车用生物燃气工程范例余热定量评估及可利用性分析--《农业工程学报》2017年17期
车用生物燃气工程范例余热定量评估及可利用性分析
【摘要】：针对车用生物燃气工程能耗高、余热利用率低的问题,该文以国内4个典型工程为基础,构建了产气规模为1万m3/d的示例工程,并对其进行余热分析。分析结果显示,此类工程用能量大,占总产能的30.01%~36.44%;余热利用率低,只有部分贫液余热得以回收;系统余热主要由脱碳塔顶气余热、脱碳贫液余热、压缩机余热、沼液余热和锅炉尾气余热5部分组成,其多为低品位余热、量大稳定。余热计算表明,在最冷月和最热月系统余热潜力分别为5.87×104、4.79×104 MJ/d,最大节能潜力分别为74.81%和73.92%,节能潜力降序排列为沼液余热贫液余热塔顶气余热压缩机余热锅炉余热。余热可利用性分析认为工程余热可利用性较高,回收价值较大。
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【分类号】：U473【正文快照】：
0引言僴车用生物燃气,是指有机废弃物厌氧发酵产生的粗沼气经净化、提纯、压缩达到车用标准的生物燃气,具有无污染、可再生和经济效益高等优点[1-2]。近年来,中国有机废弃物排放量增长迅速,资源化利用需求紧迫。与此同时,天然气等清洁能源需求逐年增长,天然气缺口较大。车用生
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400-819-9993Patent CNA - 一种改性造纸黑液生物基包膜控释肥料及其制备方法 A modified bio-based black ... - Google PatentsCN AApplicationCN Aug 22, 2017May 10, 2017May 10, 2017.8, CN
A, CN A, CN , CN-A-, CN A, CNA, CN, CN.8, , ,
一种改性造纸黑液生物基包膜控释肥料及其制备方法 A modified bio-based black liquor and preparation method of coated controlled release fertilizer translated from CN
A 本发明涉及一种改性造纸黑液生物基包膜控释肥料及其制备方法，是先将造纸黑液加入稀硫酸或稀盐酸中和至中性、浓缩烘干后制成粉末，加入液化剂液化后制得造纸黑液液化物，然后加入改性剂对该液化物进行改性，再将该改性液化物与固化剂按照重量比1:0.1～10混匀后作为包膜材料，在一定压力条件下喷涂到颗粒肥料表面，在10～100℃条件下经1～10分钟固化成膜制得生物基聚氨酯包膜控释肥料。 The present invention relates to a modified bio-based black liquor coated controlled release fertilizer and its preparation method, black liquor is first added to dilute sulfuric acid or dilute hydrochloric acid until neutral, dried and concentrated to a powder, was added liquefied after the liquefaction agent to obtain black liquor was liquefied and then modifying the modifier was liquefied, and then modifying the liquefied material and curing agent in a weight ratio of 1: 0.1 to 10 after mixing as coating material, spraying conditions under pressure to the surface of the fertilizer granules by forming 1 to 10 minutes to obtain a cured bio-based polyurethane coated controlled release fertilizer at 10 ~ 100 ℃. 根据作物所需养分控释期，调整包膜材料的重量占颗粒肥料总重量比的1％～10％。 The total weight of the granular fertilizer 1% to 10% based on the weight ratio of the desired crop nutrient release, adjusting the coating materials. 本发明是一种膜材料来源广泛、价格低廉、能耗低、包膜工艺简单、膜材易降解、低成本环保型的新型控释肥料包膜方法。 Film material of the present invention is a wide variety of sources, low cost, low energy consumption, simple coating technology, membrane easily degradable, low cost method of new controlled release fertilizer coated environmentally friendly.
1. 一种改性造纸黑液生物基包膜控释肥料，其特征在于通过如下方法制备得到： 将颗粒肥料加入到转鼓包衣机中，将肥料颗粒预热到1〇?ioo°c;将改性的造纸黑液液化物与固化剂c按照重量比1:0.1?10混合均匀后作为包膜材料，在0.1?IMPa压力条件下， 少量多次地喷涂到肥料颗粒表面，经1?10分钟固化成膜;所述包膜材料占颗粒肥料总重量比的1%?10%; 所述的固化剂C为异氰酸酯，包括甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、多亚甲基多苯基多异氰酸酯PAPI、六亚甲基二异氰酸酯HDI或异佛尔酮二异氰酸酯IPDI中的一种或几种。 1. A modified bio-based black liquor Controlled Release Fertilizer, characterized in that prepared by the following method: The granular fertilizer is added to the drum coater, the preheated fertilizer particles to 1〇~ioo ° the modified black liquor liquefied material and the curing agent according to c weight ratio of 1:, 0.1~IMPa under pressure conditions, a small amount of 0.1~10 sprayed uniformly mixed coating material as a fertilizer particle surface a plurality of times, the 1 ~ 10 said coating material based on the total weight of the granular fertilizer 1% ~ 10% curing agent C of the isocyanate comprising tolylene diisocyanate TDI, diphenylmethane diisocyanate MDI, multi-methylenedioxy Quito phenyl polyisocyanate PAPI, hexamethylene diisocyanate, HDI or isophorone diisocyanate IPDI of one or more.
