WO2018149421A1 - 腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法 - Google Patents
腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法 Download PDFInfo
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- WO2018149421A1 WO2018149421A1 PCT/CN2018/082808 CN2018082808W WO2018149421A1 WO 2018149421 A1 WO2018149421 A1 WO 2018149421A1 CN 2018082808 W CN2018082808 W CN 2018082808W WO 2018149421 A1 WO2018149421 A1 WO 2018149421A1
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- fertilizer
- caking agent
- carbon
- unsaturated fatty
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
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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
Definitions
- the invention relates to the field of fertilizer production, in particular to an anti-caking agent for humic acid fertilizer combined with fertilizer synergistic function and a preparation method thereof.
- Humic acid is the core organic substance in the soil. Over the years, the application of pure chemical fertilizers has led to more and more serious ecological and environmental problems such as current soil quality degradation and atmospheric environmental pollution. Reducing the amount of chemical fertilizer application and supplementing soil fertility by applying humic acid fertilizer is the consensus of the agricultural community. In the future, the production of humic acid fertilizer will expand.
- a humic acid fertilizer system which includes humic acid organic fertilizer, humic acid microbial fertilizer, humic acid organic-inorganic fertilizer, humic acid compound fertilizer, humic acid urea, humic acid potassium fertilizer, humic acid phosphate fertilizer, humic acid chelate 30 kinds of varieties such as Hefei, these humic acid series fertilizers are all in the form of granules, woven bag packaging, if no anti-caking treatment, the agglomeration problem in transportation and storage will affect farmers' fertilization, especially It is impossible to use when it is fertilized by mechanical means. Anti-caking treatment of humic acid fertilizer is of great significance.
- the chemical fertilizer anti-caking technology is generally used in the production process of humic acid fertilizer, that is, the oil anti-caking agent is mixed with the powder anti-caking agent on the surface of the fertilizer, wherein the oil anti-caking agent is a fatty acid + fatty amine + Mineral oil compounding, in the coating, it needs to be heated to 70-100 °C by melting tank to melt and spray onto the fertilizer surface.
- the oil anti-caking agent is a fatty acid + fatty amine + Mineral oil compounding, in the coating, it needs to be heated to 70-100 °C by melting tank to melt and spray onto the fertilizer surface.
- humic acid fertilizers including all organic fertilizers
- the grain strength is lower than that of purified fertilizers (water and grain strength are fertilizers).
- the anti-caking effect is not good, and can not prevent the phenomenon of fertilizer pulverization;
- the high temperature of the encapsulating oil will make the biological bacteria inactive;
- Perennial use of mineral oil-containing anti-caking agents can cause soil pollution;
- powder anti-caking agents are usually formulated with talc, China's main talc minerals in Anshan, Liaoning, Yantai, Guangxi, etc. due to environmental issues Most banned sources of talc raw materials have become a problem.
- the present invention is directed to solving the problems described above.
- the object of the present invention is to provide an anti-caking agent for humic acid fertilizer and having a fertilizer synergistic function and a preparation method thereof.
- the invention provides an anti-caking agent for humic acid fertilizer and having a fertilizer synergistic function, the anti-caking agent comprising the following components, the content of each component being expressed by mass percentage as follows:
- the anti-caking agent comprises the following components, and the content of each component is expressed by mass percentage as follows:
- the lubricant is flake graphite or microcrystalline graphite.
- the anti-caking agent is in the form of a dry powder, and the anti-caking agent has a powder fineness of 800 to 1250 mesh.
- the invention also provides a preparation method of an anti-caking agent for humic acid fertilizer and having a fertilizer synergistic function, the preparation method comprising the following steps:
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 800-1250 mesh to obtain an anti-caking agent for the humic acid fertilizer and having a fertilizer synergistic function.
- the preparation method comprises the following steps:
- step 2S Adding 50% of the total amount of straw ash to the blender, and spraying the mixture of the liquid unsaturated fatty acid and the carbon-16-octadecyl alcohol in step 1S) into the mixer at 1000 rpm.
- the mixture of the ash ash and the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was uniformly mixed for 4 minutes, and the ash ash modified by the mixture of the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was obtained;
- step 2S straw ash modified with a total mass of 42% lubricant, a total mass of 2% potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S Adding to the mixer and stirring at 40 rpm for 5 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 1000 mesh, that is, an anti-caking agent having a fertilizer synergistic function for the humic acid fertilizer is obtained.
- the lubricant is flake graphite or microcrystalline graphite.
- the step 2S) comprises: adding a total amount of 40% to 55% of straw ash to a volume of 1 cubic mixer and stirring uniformly, and spraying the uniform liquid in step 1S) in a volume of 1 cubic mixer.
- the step 3S) comprises: a lubricant having a total mass of 39% to 50%, a potassium polyacrylate having a total mass of 1.5% to 3%, and an unsaturated fatty acid obtained in the step 2S and a carbon sixteen-ten a mixture of eight fatty alcohol modified straw ash is added to a volume of 2 cubic mixer;
- the step 4S) comprises: putting the mixed powder in the step 3S into a volumetric 2 cubic flow mill.
- the humic acid fertilizer uses an anti-caking agent with a synergistic effect of fertilizer to introduce a straw ash which can provide potassium for crops and improve anti-caking property; using unsaturated fatty acid and carbon 16-octadecanol Surfactant, on the one hand, inhibits the agglomeration problem caused by repeated "dissolution-crystallization" of urea component in fertilizer due to temperature change; on the other hand, it improves the adsorption of anti-caking agent on the surface of fertilizer; introduces flake graphite with lubricating effect Or microcrystalline graphite further improves the anti-caking property, and at the same time introduces polyacrylic acid potassium to solve the problem of agglomeration and pulverization of the surface layer of the fertilizer particles.
- the anti-caking agent Adding the anti-caking agent to the fertilizer makes the anti-caking effect of the fertilizer good, and the anti-caking agent has the functions of preventing fertilizer pulverization, increasing fertilizer utility, environmental protection, low cost, and effectively avoiding humic acid organisms under normal conditions. Fertilizer due to the high temperature of the coating oil to make the biological bacteria inactive.
- the anti-caking agent with the synergistic function of the fertilizer has the main innovations: first, the introduction of straw ash, the main chemical component of the ash is a mixture of potassium carbonate, potassium sulfate and potassium chloride. These mixtures are all soluble potassium salts.
- the potassium salt molecules can combine some of the free water to become crystal water, which reduces the agglomeration of fertilizers.
- it can directly provide the potassium needed for crops, and prevent the agglomeration of fertilizers. At the same time, the effect of increasing the fertilizer efficiency is achieved.
- the unsaturated fatty acid is used to replace the stearic acid commonly used in the fertilizer anti-caking agent industry as a surfactant, and the powder anti-caking agent is prepared to improve the agglomerating agent in the fertilizer.
- the addition of octa-fatty alcohol can inhibit the agglomeration problem caused by repeated "dissolution-crystallization" of urea components in fertilizers due to temperature changes, because rot value acid fertilizer usually contains higher than pure chemical fertilizer.
- fatty alcohol has better anti-knot effect than fatty amine; Fourth, it can further improve anti-caking property by introducing lubricated flake graphite or microcrystalline graphite, specifically, flake graphite or microcrystalline graphite Adsorption to the surface of the fertilizer granules allows the fertilizer granules to slide against each other, reducing the degree of agglomeration under the pressure of the fertilizer stacking, and the two graphites are consistent with the color of the humic acid fertilizer, and do not affect the color of the humic acid fertilizer itself, and These two kinds of graphite have luster and can make the fertilizer particles beautiful.
