WO2020093893A1 - Preparation method for alginic acid synergistic carrier for reducing urea conversion - Google Patents

Preparation method for alginic acid synergistic carrier for reducing urea conversion Download PDF

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WO2020093893A1
WO2020093893A1 PCT/CN2019/113605 CN2019113605W WO2020093893A1 WO 2020093893 A1 WO2020093893 A1 WO 2020093893A1 CN 2019113605 W CN2019113605 W CN 2019113605W WO 2020093893 A1 WO2020093893 A1 WO 2020093893A1
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weight
parts
alginic acid
urea
preparation
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PCT/CN2019/113605
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French (fr)
Chinese (zh)
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李燕婷
袁亮
赵秉强
林治安
张水勤
王薇
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中国农业科学院农业资源与农业区划研究所
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Publication of WO2020093893A1 publication Critical patent/WO2020093893A1/en

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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
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds

Definitions

  • the invention belongs to the technical field of fertilizer production. More specifically, the present invention relates to a method for preparing an alginic acid synergistic carrier that slows the conversion of urea.
  • Urea is the most important nitrogen fertilizer variety in China, but due to its high activity and easy conversion loss, the current season utilization rate is only 30% to 35%, causing huge economic losses and bringing serious environmental risks, such as ammonia in PM 2.5
  • the mass concentration in is about 30%, and some heavily polluted weather exceeds 60%.
  • Slowing down the decomposition rate of urea and reducing the activity of soil urease are the main ways to reduce its loss.
  • Alginic acid is rich in quinone groups, ketone groups and other functional groups, which can inhibit soil urease activity to a certain extent, thereby reducing the loss of urea nitrogen fertilizer.
  • the existing extraction method of alginic acid is mainly to use inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc. to form water-soluble alginate through violent reaction, which is destructive to the acid group of alginic acid itself. Since the prepared alginate is more alkaline, the ammonium formed by the conversion of urea will soon be volatilized and lost in the form of ammonia, resulting in unstable application of alginic acid on urea. People have used microbial method or enzymatic extraction, but these methods have the disadvantages of high production cost and unstable extraction products.
  • CN102701866A discloses a fermented seaweed liquid fertilizer synergist and its production method and use. It uses natural seaweed as a raw material, undergoes microbial fermentation, and then undergoes alkaline extraction, pressure filtration and other processes to prepare seaweed extract, and then extracts from this Chelated trace elements are added to the liquid to obtain a fermented seaweed fertilizer synergist.
  • CN104761413A discloses an alginic acid fertilizer synergist with ammonia volatilization inhibitory effect and its preparation method. It uses kelp, strains, carbon source, nitrogen source, medium and trace elements as the main raw materials, after fermentation, extraction and compounding Prepared by other processes.
  • CN107236766A discloses a method for preparing a seaweed plant growth regulator by a whole-body biological enzymolysis method, which includes preparation before production, raw material pretreatment, first-level enzymolysis, enzymolysis solution removal, homogenization of enzymolysis solution, and second-level enzymolysis , Post-treatment, somatotropin separation and purification, fertilizer final preparation and other steps, the preparation process has a long and complicated process flow.
  • the object of the present invention is to provide a method for preparing an alginic acid synergistic carrier that slows the conversion of urea.
  • the invention provides a method for preparing an alginic acid synergistic carrier which can slow down the conversion of urea.
  • the steps of the preparation method are as follows:
  • step B Add 100 parts by weight of algae powder to 800-1500 parts by weight of the alginic acid organic extractant obtained in step A, and then gradually increase its temperature to 70-90 ° C under stirring, and maintain at this temperature 6 ⁇ 12h, then cooled to room temperature, centrifuged, discarded the precipitate, and obtained the alginic acid extract;
  • step C Add 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in step B, and heat to a temperature of 50 °C, then add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight of o Phthalic acid alkyl amide, cooled, and adjusted its pH to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier.
  • the alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
  • the stirring rotation speed is 60-180 rpm; the temperature of the cooled solution is ⁇ 30 ° C.
  • the weight ratio of the dimethylformamide, alcoholamine, aniline, ethylene glycol and water is 100: 28-42: 6-9: 6-9: 2200-2800.
  • the seaweed raw material of the seaweed powder is brown algae, kelp or phyllodes; the particle size of the seaweed powder is less than 2 mm.
  • the rotation speed of the stirring is 100-200 rpm.
  • the rotation speed of the centrifugation is 1000-5000 rpm; the time of the centrifugation is 10-30 min.
  • the benzenecarboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
  • the concentration of the pyrophosphate aqueous solution is 1 to 5 mol / L.
  • the temperature of the cooled solution is 15-30 ° C.
  • the present invention provides a method for preparing an alginic acid synergistic carrier that slows the conversion of urea.
  • the alginic acid synergistic carrier prepared by the present invention is rich in organic acidic functional groups, and can react with urea amine groups to form long-chain compounds, which can slow down the decomposition rate of urea;
  • the alginic acid synergistic carrier prepared by the present invention can reduce the pH value of granular urea fertilizer by 0.3 to 1 unit, retain the converted ammonium and reduce the ammonia state Loss of nitrogen volatilization; on the basis of reducing nitrogen loss, the alginic acid synergistic carrier of the present invention also has the functions of stimulating the growth of crop roots, activating phosphorus, potassium and trace elements in the soil, and further improving the application effect of the synergistic carrier; seaweed
  • the freshness of the alginic acid synergistic carrier for the conversion of ammonium, the residual rate of urea is increased by more than 5
  • the invention provides a method for preparing an alginic acid synergistic carrier which can slow down the conversion of urea.
  • the steps of the preparation method are as follows:
  • step B Add 100 parts by weight of algae powder to 800-1500 parts by weight of the alginic acid organic extractant obtained in step A, and then gradually increase its temperature to 70-90 ° C under stirring, and maintain at this temperature 6 ⁇ 12h, then cooled to room temperature, centrifuged, discarded the precipitate, and obtained the alginic acid extract;
  • step C Add 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in step B, and heat to a temperature of 50 °C, then add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight of o Phthalic acid alkyl amide, cooled, and adjusted its pH to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier.
  • dimethylformamide is an organic base, which can react with acid groups such as carboxyl group and phenolic hydroxyl group in alginic acid to generate water-soluble alginic acid, so that it can extract seaweed from seaweed raw materials Acid, and it can also increase the content of methyl and methoxy functional groups in the seaweed extract.
  • the dimethylformamide used in the present invention is a product currently on the market, for example, the product sold by Nanjing Kezheng Chemical Co., Ltd. under the trade name N, N-dimethylformamide (DMF).
  • the alcohol amine used in the present invention is a compound that takes the nitrogen atom of ammonia as the core and the hydrogen atom of ammonia is replaced by an alcohol. It can chelate with calcium, magnesium, iron and other ions in the raw material of seaweed powder to improve the Water solubility helps to increase the extraction rate of alginic acid from algae raw materials.
  • the alcoholamine used in the present invention is one or more alcoholamines selected from monoethanolamine, diethanolamine, triethanolamine or N-methyldiethanolamine.
  • the alcohol amines mentioned are all products currently on the market, such as those sold by Shanghai Minchen Chemical Co., Ltd. under the trade name monoethanolamine (MEA), and Zouping Guoan Chemical Co., Ltd. under the trade name N-methyldiethanolamine (MDEA) products sold.
  • MEA monoethanolamine
  • MDEA N-methyldiethanolamine
  • Aniline has an amino group, which can react with the alginic acid group to connect with the benzene ring, thus enhancing the stability of the algae extract.
  • the aniline used in the present invention is a product currently on the market, such as the product sold by Georgia Chemical Industry Co., Ltd. under the trade name of aniline MDI grade.
  • Ethylene glycol can enhance the liquid stability and fluidity of alginic acid organic extractant due to its good miscibility with water and low temperature resistance.
  • the ethylene glycol used in the present invention is a product currently on the market, for example, the product sold by Zhengzhou Zhengsheng Chemical Products Co., Ltd. under the trade name ethylene glycol for antifreeze.
  • the amount of alcohol amine when the amount of other raw materials is within the stated range, if the amount of alcohol amine is less than 20 parts by weight, the alginic acid extraction rate will be reduced; if the amount of alcohol amine is more than 50 parts by weight, it will There are too many bubbles in the seaweed extract, and fine impurities are mixed in the extract, and the purity of the extracted alginic acid liquid is reduced; therefore, the amount of alcohol amine is 20-50 parts by weight, preferably 28-42 parts by weight, more It is preferably 30 to 36 parts by weight.
  • the amount of other raw materials is within the stated range, if the amount of aniline is less than 5 parts by weight, the effect of enhancing the stability of the seaweed extract will not be obvious; if the amount of aniline is more than 10 parts by weight, it will not continue The stability of the seaweed extract is significantly improved; therefore, the amount of aniline used is 5 to 10 parts by weight, preferably 6 to 9 parts by weight.
  • the amount of other raw materials is within the stated range, if the amount of ethylene glycol is less than 5 parts by weight, the effect of improving the stability of the algae extract at low temperatures will be insignificant; if the amount of ethylene glycol is greater than 10 parts by weight Parts, because of its high hydroxyl content, it may cause partial viscous alginic acid precipitation with storage time extension; therefore, the amount of ethylene glycol is 5 to 10 parts by weight, preferably 6 to 9 parts by weight Copies.
  • the amount of water used is 2000-3000 parts by weight, preferably 2200-2800 parts by weight, more preferably The ground is 2400-2600 parts by weight.
  • the weight ratio of dimethylformamide, alcohol amine, aniline, ethylene glycol and water is 100: 28-42: 6-9: 6-9: 2200-2800.
  • the weight ratio of dimethylformamide, alcoholamine, aniline, ethylene glycol and water is 100: 30-36: 7-8: 7-8: 2400-2600.
  • a solution obtained by stirring and dissolving raw materials such as dimethylformamide at a rotation speed of 60 to 180 rpm is cooled to a temperature of 30 ° C. or lower.
  • the present invention adds 100 parts by weight of alginate powder to 800-1500 parts by weight of alginic acid organic extractant, and then gradually raises its temperature to 70-90 ° C under stirring, and at this temperature Keep for 6 to 12 hours, then cool to room temperature, centrifuge, and discard the precipitate to obtain the alginic acid extract.
  • the seaweed is brown algae, megaalgae or leaf algae.
  • the seaweeds used in the present invention are all products currently on the market.
  • the brown algae used in the present invention are sold by Yantai Changdao Sanyou Company under the trade name kelp Brown algae
  • the macroalgae used in the present invention is the macroalgae sold by Shaanxi Snote Biotechnology Co., Ltd. under the trade name of macroalgae raw powder.
  • the existing conventional crushing equipment is used to pulverize the brown algae, megaalgae or leaf algae, and the algae powder with a particle size of less than 2 mm is collected as a raw material to prepare an alginic acid extraction solution.
  • the amount of the extractant when the raw material of seaweed powder is 100 parts by weight, if the amount of the extractant is less than 800 parts by weight, it will cause the thick liquid to be difficult to perform subsequent centrifugal treatment; if the amount of the extractant is more than 1500 parts by weight, It will cause the water content of the extracted alginic acid liquid to affect the application in urea. Therefore, it is appropriate that the amount of the extractant is 800-1500 parts by weight.