2. 如权利要求1所述的一种改性造纸黑液生物基包膜控释肥料，其特征在于所述的造纸黑液液化物的制备方法为:造纸黑液中加入酸中和至中性、浓缩烘干后制成粉末，按照造纸黑液粉末与液化剂A重量比1:1?10混合加入到带有加热、搅拌、冷凝装置的反应釜中，升温至50?180°C，然后加入液化剂A重量比1 %?10%的催化剂浓硫酸，不断搅拌30?1〇〇分钟，即可制得造纸黑液液化物;所述的液化剂A为聚乙二醇、乙二醇、甘油或碳酸乙烯酯中的一种或几种。 2. A modified bio-based black liquor coated controlled release fertilizer according to claim 1, characterized in that said preparation liquefied material is black liquor: adding black liquor to the acid and sex, dried and concentrated to a powder, the powder according to the black liquor with a liquefying agent a weight ratio of 1: 1~10 were added to the mixture with heating, stirring, condensing reactor apparatus, was heated to 50~180 ° C, a liquefying agent is then added to 1% ~ 10% by weight of concentrated sulfuric acid catalyst, stirring constantly 30~1〇〇 minutes, can be prepared with black liquo said a liquefying agent is polyethylene glycol, ethylene one or more alcohols, glycerol, or ethylene carbonate.
3. 如权利要求1所述的一种改性造纸黑液生物基包膜控释肥料，其特征在于所述的造纸黑液液化物的改性方法为:将所述的造纸黑液液化物中加入改性剂B进行改性，改性剂B 添加量占造纸黑液液化物重量比的0.1%?1〇%;，搅拌混匀后超声震荡10?60分钟;所述的改性剂B为具有链烷烃基、环烷烃基、芳香烃基、硝基、卤素等憎水基团的高分子物质，包括氟烷、氟硅烷、全氟烷/烯醚、氟醇、含氟丙烯酸酯和纳米二氧化硅或纳米碳酸钙等疏水性化合物中的一种或几种的混合。 3. A modified bio-based black liquor coated controlled release fertilizer according to claim 1, wherein the modified method of liquefied material is black liquor: the liquefied material of the black liquor was added modifying agent B is modified, added amount ~1〇% 0.1% black liquor B liquefied modifier weight ratio of , sonotrode 10 to 60 the modifier B is a group having a high molecular weight substance alkane, cycloalkane group, an aromatic hydrocarbon group, a nitro group, a hydrophobic group such as halogen, including fluoroalkyl, fluoro silane, a perfluoroalkyl / alkenyl ether, a fluorine alcohol, fluorine-containing acrylate and mixing one or more hydrophobic compounds nanosilica nano-calcium carbonate or the like.
4.如权利要求1所述的一种改性造纸黑液生物基包膜控释肥料，其特征在于所述的颗粒肥料选自市售的单质的氮肥、磷肥、钾肥及其复合肥、微量兀素肥料、中量元素肥料或微生物肥料中的一种或几种。 4. A modified bio-based black liquor coated controlled release fertilizer according to claim 1, wherein said fertilizer particles are selected from the commercially available elemental nitrogen, phosphate, potash and fertilizer, trace Wu fertilizer one or more factors, or the amount of elemental microbial fertilizer in the fertilizer.