- lubricated flake graphite or microcrystalline graphite specifically, flake graphite or microcrystalline graphite Adsorption to the surface of the fertilizer granules allows the fertilizer granules to slide against each other, reducing the degree of agglomeration under the pressure of the fertilizer stacking, and the two graphites are consistent with the color of the
- potassium polyacrylate itself is a highly absorbent material, which not only solves the water problem, but also has a fast water absorption.
- the double expansion property increases the physical isolation between the fertilizer particles.
- the process of water absorption and release of water in the soil plays a role in the sustained release of fertilizer.
- the substance remaining in the soil after the degradation of the substance is finally soluble. Potassium salts provide nutrients for crops.
- the low anti-caking agent and the anti-caking agent can effectively avoid the disadvantages of the traditional anti-caking technology for the humic acid bio-fertilizer to lose the activity of the biological bacteria due to the high temperature of the encapsulating oil.
- the preparation components of the above anti-caking agent for humic acid fertilizer include straw ash, unsaturated fatty acid, carbon hexadecyl-octadecyl alcohol, lubricant and potassium polyacrylate.
- the humic acid fertilizer is prepared by using an anti-caking agent which has a fertilizer synergistic function, and the functions and contents of each component are as follows:
- straw ash is introduced, and the main chemical components of ash are a mixture of potassium carbonate, potassium sulfate and potassium chloride. These mixtures are all soluble potassium salts.
- the potassium salt molecules can combine some free water to become crystalline. Water, which reduces the factors of fertilizer agglomeration, on the other hand, can directly provide the potassium needed for crops, and achieve the effect of increasing fertilizer efficiency while preventing fertilizer agglomeration.
- the greater the proportion of ash the lower the cost of the anti-caking agent, but the anti-caking agent formed by the excessive proportion is wrapped on the surface of the humic acid fertilizer granules, which will affect the color of the humic acid fertilizer itself.
- the humic acid fertilizer itself is black, and the ash is grayish white. Adding a larger proportion of the ash ash anti-caking agent to the humic acid fertilizer will make the black of the humic acid fertilizer itself appear gray, which cannot satisfy the customer's Claim. Therefore, controlling the ash content to 40%-55% is the best choice to ensure anti-caking effect, cost and fertilizer color.
- the preferred source of straw ash is straw power plant. In recent years, power plants in various parts of the country use a large amount of straw to generate electricity, and a large amount of straw ash is generated in the power generation process, and raw materials are easily obtained from a power plant, and the cost is low.
- Another focus of the present invention is to add an unsaturated fatty acid as a surfactant, replace stearic acid in a conventional anti-caking agent and control its quality to 3%-5%, and the unsaturated fatty acid is liquid or paste at normal temperature. It plays a role in dust reduction and is beneficial to pure powder.
- stearic acid is usually added as a surfactant in the conventional anti-caking agent, and the powdery anti-caking agent added with stearic acid is used alone.
- the dust is floating during the use. ecosystem. Therefore, almost all compound fertilizer manufacturers use oil and powder anti-caking agents together, and add 1.5-2.5 kg of oil and 3-4 kg of powder to one ton of fertilizer.
- the combination of oil and powder anti-caking agent is not only costly, but more importantly, if the oil agent is used in combination with the oil and powder anti-caking agent, the anti-knot effect is low and the use process is low.
- the unsaturated fatty acid in the invention is liquid or paste at normal temperature, and the anti-caking agent prepared by using unsaturated fatty acid has a slight moist feeling and has better adsorption property; and can be used without using an oil agent alone. It can achieve the effect of conventional fertilizer anti-caking agent oil powder, so that the user's anti-caking cost can be greatly reduced; it can also effectively solve the problem of dust floating.
- the quality is controlled to 3%-5%, on the one hand, the anti-caking agent can achieve the best adsorption effect on the fertilizer particles, on the other hand, it can effectively avoid the anti-caking agent due to the high proportion of unsaturated fatty acids. Produce the auger without cutting, and the proportion is too low will produce floating dust.
- the invention also adds another surfactant, carbon c-octadecyl fatty alcohol, and carbon 16-octadecyl alcohol, because the carbon chain is too high, the fatty alcohol has no surface activity, and the carbon chain is too low.
- the alcohol not only reduces the surface activity but also irritates the pungent odor.
- the hydroxyl group in the carbon sixteen-octadecyl alcohol has affinity with the urea molecules contained in the fertilizer, and can exhibit better activity, and the practice also proves that the carbon compound containing urea is sixteen-eighteen Fatty alcohols are better than other surfactants.
- Most of the chemical anti-caking agents on the market currently use 18 primary amines. It has been proved that the effect of 18 primary amines on the anti-caking effect of urea-based compound fertilizers is not obvious.
- two aliphatic surfactants an unsaturated fatty acid and a carbon sixteen-octadecyl fatty alcohol, are added, and the two different surfactants are used for compounding, and the synergistic effect is better.
- the addition of unsaturated fatty acids and carbon hexadecyl-octadecyl alcohol can inhibit the agglomeration problem caused by repeated "dissolution-crystallization" of the urea component in the fertilizer due to temperature changes, and on the other hand, unsaturated fatty acid molecules
- the hydroxy polar group of carboxylic acid and carbon hexadecyl-octadecyl alcohol can form a salt group with metal ions in the fertilizer, and has stronger activity, further improving the adsorption of the anti-caking agent on the surface of the fertilizer.
- the conventional surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate can only exhibit activity in an aqueous solution, and are provided in a powdery anti-caking agent without any anti-caking effect.
- fertilizers must prevent water from agglomerating, so surfactants such as sodium dodecyl benzene sulfonate and sodium lauryl sulfate are no longer used regardless of the powder or liquid anti-caking agent.
- the content of the unsaturated fatty acid therein is from 3% to 5%, preferably 4%; and the content of the carbonhexadecyl-octadecyl alcohol is from 1.5% to 3%, preferably 2%.
- flake graphite or microcrystalline graphite as a lubricant is mainly because flake graphite or microcrystalline graphite has excellent slip and luster, has good anti-caking function during fertilizer storage, and can make the fertilizer particles beautiful.
- the size of the flake graphite or the microcrystalline graphite is small, the corresponding comparative area is large, and the color of the ash (grey white) can be effectively covered, thereby further ensuring the blackness of the fertilizer itself. Controlling the content of flake graphite or microcrystalline graphite to 40%-50% is the best choice considering the anti-caking effect, fertilizer color, brightness and manufacturing cost.
- the component polypotassium acrylate is a super absorbent resin, and its water absorption ratio can reach 800-900 times, which can effectively solve the problem of moisture in the surface layer of the fertilizer granule, that is, solve the problem of agglomeration and pulverization, and the substance absorbs water in the soil.
- the process of releasing water plays a role of slow release of fertilizer, can absorb fertilizer and release slowly, increase fertilizer efficiency, and has excellent function of protecting and maintaining fat before degradation.
- the substance left in the soil after the substance has been degraded for a long time is finally a soluble potassium salt, which provides nutrients for the crop.
- the content of potassium polyacrylate is controlled to 1.5%-3%, which can ensure the optimal process of water absorption and water release of potassium polyacrylate, and is the best choice for solving agglomeration and pulverization.
