CN113277954B - 一种氨基酸金属螯合物微纳米粉体及其制备方法 - Google Patents
一种氨基酸金属螯合物微纳米粉体及其制备方法 Download PDFInfo
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- CN113277954B CN113277954B CN202110672224.7A CN202110672224A CN113277954B CN 113277954 B CN113277954 B CN 113277954B CN 202110672224 A CN202110672224 A CN 202110672224A CN 113277954 B CN113277954 B CN 113277954B
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- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- DOMFLPVGNPNTDL-JEDNCBNOSA-N cobalt;(2s)-2,6-diaminohexanoic acid Chemical compound [Co].NCCCC[C@H](N)C(O)=O DOMFLPVGNPNTDL-JEDNCBNOSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RUBFCLDQBHUROT-WCCKRBBISA-N copper;(2s)-pyrrolidine-2-carboxylic acid Chemical compound [Cu].OC(=O)[C@@H]1CCCN1 RUBFCLDQBHUROT-WCCKRBBISA-N 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009791 electrochemical migration reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
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- 229960002449 glycine Drugs 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
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- BTJRKNUKPQBLAL-UHFFFAOYSA-N hydron;4-methylmorpholine;chloride Chemical compound Cl.CN1CCOCC1 BTJRKNUKPQBLAL-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- 235000008729 phenylalanine Nutrition 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
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Abstract
本发明涉及一种氨基酸金属螯合物微纳米粉体及其制备方法,其特征在于:(1)0~38℃下,按反应物正负电荷摩尔比氨基酸:Men+=n:1,将固体氨基酸和带结晶水的金属卤盐或硝酸盐加到研钵中,加入5~10%的离子液体,混匀;(2)研磨10~20 min,充分混合与反应,得糊状物,静置1~2h;(3)向糊状物中加去离子水搅拌溶解,抽滤洗涤6‑8次得滤饼;或向糊状物中加去离子水搅拌溶解后静置6~10天蒸发结晶,并水洗2~3次得固体晶体;(4)将滤饼或晶体在60‑90℃烘箱中烘干2‑3h,冷却、取出研细,即可。本发明优点:室温下进行固相合成,工艺简单、适用范围广、离子液体可回收再用、成本低;原材料来源广泛,廉价易得,产品收率高,纯度高,不需再次提纯,可直接应用于饲料添加。
Description
技术领域
本发明属于动物饲料添加剂制备技术领域,涉及一种氨基酸金属螯合物微纳米粉体及其制备方法。