一种改性造纸黑液生物基包膜控释肥料及其制备方法(一) A modified bio-based black liquor and preparation method of coated controlled release fertilizer (a)
技术领域 FIELD
[0001] 本发明涉及一种改性造纸黑液生物基包膜控释肥料及其制备方法，属于新型肥料生产领域。 [0001] The present invention relates to a modified bio-based black liquor coated controlled release fertilizer and its preparation method, is a new type of fertilizer production. (二) (two)
背景技术 Background technique
[0002] 化肥对于农业生产具有十分重要的作用，是农业生产中最大的物质投资。 [0002] fertilizer for agricultural production has a very important role in agricultural production in the largest physical investments. 随着世界人口的增加，人类对于粮食产量的需求也不断增加，化肥的用量也呈不断增加的趋势。 As the world population increases, the demand for human food production is also increasing the amount of fertilizer also showed a rising trend. 我国是世界人口大国，也是化肥消费大国。 China is the world's most populous country, is also a fertilizer consuming country. 目前我国的化肥利用率较低，氮肥当季利用率为30%?35%，磷肥为10%?20%，钾肥为35%?50%，低于发达国家15?20个百分点。 The current low utilization rate of fertilizer, nitrogen utilization rate of the quarter was 30% ~ 35%, 10% ~ 20% phosphate, potash 35% ~ 50%, 15 ~ 20 percentage points lower than in developed countries. 化肥的利用率低，不仅造成大量肥料的浪费，而且还产生了一系列环境问题，造成地下水污染， 河流水体富营养化，以及产生大量温室气体，加速全球气候变暖等。 Low utilization rate of fertilizer, not only resulting in substantial waste of fertilizer, but also produced a series of environmental problems caused by pollution of groundwater, river water eutrophication, and produce large amounts of greenhouse gases, accelerating global warming. 控释肥料在提高化肥利用率、减少化肥用量方面，具有显著的效果。 In controlled release fertilizer to increase fertilizer efficiency, reduce the amount of fertilizer aspect, having a significant effect. 但是当前市售的控释肥料价格一般比常规速效肥料高3?S倍，一方面其包膜材料多来源于石油等不可再生资源；另一方面其生产技术含量高、工艺复杂、设备昂贵，因而控释肥料价格相对较贵。 However, current commercially available controlled release fertilizer material prices are generally higher than conventional rapid-acting fertilizer 3~S times, on the one hand that multiple coating materials derived from petroleum and other non- on the other hand the production of high-tech, complex process, expensive equipment, controlled release fertilizers thus relatively expensive. 大多数在用的控释肥料以聚合物为包膜材料，其在土壤中不可降解，在缓释养分、创造经济价值的同时对土壤造成了二次污染。 Most controlled-release fertilizer with the polymer-coated material, which is non-degradable in the soil, in the slow release of nutrients, while creating economic value of soil caused secondary pollution. 因此，为促进农业的可持续发展，应该发明一种新的方法，充分利用一些工业、农业废弃物作为包膜原料，变废为宝，用其生产出成本低廉、高效、环保的新型控释肥料。 Therefore, in order to promote sustainable development of agriculture, it should invent a new way to take advantage of a number of industrial, agricultural waste used as coating materials, turning waste into treasure, with its production of low cost, high efficiency, environmental protection, new release fertilizer.
[0003]我国是纸制品生产和消费大国，造纸厂利用麦草秸秆生产纸张后产生大量的造纸黑液。 [0003] Our country is paper products production and consumption country, a large amount of paper mill black liquor after using the straw to produce straw paper. 造纸所用的植物原料主要由纤维素、木质素、聚糖类物质组成。 The plant material used in paper mainly composed of cellulose, lignin, polysaccharides substance. 纤维素为造纸的有效成分，约占40%。 Cellulose papermaking active ingredient, about 40%. 占原料约6〇%的聚糖类和木质素等，在制浆过程中被分离与加入的水和碱一起形成黑液，难以处理。 6〇% starting material accounted for about glycans and lignin, black liquor formed is separated together with added water and a base in the pulping process, difficult to handle. 以草类为原料造纸废水的处理技术，许多方法虽获得了成功，但依旧有不少问题存在，如有些方法不是处理效果差,就是成本太高。 With grass as raw material for paper waste water treatment technology, although many methods have been successful, but there are still many problems, some methods such as treatment effect is not bad, but the cost is too high. 因此，通过改性造纸黑液，作为制备控释肥料膜材的原料，变废为宝，既能解决造纸黑液利用难的问题，又降低^ 控释包膜肥料的生产成本，促进工业和农业的共同发展。 Therefore, the modified black liquor as a raw material for preparing controlled release fertilizer membranes, turning waste into treasure, both to solve the difficult problem of the use of black liquor, but also reduce production costs ^ controlled release coated fertilizers, and promote industrial and common development of agriculture.