- the preparation component of the anti-caking agent for humic acid fertilizer includes the following components, and the content of each component is expressed by mass percentage as follows:
- the anti-caking agent of the present invention is in the form of powder, and the pulverization fineness of the anti-caking agent is 800 to 1,250 mesh.
- the finer the fineness of the pulverization the better the product efficiency, but the higher the energy consumption, the higher the 800-1250 mesh is the best choice of cost and benefit, and the anti-caking agent of the invention is a light ultra-fine powder with excellent
- the adsorption, humic acid fertilizer is usually higher than the pure chemical fertilizer, and the product can be adsorbed to the surface of the fertilizer granule by nearly 100% in the absence of oil.
- a method for preparing an anti-caking agent for use in a humic acid fertilizer and having a fertilizer synergistic function comprising the steps of:
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 800-1250 mesh to obtain an anti-caking agent for the humic acid fertilizer and having a fertilizer synergistic function.
- the preparation method comprises the following steps:
- step 2S Adding 50% of the total amount of straw ash to the blender, and spraying the mixture of the liquid unsaturated fatty acid and the carbon-16-octadecyl alcohol in step 1S) into the mixer at 1000 rpm.
- the mixture of the ash ash and the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was uniformly mixed for 4 minutes, and the ash ash modified by the mixture of the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was obtained;
- step 2S straw ash modified with a total mass of 42% lubricant, a total mass of 2% potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S Adding to the mixer and stirring at 40 rpm for 5 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 1000 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- the above production method is carried out in the order of 1S) to 4S). It should be noted that the above steps include surface modification of straw ash with a mixture of unsaturated fatty acid and carbon hexadecyl octadecyl alcohol to obtain a mixture of unsaturated fatty acid and carbon hexadecyl octadecyl alcohol.
- Sexual straw ash step unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol are surfactants, which can act as anti-caking agents when dispersed on the surface of fertilizer granules, but the amount is very small, requiring a carrier, traditional The fertilizer anti-caking agent is used in mineral oil.
- the invention uses the ash as a carrier to melt the surfactant into a liquid state to cover the surface of the ash particles, and has the function of preventing ash particles from agglomerating and enabling ash.
- the particles are uniformly dispersed and adsorbed on the fertilizer particles.
- the modification of the lubricant and the potassium polyacrylate is not performed because the modification of the lubricant affects the brightness and the slip of the lubricant, and the modification of the potassium polyacrylate affects the water absorption function and reduces the anti-caking property.
- the amount of each component in the above preparation process needs to satisfy the proportional relationship described in the present invention, and those skilled in the art can perform adaptive adjustment based on the above-mentioned preparation methods according to actual conditions.
- the main chemical composition of ash is a mixture of potassium carbonate, potassium sulfate, potassium chloride, these mixtures are all soluble potassium salts, on the one hand, potassium salt molecules can combine some free water to crystal water, reduce fertilizer
- the agglomeration factor on the other hand, can directly provide the potassium required for crops, and achieve the effect of increasing fertilizer efficiency while preventing fertilizer agglomeration.
- the straw ash of most power plants is treated as “waste”, and the cost of talcum powder used in place of the traditional powder anti-caking agent is greatly reduced.
- the use of unsaturated fatty acids and carbon sixteen-octadecyl alcohol as a surfactant on the one hand, the addition of unsaturated fatty acids and carbon sixteen-octadecyl alcohol can inhibit the urea component of the fertilizer repeatedly "dissolved” due to temperature changes -Caking" causes agglomeration problems, and on the other hand, improves the adsorption of the anti-caking agent on the surface of the fertilizer.
- the anti-caking property is improved by introducing flake graphite or microcrystalline graphite having lubricating effect, and at the same time, the two kinds of graphite are lustrous, and the fertilizer particles can be beautiful.
- potassium acrylate itself is a highly absorbing material, which not only solves the problem of moisture, but also has the characteristic of rapid double expansion of water absorption. , which increases the physical isolation between the fertilizer granules.
- the process of water absorption and release of water in the soil plays a role in the sustained release of fertilizer.
- the substance remaining in the soil after the degradation of the substance is finally soluble potassium salt. Crops provide nutrients.
- the preparation component of the anti-caking agent and the content of the anti-caking agent with the fertilizer synergistic function of the humic acid fertilizer of the present invention, and the beneficial effects of the preparation method of the anti-caking agent for the humic acid fertilizer will be given specific experimental data by the examples. Be explained.
- an anti-caking agent for humic acid fertilizer is prepared as follows:
- step 2S Adding 50% of the total amount of straw ash to the blender, and spraying the mixture of the liquid unsaturated fatty acid and the carbon-16-octadecyl alcohol in step 1S) into the mixer at 1000 rpm.
- the mixture of the ash ash and the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was uniformly mixed for 4 minutes, and the ash ash modified by the mixture of the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was obtained;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 1000 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- an anti-caking agent for humic acid fertilizer is prepared as follows:
- step 2S straw having a total mass of 47% of microcrystalline graphite, a total mass of 2% of potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S
- the ash was added to the mixer and stirred at 38 rpm for 6 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 900 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- an anti-caking agent for humic acid fertilizer is prepared as follows:
- step 2S Adding 55% of the total amount of straw ash to the blender, and spraying a mixture of the liquid unsaturated fatty acid and the carbon-16-octadecyl alcohol in step 1S) in a mixer to 1050 rpm.
- the mixture of the ash ash and the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was uniformly mixed for 4 minutes, and the ash ash modified by the mixture of the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was obtained;
- step 2S straw having a total mass of 39% of microcrystalline graphite, a total mass of 1.5% of potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S
- the ash was added to the mixer and stirred at 42 rpm for 4 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 800 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- an anti-caking agent for humic acid fertilizer is prepared as follows:
- step 2S straw ash modified by a total amount of 40% flake graphite, a total mass of 2.5% potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S Adding to the mixer and stirring at 40 rpm for 5 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 1100 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- step 2S Adding 40% of the total amount of straw ash to the blender, and spraying the mixture of the liquid unsaturated fatty acid and the carbon-16-octadecyl alcohol in step 1S) into the mixer at 1000 rpm.
- the mixture of the ash ash and the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was uniformly mixed for 4 minutes, and the ash ash modified by the mixture of the unsaturated fatty acid and the carbon hexadecyl-octadecyl alcohol was obtained;
- step 2S straw ash modified with a total of 50% of flake graphite, a total mass of 3% of potassium polyacrylate, and a mixture of unsaturated fatty acid and carbon hexadecyl-octadecyl alcohol obtained in step 2S Adding to the mixer and stirring at 41 rpm for 4 minutes to obtain a uniformly mixed powder;
- the mixed powder in the step 3S is put into a jet mill, and the mixed powder is pulverized to 1,250 mesh to obtain an anti-caking agent for the humic acid fertilizer.
- a Shandong GY powdery anti-caking agent which is currently commonly used as a humic acid fertilizer is selected as a comparative example.
- the powdery anti-caking agent of the above examples and comparative examples was applied to a humic acid fertilizer, and the anti-caking property and other effects were tested.
- 4 kg of each of the powdery anti-caking agents in the above examples and the comparative examples were added (no oil anti-caking agent was added) to one ton of humic acid compound fertilizer (ton of fertilizer), wherein humic acid composite
- the fertilizer is 15-15-15 compound fertilizer.
- the content of humic acid and other organic matter in the humic acid compound fertilizer is ⁇ 10%.
