CN117534580A - 一种分离提纯甜菜碱的方法 - Google Patents
一种分离提纯甜菜碱的方法 Download PDFInfo
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229960003237 betaine Drugs 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 25
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 24
- 230000008025 crystallization Effects 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 230000006837 decompression Effects 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 40
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 15
- 229940106681 chloroacetic acid Drugs 0.000 claims description 15
- IZHVBANLECCAGF-UHFFFAOYSA-N 2-hydroxy-3-(octadecanoyloxy)propyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCCCCCCCCCCC IZHVBANLECCAGF-UHFFFAOYSA-N 0.000 claims description 14
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 13
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229940074045 glyceryl distearate Drugs 0.000 claims description 7
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 6
- 239000013078 crystal Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000019742 Vitamins premix Nutrition 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 230000008642 heat stress Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000020997 lean meat Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于甜菜碱的纯化技术领域,具体涉及一种分离提纯甜菜碱的方法,包括如下步骤:S1.化学合成甜菜碱母液;S2.一次减压浓缩;S3.一次结晶/过滤:向S2浓缩液中加入不良溶剂,搅拌后过滤分别收集滤饼、滤液;S4.二次减压浓缩:将S3中滤液进行减压浓缩;当溶液固含量为30wt%时,加入抑制剂继续浓缩,当出现盐结晶时,停止加热;S5.二次结晶/热滤:对S4得到的浓缩液,搅拌结晶2~8h,然后趁热过滤除去氯化钠,将滤液冷却稀释,离心去除抑制剂,收集离心液;S6.成品烘干:将S5中离心液溶剂蒸干并收集甜菜碱成品,本发明的方法操作简单、低成本分离甜菜碱中氯化钠,提纯后甜菜碱的纯度和收率高。
Description
技术领域
本发明属于甜菜碱的纯化技术领域,具体涉及一种分离提纯甜菜碱的方法。
背景技术