背景技术
氨基酸金属螯合物是氨基酸与金属离子以一定的摩尔比螯合的产物,具有稳定性强,生物效价高,易被生物体吸收等特点,是一种新型、高效的营养元素添加剂。
目前,市面上常有的氨基酸金属螯合物多为氨基酸铁、氨基酸锌、氨基酸锰、氨基酸铜、氨基酸钴、氨基酸硒等;产品种类较为单一,不能满足市场多样化的需求。
目前氨基酸金属螯合物的生产中多采用“水热合成”的方法来合成氨基酸金属螯合物,该方法需要在溶剂中进行,基于氨基酸金属螯合物在水中的溶度积常数而获得产品,因而对某些配位数较低的氨基酸金属螯合物来说会存在金属离子与氨基酸的解离平衡与水解平衡,导致反应的不完全,造成反应物氨基酸或金属离子的利用率相对降低,转化率不理想(转化率通常在70- 80%);而且反应过程中需要添加有机溶剂,调pH值的酸碱试剂、需要加热等操作,导致生产成本较高,后续废水处理困难。
专利公开号CN1284766C中提供了一种气流增效微波技术固相合成氨基酸螯合物的方法,该方法尽管工艺过程简单,易于操作、产品纯度高,但微波加热与气流降温能耗大、产品运行费用高。专利公开号CN110770246A中提供了一种生产金属螯合物的节能的无溶剂方法,该方法是将反应前驱物金属碳酸盐或金属草酸盐与氨基酸以颗粒形式引入流化床对置喷射研磨机的流体射流中,使反应物发生颗粒-颗粒碰撞、产生固相反应而得到产物,但所得产品能耗大,成本高,产出率受反应前驱物种类的影响较大。
发明内容
本发明的目的一是为了解决现有市场中氨基酸金属螯合物种类单一的问题,二是为了解决现有氨基酸金属螯合物制备方法中存在投资成本高、操作费用高、能耗大等问题,提供一种氨基酸金属螯合物微纳米粉体及其制备方法。
为了实现上述目的,本发明采用的技术方案如下:
一种氨基酸金属螯合物微纳米粉体,其特征在于结构通式如下:(RCHNH2COOH)n-Men+,其中,Me为(饲料)所需的第IIA、IIIA主族元素、稀土金属和过渡金属元素。
进一步,第IIA主族元素为 镁、钙、锶、钡。
进一步,第IIIA主族元素为 硼、铝、镓、铟。
进一步,稀土金属为 镧、铈、镨、钕、钐。
进一步,过渡金属元素为 锌、铜、铁、钼、钴、铬、铋。
进一步,所述氨基酸(RCHNH2COOH)均为L型的甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸(蛋氨酸)、脯氨酸、色氨酸、丝氨酸、酪氨酸、半胱氨酸、苯丙氨酸、天冬酰胺、谷氨酰胺、苏氨酸、天冬氨酸、谷氨酸、赖氨酸、精氨酸和组氨酸等二十种氨基酸。
一种氨基酸金属螯合物微纳米粉体的制备方法,其特征在于包括如下步骤:
(1)在0~38℃的室温下,按反应物的正负电荷摩尔比氨基酸:Men+=n:1将固体氨基酸和带结晶水的金属盐(即卤盐或硝酸盐)加入到研钵中,并加入混合物(固体氨基酸和带结晶水的金属盐)总质量5~10%的催化剂离子液体,混合均匀;
在该步骤中金属盐必须是金属卤盐或硝酸盐,并且带结晶水;如果不带结晶水,在常温下反应很慢甚至不发生反应(因为带结晶水金属卤盐或硝酸盐的晶格能相较于其不带结晶水金属卤盐或硝酸盐的晶格能要小);
离子液体的选择也是至关重要的,离子液体本身具有较大的活性,不同种类的离子液体,其活性各不相同,并具有一定的方向性与选择性,反应后离子液体的活性降低,对氨基酸螯合物的溶解能力下降,会直接影响产出率,而且离子液体本身具有一定的毒性且难以生物降解的,因此,离子液体的选择不仅需要考虑离子液体本身的活性,还需要综合考虑离子液体的回收利用以及后续废水的处理;
(2)将步骤(1)中混合物在研钵中研磨10~20 min,使反应得到充分混合与反应,并得到糊状物,静置1~2h使反应物尽量完全反应;
在该步骤中研磨即机械活化,使金属盐的晶格表面原子获得能量,结合水变成自由水;利用(固/液)离子液体本身的活性来进行催化固相反应;
(3)向步骤(2)制备的糊状物中加入糊状物体积200~300%的去离子水,搅拌溶解未完全反应的氨基酸和金属盐后,进行抽滤洗涤6-8次,以去除离子液体和未反应的氨基酸和金属盐并获得滤饼;其中用硝酸银溶液定性检测滤液中是否残留卤离子(Cl-、Br-、I-),若有卤离子残留则继续抽滤洗涤,直至卤离子全部除去;或通过6次以上的去离子水洗涤,以移除硝酸根离子;
