CN102351916A - Method for preparing D-arabinose - Google Patents
Method for preparing D-arabinose Download PDFInfo
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- CN102351916A CN102351916A CN2011102431003A CN201110243100A CN102351916A CN 102351916 A CN102351916 A CN 102351916A CN 2011102431003 A CN2011102431003 A CN 2011102431003A CN 201110243100 A CN201110243100 A CN 201110243100A CN 102351916 A CN102351916 A CN 102351916A
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- pectinose
- liquid glucose
- arabinose
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- calglucon
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Abstract
The invention relates to a method for preparing D-arabinose, and belongs to the technical field of functional sugar. In the method, hydrogen peroxide is controllably added to convert calcium gluconate serving as a raw material into the D-arabinose in the presence of iron sulfate serving as a catalyst; D-arabinose liquid obtained through reaction is subjected to subsequent treatment processes of precipitation reaction, filtration, decolorization, ion exchange and chromatographic separation to form D-arabinose liquid with the purity of over 85 percent; and the D-arabinose liquid is subjected to evaporation concentration and natural cooling crystallization to form D-arabinose crystals. The method comprises the following process steps of: (1) preparing the D-arabinose liquid; (2) refining the D-arabinose liquid; and (3) crystallizing to obtain the D-arabinose crystals with the purity of 96 to 99.9 percent. The calcium gluconate is converted into the D-arabinose, and the steps are simple; and relatively cheap iron sulfate is used as the catalyst, so that the production cost of the D-arabinose is reduced, and the yield of the D-arabinose is improved.
Description
Technical field
The invention belongs to technical field of functional sugar, relating to a kind of is the method for raw material production D-pectinose with the calglucon.
Background technology
The D-pectinose is of many uses at food and biomedicine field.The D-pectinose, perhaps the D-arabonic acid that generates after its oxidation can be used to produce riboflavin.The D-pectinose is still produced the intermediate of cancer therapy drug cytosine arabinoside.Owing to lack the technology of low-cost economic production D-pectinose, these purposes receive the restriction of expensive pectinose price.The working method of D-pectinose has multiple.
English Patent 953012 in the patent by the application of Sankyo company, has been introduced a kind of technology for preparing the D-pectinose with complete synthesizing process.This method needs five kinds of intermediate reaction products of preparation, therefore considers that by industrialization technology is too loaded down with trivial details.
Another kind method is on record RUFF method, and calglucon can obtain the D-pectinose with the ydrogen peroxide 50 degraded under the situation that iron acetate exists.Hocket and Hudson improved the RUFF reaction (JACS Vol. 56, page 1632; 1934), calglucon carries out two-way decomposition and prepares the D-pectinose under ferric sulfate and barium acetate catalysis.The yield 34-40% of this method D-pectinose, still on the low side.United States Patent (USP) (usp3755294) reacts the technology of making D-pectinose with ydrogen peroxide 50 with calglucon in the presence of an amount of ferrous gluconate, though its yield can reach 60% of theoretical value.But use ferrous gluconate in this method, cost an arm and a leg, the production cost of D-pectinose is improved greatly, further influence applying of this method.
Summary of the invention
The method that the purpose of this invention is to provide a kind of D-of preparation pectinose, numerous and diverse to solve prior art processes, intermediate feed costs an arm and a leg, and the yield of D-pectinose is low, problems such as production cost height.
The technical solution adopted for the present invention to solve the technical problems is to be raw material with the calglucon, is catalyzer with ferric sulfate, accomplishes the conversion of calglucon to the D-pectinose through controlledly adding ydrogen peroxide 50.The Arabic liquid glucose of the D-that obtains of reaction through precipitin reaction, filtration, decolouring, from handing over and chromatographic separation subsequent disposal operation, obtains the Arabic liquid glucose of the D-of purity 85% or more, and natural decrease temperature crystalline obtains D-pectinose crystal after the process evaporation concentration.Concrete processing step is following:
(1) preparation of the Arabic liquid glucose of D-
By weight percentage raw materials used; Calglucon is dissolved in the water; Consumption is 5%-30%; Add ferric sulfate and make catalyzer, consumption is the 1.5%-4.5% of calglucon quality, slowly adds ydrogen peroxide 50 while stirring; Concentration of hydrogen peroxide is 25%-35% in the ydrogen peroxide 50; Temperature of reaction is 71 ℃-80 ℃, and the adding speed of ydrogen peroxide 50 is 30mL/h-150mL/h, and the equivalent of hydrogen peroxide is the normal 6-10 of calglucon times.