- the appearance of the compound fertilizer is black and the water content is ⁇ 3.0%.
- the performance test results are shown in Table 2. Shown. Among them, performance testing has been characterized by the same conditions at the same time:
- the average adsorption rate of the anti-caking agent in the embodiment is 99% for the compound fertilizer, and the adsorption ratio of the anti-caking agent to the compound fertilizer in the comparative example is 75%.
- the anti-caking agent of the present application adsorbs the compound fertilizer. The rate is much higher than the comparative example, indicating that the anti-caking agent of the present application has good adsorption property to the compound fertilizer; the average anti-caking ratio of the compound fertilizer using the embodiment is 96%, and the compound fertilizer in the comparative example is used.
- Anti-caking rate is 75%, use this application
- the anti-caking rate of the agglomerating agent fertilizer is much higher than that of the comparative example, indicating that the use of the anti-caking agent of the present application can effectively reduce the agglomeration of the humic acid fertilizer; using the K 2 O of the compound fertilizer of the embodiment
- the content of the compound increased by 0.0252% on average, and the K 2 O content in the compound fertilizer used in the comparative example did not increase, indicating that the use of the anti-caking agent of the present application can increase the fertilizer efficiency.
- the powdery anti-caking agent of the present application will not be
- the color of the humic acid fertilizer raw fertilizer has an effect, the adsorption performance is better, the anti-caking and anti-pulverization effect is better and the fertilizer efficiency can be increased.
- the powdery anti-caking agent of the above Example 1 and the comparative example was applied to humic acid fertilizer, and the anti-caking property and other effects were tested. Among them, the Shandong GY powdery anti-caking agent and oil in the comparative example were used. The anti-caking agent was used in combination, and the powdery anti-caking agent of Comparative Example 1 was used alone without adding an anti-caking agent for the oil. Take 4 kg of powdery anti-caking agent in Example 1 (without adding oil anti-caking agent) to one ton of humic acid compound fertilizer, take 4 kg of powdery anti-caking agent in the comparative example and match with 1.8 One kilogram of oil anti-caking agent is added to one ton of humic acid compound fertilizer.
- the humic acid compound fertilizer is 15-15-15 compound fertilizer
- the humic acid and other organic matter content in the humic acid compound fertilizer is ⁇ 10%
- the appearance of the compound fertilizer is black
- the water content is ⁇ 3.0%
- the performance test The results are shown in Table 3, in which the performance tests have been characterized by the same conditions at the same time:
- the comparative proportion of Shandong GY anti-caking powder with oil anti-caking agent reaches the similar adsorption rate and anti-caking rate as the anti-caking powder in this application, the cost is far Far higher than the present application, the cost of the anti-caking agent of the ton fertilizer in the present invention is 64.3% lower than that of the conventional fertilizer anti-caking agent in the comparative example.
- the anti-caking agent of the oil-containing powder in the comparative example is coated on the surface of the compound fertilizer, so that the appearance color of the compound fertilizer is faded white, dull, and the surface layer of the compound fertilizer is powdered, and more importantly, the fertilizer efficiency is not increased.
- the compound fertilizer coated in Example 1 was still black in appearance and the compound fertilizer had luster, and the compound fertilizer was not powdered, the K 2 O content in the compound fertilizer was increased, and the fertilizer efficiency was increased.
- the present invention has the following beneficial effects:
- the main chemical composition of ash is a mixture of potassium carbonate, potassium sulfate, potassium chloride, these mixtures are all soluble potassium salts, on the one hand, potassium salt molecules can combine some free water to crystal water, reduce fertilizer