[0004]本发明的包膜控释肥料就是利用造纸黑液进行改性后，合成一种生物基聚氨酯膜材，制备包膜控释肥料。 [0004] The coated controlled release fertilizer of the present invention is the use of the modified black liquor, one bio-based polyurethane synthetic membrane, preparation of a coated controlled release fertilizer. 该发明的包膜控释肥料具有如下优点：①采用造纸黑液为原料，成本低、来源广泛、废物再利用;②以废造纸黑液为原料制备的控释肥料产品，施入土壤后，残留在土壤中的膜壳易降解，不会对土壤造成二次污染;③加工工艺简单、能耗低、易大规模产业化加工生产；④产品养分释放期可控，符合植物生长营养所需，可提高肥料养分利用率，减少肥料资源的浪费和环境污染等。 Coated controlled release fertilizer of the invention has the following advantages: ① use of papermaking, low cost, widely available, ② spent black liquor to a controlled release fertilizer product prepared raw material, applied to soil, residues in soil degradation membrane shell easily, will not cause secondary p ③ process is simple, low energy consumption, easy processing of large-scale i ④ product controlled nutrient release period, in line with nutrients required for plant growth can increase fertilizer nutrient use efficiency, reduce waste and environmental pollution fertilizer resources. (三) (three)
发明内容 SUMMARY
[0005]为了解决上述问题，本发明提供了一种改性造纸黑液生物基包膜控释肥料及其制备方法，是利用造纸黑液经过液化、改性后，作为包膜原材料，将其喷涂在颗粒肥料表面形成致密膜层生产包膜控释肥料的方法。 [0005] In order to solve the above problems, the present invention provides a modified bio-based black liquor coated controlled release fertilizer and its preparation method, after the black liquor using liquefied modified, as coating material, which is the method of producing a dense film coated controlled release fertilizer in the fertilizer spray forming surface of the particles. 本发明是一种膜材料来源广泛、价格低廉、能耗低/ 包膜工艺简单、膜材易降解、低成本环保型的新型包膜控释肥料，具有重大的社会效益和经济效益。 Film material of the present invention is a wide variety of sources, low cost, low power consumption / envelope process is simple, easy to membrane degradation, low cost and environment-friendly new coated controlled release fertilizer has great social and economic benefits.
[0006] 一种改性造纸黑液生物基包膜控释肥料的制备方法，是将颗粒肥料加入到转鼓包衣机中，将肥料颗粒预热到1〇?i〇〇°c;将改性的造纸黑液液化物与固化剂c按照重量比i: 0.1?10混合均匀后作为包膜材料，在〇_1?IMPa压力条件下，少量多次地喷涂到肥料颗粒表面，经1?10分钟固化成膜。 [0006] The method for producing a modified bio-based black liquor coated controlled release fertilizer, the granular fertilizer is added to the drum coater, the fertilizer particles are preheated to 1〇~i〇〇 ° will change liquefied material of black liquor and the curing agent in a weight ratio c i: 0.1~10 mixing as coating material, under pressure conditions 〇_1~IMPa, a few times sprayed uniformly to the surface of the fertilizer granules, after 1 ~ 10 minutes curing film. 所述包膜材料占颗粒肥料总重量比的1 %?10 %。 The coating material accounts for 1% ~ 10% of the total weight ratio of the granular fertilizer.
[0007] 所述的造纸黑液液化物的制备方法为:造纸黑液中加入稀硫酸或稀盐酸中和至中性、浓缩烘干后制成粉末，按照造纸黑液粉末与液化剂A重量比1:1?10混合加入到带有加热、搅拌、冷凝装置的反应釜中，升温至50?180°C，然后加入液化剂A重量比1 %?10%的催化剂浓硫酸，不断搅拌30?100分钟，即可制得造纸黑液液化物。 Preparation of black liquor liquefied material [0007] according to: black liquor was added dilute sulfuric acid or dilute hydrochloric acid until neutral, dried and concentrated to a powder, according to the black liquor A powder with a liquefying agent by weight ratio of 1: 1~10 were added to the mixture with heating, stirring, condensing reactor apparatus and heated to 50~180 ° C, followed by addition of liquefying agent a 1% ~ 10% by weight of concentrated sulfuric acid catalyst, stirring constantly 30 ~ 100 minutes, to obtain a liquefied material with black liquor.
[0008] 所述的液化剂A为聚乙二醇、乙二醇、甘油或碳酸乙烯酯中的一种或几种。 [0008] A said liquefying agent is polyethylene glycol, ethylene glycol, glycerol or ethylene carbonate is one or several.
[0009] 所述的造纸黑液液化物的改性方法为:将上述制得的造纸黑液液化物中加入改性剂B进行改性，改性剂B添加量占造纸黑液液化物重量比的〇o 1%?10%。 [0009] The method of modifying the liquefied material is black liquor: the modifying agent B was added in the above-described modified black liquor obtained liquefied material, an amount of the modifier added black liquor B liquefied by weight than the square o 1% ~10%. ，搅拌混匀后超声震荡10?60分钟。 After stirring for 10 to 60 minutes mixing sonotrode.