  • the temperature of the mixture of the algae powder raw material and the alginic acid organic extractant is gradually increased to 70 to 90 ° C under stirring at a rotation speed of 100 to 200 rpm, and maintained at this temperature for 6 to 12 hours. It is undesirable that the extraction temperature and extraction time exceed the above range. If the extraction time is shorter than 6h, the extraction of alginic acid is incomplete, resulting in loss of alginic acid; if the extraction time exceeds 12h, the energy consumption and cost of extracting alginic acid increase. Therefore, the extraction time of alginic acid is 6 ⁇ 12h is feasible.
  • the extract cooled to room temperature is centrifuged at a speed of 1000 to 5000 rpm for 10 to 30 minutes using a centrifuge.
  • the centrifuge is a product sold on the existing market, for example, a product sold by Shanghai Centrifuge Machinery Research Institute Co., Ltd. under the trade name of two-phase separation decanter centrifuge.
  • the present invention adds 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid, and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of alginic acid extract, and heats to At a temperature of 50 ° C, add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight A portion of alkyl phthalate amide, cooled, and adjusted its pH value to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier that slows the conversion of urea.
  • gallic acid is grafted with benzene carboxylic acid and the alginic acid obtained in step B, so that the alginic acid functional group is further increased
  • the purpose of the species and quantity is to make the alginic acid more tightly bound to the amino group in the urea molecule, and significantly slow down the decomposition rate of urea in the soil.
  • the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid; they are all products currently on the market, for example, sold by Jiangsu Shunfeng Chemical Co., Ltd. under the trade name of benzoic acid Products, products sold by Shandong Xinhua Longxin Chemical Co., Ltd. under the trade name of industrial salicylic acid, and products sold by Zhengzhou Jiahong Chemical Co., Ltd. under the trade name of acetylsalicylic acid.
  • the amount of other raw materials when the amount of other raw materials is within the range, if the amount of gallic acid is less than 10 parts by weight, it will have a limited effect on increasing the content of functional groups of the seaweed extract; if the amount of gallic acid is more than 20 parts by weight, The cost is too high; therefore, it is reasonable to use gallic acid in an amount of 10-20 parts by weight;
  • the amount of other raw materials is within the range, if the amount of benzene carboxylic acid is less than 5 parts by weight, the increase of benzene carboxyl functional groups will be low; if the amount of benzene carboxylic acid is more than 10 parts by weight, it will cause some algae Acid precipitation; therefore, the amount of benzene carboxylic acid is 5 to 10 parts by weight is appropriate;
  • the amount of other raw materials is within the range, if the amount of dicumyl peroxide is less than 2 parts by weight, it will result in low grafting efficiency; if the amount of dicumyl peroxide is more than 3 parts by weight, it will cause reaction Too fast; therefore, the amount of dicumyl peroxide is 2 to 3 parts by weight is feasible;
  • the amount of other raw materials is within the range, if the amount of polyethylene glycol is less than 0.02 parts by weight, the grafting effect is not ideal due to low dispersibility; if the amount of polyethylene glycol is more than 0.1 parts by weight, it will form Large molecular clusters affect the grafting effect; therefore, it is feasible to use polyethylene glycol in an amount of 0.02 to 0.1 parts by weight;
  • This reaction is carried out at a temperature of 100 ° C for 60 to 120 min. If the reaction time is shorter than 60 min, the stability of the binding of gallic acid, benzenecarboxylic acid and alginic acid is insufficient; if the reaction time is longer than 120 min, the energy consumption increases significantly. Therefore, the reaction time of 90 ⁇ 120min is feasible.
  • Polyoxyethylene ether has both resin and nonionic surfactant properties in the present invention. It can be used as a stationary phase to further slow down the movement of urea in the soil solution, and can also be used as a penetrating agent to promote the combination of alginic acid and urea.
  • the phthalic acid alkylamide nonionic surfactant can not only enhance the penetration effect of polyoxyethylene ether, but also improve the stability of the synergistic carrier.
  • pyrophosphoric acid can not only adjust pH, form a buffer system, but also increase the strength of urea particles and slow down the dissolution and release rate of urea in soil solutions.
  • the amount of polyoxyethylene ether when the amount of polyoxyethylene ether is 3-8 parts by weight, if the amount of polyoxyethylene ether is less than 3 parts by weight, the dispersion and penetration properties are not obvious; if the amount of polyoxyethylene ether is more than 8 parts by weight, The viscosity of the synergistic carrier is too high; therefore, it is appropriate to use 3 to 8 parts by weight of polyoxyethylene ether.
  • the amount of phthalic acid alkyl amide is 0.5-2.0 parts by weight, if the amount of phthalic acid alkyl amide is less than 0.5 parts by weight, the penetration effect of enhanced polyoxyethylene ether is not significant; If the amount of dicarboxylic acid alkyl amide is higher than 2 parts by weight, it will affect the dispersion performance of polyoxyethylene ether; therefore, the amount of phthalic acid alkyl amide is 0.5 to 2.0 parts by weight is appropriate.
  • the concentration of the pyrophosphate aqueous solution is 1 to 5 mol / L.
  • the solution is cooled to a temperature of 15-30 ° C.
  • the gallic acid, polyethylene glycol, dicumyl peroxide, polyoxyethylene ether, alkyl phthalate and pyrophosphoric acid used in the present invention are all products currently on the market, such as Shanghai Aladdin Biochemical Technology Co., Ltd. products sold under the trade name gallic acid, Shaanxi Shuangli Chemical Co., Ltd. sold under the trade name dicumyl peroxide DCP, and Jiangsu Provincial Haian Petrochemical Plant under the trade name polyoxyethylene ether emulsifier OP -7 Products sold by Guangzhou Zongyu Chemical Technology Co., Ltd. under the trade name TAB-2 phthalic acid alkylamide.
  • the alginic acid synergistic carrier prepared by the invention can be combined with a urea production process or a granular urea product to produce a new urea product with high nitrogen fertilizer utilization rate.
  • the method of using the alginic acid synergistic carrier for slowing the conversion of urea according to the present invention is as follows:
  • the first method in the process of urea production, add 5 to 50 parts by weight of the alginic acid synergistic carrier prepared by the method of the present invention to 1000 parts by weight of urea melt, and spray the tower to obtain alginic acid synergistic carrier particles Urea.
  • the second method add 5-50 parts by weight of alginic acid synergistic carrier to 1000 parts by weight of granular urea heated to 40-75 ° C, stir quickly for 2min, mix and dry at 100 ° C to obtain alginic acid-containing Effective carrier granular urea.
  • Example 1 Preparation of an alginic acid synergistic carrier with slowed urea conversion
  • step A Add 100 parts by weight of kelp brown algae powder raw material with a particle size of less than 2mm to 1000 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually increase its temperature to 90 ° C under stirring at 180 rpm, and at this temperature Hold for 10 hours, then cool to room temperature, centrifuge at 1000 rpm for 26 min, discard the precipitate, and obtain the alginic acid extract;
  • Example 2 Preparation of an alginic acid synergistic carrier with slowed urea conversion
  • Example 3 Preparation of an alginic acid synergistic carrier with slowed urea conversion
  • step A Add 100 parts by weight of the raw material of Ascophyllum nodosum powder with a particle size of less than 2 mm to 1500 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually raise its temperature to 80 ° C under stirring at a rotation speed of 200 rpm. Maintain the temperature for 12h, then cool to room temperature, centrifuge at 5000rpm for 30min, and discard the precipitate to obtain the alginic acid extract;
  • step A Add 100 parts by weight of the raw material of wild kelp brown algae powder with a particle size of less than 2mm to 1200 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually raise its temperature to 80 ° C with stirring at a rotation speed of 140 rpm. Maintain the temperature for 6h, then cool to room temperature, centrifuge at 3800rpm for 18min, discard the precipitate, and obtain the alginic acid extract;
  • Test Example 1 The effect of the alginic acid synergistic carrier of the present invention on the residual rate of urea
  • Sample preparation The alginic acid synergistic carriers prepared in Example 1, Example 2 and Example 3 were added to three molten urea at a temperature of 118 ° C according to its weight ratio of 2: 100 to urea, and let it be at this temperature After 5 minutes of reaction, and then cooling, urea alginate A, urea alginate B and urea alginate C were obtained respectively.
  • the commercially available urea (Rising Group Co., Ltd., nitrogen content 46%) was treated in the same manner, and the obtained sample was the control sample U.
  • Test procedure Weigh 1.0g of a commercially available urea control sample and alginate urea A, alginate urea B and alginate urea C containing 1.0g urea in a culture bottle, then add 100mL of sterile water to dissolve, and then to these cultures Add 0.2g of urease (enzyme activity is 1U) to the bottle, shake well, and then place in a light-free incubator with a temperature of 37 ⁇ 2 °C for 12 hours. During the cultivation period, shake it every 2 hours.
  • the amount of remaining urea (g) in the solution was determined by the diacetyl-oxime colorimetric method specified in HG / T 4135-2010, and the residual difference rate of urea was calculated according to the following formula:
  • the test results in Table 1 show that the alginic acid synergistic carrier of the present invention can significantly slow down the decomposition and conversion of urea.
  • the residual rate of urea in the samples of alginate urea A, alginate urea B, and alginate urea C are respectively increased by 64.7% and 115.5 compared to urea % And 91.2%.
  • Test Example 2 Effect of the alginic acid synergistic carrier of the present invention on soil pH and nitrogen conversion of urea fertilizer
  • Sample preparation The melting process is the same as in Test Example 1.
  • Test procedure Place the cube urea blocks A, B, C and U in calcareous Chao soil (Shandong Dezhou) with a water content of 18% by weight, and compact the soil to a bulk density of 1.3 g / cm 3 at a temperature of 25 Incubate at ⁇ 2 °C for 12h. After the cultivation is completed, the blade is used to cut out the soil 1.5 to 2 cm, 1 to 1.5 cm, 0.5 to 1 cm, and 0 to 0.5 cm from the edge of the urea block, respectively.
  • Test detection According to (Lu Rukun. "Analysis Method of Soil Agricultural Chemistry”. Beijing: China Agricultural Science and Technology Press, 2000.) Standard analysis method to test the pH, urea nitrogen, ammonium nitrogen content in the urea block fertilizer soil, The results are shown in Table 2.
  • Table 2 Comparison of soil pH, urea nitrogen content and ammonium nitrogen content in the fertilizer soil with the synergistic carrier urea and commercial urea
  • Fertilization is the initial stage of fertilizer conversion and determines the later urea conversion and loss process.
  • the test results show that the alginic acid synergistic carrier prepared by the present invention can significantly reduce the soil pH of the urea fertilizer, especially the soil pH within 1 cm of the fertilizer, and the reduction range is 0.3 to 1.0 pH units, that is, H in the fertilizer solution + Concentration increased by 3 to 11 times; urea was significantly higher within 2 cm of the fertilizer, and ammonium nitrogen was significantly lower than that of commercially available urea treatment, indicating that the decomposition and conversion rate of alginate urea was significantly slowed.
  • Test Example 3 The effect of the alginic acid synergistic carrier of the present invention on the growth and vigor of wheat and corn roots
  • Example 4 Using the alginic acid synergistic carriers prepared in Example 1, Example 2 and Example 4, a sand culture experiment was used to study the effect of the synergistic carrier on the growth and vigor of wheat and corn roots.