(2) the Arabic liquid glucose of D-is refining
The Arabic liquid glucose of the D-of step (1) preparation removes by filter the insolubles that reaction produces.Through checking, this insolubles main component is a calcium hydroxide.Remove the Arabic liquid glucose of calcium hydroxide D-afterwards, solid content is 3%-18%, and the purity of D-pectinose is 55%-65%, but also contains a certain amount of calcium ion in the liquid glucose.
Under 75 ℃-85 ℃, in liquid glucose, slowly add sulphuric acid soln, slowly stir, calcium ion changes into calcium sulfate precipitation, filters.Employed vitriolic concentration is 10%-30%.The purity of D-pectinose increases to 58%-68%.
Above-mentioned liquid glucose is removed salt ion through ion exchange resin again, and under 70 ℃ of-75 ℃ of temperature, vacuum concentration to solid content is 40%-45%, through chromatographic separation, and the D-pectinose liquid glucose component and the assorted sugar component that obtain.D-pectinose component wherein, solid content is 20%-30%, the purity of D-pectinose is 75%-80%.
(3) crystallization
With the Arabic liquid glucose of the D-of step (2) preparation; Under 70 ℃ of-75 ℃ of temperature; Being concentrated in vacuo to solid content is 65-75%; Naturally cooling adds perhaps and does not add crystal seed, stirs 15-24 hour; Centrifugal oven dry; Make D-pectinose crystal, purity is 96%-99.9%, measures fusing point and should be 156.5 ℃ to 175 ℃.
Positively effect of the present invention is to realize the conversion of calglucon to the D-pectinose; Step is succinct; And use relatively cheap ferric sulfate to make catalyzer, and having reduced the production cost of D-pectinose, the yield of the D-pectinose of reaction reaches more than 72% of theoretical yield.
Embodiment
Be fabricating technology parameter of the present invention prepares the D-pectinose under different end values example below:
Embodiment 1
(1) preparation of the Arabic liquid glucose of D-
Composition of raw materials adopts weight percent; 150 gram calglucons are dissolved in the water; Concentration is 5%; Add ferric sulfate and make catalyzer, catalyst consumption is 1.5% of a calglucon quality, slowly adds ydrogen peroxide 50 while stirring; Concentration of hydrogen peroxide is 30% in the ydrogen peroxide 50; Temperature of reaction is 71 ℃, and the adding speed of ydrogen peroxide 50 is 30 mL/h, and the equivalent of hydrogen peroxide is normal 6 times an of calglucon.
(2) the Arabic liquid glucose of D-is refining
The Arabic liquid glucose of the D-of step (1) preparation, remove by filter reaction produce insolubles.Insolubles is slightly soluble in water, in insolubles solution, adds yellow soda ash, produces white precipitate, and white precipitate is dissolved in dilute hydrochloric acid, and produces great amount of bubbles, and it is calcium hydroxide that combination anchor draws this insolubles main component.Remove the Arabic liquid glucose of calcium hydroxide D-afterwards, solid content is 3%, and the purity of D-pectinose is 60%.Under 80 ℃, in liquid glucose, slowly add 10% sulphuric acid soln, slowly stir, produce deposition, filter.The purity of D-pectinose increases to 65%.Above-mentioned liquid glucose is removed salt ion through ion exchange resin again, and under 75 ℃ of temperature, vacuum concentration to solid content is 43%, through chromatographic separation, and the D-pectinose liquid glucose component and the assorted sugar component that obtain.D-pectinose component wherein, solid content is 22%, the purity of D-pectinose is 80%.
