CN1217901C - High-yield manna sugar preparation process - Google Patents
High-yield manna sugar preparation process Download PDFInfo
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- CN1217901C CN1217901C CN 03134955 CN03134955A CN1217901C CN 1217901 C CN1217901 C CN 1217901C CN 03134955 CN03134955 CN 03134955 CN 03134955 A CN03134955 A CN 03134955A CN 1217901 C CN1217901 C CN 1217901C
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Abstract
The present invention relates to a process for preparing mannitol in high yield using glucose as a raw material. A mannose-glucose mixture is obtained by the epimerization reaction of the glucose under an acid condition. Mannose-glucose separation is carried out by a simulated moving bed device. When separation temperature is from 40 to 85 DEG C, under the conditions that calcium type cation exchange resin is used as an adsorbing agent and water is used as an eluting agent, a constituent containing the glucose and a constituent containing the mannose can be continuously obtained. The epimerization reaction can be carried out for the constituent containing the glucose repeatedly, and the constituent containing the mannose can be generated into the mannitol by hydrogenation. The content of the mannitol in mixed alcohol after hydrogenation reaches more than 75%. A mannitol product is obtained after crystallization, centrifugation and drying. The yield of the mannitol is the 70% of the material input of the dry matters of the glucose.
Description
Technical field:
The invention belongs to the preparation field of organic compound.Especially a kind of is the technology of feedstock production N.F,USP MANNITOL with glucose.
Background technology:
N.F,USP MANNITOL is a kind of hydragog(ue) commonly used, dehydrant, also is one of a large amount of pharmaceutical preparations that use and transfusion medication, industrially also can be applicable to make sugar-free chewing gum, polyethers, explosive etc.
The preparation method of industrial N.F,USP MANNITOL has following several approach:
(1) sea-tangle extraction method: contain N.F,USP MANNITOL 5～10% in the dried sea-tangle, can extract with the method for physical crystal through after concentrating, N.F,USP MANNITOL that this method is produced of poor quality, sad filter, thermal source height, be unsuitable for pharmaceutically, and this method expends a large amount of steam, energy and manpower, the production cost height.
(2) electrolytic reduction: the mixture of glucose (or Nulomoline) reducible generation N.F,USP MANNITOL and sorbyl alcohol under electrolytic condition, again through crystallization extract and N.F,USP MANNITOL, this method long reaction time, efficient is low, the power consumption height, N.F,USP MANNITOL productive rate low (only reaching 15%) is eliminated already.
(3) be raw material with fructose: behind the fructose hydrogenation, get N.F,USP MANNITOL and sorbyl alcohol and respectively account for the mixed alcohol of half, can make N.F,USP MANNITOL through crystallization treatment, theoretical yield is 50%.But the price of fructose is higher, is not suitable for industrial production reality with pure fructose or high-purity fructose for raw material production N.F,USP MANNITOL.
(4) with the seminose be raw material: seminose can all transform generation N.F,USP MANNITOL through hydrogenation.But be a problem in the source of pure seminose, is not suitable for industrial production reality.
(5) be the synthesis method of raw material with sucrose: with sucrose hydrolysis, get fructose and glucose and respectively account for the Nulomoline of half, after handing over processing, carry out hydrogenation reaction, mannitol content is about 25% in the mixed alcohol of gained, and surplus is sorbyl alcohol.Through from hand over, concentrate, crystallization, centrifugation, drying can make the N.F,USP MANNITOL product, productive rate is about 19～20%.This method has in fact only been utilized the fructose component behind the sucrose hydrolysis, and the productive rate of gained N.F,USP MANNITOL is lower, and most product is the low sorbyl alcohol of value, and contained N.F,USP MANNITOL is about 8% in the sorbyl alcohol, and is second-rate.The industrial existing production of this method.
(6) with glucose be raw material: glucose is carried out epimerization change into seminose (transformation efficiency is generally 30%),, can obtain the N.F,USP MANNITOL product through crystallization with transforming the N.F,USP MANNITOL sorbitol mixture that back liquid glucose hydrogenation can obtain 30% left and right sides content.This method has industrial installation, but the yield of N.F,USP MANNITOL is not high, only reaches 24～26%.If the liquid glucose behind the epimerization is carried out the enzyme isomery with glucose isomerase again, to there be the conversion of glucose about 30% to generate fructose, like this, behind epimerization and enzyme isomery, containing seminose in the liquid glucose is 30～33%, contains fructose 28～30%, surplus is glucose, the mannitol content that mixes alcohol through gained behind the hydrogenation can reach about 42%, and the N.F,USP MANNITOL productive rate that crystallization is extracted is about 35%, and all the other are sorbyl alcohol.This with glucose be raw material improvement working system be main N.F,USP MANNITOL production method, abroad generally adopt.
