CN103804210B - Purification method for betaine hydrochloride - Google Patents
Purification method for betaine hydrochloride Download PDFInfo
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- CN103804210B CN103804210B CN201410059368.5A CN201410059368A CN103804210B CN 103804210 B CN103804210 B CN 103804210B CN 201410059368 A CN201410059368 A CN 201410059368A CN 103804210 B CN103804210 B CN 103804210B
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Abstract
The invention discloses a purification method for betaine hydrochloride. The purification method comprises the steps: preparing the crude betaine hydrochloride through adopting a calcium method, firstly adding alcohol into a water solution so as to remove a part of calcium sulfide, and then adding acid to separate out betaine hydrochloride, thus purifying the betaine hydrochloride. The method is simple in operation steps, has no generation of three wastes, thus meeting the environment-friendly requirement; and the purity of the refined betaine hydrochloride is greater than 99%, the burning residue content is reduced 0.2% below, thus meeting the national quality standard and being obvious in economic and social benefits.
Description
Technical field
The present invention relates to a kind of purification process of beet alkali hydrochlorate, be specifically related to the purification process of the beet alkali hydrochlorate crude product that a kind of calcium method makes, belong to fine chemical technology field.
Background technology
Beet alkali hydrochlorate, chemical name: Trimethyl glycine lactone hydrochlorate, trimethylaminyl ethlyl lactone hydrochloride, English name: (Carboxymethyl) trimethylammonium hydrochloride, white is to micro-yellow crystalline powder, fusing point 241-242 ℃, it is sour and astringent that taste is, tool moisture absorption, water-soluble, ethanol, be insoluble in ether, trichloromethane, meet alkali reaction.
Beet alkali hydrochlorate, as fodder additives, is mainly a kind of nutritional type additive that is widely used in the food attractant-growth promoting of poultry, fowl, aquaculture.In addition, beet alkali hydrochlorate also can be used for preparing veterinary drug " safe Lip river rhzomorph ".
At present, the preparation method of beet alkali hydrochlorate mainly contains calcium method and sodium method two classes, and the elementary tactics of calcium method is: first, calcium hydroxide or calcium oxide neutralization Mono Chloro Acetic Acid make calcium chloroacetate; Then, add Trimethylamine 99 generation quaternary ammonium reaction; Then, carry out sulfuric acid acidation and generate beet alkali hydrochlorate and calcium sulfate; Finally, remove by filter calcium sulfate, filtrate is concentrated, crystallization, filtration drying obtain beet alkali hydrochlorate.Its synthetic route is as follows:
Patent CN1166625C, patent CN102807499A, CN101863785A and patent CN1374293A are the particular embodimenies of calcium method technique, although preparation process is slightly different, finally all need sulfuric acid acidation to obtain beet alkali hydrochlorate and calcium sulfate.Because byproduct calcium sulfate belongs to slightly soluble material (30 ℃, 0.2090g/100g water), so most of calcium sulfate can direct filtration be removed, substantially do not produce the three wastes, beet alkali hydrochlorate is crystallization from reaction solution directly.But, the method still has a small amount of calcium sulfate can be dissolved in the supersaturated aqueous solution of beet alkali hydrochlorate, cannot remove completely, cause the bright residual content of product up to 2-3%, surpass national standard (NY399-2009, the bright residual content of beet alkali hydrochlorate is 0.2%) more than ten times, had a strong impact on the quality of the beet alkali hydrochlorate of calcium method explained hereafter, greatly limited promoting the use of of calcium method technique, so factory all adopts the sodium method technique that raw materials cost is higher, three wastes discharge capacity is large at present.
Therefore; develop a kind of suitable refining pure metallization processes; efficiently remove the calcium sulfate adulterating in the beet alkali hydrochlorate of calcium method production; mass-producing amplification to calcium method technique is produced significant; also there is significant economic and social benefit, but lack at present research and the report of related direction both at home and abroad simultaneously.
Summary of the invention
For the bright high deficiency of residual content of beet alkali hydrochlorate that in prior art, calcium method makes, the invention provides a kind of purification process of beet alkali hydrochlorate, the method can improve the purity of beet alkali hydrochlorate, reduce inorganic salt content, the bright residual of beet alkali hydrochlorate is down to below 0.2%, meets related request.
