal with 1kg of ferroferric oxide, and stirring at 120r/min for 25min to obtain a mixture 1;
s2, adding 60kg of distilled water into the mixture 1, placing the mixture in a KQ2200B ultrasonic instrument, controlling the ultrasonic power to be 250W, and carrying out ultrasonic treatment for 8min to obtain a mixture 2;
and S3, naturally drying the mixture 2 to constant weight to obtain the iron modified biomass charcoal.
Preparation example 7: preparation of Fe-Zn composite modified biomass charcoal
S1, weighing 30kg of straw biomass charcoal prepared in preparation example 1, mixing with 0.8kg of ferroferric oxide and 0.6kg of zinc oxide, and stirring for 50min at the speed of 150r/min to obtain a mixture 1;
s2, adding 60kg of distilled water into the mixture 1, placing the mixture in a KQ2200B ultrasonic instrument, controlling the ultrasonic power to be 250W, and carrying out ultrasonic treatment for 20min to obtain a mixture 2;
s3, naturally drying the mixture 2 to constant weight to obtain the Fe-Zn composite modified biomass charcoal.
Examples
Examples 1 to 5
As shown in Table 1, examples 1 to 5 are different in the ratio of raw materials.
The following will explain by way of example 1; wherein, the biomass charcoal is prepared by the preparation example 1, the water-soluble potassium fertilizer is potassium sulfate, the water-soluble nitrogen fertilizer is ammonium phosphate, and the water-soluble phosphate fertilizer is calcium phosphate.
Embodiment 1 a preparation method of an environment-friendly slow-release compound fertilizer based on humic acid comprises the following steps:
s1, weighing the biomass charcoal, the urea and the mineral substances, putting into a stirrer, and wet-mixing for 30min at the speed of 100r/min to obtain a mixture 1;
s2, placing the mixture 1 in a constant-temperature blast oven, controlling the temperature to be 150 ℃, and drying to constant weight to obtain a mixture 2;
s3, weighing humic acid, a water-soluble potassium fertilizer, a water-soluble nitrogen fertilizer and a water-soluble phosphate fertilizer, mixing the humic acid, the water-soluble potassium fertilizer, the water-soluble nitrogen fertilizer and the water-soluble phosphate fertilizer into the mixture 2, and mixing for 2 hours at a speed of 120r/min to obtain the compound fertilizer.
TABLE 1
Examples 6 to 9
Examples 6 to 9 are different from example 3 in that the biomass charcoal is metal-modified biomass charcoal; of these, the calcium-modified biomass char of example 6 was obtained in preparation example 4, the magnesium-modified biomass char of example 7 was obtained in preparation example 5, the iron-modified biomass char of example 8 was obtained in preparation example 6, and the Fe — Zn composite modified biomass char of example 9 was obtained in preparation example 7.
As shown in table 2, examples 6 to 9 are different in the kind of the metal-modified biomass char.
TABLE 2
Examples 10 to 18
Examples 10 to 18 are different from example 9 in that a pH adjuster is further added in step S3 of the preparation method.
As shown in Table 3, examples 10 to 18 are different in the ratio of raw materials.
TABLE 3
Comparative example 1
This comparative example is compared with example 3, except that biomass char was prepared from preparation example 2.
Comparative example 2
This comparative example is compared with example 3, except that biomass char was prepared from preparation example 3.
Comparative example
Comparative example 1
An organic water-soluble carbon fertilizer is prepared by the preparation method disclosed in the embodiment 2 of the Chinese patent with the publication number of CN 107011047B.
Comparative example 2
This comparative example is different from example 3 in that the urea is absent from the composition.
Comparative example 3
This comparative example is different from example 3 in that the mineral is absent from the composition.
Detection method/test method
Entrusted the soil fertilizer workstation of Changsha city of Hunan province, carried out technical index detection to example 3, and the testing result is: organic matter is more than or equal to 360g/L, pH is as follows: 7.5-8.5.
In order to verify the fertilizer efficiency of the compound fertilizer and the effect of reducing harmful substances in soil, in 4 months of 2020, two test plots, namely test plot 1 and test plot 2, are selected from a soil fertilizer workstation in Changsha city in Ningxiang county in Changsha city, wherein the crop planted in the test plot 1 is rice, and the variety is Xiangzao 143; the crop planted in the test field 2 is tomato, and the variety is pink queen; the soil nutrient status of test plots 1 and 2 is shown in table 4.