[0010] 所述的改性剂B为具有链烷烃基、环烷烃基、芳香烃基、硝基、卤素等憎水基团的高分子物质，包括氟烷、氟硅烷、全氟烷/烯醚、氟醇、含氟丙烯酸酯和纳米二氧化硅或纳米碳酸钙等疏水性化合物中的一种或几种的混合。 Modifying agent B [0010] the group of paraffins having high molecular substance cycloalkane group, an aromatic hydrocarbon group, a nitro group, a hydrophobic group such as halogen, including fluoroalkyl, fluoro silane, a perfluoroalkyl / enol ether , mixing one or more hydrophobic compounds containing fluorine alcohol, fluorine-containing acrylate or nano silica and nano-calcium carbonate and the like.
[0011] 所述的固化剂c为异氰酸酯，包括甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酷MDI、多亚甲基多苯基多异氰酸酯PAPI、六亚甲基二异氰酸酯HDI或异佛尔酮二异氰酸酷IPDI中的一种或几种。 According to [0011] the curing agent c is an isocyanate comprising tolylene diisocyanate TDI, diphenylmethane diisocyanate cool MDI, multi polymethylene polyphenyl polyisocyanate PAPI, hexamethylene diisocyanate HDI or isoforskolin chalcone diisocyanate IPDI cool one or more of.
[0012]所述的颗粒肥料选自市售的单质的氮肥、磷肥、钾肥及其复合肥、微量元素肥料、 中量元素肥料或微生物肥料中的一种或几种。 [0012] The granular fertilizer is selected from the group of commercially available elemental nitrogen, phosphate, potash and fertilizer, micronutrient fertilizer, a fertilizer or the amount of microbial fertilizer elements of one or more. 根据所需的肥料养分控释期调整肥料表面包膜材料的重量比。 Adjusting the weight ratio of the surface of the fertilizer according to the desired coating material of the controlled release of fertilizers.
[0013]本发明的显著效果是： [0013] The significant effect of the present invention are:
[0014]利用造纸工业的废弃物造纸黑液作为控释肥料包膜的原材料，变废为宝，不仅解决了造纸废水的难处理问题，而且因其原料来源广泛，成本低廉，所以降低了控释肥料的生产成本，具有重大的经济效益和环境效益。 [0014] the use of black liquor waste paper industry as coated controlled release fertilizer raw materials, turning waste into treasure, not only to solve the intractable problem of papermaking wastewater, but also because of its wide range of sources of raw materials, low cost, so the lower control release fertilizer production costs, it has a significant economic and environmental benefits.
[0015] 1 o通过加入液化剂将造纸黑液中的木质素、半纤维素、多糖等有机高分子物质分解成低分子的多元醇，替代石油基多元醇，合成聚氨酯包膜材料，降低了控释包膜肥料的生产成本，同时生物基聚氨酯有利于膜材料的降解，避免土壤环境的二次污染。 [0015] 1 o by adding a liquefying agent in the black liquor lignin, hemicellulose, polysaccharides and other organic polymer material is decomposed into low molecular weight polyhydric alcohols, polyhydric alcohol substitute petroleum-based, synthetic polyurethane coating materials, reduced Controlled release coated fertilizers production costs, while the bio-based polyurethane as to degrade the film material, to avoid secondary pollution of the soil environment.
[0016] 2 o通过加入疏水性改性剂氟烷、氟硅烷、全氟烷/嫌醚、氟醇、含氟丙烯酸酸和纳米二氧化硅、纳米碳酸钙等，将疏水基团通过物理共混或者化学结合方式嫁接在包膜肥料的聚氨酯膜材上，通过增强包膜肥料膜材的疏水性，降低膜材的表面能，减缓水分通过聚氨酯膜材进入肥芯的速率，进一步提高控释肥料的养分释放期，提高肥料的养分利用率，满足不同的作物需肥要求。 [0016] 2 o by adding a hydrophobic modifier fluoroalkyl, fluoro silane, a perfluoroalkyl / too ether, fluoroalcohol, a fluorinated acrylic acid and nano silica, nano-calcium carbonate and the like, the hydrophobic group by physical co mixed mode or chemically grafted onto the polyurethane binding membrane coated fertilizers, coated fertilizers by enhancing the hydrophobic membrane, the membrane material to reduce the surface energy, slowing the rate of water into the core of the fertilizer by a polyurethane membrane, to further improve the controlled release nutrient release of fertilizers, improve nutrient utilization of fertilizer, crops need fertilizer to meet different requirements.
