技术领域technical field
本发明涉及中草药种植土壤修复剂及其制备方法，是一种适用于中草药种植和农业种植的土壤修复剂，尤其适用于高重金属含量土壤的修复。The invention relates to a soil remediation agent for planting Chinese herbal medicine and a preparation method thereof, which is a soil remediation agent suitable for planting Chinese herbal medicine and agricultural planting, and is especially suitable for remediation of soil with high heavy metal content.
背景技术Background technique
随着城市工业化的快速发展，各种工矿企业排放的“三废”，以及矿物燃料的燃烧和化肥农药的过度使用，重金属、化学污染物通过各种途径进入土壤，数量与速度已经远超土壤的容纳能力和净化速度。我国目前的土壤重金属污染问题十分严峻，中国地质调查局实施的我国多目标区域地球化学调查结果显示13％国土面积区域的土壤存在污染，南方以重金属问题为主，重金属污染破坏了土壤的自我修复能力，导致土壤质量恶化，直接影响了中草药的正常生长发育，导致中草药产品产量和质量下降，严重影响了中草药的药效，降低了中草药治病救人的功效，由于重金属残留的问题，我国目前中药材的总出口额仅占世界植物药1％左右的销售量。With the rapid development of urban industrialization, the "three wastes" discharged by various industrial and mining enterprises, as well as the burning of fossil fuels and the excessive use of chemical fertilizers and pesticides, heavy metals and chemical pollutants enter the soil through various channels, and the quantity and speed have far exceeded that of the soil. Capacity and purification speed. my country's current soil heavy metal pollution is very serious. The results of my country's multi-target regional geochemical survey conducted by the China Geological Survey show that 13% of the country's land area is polluted, and the south is dominated by heavy metals. Heavy metal pollution has destroyed the self-healing of the soil. capacity, leading to deterioration of soil quality, directly affecting the normal growth and development of Chinese herbal medicines, leading to a decline in the output and quality of Chinese herbal medicines, seriously affecting the efficacy of Chinese herbal medicines, and reducing the efficacy of Chinese herbal medicines in curing diseases and saving lives. Due to the problem of heavy metal residues, the current Chinese herbal medicines in my country The total export value only accounts for about 1% of the world's botanical medicine sales.
长期以来，人们对水污染和大气污染认识比较深刻，但对土壤污染的认识普遍存在不足，土壤污染问题在我国并不像水污染和大气污染引人关注，近年来，美国等发达国家纷纷开始研究土壤污染问题，我国也开始制定《土壤污染防治法》初稿，重视土壤污染问题。土壤污染中常见的重金属污染包括铜、锌、铅、铬、镍等，食药安全方面主要限制的是铜、铬等，在现行的各项标准中，重金属元素在中药材中含量的高低逐渐成为衡量中药材质量、品质优劣的一项关键评测指标，因此，中草药种植基地土壤中重金属含量的防控与治理是中药材亟需解决的重要问题。For a long time, people have a deep understanding of water pollution and air pollution, but the understanding of soil pollution is generally insufficient. The problem of soil pollution in my country is not as much concerned as water pollution and air pollution. In recent years, developed countries such as the United States have begun to To study the problem of soil pollution, my country has also begun to formulate the first draft of the "Law on the Prevention and Control of Soil Pollution", which attaches great importance to the problem of soil pollution. Common heavy metal pollution in soil pollution includes copper, zinc, lead, chromium, nickel, etc. The main restrictions on food and drug safety are copper, chromium, etc. According to the current standards, the content of heavy metal elements in Chinese medicinal materials is gradually increasing. It has become a key evaluation index to measure the quality and quality of Chinese herbal medicines. Therefore, the prevention, control and management of heavy metal content in the soil of Chinese herbal medicine planting bases is an important problem that needs to be solved urgently in Chinese herbal medicines.