TABLE 4
The specific test method comprises the following steps:
s1, taking 23 sample units from the test site 1 and the test site 2 respectively, and applying the fertilizers of examples 1-18, comparative examples 1-2 and comparative examples 1-3 to the sample units;
s2, calculating the thousand seed weight of the rice of each sample unit of the test field 1 independently;
s3, randomly sampling tomatoes in each sample unit of the test field 2 respectively, and calculating the average plant height;
s4, performing sulfide detection and total phosphorus detection on the soil of the sample unit of the test field 1 on the 30 th day, the 60 th day and the 90 th day of fertilization respectively;
s5, after fertilization for 3 months, pH measurement was performed on the soil in the test site 2 sample unit.
The detection method comprises the following steps:
detection of soil sulfide: the results of measurement according to the method described in HJ833-2017 methylene blue spectrophotometry for measuring sulfides in soil and sediments are shown in Table 5;
and (3) detecting the total phosphorus of the soil: the results of measurement according to the method described in GBT9837-1988, soil total phosphorus measurement, are shown in Table 5;
the plant height of the tomatoes was measured manually by a tape measure, and the results are shown in table 6;
the pH in the soil was measured using an acid-base titrator and the results are shown in table 6.
Performance test
Table 5: test results of test site 1
Table 6: test results of test site 2
The present application is further described below with reference to tables 5 and 6.
By combining the examples 1-5 and the comparative example 1, the improvement of soil sulfides in the sample unit of the application examples 1-5 is better than that in the comparative example 1, and the thousand-grain weight of wheat is obviously increased; this is because the humic acid in comparative example 1 has a strong flocculation property, can aggregate harmful substances such as sulfides in the soil, is not favorable for the degradation of the harmful substances, and compared with the soil in an initial state, the sulfides in the soil are accumulated into clusters, and the accumulation of the sulfides can cause damage to the quality of the soil if the self-cleaning capability of the soil is poor; the components of examples 1 to 5 contain biomass charcoal, the biomass charcoal has a loose and porous structure, and the surface of the biomass charcoal contains abundant polar functional groups, and the polar functional groups can generate van der Waals force with harmful substances such as sulfide, so that the biomass charcoal can effectively adsorb the harmful substances; the components of the embodiments 1 to 5 also contain urea, when the fertilizer of the embodiments 1 to 5 is prepared, the urea is firstly mixed with the biomass charcoal, so that the urea is attached to the pores of the biomass charcoal, the urea decomposes ammonia gas at the temperature of about 160 ℃, the porosity of the biomass charcoal is increased, and the adsorption effect of the biomass charcoal on harmful substances such as sulfide is increased; meanwhile, the components of the embodiments 1 to 5 also contain mineral substances which are rich in trace elements and increase the nano structure of the biomass charcoal, so that the van der Waals force between the biomass charcoal and harmful substances such as sulfide is increased, and the problem of reduction of the nano structure of the biomass charcoal caused by adding urea is solved;
in addition, besides the influence on the performance of the biomass charcoal, the minerals and the urea can be applied to crops as fertilizers, so that sufficient nitrogen sources and trace elements are provided for the crops, the growth of the crops is facilitated, and the thousand-grain weight of the rice is increased.
To sum up, the fertilizer of this application can effectual solution nitrogen loss's problem based on humic acid, can also play effectual adsorption to harmful substance such as sulphide in the soil simultaneously, plays positive effect to the improvement of soil property.
In the combination of example 3 and comparative example 2, soil sulfide improvement was better in the sample unit of application example 3 than in comparative example 2 due to the lack of urea in comparative example 2; in the preparation process of preparation example 1, the straw is pyrolyzed into biochar at high temperature, organic matters on the surface of the biochar volatilize at the moment, and pores are formed on the surface of the biomass, but a carbon layer with a compact structure is formed inside the biochar at high temperature, so that the pores on the surface of the biochar are difficult to communicate with each other, the porosity of the biochar is small, and the adsorption effect on sulfides is weak; when mixing urea and biomass charcoal, urea at first attaches to the surface of biomass charcoal, decomposes the ammonia production at 140 ℃ afterwards, and the ammonia plays the impact effect to the charcoal layer of biomass charcoal to make the hole on biomass charcoal surface communicate, thereby increased the porosity on biomass charcoal layer, increased the adsorption effect of biomass charcoal to the sulphide.