[0017] 3 o本发明所采用的方法，包括造纸黑液的液化及改性、肥料的包膜过程，加工工艺简单、设备要求低、能耗低、可大规模批量加工生产。 [0017] The method employed 3 o the present invention, black liquor coating process comprising liquefaction and modified, fertilizer, simple process, low equipment requirements and lower energy consumption, a large-scale batch processing. (四)附图说明 (Iv) Brief Description of Drawings
[0018]图1:改性的造纸黑液液化物制备包膜控释肥料的方法工艺流程图L〇〇19」图中1首先将造纸黑液浓缩，加入稀硫酸或者稀盐酸中和至中性，烘干，制成粉末； 2在反应釜中按重量比加入1中的造纸黑液粉末和液化剂，升至一定温度，加入催化剂浓硫酸，在不断搅拌中反应30?100分钟;3加入改性剂对造纸黑液液化物进行改性;4将改性的造纸黑液液化物与固化剂按一定比例混合均匀制备包膜材料;5在转鼓包衣机中加入一定量的颗粒肥料，预热到10?100°C ; 6将4中的包膜材料在一定压力条件下，按照少量多次的方式喷涂到预热好的肥料颗粒表面，反应1?10分钟固化成膜，制得控释肥料;7肥料冷却、 称量、包装、入库。 [0018] FIG. 1: Preparation of coated controlled release fertilizer modified black liquor L〇〇19 liquefied material process flow diagram of a method &in FIG. 1 the black liquor is first concentrated, and dilute sulfuric acid or dilute hydrochloric acid to of drying, in reactor 2 ratio by weight in powder and black liquor is added in a liquefaction agent, up to a certain temperature, was added concentrated sulfuric acid catalyst, the reaction in the continuously stirred for 30~100 3 modifiers added to black liquor liquefied
4 modified black liquor liquefied material and the curing agent mixed coating material was prepared by
5 certain amount of fertilizer particles in a drum coater , preheated to 10~100 ° C; 6 to 4 in coating materials under pressure conditions, in accordance with small portions preheated fertilizer particles sprayed onto the surface, the reaction 1~10 minutes curing film, prepared obtain controlle 7 fertilizers cooling, weighing, packaging, warehousing. (五)具体实施方式 (E) Detailed Description
[0020] 实施例1: [0020] Example 1:
[0021] 将造纸黑液浓缩，加入稀硫酸中和至中性，干燥成粉末。 [0021] The black liquor was concentrated, and dilute sulfuric acid was added to neutral, dried to a powder. 称取200g粉末，加入到带有加热、搅拌和冷凝装置的反应釜里，加入800g液化剂（聚乙二醇与乙二醇按重量比1:1混合均匀后作为液化剂），搅拌条件下，开启反应釜快速升温至9〇。 200g powder was weighed, added to with heating, and stirring the reaction kettle condenser device, the liquefying agent is added 800g (polyethylene glycol and ethylene glycol by weight ratio of 1: 1 and uniformly mixed as the liquefying agent), with stirring under , rapid temperature rise to open the reactor 9〇. (：，按照液化剂重量比的3% 加入浓硫酸作为催化剂，持续搅拌反应60分钟，制得造纸黑液液化产物。将造纸黑液液化产物中加入占造纸黑液液化物重量比〇_1%的改性剂(氟烷、氟硅烷、全氟(烧)烯醚、氟醇、含氟丙烯酸酯和纳米二氧化娃、纳米碳酸耗等其中的一种或几种），混合均匀后在超声波中震荡30分钟，制得改性液化产物。将此改性液化产物与固化剂异氰酸酯按照重量比1:1的比例混合均匀作为肥料的包膜材料，称取lkg尿素颗粒于转鼓包衣机中，预热到60。(：，将上述混匀的包膜材料在一定压力条件下，按照少量多次的方式喷涂到肥料颗粒表面，继续加热，反应5分钟，在肥料颗粒表面固化成膜。根据所需的肥料养分控释期，重复上述固化过程，调整肥料表面包膜材料的厚度为3%，所得肥料的养分释放期可达丨个月。 (:, In accordance with the liquefying agent 3% by weight of concentrated sulfuric acid was added as a catalyst for the reaction stirred for 60 minutes, to obtain a liquefied product was added to black liquor black liquor liquefied liquefied product accounted for papermaking black weight ratio 〇_1. % of the modifier (fluoroalkyl, fluoro silane, perfluoro (burning) allyl ethers, fluorine alcohols, fluorine-containing acrylate and nano baby dioxide, nano consumption carbonate and the like wherein one or several), mixed uniformly in in the ultrasonic oscillation for 30 minutes to obtain a modified product liquefied liquefied products of this modified polyisocyanate with a curing agent in a weight ratio of 1: 1 mixing ratio homogeneous fertilizer as coating material, said drum coater to take lkg urea granules and preheated to 60. (:, kneading the above coating materials under certain pressure conditions, in accordance with small portions sprayed onto the surface of the fertilizer particles, heating was continued for 5 minutes, the cured film-forming surface of the particles of fertilizer . Depending on the desired controlled release of fertilizers, the curing process is repeated, adjusting the surface coated fertilizer material thickness is 3%, the resulting fertilizer nutrient release of up Shu months.