- the agglomeration factor on the other hand, can directly provide the potassium required for crops, and achieve the effect of increasing fertilizer efficiency while preventing fertilizer agglomeration.
- the use of unsaturated fatty acids and carbon sixteen-octadecyl alcohol as a surfactant on the one hand, the addition of unsaturated fatty acids and carbon sixteen-octadecyl alcohol can inhibit the urea component of the fertilizer repeatedly "dissolved” due to temperature changes -Caking" causes agglomeration problems, and on the other hand, improves the adsorption of the anti-caking agent on the surface of the fertilizer.
- the anti-caking property is improved by introducing flake graphite or microcrystalline graphite having lubricating effect, and at the same time, the two kinds of graphite are lustrous, and the fertilizer particles can be beautiful.
- potassium acrylate itself is a highly absorbing material, which not only solves the problem of moisture, but also has the characteristic of rapid double expansion of water absorption. , which increases the physical isolation between the fertilizer granules.
- the process of water absorption and release of water in the soil plays a role in the sustained release of fertilizer.
- the substance remaining in the soil after the degradation of the substance is finally soluble potassium salt. Crops provide nutrients.
- the use of straw ash and potassium polyacrylate can effectively increase the efficiency of fertilizers, provide sufficient nutrients for crops, and replace traditional powders by using straw ash.
- the talc powder used in the anti-caking agent can greatly reduce the cost of production and has high economic value.
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Abstract
本发明提供了腐植酸肥料用并具肥料增效功能的防结块剂，该防结块剂由秸秆灰烬、不饱和脂肪酸、碳十六-十八脂肪醇、润滑剂、聚丙烯酸钾制得。使用本发明提供的腐植酸肥料用并具肥料增效功能的防结块剂，可以有效提高肥料的防结块率，防止肥料粉化，增加肥料效用，具有环保、成本低的特点，并且可以有效避免通常情况下对于腐植酸生物肥因包膜油的高温使生物菌失去活性的弊端。本发明还提供腐植酸肥料用并具肥料增效功能的防结块剂的制备方法。
Description
本申请要求在2017年08月10日提交中国专利局、申请号为201710678988.0、发明名称为“腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本发明涉及肥料生产领域，尤其涉及一种腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法。
腐植酸是土壤的核心有机物质。多年来，因施用纯化学肥料，已导致了目前的土壤质量退化、大气环境污染等越来越严重的生态环境问题。减少化肥施用量，通过施用腐植酸肥料补充土壤地力，是农业界的共识，未来腐植酸肥料生产将会膨胀式的发展。
目前，腐植酸肥料体系已经形成，该体系包括腐植酸有机肥、腐植酸微生物肥、腐植酸有机-无机肥，腐植酸复混肥、腐植酸尿素、腐植酸钾肥、腐植酸磷肥、腐植酸螯合肥等30种类的品种，这些腐植酸系列肥料成品都是颗粒状的形态，编织袋包装，如不进行防结块处理，在运输、储存过程中存在的结块问题，将影响农民施肥，特别是用机械施肥时根本无法使用。对腐植酸肥料进行防结块处理具有重要意义。
目前腐植酸肥料生产过程中普遍采用化学肥料防结块技术进行处理，即采用油剂防结块剂配粉体防结块剂包裹在肥料表面，其中油剂防结块剂是脂肪酸+脂肪胺+矿物油复配，在包膜时需要用熔解槽加热至70-100℃熔化喷涂到肥料表面。这种方法用于腐植酸肥料存在多种弊端：(1)腐植酸肥料(包括所有含有机质的肥料)水份通常高于化学肥料，颗粒强度低于纯化学肥料(水份与颗粒强度是肥料结块及粉化的主要相关因素)，防结块效果不好，且不能防止肥料粉化现象；(2)对于腐植酸生物肥因包膜油的高温将使生物菌失去活性；(3)常年使用含有矿物油的防结块剂会对土壤产生污染；(4)粉体防结块剂通常用滑石粉配制，中国主要滑石矿产地辽宁鞍山、山东烟台、广西等地因环保问题现今已大多数禁采，滑石粉原料来源已成问题。
发明内容
本发明旨在解决上面描述的问题。本发明的目的是提供一种腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法。
本发明提供一种腐植酸肥料用并具肥料增效功能的防结块剂，所述防结块剂包括下述组分，所述各组分的含量以质量百分比表示如下：
其中，所述防结块剂包括下述组分，所述各组分的含量以质量百分比表示如下：
其中，所述润滑剂为鳞片石墨或微晶石墨。
其中，所述防结块剂为干粉状，所述防结块剂的粉末细度为800～1250目。
本发明还提供一种腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，所述制备方法包括下述步骤：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量3％～5％的不饱和脂肪酸与质量为总量1.5％-3％的碳十六-十八脂肪醇加入熔解槽中，在75～85℃的温度下熔化为完全液态，得到混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量40％～55％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以950～1100转/分钟的转速搅拌3-5min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量39％～50％的润滑剂、质量为总量1.5％～3％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以38～42转/分钟的转速搅拌4～6分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至800-1250目，得到所述腐植酸肥料用并具肥料增效功能的防结块剂。
其中，所述制备方法包括下述步骤：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量4％的不饱和脂肪酸与质量为总量2％的碳十六-十八脂肪醇加入熔解槽中，在80℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量50％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1000转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量42％的润滑剂、质量为总量2％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以40转/分钟的转速搅拌5分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1000目，即得腐植酸肥料用并具肥料增效功能的防结块剂。
其中，所述步骤3S)中，所述润滑剂为鳞片石墨或微晶石墨。
其中，所述步骤2S)包括：将质量为总量40％～55％的秸秆灰烬加入体积1立方的搅拌机中搅拌均匀，在体积1立方的搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
所述步骤3S)包括：将质量为总量39％～50％的润滑剂、质量为总量1.5％～3％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到体积2立方的混合机中；
所述步骤4S)包括：将步骤3S中的混合粉料投入体积2立方的气流磨中。
