CN102718823B - Process method for elution, crystallization and refining of 5'-flavor nucleotide disodium - Google Patents
Process method for elution, crystallization and refining of 5'-flavor nucleotide disodium Download PDFInfo
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- CN102718823B CN102718823B CN201210214154.1A CN201210214154A CN102718823B CN 102718823 B CN102718823 B CN 102718823B CN 201210214154 A CN201210214154 A CN 201210214154A CN 102718823 B CN102718823 B CN 102718823B
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Abstract
The invention discloses a process method for elution, crystallization and refining of 5'-flavor nucleotide disodium. Mother solution of 5'-flavor nucleotide disodium after being treated via decoloration, hot water extraction and sodium filtration is used as raw material; and the pH value of the solution is adjusted to 7.0-10; the elution agent absolute ethyl alcohol is dropped into the solution with the flow speed controlled, and the growth of the crystal is controlled effectively via adjusting the temperature under mixing conditions; and finally the prepared mixture is filtered under the atmospheric pressure, the supernatant is removed, and the product is dried under vacuum condition. The precipitation of the crystal nucleus and the growth of the crystal can be well controlled via optimization of the dropping rate of the elution agent and the temperature adjustment, the crystal form and particle size of the 5'-flavor nucleotide disodium crystal can be improved greatly, the average particle diameter can be increased from 35mum to 60mum, and the product quality can be improved significantly.
Description
Technical field
The present invention relates to a kind of method for purification of 5 '-flavour nucleotide disodium, specifically, relate to a kind of processing method of 5 '-flavour nucleotide disodium dilution crystallization.
Background technology
5 '-flavour nucleotide disodium (Disodium5 '-Ribonucleotide, I+G), by IMP (Disodium5 '-Inosine, IMP) with 5'-GMP2Na (Disodium5 '-Guanylate, GMP) forming, is new food additive important in food service industry, and it is remarkable that it increases fresh effect, share very strong synergistic effect with Sodium Glutamate, can make to increase fresh effect and strengthen 10～20 times.At present, I+G is applied to chickens' extract, increases delicate flavour essence, flavouring like sauce and meat curing etc.In addition, IMP has certain auxiliary therapeutic action to white corpuscle and thrombocytopenia and various acute and chronic hepatic diseases.
The production method of 5 '-flavour nucleotide disodium mainly contains enzymolysis process and fermentation method, and the conversion method that wherein ferments is current industrial utilization method the most widely.And the crystallization of 5 '-flavour nucleotide disodium is one of most important part in fermentation conversion method production technique.In China's industrial production, mainly adopt at present dilution crystallization method.The research of external high 5 '-flavour nucleotide disodium crystallization is comparative maturity, and every quality index has has all met or exceeded foodstuff additive---the quality standard of 5'-GMP2Na that Japan formulates for 1972.On the other hand, high-purity 5 '-flavour nucleotide disodium crystallization technique has been carried out to blockade on new techniques abroad, and for a long time its basic data has been maintained secrecy.And there is the problems such as crystallization yield is low, product purity is not high, production cost is large in domestic existing technique; And quality product is compared with imported product, exist larger gap, be mainly manifested in the aspects such as purity, crystalline form, granularity, in world market, lack competitiveness.
Summary of the invention
The object of the invention is to overcome the shortcoming that prior art exists, provide a kind of crystalline form, granularity, purity of 5 '-flavour nucleotide, two sodium crystals of making to obtain effectively improving and the crystallization control method improving, make the median size of 5 '-flavour nucleotide, two sodium crystals bring up to 42～60 μ m from 35 μ m.
For realizing the object of the invention, the present invention adopts following technical scheme:
1, a method for 5 '-flavour nucleotide disodium crystal refining, is characterized in that comprising following processing step:
(1) regulating mother liquor pH value: 5 '-flavour nucleotide, two mother liquid of sodium of processing through decolouring, hot-water extraction and nanofiltration of take are raw material, is at 45 ℃～65 ℃, to make mother liquor dissolve to form solution in temperature, and hydro-oxidation sodium solid regulates initial pH value to 7.0～10;
(2) dilution crystallization: adopt speed change dropping mode to add dissolved agent in step (1) gained 5 '-flavour nucleotide two sodium solutions, under the agitation condition with rotating speed 150rpm～250rpm, impel 5 '-flavour nucleotide disodium to crystallize out from solution; Dehydrated alcohol is selected in dissolved agent, and dissolved agent and mother liquor volume ratio are 1:2～1:5; Described speed change dropping mode is that the first speed with 0.8-1ml/min drips, and along with separating out of crystal, when dissolved agent is added drop-wise to 1/2-2/3, accelerates drop rate to 2.5-3ml/min;
(3) temperature is controlled: under 150rpm～250rpm rotating speed agitation condition to carrying out temperature control under step (2) gained 5 '-flavour nucleotide disodium liquid-solid system, first be cooled to 20 ℃～40 ℃, maintain after 0.5～2 hour, be warming up to 65 ℃ and be incubated 1～2 hour, stepless control is cooled to 10 ℃ again, to improve 5 '-flavour nucleotide disodium crystal mass;
(4) filtration drying: 5 '-flavour nucleotide, the two sodium crystal normal pressures that will obtain through step (3) filter, vacuum-drying can obtain white 5 '-flavour nucleotide disodium product.
