CN103804210B - A kind of purification method of betaine hydrochloride - Google Patents
A kind of purification method of betaine hydrochloride Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000746 purification Methods 0.000 title claims abstract description 17
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 title abstract description 66
- 229960003403 betaine hydrochloride Drugs 0.000 title abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OLBJZJZARFENTH-UHFFFAOYSA-L calcium;2-chloroacetate Chemical compound [Ca+2].[O-]C(=O)CCl.[O-]C(=O)CCl OLBJZJZARFENTH-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 claims 10
- 241000335053 Beta vulgaris Species 0.000 claims 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010992 reflux Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 4
- 229940106681 chloroacetic acid Drugs 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- -1 betaine hydrochlorides Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010013911 Dysgeusia Diseases 0.000 description 1
- 229930194936 Tylosin Natural products 0.000 description 1
- 239000004182 Tylosin Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000020939 nutritional additive Nutrition 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 description 1
- 229960004059 tylosin Drugs 0.000 description 1
- 235000019375 tylosin Nutrition 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种甜菜碱盐酸盐的纯化方法，具体涉及一种钙法制得的甜菜碱盐酸盐粗品的纯化方法，属于精细化工技术领域。 The present invention relates to a method for purifying betaine hydrochloride, in particular to a method for purifying crude betaine hydrochloride prepared by the calcium method, and belongs to the technical field of fine chemicals.
背景技术 Background technique
甜菜碱盐酸盐，化学名称：三甲基甘氨酸内酯盐酸盐，三甲胺乙内酯盐酸盐，英文名称：（Carboxymethyl) trimethylammonium hydrochloride，白色至微黄色结晶性粉末，熔点241-242℃，味呈酸涩，具吸潮性，溶于水、乙醇，难溶于乙醚、三氯甲烷，遇碱反应。 Betaine hydrochloride, chemical name: Trimethylglycinolactone hydrochloride, trimethylbetaine hydrochloride, English name: (Carboxymethyl) trimethylammonium hydrochloride, white to light yellow crystalline powder, melting point 241-242°C , taste sour, hygroscopic, soluble in water, ethanol, insoluble in ether, chloroform, reaction with alkali.
甜菜碱盐酸盐主要用作饲料添加剂，是一种广泛应用于畜、禽、水产养殖的诱食促长的营养型添加剂。除此以外，甜菜碱盐酸盐还可用于制备兽药“泰洛菌素”。 Betaine hydrochloride is mainly used as a feed additive. It is a nutritional additive widely used in livestock, poultry and aquaculture to induce food and promote growth. In addition, betaine hydrochloride can also be used to prepare veterinary drug "tylosin".
目前，甜菜碱盐酸盐的制备方法主要有钙法和钠法两类，钙法的基本策略为：首先，氢氧化钙或氧化钙中和氯乙酸制得氯乙酸钙；然后，加入三甲胺发生季胺化反应；接着，进行硫酸酸化生成甜菜碱盐酸盐和硫酸钙；最后，过滤除去硫酸钙，将滤液浓缩、结晶、过滤干燥得甜菜碱盐酸盐。其合成路线如下： At present, the preparation methods of betaine hydrochloride mainly include the calcium method and the sodium method. The basic strategy of the calcium method is: first, calcium hydroxide or calcium oxide neutralizes chloroacetic acid to obtain calcium chloroacetate; then, adding trimethylamine A quaternization reaction occurs; then, sulfuric acid acidification is carried out to generate betaine hydrochloride and calcium sulfate; finally, calcium sulfate is removed by filtration, the filtrate is concentrated, crystallized, filtered and dried to obtain betaine hydrochloride. Its synthetic route is as follows:
专利CN1166625C、专利CN102807499A、CN101863785A和专利CN1374293A都是钙法工艺的具体体现，虽然制备过程略有不同，但最后都需硫酸酸化得到甜菜碱盐酸盐和硫酸钙。由于副产物硫酸钙属微溶物质（30℃，0.2090g/100g水），故而大部分硫酸钙可以直接过滤除去，基本上不产生三废，甜菜碱盐酸盐可以直接从反应液中结晶析出。但是，该方法仍有少量硫酸钙可以溶解于甜菜碱盐酸盐的过饱和水溶液中，无法完全去除，导致产品的灼残含量高达2—3％，超过国家标准（NY399-2009，甜菜碱盐酸盐的灼残含量为0.2％）十倍多，严重影响了钙法工艺生产的甜菜碱盐酸盐的品质，大大限制了钙法工艺的推广使用，故而目前工厂都采用原料成本更加高昂、三废排量大的钠法工艺。 Patent CN1166625C, patent CN102807499A, CN101863785A and patent CN1374293A are all concrete manifestations of the calcium process. Although the preparation process is slightly different, they all need sulfuric acid acidification to obtain betaine hydrochloride and calcium sulfate. Since the by-product calcium sulfate is a slightly soluble substance (30°C, 0.2090g/100g water), most of the calcium sulfate can be directly filtered out, basically no three wastes are produced, and betaine hydrochloride can be crystallized directly from the reaction solution. However, this method still has a small amount of calcium sulfate that can be dissolved in the supersaturated aqueous solution of betaine hydrochloride and cannot be completely removed, resulting in a product with a burnt residual content of up to 2-3%, exceeding the national standard (NY399-2009, betaine salt The burnt residual content of betaine hydrochloride is 0.2%) more than ten times, which has seriously affected the quality of betaine hydrochloride produced by the calcium process and greatly limited the popularization and use of the calcium process. Sodium process with large discharge of three wastes.
