- ISSN 1008-505X
- CN 11-3996/S
| Citation: |
XIANG Yang, MIAO Rui, LIU Ya-qing, ZHAO Gui-zhe. Preparation of and properties of urea-formaldehyde slow-release fertilizer by high-temperature polycondensation of paraformaldehyde and urea[J]. Journal of Plant Nutrition and Fertilizers, 2022, 28(9): 1699-1707. DOI: 10.11674/zwyf.2022203
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Urea-formaldehyde slow-release fertilizer prepared by the traditional solution of polycondensation (SUF) usually has a high moisture content, which makes the product adhere strongly to equipment. Consequently, it is difficult to achieve continuous production due lack of automatic discharge from the reactor. Moreover, the high moisture content also increases energy consumption during drying. Therefore, we improved the process technology to overcome this bottleneck.
Urea-formaldehyde slow-release fertilizer (HUF) was prepared by a high-temperature gas-solid polycondensation process of paraformaldehyde and urea. The principle is that under high temperature and sealing conditions, paraformaldehyde is depolymerized into formaldehyde gas, which combines with urea in the reaction kettle to form urea-formaldehyde and water. A small amount of urea will decompose at a high temperature to produce ammonia gas, which combines with water to form ammonia water and drives the polycondensation reaction to form a urea-formaldehyde molecular chain with a high degree of polymerization. Slow-release fertilizers were prepared by high-temperature gas-solid polycondensation and conventional solution concentration, denoted as HUF and SUF, respectively. Samples with mole ratios of urea to formaldehyde of 2, 4, and 6 were prepared for each method. We studied the drying time of the products and characterized the composition and structure of urea-formaldehyde by the Acetylacetone method, Kjeldahl method, Thermal weight loss (TWL), Thermogravimetry (TG), Fourier transform infrared spectroscopy (FTIR), Gel permeation chromatography (GPC), and X-ray diffraction (XRD). Furthermore, the performance of urea formaldehyde slow-release fertilizer was tested by immersion method.
In a high-temperature gas-solid polycondensation reaction, the higher the reaction temperature, the higher the formaldehyde conversion rate. The formaldehyde conversion rate slightly increased when the reaction temperature was higher than 100℃. Also, the decomposition rate of urea increased sharply beyond 100℃, leading to the reduction of urea-formaldehyde nitrogen content. Therefore, 100℃ was the best reaction temperature for the high-temperature gas-solid polycondensation process. The high-temperature gas-solid polycondensation process significantly reduced the water content of the reaction product; the highest water content was 11.72%, and the drying time was shortened by at least 1 h compared with SUF. The process also improved the raw formaldehyde conversion rate and the average chain length of urea-formaldehyde molecules. When the mole ratio of urea and formaldehyde was 2∶1, the formaldehyde conversion rate of HUF was 88.22%, which was 9.26 percentage points higher than that of SUF. The average molecular weight of HUF and SUF were 4445 and 949, respectively. HUF's slow-release available nitrogen content was 21.05%, which was 12.48 percentage points higher than SUF. The activity coefficient of HUF was 42.33%, which was 20.48 percentage points higher than SUF. HUF's nitrogen release in 24 h was 49.6%, 12.1 percentage points lower than SUF. The cumulative nitrogen release of HUF in 28 days was 73.6%, which was 3.5 percentage points higher than SUF.
Urea formaldehyde slow-release fertilizer prepared by high-temperature gas-solid polycondensation process can effectively reduce the moisture content of the product and thus achieve continuous production of the equipment, without affecting the slow-release performance.