(3) crystallization
With the Arabic liquid glucose of the D-of step (2) preparation, under 75 ℃, being concentrated in vacuo to solid content is 71%, naturally cooling; Stirred 22 hours, and had crystal to separate out, centrifugal oven dry; Make D-pectinose crystal 76.88 grams, purity is 98.7%, measures fusing point and should be 156.5 ℃ to 175 ℃.
(4) yield calculates
Calglucon prepares the chemical equation of D-pectinose:
Theoretical yield: 300 ÷ 430 * 100%=69.77%
Actual recovery: 76.88 * 98.7% ÷ 150 * 100%=50.59%
Actual recovery is the per-cent of theoretical yield: 50.59% ÷ 69.77% * 100%=72.51%
The yield of D-pectinose is 50.59%, is 72.51% of theoretical yield.
Embodiment 2
Composition of raw materials adopts weight percent, and 235 gram calglucons are dissolved in the water, and concentration is 30%, adds ferric sulfate and makes catalyzer, and catalyst consumption is 4.5% of a calglucon quality, slowly adds ydrogen peroxide 50 while stirring.Concentration of hydrogen peroxide is 30% in the ydrogen peroxide 50, and temperature of reaction is 75 ℃, and the adding speed of ydrogen peroxide 50 is 150 mL/h, and the equivalent of hydrogen peroxide is normal 10 times an of calglucon.The Arabic liquid glucose of reacted D-removes by filter calcium hydroxide.Under 80 ℃, in liquid glucose, slowly add 30% sulphuric acid soln, slowly stir, produce deposition, filter.Liquid glucose is through ion exchange resin.Under 75 ℃ of temperature, vacuum concentration to solid content 43%.Through after the chromatographic separation, the D-pectinose liquid glucose component and the assorted sugar component that obtain.D-pectinose component wherein, solid content is 30%, the purity of D-pectinose is 75%.Under 75 ℃, being concentrated in vacuo to solid content is 65%, and cooling naturally adds 1 gram crystal seed, stirs 15 hours, has crystal to separate out, and centrifugal oven dry makes D-pectinose crystal 119.86 grams, and purity is 99.0%, measures fusing point and should be 156.5 ℃ to 175 ℃.The yield of D-pectinose is 50.49%, is 72.37% of theoretical yield.
Embodiment 3
Composition of raw materials adopts weight percent, and 400 gram calglucons are dissolved in the water, and concentration is 20%, adds ferric sulfate and makes catalyzer, and catalyst consumption is 3% of a calglucon quality, slowly adds ydrogen peroxide 50 while stirring.Concentration of hydrogen peroxide is 30% in the ydrogen peroxide 50, and temperature of reaction is 75 ℃, and the adding speed of ydrogen peroxide 50 is 100 mL/h, and the equivalent of hydrogen peroxide is normal 7 times an of calglucon.The Arabic liquid glucose of reacted D-removes by filter calcium hydroxide.Under 80 ℃, in liquid glucose, slowly add 20% sulphuric acid soln, slowly stir, produce deposition, filter.Liquid glucose is through ion exchange resin.Under 75 ℃ of temperature, vacuum concentration to solid content 45%.Through after the chromatographic separation, the D-pectinose liquid glucose component and the assorted sugar component that obtain.D-pectinose component wherein, solid content is 20%, the purity of D-pectinose is 78%.Under 75 ℃, being concentrated in vacuo to solid content is 75%, and cooling naturally adds 1 gram crystal seed, stirs 24 hours, has crystal to separate out, and centrifugal oven dry makes D-pectinose crystal 2 15.32 grams, and purity is 99.2%, measures fusing point and should be 156.5 ℃ to 175 ℃.The yield of D-pectinose is 53.4%, is 76.54% of theoretical yield.