因此，开发一种合适的精制纯化工艺，高效脱除钙法生产的甜菜碱盐酸盐中掺杂的硫酸钙，对钙法工艺的规模化放大生产具有重要意义，同时也具有显著的经济和社会效益，但目前国内外缺乏相关方向的研究和报道。 Therefore, the development of a suitable refining and purification process to efficiently remove the calcium sulfate doped in the betaine hydrochloride produced by the calcium method is of great significance to the large-scale production of the calcium process, and it also has significant economic and economic benefits. Social benefits, but at present there is a lack of research and reports in the relevant direction at home and abroad.
发明内容 Contents of the invention
针对现有技术中钙法制得的甜菜碱盐酸盐灼残含量高的不足，本发明提供了一种甜菜碱盐酸盐的纯化方法，该方法能提高甜菜碱盐酸盐的纯度，降低无机盐含量，使甜菜碱盐酸盐的灼残降至0.2%以下，符合相关要求。 Aiming at the deficiency of high burning residue content of betaine hydrochloride prepared by calcium method in the prior art, the invention provides a method for purifying betaine hydrochloride, which can improve the purity of betaine hydrochloride and reduce inorganic Salt content, so that the residue on ignition of betaine hydrochloride is reduced to less than 0.2%, which meets the relevant requirements.
发明人通过研究，发现甜菜碱盐酸盐和硫酸钙在水、酸、醇等不同溶剂中的溶解度规律存在一定的差异。通过这一规律，可以实现除去硫酸钙，达到提高甜菜碱盐酸盐纯度的目的。 Through research, the inventor has found that there are certain differences in the solubility rules of betaine hydrochloride and calcium sulfate in different solvents such as water, acid, and alcohol. Through this rule, the removal of calcium sulfate can be achieved, and the purpose of improving the purity of betaine hydrochloride can be achieved.
甜菜碱盐酸盐在常用醇溶剂、酸溶剂、水的溶解度情况见表1。 The solubility of betaine hydrochloride in common alcohol solvents, acid solvents and water is shown in Table 1.
从上表可以看出，室温下甜菜碱盐酸盐在水中的溶解度大于甜菜碱盐酸盐在醇溶剂、酸溶剂中的溶解度，而且甜菜碱盐酸盐的溶解度随温度升高而逐渐变大。 It can be seen from the above table that the solubility of betaine hydrochloride in water at room temperature is greater than that of betaine hydrochloride in alcohol solvents and acid solvents, and the solubility of betaine hydrochloride gradually increases with the increase of temperature .
《无机盐工业手册》显示硫酸钙在水中的溶解曲线呈倒U型，即在高温或低温时溶解度偏小，而40-50℃时溶解度最大；而且，硫酸钙在酸性溶剂中的溶解度明显大于在水中的溶解度；除此以外，硫酸钙不溶于乙醇和异丙醇。 "Inorganic Salt Industry Handbook" shows that the dissolution curve of calcium sulfate in water is inverted U-shaped, that is, the solubility is relatively small at high or low temperatures, and the solubility is the highest at 40-50°C; moreover, the solubility of calcium sulfate in acidic solvents is significantly greater than that of Solubility in water; otherwise, calcium sulfate is insoluble in ethanol and isopropanol.