Above-described various N.F,USP MANNITOL working system, the not possibility industrialization that has is the method for raw material with fructose or seminose for example; The current consumption that has, the consumption quantity of steam higher, the production cost height is eliminated, for example electrolytic reduction and sea-tangle extraction method; Though suitability for industrialized production that has and running, but the N.F,USP MANNITOL productive rate is lower, only reach 19～20% as sucrose hydrolysis technology hydrogenation method productive rate, the productive rate of glucose epimerization and enzyme isomery repeated hydrogenation technology only reaches 35%, all the other a large amount of by products are for being worth low, ropy sorbyl alcohol liquid product, and economic benefit has much room for improvement.
Summary of the invention:
The purpose of this invention is to provide a kind of can suitability for industrialized production, the productive rate that can make glucose feed produce N.F,USP MANNITOL raises significantly, the productive rate of the sorbyl alcohol byproduct that is produced reduces as far as possible, and improves a kind of production method of the economic benefit of glucose production N.F,USP MANNITOL greatly.
Method of the present invention mainly is divided into following four steps:
(1) is catalyzer with the molybdate, under acidic conditions, D/W carried out epimerization reaction, a part of conversion of glucose is become seminose; Again mixed solution is carried out cationic, anionic exchange resin and handle, obtain refining back liquid glucose from handing over;
(2) utilize simulation moving-bed device that (1) resulting mixed sugar liquid is separated, the component Y that obtains being rich in the component X of seminose and be rich in glucose;
(3) being rich in the glucose component gets back to and carries out epimerization reaction in (1) again; Be rich in the seminose component through positive and negative after handing over, carry out hydrogenation reaction, obtain being rich in the mixed solution of N.F,USP MANNITOL;
(4) the resulting mixed solution that is rich in N.F,USP MANNITOL is through from handing over, concentrate, obtaining the N.F,USP MANNITOL product after the crystallization, centrifugal, drying.
(1) step process of the present invention, be earlier glucose to be dissolved in the proper amount of deionized water, the concentration that makes liquid glucose is 40～60%, the molybdate catalyst (molybdate catalyst is generally selected Sodium orthomolybdate for use) that adds sugar substance amount 0.05～2%, add appropriate hydrochloric acid again, the pH value of liquid glucose is adjusted to 0.5～5, under 90～105 ℃ condition, reacted 0.5～5 hour then.The major influence factors of epimerization reaction respond temperature, pH value, add the consumption of molybdate and reaction times etc.In general, temperature of reaction is high more, the pH value is low more, the molybdate consumption is high more, the reaction times is long more, and resulting seminose transformation efficiency is high more, but the also corresponding increase of side reaction simultaneously, the color of liquid glucose is also darker.React according to above-described condition, resulting seminose transformation efficiency is 28～33%.Epimerized sugar liquid carries out handling from handing over Zeo-karb and anionite-exchange resin, obtains refining back liquid glucose.
(2) step process of the present invention, be to make with extra care the back liquid glucose to carry out seminose-glucose separation, select for use calcium type Zeo-karb, use water as eluent as sorbent material with simulation moving-bed device, separation temperature is 40～85 ℃, and input concentration is 40～70%.Continuously feeding, discharging operation through after the simulation moving-bed separation, can obtain being rich in seminose component X and be rich in glucose component Y.Used simulation moving-bed be that 12 posts or 24 posts are end to end, each post all is connected to opening for feed, discharge port, water-in, circulation import and export, change the position that each opening for feed, discharge port, water-in, circulation are imported and exported by rotary valve or magnetic valve form, reach isolating purpose.Through after the simulation moving-bed separation, the mannose content that obtains being rich in seminose component X is 75～90%, concentration 18～36%; The mannose content that is rich in glucose component Y is 2～8%, and concentration is 15～28%.
To be rich in glucose component Y and glucose feed and merge, recirculation is carried out isomerization reaction.
Be rich in seminose component X earlier through from handing over refining back end hydrogenation, under the effect of hydrogenation catalyst, be heated to 100～180 ℃, carried out hydrogenation reaction 1～3 hour with the hydrogen of 1～10Mpa.Behind the hydrogenation, the seminose component all changes into N.F,USP MANNITOL, and the glucose component all changes into sorbyl alcohol.Perhaps with after a part of epimerized sugar liquid mixes, again from the hydrogen that accompanies each other, these two kinds of approach can make content and reach 75%～85% mannitol solution, pass through after friendship, crystallization, centrifugal, drying again, can obtain the N.F,USP MANNITOL product.