  • the added amount of the synergistic carrier of the present invention in Hogeland's nutrient solution is 0.2 g / L, which are respectively referred to as treatment A, treatment B, and treatment C.
  • the treated crops were planted in cultivation pottery and repeated 6 times. Irrigate the nutrient solution every 4 days, 100mL each time, to maintain a certain humidity and nutrient concentration.
  • the absorption capacity of the crop root system is an important factor that determines the fertilizer utilization rate. From the results listed in Table 3, it can be seen that the fresh weight and vitality of wheat roots treated with alginic acid synergistic carriers A, B and C increased by an average of 54.9% and 36.3%, respectively, and that of corn roots increased by 38.5% and 26.7 %.
  • the combination of the alginic acid synergistic carrier prepared by the present invention and urea can significantly slow down the decomposition, release and conversion of urea, enhance the stability of urea, and improve the vitality of crop roots by affecting the fertilization process of urea conversion. Promote crop nutrient absorption.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a preparation method for an alginic acid synergistic carrier for reducing urea conversion. The preparation method comprises steps such as preparation of an alginic acid organic extract agent, preparation of an alginic acid extract solution and preparation of an alginic acid synergistic carrier. The combination of the alginic acid synergistic carrier with urea can significantly slow the decomposition, release and conversion speed of urea, the urea residue ratio being increased by 90% compared with the commercially available urea, and can enhance the sustained release of urea by influencing fertilizer processes such as the pH of the urea conversion, the soil pH within 1 cm of a fertilizer being decreased by 0.3-1.1 units compared with commercially available urea. The fresh weight and viability of an alginic acid synergistic carrier treated wheat root system respectively increase 54.9% and 36.3% in average compared to the control, and the fresh weight and viability of a corn root system respectively increase 38.5% and 26.7%.

Description

一种具有减缓尿素转化的海藻酸增效载体的制备方法Preparation method of alginic acid synergistic carrier for slowing urea conversion
本申请要求于2018年11月09日提交中国专利局、申请号为201811329005.3、发明名称为“一种具有减缓尿素转化的海藻酸增效载体的制备方法”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。This application requires the priority of the Chinese patent application filed on November 09, 2018 in the China Patent Office with the application number 201811329005.3 and the invention titled "A method for preparing an alginic acid-enhancing carrier that slows the conversion of urea". The content is incorporated into this application by reference.
技术领域Technical field
本发明属于肥料生产技术领域。更具体地，本发明涉及一种具有减缓尿素转化的海藻酸增效载体的制备方法。The invention belongs to the technical field of fertilizer production. More specifically, the present invention relates to a method for preparing an alginic acid synergistic carrier that slows the conversion of urea.
背景技术Background technique
尿素是我国最重要的氮肥品种，但因其活性高，易转化损失，当季利用率仅为30％～35％，造成巨大的经济损失，并带来严重的环境风险，例如氨在PM 2.5中的质量浓度占比为30％左右，部分重污染天气超过60％。减缓尿素分解速度、降低土壤脲酶活性是降低其损失的主要途径。海藻酸中含有丰富的醌基、酮基等官能团，可在一定程度上抑制土壤脲酶活性，从而减少尿素氮肥损失。但现有海藻酸的提取方法主要是利用氢氧化钠、氢氧化钾、碳酸钠等无机碱提取，经剧烈反应形成水溶性海藻酸盐，对海藻酸本身的酸性基团具有一定破坏性，同时由于制备的海藻酸盐碱性较强，尿素转化形成的铵很快以氨的形式挥发损失，导致海藻酸在尿素上的应用效果不稳定。人们曾采用微生物法或酶解法提取，但这些方法存在生产成本高，提取产物不稳定等缺点。Urea is the most important nitrogen fertilizer variety in China, but due to its high activity and easy conversion loss, the current season utilization rate is only 30% to 35%, causing huge economic losses and bringing serious environmental risks, such as ammonia in PM 2.5 The mass concentration in is about 30%, and some heavily polluted weather exceeds 60%. Slowing down the decomposition rate of urea and reducing the activity of soil urease are the main ways to reduce its loss. Alginic acid is rich in quinone groups, ketone groups and other functional groups, which can inhibit soil urease activity to a certain extent, thereby reducing the loss of urea nitrogen fertilizer. However, the existing extraction method of alginic acid is mainly to use inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc. to form water-soluble alginate through violent reaction, which is destructive to the acid group of alginic acid itself. Since the prepared alginate is more alkaline, the ammonium formed by the conversion of urea will soon be volatilized and lost in the form of ammonia, resulting in unstable application of alginic acid on urea. People have used microbial method or enzymatic extraction, but these methods have the disadvantages of high production cost and unstable extraction products.
CN102701866A公开了一种发酵海藻液肥料增效剂及其生产方法与用途，它以天然海藻为原料，经微生物发酵，再经碱提取、压滤等工序制取海藻提取液，然后向这种提取液里添加螯合态微量元素，得到一种发酵海藻肥料增效剂。CN104761413A公开了一种具有氨挥发抑制作用的海藻酸肥料增效剂及其制作方法，它以海带、菌种、碳源、氮源、中微量元素等为主要原料，经发酵、提取、复配等工序制备得到。CN107236766A公开了一种整体生物酶解法制备海藻植物生长调节剂的方法，该方法包括生产前准备、原料预处理、一级酶解、酶解液除杂、酶解液均质、二级酶解、后处理、促生长素分离纯化、肥料终配等步骤，该制备方法工艺流程长而复杂。CN102701866A discloses a fermented seaweed liquid fertilizer synergist and its production method and use. It uses natural seaweed as a raw material, undergoes microbial fermentation, and then undergoes alkaline extraction, pressure filtration and other processes to prepare seaweed extract, and then extracts from this Chelated trace elements are added to the liquid to obtain a fermented seaweed fertilizer synergist. CN104761413A discloses an alginic acid fertilizer synergist with ammonia volatilization inhibitory effect and its preparation method. It uses kelp, strains, carbon source, nitrogen source, medium and trace elements as the main raw materials, after fermentation, extraction and compounding Prepared by other processes. CN107236766A discloses a method for preparing a seaweed plant growth regulator by a whole-body biological enzymolysis method, which includes preparation before production, raw material pretreatment, first-level enzymolysis, enzymolysis solution removal, homogenization of enzymolysis solution, and second-level enzymolysis , Post-treatment, somatotropin separation and purification, fertilizer final preparation and other steps, the preparation process has a long and complicated process flow.
发明内容Summary of the invention
本发明的目的是提供一种具有减缓尿素转化的海藻酸增效载体的制备方 法。The object of the present invention is to provide a method for preparing an alginic acid synergistic carrier that slows the conversion of urea.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above object of the invention, the present invention provides the following technical solutions:
本发明提供了一种具有减缓尿素转化的海藻酸增效载体的制备方法，该制备方法的步骤如下：The invention provides a method for preparing an alginic acid synergistic carrier which can slow down the conversion of urea. The steps of the preparation method are as follows:
A、将100重量份二甲基甲酰胺、20～50重量份醇胺、5～10重量份苯胺和5～10重量份乙二醇加到2000～3000重量份温度为60～70℃的水中，搅拌溶解，冷却，得到海藻酸有机提取剂；A. Add 100 parts by weight of dimethylformamide, 20-50 parts by weight of alcohol amine, 5-10 parts by weight of aniline and 5-10 parts by weight of ethylene glycol to 2000-3000 parts by weight of water at a temperature of 60-70 ° C , Stir to dissolve, cool to obtain alginic acid organic extractant;
B、将100重量份海藻粉添加到800～1500重量份步骤A得到的所述海藻酸有机提取剂中，然后在搅拌下将其温度逐渐升至70～90℃，并在这个温度下保持6～12h，接着冷却至室温，离心分离，沉淀弃去，得到的海藻酸提取液；B. Add 100 parts by weight of algae powder to 800-1500 parts by weight of the alginic acid organic extractant obtained in step A, and then gradually increase its temperature to 70-90 ° C under stirring, and maintain at this temperature 6 ～ 12h, then cooled to room temperature, centrifuged, discarded the precipitate, and obtained the alginic acid extract;
C、将10～20重量份没食子酸、5～10重量份苯羧酸和0.02～0.1重量份聚乙二醇加到100重量份步骤B得到的所述海藻酸提取液中，加热至温度50℃，再加入2～3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应60～120min，再加入3～8重量份聚氧乙烯醚和0.5～2.0重量份邻苯二甲酸烷基酰胺，冷却，使用焦磷酸水溶液将其pH调节至5～6，得到海藻酸增效载体。C. Add 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in step B, and heat to a temperature of 50 ℃, then add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight of o Phthalic acid alkyl amide, cooled, and adjusted its pH to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier.
优选的，在步骤A中，所述醇胺选自一乙醇胺、二乙醇胺、三乙醇胺和N-甲基二乙醇胺中的一种或几种。Preferably, in step A, the alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
优选的，在步骤A中，所述搅拌的转速60～180rpm；所述冷却后的溶液的温度为≤30℃。Preferably, in step A, the stirring rotation speed is 60-180 rpm; the temperature of the cooled solution is ≤30 ° C.
优选的，在步骤A中，所述二甲基甲酰胺、醇胺、苯胺、乙二醇与水的重量比是100：28～42：6～9：6～9：2200～2800。Preferably, in step A, the weight ratio of the dimethylformamide, alcoholamine, aniline, ethylene glycol and water is 100: 28-42: 6-9: 6-9: 2200-2800.
优选的，在步骤B中，所述海藻粉的海藻原料为褐藻、巨藻或泡叶藻；所述海藻粉的粒度小于2mm。Preferably, in step B, the seaweed raw material of the seaweed powder is brown algae, kelp or phyllodes; the particle size of the seaweed powder is less than 2 mm.
优选的，在步骤B中，所述搅拌的转速为100～200rpm。Preferably, in step B, the rotation speed of the stirring is 100-200 rpm.
优选的，在步骤B中，所述离心的转速为1000～5000rpm；所述离心的时间为10～30min。Preferably, in step B, the rotation speed of the centrifugation is 1000-5000 rpm; the time of the centrifugation is 10-30 min.
优选的，在步骤C中，所述苯羧酸为苯甲酸、苯乙酸、水杨酸或乙酰水杨酸。Preferably, in step C, the benzenecarboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
优选的，在步骤C中，所述焦磷酸水溶液的浓度是1～5mol/L。Preferably, in step C, the concentration of the pyrophosphate aqueous solution is 1 to 5 mol / L.
优选的，在步骤C中，所述冷却后的溶液的温度为15～30℃。Preferably, in step C, the temperature of the cooled solution is 15-30 ° C.