或向步骤(2)制备的糊状物中加入糊状物体积200~300%的去离子水进行搅拌溶解后静置6~10天使其自然蒸发结晶或冷却结晶,并将所得晶体水洗2~3次,得氨基酸螯合物固体晶体;
(4)将步骤(3)获得的固体滤饼或晶体在60-90oC烘箱中烘干2-3h,冷却至室温后取出并研细,即获得一种氨基酸金属螯合物微纳米粉体(含量99.0~99.9 %)。
进一步,所述步骤(1)中离子液体为固体离子液体或液体离子液体。
进一步,所述固体离子液体为1,3-二甲基咪唑硫酸甲酯盐(MDLS)、1-乙基3-甲基咪唑硫酸甲酯盐、1-丁基-3-甲基咪唑鎓六氟磷酸盐、1-丁基-3-甲基咪唑四氟硼酸盐等。
进一步,所述液体离子液体为咪唑型离子液体(如:溴化1-丙基-3-甲基咪唑、碘化1-丙基-3-甲基咪唑、1-乙基-3-甲基咪唑硫酸甲酯盐、1-乙基-3-甲基咪唑硝酸盐、1-乙基-3-甲基咪唑乙酸盐、1-乙基-3-甲基咪唑甲磺酸盐)、吡啶型离子液体液体(如:1-乙基吡啶盐酸盐、1-乙基吡啶盐酸盐四氟硼酸、1-乙基吡啶六氟磷酸盐、1-乙基吡啶三氟甲磺酸盐)、吡咯烷型离子液体(如:N-甲基,乙基吡咯烷双三氟甲磺酰亚胺、氯化N-甲基丁基吡咯烷、N-甲基丁基吡咯烷甲磺酸盐、N-甲基丁基吡咯烷对甲苯磺酸盐)、季铵型离子液体(如:三丁基甲基氯化铵、三丁基甲基铵双(三氟甲烷磺酰)亚胺盐)、吗啉型离子液体(如:氯化N-甲基乙基吗啉、氯化N-甲基丙基吗啉和氯化N-甲基丁基吗啉、N-甲基-N-丁基吗啉氟硼酸盐)等。
进一步,当步骤(1)中固体氨基酸溶解度(25℃)> 400g/L时,离子液体可替换成阴、阳表面活性剂作催化剂。
进一步,所述阴离子表面活性剂为苯磺酸钠及其同系物(如:对甲基苯磺酸钠、二甲基苯磺酸钠、4-乙基苯磺酸钠、异丙基苯磺酸钠等)、 十二烷基苯磺酸钠、十六烷基苯磺酸钠。
进一步,所述阳离子表面活性剂为C6~C18烷基三甲基卤化铵,其中卤原子X=F、Cl、Br、I。
本发明的特征是利用不同分子结构的固体离子液体与液体离子液体的活性能降低固体表面晶格能或界面能,使固体的带结晶水金属盐与氨基酸固体进行简单的固相反应,而获得转化率很高(90~99%)的单金属、二元金属及多元金属的氨基酸金属螯合物微纳米粉体,以及两种或三种以上氨基酸单(双)金属或多金属的复合氨基酸金属螯合物。
当Me为二价的金属离子时,在离子液体的作用下,其带结晶水的卤盐及其硝酸盐分别与二十种氨基酸去质子化反应,得到的氨基酸金属盐具有的分子晶体结构为:(RCHNH2COO)2Me;
当Me为三价的金属离子时,在离子液体的作用下,其带结晶水的卤盐及其硝酸盐分别与二十种氨基酸去质子化反应,得到的氨基酸金属螯合物具有的分子晶体结构为:(RCHNH2COO)3Me;
当Me为四价的金属离子时,在离子液体的作用下,其带结晶水的卤盐及其硝酸盐分别与二十种氨基酸去质子化反应,得到的氨基酸金属螯合物具有的分子晶体结构为:(RCHNH2COO)4Me;
当反应体系同时存有两种不同价态的金属离子,在离子液体的作用下,其带结晶水的卤盐或硝酸盐分别与同一氨基酸反应,得到的氨基酸金属螯合物的分子晶体结构是由此两种金属分别与该氨基酸组成的氨基酸金属螯合物;两种氨基酸金属螯合物的百分组成不仅与金属离子的电荷数、离子半径尺寸、离子迁移速率有关,而且与离子液体中的阴阳离子结构与及其组成、种类紧密相关;如以家畜、家禽所需要的微量元素(锌、钴、锰、铜、铁)及难溶于水的组氨酸为例,当ZnCl2.6H2O: FeCl3.6H2O: 组氨酸的摩尔比分别为1: 1: 5, 1:0.8: 5, 1:0.6:5时,复合组氨酸金属盐中所含组氨酸铁与组氨酸锌所占比例分别为(58.15%, 41.85%), (52.64%, 47.36%), (45.46%, 54.54%)。以不同分子结构的离子液体为催化剂,均可获得不同转化率的氨基酸金属螯合物及其复合物微纳米粉体。其中,在相同的操作条件下,本身溶入水的氨基酸与带结晶水金属盐反应,其转化率很高,可达95%以上;这丰富与完善了氨基酸金属螯合物的种类,进一步扩大了现阶段固相合成法的应用领域,扩大了现有离子液体的应用范畴,实现了氨基酸(蛋白质)与无机物的固/固、固/液反应,为新型氨基酸(蛋白质)金属盐的合成提供了新合成工艺和新方法。
与现有技术相比,本发明的有益效果:
1.本发明所述制备方法在室温条件下进行固相合成,适用范围广、离子液体可回收再利用、成本低、工艺简单;