Through after the simulation moving-bed separating treatment, the resulting mannose content that is rich in the seminose component is 75～90% among the present invention, and concentration is 18～36%; The mannose content that is rich in the glucose component is 2～8%, and concentration is 15～28%.Behind hydrogenation, can generate the very high mannitol solution of content.Because mannitol content surpasses mixed alcohol 85% or more in friendship, course of conveying, particularly very easily crystallization in the low environment of winter temperature, therefore the result in blockage trouble of equipment and pipeline there is no need to regulate the mannose content before the hydrogenation too high, only need reach 75～85% and get final product.When the mannose content in being rich in the seminose component is higher than 85%, can mix, mannose content before the hydrogenation be guaranteed be 75～85% to get final product with a part of epimerized sugar liquid.Blending means as example 3.
Use method of the present invention, can make most conversion of glucose generate seminose, repeated hydrogenation generates N.F,USP MANNITOL, and the sorbyl alcohol byproduct of gained seldom.Key of the present invention is to have adopted simulated moving bed technology to separate seminose glucose, and the resulting seminose component that is rich in carries out hydrogenation generation N.F,USP MANNITOL, and the resulting glucose component that is rich in repeats epimerization reaction.
Use method of the present invention, resulting N.F,USP MANNITOL productive rate is 70% of a glucose charging capacity (dry meter).
Advantage of the present invention is as follows: with liquid glucose behind simulation moving-bed (12 posts or 24 posts) tripping device continuity ground separating isomerism, the resulting seminose component (mannose content is about 75%) that is rich in carries out hydrogenation reaction, but high yield generates N.F,USP MANNITOL, resultingly is rich in the utilization of glucose component recirculation.The production that can make the high yield of glucose prepare N.F,USP MANNITOL with method of the present invention becomes industry reality.The productive rate of resulting low-value product sorbyl alcohol is very low, only reaches 30%.Therefore, the present invention has improved the productive rate that glucose hydrogenation prepares N.F,USP MANNITOL greatly.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Describe the present invention in detail below in conjunction with drawings and Examples.
Embodiment:
Embodiment 1:
The oral crystalline dextrose of 1100 grams (contains 1 crystal water molecule, the actual glucose amount of dry matter is 1000 grams) be dissolved in the 900ml deionized water, be mixed with B * 50.30% D/W, add 1.5 gram Sodium orthomolybdates, after the stirring and dissolving, the pH value of regulating liquid glucose with hydrochloric acid is 3.85 again, heats then and keeps under 100 ℃ of conditions stirring reaction 2 hours.Behind cationic, anionic exchange resin deionizing impurity, obtain epimerized sugar liquid, composed as follows: seminose 30.4%, glucose 69.6%.
Utilizing simulation moving-bed device to carry out seminose-glucose separates, separation temperature is 58 ℃, with calcium type Zeo-karb is sorbent material, water is eluent, can obtain being rich in the seminose component continuously and be rich in the glucose component, will be rich in glucose component recirculation and carry out epimerization reaction; To be rich in the seminose component after handing over processing, the resulting seminose component concentration that is rich in is 34%, and mannose content is 75.2%; The resulting glucose component concentration that is rich in is 24%, and mannose content is 3.85%.
Get the liquid glucose volume 2500ml that is rich in the seminose component, add 80 gram Raney's nickels, in the high-pressure hydrogenation still, at the 7Mpa pressure condition, be warmed up to 165 ℃ and carried out hydrogenation reaction 2 hours, obtain mixing alcohol behind the hydrogenation, wherein contain N.F,USP MANNITOL 75%, after removing nickel catalyzator after filtration, after handling with the positive and negative ion-exchange resins again, cooling, crystallization treatment, after passing through centrifugation, drying again, obtain the N.F,USP MANNITOL product, add up to 718 grams.The N.F,USP MANNITOL productive rate counts 71.8% by glucose dry-matter charging capacity.
Embodiment 2:
Epimerization reaction is through resulting epimerized sugar liquid 5320 grams after handing over, and concentration is 50%, and its chemical constitution is as follows: seminose 310 grams, account for 30.45%, and glucose 1850 grams account for 69.55%.Utilize simulation moving-bed device to carry out the separation of seminose-glucose, input concentration is 50%, under 57 ℃ separation temperature, with calcium type Zeo-karb as sorbent material, water is eluent, after the simulation moving-bed device separation of 12 posts, obtain being rich in seminose component 2900 grams, concentration is 32.07%, wherein seminose 700 restrains, glucose 230 grams, the content of seminose is 75.27%, can carry out hydrogenation and produce N.F,USP MANNITOL; Be rich in glucose component 7680 grams, concentration is 22.53%, and wherein seminose 110 restrains, glucose 1620 grams, and mannose content is 6.36%.
Be rich in adding oral glucose 1020 grams in the glucose component toward above-mentioned 7680 grams, being mixed with 8700 gram concentration is 30.5% liquid glucose, being concentrated in vacuo to concentration is 50%, add 3 gram Sodium orthomolybdate catalyzer, regulating liquid glucose pH with hydrochloric acid is 3.5, and heating and reaction 2 hours under 100 ℃ of conditions then removed ion in the liquid glucose with cationic, anionic exchange resin again, obtain epimerized sugar liquid, the mannose content in the epimerized sugar liquid is 30.66% by analysis.