Contriver, by research, finds that beet alkali hydrochlorate and the solubleness rule of calcium sulfate in the different solvents such as water, acid, alcohol exist certain difference.By this rule, can realize and remove calcium sulfate, reach the object that improves beet alkali hydrochlorate purity.
Beet alkali hydrochlorate in the solubleness situation of conventional alcoholic solvent, sour solvent, water in Table 1.
As can be seen from the above table, under room temperature, the solubleness of beet alkali hydrochlorate in water is greater than the solubleness of beet alkali hydrochlorate in alcoholic solvent, sour solvent, and the solubility with temperature of beet alkali hydrochlorate raises and becomes gradually large.
< < inorganic chemicals industry handbook > > shows that the solubility curve of calcium sulfate in water is inverted U, when high temperature or low temperature, solubleness is less than normal, and solubleness is maximum 40-50 ℃ time; And the solubleness of calcium sulfate in acid solvent is obviously greater than the solubleness in water; In addition, calcium sulfate is insoluble to ethanol and Virahol.
Dissolubility difference according to above-mentioned beet alkali hydrochlorate and calcium sulfate, while is in conjunction with the trend of the solubility with temperature variation of beet alkali hydrochlorate and calcium sulfate, contriver has developed the ladder refining pure metallization processes of beet alkali hydrochlorate uniqueness, by adjusting temperature and solvent, realizes the purifying to beet alkali hydrochlorate.Concrete technical scheme is as follows:
A purification process for beet alkali hydrochlorate, is characterized in that comprising the following steps: get the beet alkali hydrochlorate crude product that calcium method makes, be added to the water it is dissolved completely; And then add alcohol, and be warming up to backflow, there is solid to separate out; Heat filtering is removed solid, in filtrate, adds acid, is then down to room temperature, has solid to separate out, and filters, is dried, and gained solid is beet alkali hydrochlorate sterling.
In aforesaid method, the beet alkali hydrochlorate crude product that described calcium method makes is according to the reaction solution of calcium chloroacetate and Trimethylamine 99 is added to sulfuric acid acidation, remove by filter calcium sulfate, the method for filtrate decrease temperature crystalline obtains.
In aforesaid method, the consumption of water is generally 0.1～2 times of crude product quality, preferred, and the consumption of water meets makes beet alkali hydrochlorate crude product just entirely molten.
In aforesaid method, the preferred water dissolution with 50 ℃ by beet alkali hydrochlorate crude product.
In aforesaid method, beet alkali hydrochlorate crude product: alcohol: the mass ratio of acid is 1:0.1～1:0.1～1, preferred mass is than being 1:0.22:0.22.
In aforesaid method, described alcohol is C1-C4 water-soluble alcohol, is preferably ethanol or Virahol; Described acid is mineral acid or organic acid, is preferably concentrated hydrochloric acid, the vitriol oil, strong phosphoric acid, acetic acid or formic acid, more preferably concentrated hydrochloric acid or acetic acid.
In aforesaid method, in gained beet alkali hydrochlorate sterling, beet alkali hydrochlorate content is more than 99%, and sterling ignition residue is below 0.2%.
In the inventive method, first in the aqueous solution of beet alkali hydrochlorate, add a certain amount of alcohol, the solubleness in the time of can obviously reducing calcium sulfate high temperature, thus guarantee that heat filtering can remove calcium sulfate as much as possible.
In the inventive method, according to beet alkali hydrochlorate solubleness minimizing in alcohol, acid system, the calcium sulfate characteristic that solubleness increases in acid system, before cooling, add a certain amount of acid, can effectively reduce the solubleness of dissolved liquid to beet alkali hydrochlorate, can increase the solubleness of calcium sulfate again simultaneously, greatly reduce the calcium sulfate quality of the beet alkali hydrochlorate of separating out, thereby guaranteed to obtain the low residual high purity product that burns.
The beet alkali hydrochlorate crude product that the present invention obtains calcium method adds in the mixing solutions of water, alcohol, acid, by this three's consumption collocation and addition sequence, increase the solubleness of calcium sulfate, reduced the solubleness of beet alkali hydrochlorate simultaneously, realized the purifying of beet alkali hydrochlorate.The method operation steps is simple, without the three wastes, produces, and meets environmental requirement, and the refining beet alkali hydrochlorate purity obtaining is greater than 99%, and the residual content that burns is down to below 0.2%, meets state quality standard, and economic and social benefit is remarkable.