本发明的有益效果：本发明提供了一种具有减缓尿素转化的海藻酸增效载体的制备方法。本发明制备得到的海藻酸增效载体含有丰富的有机酸性官能团，可与尿素胺基反应形成长链化合物，减缓尿素分解速度；本发明海藻酸增效载体能够钝化土壤脲酶，从而减缓尿素向铵的转化，尿素残留率比市售尿素提高52％以上；本发明制备得到的海藻酸增效载体能够降低颗粒尿素肥际pH值0.3～1个单位，固持已转化形成的铵，减少氨态氮挥发损失；在减少氮损失的基础上，本发明海藻酸增效载体还具有刺激作物根系生长，活化土壤中的磷、钾及中微量元素的功能，进一步提升增效载体的应用效果；海藻酸增效载体处理的小麦根系鲜重和活力分别比对照平均提高54.9％和36.3％，玉米根系鲜重和活力分别提高38.5％和26.7％。Beneficial effect of the present invention: The present invention provides a method for preparing an alginic acid synergistic carrier that slows the conversion of urea. The alginic acid synergistic carrier prepared by the present invention is rich in organic acidic functional groups, and can react with urea amine groups to form long-chain compounds, which can slow down the decomposition rate of urea; For the conversion of ammonium, the residual rate of urea is increased by more than 52% compared with the commercially available urea; the alginic acid synergistic carrier prepared by the present invention can reduce the pH value of granular urea fertilizer by 0.3 to 1 unit, retain the converted ammonium and reduce the ammonia state Loss of nitrogen volatilization; on the basis of reducing nitrogen loss, the alginic acid synergistic carrier of the present invention also has the functions of stimulating the growth of crop roots, activating phosphorus, potassium and trace elements in the soil, and further improving the application effect of the synergistic carrier; seaweed The fresh weight and vitality of wheat roots treated with acid-enhancing carrier increased by an average of 54.9% and 36.3%, respectively, and the fresh weight and vitality of corn roots increased by 38.5% and 26.7%, respectively.
具体实施方式detailed description
本发明提供了一种具有减缓尿素转化的海藻酸增效载体的制备方法，该制备方法的步骤如下：The invention provides a method for preparing an alginic acid synergistic carrier which can slow down the conversion of urea. The steps of the preparation method are as follows:
A、将100重量份二甲基甲酰胺、20～50重量份醇胺、5～10重量份苯胺和5～10重量份乙二醇加到2000～3000重量份温度为60～70℃的水中，搅拌溶解，冷却，得到海藻酸有机提取剂；A. Add 100 parts by weight of dimethylformamide, 20-50 parts by weight of alcohol amine, 5-10 parts by weight of aniline and 5-10 parts by weight of ethylene glycol to 2000-3000 parts by weight of water at a temperature of 60-70 ° C , Stir to dissolve, cool to obtain alginic acid organic extractant;
B、将100重量份海藻粉添加到800～1500重量份步骤A得到的所述海藻酸有机提取剂中，然后在搅拌下将其温度逐渐升至70～90℃，并在这个温度下保持6～12h，接着冷却至室温，离心分离，沉淀弃去，得到的海藻酸提取液；B. Add 100 parts by weight of algae powder to 800-1500 parts by weight of the alginic acid organic extractant obtained in step A, and then gradually increase its temperature to 70-90 ° C under stirring, and maintain at this temperature 6 ～ 12h, then cooled to room temperature, centrifuged, discarded the precipitate, and obtained the alginic acid extract;
C、将10～20重量份没食子酸、5～10重量份苯羧酸和0.02～0.1重量份聚乙二醇加到100重量份步骤B得到的所述海藻酸提取液中，加热至温度50℃，再加入2～3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应60～120min，再加入3～8重量份聚氧乙烯醚和0.5～2.0重量份邻苯二甲酸烷基酰胺，冷却，使用焦磷酸水溶液将其pH调节至5～6，得到海藻酸增效载体。C. Add 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in step B, and heat to a temperature of 50 ℃, then add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight of o Phthalic acid alkyl amide, cooled, and adjusted its pH to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier.
本发明首先将100重量份二甲基甲酰胺、20～50重量份醇胺、5～10重量份苯胺与5～10重量份乙二醇加到2000～3000重量份温度为60～70℃的水中， 搅拌溶解，冷却，得到海藻酸有机提取剂。In the present invention, first, 100 parts by weight of dimethylformamide, 20-50 parts by weight of alcohol amine, 5-10 parts by weight of aniline and 5-10 parts by weight of ethylene glycol are added to 2000-3000 parts by weight at a temperature of 60-70 ° C In water, stir to dissolve and cool to obtain alginic acid organic extractant.
在本发明中，二甲基甲酰胺是一种有机碱，它可与海藻酸中的羧基、酚羟基等酸性基团进行反应而生成水溶性的海藻酸，从而能够从海藻原料中提取出海藻酸，并且它还能增加在海藻提取液中的甲基、甲氧基官能团含量。本发明使用的二甲基甲酰胺是目前市场上销售的产品，例如由南京科正化工有限公司以商品名N,N-二甲基甲酰胺(DMF)销售的产品。In the present invention, dimethylformamide is an organic base, which can react with acid groups such as carboxyl group and phenolic hydroxyl group in alginic acid to generate water-soluble alginic acid, so that it can extract seaweed from seaweed raw materials Acid, and it can also increase the content of methyl and methoxy functional groups in the seaweed extract. The dimethylformamide used in the present invention is a product currently on the market, for example, the product sold by Nanjing Kezheng Chemical Co., Ltd. under the trade name N, N-dimethylformamide (DMF).
本发明使用的醇胺是一种以氨的氮原子为核心，而氨的氢原子被醇取代的化合物，它可与海藻粉原料中的钙、镁、铁等离子螯合，提高这种原料的水溶性，从而有助于提高从海藻原料中提取海藻酸的提取率。The alcohol amine used in the present invention is a compound that takes the nitrogen atom of ammonia as the core and the hydrogen atom of ammonia is replaced by an alcohol. It can chelate with calcium, magnesium, iron and other ions in the raw material of seaweed powder to improve the Water solubility helps to increase the extraction rate of alginic acid from algae raw materials.
本发明使用的醇胺是一种或多种选自一乙醇胺、二乙醇胺、三乙醇胺或N-甲基二乙醇胺的醇胺。所述的醇胺都是目前市场上销售的产品，例如由上海敏晨化工有限公司以商品名一乙醇胺(MEA)销售的产品、由邹平县国安化工有限公司以商品名N-甲基二乙醇胺(MDEA)销售的产品。The alcoholamine used in the present invention is one or more alcoholamines selected from monoethanolamine, diethanolamine, triethanolamine or N-methyldiethanolamine. The alcohol amines mentioned are all products currently on the market, such as those sold by Shanghai Minchen Chemical Co., Ltd. under the trade name monoethanolamine (MEA), and Zouping Guoan Chemical Co., Ltd. under the trade name N-methyldiethanolamine (MDEA) products sold.
苯胺有一个氨基基团，它可与海藻酸酸性基团反应，与苯环连接，这样增强海藻提取液的稳定性。本发明使用的苯胺是目前市场上销售的产品，例如由康奈尔化学工业股份有限公司以商品名苯胺MDI级销售的产品。Aniline has an amino group, which can react with the alginic acid group to connect with the benzene ring, thus enhancing the stability of the algae extract. The aniline used in the present invention is a product currently on the market, such as the product sold by Cornell Chemical Industry Co., Ltd. under the trade name of aniline MDI grade.
乙二醇因与水良好的互溶性和抗低温性能而能增强海藻酸有机提取剂液体稳定性和流动性。本发明使用的乙二醇是目前市场上销售的产品，例如由郑州正昇化工产品有限公司以商品名防冻液用乙二醇销售的产品。Ethylene glycol can enhance the liquid stability and fluidity of alginic acid organic extractant due to its good miscibility with water and low temperature resistance. The ethylene glycol used in the present invention is a product currently on the market, for example, the product sold by Zhengzhou Zhengsheng Chemical Products Co., Ltd. under the trade name ethylene glycol for antifreeze.
在本发明中，其它原料用量在所述的范围内时，如果醇胺的用量低于20重量份时，则会降低海藻酸提取率；如果醇胺的用量高于50重量份时，则会海藻提取液气泡过多，细小的杂质混于提取液中，提取的海藻酸液体纯度降低；因此，醇胺的用量为20～50重量份是合适的，优选地是28～42重量份，更优选地是30～36重量份。In the present invention, when the amount of other raw materials is within the stated range, if the amount of alcohol amine is less than 20 parts by weight, the alginic acid extraction rate will be reduced; if the amount of alcohol amine is more than 50 parts by weight, it will There are too many bubbles in the seaweed extract, and fine impurities are mixed in the extract, and the purity of the extracted alginic acid liquid is reduced; therefore, the amount of alcohol amine is 20-50 parts by weight, preferably 28-42 parts by weight, more It is preferably 30 to 36 parts by weight.
其它原料用量在所述的范围内时，如果苯胺的用量低于5重量份时，则会对增强海藻提取液稳定性效果不明显；如果苯胺的用量高于10重量份时，则不会继续明显提高海藻提取液的稳定性；因此，苯胺的用量为5～10重量份是恰当的，优选地是6～9重量份。When the amount of other raw materials is within the stated range, if the amount of aniline is less than 5 parts by weight, the effect of enhancing the stability of the seaweed extract will not be obvious; if the amount of aniline is more than 10 parts by weight, it will not continue The stability of the seaweed extract is significantly improved; therefore, the amount of aniline used is 5 to 10 parts by weight, preferably 6 to 9 parts by weight.
其它原料用量在所述的范围内时，如果乙二醇的用量低于5重量份时，则会对低温时提高海藻提取液的稳定性效果不明显；如果乙二醇的用量高于 10重量份时，则会因其羟基含量较高，随储存时间延长可能引起部分粘稠的海藻酸沉淀；因此，乙二醇的用量为5～10重量份是恰当的，优选地是6～9重量份。When the amount of other raw materials is within the stated range, if the amount of ethylene glycol is less than 5 parts by weight, the effect of improving the stability of the algae extract at low temperatures will be insignificant; if the amount of ethylene glycol is greater than 10 parts by weight Parts, because of its high hydroxyl content, it may cause partial viscous alginic acid precipitation with storage time extension; therefore, the amount of ethylene glycol is 5 to 10 parts by weight, preferably 6 to 9 parts by weight Copies.
其它原料用量在所述的范围内时，如果水的用量低于2000重量份时，则会因提取剂浓度过高，水用量低，海藻酸溶解度有限，提取海藻酸效率下降；如果水的用量高于3000重量份时，则会因提取剂浓度过低，同样导致海藻酸提取率下降；因此，水的用量为2000～3000重量份是合适的，优选地是2200～2800重量份，更优选地是2400～2600重量份。When the amount of other raw materials is within the stated range, if the amount of water is less than 2000 parts by weight, the extraction efficiency of alginic acid will be reduced due to the high concentration of extractant, low water consumption, and limited solubility of alginic acid; if the amount of water is When it is higher than 3000 parts by weight, the alginic acid extraction rate will also be reduced due to the low concentration of the extractant; therefore, the amount of water used is 2000-3000 parts by weight, preferably 2200-2800 parts by weight, more preferably The ground is 2400-2600 parts by weight.
优选地，二甲基甲酰胺、醇胺、苯胺、乙二醇与水的重量比是100：28～42：6～9：6～9：2200～2800。Preferably, the weight ratio of dimethylformamide, alcohol amine, aniline, ethylene glycol and water is 100: 28-42: 6-9: 6-9: 2200-2800.
更优选地，二甲基甲酰胺、醇胺、苯胺、乙二醇与水的重量比是100：30～36：7～8：7～8：2400～2600。More preferably, the weight ratio of dimethylformamide, alcoholamine, aniline, ethylene glycol and water is 100: 30-36: 7-8: 7-8: 2400-2600.