甜菜碱(betaine,Bet)又名甘氨酸甜菜碱、甜菜素,化学名称是三甲基甘氨酸,19世纪最早发现于欧洲,是一种季铵型水溶性生物碱,广泛存在于动植物和微生物体内。自20世纪70年代以来,Bet的研究渐成热点,已被广泛应用于畜牧、医药、农林、食品和日化等领域。甜菜碱早期是从天然植物的根、茎、叶及果实中提取,随着生产工艺的发展目前可采用三甲胺和氯乙酸为原料进行化学合成。该产品广泛应用于医药、日用化工、食品添加剂及饲料添加剂中,是一种重要的基础原料。三甲基甘氨酸在动物体内作为一种高效活性甲基供体,在甲基代谢中起重要的营养调控作用,可取代部分蛋氨酸和胆碱,具有促进脂肪代谢、改善饲料的适口性,缓和热应激,调节机体的渗透压,提高腹泻药的疗效,并可维护维生素预混料的稳定性,显著提高畜禽生长性能,降低胴体脂肪、增加瘦肉率和改善胴体品质等功能。
随着市场对三甲基甘氨酸需求量的增加,依靠从甜菜糖蜜中提取三甲基甘氨酸已不能满足需要,人们又成功研究了化学合成三甲基甘氨酸的方法。以氯乙酸钠和三甲胺为原料,在水溶液中常压反应,很容易合成三甲基甘氨酸,但同时也会生成氯化钠,掺杂于主产物中,也会有少量重金属物质混于产物中。这些杂质都大大的破坏了主产物甜菜碱的品质。
因此,化学合成法制备甜菜碱的难点在于除盐,目前常用的除盐方法有蒸馏、膜分离、通过离子交换树脂等。CN201110172737公开了一种甜菜碱的制备方法,将氯乙酸与三甲胺反应过后的母液通过阴离子交换树脂,然后浓缩结晶,该法的缺点在于产生大量废水,且原料消耗大,效率低。CN201910158151公开了一种氨法甜菜碱的制备方法,由氯乙酸铵和三甲胺进行季铵化反应,通过蒸发浓缩、电渗析、再蒸发浓缩、离心干燥得到甜菜碱产品,该法的缺点在于成本高、分离提纯操作复杂。
发明内容
为了解决现有技术中的问题,本发明提供一种分离提纯甜菜碱的方法,以实现简单低成本分离甜菜碱中氯化钠,提高甜菜碱的纯度的目的。
本发明解决其技术问题是采用以下技术方案实现的:
本发明目的在于提供一种分离提纯甜菜碱的方法,包括如下步骤:
S1.化学合成甜菜碱母液;
S2.一次减压浓缩;
S3.一次结晶/过滤:向S2浓缩液中加入不良溶剂,搅拌后过滤分别收集滤饼、滤液;
S4.二次减压浓缩:将S3中滤液进行减压浓缩;当溶液固含量为30wt%时,加入抑制剂继续浓缩,当出现盐结晶时,停止加热;
S5.二次结晶/热滤:对S4得到的浓缩液,搅拌结晶2~8h,然后趁热过滤除去氯化钠,将滤液冷却稀释,离心去除抑制剂,收集离心液;
S6.成品烘干:将S5中离心液溶剂蒸干并收集甜菜碱成品。
进一步的,S1中化学合成甜菜碱母液的方法如下:
A1:中和:以氢氧化钠中和氯乙酸,控制温度在30℃以下,调节pH为7.8±0.3。
A2:胺化:向A1中和液中滴加三甲胺溶液,氯乙酸与三甲胺按摩尔比1:1.5称取,滴加完毕后于40~60℃反应2~4小时,反应后得到甜菜碱母液。
进一步的,S2一次减压浓缩温度为40~60℃、压力为0.6MPa,浓缩终点为溶液固含量为25wt%,先脱除部分水、三甲胺及其他挥发性有机杂质。
进一步的,S3一次结晶添加的不良溶剂为无水乙醇,添加量为一次浓缩液体积的15~20倍,搅拌1h后过滤。
进一步的,S4二次减压浓缩温度为60~80℃、压力为0.6MPa。
进一步的,S4中的抑制剂为单、双硬脂酸甘油酯,其添加量为浓缩液质量的100ppm。
进一步的,单、双硬脂酸甘油酯中,双硬脂酸甘油酯质量百分比含量为40~70%。
进一步的,S5中搅拌结晶温度为105℃。
与现有技术相比,本发明的有益技术效果在于:
1、本发明分离提纯方法合成成本低、分离提纯步骤简洁、操作简便,加入的抑制剂辅助甜菜碱结晶,可生产得到高纯度高收率的甜菜碱产品,且改善了产品晶体颗粒均匀度及产品粉末流动性。
2、本发明主要利用单、双硬脂酸甘油酯为甜菜碱提供氢键供体,单、双硬脂酸甘油酯的氢键供体与甜菜碱的氢键受体联结从而形成弱氢键作用,增大甜菜碱在溶剂中的溶解度,以达到在减压浓缩步骤中甜菜碱不跟随氯化钠晶体析出的目的,从而分离提纯甜菜碱,提高甜菜碱的纯度和收率,纯度可以达到98.5%以上,收率可以达到98%以上。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述内容和其目的、特征和优点能够更明显易懂,以下特举本发明的具体实施方式。
附图说明
图1为本发明中实施例1所制备甜菜碱的HPLC检测图谱。