2.本发明所述方法,原材料来源广泛,廉价易得,成本低,制得的产品收率高(90.0-99.0%),纯度高(99.0-99.9%),易达到国家要求,不需再次进行提纯;
3.制得的产品可直接应用于饲料添加,并可根据饲用需要及时调整生产配方和饲用配方,制备过程中残留废水可回收利用、绿色无污染。
具体实施方式
一种氨基酸金属螯合物微纳米粉体的制备方法,具体实施步骤如下:
实施例1(以第二主族元素钙为例)
(1)在25℃下,将1.47g L-谷氨酸、1.47 g CaCl2.2H2O加入到研钵中,并加入0.294g 固体1,3-二甲基咪唑硫酸甲酯盐(MDLS)粉体作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨12 min,使反应得到充分混合与反应,并得到糊状物,静置2h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入30mL去离子水,搅拌溶解未完全反应L-谷氨酸和CaCl2.2H2O后,进行抽滤洗涤6次,以去除离子液体和未反应的L-谷氨酸和CaCl2.2H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在70oC烘箱中烘干3h,冷却至室温后取出并研细至200nm及以下,即获得产品L-谷氨酸钙(1.55g,含量99.1%)。
该产品可用作食品添加剂及人体消化系统药物。
实施例2(以第三主族元素铝为例)
(1)在25℃下,将2.25g L-甘氨酸、2.415g AlCl3.6H2O加入到研钵中,并加入0.373g液体1-乙基-3-甲基咪唑硫酸甲酯盐作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨10 min,使反应得到充分混合与反应,并得到糊状物,静置1.5h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入20mL去离子水,搅拌溶解未完全反应L-甘氨酸和AlCl3.6H2O后,进行抽滤洗涤5次,以去除离子液体和未反应的L-甘氨酸和AlCl3.6H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在80oC烘箱中烘干2h,冷却至室温后取出并研细至200nm及以下,即获得产品L-甘氨酸铝(2.46g,含量99.1%)。
该产品可应用于洗涤剂、电镀液、医药工业等。
实施例3(以稀土金属元素镧为例)
(1)在25℃下,将6.12g L-色氨酸、4.15g La(NO3)3.5H2O加入到研钵中,并加入1.03 g三丁基甲基氯化铵作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨10 min,使反应得到充分混合与反应,并得到糊状物,静置1.5h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入25 mL去离子水,搅拌溶解未完全反应L-色氨酸和La(NO3)3.5H2O后,进行抽滤洗涤6次,以去除离子液体和未反应的L-色氨酸和La(NO3)3.5H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在80oC烘箱中烘干3h,冷却至室温后取出并研细至200nm及以下,即获得产品色氨酸镧(3.32g,含量99.0%)。
该产品可应用于高分子材料的热稳定剂。
实施例4(以过渡金属元素铜为例)
(1)在25℃下,将2.30g L-脯氨酸、2.42 g Cu(NO3)2.3H2O加入到研钵中,并加入0.472 g 固体1,3-二甲基咪唑硫酸甲酯盐(MDLS)粉体作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨15 min,使反应得到充分混合与反应,并得到糊状物,静置1.5h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入30mL去离子水,搅拌溶解未完全反应L-脯氨酸和Cu(NO3)2.3H2O后,进行抽滤洗涤7次,以去除离子液体和未反应的L-脯氨酸和Cu(NO3)2.3H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在75oC烘箱中烘干2.5h,冷却至室温后取出并研细,即获得产品L-脯氨酸铜(2.90g,含量99.3%)。