该腐植酸肥料用并具肥料增效功能的防结块剂引入了可以提供给农作物所需钾元素以及改进防结块性能的秸秆灰烬；采用不饱和脂肪酸以及碳十六-十八脂肪醇做表面活性剂，一方面抑制肥料中尿素成分因气温变化反复“溶解-结晶”从而导致的结块问题，另一方面提高了防结块剂在肥料表面的吸附性；引入具有润滑作用的鳞片石墨或微晶石墨进一步改进防结块性能，同时引入聚丙烯酸钾解决肥料颗粒表层的结块与粉化问题。将此防结块剂添加至肥料中使得肥料的防结块效果好，并且此防结块剂具有防止肥料粉化、增加肥料效用、环保、成本低以及有效的避免常规情况下对于腐植酸生物肥因包膜油的高温使生物菌失去活性的弊端。
根据本发明提供的腐植酸肥料用并具肥料增效功能的防结块剂，主要的创新点是：第一，引入秸秆灰烬，灰烬主要化学成份为碳酸钾、硫酸钾、氯化钾的混合物，这些混合物皆为可溶性钾盐，一方面，钾盐分子能结合部分游离水变为结晶水，减少肥料结块的因素，另一方面，能直接提供农作物所需钾元素，在防止肥料结块的同时达到增加肥料效能的效果；第二， 使用不饱和脂肪酸取代化肥防结块剂行业常用的硬脂酸做表面活性剂，由此配出的粉体防结块剂提高了结块剂在肥料表面的吸附性，并且在使用中减少了粉尘飘浮；第三，使用碳十六-十八脂肪醇做表面活性剂，取代化肥防结块剂行业常用的十八伯胺，碳十六-十八脂肪醇的加入能抑制肥料中尿素成分因气温变化反复“溶解-结晶”从而导致的结块问题，因腐值酸肥通常比纯化学肥料含有更高的水份，用脂肪醇比用脂肪胺有更好的防结效果；第四，通过引入具有润滑作用的鳞片石墨或微晶石墨能进一步提高防结块性能，具体地，鳞片石墨或微晶石墨吸附到肥料颗粒表面能使肥料颗粒间相互滑动，在肥料堆放受压的情况下降低结块程度，同时这两种石墨与腐植酸肥料颜色一致，不会对腐植酸肥料自身颜色造成影响，并且这两种石墨具有光泽，能使肥料颗粒美观；第五，通过引入聚丙烯酸钾解决肥料颗粒表层的水份问题，聚丙烯酸钾本身是高吸水物质，不仅能解决水份问题，还具有吸水快速加倍膨胀的特性，增加了肥料颗粒间的物理隔离性，该物质在土壤中吸水与释水的过程起到了肥料缓释的作用，另外该物质日久降解后留在土壤中的物质最终为可溶性钾盐，为农作物提供养份。通过秸秆灰烬、不饱和脂肪酸、碳十六-十八脂肪醇、润滑剂、聚丙烯酸钾物质的相互配合，制备得到具有防结块性能好、防止肥料粉化、有效增加肥料效能、环保、成本低的防结块剂，并且采用该防结块剂可以有效的避免传统的防结块技术中对于腐植酸生物肥因包膜油的高温使生物菌失去活性的弊端。
具体地，上述腐植酸肥料用防结块剂的制备组分包括秸秆灰烬、不饱和脂肪酸、碳十六-十八脂肪醇、润滑剂和聚丙烯酸钾。
该腐植酸肥料用并具肥料增效功能的防结块剂的制备组分中，各组分的作用及含量说明如下：
作为本发明的一个重点，引入秸秆灰烬，灰烬主要化学成份为碳酸钾、硫酸钾、氯化钾的混合物，这些混合物皆为可溶性钾盐，一方面，钾盐分子能结合部分游离水变为结晶水，减少肥料结块的因素，另一方面，能直接提供农作物所需钾元素，在防止肥料结块的同时达到增加肥料效能的效果。灰烬所占质量比例越大防结剂成品的成本越低，但比例过大构成的防结块剂包裹到腐植酸肥料颗粒表面，将会影响腐殖酸肥料自身的色泽。具体地，腐殖酸肥料自身为黑色，灰烬是灰白色的，添加较大比例的灰烬的防结剂添加到腐殖酸肥料中将使腐殖酸肥料自身的黑色呈现为灰白，不能满足客户的要求。因此，将灰烬含量控制为40％-55％是保证防结块效果、成本以及肥料颜色较佳的最优选择。另外，秸秆灰烬优选来源为秸秆发电厂，近年来全国各地的发电厂大量使用秸秆发电，发电过程中产生大量的秸秆灰烬，从电厂中容易获得原料，并且成本较低。
本发明的另一个重点是添加不饱和脂肪酸作表面活性剂，取代常规防结块剂中的硬脂酸并将其质量控制为3％-5％，不饱和脂肪酸常温下为液态或糊状，起降尘作用，有利于纯粉使 用。目前常规防结块剂中通常添加硬脂酸作表面活性剂，添加硬脂酸的粉状防结块剂单独使用除防结块效果不理想外，在使用过程中还会产生粉尘飘浮，污染生态环境。因此，几乎所有的复合肥生产厂家都是油剂与粉状防结块剂配合使用，并且一吨肥中添加1.5-2.5公斤的油剂以及3-4公斤粉剂。油剂与粉状防结块剂配合使用不仅成本较高，更重要的是在油剂与粉状防结块剂配合使用中如果油剂用量较低，也会造成防结效果低、使用过程中粉尘飘浮，污染环境的现象。本发明中的不饱和脂肪酸常温下是液态或糊状，用不饱和脂肪酸配制的防结剂成品有稍微的潮湿感，有较佳的吸附性；在不用油剂配合单独使用的前提下即能达到常规化肥防结块剂油配粉的效果，使用户的防结块成本大幅度下降；还可以有效的解决粉尘飘浮的问题。另外，将其质量控制为3％-5％，一方面可以使防结块剂达到对化肥颗粒最佳的吸附效果，另一方面可以有效避免由于不饱和脂肪酸比例过高会使防结块剂产生绞龙不下料，以及比例过低会产生飘浮粉尘的问题。
本发明还添加了另一种表面活性剂即碳十六-十八脂肪醇，选择碳十六-十八脂肪醇，是因为碳链过高的脂肪醇无表面活性，碳链过低的脂肪醇不仅会使表面活性降低还会挥发刺鼻气味。并且碳十六-十八脂肪醇中的羟基与肥料中所含的尿素分子具有亲和作用，能表现出更好的活性，实践也证明对含尿素的复混肥用碳十六-十八脂肪醇比用其他表面活性剂效果更好，目前市场上的化肥防结块剂大多数用十八伯胺，实践证明十八伯胺对尿基复混肥防结块效果并不明显。
本申请添加不饱和脂肪酸与碳十六-十八脂肪醇这两种脂肪族类的表面活性剂，应用这两种不同的表面活性剂进行复配，协同作用效果更好。具体地，一方面不饱和脂肪酸以及碳十六-十八脂肪醇的加入能抑制肥料中尿素成分因气温变化反复“溶解-结晶”从而导致的结块问题，另一方面，不饱和脂肪酸分子的羧酸、碳十六-十八脂肪醇的羟基极性基团，能与肥料中的金属离子形成盐类基团，具有更强的活性，进一步提高了防结块剂在肥料表面的吸附性。常规的十二烷基苯磺酸钠、十二烷基硫酸钠之类的表面活性剂，只能在水溶液中才能显现活性，配备到粉状防结块剂中，没有任何防结块效果，而肥料要防结块必忌水，因此无论配粉剂的或液态防结块剂，十二烷基苯磺酸钠、十二烷基硫酸钠之类的表面活性剂已不再被使用。进一步地，其中不饱和脂肪酸的含量为3％-5％，优选为4％；碳十六-十八脂肪醇的含量为1.5％-3％，优选为2％。
选择鳞片石墨或微晶石墨作为润滑剂，主要是因为鳞片石墨或微晶石墨具有极好的滑度、光泽，在肥料存放过程中具有良好的防结块功能，同时能使肥料颗粒美观。另外，由于鳞片石墨或微晶石墨的粒度较小，相应的比较面积较大，可以有效的覆盖灰烬(灰白)的颜色，这样进一步保证了肥料本身的黑色。将鳞片石墨或微晶石墨的含量控制为40％-50％，是综合考虑防结块效果、肥料颜色、亮度以及制造成本的最优选择。
组分聚丙烯酸钾是一种高吸水树脂，其吸水倍率能达到800-900倍，可以有效的解决肥料颗粒表层的水份问题，即解决了结块与粉化问题，该物质在土壤中吸水与释水的过程起到了肥料缓释的作用，能吸收肥料并缓慢释放，增加肥效，降解前具有优良的保墒保肥功能。另外该物质日久降解后留在土壤中的物质最终为可溶性钾盐，为农作物提供养份。将聚丙烯酸钾的含量控制为1.5％-3％，此含量可以保证聚丙烯酸钾吸水与释水的过程的最佳进行，是解决结块与粉化的最优选择。作为本发明的优选示例，所述腐植酸肥料用防结块剂的制备组分包括下述组分，所述各组分的含量以质量百分比表示如下：
另外，本发明的防结块剂为粉状，防结块剂的粉碎细度为800～1250目。粉碎细度越细产品功效越好，但越细能耗越高，800-1250目是成本与效益的最佳选择范围，并且本发明的防结块剂为轻质超细粉体，具有优良的吸附性，腐植酸肥通常比纯化学肥料水份高，使用本品能在无油剂配合的情况下接近100％吸附到肥料颗粒表面。
根据本发明的另一个方面，提供一种上述腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，包括下述步骤：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量3％～5％的不饱和脂肪酸与质量为总量1.5％-3％的碳十六-十八脂肪醇加入熔解槽中，在75～85℃的温度下熔化为完全液态，得到混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量40％～55％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以950～1100转/分钟的转速搅拌3-5min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量39％～50％的润滑剂、质量为总量1.5％～3％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以38～42转/分钟的转速搅拌4～6分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至800-1250目，得到所述腐植酸肥料用并具肥料增效功能的防结块剂。
优选得，所述制备方法包括下述步骤：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量4％的不饱和脂肪酸与质 量为总量2％的碳十六-十八脂肪醇加入熔解槽中，在80℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量50％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1000转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量42％的润滑剂、质量为总量2％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以40转/分钟的转速搅拌5分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1000目，即得腐植酸肥料用防结块剂。
上述制备方法按照1S)～4S)的顺序依次进行。需要说明的是，上述步骤中包括用不饱和脂肪酸与碳十六-十八脂肪醇的混合液对秸秆灰烬进行表面改性得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬的步骤，不饱和脂肪酸与碳十六-十八脂肪醇是表面活性剂，分散到肥料颗粒表面能起到防结块的作用，但其量非常小，需要一种载体，传统上的化肥防结块剂是把它配到矿物油中使用的，本发明是把灰烬作为载体，把表面活性剂熔化成液态覆盖到灰烬微粒表层，具有防止灰烬微粒团聚的作用，能使灰烬微粒均匀分散地吸附在肥料颗粒上。但是，未进行润滑剂与聚丙烯酸钾的改性，原因是润滑剂改性会影响润滑剂的亮度及滑度，聚丙烯酸钾改性会影响吸水功能，降低防结块性能。以上制备过程中各组分的用量需满足本发明所述的比例关系，本领域技术人员可以根据实际情况基于上述制备方法进行适应性调整。