目前我国在土壤治理方面应用较多的是微生物修复、化学修复以及植物修复。目前化学修复经常使用的金属螯合剂有羟基羧酸类和聚羧酸类等，这些螯合剂虽然可以很好地螯合金属，但是螯合后重金属仍然会残存在土壤中，一段时间后又会游离在土壤中，“治标不治本”，微生物修复对微生物的选择比较苛刻，而且很难保证微生物的生存率，植物修复的周期过长并且对富集重金属植物的选择比较困难。化学修复属于原位修复，操作易于实施并且成本易控制，对于中轻度重金属污染的土壤，修复效果较佳，而且适宜于大面积中草药种植土壤污染的修复。At present, microbial remediation, chemical remediation and phytoremediation are widely used in soil treatment in my country. At present, the metal chelating agents commonly used in chemical restoration include hydroxycarboxylic acids and polycarboxylic acids, etc. Although these chelating agents can chelate metals well, heavy metals will still remain in the soil after chelation, and will reappear after a period of time. Free in the soil, "treat the symptoms but not the root cause". Microbial remediation is relatively harsh on the selection of microorganisms, and it is difficult to ensure the survival rate of microorganisms. The cycle of phytoremediation is too long and it is difficult to select heavy metal-enriched plants. Chemical remediation belongs to in-situ remediation, which is easy to implement and cost controllable. It has a better remediation effect on soil with moderate to light heavy metal pollution, and is suitable for remediation of soil contaminated by large-scale Chinese herbal medicine planting.
CN20031010891.0中公开了一种化学调控剂治理土壤污染，主要成分是低分子量壳聚糖，其主要作用是作为淋洗剂来使用，CN20121023142.2公开了一种重金属吸附絮凝剂，主要用来吸附水体中的絮凝剂，这些螯合剂虽然可以很好地螯合金属，但是螯合后重金属仍然会残存在土壤中，一段时间后又会游离在土壤中，“治标不治本”。CN20031010891.0 discloses a chemical regulator to control soil pollution, the main component is low molecular weight chitosan, its main function is to use as a washing agent, CN20121023142.2 discloses a heavy metal adsorption flocculant, mainly used Adsorb the flocculants in the water body. Although these chelating agents can chelate metals well, heavy metals will still remain in the soil after chelation, and will be free in the soil after a period of time.
因此，开发一种即能修复重金属污染土壤，又能可回收利用的土壤修复剂，对于治理我国中草药种植土壤重金属污染的修复具有重大的应用价值和环保意义。本发明的目的在于提供一种中草药种植土壤修复剂及其应用，该土壤修复剂具有优异的吸附重金属性能，对环境友好可以回收再利用。Therefore, the development of a soil remediation agent that can repair heavy metal-contaminated soil and can be recycled has great application value and environmental protection significance for the restoration of heavy metal pollution in Chinese herbal medicine planting soil in my country. The object of the present invention is to provide a soil remediation agent for planting Chinese herbal medicine and its application. The soil remediation agent has excellent heavy metal adsorption performance, is environmentally friendly and can be recycled and reused.
发明内容Contents of the invention
技术问题：本发明采用携带含聚丙二醇结构的单体与丙烯酸、马来酸酐、烯丙基磺酸钠等含羧酸基团的小分子单体和可以荧光示踪的荧光单体以及含有羟基的磁性四氧化三铁颗粒合成可回收的无磷的共聚物金属螯合剂，具有优异的螯合重金属效果，同时在磁场作用下具有可回收再利用性能，是一种环境友好的环保型土壤修复剂。Technical problem: The present invention adopts monomers containing polypropylene glycol structure and small molecule monomers containing carboxylic acid groups such as acrylic acid, maleic anhydride, sodium allyl sulfonate and fluorescent monomers that can be traced by fluorescence and containing hydroxyl groups The recyclable phosphorus-free copolymer metal chelating agent synthesized by the magnetic iron ferric oxide particles has excellent chelating effect on heavy metals, and has recyclable and reusable performance under the action of a magnetic field. It is an environmentally friendly and environmentally friendly soil remediation agent.