In the combination of example 3 and comparative example 3, soil sulfide improvement was better in the sample unit of application example 3 than in comparative example 3 due to the lack of minerals in the components of comparative example 3; in comparative example 3, the porosity of the biomass charcoal was increased only by urea, but when urea acted on the biomass charcoal, the pores on the surface of the biomass charcoal became larger, the nano-scale structure decreased, and van der waals' force with harmful substances decreased, which was not favorable for adsorbing sulfides; the mineral substance in the embodiment 3 is rich in trace elements, can be attached to the pores of the biomass charcoal, and increases the nano-scale structure of the biomass charcoal, thereby increasing the adsorption effect of the biomass charcoal on sulfides.
In the case of applying the sample unit of example 3 in combination with example 3 and comparative examples 1 to 2, the improvement of soil sulfide was superior to that of comparative examples 1 to 2, because example 3 is different from the biomass charcoal of comparative examples 1 to 2; example 3 the biomass char used was prepared from preparation example 1, and the pyrolysis temperature was 520 ℃; the biomass char of comparative example 1 was prepared from preparation example 2, and the pyrolysis temperature was 480 ℃; the biomass char of comparative example 2 was prepared from preparation example 3, and the pyrolysis temperature was 550 ℃; when the straw is pyrolyzed, the biomass is heated and pyrolyzed into small molecular substances, and water vapor, carbon dioxide, carbon monoxide and the like are volatilized; in the initial stage of pyrolysis, the compactness of the pore structure of the biomass charcoal is positively correlated with the temperature; when the temperature reaches 520 ℃, the pore structure of the biomass charcoal becomes compact, the specific surface area is larger, and the biomass charcoal has stronger adsorption capacity on harmful substances such as sulfide; when the carbonization temperature is higher than 520 ℃, the rate of heating and removing carboxylate radicals on the surface of the biomass carbon is obviously increased, so that the weakening degree of the adsorption of the biomass carbon is large, and the adsorption of the biomass carbon on harmful substances in soil is not facilitated.
In the combination of example 3 and examples 6-9, the reduction of the total phosphorus content of the soil in the sample unit applied in example 3 is lower than that in examples 6-9, because the biomass charcoal is metal modified biomass charcoal in the components of examples 6-9; phosphorus is an essential element for the growth and development of crops, and mainly exists in the form of phosphate radical in the fertilizer, so that the phosphorus is convenient for the crops to absorb and utilize; however, the absorption rate of the crops to phosphate radicals is slow, most of the phosphate radicals in the fertilizer exist in soil and flow into rivers, lake water or underground water in modes of irrigation, runoff and the like, so that environmental problems such as water eutrophication and the like are caused, and a large negative effect is generated on an aquatic ecosystem; in the examples 6 to 9, the metal modified biomass carbon is selected, the metal cations are attached to the biomass carbon, so that the electropositivity of the biomass carbon is increased, and the biomass carbon increases the adsorption between the biomass carbon and anions such as phosphate radicals by virtue of the attraction between positive and negative charges, thereby reducing the possibility of phosphate radical loss and playing a positive role in preventing and treating water eutrophication.
In combination with examples 6-9, the three metal elements of calcium, magnesium and iron can be attached to the biomass charcoal, and can effectively increase the adsorption capacity of the biomass charcoal on phosphate radical and other anions; compared with the three, the iron-modified biomass carbon has stronger adsorption effect on phosphorus, and meanwhile, the ferroferric oxide has certain magnetism, so that the biomass carbon is convenient to recycle; compared with the former three, the Fe-Zn composite modified biomass carbon can remarkably increase the adsorption effect of the biomass carbon on phosphate radicals, and is more beneficial to preventing water eutrophication; meanwhile, Zn and Fe are essential trace elements for crop growth, and when the iron and the zinc are attached to the biomass charcoal, the iron and the zinc can be slowly released in soil, so that the trace elements are provided for crops for a long time, and the absorption and the utilization of the crops are facilitated; meanwhile, due to the existence of ferroferric oxide, the Fe-Zn composite modified biomass carbon has certain magnetism and is beneficial to recovery and cyclic utilization.