Claims (1)
1. method for preparing the D-pectinose; It is characterized in that with the calglucon being raw material; With ferric sulfate is catalyzer; Accomplish the conversion of calglucon through controlledly adding ydrogen peroxide 50 to the D-pectinose; The Arabic liquid glucose of the D-that obtains of reaction through precipitin reaction, filtration, decolouring, from handing over and chromatographic separation subsequent disposal operation, obtains the D-Arab liquid glucose of purity 85% or more; Obtain D-pectinose crystal through natural decrease temperature crystalline after the evaporation concentration, concrete processing step is following:
(1) preparation of the Arabic liquid glucose of D-
By weight percentage raw materials used; Calglucon is dissolved in the water; Consumption is 5%-30%; Add ferric sulfate and make catalyzer, consumption is the 1.5%-4.5% of calglucon quality, slowly adds ydrogen peroxide 50 while stirring; Concentration of hydrogen peroxide is 25%-35% in the ydrogen peroxide 50; Temperature of reaction is 71 ℃-80 ℃, and the adding speed of ydrogen peroxide 50 is 30mL/h-150 mL/h, and the equivalent of hydrogen peroxide is the normal 6-10 of calglucon times;
(2) the Arabic liquid glucose of D-is refining
The Arabic liquid glucose of the D-of step (1) preparation; Remove by filter reaction and produce insolubles; Through checking; This insolubles main component is a calcium hydroxide; Remove the Arabic liquid glucose of calcium hydroxide D-afterwards; Solid content is 3%-18%, and the purity of D-pectinose is 55%-65%, but also contains a certain amount of calcium ion in the liquid glucose;
Under 75 ℃-85 ℃, in liquid glucose, slowly add sulphuric acid soln, slowly stir, calcium ion changes into calcium sulfate precipitation, filters, and employed vitriolic concentration is 10%-30%, and the purity of D-pectinose increases to 58%-68%;
Above-mentioned liquid glucose is removed salt ion through ion exchange resin again; Under 70 ℃ of-75 ℃ of temperature; Vacuum concentration to solid content is 40%-45%; Through chromatographic separation; The D-pectinose liquid glucose component and the assorted sugar component that obtain; D-pectinose component wherein, solid content is 20%-30%, the purity of D-pectinose is 75%-80%;
(3) crystallization
With the Arabic liquid glucose of the D-of step (2) preparation; Under 70 ℃ of-75 ℃ of temperature; Being concentrated in vacuo to solid content is 65-75%; Naturally cooling adds perhaps and does not add crystal seed, stirs 15-24 hour; Centrifugal oven dry; Make D-pectinose crystal, purity is 96%-99.9%, measures fusing point and should be 156.5 ℃ to 175 ℃.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659854A (en) * | 2012-03-15 | 2012-09-12 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN102850409A (en) * | 2012-09-26 | 2013-01-02 | 山东福田药业有限公司 | Preparation method of D-arabinose |
| CN103896993A (en) * | 2014-04-10 | 2014-07-02 | 山东福洋生物科技有限公司 | Control method for production of D-gum sugar by using chemical method |
| CN104262415A (en) * | 2014-08-18 | 2015-01-07 | 山东福洋生物科技有限公司 | Efficient production method of D-arabinose |
| CN106349296A (en) * | 2016-08-24 | 2017-01-25 | 山东福洋生物科技有限公司 | Preparation method of high-concentration D-arabinose |
| CN106632523A (en) * | 2016-12-12 | 2017-05-10 | 广西轻工业科学技术研究院 | Purification method of D-arabinose |
| CN111704542A (en) * | 2020-07-02 | 2020-09-25 | 浙江晟格生物科技有限公司 | Method for preparing calcium threonate by taking calcium xylonate as raw material |
| CN111704539A (en) * | 2020-07-02 | 2020-09-25 | 浙江晟格生物科技有限公司 | Method for preparing calcium threonate by using half calcium lactobionate as raw material |
| CN114988993A (en) * | 2022-06-10 | 2022-09-02 | 万华化学集团股份有限公司 | Method for preparing vanillin by one-step method |