依据上述甜菜碱盐酸盐和硫酸钙的溶解度差异，同时结合甜菜碱盐酸盐和硫酸钙的溶解度随温度变化的趋势，发明人研制出了甜菜碱盐酸盐独特的阶梯精制纯化工艺，通过调整温度和溶剂实现对甜菜碱盐酸盐的纯化。具体技术方案如下： Based on the above-mentioned solubility difference of betaine hydrochloride and calcium sulfate, combined with the trend of the solubility of betaine hydrochloride and calcium sulfate with temperature, the inventor has developed a unique stepwise refining and purification process for betaine hydrochloride, through Adjust the temperature and solvent to realize the purification of betaine hydrochloride. The specific technical scheme is as follows:
一种甜菜碱盐酸盐的纯化方法，其特征是包括以下步骤：取钙法制得的甜菜碱盐酸盐粗品，加入水中使其完全溶解；然后再加入醇，升温至回流，有固体析出；热过滤除去固体，向滤液中加入酸，然后降至室温，有固体析出，过滤、干燥，所得固体即为甜菜碱盐酸盐纯品。 A method for purifying betaine hydrochloride, which is characterized in that it comprises the following steps: taking the crude product of betaine hydrochloride obtained by the calcium method, adding it into water to completely dissolve it; then adding alcohol, heating to reflux, and solids are precipitated; Remove the solid by hot filtration, add acid to the filtrate, then cool down to room temperature, a solid precipitates, filter and dry, the obtained solid is pure betaine hydrochloride.
上述方法中，所述钙法制得的甜菜碱盐酸盐粗品是按照将氯乙酸钙与三甲胺的反应液加入硫酸酸化、过滤除去硫酸钙、滤液降温结晶的方法得到的。 In the above method, the crude betaine hydrochloride obtained by the calcium method is obtained by adding sulfuric acid to the reaction solution of calcium chloroacetate and trimethylamine for acidification, filtering to remove calcium sulfate, and cooling the filtrate to crystallize.
上述方法中，水的用量一般为粗品质量的0.1～2倍，优选的，水的用量满足使甜菜碱盐酸盐粗品刚好全溶。 In the above method, the amount of water used is generally 0.1 to 2 times the mass of the crude product. Preferably, the amount of water used is sufficient to completely dissolve the crude betaine hydrochloride.
上述方法中，优选将甜菜碱盐酸盐粗品用50℃的水溶解。 In the above method, preferably, the crude product of betaine hydrochloride is dissolved in water at 50°C.
上述方法中，甜菜碱盐酸盐粗品：醇：酸的质量比为1:0.1～1:0.1～1，优选质量比为1:0.22:0.22。 In the above method, the mass ratio of crude betaine hydrochloride: alcohol: acid is 1:0.1-1:0.1-1, preferably 1:0.22:0.22.
上述方法中，所述醇为C1-C4水溶性醇，优选为乙醇或异丙醇；所述酸为无机酸或有机酸，优选为浓盐酸、浓硫酸、浓磷酸、乙酸或甲酸，更优选为浓盐酸或乙酸。 In the above method, the alcohol is C1-C4 water-soluble alcohol, preferably ethanol or isopropanol; the acid is an inorganic acid or an organic acid, preferably concentrated hydrochloric acid, concentrated sulfuric acid, concentrated phosphoric acid, acetic acid or formic acid, more preferably For concentrated hydrochloric acid or acetic acid.
上述方法中，所得甜菜碱盐酸盐纯品中，甜菜碱盐酸盐含量在99%以上，纯品灼烧残渣在0.2%以下。 In the above method, in the obtained pure product of betaine hydrochloride, the content of betaine hydrochloride is above 99%, and the residue on ignition of the pure product is below 0.2%.
本发明方法中，先向甜菜碱盐酸盐的水溶液中加入一定量的醇，可以明显减少硫酸钙高温时的溶解度，从而确保热过滤可以除去尽可能多的硫酸钙。 In the method of the present invention, a certain amount of alcohol is first added to the aqueous solution of betaine hydrochloride, which can obviously reduce the solubility of calcium sulfate at high temperature, thereby ensuring that the hot filtration can remove as much calcium sulfate as possible.
本发明方法中，依据甜菜碱盐酸盐在醇、酸体系中溶解度减少、硫酸钙在酸体系中溶解度增大的特性，降温前加入一定量的酸，可以有效减少常温下溶液对甜菜碱盐酸盐的溶解度，同时又能增加硫酸钙的溶解度，大大减少了析出的甜菜碱盐酸盐的硫酸钙质量，从而确保得到低灼残的高纯产品。 In the method of the present invention, according to the characteristics that the solubility of betaine hydrochloride decreases in alcohol and acid systems, and the solubility of calcium sulfate in acid systems increases, a certain amount of acid is added before cooling, which can effectively reduce the impact of the solution on betaine salts at normal temperatures. At the same time, it can increase the solubility of calcium sulfate, greatly reducing the quality of calcium sulfate in the precipitated betaine hydrochloride, thus ensuring a high-purity product with low ignition residue.