该产品可用作植物微肥。
实施例5(以阴离子表面活性剂苯磺酸钠与金属元素锌为例)
(1)在25℃下,将2.30 g能溶入水的L-脯氨酸、2.44 g ZnCl2.6H2O加入到研钵中,并加入0.474 g 阴离子表面活性剂苯磺酸钠粉体作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨12 min,使反应得到充分混合与反应,并得到糊状物,静置2.5h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入35mL去离子水,搅拌溶解未完全反应L-脯氨酸和ZnCl2.6H2O后,进行抽滤洗涤5次,以去除苯磺酸钠和未反应的L-脯氨酸和ZnCl2.6H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在90oC烘箱中烘干3h,冷却至室温后取出并研细,即获得产品 L-脯氨酸锌(2.82g,含量99.4%)。
该产品可用作催化剂。
实施例6(以阳离子表面活性剂与过渡金属元素锰为例)
(1)在25℃下,将3.48g L-精氨酸、2.16 g MnCl2.5H2O加入到研钵中,并加入0.564 g 阳离子表面活性剂十六烷基三甲基氯化铵粉体作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨10 min,使反应得到充分混合与反应,并得到糊状物,静置1.5h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入30mL去离子水,搅拌溶解未完全反应L-精氨酸和MnCl2.5H2O后,进行抽滤洗涤5次,以去除离子液体和未反应的L-精氨酸和MnCl2.5H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在90oC烘箱中烘干3h,冷却至室温后取出并研细,即获得产品L-精氨酸锰(3.86g,含量99.0%)。
该产品可用作动物饲料。
实施例7(以两种金属元素:铁、钴为例)
(1)在25℃下,将7.31 g L-赖氨酸、2.70 g FeCl3.6H2O、2.38 g CoCl2.6H2O加入到研钵中,并加入0.472 g 液体1-乙基吡啶盐酸盐作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨15 min,使反应得到充分混合与反应,并得到糊状物,静置2h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入30mL去离子水,搅拌溶解未完全反应L-赖氨酸和 FeCl3.6H2O、CoCl2.6H2O后,进行抽滤洗涤6次,以去除离子液体1-乙基吡啶盐酸盐和未反应的L-赖氨酸、FeCl3.6H2O、CoCl2.6H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在85oC烘箱中烘干3h,冷却至室温后取出并研细,即获得产品L-赖氨酸铁钴(8.29g,其中L-赖氨酸铁含量占58.1 %,L-赖氨酸钴占41.9%)。
该产品可用作微量元素饲料添加剂。
实施例8 (酪氨酸、苏氨酸)
(1)在20℃下,将 1.81 g L-酪氨酸、1.19g L-苏氨酸、2.36gCa(NO3)2.4H2O加入到研钵中,并加入 0.536 g 液体N-甲基丁基吡咯烷甲磺酸盐作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨10 min,使反应得到充分混合与反应,并得到糊状物,静置2h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入30mL去离子水,搅拌溶解未完全反应L-酪氨酸、L-苏氨酸和Ca(NO3)2.4H2O 后,进行抽滤洗涤6次,以去除离子液体N-甲基丁基吡咯烷甲磺酸盐和未反应的L-酪氨酸、L-苏氨酸和Ca(NO3)2.4H2O并获得滤饼;