Embodiment
Below by specific embodiment, flesh and blood of the present invention is further detailed, but does not form limiting the scope of the invention.
Beet alkali hydrochlorate crude product of the present invention is to take calcium hydroxide, Mono Chloro Acetic Acid, Trimethylamine 99 and sulfuric acid to make as raw material, or take calcium chloroacetate, Trimethylamine 99 and sulfuric acid and make as raw material, and preparation method can directly obtain from prior art.
In following embodiment, crude product used all makes by the following method: in the chloroacetic aqueous solution, add calcium hydroxide in batches, control temperature of reaction lower than 30 ℃; Then, drip the trimethylamine aqueous solution of 30wt%, control temperature of reaction at 30 ℃; Dropwise, continue to stir 0.5 hour; Reinforced complete, at 60 ℃, continue to stir 0.5 hour, vacuum decompression, takes unnecessary Trimethylamine 99 away; The sulfuric acid that adds 50wt%; Stir after 1 hour, remove by filter calcium sulfate; Filtrate is concentrated, crystallization, filtration, the dry beet alkali hydrochlorate crude product that to obtain.Mono Chloro Acetic Acid: Trimethylamine 99: calcium hydroxide: H
2sO
4mol ratio be 1:1.05:0.5:0.49.In gained crude product, beet alkali hydrochlorate content is 96.8%, and ignition residue is 2.66%.
embodiment 1
Get 100g beet alkali hydrochlorate crude product (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 22 grams of ethanol, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.5 gram of filter cake, add 22 grams of concentrated hydrochloric acids in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 68 grams of beet alkali hydrochlorates, content 99.21%, and the residual content that burns is 0.12%.
embodiment 2
Get 100 grams of beet alkali hydrochlorate crude products (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 22 grams of Virahols, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.5 gram of filter cake, add 22 grams of concentrated hydrochloric acids in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 70 grams of beet alkali hydrochlorates, content 99.28%, and the residual content that burns is 0.11%.
embodiment 3
Get 100 grams of beet alkali hydrochlorate crude products (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 22 grams of ethanol, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.5 gram of filter cake, add 22 grams of acetic acid in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 83 grams of beet alkali hydrochlorates, content 99.35%, and the residual content that burns is 0.09%.
embodiment 4
Get 100 grams of beet alkali hydrochlorate crude products (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 22 grams of ethanol, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.5 gram of filter cake, add 22 grams of vitriol oils in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 73 grams of beet alkali hydrochlorates, content 99.22%, and the residual content that burns is 0.15%.
embodiment 5
Get 100g beet alkali hydrochlorate crude product (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 10 grams of ethanol, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.2 gram of filter cake, add 10 grams of concentrated hydrochloric acids in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 35 grams of beet alkali hydrochlorates, content 99.25%, and the residual content that burns is 0.13%.
embodiment 6
Get 100g beet alkali hydrochlorate crude product (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 100 grams of ethanol, be warming up to backflow, have a small amount of white solid form to separate out; After heat filtering, obtain 0.7 gram of filter cake, add 100 grams of concentrated hydrochloric acids in filtrate, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 47 grams of beet alkali hydrochlorates, content 99.31%, and the residual content that burns is 0.11%.
comparative example 1
Get 100 grams of beet alkali hydrochlorate crude products (ignition residue 2.66%), join in 110 grams of 50 ℃ of water, just dissolve completely; Then, add 22 grams of ethanol and 22 grams of concentrated hydrochloric acids, be warming up to backflow, do not have white solid to separate out; Then, system is down to room temperature gradually, separates out a large amount of white solids, filters, is dried, and obtains 66 grams of beet alkali hydrochlorates, content 98.63%, and the residual content that burns is 0.76%.
Claims (10)
1. a purification process for beet alkali hydrochlorate, is characterized in that comprising the following steps: get the beet alkali hydrochlorate crude product that calcium method makes, be added to the water it is dissolved completely; And then add alcohol, and be warming up to backflow, there is solid to separate out; Heat filtering is removed solid, in filtrate, adds acid, is then down to room temperature, has solid to separate out, and filters, is dried, and gained solid is beet alkali hydrochlorate sterling; Described alcohol is C1-C4 water-soluble alcohol.