根据本发明，将二甲基甲酰胺等原料在转速60～180rpm的条件下搅拌溶解得到的溶液冷却至温度30℃以下。According to the present invention, a solution obtained by stirring and dissolving raw materials such as dimethylformamide at a rotation speed of 60 to 180 rpm is cooled to a temperature of 30 ° C. or lower.
得到海藻酸有机提取剂后，本发明将100重量份海藻粉添加到800～1500重量份的海藻酸有机提取剂中，然后在搅拌下将其温度逐渐升至70～90℃，并在这个温度下保持6～12h，接着冷却至室温，离心分离，沉淀弃去，得到所述的海藻酸提取液。After obtaining the alginic acid organic extractant, the present invention adds 100 parts by weight of alginate powder to 800-1500 parts by weight of alginic acid organic extractant, and then gradually raises its temperature to 70-90 ° C under stirring, and at this temperature Keep for 6 to 12 hours, then cool to room temperature, centrifuge, and discard the precipitate to obtain the alginic acid extract.
根据本发明，所述的海藻是褐藻、巨藻或泡叶藻，本发明使用的海藻都是目前市场上销售的产品，例如本发明使用的褐藻是由烟台长岛三友公司以商品名海带销售的褐藻；本发明使用的巨藻是由陕西斯诺特生物技术有限公司以商品名巨藻原粉销售的巨藻。According to the present invention, the seaweed is brown algae, megaalgae or leaf algae. The seaweeds used in the present invention are all products currently on the market. For example, the brown algae used in the present invention are sold by Yantai Changdao Sanyou Company under the trade name kelp Brown algae; the macroalgae used in the present invention is the macroalgae sold by Shaanxi Snote Biotechnology Co., Ltd. under the trade name of macroalgae raw powder.
根据本发明，采用现有常规破碎设备将褐藻、巨藻或泡叶藻进行粉碎，收集粒度小于2mm的海藻粉作为原料制备海藻酸提取液。According to the present invention, the existing conventional crushing equipment is used to pulverize the brown algae, megaalgae or leaf algae, and the algae powder with a particle size of less than 2 mm is collected as a raw material to prepare an alginic acid extraction solution.
在本发明中，海藻粉原料为100重量份时，如果所述提取剂用量低于800重量份，则会导致液体浓稠难以进行后续离心处理；如果所述提取剂用量高于1500重量份，则会导致提取的海藻酸液体含水量影响在尿素中的应用。因此，所述提取剂用量为800～1500重量份是恰当的。In the present invention, when the raw material of seaweed powder is 100 parts by weight, if the amount of the extractant is less than 800 parts by weight, it will cause the thick liquid to be difficult to perform subsequent centrifugal treatment; if the amount of the extractant is more than 1500 parts by weight, It will cause the water content of the extracted alginic acid liquid to affect the application in urea. Therefore, it is appropriate that the amount of the extractant is 800-1500 parts by weight.
在这个步骤中，在转速为100～200rpm的搅拌下将海藻粉原料与海藻酸有机提取剂混合物的温度逐渐升至70～90℃，并在这个温度下保持6～12h。其提 取温度与提取时间超过所述范围是不可取的。如果提取时间短于6h，则海藻酸提取不完全，造成海藻酸损失；如果提取时间超过12h，则导致提取海藻酸的能耗增加，成本增加。因此，海藻酸提取时间为6～12h是可行的。In this step, the temperature of the mixture of the algae powder raw material and the alginic acid organic extractant is gradually increased to 70 to 90 ° C under stirring at a rotation speed of 100 to 200 rpm, and maintained at this temperature for 6 to 12 hours. It is undesirable that the extraction temperature and extraction time exceed the above range. If the extraction time is shorter than 6h, the extraction of alginic acid is incomplete, resulting in loss of alginic acid; if the extraction time exceeds 12h, the energy consumption and cost of extracting alginic acid increase. Therefore, the extraction time of alginic acid is 6 ~ 12h is feasible.
根据本发明，冷却至室温的提取物使用离心机在转速1000～5000rpm的条件下离心分离10～30min。所述的离心机是现有市场上销售的产品，例如由上海市离心机械研究所有限公司以商品名二相分离卧螺沉降离心机销售的产品。According to the present invention, the extract cooled to room temperature is centrifuged at a speed of 1000 to 5000 rpm for 10 to 30 minutes using a centrifuge. The centrifuge is a product sold on the existing market, for example, a product sold by Shanghai Centrifuge Machinery Research Institute Co., Ltd. under the trade name of two-phase separation decanter centrifuge.
得到海藻酸提取液后，本发明将10～20重量份没食子酸、5～10重量份苯羧酸和0.02～0.1重量份聚乙二醇加入到100重量份的海藻酸提取液中，加热至温度50℃，再加入2～3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应60～120min，再加入3～8重量份聚氧乙烯醚与0.5～2.0重量份邻苯二甲酸烷基酰胺，冷却，使用焦磷酸水溶液将其pH值调节至5～6，得到一种具有减缓尿素转化的海藻酸增效载体。After obtaining the alginic acid extract, the present invention adds 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid, and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of alginic acid extract, and heats to At a temperature of 50 ° C, add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight A portion of alkyl phthalate amide, cooled, and adjusted its pH value to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier that slows the conversion of urea.
在本发明中，在过氧化二异丙苯引发剂与聚乙二醇表面活性剂存在下，没食子酸与苯羧酸和步骤B得到的海藻酸进行接枝反应，于是进一步增加海藻酸酸性官能团种类和数量，其目的是让海藻酸与尿素分子中的氨基结合更加紧密，明显延缓尿素在土壤中的分解速度。In the present invention, in the presence of dicumyl peroxide initiator and polyethylene glycol surfactant, gallic acid is grafted with benzene carboxylic acid and the alginic acid obtained in step B, so that the alginic acid functional group is further increased The purpose of the species and quantity is to make the alginic acid more tightly bound to the amino group in the urea molecule, and significantly slow down the decomposition rate of urea in the soil.
在本发明中，所述的苯羧酸是苯甲酸、苯乙酸、水杨酸或乙酰水杨酸；它们都是目前市场上销售的产品，例如由江苏顺丰化工有限公司以商品名苯甲酸销售的产品、山东新华隆信化工有限公司以商品名工业水杨酸销售的产品、由郑州佳鸿化工有限公司以商品名乙酰水杨酸销售的产品。In the present invention, the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid; they are all products currently on the market, for example, sold by Jiangsu Shunfeng Chemical Co., Ltd. under the trade name of benzoic acid Products, products sold by Shandong Xinhua Longxin Chemical Co., Ltd. under the trade name of industrial salicylic acid, and products sold by Zhengzhou Jiahong Chemical Co., Ltd. under the trade name of acetylsalicylic acid.
在本发明中，其它原料用量在所述范围内时，如果没食子酸用量低于10重量份，则会对提高海藻提取液官能团含量的作用有限；如果没食子酸用量高于20重量份，则会成本过高；因此，没食子酸用量为10～20重量份是合理的；In the present invention, when the amount of other raw materials is within the range, if the amount of gallic acid is less than 10 parts by weight, it will have a limited effect on increasing the content of functional groups of the seaweed extract; if the amount of gallic acid is more than 20 parts by weight, The cost is too high; therefore, it is reasonable to use gallic acid in an amount of 10-20 parts by weight;
同样地，其它原料用量在所述范围内时，如果苯羧酸用量低于5重量份，则会苯羧基官能团增加量偏低；如果苯羧酸用量高于10重量份，则会引起部分海藻酸沉淀；因此，苯羧酸用量为5～10重量份是恰当的；Similarly, when the amount of other raw materials is within the range, if the amount of benzene carboxylic acid is less than 5 parts by weight, the increase of benzene carboxyl functional groups will be low; if the amount of benzene carboxylic acid is more than 10 parts by weight, it will cause some algae Acid precipitation; therefore, the amount of benzene carboxylic acid is 5 to 10 parts by weight is appropriate;
其它原料用量在所述范围内时，如果过氧化二异丙苯用量低于2重量份，则会导致接枝效率低；如果过氧化二异丙苯用量高于3重量份，则会导致反 应过快；因此，过氧化二异丙苯用量为2～3重量份是可行的；When the amount of other raw materials is within the range, if the amount of dicumyl peroxide is less than 2 parts by weight, it will result in low grafting efficiency; if the amount of dicumyl peroxide is more than 3 parts by weight, it will cause reaction Too fast; therefore, the amount of dicumyl peroxide is 2 to 3 parts by weight is feasible;
其它原料用量在所述范围内时，如果聚乙二醇用量低于0.02重量份，则会因分散性低，接枝效果不理想；如果聚乙二醇用量高于0.1重量份，则会形成大分子团，影响接枝效果；因此，聚乙二醇用量为0.02～0.1重量份是可行的；When the amount of other raw materials is within the range, if the amount of polyethylene glycol is less than 0.02 parts by weight, the grafting effect is not ideal due to low dispersibility; if the amount of polyethylene glycol is more than 0.1 parts by weight, it will form Large molecular clusters affect the grafting effect; therefore, it is feasible to use polyethylene glycol in an amount of 0.02 to 0.1 parts by weight;
这个反应在温度100℃下进行60～120min，如果该反应时间短于60min，则没食子酸、苯羧酸与海藻酸结合稳定性不够；如果该反应时间长于120min，则能耗增加明显。因此，这个反应时间为90～120min是可行的。This reaction is carried out at a temperature of 100 ° C for 60 to 120 min. If the reaction time is shorter than 60 min, the stability of the binding of gallic acid, benzenecarboxylic acid and alginic acid is insufficient; if the reaction time is longer than 120 min, the energy consumption increases significantly. Therefore, the reaction time of 90 ~ 120min is feasible.
聚氧乙烯醚在本发明中兼具树脂与非离子表面活性剂性能，它既可作为固定相进一步减缓尿素在土壤溶液中移动，又可作为渗透剂，促进海藻酸与尿素结合。邻苯二甲酸烷基酰胺非离子表面活性剂在本发明中既能增强聚氧乙烯醚的渗透效果，又能提高增效载体稳定性。焦磷酸在本发明中既可以调节pH、形成缓冲体系，还可以增加尿素颗粒强度，减慢尿素在土壤溶液中的溶解和释放速度。Polyoxyethylene ether has both resin and nonionic surfactant properties in the present invention. It can be used as a stationary phase to further slow down the movement of urea in the soil solution, and can also be used as a penetrating agent to promote the combination of alginic acid and urea. In the present invention, the phthalic acid alkylamide nonionic surfactant can not only enhance the penetration effect of polyoxyethylene ether, but also improve the stability of the synergistic carrier. In the present invention, pyrophosphoric acid can not only adjust pH, form a buffer system, but also increase the strength of urea particles and slow down the dissolution and release rate of urea in soil solutions.
在本发明中，聚氧乙烯醚用量为3～8重量份时，如果聚氧乙烯醚用量低于3重量份，则分散及渗透性能不明显；如果聚氧乙烯醚用量高于8重量份，则增效载体粘度过高；因此，聚氧乙烯醚用量为3～8重量份是恰当的。In the present invention, when the amount of polyoxyethylene ether is 3-8 parts by weight, if the amount of polyoxyethylene ether is less than 3 parts by weight, the dispersion and penetration properties are not obvious; if the amount of polyoxyethylene ether is more than 8 parts by weight, The viscosity of the synergistic carrier is too high; therefore, it is appropriate to use 3 to 8 parts by weight of polyoxyethylene ether.