| CN115785174A (en) * | 2022-12-17 | 2023-03-14 | 浙江华康药业股份有限公司 | Preparation method of high-purity arabinose crystal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755294A (en) * | 1970-10-26 | 1973-08-28 | Cpc Inc | Process for the production of d-arabinose |
| WO1999057326A1 (en) * | 1998-05-01 | 1999-11-11 | Sanwa Kosan Kabushiki Kaisha | Process for producing l-arabinose by acid hydrolysis method |
| CN101367844A (en) * | 2008-09-17 | 2009-02-18 | 无锡绿色分离应用技术研究所有限公司 | Method for extracting pectinos from gum arabic hydrolysate |
| CN101845065A (en) * | 2010-05-02 | 2010-09-29 | 宜昌市天楚化工科技有限公司 | Method for preparing D-arabinose |
-
2011
- 2011-08-24 CN CN2011102431003A patent/CN102351916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3755294A (en) * | 1970-10-26 | 1973-08-28 | Cpc Inc | Process for the production of d-arabinose |
| WO1999057326A1 (en) * | 1998-05-01 | 1999-11-11 | Sanwa Kosan Kabushiki Kaisha | Process for producing l-arabinose by acid hydrolysis method |
| CN101367844A (en) * | 2008-09-17 | 2009-02-18 | 无锡绿色分离应用技术研究所有限公司 | Method for extracting pectinos from gum arabic hydrolysate |
| CN101845065A (en) * | 2010-05-02 | 2010-09-29 | 宜昌市天楚化工科技有限公司 | Method for preparing D-arabinose |
Non-Patent Citations (4)
| Title |
|---|
| GWENAELLE HOURDIN，等: "The Catalysis of the Ruff Oxidative Degradation of Aldonic Acids by Copper(II)-Containing Solids", 《JOURNAL OF CATALYSIS》 * |
| R. C. HOCKETT，等: "Improvements in the Preparation of &Arabinose from Calcium Gluconate", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| VENANCIOD EULOBEU: "CCCXLVI.-Degradations in the Sugar Group.", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
| 邢其毅，等: "《基础有机化学 下册》", 31 December 2005 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659854A (en) * | 2012-03-15 | 2012-09-12 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN102659854B (en) * | 2012-03-15 | 2014-08-13 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN102850409A (en) * | 2012-09-26 | 2013-01-02 | 山东福田药业有限公司 | Preparation method of D-arabinose |
| CN103896993A (en) * | 2014-04-10 | 2014-07-02 | 山东福洋生物科技有限公司 | Control method for production of D-gum sugar by using chemical method |
| CN104262415A (en) * | 2014-08-18 | 2015-01-07 | 山东福洋生物科技有限公司 | Efficient production method of D-arabinose |
| CN104262415B (en) * | 2014-08-18 | 2017-09-26 | 山东福洋生物科技有限公司 | D arabinose production methods |
| CN106349296A (en) * | 2016-08-24 | 2017-01-25 | 山东福洋生物科技有限公司 | Preparation method of high-concentration D-arabinose |
| CN106349296B (en) * | 2016-08-24 | 2019-08-27 | 山东福洋生物科技股份有限公司 | A kind of preparation method of high concentration D-arabinose |
| CN106632523B (en) * | 2016-12-12 | 2019-04-16 | 广西轻工业科学技术研究院有限公司 | A kind of purification process of D-arabinose |
| CN106632523A (en) * | 2016-12-12 | 2017-05-10 | 广西轻工业科学技术研究院 | Purification method of D-arabinose |
| CN111704542A (en) * | 2020-07-02 | 2020-09-25 | 浙江晟格生物科技有限公司 | Method for preparing calcium threonate by taking calcium xylonate as raw material |
| CN111704539A (en) * | 2020-07-02 | 2020-09-25 | 浙江晟格生物科技有限公司 | Method for preparing calcium threonate by using half calcium lactobionate as raw material |
| CN114988993A (en) * | 2022-06-10 | 2022-09-02 | 万华化学集团股份有限公司 | Method for preparing vanillin by one-step method |
| CN114988993B (en) * | 2022-06-10 | 2023-12-19 | 万华化学集团股份有限公司 | Method for preparing vanillin by one-step method |
| CN115785174A (en) * | 2022-12-17 | 2023-03-14 | 浙江华康药业股份有限公司 | Preparation method of high-purity arabinose crystal |
| WO2024124812A1 (en) * | 2022-12-17 | 2024-06-20 | 浙江华康药业股份有限公司 | Preparation method for high-purity arabinose crystal |
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Application publication date: 20120215 |