具体实施方式
以下结合附图和具体实施例对本发明技术方案作进一步详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
另外,除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备均可通过市场购买获得或现有方法制备得到。
实施例1:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和,控制温度不高于30℃,调节pH为7.8±0.3;滴加三甲胺溶液,氯乙酸与三甲胺摩尔比为1:1.5,滴加完毕后升温至40℃反应4h得到甜菜碱母液;母液移至浓缩釜,启动浓缩釜的加热器、真空泵,开始减压浓缩,温度由室温升至60℃,压力为0.6MPa,浓缩至溶液固含量为25wt%时停止浓缩;将一次浓缩液转移至结晶釜,加入15倍浓缩液体积的无水乙醇,搅拌1h后过滤,分别收集滤饼、滤液;将滤液转移至浓缩釜减压60℃浓缩蒸发,压力为0.6MPa,当溶液固含量为30wt%时,加入浓缩液质量100ppm的单、双硬脂酸甘油酯,继续搅拌浓缩至出现盐结晶,停止加热,关闭真空泵;将二次浓缩液移至结晶釜内,启动结晶釜加热器及搅拌器,于105℃搅拌结晶8h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到高纯度甜菜碱晶体,纯度99%,收率98%。
实施例2:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和。控制温度不高于30℃,调节pH为7.8±0.3。滴加三甲胺溶液,氯乙酸与三甲胺摩尔比为1:1.5,滴加完毕后升温至50℃反应3h得到甜菜碱母液。母液移至浓缩釜,启动浓缩釜的加热器、真空泵,开始减压浓缩,温度由室温升至40℃,压力为0.6MPa,浓缩至溶液固含量为25wt%时停止浓缩,将一次浓缩液转移至结晶釜,加入18倍浓缩液体积的无水乙醇,搅拌1h后过滤,分别收集滤饼、滤液,将滤液转移至浓缩釜减压80℃浓缩蒸发,压力为0.6MPa,当溶液固含量为30wt%时,加入浓缩液质量100ppm的单、双硬脂酸甘油酯,继续搅拌浓缩至出现盐结晶,停止加热,关闭真空泵,将二次浓缩液移至结晶釜内,启动结晶釜加热器及搅拌器,于105℃搅拌结晶5h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到高纯度甜菜碱晶体,纯度99.3%,收率98.1%。
实施例3:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和。控制温度不高于30℃,调节pH为7.8±0.3。滴加三甲胺溶液,氯乙酸与三甲胺摩尔比为1:1.5,滴加完毕后升温至60℃反应2h得到甜菜碱母液。母液移至浓缩釜,启动浓缩釜的加热器、真空泵,开始减压浓缩,温度由室温升至50℃,压力为0.6MPa,浓缩至溶液固含量为25wt%时停止浓缩,将一次浓缩液转移至结晶釜,加入20倍浓缩液体积的无水乙醇,搅拌1h后过滤,分别收集滤饼、滤液,将滤液转移至浓缩釜减压70℃浓缩蒸发,压力为0.6MPa,当溶液固含量为30wt%时,加入浓缩液质量100ppm的单、双硬脂酸甘油酯,继续搅拌浓缩至出现盐结晶,停止加热,关闭真空泵,将二次浓缩液移至结晶釜内,启动结晶釜加热器及搅拌器,于105℃搅拌结晶2h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到高纯度甜菜碱晶体,纯度98.8%,收率98%。
对比例1:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和。滴加三甲胺溶液,滴加完毕后升温至40℃反应4h得到甜菜碱母液。母液移至浓缩釜开始减压浓缩,温度由室温升至60℃,浓缩至溶液固含量为25wt%时停止浓缩,加入15倍体积无水乙醇,搅拌1h后过滤,将滤液转移至浓缩釜减压60℃浓缩蒸发,当溶液固含量为30wt%时,不加入任何抑制剂,继续搅拌浓缩至出现盐结晶,移至结晶釜内于105℃搅拌结晶8h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到甜菜碱晶体,纯度95.8%,收率95.7%。