Combining example 3 and examples 10-18, in the sample unit of the experimental site 2, the gain of examples 10-18 on the plant height of tomato is obviously better than that of example 3, and the reduction amplitude of examples 10-18 on the soil pH is obviously larger, because the components of examples 10-18 also contain pH regulators compared with example 3; the biomass charcoal in example 3 mostly has strong alkali and weak acid salt on the surface, is alkaline overall, and has no obvious effect on the growth and development of tomatoes after being applied to high-pH-sensitive crops such as tomatoes; the pH regulators in examples 10-18 can reduce the alkalinity of the biomass charcoal, so that the biomass charcoal tends to be neutral, and is more suitable for high pH sensitive crops, and therefore, the gain to the tomato plant is more significant.
With reference to examples 10-18, of the three pH regulators of examples 10-18, all of the three can effectively reduce the alkalinity of the biomass charcoal, so that the biomass charcoal has a significant effect of increasing tomato plants; wherein ammonium sulfate molecules also contain ammonium ions which are easily absorbed by crops, so that the absorption of nitrogen elements by tomatoes is supplemented, and the nitrogen source of the tomatoes is increased; ammonium ions and nitrate ions in ammonium nitrate molecules can provide nitrogen elements, so that the nitrogen source of crops is further increased, and the growth and development of the crops are promoted; ammonium acetate is weak acid weak base salt, and slowly ionizes ammonium ions after being dissolved in water, so that the fertility slow release of the mixed material is improved, the possibility that the ammonium ions are retained in soil and run off is reduced, the long-term absorption of crops is facilitated, and the promotion effect on the plant height of tomatoes is more remarkable.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. An environment-friendly slow-release compound fertilizer based on humic acid is characterized by comprising the following components in parts by weight:
45-55 parts of humic acid, 12-20 parts of biomass charcoal, 4-8 parts of urea, 2-4 parts of mineral substances, 2-5 parts of water-soluble potash fertilizer, 2-5 parts of water-soluble nitrogenous fertilizer and 1-3 parts of water-soluble phosphate fertilizer.
2. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 1, wherein: the preparation method of the biomass charcoal comprises the following steps:
weighing biomass such as wood, manure or dead leaves, removing impurities, crushing, and sieving to obtain a mixture 1;
weighing 50% by volume of phosphoric acid according to the weight ratio of the biomass to the phosphoric acid of 25:1, and fully mixing the phosphoric acid and the biomass to obtain a mixture 2;
fully pyrolyzing the mixture 2 at the temperature of 300-700 ℃ to obtain a mixture 3;
and fully performing ultrasonic treatment on the mixture 3 at room temperature to obtain the biomass charcoal.
3. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 2, wherein: in the above preparation method, the heating temperature at the time of pyrolysis was 520 ℃.
4. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 1, wherein: the biomass charcoal is metal modified biomass charcoal.
5. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 4, wherein: the metal modified biomass carbon is calcium modified biomass carbon, magnesium modified biomass carbon or iron modified biomass carbon.
6. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 4, wherein: the metal modified biomass charcoal is Fe-Zn composite modified biomass charcoal.
7. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 1, wherein: also comprises 3-5 parts of pH regulator.
8. The humic acid-based environment-friendly slow-release compound fertilizer as claimed in claim 7, wherein: the pH regulator is ammonium sulfate, ammonium nitrate or ammonium acetate.
9. The method for preparing the humic acid-based environment-friendly slow-release compound fertilizer is characterized by comprising the following steps of:
weighing biomass carbon, urea and mineral substances according to the parts by weight, fully wet-mixing, and drying at 140-200 ℃ to constant weight to obtain a mixture 1;
and (3) weighing humic acid, a water-soluble potassium fertilizer, a water-soluble nitrogen fertilizer and a water-soluble phosphate fertilizer, adding into the mixture 1, and fully mixing to obtain the compound fertilizer.
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