技术方案：一种绿色环保型土壤修复剂(AZTR)是以聚丙二醇酯单体与含乙烯基不饱和双键的单体和可以荧光示踪的荧光单体以及含有不饱和双键的磁性四氧化三铁进行自由基共聚后而得，其结构通式如下：Technical solution: A green and environment-friendly soil remediation agent (AZTR) is based on polypropylene glycol ester monomers, monomers containing ethylenically unsaturated double bonds, fluorescent monomers that can be fluorescently traced, and magnetic quadrilaterals containing unsaturated double bonds Ferric oxide is obtained by free radical copolymerization, and its general structural formula is as follows:
其中：A是含乙烯基不饱和双键的单体共聚后的重复结构单元，B是含不饱和双键的荧光单体聚合后的重复结构单元，C是含不饱和双键的磁性四氧化三铁，聚合度x、y、z为1～5000，重复单元数m、n为1～100。Among them: A is the repeating structural unit after copolymerization of monomers containing vinyl unsaturated double bonds, B is the repeating structural unit after polymerization of fluorescent monomers containing unsaturated double bonds, C is the magnetic tetroxide containing unsaturated double bonds Three irons, the degree of polymerization x, y, z is 1-5000, and the number of repeating units m, n is 1-100.
上述的一种土壤修复剂的制备方法为：The preparation method of above-mentioned a kind of soil restoration agent is:
在N2氛下，以烯丙基聚丙二醇醚质量为基准，将烯丙基聚丙二醇醚和0.05～5倍烯丙基聚丙二醇醚质量的顺丁烯二酸酐加入反应釜中，60～160℃下反应1～10h，得聚醚羧酸酯反应单体。将反应温度调至50～95℃后，再加入0.2～5倍烯丙基聚丙二醇醚质量的含乙烯基不饱和双键的单体、0.001～0.5倍烯丙基聚乙二醇单醚质量的含不饱和双键的荧光单体、0.001～0.5倍烯丙基聚乙二醇单醚质量的含不饱和双键的四氧化三铁、0.1～5倍烯丙基聚丙二醇醚质量的水，混匀后滴加质量百分浓度为5％～50％的无机引发剂水溶液，无机引发剂的加入量为0.01～0.5倍烯丙基聚丙二醇醚质量，1～5h滴完，滴完后继续在50～95℃下反应0.5～10h，冷至室温，制得固含量为5～70wt％的绿色环保型土壤修复剂。UnderN2 atmosphere, based on the mass of allyl polypropylene glycol ether, add allyl polypropylene glycol ether and maleic anhydride 0.05 to 5 times the mass of allyl polypropylene glycol ether into the reaction kettle, 60 to 160 Reaction at ℃ for 1-10 hours to obtain polyether carboxylate reaction monomer. After adjusting the reaction temperature to 50-95°C, add 0.2-5 times the mass of allyl polypropylene glycol ether, monomers containing vinyl unsaturated double bonds, and 0.001-0.5 times the mass of allyl polyethylene glycol monoether Fluorescent monomers containing unsaturated double bonds, 0.001 to 0.5 times the mass of allyl polyethylene glycol monoether, ferric oxide containing unsaturated double bonds, 0.1 to 5 times the mass of allyl polypropylene glycol ether, and water , after mixing, add dropwise an inorganic initiator aqueous solution with a mass percentage concentration of 5% to 50%. The amount of the inorganic initiator added is 0.01 to 0.5 times the mass of allyl polypropylene glycol ether, and the dripping is completed within 1 to 5 hours. Continue to react at 50-95° C. for 0.5-10 hours, and cool to room temperature to prepare a green and environment-friendly soil restoration agent with a solid content of 5-70 wt%.