| [1] |
Naz M Y, Sulaiman S A. Slow release coating remedy for nitrogen loss from conventional urea: A review[J]. Journal of Controlled Release, 2016, 225: 109–120. DOI: 10.1016/j.jconrel.2016.01.037
|
| [2] |
Mikula K, Izydorczyk G, Skrzypczak D, et al. Controlled release micronutrient fertilizers for precision agriculture - A review[J]. Science of the Total Environment, 2020, 712: 136365–136373. DOI: 10.1016/j.scitotenv.2019.136365
|
| [3] |
Zhou L L, Zhao P, Chi Y, et al. Controlling the hydrolysis and loss of nitrogen fertilizer (urea) by using a nanocomposite favors plant growth[J]. ChemSusChem, 2017, 10(9): 2068–2079. DOI: 10.1002/cssc.201700032
|
| [4] |
赵蒙, 曾科, 姚元林, 等. 聚脲甲醛缓释肥对太湖稻麦轮作体系氨挥发及产量的影响[J]. 植物营养与肥料学报, 2019, 25(1): 55–63. Zhao M, Zeng K, Yao Y L, et al. Effects of polyurea-formaldehyde on ammonia volatilization and yields under rice-wheat rotation in Taihu Region[J]. Journal of Plant Nutrition and Fertilizers, 2019, 25(1): 55–63. DOI: 10.11674/zwyf.18028
Zhao M, Zeng K, Yao Y L, et al. Effects of polyurea-formaldehyde on ammonia volatilization and yields under rice-wheat rotation in Taihu Region[J]. Journal of Plant Nutrition and Fertilizers, 2019, 25(1): 55-63. DOI: 10.11674/zwyf.18028
|
| [5] |
Cahill S, Osmond D, Crozier C, et al. Winter wheat and maize response to urea ammonium nitrate and a new urea formaldehyde polymer fertilizer[J]. Agronomy Journal, 2007, 99(6): 1645–1653. DOI: 10.2134/agronj2007.0132
|
| [6] |
Guo Y L, Liu Z G, Zhang M, et al. Synthesis and application of urea-formaldehyde for manufacturing a controlled-release potassium fertilizer[J]. Industrial & Engineering Chemistry Research, 2018, 57(5): 1593–1606.
|
| [7] |
Yamamoto C F, Pereira E I, Mattoso L H C, et al. Slow release fertilizers based on urea/urea-formaldehyde polymer nanocomposites[J]. Chemical Engineering Journal, 2016, 287: 390–397. DOI: 10.1016/j.cej.2015.11.023
|
| [8] |
蔡英强, 王静, 王志强, 等. 一种颗粒脲甲醛缓释复合肥的生产方法[J]. 磷肥与复肥, 2017, 32(10): 18–19,46. Cai Y Q, Wang J, Wang Z Q, et al. A production method of granular urea formaldehyde slow-release compound fertilizer[J]. Phosphate & Compound Fertilizer, 2017, 32(10): 18–19,46. DOI: 10.3969/j.issn.1007-6220.2017.10.007
Cai Y Q, Wang J, Wang Z Q, et al. A production method of granular urea formaldehyde slow-release compound fertilizer[J]. Phosphate & Compound Fertilizer, 2017, 32(10): 18-19, 46. DOI: 10.3969/j.issn.1007-6220.2017.10.007
|
| [9] |
沈敏祥, 郎克红. 脲醛树脂包膜尿素的制备研究[J]. 磷肥与复肥, 2016, 31(1): 11–12. Shen M X, Lang K H. Study on preparation of urea formaldehyde resin coated urea[J]. Phosphate & Compound Fertilizer, 2016, 31(1): 11–12. DOI: 10.3969/j.issn.1007-6220.2016.01.005
Shen M X, Lang K H. Study on preparation of urea formaldehyde resin coated urea[J]. Phosphate & Compound Fertilizer, 2016, 31(1): 11-12. DOI: 10.3969/j.issn.1007-6220.2016.01.005
|
| [10] |
李露, 曹海波, 彭何欢, 等. 多聚甲醛合成热塑性酚醛树脂过程中游离酚含量的研究[J]. 塑料工业, 2018, 46(12): 33–36. Li L, Cao H B, Peng H H, et al. Study on the content of free phenol in the synthesis of thermoplastic phenolic resin by paraformaldehyde[J]. China Plastics Industry, 2018, 46(12): 33–36. DOI: 10.3969/j.issn.1005-5770.2018.12.008
Li L, Cao H B, Peng H H, et al. Study on the content of free phenol in the synthesis of thermoplastic phenolic resin by paraformaldehyde[J]. China Plastics Industry, 2018, 46(12): 33-36. DOI: 10.3969/j.issn.1005-5770.2018.12.008
|
| [11] |
潘贝贝, 王晓莉, 张文辉, 谷守玉. 多聚甲醛合成脲甲醛缓释肥工艺初探[J]. 磷肥与复肥, 2014, 29(1): 23–24. Pan B B, Wang X L, Zhang W H, Gu S Y. Study on sythesis of urea-formaldehyde slow-release fertilizer by paraformaldehyde[J]. Phosphate & Compound Fertilizer, 2014, 29(1): 23–24. DOI: 10.3969/j.issn.1007-6220.2014.01.006
Pan B B, Wang X L, Zhang W H, Gu S Y. Study on sythesis of urea-formaldehyde slow-release fertilizer by paraformaldehyde[J]. Phosphate & Compound Fertilizer, 2014, 29(1): 23-24. DOI: 10.3969/j.issn.1007-6220.2014.01.006
|
| [12] |
Liu S L, Fan W D, Wu X F, et al. Heterogeneous reaction of N2O with phenol-formaldehyde resin char and NO formation, reduction and inhibition at high temperature[J]. Fuel Processing Technology, 2021, 216: 106791. DOI: 10.1016/j.fuproc.2021.106791
|
| [13] |
Xiang Y, Ru X D, Shi J G, et al. Granular, slow-release fertilizer from urea-formaldehyde, ammonium polyphosphate, and amorphous silica gel: A new strategy using cold extrusion[J]. Journal of Agricultural and Food Chemistry, 2018, 66(29): 7606–7615. DOI: 10.1021/acs.jafc.8b02349
|
| [14] |
于凤兰. 多聚甲醛含量的快速测定[J]. 天津化工, 1996, (1): 36–37, 27. Yu F L. Rapid determination of paraformaldehyde content[J]. Tianjin Chemical Industry, 1996, (1): 36–37, 27.