本发明将钙法得到的甜菜碱盐酸盐粗品加入水、醇、酸的混合溶液中，通过这三者的用量搭配和加入顺序，增加了硫酸钙的溶解度，同时减少了甜菜碱盐酸盐的溶解度，实现了甜菜碱盐酸盐的纯化。该方法操作步骤简单，无三废产生，符合环保要求，精制得到的甜菜碱盐酸盐纯度大于99％，灼残含量降至0.2％以下，符合国家质量标准，经济和社会效益显著。 In the present invention, the crude product of betaine hydrochloride obtained by the calcium method is added into the mixed solution of water, alcohol and acid, and the solubility of calcium sulfate is increased and the amount of betaine hydrochloride is reduced at the same time through the dosage matching and adding sequence of the three. Solubility, to achieve the purification of betaine hydrochloride. The method has simple operation steps, does not generate three wastes, and meets environmental protection requirements. The purity of the refined betaine hydrochloride is greater than 99%, and the burning residue content is reduced to less than 0.2%, which meets the national quality standard and has remarkable economic and social benefits.
具体实施方式 Detailed ways
下面通过具体实施例对本发明实质内容进行进一步的说明，但并不构成对本发明保护范围的限制。 The essence of the present invention will be further described below through specific examples, but this does not constitute a limitation to the protection scope of the present invention.
本发明甜菜碱盐酸盐粗品是以氢氧化钙、氯乙酸、三甲胺和硫酸为原料制成，或者以氯乙酸钙、三甲胺和硫酸为原料制成，制备方法可以从现有技术中直接获取。 Betaine hydrochloride crude product of the present invention is to be made with calcium hydroxide, chloroacetic acid, trimethylamine and sulfuric acid as raw material, or is made with calcium chloroacetate, trimethylamine and sulfuric acid as raw material, and preparation method can be directly from prior art Obtain.
下述实施例中所用粗品均按照下述方法制得：向氯乙酸的水溶液中分批加入氢氧化钙，控制反应温度低于30℃；然后，滴加30wt%的三甲胺水溶液，控制反应温度在30℃；滴加完毕，继续搅拌0.5小时；加料完毕，在60℃下继续搅拌0.5小时，真空减压，抽走多余的三甲胺；加入50wt%的硫酸；搅拌1小时后，过滤除去硫酸钙；滤液浓缩、结晶、过滤，干燥得甜菜碱盐酸盐粗品。氯乙酸：三甲胺：氢氧化钙：H2SO4的摩尔比为1:1.05:0.5:0.49。所得粗品中甜菜碱盐酸盐含量为96.8%，灼烧残渣为2.66%。 The crude products used in the following examples were prepared according to the following method: calcium hydroxide was added in batches to the aqueous solution of chloroacetic acid, and the reaction temperature was controlled to be lower than 30° C.; then, 30 wt % trimethylamine aqueous solution was added dropwise, and the reaction temperature was controlled At 30°C; after the dropwise addition, continue to stir for 0.5 hours; after the addition, continue to stir at 60°C for 0.5 hours, vacuum and reduce pressure, and remove excess trimethylamine; add 50wt% sulfuric acid; after stirring for 1 hour, filter to remove sulfuric acid Calcium; the filtrate is concentrated, crystallized, filtered, and dried to obtain crude betaine hydrochloride. The molar ratio of chloroacetic acid: trimethylamine: calcium hydroxide: H2SO4 is 1:1.05:0.5:0.49. The content of betaine hydrochloride in the obtained crude product is 96.8%, and the residue on ignition is 2.66%.
实施例1Example 1
取100g甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入22克乙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.5克滤饼，滤液中加入22克浓盐酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到68克甜菜碱盐酸盐，含量99.21％，灼残含量为0.12％。 Take 100g of betaine hydrochloride crude product (burning residue 2.66%), add it to 110 grams of 50 ℃ water, just completely dissolve; then, add 22 grams of ethanol, heat up to reflux, a small amount of white solid form is precipitated; after hot filtration, 0.5 g of filter cake was obtained, 22 g of concentrated hydrochloric acid was added to the filtrate, the system gradually dropped to room temperature, and a large amount of white solid was precipitated, filtered and dried to obtain 68 g of betaine hydrochloride with a content of 99.21% and a residual content of 0.12%.