上述的绿色环保型土壤修复剂的制备方法中所述的含乙烯基不饱和双键单体为丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、马来酸酐、丙烯酸羟丙酯、马来酸、衣康酸的一种或多种的组合。所述的含不饱和双键的荧光单体为N-苯基-乙烯基苄-1-萘胺8-磺酸钠和N-苯基-丙烯酰基-1-萘胺8-磺酸钠中的一种或者两种的组合；The ethylenically unsaturated double bond-containing monomer described in the preparation method of the above-mentioned green environment-friendly soil restoration agent is acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, maleic anhydride , hydroxypropyl acrylate, maleic acid, itaconic acid or a combination of one or more. The fluorescent monomer containing unsaturated double bonds is N-phenyl-vinylbenzyl-1-naphthylamine 8-sodium sulfonate and N-phenyl-acryloyl-1-naphthylamine 8-sodium sulfonate one or a combination of two;
该制备方法中所述的无机引发剂为过硫酸钠、过硫酸钾、偏重亚磺酸钠、偏重亚磺酸钾、过磺酸钠、过磺酸钾、过氧化氢中的一种或者多种的组合。The inorganic initiator described in the preparation method is one or more of sodium persulfate, potassium persulfate, sodium metabisulfinate, potassium metabisulfinate, sodium persulfonate, potassium persulfate, hydrogen peroxide combination of species.
有益效果：本发明的土壤修复剂具有以下优异性能：Beneficial effect: the soil remediation agent of the present invention has the following excellent properties:
(1)该土壤修复剂不含氮磷等，具有良好的重金属螯合性能，是一种新型的环保型土壤修复剂。其制备工艺绿色环境友好，合成过程采用环保、价廉的水作为反应溶剂，反应过程采用“一锅煮”方式，无需分离，操作简单方便、生产成本较低。(1) The soil remediation agent does not contain nitrogen, phosphorus, etc., has good heavy metal chelating performance, and is a new type of environmental protection soil remediation agent. The preparation process is green and environment-friendly, the synthesis process uses environmentally friendly and cheap water as the reaction solvent, the reaction process adopts the "one-pot cooking" method, no separation is required, the operation is simple and convenient, and the production cost is low.
(2)该土壤修复剂结构中含有亲水性强的磺酸基团，以及能与重金属离子螯合的羧酸根离子，对中草药种植土壤中的重金属离子有高效的抑制作用，另外该土壤修复剂含有的磁性四氧化三铁具有良好的可回收性能。(2) The structure of the soil remediation agent contains sulfonic acid groups with strong hydrophilicity and carboxylate ions that can be chelated with heavy metal ions, which can effectively inhibit the heavy metal ions in the soil for planting Chinese herbal medicines. In addition, the soil remediation The magnetic ferric iron tetroxide contained in the agent has good recyclability.
(3)该土壤修复剂的配伍性好，可与海泡石、石灰等土壤修复剂复配使用，也可单独使用。(3) The soil remediation agent has good compatibility and can be compounded with sepiolite, lime and other soil remediation agents, or used alone.