Yu F L. Rapid determination of paraformaldehyde content[J]. Tianjin Chemical Industry, 1996, (1): 36-37, 27.
|
| [15] |
Bremner J M. Determination of nitrogen in soil by the Kjeldahl method[J]. Journal of Agricultural Science, 1960, 55(1): 11–33. DOI: 10.1017/S0021859600021572
|
| [16] |
GB/T 34763—2017. 脲醛缓释肥料[S].
GB/T 34763-2017. Urea aldehyde slow release fertilizer[S].
|
| [17] |
段路路, 张民, 刘刚, 等. 缓控释肥料养分释放特性评价及快速测定方法研究[J]. 土壤学报, 2009, 46(2): 299–307. Duan L L, Zhang M, Liu G, et al. Evaluation of nutrient release characteristics of slow and controlled-release fertilizers and fast measurement method[J]. Acta Pedologica Sinica, 2009, 46(2): 299–307. DOI: 10.3321/j.issn:0564-3929.2009.02.015
Duan L L, Zhang M, Liu G, et al. Evaluation of nutrient release characteristics of slow and controlled-release fertilizers and fast measurement method[J]. Acta Pedologica Sinica, 2009, 46(2): 299-307. DOI: 10.3321/j.issn:0564-3929.2009.02.015
|
| [18] |
肖春妹, 陶川东, 刘旋, 李杰灵. 碱催化多聚甲醛的解聚工艺条件研究[J]. 天然气化工–C1化学与化工, 2017, 42(3): 20–22. Xiao C M, Tao C D, Liu X, Li J L. Reaction conditions study for base-catalyzed depolymerization of paraformaldehyde[J]. Natural Gas Chemical Industry, 2017, 42(3): 20–22.
Xiao C M, Tao C D, Liu X, Li J L. Reaction conditions study for base-catalyzed depolymerization of paraformaldehyde[J]. Natural Gas Chemical Industry, 2017, 42(3): 20-22.
|
| [19] |
Xiang Y, Li C Y, Hao H B, et al. Performances of biodegradable polymer composites with functions of nutrient slow-release and water retention in simulating heavy metal contaminated soil: Biodegradability and nutrient release characteristics[J]. Journal of Cleaner Production, 2021, 294: 126278. DOI: 10.1016/j.jclepro.2021.126278
|
| [20] |
张蕊鑫, 王智慧, 丛威, 等. 一种用高效凝胶渗透色谱测试褐藻胶分子量及分子量分布的方法[J]. 过程工程学报, 2020, 20(1): 99–107. Zhang R X, Wang Z H, Cong W, et al. Molecular weight and molecular weight distribution of alginate determination by gel permeation chromatography[J]. The Chinese Journal of Process Engineering, 2020, 20(1): 99–107. DOI: 10.12034/j.issn.1009-606X.219177
Zhang R X, Wang Z H, Cong W, et al. Molecular weight and molecular weight distribution of alginate determination by gel permeation chromatography[J]. The Chinese Journal of Process Engineering, 2020, 20(1): 99-107. DOI: 10.12034/j.issn.1009-606X.219177
|
| [21] |
付弯弯. 新型无机水合盐定形复合相变材料的制备及性能[D]. 广州: 华南理工大学博士学位论文, 2019.
Fu W W. Preparation and performances of novel form-stable composite phase change materials based on salt hydrates[D]. Guangzhou: PhD Dissertation of South China University of Technology, 2019.
|
| [22] |
Wibowo E S, Park B-D, Causin V. Hydrogen-bond-induced crystallization in low-molar-ratio urea–formaldehyde resins during synthesis[J]. Industrial & Engineering Chemistry Research, 2020, 59(29): 13095–13104.
|
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