同样地，邻苯二甲酸烷基酰胺用量为0.5～2.0重量份时，如果邻苯二甲酸烷基酰胺用量低于0.5重量份，则对强化聚氧乙烯醚的渗透效果不显著；如果邻苯二甲酸烷基酰胺用量高于2重量份，则影响聚氧乙烯醚的分散性能；因此，邻苯二甲酸烷基酰胺用量为0.5～2.0重量份是恰当的。Similarly, when the amount of phthalic acid alkyl amide is 0.5-2.0 parts by weight, if the amount of phthalic acid alkyl amide is less than 0.5 parts by weight, the penetration effect of enhanced polyoxyethylene ether is not significant; If the amount of dicarboxylic acid alkyl amide is higher than 2 parts by weight, it will affect the dispersion performance of polyoxyethylene ether; therefore, the amount of phthalic acid alkyl amide is 0.5 to 2.0 parts by weight is appropriate.
根据本发明，所述焦磷酸水溶液的浓度是1～5mol/L。According to the present invention, the concentration of the pyrophosphate aqueous solution is 1 to 5 mol / L.
根据本发明，加入聚氧乙烯醚和邻苯二甲酸烷基酰胺后将其溶液冷却至温度15～30℃。According to the present invention, after adding polyoxyethylene ether and phthalic acid alkylamide, the solution is cooled to a temperature of 15-30 ° C.
本发明使用的没食子酸、聚乙二醇、过氧化二异丙苯、聚氧乙烯醚、邻苯二甲酸烷基酰胺与焦磷酸都是目前市场上销售的产品，例如由上海阿拉丁生化科技股份有限公司以商品名没食子酸销售的产品、由陕西双力化工有限公司以商品名过氧化二异丙苯DCP销售的产品、由江苏省海安石油化工厂以商品名聚氧乙烯醚乳化剂OP-7销售的产品、由广州纵宇化工科技有限公司以商品名悬浮稳定剂TAB-2邻苯二甲酸烷基酰胺销售的产品。The gallic acid, polyethylene glycol, dicumyl peroxide, polyoxyethylene ether, alkyl phthalate and pyrophosphoric acid used in the present invention are all products currently on the market, such as Shanghai Aladdin Biochemical Technology Co., Ltd. products sold under the trade name gallic acid, Shaanxi Shuangli Chemical Co., Ltd. sold under the trade name dicumyl peroxide DCP, and Jiangsu Provincial Haian Petrochemical Plant under the trade name polyoxyethylene ether emulsifier OP -7 Products sold by Guangzhou Zongyu Chemical Technology Co., Ltd. under the trade name TAB-2 phthalic acid alkylamide.
本发明制备海藻酸增效载体可与尿素生产工艺或颗粒尿素产品结合，生产出高氮肥利用率的新尿素产品。The alginic acid synergistic carrier prepared by the invention can be combined with a urea production process or a granular urea product to produce a new urea product with high nitrogen fertilizer utilization rate.
本发明具有减缓尿素转化的海藻酸增效载体的使用方法如下：The method of using the alginic acid synergistic carrier for slowing the conversion of urea according to the present invention is as follows:
第一种方法：在尿素生产过程中，将5～50重量份本发明方法制备的海藻酸增效载体加入到1000重量份尿素熔融液中，经高塔喷淋得到含海藻酸增效载体颗粒尿素。The first method: in the process of urea production, add 5 to 50 parts by weight of the alginic acid synergistic carrier prepared by the method of the present invention to 1000 parts by weight of urea melt, and spray the tower to obtain alginic acid synergistic carrier particles Urea.
第二种方法：将5～50重量份海藻酸增效载体加入到1000重量份加热至40～75℃的颗粒尿素中，快速搅拌2min，混匀后于100℃烘干，得到含海藻酸增效载体颗粒尿素。The second method: add 5-50 parts by weight of alginic acid synergistic carrier to 1000 parts by weight of granular urea heated to 40-75 ° C, stir quickly for 2min, mix and dry at 100 ° C to obtain alginic acid-containing Effective carrier granular urea.
下面结合实施例对本发明提供的技术方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The technical solutions provided by the present invention will be described in detail below with reference to examples, but they cannot be construed as limiting the protection scope of the present invention.
一、制备实施例1. Preparation Examples
实施例1：一种具有减缓尿素转化的海藻酸增效载体制备Example 1: Preparation of an alginic acid synergistic carrier with slowed urea conversion
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、海藻酸有机提取剂制备A. Preparation of alginic acid organic extractant
将100重量份二甲基甲酰胺、36重量份一乙醇胺、5重量份苯胺与6重量份乙二醇加到2400重量份温度为60℃的水中，将在转速140rpm的条件下搅拌溶解得到的溶液冷却至温度30℃以下，得到所述的海藻酸有机提取剂；100 parts by weight of dimethylformamide, 36 parts by weight of monoethanolamine, 5 parts by weight of aniline, and 6 parts by weight of ethylene glycol were added to 2400 parts by weight of water at a temperature of 60 ° C, and the mixture was stirred and dissolved at a speed of 140 rpm. The solution is cooled to a temperature below 30 ° C to obtain the alginic acid organic extractant;
B、海藻酸提取液制备B. Preparation of alginic acid extract
将100重量份粒度小于2mm的海带褐藻粉原料添加到1000重量份在步骤A得到的海藻酸有机提取剂中，然后在转速为180rpm的搅拌下将其温度逐渐升至90℃，并在这个温度下保持10h，接着冷却至室温，在转速1000rpm的条件下离心分离26min，沉淀弃去，得到所述的海藻酸提取液；Add 100 parts by weight of kelp brown algae powder raw material with a particle size of less than 2mm to 1000 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually increase its temperature to 90 ° C under stirring at 180 rpm, and at this temperature Hold for 10 hours, then cool to room temperature, centrifuge at 1000 rpm for 26 min, discard the precipitate, and obtain the alginic acid extract;
C、海藻酸增效载体制备C. Preparation of alginic acid synergistic carrier
将16重量份没食子酸、5重量份苯甲酸和0.04重量份聚乙二醇加入到100重量份在步骤B得到的海藻酸提取液中，加热至温度50℃，再加入2重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应80min，再加入5重量份聚氧乙烯醚与0.5重量份邻苯二甲酸烷基酰胺，冷却至温度25℃，使用浓度为3mol/L的焦磷酸水溶液将其pH值调节至5，得到一种减 缓尿素转化的海藻酸增效载体。Add 16 parts by weight of gallic acid, 5 parts by weight of benzoic acid and 0.04 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in Step B, heat to a temperature of 50 ° C, and then add 2 parts by weight of diperoxide Cumene, then heated to a temperature of 100 ° C, reacted at this temperature for 80 min, then added 5 parts by weight of polyoxyethylene ether and 0.5 parts by weight of phthalic acid alkylamide, cooled to a temperature of 25 ° C, and used concentration of 3mol / The pH of L pyrophosphate aqueous solution is adjusted to 5 to obtain an alginic acid synergistic carrier that slows the conversion of urea.
实施例2：一种具有减缓尿素转化的海藻酸增效载体制备Example 2: Preparation of an alginic acid synergistic carrier with slowed urea conversion
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、海藻酸有机提取剂制备A. Preparation of alginic acid organic extractant
将100重量份二甲基甲酰胺、20重量份二乙醇胺、10重量份苯胺与9重量份乙二醇加到2000重量份温度为64℃的水中，将在转速60rpm的条件下搅拌溶解得到的溶液冷却至温度30℃以下，得到所述的海藻酸有机提取剂；100 parts by weight of dimethylformamide, 20 parts by weight of diethanolamine, 10 parts by weight of aniline, and 9 parts by weight of ethylene glycol were added to 2000 parts by weight of water at a temperature of 64 ° C, and the mixture was stirred and dissolved at a speed of 60 rpm. The solution is cooled to a temperature below 30 ° C to obtain the alginic acid organic extractant;
B、海藻酸提取液制备B. Preparation of alginic acid extract
将100重量份粒度小于2mm的巨藻原粉添加到800重量份在步骤A得到的海藻酸有机提取剂中，然后在转速为100rpm的搅拌下将其温度逐渐升至70℃，并在这个温度下保持8h，接着冷却至室温，在转速2400rpm的条件下离心分离10min，沉淀弃去，得到所述的海藻酸提取液；Add 100 parts by weight of macroalgae raw powder with a particle size of less than 2 mm to 800 parts by weight of the organic extract of alginic acid obtained in Step A, and then gradually increase its temperature to 70 ° C under stirring at 100 rpm, and at this temperature Hold for 8h, then cool to room temperature, centrifuge at 2400rpm for 10min, discard the precipitate, and obtain the alginic acid extract;
C、海藻酸增效载体制备C. Preparation of alginic acid synergistic carrier
将10重量份没食子酸、10重量份苯乙酸和0.06重量份聚乙二醇加入到100重量份在步骤B得到的海藻酸提取液中，加热至温度50℃，再加入3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应60min，再加入3重量份聚氧乙烯醚与1.0重量份邻苯二甲酸烷基酰胺，冷却至温度15℃，使用浓度为1mol/L的焦磷酸水溶液将其pH值调节至6，得到一种减缓尿素转化的海藻酸增效载体。Add 10 parts by weight of gallic acid, 10 parts by weight of phenylacetic acid and 0.06 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in Step B, heat to a temperature of 50 ° C, and then add 3 parts by weight of diperoxide Cumene, then heated to a temperature of 100 ° C, reacted at this temperature for 60 min, then added 3 parts by weight of polyoxyethylene ether and 1.0 parts by weight of phthalic acid alkylamide, cooled to a temperature of 15 ° C, and used concentration of 1 mol / The pH value of L pyrophosphate aqueous solution is adjusted to 6 to obtain an alginic acid synergistic carrier that slows the conversion of urea.
实施例3：一种具有减缓尿素转化的海藻酸增效载体制备Example 3: Preparation of an alginic acid synergistic carrier with slowed urea conversion
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、海藻酸有机提取剂制备A. Preparation of alginic acid organic extractant
将100重量份二甲基甲酰胺、50重量份三乙醇胺、6重量份苯胺与5重量份乙二醇加到3000重量份温度为70℃的水中，将在转速180rpm的条件下搅拌溶解得到的溶液冷却至温度30℃以下，得到所述的海藻酸有机提取剂；100 parts by weight of dimethylformamide, 50 parts by weight of triethanolamine, 6 parts by weight of aniline, and 5 parts by weight of ethylene glycol were added to 3000 parts by weight of water at a temperature of 70 ° C, and the mixture was stirred and dissolved at a rotation speed of 180 rpm. The solution is cooled to a temperature below 30 ° C to obtain the alginic acid organic extractant;
B、海藻酸提取液制备B. Preparation of alginic acid extract
将100重量份粒度小于2mm的泡叶藻粉原料添加到1500重量份在步骤A得到的海藻酸有机提取剂中，然后在转速为200rpm的搅拌下将其温度逐渐升至80℃，并在这个温度下保持12h，接着冷却至室温，在转速5000rpm的条件下离心分离30min，沉淀弃去，得到所述的海藻酸提取液；Add 100 parts by weight of the raw material of Ascophyllum nodosum powder with a particle size of less than 2 mm to 1500 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually raise its temperature to 80 ° C under stirring at a rotation speed of 200 rpm. Maintain the temperature for 12h, then cool to room temperature, centrifuge at 5000rpm for 30min, and discard the precipitate to obtain the alginic acid extract;
C、海藻酸增效载体制备C. Preparation of alginic acid synergistic carrier
将12重量份没食子酸、8重量份水杨酸和0.02重量份聚乙二醇加入到100重量份在步骤B得到的海藻酸提取液中，加热至温度50℃，再加入2重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应120min，再加入8重量份聚氧乙烯醚与1.5重量份邻苯二甲酸烷基酰胺，冷却至温度20℃，使用浓度为5mol/L的焦磷酸水溶液将其pH值调节至5，得到一种减缓尿素转化的海藻酸增效载体。Add 12 parts by weight of gallic acid, 8 parts by weight of salicylic acid and 0.02 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in Step B, heat to a temperature of 50 ° C, and then add 2 parts by weight of peroxide Dicumene, then heated to a temperature of 100 ° C, reacted at this temperature for 120 min, then added 8 parts by weight of polyoxyethylene ether and 1.5 parts by weight of phthalic acid alkylamide, cooled to a temperature of 20 ° C, and used a concentration of 5 mol / L pyrophosphate aqueous solution adjusts its pH value to 5 to obtain an alginic acid synergistic carrier that slows the conversion of urea.