Further, described 5 '-flavour nucleotide disodium mother liquid concentration is 200g/L～300g/L.
5 '-flavour nucleotide disodium pH that described hydro-oxidation sodium solid regulates is 7.5～9.0.
Described dissolved agent and mother liquor volume ratio are 1:2～1:4.
Described temperature controlling step, for being first cooled to 30 ℃～40 ℃, maintains after one hour, be warming up to 65 ℃ and be incubated 1～2 hour, then stepless control is cooled to 10 ℃.
The present invention compared with prior art, has following features and beneficial effect:
(1) variation of solid particulate number and median size in the present invention's 5 '-flavour nucleotide disodium crystallisation process that in earlier stage utilized FBRM on-line monitoring, when the increase speed of particle median size slows down, accelerates dissolved agent drop rate to adapt to the growth of particle.This dropping mode is from the different of conventional dropping mode: can reach the effect of crystallization and growing the grain simultaneously, and meet better the process of growth of crystal---when crystal grain is less, less dissolved speed can be corresponding to slower solid settlement speed; When solid particulate is increased to certain number, larger dissolved speed is conducive to the growth velocity of crystal.By repeatedly testing, the present invention has grasped the control that speed change drips well.And the application of FBRM technology is few in general industry is produced, all adopt disposable add dissolved agent or constant speed dropping, can not effectively realize the control to granular size.
(2) different from traditional crystallisation by cooling method, in the present invention, adopt the temperature-controlled process of alternating temperature.Present method is used for reference other systems, precipitate particle at 65 ℃ of comparatively high tempss, first by cooling, separate out a large amount of particles, then heat up small-particle is dissolved, progressively cooling makes macrobead growth again, reach better the effect of growing the grain, and almost there is no amorphous small-particle in the product particle obtaining, all changed into the crystal grain with good crystalline form and larger granularity.The median size of 5 '-flavour nucleotide, two sodium crystals is also brought up to 42～60 μ m from 35 μ m effectively, has greatly improved the efficiency of the downstream process of crystallization processes.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 gained 5 '-flavour nucleotide disodium crystalline product amplifies 100 times after dry and takes displaing micro pictures under electron microscope;
Fig. 2 is that embodiment 2 gained 5 '-flavour nucleotide disodium crystalline product amplifies 100 times after dry and takes displaing micro pictures under electron microscope;
Fig. 3 is that embodiment 3 gained 5 '-flavour nucleotide disodium crystalline product amplifies 100 times after dry and takes displaing micro pictures under electron microscope;
Fig. 4 is that embodiment 4 gained 5 '-flavour nucleotide disodium crystalline product amplifies 100 times after dry and takes displaing micro pictures under electron microscope;
Fig. 5 is that embodiment 5 gained 5 '-flavour nucleotide disodium crystalline product amplifies 100 times after dry and takes displaing micro pictures under electron microscope;
Fig. 6 is embodiment 1 product crystallisation process particle median size curve over time;
Fig. 7 is embodiment 2 product crystallisation process particle median sizes curves over time;
Fig. 8 is embodiment 3 product crystallisation process particle median sizes curves over time;
Fig. 9 is embodiment 4 product crystallisation process particle median sizes curves over time;
Figure 10 is embodiment 5 product crystallisation process particle median sizes curves over time.
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the invention will be described further, but it should be noted that, the scope of protection of the presently claimed invention is not limited to the scope that embodiment explains.
Embodiment 1
Get 5 '-flavour nucleotide, two mother liquid of sodium that 300ml processes through decolouring, hot-water extraction and nanofiltration, wherein 5 ' of mother liquor-flavour nucleotide two na concns are 200g/L.Add hot mother liquor to 65 ℃, with sodium hydroxide, regulate the pH value to 7.5 of mother liquor; This mother liquor is proceeded in crystallization kettle, at 65 ℃, stir, rotating speed is 200rpm.Add 120ml dehydrated alcohol, according to the situation segmentation of crystallization, by different speed, drip dehydrated alcohol, wherein the drop rate of front 80ml is 1ml/min, and rear 40ml is 1ml/min.Then enter temperature controlling stages, 1h to 35 ℃ of first naturally cooling, is then rapidly heated to 65 ℃ and maintains 1h, then continuous cooling to 10 ℃.Crystallisation process finishes, filter, be dried to obtain 56.19g5 '-flavour nucleotide disodium finished product, yield is 93.65%, crystalline form see in accompanying drawing 1(accompanying drawing 1 picture be dry after product under electron microscope, amplify 100 times of shootings), as seen from Figure 1, in products obtained therefrom, almost there is no amorphous powder, be converted into crystal completely, and the pattern of crystal all improves a lot than prior art on width and thickness, significantly improved product crystalline form.Product median size is 52 μ m, refer in accompanying drawing 6(accompanying drawing 6 chart by FBRM on-line measurement crystallisation process gained), from change curve, along with the median size of carrying out particle of crystallisation process is totally increase tendency, by 35 μ m, increase to 52 μ m, this has improved the efficiency of the downstream process of crystallization processes greatly.