Embodiment 3:
Epimerized sugar liquid through the simulation moving-bed separation of 24 posts after, the resulting mannose content that is rich in the seminose component is 88.8%, concentration is 33.66%, mix with liquid glucose behind a part of epimerization, being adjusted to the mannose content that mixes the back liquid glucose is 75.63%, produces N.F,USP MANNITOL through carry out hydrogenation reaction after handing over.
Be allotment blended example below:
| Material | Be rich in the seminose component | Epimerized sugar liquid | Both mix the back liquid glucose |
| Mannose content | 88.80％ | 30.0％ | 75.63％ |
| Concentration | 33.66％ | 50.0％ | 36.35％ |
| The volume number | 1000ml | 180ml | 1180ml |
Simulation moving-bedly separate that the back is resulting is rich in mannose content in the seminose component when too high, can be by the way of example 3, to be rich in the seminose component and mix with a part of epimerized sugar liquid, the mannose content of liquid glucose is 75.63% after obtaining mixing, and can guarantee the hydrogenation requirement.
Claims (5)
1, a kind of N.F,USP MANNITOL preparation technology is characterized in that:
1. D/W is carried out epimerization reaction, a part of conversion of glucose is become seminose;
2. utilize simulation moving-bed device 1. resulting mixed sugar liquid separate the component that obtains being rich in the component of glucose and be rich in seminose;
3. be rich in the glucose component and carry out epimerization reaction again in getting back to 1.; Be rich in the seminose component obtains being rich in N.F,USP MANNITOL behind hydrogenation mixed solution;
4. the resulting mixed solution that is rich in N.F,USP MANNITOL is through from handing over, concentrate, obtaining the N.F,USP MANNITOL product after the crystallization, centrifugal, drying.
2, N.F,USP MANNITOL preparation technology according to claim 1, it is characterized in that: glucose feed is to carry out epimerization reaction under the following conditions to generate seminose: sugar concentration is 40～60%, 90～105 ℃ of temperature of reaction, add molybdate catalyst by 0.05～2% of glucose substance amount, regulating liquid glucose pH value with hydrochloric acid is 0.5～5,0.5～5 hour reaction times.
3, N.F,USP MANNITOL preparation technology according to claim 1, it is characterized in that: described simulation moving-bed be 12 posts or 24 column devices, input concentration is 40～70%, separation temperature is 40～85 ℃, with calcium type Zeo-karb is sorbent material, with water is eluent, and continuously feeding, discharging operation obtain being rich in the seminose component and be rich in the glucose component.
4, N.F,USP MANNITOL preparation technology according to claim 1, it is characterized in that: the resulting seminose component warp that is rich in is from handing over back end hydrogenation, perhaps with after a part of epimerized sugar liquid mixes, again from the hydrogen that accompanies each other, these two kinds of approach all make the mannitol solution of content 75～85%.
5, N.F,USP MANNITOL preparation technology according to claim 1 is characterized in that: epimerized sugar liquid is after simulation moving-bed separation, and the resulting mannose content that is rich in the seminose component is 75～90%, and concentration is 18～36%; The mannose content that is rich in the glucose component is 2～8%, and concentration is 15～28%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134955 CN1217901C (en) | 2003-09-28 | 2003-09-28 | High-yield manna sugar preparation process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03134955 CN1217901C (en) | 2003-09-28 | 2003-09-28 | High-yield manna sugar preparation process |
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| CN1528728A CN1528728A (en) | 2004-09-15 |
| CN1217901C true CN1217901C (en) | 2005-09-07 |
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| CN 03134955 Expired - Fee Related CN1217901C (en) | 2003-09-28 | 2003-09-28 | High-yield manna sugar preparation process |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215580B (en) * | 2007-12-26 | 2012-03-21 | 广西南宁化学制药有限责任公司 | Method for preparing D-mannitol from konjak refined powder |
| CN101851689B (en) * | 2010-06-11 | 2012-01-11 | 谭卫星 | Preparation process of D-mannose |
| CN106032386B (en) * | 2015-03-16 | 2019-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of catalysis conversion method of aldehyde ketone sugar |
| CN105906475A (en) * | 2016-05-09 | 2016-08-31 | 河北乐开节能科技股份有限公司 | Production method and production device of crystal mannite |
| CN113274362A (en) * | 2021-03-31 | 2021-08-20 | 海南通用康力制药有限公司 | Method for producing entacapone tablets |
| CN114436768A (en) * | 2021-12-28 | 2022-05-06 | 广东焕发药业有限公司 | Method for recovering sorbitol and mannitol from mannitol mother liquor |
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