实施例4：一种具有减缓尿素转化的海藻酸增效载体制备Example 4: Preparation of an alginic acid synergistic carrier with slowed urea conversion
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、海藻酸有机提取剂制备A. Preparation of alginic acid organic extractant
将100重量份二甲基甲酰胺、30重量份N-甲基二乙醇胺醇胺、9重量份苯胺与10重量份乙二醇加到2800重量份温度为68℃的水中，将在转速100rpm的条件下搅拌溶解得到的溶液冷却至温度30℃以下，得到所述的海藻酸有机提取剂；Add 100 parts by weight of dimethylformamide, 30 parts by weight of N-methyldiethanolamine alcoholamine, 9 parts by weight of aniline, and 10 parts by weight of ethylene glycol to 2800 parts by weight of water at a temperature of 68 ° C. The solution obtained by stirring and dissolving is cooled to a temperature below 30 ° C under conditions to obtain the alginic acid organic extractant;
B、海藻酸提取液制备B. Preparation of alginic acid extract
将100重量份粒度小于2mm的野生海带褐藻粉原料添加到1200重量份在步骤A得到的海藻酸有机提取剂中，然后在转速为140rpm的搅拌下将其温度逐渐升至80℃，并在这个温度下保持6h，接着冷却至室温，在转速3800rpm的条件下离心分离18min，沉淀弃去，得到所述的海藻酸提取液；Add 100 parts by weight of the raw material of wild kelp brown algae powder with a particle size of less than 2mm to 1200 parts by weight of the organic extract of alginic acid obtained in step A, and then gradually raise its temperature to 80 ° C with stirring at a rotation speed of 140 rpm. Maintain the temperature for 6h, then cool to room temperature, centrifuge at 3800rpm for 18min, discard the precipitate, and obtain the alginic acid extract;
C、海藻酸增效载体制备C. Preparation of alginic acid synergistic carrier
将20重量份没食子酸、6重量份乙酰水杨酸和0.1重量份聚乙二醇加入到100重量份在步骤B得到的海藻酸提取液中，加热至温度50℃，再加入3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应100min，再加入6重量份聚氧乙烯醚与2.0重量份邻苯二甲酸烷基酰胺，冷却至温度30℃，使用浓度为2mol/L的焦磷酸水溶液将其pH值调节至6，得到一种减缓尿素转化的海藻酸增效载体。Add 20 parts by weight of gallic acid, 6 parts by weight of acetylsalicylic acid and 0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in Step B, heat to a temperature of 50 ° C, and then add 3 parts by weight of Dicumyl oxide is oxidized, then heated to a temperature of 100 ° C, and reacted at this temperature for 100 min, then 6 parts by weight of polyoxyethylene ether and 2.0 parts by weight of alkyl phthalate are added, cooled to a temperature of 30 ° C, and the use concentration is A 2 mol / L pyrophosphoric acid aqueous solution adjusted its pH value to 6 to obtain an alginic acid synergistic carrier that slowed down the conversion of urea.
二、试验实施例2. Test Example
试验实施例1：本发明海藻酸增效载体对尿素残留率的影响Test Example 1: The effect of the alginic acid synergistic carrier of the present invention on the residual rate of urea
样品制备：实施例1、实施例2和实施例3制备的海藻酸增效载体按照它与尿素重量比2：100分别添加到三个温度为118℃的熔融尿素中，让其在 这个温度下反应5min，然后冷却，分别得到海藻酸尿素A、海藻酸尿素B和海藻酸尿素C。同时，按照同样的方式处理市售尿素(瑞星集团股份有限公司，含氮量46％)，得到的样品为对照样品U。Sample preparation: The alginic acid synergistic carriers prepared in Example 1, Example 2 and Example 3 were added to three molten urea at a temperature of 118 ° C according to its weight ratio of 2: 100 to urea, and let it be at this temperature After 5 minutes of reaction, and then cooling, urea alginate A, urea alginate B and urea alginate C were obtained respectively. At the same time, the commercially available urea (Rising Group Co., Ltd., nitrogen content 46%) was treated in the same manner, and the obtained sample was the control sample U.
试验步骤：分别称取1.0g市售尿素对照样品以及含1.0g尿素的海藻酸尿素A、海藻酸尿素B与海藻酸尿素C于培养瓶中，再加入100mL无菌水溶解，然后往这些培养瓶中分别加入0.2g脲酶(酶活力为1U)，摇匀，接着置于温度为37±2℃的无光培养箱中培养12h，在培养期间，每隔2h摇匀一次。培养结束后，采用HG/T 4135-2010规定的二乙酰一肟比色法测定溶液中剩余的尿素量(g)，根据下式计算尿素残留差异率：Test procedure: Weigh 1.0g of a commercially available urea control sample and alginate urea A, alginate urea B and alginate urea C containing 1.0g urea in a culture bottle, then add 100mL of sterile water to dissolve, and then to these cultures Add 0.2g of urease (enzyme activity is 1U) to the bottle, shake well, and then place in a light-free incubator with a temperature of 37 ± 2 ℃ for 12 hours. During the cultivation period, shake it every 2 hours. After the incubation, the amount of remaining urea (g) in the solution was determined by the diacetyl-oxime colorimetric method specified in HG / T 4135-2010, and the residual difference rate of urea was calculated according to the following formula:
尿素残留率＝(1.0-剩余尿素量)×100，单位％，Urea residual rate = (1.0-remaining urea amount) × 100, unit%,
其试验结果列于表1中。The test results are listed in Table 1.
表1：添加增效载体的尿素与市售尿素的尿素残留率比较Table 1: Comparison of residual urea ratio of urea added with synergistic carrier and commercial urea
种类kind 尿素残留率，％Urea residual rate,% 与尿素样品相比提高，％Compared with urea samples,%
市售尿素UCommercially available Urea U 28.3％28.3% --
海藻酸尿素AAlginate Urea A 46.6％46.6% 64.764.7
海藻酸尿素BAlginate Urea B 61.0％61.0% 115.5115.5
海藻酸尿素CAlginate Urea C 54.1％54.1% 91.291.2
表1的试验结果表明，本发明海藻酸增效载体可显著减缓尿素的分解和转化，海藻酸尿素A、海藻酸尿素B、海藻酸尿素C样品的尿素残留率分别比尿素提高64.7％、115.5％和91.2％。The test results in Table 1 show that the alginic acid synergistic carrier of the present invention can significantly slow down the decomposition and conversion of urea. The residual rate of urea in the samples of alginate urea A, alginate urea B, and alginate urea C are respectively increased by 64.7% and 115.5 compared to urea % And 91.2%.
试验实施例2：本发明海藻酸增效载体对尿素肥际土壤pH和氮素转化的影响Test Example 2: Effect of the alginic acid synergistic carrier of the present invention on soil pH and nitrogen conversion of urea fertilizer
样品制备：熔融过程与试验实施案例1相同。海藻酸尿素熔融液及尿素熔融液分别倾倒于长×宽×高＝5cm×5cm×5cm的不锈钢模具中，冷却，取出，获得正方体尿素块A、正方体尿素块B、正方体尿素块C、正方体尿素块U。Sample preparation: The melting process is the same as in Test Example 1. The alginic acid urea melt and the urea melt are poured into stainless steel molds of length × width × height = 5cm × 5cm × 5cm, cooled and taken out to obtain cube urea block A, cube urea block B, cube urea block C, cube urea Block U.
试验步骤：分别将正方体尿素块A、B、C、U置于含水量为以重量计18％的石灰性潮土(山东德州)中，压实土壤至容重1.3g/cm 3，在温度25±2℃下培养12h。培养结束后，用刀片分别切出距离尿素块边缘1.5～2cm、1～1.5cm、0.5～1cm、0～0.5cm的土壤。 Test procedure: Place the cube urea blocks A, B, C and U in calcareous Chao soil (Shandong Dezhou) with a water content of 18% by weight, and compact the soil to a bulk density of 1.3 g / cm 3 at a temperature of 25 Incubate at ± 2 ℃ for 12h. After the cultivation is completed, the blade is used to cut out the soil 1.5 to 2 cm, 1 to 1.5 cm, 0.5 to 1 cm, and 0 to 0.5 cm from the edge of the urea block, respectively.
试验检测：根据(鲁如坤.《土壤农业化学分析方法》.北京：中国农业科 技出版社，2000.)标准分析方法测试尿素块肥际土壤中的pH、尿素态氮、铵态氮含量，其结果列于表2中。Test detection: According to (Lu Rukun. "Analysis Method of Soil Agricultural Chemistry". Beijing: China Agricultural Science and Technology Press, 2000.) Standard analysis method to test the pH, urea nitrogen, ammonium nitrogen content in the urea block fertilizer soil, The results are shown in Table 2.
表2：添加增效载体尿素与市售尿素的肥际土壤pH、尿素态氮含量、铵态氮含量比较Table 2: Comparison of soil pH, urea nitrogen content and ammonium nitrogen content in the fertilizer soil with the synergistic carrier urea and commercial urea
Figure PCTCN2019113605-appb-000001
Figure PCTCN2019113605-appb-000001
肥际是肥料转化的最初阶段，决定着后期的尿素转化和损失过程。试验结果表明，本发明制备的海藻酸增效载体可显著降低尿素肥际土壤pH，特别是降低肥际1cm以内的土壤pH，降低幅度0.3～1.0个pH单位，即肥际土壤溶液中的H +浓度提高3～11倍；肥际2cm内尿素显著高、铵态氮均显著低于市售尿素处理，说明海藻酸尿素的分解和转化速度明显减缓。 Fertilization is the initial stage of fertilizer conversion and determines the later urea conversion and loss process. The test results show that the alginic acid synergistic carrier prepared by the present invention can significantly reduce the soil pH of the urea fertilizer, especially the soil pH within 1 cm of the fertilizer, and the reduction range is 0.3 to 1.0 pH units, that is, H in the fertilizer solution + Concentration increased by 3 to 11 times; urea was significantly higher within 2 cm of the fertilizer, and ammonium nitrogen was significantly lower than that of commercially available urea treatment, indicating that the decomposition and conversion rate of alginate urea was significantly slowed.