2. purification process according to claim 1, is characterized in that: the beet alkali hydrochlorate crude product that described calcium method makes is according to the reaction solution of calcium chloroacetate and Trimethylamine 99 is added to sulfuric acid acidation, remove by filter calcium sulfate, the method for filtrate decrease temperature crystalline obtains.
3. purification process according to claim 1 and 2, is characterized in that: the add-on of water makes beet alkali hydrochlorate crude product just entirely molten.
4. purification process according to claim 3, is characterized in that: the water dissolution by beet alkali hydrochlorate crude product with 50 ℃.
5. purification process according to claim 1 and 2, is characterized in that: beet alkali hydrochlorate crude product: alcohol: the mass ratio of acid is 1:0.1～1:0.1～1.
6. purification process according to claim 5, is characterized in that: beet alkali hydrochlorate crude product: alcohol: the mass ratio of acid is 1:0.22:0.22.
7. purification process according to claim 1 and 2, is characterized in that: described acid is mineral acid or organic acid.
8. purification process according to claim 7, is characterized in that: described alcohol is ethanol or Virahol; Described acid is concentrated hydrochloric acid, the vitriol oil, strong phosphoric acid, acetic acid or formic acid.
9. purification process according to claim 8, is characterized in that: described acid is hydrochloric acid or acetic acid.
10. purification process according to claim 5, is characterized in that: in gained beet alkali hydrochlorate sterling, beet alkali hydrochlorate content is more than 99%, and sterling ignition residue is below 0.2%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196351A (en) * | 1997-12-30 | 1998-10-21 | 河北省固安县宏峰化工有限公司 | Synthesis and separation of trimethyl glycine (betaine) |
| CN1374293A (en) * | 2002-03-18 | 2002-10-16 | 浙江大学 | Green synthesis process of betaine hydrochloride |
| CN101863784A (en) * | 2010-06-07 | 2010-10-20 | 房照智 | Methods for preparing and extracting betaine and betaine hydrochloride |
| CN102807499A (en) * | 2012-08-27 | 2012-12-05 | 陈林世 | Method for preparing betaine hydrochloride |
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2014
- 2014-02-21 CN CN201410059368.5A patent/CN103804210B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196351A (en) * | 1997-12-30 | 1998-10-21 | 河北省固安县宏峰化工有限公司 | Synthesis and separation of trimethyl glycine (betaine) |
| CN1374293A (en) * | 2002-03-18 | 2002-10-16 | 浙江大学 | Green synthesis process of betaine hydrochloride |
| CN101863784A (en) * | 2010-06-07 | 2010-10-20 | 房照智 | Methods for preparing and extracting betaine and betaine hydrochloride |
| CN102807499A (en) * | 2012-08-27 | 2012-12-05 | 陈林世 | Method for preparing betaine hydrochloride |
Non-Patent Citations (4)
| Title |
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| 夏士朋.甜菜碱盐酸盐合成工艺的改进.《化学试剂》.2004, * |
| 甜菜碱盐酸盐合成工艺的改进;夏士朋;《化学试剂》;20040630;378 * |
| 甜菜碱盐酸盐的合成方法研究;阿不都拉江·那斯尔等;《化学试剂》;20131130;983-986 * |
| 阿不都拉江·那斯尔等.甜菜碱盐酸盐的合成方法研究.《化学试剂》.2013, * |
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Application publication date: 20140521 Assignee: Jinan IFT Science & Technology Co., Ltd. Assignor: Chemical Inst., Shandong Prov. Contract record no.: 2015370000054 Denomination of invention: Purification method for betaine hydrochloride Granted publication date: 20141119 License type: Common License Record date: 20150416 |
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Inventor after: Yue Tao Inventor after: Xing Wenguo Inventor after: Feng Weichun Inventor after: Hu Bo Inventor after: Lu Linlin Inventor after: Yang Xu Inventor after: Liu Lixiu Inventor after: Wang Hao Inventor after: Meng Xianxing Inventor before: Zhao Jingrui Inventor before: Feng Weichun Inventor before: Hu Bo Inventor before: Lu Linlin Inventor before: Yang Xu Inventor before: Liu Lixiu Inventor before: Wang Hao Inventor before: Meng Xianxing |
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