具体实施方式Detailed ways
实例1：Example 1:
在N2保护的反应釜中加入100g烯丙基聚丙二醇醚，70℃下加入80g顺丁烯二酸酐(溶于100g水)和100g水，再加入80g马来酸酐、0.5g N-苯基-乙烯基苄-1-萘胺8-磺酸钠，100g水，混匀后滴加10g过硫酸钠(溶于50g水)，滴加完毕后，继续在80℃下反应2h，降至室温后，制得一种土壤修复剂(AZTR1)Add 100g of allyl polypropylene glycol ether to a reactor protected byN2 , add 80g of maleic anhydride (dissolved in 100g of water) and 100g of water at 70°C, then add 80g of maleic anhydride, 0.5g of N-phenyl -Vinylbenzyl-1-naphthylamine 8-sodium sulfonate, 100g water, mix well, add 10g sodium persulfate (dissolved in 50g water) dropwise, after the dropwise addition, continue to react at 80°C for 2h, and cool to room temperature Afterwards, a soil remediation agent (AZTR1) was prepared
实例2：在N2保护的反应釜中加入100g烯丙基聚丙二醇醚，50℃下加入65g顺丁烯二酸酐(溶于100g水)和100g水，再加入70g马来酸酐、0.4g N-苯基-丙烯酰基-1-萘胺8-磺酸钠，100g水，混匀后滴加12g过硫酸钠(溶于50g水)，滴加完毕后，继续在75℃下反应2h，降至室温后，制得一种土壤修复剂(AZTR2)Example 2: Add 100g allyl polypropylene glycol ether inN2 protected reactor, add 65g maleic anhydride (dissolved in 100g water) and 100g water at 50°C, then add 70g maleic anhydride, 0.4g N -Phenyl-acryloyl-1-naphthylamine 8-sodium sulfonate, 100g water, after mixing, add dropwise 12g sodium persulfate (dissolved in 50g water), after the dropwise addition, continue to react at 75°C for 2h, drop After reaching room temperature, a kind of soil remediation agent (AZTR2) was prepared
实例3：在N2保护的反应釜中加入100g烯丙基聚丙二醇醚，37℃下加入45g顺丁烯二酸酐(溶于100g水)和100g水，再加入60g马来酸酐、0.3g N-苯基-丙烯酰基-1-萘胺8-磺酸钠，100g水，混匀后滴加16g过硫酸钠(溶于50g水)，滴加完毕后，继续在75℃下反应2h，降至室温后，制得一种土壤修复剂(AZTR3)Example 3: Add 100g allyl polypropylene glycol ether in the reactor protected byN2 , add 45g maleic anhydride (dissolved in 100g water) and 100g water at 37°C, then add 60g maleic anhydride, 0.3g N -Phenyl-acryloyl-1-naphthylamine 8-sodium sulfonate, 100g water, after mixing, add 16g sodium persulfate (dissolved in 50g water) dropwise, after the dropwise addition, continue to react at 75°C for 2h, drop After reaching room temperature, a kind of soil remediation agent (AZTR3) was prepared
含重金属Cu2+的土壤中铜离子含量为20mg/L，将实施例1至3的土壤修复剂用去离子水稀释，配置成固定浓度(土壤修复剂含量为20mg浓度)水溶液，将水溶液加入土壤溶解液中(含铜离子的土壤用去离子水溶解取出上层澄清液)，3h后测定土壤溶解液中铜离子含量，结果如下：Copper ion content is 20mg/L in the soil containing heavy metal Cu2+ , and the soil remediation agent of embodiment 1 to 3 is diluted with deionized water, is configured into fixed concentration (soil remediation agent content is 20mg concentration) aqueous solution, aqueous solution is added In the soil solution (the soil containing copper ions is dissolved with deionized water to take out the upper clarified solution), measure the copper ion content in the soil solution after 3 hours, and the results are as follows:
从实施例的修复土壤中铜离子的结果看，本发明的土壤修复剂对于铜离子的螯合能力效果显著。From the results of the repairing of copper ions in the soil in the examples, the soil repairing agent of the present invention has a remarkable effect on the chelating ability of copper ions.
| Application Number | Priority Date | Filing Date | Title |
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| CN201710220388.XACN108659847A (en) | 2017-03-28 | 2017-03-28 | A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof |
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| CN201710220388.XACN108659847A (en) | 2017-03-28 | 2017-03-28 | A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof |
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| CN108659847Atrue CN108659847A (en) | 2018-10-16 |
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| CN201710220388.XAPendingCN108659847A (en) | 2017-03-28 | 2017-03-28 | A kind of Chinese herbal medicine planting soil renovation agent and preparation method thereof |
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| Date | Code | Title | Description |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20181016 |