试验实施例3：本发明海藻酸增效载体对小麦和玉米根系生长和活力的影响Test Example 3: The effect of the alginic acid synergistic carrier of the present invention on the growth and vigor of wheat and corn roots
利用实施例1、实施例2和实施例4制备的海藻酸增效载体，采用砂培试验研究增效载体对小麦和玉米根系生长和活力的影响。Using the alginic acid synergistic carriers prepared in Example 1, Example 2 and Example 4, a sand culture experiment was used to study the effect of the synergistic carrier on the growth and vigor of wheat and corn roots.
在霍格兰营养液中本发明增效载体的添加量为0.2g/L，分别记为处理A、处理B、处理C。将处理的石英砂装到500mL培养砵(底部有排水孔)中，其表面距离砵沿2～3cm。将处理的作物定植于培养砵中，重复6次。每隔4天浇灌1次营养液，每次100mL，以保持一定的湿度和养分浓度。在作物出苗后21天取样，测定根系鲜重，采用《植物生理学实验指导》(华南理工大学出版社，2015年)常规比色方法测定TTC活力。其试验结果列于表3中。The added amount of the synergistic carrier of the present invention in Hogeland's nutrient solution is 0.2 g / L, which are respectively referred to as treatment A, treatment B, and treatment C. Pack the treated quartz sand into a 500mL culture pottery (with a drain hole at the bottom), the surface of which is 2 to 3 cm away from the pottery edge. The treated crops were planted in cultivation pottery and repeated 6 times. Irrigate the nutrient solution every 4 days, 100mL each time, to maintain a certain humidity and nutrient concentration. Samples were taken 21 days after the emergence of the crops to determine the fresh weight of the root system, and the TTC activity was measured using the conventional colorimetric method of "Plant Physiology Experiment Guide" (South China University of Technology Press, 2015). The test results are listed in Table 3.
表3：本发明海藻酸增效载体对作物根系生长和活力的影响Table 3: Effect of the alginic acid synergistic carrier of the present invention on the growth and vitality of crop roots
Figure PCTCN2019113605-appb-000002
Figure PCTCN2019113605-appb-000002
Figure PCTCN2019113605-appb-000003
Figure PCTCN2019113605-appb-000003
作物根系的吸收能力是决定肥料利用率的重要因素。由表3列出的结果可知，海藻酸增效载体A、B、C处理的小麦根系鲜重和活力分别比对照平均提高54.9％和36.3％，玉米根系鲜重和活力分别提高38.5％和26.7％。The absorption capacity of the crop root system is an important factor that determines the fertilizer utilization rate. From the results listed in Table 3, it can be seen that the fresh weight and vitality of wheat roots treated with alginic acid synergistic carriers A, B and C increased by an average of 54.9% and 36.3%, respectively, and that of corn roots increased by 38.5% and 26.7 %.
由此可见，本发明制备的海藻酸增效载体与尿素结合后，可通过影响尿素转化的肥际过程显著减缓尿素的分解、释放和转化，增强尿素的稳定性，并可提高作物根系活力，促进作物养分吸收。It can be seen that the combination of the alginic acid synergistic carrier prepared by the present invention and urea can significantly slow down the decomposition, release and conversion of urea, enhance the stability of urea, and improve the vitality of crop roots by affecting the fertilization process of urea conversion. Promote crop nutrient absorption.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only the preferred embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present invention, several improvements and retouches can be made. These improvements and retouches also It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种具有减缓尿素转化的海藻酸增效载体的制备方法，其特征在于该制备方法的步骤如下：A method for preparing an alginic acid synergistic carrier for slowing urea conversion, characterized in that the steps of the preparation method are as follows:
    A、将100重量份二甲基甲酰胺、20～50重量份醇胺、5～10重量份苯胺和5～10重量份乙二醇加到2000～3000重量份温度为60～70℃的水中，搅拌溶解，冷却，得到海藻酸有机提取剂；A. Add 100 parts by weight of dimethylformamide, 20-50 parts by weight of alcohol amine, 5-10 parts by weight of aniline and 5-10 parts by weight of ethylene glycol to 2000-3000 parts by weight of water at a temperature of 60-70 ° C , Stir to dissolve, cool to obtain alginic acid organic extractant;
    B、将100重量份海藻粉添加到800～1500重量份步骤A得到的所述海藻酸有机提取剂中，然后在搅拌下将其温度逐渐升至70～90℃，并在这个温度下保持6～12h，接着冷却至室温，离心分离，沉淀弃去，得到的海藻酸提取液；B. Add 100 parts by weight of algae powder to 800-1500 parts by weight of the alginic acid organic extractant obtained in step A, and then gradually increase its temperature to 70-90 ° C under stirring, and maintain at this temperature 6 ～ 12h, then cooled to room temperature, centrifuged, discarded the precipitate, and obtained the alginic acid extract;
    C、将10～20重量份没食子酸、5～10重量份苯羧酸和0.02～0.1重量份聚乙二醇加到100重量份步骤B得到的所述海藻酸提取液中，加热至温度50℃，再加入2～3重量份过氧化二异丙苯，接着加热至温度100℃，在这个温度下反应60～120min，再加入3～8重量份聚氧乙烯醚和0.5～2.0重量份邻苯二甲酸烷基酰胺，冷却，使用焦磷酸水溶液将其pH调节至5～6，得到海藻酸增效载体。C. Add 10-20 parts by weight of gallic acid, 5-10 parts by weight of benzenecarboxylic acid and 0.02-0.1 parts by weight of polyethylene glycol to 100 parts by weight of the alginic acid extract obtained in step B, and heat to a temperature of 50 ℃, then add 2 to 3 parts by weight of dicumyl peroxide, then heat to a temperature of 100 ° C, react at this temperature for 60 to 120 minutes, and then add 3 to 8 parts by weight of polyoxyethylene ether and 0.5 to 2.0 parts by weight of o Phthalic acid alkyl amide, cooled, and adjusted its pH to 5-6 using an aqueous pyrophosphate solution to obtain an alginic acid synergistic carrier.
  2. 根据权利要求1所述的制备方法，其特征在于，在步骤A中，所述醇胺选自一乙醇胺、二乙醇胺、三乙醇胺和N-甲基二乙醇胺中的一种或几种。The preparation method according to claim 1, wherein in step A, the alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine and N-methyldiethanolamine.
  3. 根据权利要求1所述的制备方法，其特征在于，在步骤A中，所述搅拌的转速60～180rpm；所述冷却后的溶液的温度为≤30℃。The preparation method according to claim 1, characterized in that, in step A, the rotation speed of the stirring is 60 to 180 rpm; the temperature of the cooled solution is ≤30 ° C.
  4. 根据权利要求1所述的制备方法，其特征在于，在步骤A中，所述二甲基甲酰胺、醇胺、苯胺、乙二醇与水的重量比是100：28～42：6～9：6～9：2200～2800。The preparation method according to claim 1, characterized in that, in step A, the weight ratio of the dimethylformamide, alcoholamine, aniline, ethylene glycol and water is 100: 28-42: 6-9 : 6-9: 2200-2800.
  5. 根据权利要求1所述的制备方法，其特征在于，在步骤B中，所述海藻粉的海藻原料为褐藻、巨藻或泡叶藻；所述海藻粉的粒度小于2mm。The preparation method according to claim 1, characterized in that, in step B, the seaweed raw material of the seaweed powder is brown algae, kelp or phyllodes; the particle size of the seaweed powder is less than 2 mm.
  6. 根据权利要求1所述的制备方法，其特征在于，在步骤B中，所述搅拌的转速为100～200rpm。The preparation method according to claim 1, wherein in step B, the rotation speed of the stirring is 100-200 rpm.
  7. 根据权利要求1所述的制备方法，其特征在于，在步骤B中，所述 离心的转速为1000～5000rpm；所述离心的时间为10～30min。The preparation method according to claim 1, characterized in that, in step B, the rotation speed of the centrifugation is 1000-5000 rpm; the time of the centrifugation is 10-30 min.
  8. 根据权利要求1所述的制备方法，其特征在于，在步骤C中，所述苯羧酸为苯甲酸、苯乙酸、水杨酸或乙酰水杨酸。The preparation method according to claim 1, wherein in step C, the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
  9. 根据权利要求1所述的制备方法，其特征在于，在步骤C中，所述焦磷酸水溶液的浓度是1～5mol/L。The preparation method according to claim 1, wherein in step C, the concentration of the pyrophosphate aqueous solution is 1 to 5 mol / L.
  10. 根据权利要求1所述的制备方法，其特征在于，在步骤C中，所述冷却后的溶液的温度为15～30℃。The preparation method according to claim 1, wherein in step C, the temperature of the cooled solution is 15-30 ° C.
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CN109438139A (en) * 2018-11-09 2019-03-08 中国农业科学院农业资源与农业区划研究所 A kind of preparation method with the alginic acid synergistic carrier for slowing down urea conversion
CN110256138A (en) * 2019-04-17 2019-09-20 青岛明月蓝海生物科技有限公司 A kind of clear liquid type water-soluble fertilizer and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102701866A (en) * 2012-06-27 2012-10-03 中国农业科学院农业资源与农业区划研究所 Fermented alga liquid fertilizer synergist and production method and application thereof
CN103274854A (en) * 2013-06-17 2013-09-04 中国农业科学院农业资源与农业区划研究所 Algae synergistic high-tower compound fertilizer and production method thereof
CN104761413A (en) * 2015-03-25 2015-07-08 青岛海力源生物科技有限公司 Alginic acid fertilizer synergist with ammonia volatilization inhibiting effect and preparation method of alginic acid fertilizer synergist
CN107445780A (en) * 2017-08-04 2017-12-08 史丹利化肥扶余有限公司 It is a kind of containing alginic acid and middle micro- compound fertilizer and preparation method thereof
CN109438139A (en) * 2018-11-09 2019-03-08 中国农业科学院农业资源与农业区划研究所 A kind of preparation method with the alginic acid synergistic carrier for slowing down urea conversion

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515945B (en) * 2011-12-06 2014-02-05 中国农业科学院农业资源与农业区划研究所 Algae-enhanced urea, production method thereof, and purpose thereof
CN103617830B (en) * 2013-10-25 2016-07-06 复旦大学 A kind of preparation method of conductive metal film
CN107337504A (en) * 2017-06-13 2017-11-10 安徽奥利休闲农业发展有限公司 Excellent magnet organic fertilizer material containing sodium alginate of a kind of retain water and nutrients and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102701866A (en) * 2012-06-27 2012-10-03 中国农业科学院农业资源与农业区划研究所 Fermented alga liquid fertilizer synergist and production method and application thereof
CN103274854A (en) * 2013-06-17 2013-09-04 中国农业科学院农业资源与农业区划研究所 Algae synergistic high-tower compound fertilizer and production method thereof
CN104761413A (en) * 2015-03-25 2015-07-08 青岛海力源生物科技有限公司 Alginic acid fertilizer synergist with ammonia volatilization inhibiting effect and preparation method of alginic acid fertilizer synergist
CN107445780A (en) * 2017-08-04 2017-12-08 史丹利化肥扶余有限公司 It is a kind of containing alginic acid and middle micro- compound fertilizer and preparation method thereof
CN109438139A (en) * 2018-11-09 2019-03-08 中国农业科学院农业资源与农业区划研究所 A kind of preparation method with the alginic acid synergistic carrier for slowing down urea conversion

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