Embodiment 2
Get 5 '-flavour nucleotide, two mother liquid of sodium that 300ml processes through decolouring, hot-water extraction and nanofiltration, wherein mother liquor 5 '-flavour nucleotide two na concns are 200g/L.Add hot mother liquor to 65 ℃, with sodium hydroxide, regulate the pH value to 7.5 of mother liquor; This mother liquor is proceeded in crystallization kettle, at 65 ℃, stir, rotating speed is 200rpm.Add 120ml dehydrated alcohol, according to the situation segmentation of crystallization, by different speed, drip dehydrated alcohol, the drop rate of front 80ml is 1ml/min, and rear 40ml is 3ml/min.Then enter temperature controlling stages, 1h to 35 ℃ of first naturally cooling, is then rapidly heated to 65 ℃ and maintains 2h, then continuous cooling to 10 ℃.Crystallisation process finishes, and filters, and is dried to obtain 53.76g5 '-flavour nucleotide disodium finished product, and yield is 89.6%, and crystalline form is shown in accompanying drawing 2, and median size is 60 μ m, refers to accompanying drawing 7.This embodiment 2 compares with embodiment 1, is mainly that temperature controlling stages has extended 1h, and this has improved the median size of crystal grain effectively, has greatly shortened the time that downstream process filters.
Embodiment 3
Get 5 '-flavour nucleotide, two mother liquid of sodium that 300ml processes through decolouring, hot-water extraction and nanofiltration, wherein mother liquor 5 '-flavour nucleotide two na concns are 300g/L.Add hot mother liquor to 65 ℃, with sodium hydroxide, regulate the pH value to 7.5 of mother liquor; This mother liquor is proceeded in crystallization kettle, at 65 ℃, stir, rotating speed is 250rpm.Add 120ml dehydrated alcohol, _ _ _ _ _ _ _ _ _ _ according to the situation segmentation of crystallization, by different speed, dripping dehydrated alcohol, the drop rate of front 80ml is 3ml/min, rear 40ml is 1ml/min.Then enter temperature controlling stages, 1h to 45 ℃ of first naturally cooling, is then rapidly heated to 65 ℃ and maintains 1h, then continuous cooling to 10 ℃.Crystallisation process finishes, and filters, and dry that 78.62g5 '-flavour nucleotide disodium product yield is 87.36%, crystalline form is shown in accompanying drawing 3, and median size is 53 μ m, refers to accompanying drawing 8.
Embodiment 4
Get 5 '-flavour nucleotide, two mother liquid of sodium that 300ml processes through decolouring, hot-water extraction and nanofiltration, wherein mother liquor 5 '-flavour nucleotide two na concns are 200g/L.Add hot mother liquor to 45 ℃, with sodium hydroxide, regulate the pH value to 9.0 of mother liquor; This mother liquor is proceeded in crystallization kettle, at 45 ℃, stir, rotating speed is 150rpm.Add 150ml dehydrated alcohol, according to the situation segmentation of crystallization, by different speed, drip dehydrated alcohol, the drop rate of front 80ml is 1ml/min, and rear 70ml is 1ml/min.Then enter temperature controlling stages, be first warming up to 65 ℃ and maintain 1h, then continuous cooling to 10 ℃.Crystallisation process finishes, and filters, and is dried to obtain 54.2g5 '-flavour nucleotide disodium finished product, and yield is 90.33%, and crystalline form is shown in accompanying drawing 4, and particle changes into crystal completely as seen from the figure, and has good glossiness, and median size is 45 μ m, refers to accompanying drawing 9.