对比例2:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和。滴加三甲胺溶液,滴加完毕后升温至40℃反应4h得到甜菜碱母液。母液移至浓缩釜开始减压浓缩,温度由室温升至60℃,浓缩至溶液固含量为25wt%时停止浓缩,加入15倍体积无水乙醇,搅拌1h后过滤,将滤液转移至浓缩釜减压60℃浓缩蒸发,当溶液固含量为30wt%时,加入浓缩液质量100ppm的氯化钠固体晶体,继续搅拌浓缩至出现盐结晶,移至结晶釜内于105℃搅拌结晶8h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到甜菜碱晶体,纯度96.8%,收率96.5%。
对比例3:在反应器中加入氯乙酸,加入去离子水搅拌溶解,水浴控温条件下加入氢氧化钠中和。滴加三甲胺溶液,滴加完毕后升温至40℃反应4h得到甜菜碱母液。母液移至浓缩釜开始减压浓缩,温度由室温升至60℃,浓缩至溶液固含量为25wt%时停止浓缩,加入15倍体积无水乙醇,搅拌1h后过滤,将滤液转移至浓缩釜减压60℃浓缩蒸发,当溶液固含量为30wt%时,加入浓缩液质量100ppm的聚乙烯醇,继续搅拌浓缩至出现盐结晶,移至结晶釜内于105℃搅拌结晶8h,趁热过滤氯化钠晶体,然后将滤液冷却至室温后加水稀释,待抑制剂完全析出后,离心去除抑制剂,收集离心液。离心液蒸发结晶,收集结晶固体在70~80℃下烘干干燥。得到甜菜碱晶体,纯度96.4%,收率95.9%。
表1、各实施例与对比例甜菜碱纯度及收率对比
上述本发明实施例序号仅仅为了描述,不代表实施例的优劣。
上面结合附图对本发明的实施例进行了描述,但是本发明并不局限于上述的具体实施方式,上述的具体实施方式仅仅是示意性的,而不是限制性的,本领域的普通技术人员在本发明的启示下,在不脱离本发明宗旨和权利要求所保护的范围情况下,还可做出很多形式,这些均属于本发明的保护之内。
Claims (8)
1.一种分离提纯甜菜碱的方法,其特征在于,包括如下步骤:
S1.化学合成甜菜碱母液;
S2.一次减压浓缩;
S3.一次结晶/过滤:向S2浓缩液中加入不良溶剂,搅拌后过滤分别收集滤饼、滤液;
S4.二次减压浓缩:将S3中滤液进行减压浓缩;当溶液固含量为30wt%时,加入抑制剂继续浓缩,当出现盐结晶时,停止加热;
S5.二次结晶/热滤:对S4得到的浓缩液,搅拌结晶2~8h,然后趁热过滤除去氯化钠,将滤液冷却稀释,离心去除抑制剂,收集离心液;
S6.成品烘干:将S5中离心液溶剂蒸干并收集甜菜碱成品。
2.如权利要求1所述一种分离提纯甜菜碱的方法,其特征在于:S1中化学合成甜菜碱母液的方法如下:
A1:中和:以氢氧化钠中和氯乙酸,控制温度在30℃以下,调节pH为7.8±0.3。
A2:胺化:向A1中和液中滴加三甲胺溶液,氯乙酸与三甲胺按摩尔比1:1.5称取,滴加完毕后于40~60℃反应2~4小时,反应后得到甜菜碱母液。
3.如权利要求1所述一种分离提纯甜菜碱的方法,其特征在于:S2一次减压浓缩温度为40~60℃、压力为0.6MPa,浓缩终点为溶液固含量为25wt%。
4.如权利要求1所述一种分离提纯甜菜碱的方法,其特征在于:S3一次结晶添加的不良溶剂为无水乙醇,添加量为一次浓缩液体积的15~20倍,搅拌1h后过滤。
5.如权利要求1所述一种分离提纯甜菜碱的方法,其特征在于:S4二次减压浓缩温度为60~80℃、压力为0.6MPa。
6.如权利要求1或5所述一种分离提纯甜菜碱的方法,其特征在于:S4中的抑制剂为单、双硬脂酸甘油酯,其添加量为浓缩液质量的100ppm。
7.如权利要求6所述一种分离提纯甜菜碱的方法,其特征在于:单、双硬脂酸甘油酯中,双硬脂酸甘油酯质量百分比含量为40~70%。
8.如权利要求1所述一种分离提纯甜菜碱的方法,其特征在于:S5中搅拌结晶温度为105℃。
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