其有益效果体现在：
第一，引入秸秆灰烬，灰烬主要化学成份为碳酸钾、硫酸钾、氯化钾的混合物，这些混合物皆为可溶性钾盐，一方面，钾盐分子能结合部分游离水变为结晶水，减少肥料结块的因素，另一方面，能直接提供农作物所需钾元素，在防止肥料结块的同时达到增加肥料效能的效果。另外，大多数发电厂的秸秆灰烬是作为“废物”外运处理的，用其代替传统粉体防结块剂所用的滑石粉，成本大幅度下降。
第二，使用不饱和脂肪酸以及碳十六-十八脂肪醇做表面活性剂，一方面，不饱和脂肪酸以及碳十六-十八脂肪醇的加入能抑制肥料中尿素成分因气温变化反复“溶解-结晶”从而导致的结块问题，另一方面提高了防结块剂在肥料表面的吸附性。
第三，通过引入具有润滑作用的鳞片石墨或微晶石墨改进防结块性能，同时这两种石墨有光泽，能使肥料颗粒美观。
第四，通过引入聚丙烯酸钾解决肥料颗粒表层的水份问题，即解决了结块与粉化问题，聚丙烯酸钾本身是高吸水物质，不仅能解决水份问题，还具有吸水快速加倍膨胀的特性，增加了肥料颗粒间的物理隔离性，该物质在土壤中吸水与释水的过程起到了肥料缓释的作用，另外该物质日久降解后留在土壤中的物质最终为可溶性钾盐，为农作物提供养份。
本发明腐植酸肥料用并具肥料增效功能的防结块剂的制备组分及其含量的选择、腐植酸肥料用防结块剂的制备方法的有益效果将通过实施例给出具体实验数据进行说明。
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。
实施例1
按质量百分比称取各组分，其中，将各组分按如下步骤进行腐植酸肥料用防结块剂的制备：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量4％的不饱和脂肪酸与质量为总量2％的碳十六-十八脂肪醇加入熔解槽中，在80℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量50％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1000转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量42％的鳞片石墨、质量为总量2％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以40转/分钟的转速搅拌5分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1000目，即得腐植酸肥料用防结块剂。
实施例2
按质量百分比称取各组分，其中，将各组分按如下步骤进行腐植酸肥料用防结块剂的制备：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量3％的不饱和脂肪酸与质量为总量2％的碳十六-十八脂肪醇加入熔解槽中，在80℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量46％的秸秆灰烬加入搅拌机，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以950转/分钟的转速搅拌5min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇混合液改性的秸秆灰烬；
3S)将质量为总量47％的微晶石墨、质量为总量2％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以38转/分钟的转速搅拌6分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至900目，得到所述腐植酸肥料用防结块剂。
实施例3
按质量百分比称取各组分，其中，将各组分按如下步骤进行腐植酸肥料用防结块剂的制备：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量3％的不饱和脂肪酸与质量为总量1.5％的碳十六-十八脂肪醇加入熔解槽中，在85℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量55％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1050转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量39％的微晶石墨、质量为总量1.5％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以42转/分钟的转速搅拌4分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至800目，得到所述腐植酸肥料用防结块剂。
实施例4
按质量百分比称取各组分，其中，将各组分按如下步骤进行腐植酸肥料用防结块剂的制备：
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量5％的不饱和脂肪酸与质量为总量3％的碳十六-十八脂肪醇加入熔解槽中，在77℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量49.5％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1100转/分钟的转速搅拌3min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量40％的鳞片石墨、质量为总量2.5％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以40转/分钟的转速搅拌5分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1100目，得到所述腐植酸肥料用防结块剂。
实施例5
1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量4％的不饱和脂肪酸与质量为总量3％的碳十六-十八脂肪醇加入熔解槽中，在75℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；
2S)将质量为总量40％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1000转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；
3S)将质量为总量50％的鳞片石墨、质量为总量3％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以41转/分钟的转速搅拌4分钟，得到混合均匀的混合粉料；
4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1250目，得到所述腐植酸肥料用防结块剂。
实施例1～实施例5各组分的用量需满足本发明所述的比例关系，本领域技术人员可以根 据实际情况基于上述制备方法进行适应性调整。具体实施例情况如表1所示：
表1腐植酸肥料用防结块剂具体实施例列表
对比例
为了进一步说明本发明的有益效果，选择目前较为常用的腐植酸肥料用山东GY粉状防结剂作为对比实施例。
测试例1
将上述实施例与对比例的粉状防结块剂应用于腐植酸肥料，并对防结块性能及其他功效进行测试。其中，分别取上述实施例与对比例中的粉状防结块剂各4公斤添加(均不添加油剂防结块剂)至一吨腐植酸复合肥(吨肥)中，其中腐植酸复合肥选用15-15-15复混肥，此腐植酸复混肥中的腐植酸及其他有机质含量≥10％，复混肥原肥外观为黑色，水份≥3.0％，性能检测结果如表2所示。其中，性能检测均已以相同条件相同时间进行表征：
表2不同防结块剂的性能测试结果
从上述测试例1我们可以看出，将实施例1～5的防结块剂包覆到复合肥中，包覆实施例1～5的防结块剂的复合肥外观仍为黑色并且复合肥具有光泽，但是对比例的防结块剂包覆复合肥后，原本黑色的复合肥褪色泛白且无关泽，说明本申请的防结块剂不会对复合肥原本的黑色造成影响，使用本申请防结块剂的复合肥外观美观；使用实施例的的复合肥无粉化现象，使用对比例的复合肥表层粉化，说明使用本申请防结块剂的复合肥的抗粉化效果好；实施例中的防结块剂对于复合肥的平均吸附率为99％，对比例中的防结块剂对于复合肥的吸附率为75％，本申请的防结块剂对于复合肥的吸附率远远高于对比例，说明本申请的防结块剂对于复合肥具有较好的吸附性；使用实施例的复合肥的平均防结块率为96％，使用对比例中的复合肥的防结块率为75％，使用本申请防结块剂的肥料的防结块率远远高于对比例的，说明使用本申请的防结块剂可以有效的降低腐植酸肥料的结块性；使用实施例的复合肥的中K
2O的含量平均增加了0.0252％，使用对比例中的复合肥中K
2O含量并未增加，说明使用本申请的防结块剂可以增加肥料效能。在同质量的腐植酸复合肥中添加同质量的实施例与对比例中的粉状防结块剂，此时吨肥防结块成本也相同，本申请的粉状防结块剂不会对腐植酸肥料原肥的颜色产生影响，其吸附性能较佳，防结块以及抗粉化效果较好并且可以增加肥料效能。
测试例2
将上述实施例1与对比例的粉状防结块剂应用于腐植酸肥料，并对防结块的性能及其他功效进行测试，其中，将对比例中的山东GY粉状防结剂与油剂防结块剂配合使用，对比例1的粉状防结剂单独使用不添加油剂防结块剂。取实施例1中的粉状防结块剂4公斤添加(不添加油剂防结块剂)至一吨腐植酸复合肥中，取对比例中的粉状防结块剂4公斤并搭配1.8 公斤的油剂防结块剂添加至一吨腐植酸复合肥中。其中，腐植酸复合肥选用15-15-15复混肥，此腐植酸复合肥中的腐植酸及其他有机质含量≥10％，复混肥原肥外观为黑色，水份≥3.0％，性能检测结果如表3所示，其中，性能检测均已以相同条件相同时间进行表征：
表3实施例1与对比例(山东GY防结块剂产品油配粉)对比测试结果：