实施例2Example 2
取100克甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入22克异丙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.5克滤饼，滤液中加入22克浓盐酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到70克甜菜碱盐酸盐，含量99.28％，灼残含量为0.11％。 Take 100 grams of betaine hydrochloride crude product (2.66% of the burning residue), add it to 110 grams of 50 ℃ water, just dissolve completely; After filtering, 0.5 g of filter cake was obtained, 22 g of concentrated hydrochloric acid was added to the filtrate, the system gradually dropped to room temperature, and a large amount of white solid was precipitated, filtered and dried to obtain 70 g of betaine hydrochloride with a content of 99.28% and a residual content of 0.11 %.
实施例3Example 3
取100克甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入22克乙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.5克滤饼，滤液中加入22克乙酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到83克甜菜碱盐酸盐，含量99.35％，灼残含量为0.09％。 Take 100 grams of crude betaine hydrochloride (burning residue 2.66%), add it to 110 grams of water at 50°C, and dissolve it completely; then, add 22 grams of ethanol, heat up to reflux, and a small amount of white solids are precipitated; after hot filtration , Obtain 0.5 gram filter cake, add 22 gram acetic acid in the filtrate, system is down to room temperature gradually, separate out a large amount of white solids, filter, dry, obtain 83 gram betaine hydrochlorides, content 99.35%, burning residue content is 0.09%.
实施例4Example 4
取100克甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入22克乙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.5克滤饼，滤液中加入22克浓硫酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到73克甜菜碱盐酸盐，含量99.22％，灼残含量为0.15％。 Take 100 grams of crude betaine hydrochloride (burning residue 2.66%), add it to 110 grams of water at 50°C, and dissolve it completely; then, add 22 grams of ethanol, heat up to reflux, and a small amount of white solids are precipitated; after hot filtration , to obtain 0.5 gram of filter cake, add 22 gram of concentrated sulfuric acid in the filtrate, system is down to room temperature gradually, separate out a large amount of white solids, filter, dry, obtain 73 gram of betaine hydrochlorides, content 99.22%, burning residue content is 0.15%.
实施例5Example 5
取100g甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入10克乙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.2克滤饼，滤液中加入10克浓盐酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到35克甜菜碱盐酸盐，含量99.25％，灼残含量为0.13％。 Take 100g of crude betaine hydrochloride (2.66% of the residue on ignition), add it to 110 grams of water at 50°C, and dissolve it completely; then, add 10 grams of ethanol, heat up to reflux, and a small amount of white solid forms are precipitated; after hot filtration, 0.2 g of filter cake was obtained, 10 g of concentrated hydrochloric acid was added to the filtrate, the system was gradually lowered to room temperature, a large amount of white solid was precipitated, filtered and dried to obtain 35 g of betaine hydrochloride with a content of 99.25% and a residual content of 0.13%.
实施例6Example 6
取100g甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入100克乙醇，升温至回流，有少量白色固体形式析出；热过滤后，得到0.7克滤饼，滤液中加入100克浓盐酸，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到47克甜菜碱盐酸盐，含量99.31％，灼残含量为0.11％。 Take 100g of crude betaine hydrochloride (2.66% of the residue on ignition), add it to 110 grams of water at 50°C, and just dissolve it completely; then, add 100 grams of ethanol, heat up to reflux, and a small amount of white solid forms are precipitated; after hot filtration, 0.7 g of filter cake was obtained, 100 g of concentrated hydrochloric acid was added to the filtrate, the system was gradually lowered to room temperature, and a large amount of white solid was precipitated, filtered and dried to obtain 47 g of betaine hydrochloride with a content of 99.31% and a residual content of 0.11%.
对比例1Comparative example 1
取100克甜菜碱盐酸盐粗品（灼烧残渣2.66％）， 加入到110克50℃水中，刚好完全溶解；然后，加入22克乙醇和22克浓盐酸，升温至回流，没有白色固体析出；然后，体系逐渐降至室温，析出大量白色固体，过滤、干燥，得到66克甜菜碱盐酸盐，含量98.63％，灼残含量为0.76％。 Take 100 grams of crude betaine hydrochloride (2.66% of the residue on ignition), add it to 110 grams of water at 50°C, and dissolve it completely; then, add 22 grams of ethanol and 22 grams of concentrated hydrochloric acid, heat up to reflux, and no white solid precipitates out; Then, the system was gradually lowered to room temperature, and a large amount of white solids were precipitated, which were filtered and dried to obtain 66 grams of betaine hydrochloride with a content of 98.63% and a residual content of 0.76%.
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