[0022] 实施例2: [0022] Example 2:
[0023]将造纸黑液浓缩，加入稀硫酸中和至中性，干燥成粉末。 [0023] The black liquor was concentrated, and dilute sulfuric acid was added to neutral, dried to a powder. 称取200g粉末，加入到带有加热、搅拌和冷凝装置的反应釜里，加入7〇〇g液化剂(聚乙二醇、乙二醇、碳酸乙烯酯按重量比1:1:1混合均匀后作为液化剂），搅拌条件下，开启反应釜快速升温至8(rc，按照液化剂重量比的4 %加入浓硫酸作为催化剂，持续搅拌反应40分钟，制得造纸黑液液化产物。将液化产物中加入占造纸黑液液化物重量比0.5%的改性剂(氟烷、氟硅烷、全氟(烷)烯醚、氟醇、含氟丙烯酸酯和纳米二氧化硅、纳米碳酸钙等其中的一种或几种），混合均匀后在超声波中震荡20分钟，制得改性液化产物。将此改性液化产物与固化剂异氰酸酯按照重量: 1 o 2的比例混合均匀作为肥料的包膜材料，称取lkg磷肥颗粒于转鼓包衣机中，预热到6(rc， 将上述混匀的包膜材料在一定压力条件下，按照少量多次的方式喷涂到肥料颗粒表面，继续加热，反应8分钟，在
200g powder was weighed, added to with heating, and stirring the reaction kettle condenser device, the liquefying agent is added 7〇〇g (polyethylene glycol, ethylene glycol, ethylene carbonate weight ratio 1: 1 homogeneously mixing: 1 as the liquefying agent), under stirring, allowed to warm to quickly open the reactor 8 (rc, in accordance with the liquefying agent 4% by weight of concentrated sulfuric acid as a catalyst was added, the reaction continued stirring for 40 minutes to obtain a liquefied product black liquor. liquefied the product was added to account for the liquefied material with black liquor than 0.5% by weight of modifying agent (fluoroalkyl, fluoro silane, perfluoro (alkyl) allyl ether, fluoroalcohol, a fluorinated acrylate and nano silica, nano-calcium carbonate and the like wherein one or several), uniformly mixed in an ultrasonic oscillation for 20 minutes to prepare a modified product liquefied liquefied products of this modified polyisocyanate with a curing agent in a weight:. 1 o 2 ratio of the homogeneously coated fertilizers as materials, weighed lkg fertilizer particles in a drum coater, preheated to 6 (rc, the above-described coating material is mixed under pressure conditions, in accordance with small portions sprayed onto the surface of the fertilizer particles, heating was continued, for 8 minutes,
料颗粒表面固化成膜。根据所需的肥料养分控释期，重复上述固化过程，调整肥料表面包膜材料的厚度为5%，所得肥料的养分释放期可达3个月。 Curing the material forming the particle surface. Depending on the desired controlled release of fertilizers, the curing process is repeated, adjusting the thickness of the material coated the surface of the fertilizer is 5%, the resulting fertilizer nutrient release of up to three months.