从上述测试例2我们可以看出，对比例的山东GY防结块粉剂搭配油剂防结块剂达到与本申请中的防结块粉剂相似的吸附率以及防结块率时，其成本远远高于本申请，本发明中吨肥防结块成本比对比例中的常规化肥防结块剂成本下降64.3％。另外，对比例中油配粉的防结块剂包覆到复合肥表面，使复合肥外观颜色褪色泛白，无光泽，并且造成复合肥表层粉化，更重要的是也无增加肥料效能的效果。但是实施例1包覆的复合肥，外观仍为黑色并且复合肥具有光泽，并且复合肥无粉化，复合肥中的K
2O含量增加，肥料效能增加。
综上所述，本发明具有下述有益效果：
第一，引入秸秆灰烬，灰烬主要化学成份为碳酸钾、硫酸钾、氯化钾的混合物，这些混合物皆为可溶性钾盐，一方面，钾盐分子能结合部分游离水变为结晶水，减少肥料结块的因素，另一方面，能直接提供农作物所需钾元素，在防止肥料结块的同时达到增加肥料效能的效果。
第二，使用不饱和脂肪酸以及碳十六-十八脂肪醇做表面活性剂，一方面，不饱和脂肪酸以及碳十六-十八脂肪醇的加入能抑制肥料中尿素成分因气温变化反复“溶解-结晶”从而导致的结块问题，另一方面提高了防结块剂在肥料表面的吸附性。
第三，通过引入具有润滑作用的鳞片石墨或微晶石墨改进防结块性能，同时这两种石墨有光泽，能使肥料颗粒美观。
第四，通过引入聚丙烯酸钾解决肥料颗粒表层的水份问题，即解决了结块与粉化问题，聚丙烯酸钾本身是高吸水物质，不仅能解决水份问题，还具有吸水快速加倍膨胀的特性，增加了肥料颗粒间的物理隔离性，该物质在土壤中吸水与释水的过程起到了肥料缓释的作用，另外该物质日久降解后留在土壤中的物质最终为可溶性钾盐，为农作物提供养份。
最后应说明的是：在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包含一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个…”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本发明的技术方案，而非对其限制。尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
通过引入秸秆灰烬，使用不饱和脂肪酸以及碳十六-十八脂肪醇做表面活性剂，以及引入具有润滑作用的鳞片石墨或微晶石墨有效减少肥料结块的因素和聚丙烯酸钾，从多个方面上来防止肥料结块，提高肥料的使用效率，并且秸秆灰烬和聚丙烯酸钾的使用，能够有效的增加肥料的效能，为农作物提供充足的养份，另外，通过使用秸秆灰烬来代替传统粉体防结块剂所用的滑石粉，能够大幅度其降低生产的成本，具有较高的经济价值。
Claims (8)
- 腐植酸肥料用并具肥料增效功能的防结块剂，其特征在于，所述防结块剂包括下述组分，所述各组分的含量以质量百分比表示如下：
- 如权利要求1所述的腐植酸肥料用并具肥料增效功能的防结块剂，其特征在于，所述防结块剂包括下述组分，所述各组分的含量以质量百分比表示如下：
- 如权利要求1所述的腐植酸肥料用并具肥料增效功能的防结块剂，其特征在于，所述润滑剂为鳞片石墨或微晶石墨。
- 如权利要求1所述的腐植酸肥料用并具肥料增效功能的防结块剂，其特征在于，所述防结块剂为干粉状，所述防结块剂的粉末细度为800～1250目。
- 一种如权利要求1～4中任一所述的腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，其特征在于，所述制备方法包括下述步骤：1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量3％～5％的不饱和脂肪酸与质量为总量1.5％-3％的碳十六-十八脂肪醇加入熔解槽中，在75～85℃的温度下熔化为完全液态，得到混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液；2S)将质量为总量40％～55％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以950～1100转/分钟的转速搅拌3-5min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；3S)将质量为总量39％～50％的润滑剂、质量为总量1.5％～3％的聚丙烯酸钾以及步骤2S 中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以38～42转/分钟的转速搅拌4～6分钟，得到混合均匀的混合粉料；4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至800-1250目，得到所述腐植酸肥料用并具肥料增效功能的防结块剂。
- 如权利要求5所述的腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，其特征在于，所述制备方法包括下述步骤：1S)不饱和脂肪酸与碳十六-十八脂肪醇的混合：将质量为总量4％的不饱和脂肪酸与质量为总量2％的碳十六-十八脂肪醇加入熔解槽中，在80℃的温度下熔化为完全液态，得到混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；2S)将质量为总量50％的秸秆灰烬加入搅拌机中，在搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液，以1000转/分钟的转速搅拌4min使秸秆灰烬与不饱和脂肪酸与碳十六-十八脂肪醇的混合液混合均匀，得到经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬；3S)将质量为总量42％的润滑剂、质量为总量2％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到混合机中，以40转/分钟的转速搅拌5分钟，得到混合均匀的混合粉料；4S)将步骤3S中的混合粉料投入气流磨中，将混合粉料粉碎至1000目，即得腐植酸肥料用并具肥料增效功能的防结块剂。
- 如权利要求5所述的腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，其特征在于，所述步骤3S)中，所述润滑剂为鳞片石墨或微晶石墨。
- 如权利要求5所述的腐植酸肥料用并具肥料增效功能的防结块剂的制备方法，其特征在于，所述步骤2S)包括：将质量为总量40％～55％的秸秆灰烬加入体积1立方的搅拌机中搅拌均匀，在体积1立方的搅拌机中喷入步骤1S)中混合均匀的液态不饱和脂肪酸与碳十六-十八脂肪醇的混合液；所述步骤3S)包括：将质量为总量39％～50％的润滑剂、质量为总量1.5％～3％的聚丙烯酸钾以及步骤2S中所得的经不饱和脂肪酸与碳十六-十八脂肪醇的混合液改性的秸秆灰烬加入到体积2立方的混合机中；所述步骤4S)包括：将步骤3S中的混合粉料投入体积2立方的气流磨中。
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| CN101985411A (zh) * | 2010-11-02 | 2011-03-16 | 湖北富邦化工科技有限公司 | 高塔造粒尿基复合肥专用环保型防结块剂及制备方法 |
| CN102126891A (zh) * | 2011-03-23 | 2011-07-20 | 北京富瑞雪科技发展有限公司 | 一种粉体复合肥防结块剂及其制备方法和应用 |
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| CN102718598A (zh) * | 2012-07-03 | 2012-10-10 | 常州大学 | 一种肥料用缓释型可生物降解防结块的包膜材料及其应用 |
| CN102786358A (zh) * | 2012-08-29 | 2012-11-21 | 湖北富邦科技股份有限公司 | 一种水溶性防结块剂及其制备方法 |
| CN103664334A (zh) * | 2013-11-14 | 2014-03-26 | 北京富瑞雪科技发展有限公司 | 一种肥料防结块剂及其应用 |
| CN104211521A (zh) * | 2014-09-12 | 2014-12-17 | 北京富瑞雪科技发展有限公司 | 一种黑色肥料多功能添加剂、其制备方法及其应用 |
| CN104829339A (zh) * | 2015-04-30 | 2015-08-12 | 阜阳富瑞雪化工科技有限公司 | 一种防止复合肥泛白、粉化的添加剂及其制备方法和应用 |
| CN105175127A (zh) * | 2015-09-06 | 2015-12-23 | 赵月 | 肥料防结块剂、其制备方法及其应用 |
| CN106187438A (zh) * | 2016-06-30 | 2016-12-07 | 云南磷化集团有限公司 | 一种高流平性肥料包裹剂及其制备方法 |
| CN106748287A (zh) * | 2017-02-08 | 2017-05-31 | 武汉铂莱材料科技有限公司 | 一种水性肥料防结块剂及其制备方法 |
| CN107011076A (zh) * | 2017-06-09 | 2017-08-04 | 贵州大学 | 一种肥料防结块剂及其制备方法 |
| CN107500853A (zh) * | 2017-08-10 | 2017-12-22 | 阜阳富瑞雪化工科技有限公司 | 腐植酸肥料用并具肥料增效功能的防结块剂及其制备方法 |
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| US11142489B2 (en) * | 2019-01-14 | 2021-10-12 | Michael F. Forostoski | Lubricated agricultural mixture |
| CN114656293A (zh) * | 2022-04-28 | 2022-06-24 | 湖北佳玛驰生态农业有限公司 | 一种提高微生物在高无机养分肥中存活率的方法 |
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