Embodiment 5
Get 5 '-flavour nucleotide, two mother liquid of sodium that 300ml processes through decolouring, hot-water extraction and nanofiltration, wherein mother liquor 5 '-flavour nucleotide two na concns are 200g/L.Add hot mother liquor to 65 ℃, with sodium hydroxide, regulate the pH value to 7.8 of mother liquor; This mother liquor is proceeded in crystallization kettle, at 65 ℃, stir, rotating speed is 200rpm.Add 75ml dehydrated alcohol, drop rate is 1ml/min.Then enter temperature controlling stages, 1h to 30 ℃ of first naturally cooling, is then rapidly heated to 65 ℃ and maintains 1h, then continuous cooling to 10 ℃.Crystallisation process finishes, and filters, and is dried to obtain 45.86g5 '-flavour nucleotide disodium finished product, and yield is 76.43%, and crystalline form is shown in accompanying drawing 5, and median size is 42 μ m, refers to accompanying drawing 10.In this embodiment, the improvement of quality product is that amorphous granular has all changed into crystal grain, be greatly improved, and product cut size increase to a certain extent has also improved the effect of solid-liquid separation after crystallization on outward appearance and color and luster.
Claims (4)
1. a method for 5 '-flavour nucleotide disodium crystal refining, is characterized in that comprising following processing step:
(1) regulate mother liquor pH value: 5 '-flavour nucleotide, two mother liquid of sodium of processing through decolouring, hot-water extraction and nanofiltration of take are raw material, add hot mother liquor to 45 ℃ or 65 ℃, hydro-oxidation sodium solid adjusting initial pH value to 7.0～10; Described 5 '-flavour nucleotide disodium mother liquid concentration is 200g/L～300g/L;
(2) dilution crystallization: adopt speed change dropping mode to add dissolved agent in step (1) gained 5 '-flavour nucleotide two sodium solutions, under the agitation condition with rotating speed 150rpm～250rpm, impel 5 '-flavour nucleotide disodium to crystallize out from solution; Dehydrated alcohol is selected in dissolved agent, and dissolved agent and mother liquor volume ratio are 1:2～1:5; Described speed change dropping mode is that the first speed with 0.8-1ml/min drips, and along with separating out of crystal, when dissolved agent is added drop-wise to 1/2-2/3, accelerates drop rate to 2.5-3ml/min;
(3) temperature is controlled: under 150rpm～250rpm rotating speed agitation condition to carrying out temperature control under step (2) gained 5 '-flavour nucleotide disodium liquid-solid system, first be cooled to 20 ℃～40 ℃, maintain after 0.5～2 hour, be warming up to 65 ℃ and be incubated 1～2 hour, stepless control is cooled to 10 ℃ again, to improve 5 '-flavour nucleotide disodium crystal mass;
(4) filtration drying: 5 '-flavour nucleotide, the two sodium crystal normal pressures that will obtain through step (3) filter, vacuum-drying can obtain white 5 '-flavour nucleotide disodium product.
2. the method for 5 '-flavour nucleotide disodium crystal refining according to claim 1, is characterized in that: 5 '-flavour nucleotide disodium pH that described hydro-oxidation sodium solid regulates is 7.5～9.0.
3. the method for 5 '-flavour nucleotide disodium crystal refining according to claim 1, is characterized in that: described dissolved agent and mother liquor volume ratio are 1:2～1:4.
4. the method for 5 '-flavour nucleotide disodium crystal refining according to claim 1, it is characterized in that: described temperature controlling step is for being first cooled to 30 ℃～40 ℃, maintain after one hour, be warming up to 65 ℃ and be incubated 1～2 hour, then stepless control is cooled to 10 ℃.
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| CN103265467B (en) * | 2013-05-06 | 2015-07-29 | 华南理工大学 | A kind of crystallisation by cooling refines the method for L-PROLINE |
| CN105495528B (en) * | 2015-11-27 | 2018-10-26 | 天津大学 | A method of preparing high heap density the sapidity nucleotide disodium mixed crystal |
| CN108157908A (en) * | 2018-02-09 | 2018-06-15 | 武晓丹 | It is a kind of to utilize the method for vacuumizing and preparing high heap density I+G mixed crystal |
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| CN1539846A (en) * | 2003-10-29 | 2004-10-27 | 徐昌洪 | Technique for preparing 5'nucleotide bi-sodium |
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| JP2870807B2 (en) * | 1989-05-25 | 1999-03-17 | 味の素株式会社 | Method for producing nucleotide mixture |
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| GB2213815A (en) * | 1987-12-17 | 1989-08-23 | Takeda Chemical Industries Ltd | Process for producing nucleosides |
| CN1539846A (en) * | 2003-10-29 | 2004-10-27 | 徐昌洪 | Technique for preparing 5'nucleotide bi-sodium |
| CN101293907A (en) * | 2008-06-24 | 2008-10-29 | 广东肇庆星湖生物科技股份有限公司 | Technique for preparing 5'-inosine acid disodium |
| CN101619086A (en) * | 2009-06-25 | 2010-01-06 | 广东肇庆星湖生物科技股份有限公司 | Disodium 5'-ribonucleotide crystal and preparation method thereof |
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