(4)将步骤(3)获得的固体滤饼在80oC烘箱中烘干3h,冷却至室温后取出并研细,即获得产品 L-酪氨酸钙和L-苏氨酸钙的混合物3.28g,其中L-酪氨酸钙含量占59.45%,L-苏氨酸钙占40.55%)。
该产品可用作食品强化剂、饲料添加剂、医药和化工行业。
发明所述的氨基酸金属盐纳米粉体材料的熔点在130~2500C之间,复合氨基酸金属螯合物的溶解性随金属离子的荷径比的减少而增大,随金属离子的荷质比的增大而增大。氨基酸配位比太小则金属的螯合程度不高,难以形成稳定的氨基酸金属螯合物,需要蒸发结晶;氨基酸配位比太大则金属的螯合物稳定性过高,微量元素难以被动物体吸收利用,同时也会造成氨基酸的浪费,生产成本增大。氨基酸配位比通常为2~4较适宜,以保证产品质量,充分发挥金属离子的作用与氨基酸的利用。
以上所述,仅为本发明较佳的具体实施方式,本发明的保护范围不限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可显而易见地得到的技术方案的简单变化或等效替换均落入本发明的保护范围内。
Claims (4)
1.一种氨基酸金属螯合物微纳米粉体的制备方法,其特征在于包括如下步骤:
(1)在0~38℃的室温下,按反应物的正负电荷摩尔比氨基酸:Me n+ =n:1将固体氨基酸和带结晶水的金属卤盐或硝酸盐加入到研钵中,并加入混合物总质量5~10%的离子液体作为催化剂,混合均匀;
(2)将步骤(1)中混合物在研钵中研磨10~20 min,使反应得到充分混合与反应,并得到糊状物,静置1~2h使反应物尽量完全反应;
(3)向步骤(2)制备的糊状物中加入糊状物体积200~300%的去离子水,搅拌溶解未完全反应的氨基酸和金属卤盐后,进行抽滤洗涤6-8次,以去除离子液体、未反应的氨基酸和金属卤盐并获得滤饼;其中用硝酸银溶液定性检测滤液中是否残留非金属卤离子,若有卤离子残留则继续抽滤洗涤,直至卤离子全部除去;或通过6次以上的去离子水洗涤,以移除硝酸根离子;
或向步骤(2)制备的糊状物中加入糊状物体积200~300%的去离子水进行搅拌溶解后静置6~10天使其蒸发结晶,并将晶体水洗2~3次,得固体晶体;
(4)将步骤(3)获得的固体滤饼或晶体在60-90 ℃烘箱中烘干2-3h,冷却至室温后取出并研细,即获得一种氨基酸金属螯合物微纳米粉体。
2.根据权利要求1所述一种氨基酸金属螯合物微纳米粉体的制备方法,其特征在于:所述步骤(1)中离子液体为固体离子液体或液体离子液体。
3.根据权利要求2所述一种氨基酸金属螯合物微纳米粉体的制备方法,其特征在于:所述固体离子液体为1,3-二甲基咪唑硫酸甲酯盐、1-乙基3-甲基咪唑硫酸甲酯盐、1-丁基-3-甲基咪唑鎓六氟磷酸盐、1-丁基-3-甲基咪唑四氟硼酸盐;所述液体离子液体为咪唑型离子液体、吡啶型离子液体、吡咯烷型离子液体、季铵型离子液体、吗啉型离子液体;
其中咪唑型离子液体具体为溴化1-丙基-3-甲基咪唑、碘化1-丙基-3-甲基咪唑、1-乙基-3-甲基咪唑硫酸甲酯盐、1-乙基-3-甲基咪唑硝酸盐、1-乙基-3-甲基咪唑乙酸盐、1-乙基-3-甲基咪唑甲磺酸盐;吡啶型离子液体具体为:1-乙基吡啶盐酸盐、1-乙基吡啶盐酸盐四氟硼酸、1-乙基吡啶六氟磷酸盐、1-乙基吡啶三氟甲磺酸盐;吡咯烷型离子液体具体为N-甲基,乙基吡咯烷双三氟甲磺酰亚胺、氯化N-甲基丁基吡咯烷、N-甲基丁基吡咯烷甲磺酸盐、N-甲基丁基吡咯烷对甲苯磺酸盐;季铵型离子液体具体为三丁基甲基氯化铵、三丁基甲基铵双(三氟甲烷磺酰)亚胺盐;吗啉型离子液体具体为氯化N-甲基乙基吗啉、氯化N-甲基丙基吗啉和氯化N-甲基丁基吗啉、N-甲基-N-丁基吗啉氟硼酸盐。
4.根据权利要求3所述一种氨基酸金属螯合物微纳米粉体的制备方法,其特征在于:当步骤(1)中固体氨基酸溶解度>400 g/L时,离子液体可替换成阴、阳表面活性剂作催化剂;
其中阴离子表面活性剂为苯磺酸钠、对甲基苯磺酸钠、二甲基苯磺酸钠、4-乙基苯磺酸钠、异丙基苯磺酸钠、十二烷基苯磺酸钠、十六烷基苯磺酸钠,阳离子表面活性剂为C 6 ~C18 烷基三甲基卤化铵,其中卤原子X=F、Cl、Br、I。
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