[0024]实施例3: [0024] Example 3:
[0025]将造纸黑液浓缩，加入稀盐酸中和至中性，干燥成粉末。 [0025] The black liquor was concentrated, and dilute hydrochloric acid was added to neutral, dried to a powder. 称取200g粉末，加入到带有加热、搅拌和冷凝装置的反应釜里，加入8〇〇g液化剂(聚乙二醇与甘油按重量比9:丨混合均匀后作为液化剂），搅拌条件下，开启反应釜快速升温至120>>C，按照液化剂重量比的3 o5%加入浓硫酸作为催化剂，持续搅拌反应9〇分钟，制得造纸黑液液化产物。 200g powder was weighed, added to with heating, the reaction vessel was stirred and the condensing device, added 8〇〇g liquefying agent (polyethylene glycol and glycerol in a weight ratio 9: Shu mixed as the liquefying agent), stirring under open reactor quickly warmed to 120 >>C, in accordance with the liquefying agent weight ratio 3 o 5% concentrated sulfuric acid as a catalyst was added, stirring was continued reaction 9〇 minutes, to obtain a liquefied product black liquor. 将液化产物中加入占造纸黑液液化物重量比1%的改性剂(氟烷、氟硅烷、全氟(焼)烯醚、氟醇、含氟丙饰酸和纳米二氧化硅、纳米碳酸钙等其中的一种或几种），混合均匀后在超声波中震荡6〇分钟，制得改性液化产物。 The liquefied product is added representing black liquor ratio of 1% by weight of the liquefied material modifier (fluoroalkyl, fluoro silane, perfluoro (firing) allyl ether, fluoroalcohol, a fluorinated propionic acid and decorated nano silica, nano carbonate wherein one or more of calcium), mixed uniformly shock 6〇 minutes, to obtain a liquefied product modified ultrasonic waves. 将此改性液化产物与固化剂异氰酸酯按照重量比i : ：L. 5的比例混合均勾作为肥料的包膜材料，称取lkg复合肥颗粒于转鼓包衣机中，预热到7(TC，将上述混勾的包膜材料在一定压力条件下，按照少量多次的方式喷涂到肥料颗粒表面，继续加热，反应10分钟，在肥料颗粒表面固化成膜。根据所需的肥料养分控释期，重复上述固化过程，调整肥料表面包膜材料的厚度为，所得肥料的养分释放期可达6个月。 This modified liquefaction product with an isocyanate curing agent in accordance with the weight ratio of i:: L mix ratio of the material 5 are coated hook as fertilizer, compound fertilizer granules weighed lkg drum coater, preheated to 7 (TC , the above-described coating materials blended hook under certain pressure conditions, in accordance with small portions sprayed onto the surface of the fertilizer particles, heating was continued for 10 minutes, forming the solidified surface of the particles of fertilizer. Depending on the desired controlled release fertilizers period, the curing process is repeated, adjusting the surface coated fertilizer material thickness, the resulting fertilizer nutrient release of up to 6 months.
[0026] 实施例4: [0026] Example 4:
[0027]将造纸黑液浓缩，加入稀盐酸中和至中性，干燥成粉末。 [0027] The black liquor was concentrated, and dilute hydrochloric acid was added to neutral, dried to a powder. 称取200g粉末，加入到带有加热、搅拌和冷凝装置的反应釜里，加入l〇〇〇g液化剂（乙二醇与碳酸乙烯酯按重量比1:2 混合作为液化剂），搅拌条件下，开启反应釜快速升温至80。 200g powder was weighed, added to with heating, and stirring the reaction kettle condenser device, the liquefying agent is added l〇〇〇g (ethylene glycol and ethylene carbonate weight ratio of 1: 2 mixture as the liquefying agent), stirring next, to open the reactor 80 rapid heating. (：，按照液化剂重量比的3%加入浓硫酸作为催化剂，持续搅拌反应40分钟，制得造纸黑液液化产物。将液化产物中加入占造纸黑液液化物重量比2%的改性剂(氟烷、氟硅烷、全氟(焼)烯醚、氟醇、含氟丙烯酸醋和纳米二氧化硅、纳米碳酸钙等其中的一种或几种），混合均匀后在超声波中震荡60分钟，制得改性液化产物。将此改性液化产物与固化剂异氰酸酯按照重量比1:2的比例混合均匀作为肥料的包膜材料，称取lkg微量元素肥料颗粒于转鼓包衣机中，预热到5(TC，将上述混匀的包膜材料在一定压力条件下，按照少量多次的方式喷涂到肥料颗粒表面，继续加热，反应i 2 分钟，在肥料颗粒表面固化成膜。根据所需的肥料养分控释期，重复上述固化过程，调整肥料表面包膜材料的厚度为10%，所得肥料的养分释放期可达9个月。 (:, In accordance with the liquefying agent 3% by weight of concentrated sulfuric acid was added as a catalyst, the reaction was continued stirring for 40 minutes to obtain a liquefied product was added to black liquor liquefied liquefied product accounted for papermaking black modifier weight ratio of 2%. (fluoroalkyl, fluoro silane, perfluoro (firing) allyl ether, fluoroalcohol, a fluorinated acrylate, vinegar and nano silica, nano calcium carbonate and the like wherein one or several), mixed uniformly for 60 minutes in an ultrasonic shock , to obtain a modified product liquefied liquefied products of this modified polyisocyanate with a curing agent in a weight ratio of 1: 2 ratio uniform mixing as a fertilizer coating materials, weighed lkg micronutrient fertilizer particles in a drum coater, pre heated to 5 (TC, the above-described coating material is mixed under pressure conditions, in accordance with small portions sprayed onto the surface of the fertilizer particles, heating was continued, the reaction i 2 minutes and curing film on the surface of the fertilizer particles. depending on the release of fertilizers required, the curing process is repeated, adjusting the thickness of the material coated the surface of the fertilizer was 10%, the resulting fertilizer nutrient release of up to 9 months.
International Classification, , , , , , Rotate}