CN101029059A - Preparation of dulcose crystal - Google Patents
Preparation of dulcose crystal Download PDFInfo
- Publication number
- CN101029059A CN101029059A CN 200610042443 CN200610042443A CN101029059A CN 101029059 A CN101029059 A CN 101029059A CN 200610042443 CN200610042443 CN 200610042443 CN 200610042443 A CN200610042443 A CN 200610042443A CN 101029059 A CN101029059 A CN 101029059A
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- dulcose
- preparation
- melampyrin
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
A process for preparing dulcitol crystal from the mother liquod of xylose includes such steps as decoloring, ion exchanging, preparing eluting agent, using the simulative moving-bed equipment to separate said mother liquid to become the liquid mixture of galactose and arabinose, hydrogenating for converting the galactose to dulcitol and arabinose to arabic alcohol, decoloring, ion exchange, concentrating, centrifugal separation and drying.
Description
Technical field:
The present invention relates to biological technical field, is that a kind of polyvalent alcohol is the preparation method of dulcose crystal.
Background technology:
Melampyrin claims melampyrum, sweet and pure again, is colourless monocline column crystalline powder, and it is little sweet to distinguish the flavor of, be insoluble in cold water and alcohol, dissolve in boiling water, belong to biochemical reagents, being mainly used in bacterium discriminating, culture medium prescription etc., is that requisite important carbohydrate is treated in microbe research, diseases prevention.At occurring in nature, it mainly is present in the certain plants of defending Mao Ke plant and mountain trailing plants Pittosporum, because its content is very low, and usually mixes with other material, so the production of melampyrin is very difficult with preparation, market value is very high.
Xylose mother liquid is to be the byproduct that obtains behind the raw material production crystal wood sugar with the corn cob, it contains multiple components such as wood sugar, pectinose, glucose and semi-lactosi, because the content that its various components that contain have is low especially, has plenty of isomers, so be difficult to the crystallization utilization, also be difficult to separate with general method.At present, it can only be used to make caramel colorant as byproduct, and marketable value is very low.
Summary of the invention:
The objective of the invention is to adopt chromatographic separation technology, the semi-lactosi in the xylose mother liquid is separated, prepare dulcose crystal through operations such as hydrogenation, crystallizations then, reach the purpose that improves the xylose mother liquid utility value.
The present invention is achieved in that a kind of preparation method of dulcose crystal, is finished by following method:
(1) get concentration be the xylose mother liquid thin up of 50-70% to 20-40%, decolour, ion-exchange, change in the head tank.
(2) water configuration eluent changes in the eluent jar.
(3) in simulation moving-bed equipment, fill separating agent, and this system is constant at suitable separation temperature scope at 20-60 ℃ with thermostatic control system, with feedstock pump and eluent pump respectively the xylose mother liquid through purifying and the eluent that configures by deoxygenation and microfiltration equipment after, and then be injected into the different sites of chromatographic column by simulation moving-bed rotary distributor, adsorb repeatedly continuously, separate, after separating purification, the mixed solution of the mixed solution of semi-lactosi and pectinose and wood sugar and glucose flows out by rotary distributor continuously from the different sites of chromatographic column respectively, in separating finished product storage tank and separating the byproduct storage tank.
(4) semi-lactosi in the separation finished product storage tank and the mixed solution of pectinose are concentrated, when concentration is 15-35%, the pH value of regulator solution is 7.5～8.0, controlled temperature is 100～180 ℃, and pressure is 8.0～15.0MPa, and mixing speed is 200～700 rev/mins, with radium niobium nickel is that catalyzer carries out hydrogenation reaction, make the semi-lactosi in the mixed solution be converted into melampyrin, pectinose is converted into arabitol, obtains the mixed solution of melampyrin and arabitol.
(5) mixed solution to melampyrin and arabitol decolour, after the ion-exchange, evaporation concentration imports in the crystallizer and carries out decrease temperature crystalline during to 30-45%, makes it to separate out the melampyrin crystal.
(6) through operations such as centrifugal, dryings, obtain the melampyrin crystal product.
Above-mentioned water is deionized water.
Preferably being constant at suitable separation temperature scope is 40-50 ℃.
The concentration range of preferred xylose mother liquid is 25-40%.
Above-mentioned simulation moving-bed be the simulation moving-bed equipment of 12 posts.
Above-mentioned used separating agent is a chlorine type basic anion chromatographic separation resin.
1: 1 proportioning mixed solution of sodium hydroxide that above-mentioned used eluent is 0.1mol/l and the sodium-chlor of 0.02mol/l.
Optimised process step of the present invention describes in detail:
(1) be that the xylose mother liquid of 50-70% adds deionized water and is diluted to about 20-40% with concentration, the 1-9% that presses dry matter content adds Powdered Activated Carbon, controlled temperature is 50-90 ℃, mixing speed is 100-500 rev/min, after insulated and stirred 20-60 minute, filter, obtain the destainer of xylose mother liquid, this destainer transparence is more than 90%.Then this destainer through the cloudy exchange column that the D301 resin being housed respectively, the positive exchange column of 001 * 7 resin and the cloudy exchange column that the D296 resin is housed, carry out ion-exchange, to remove the various foreign ions that contain in the xylose mother liquid, xylose mother liquid after ion-exchange requires specific conductivity less than 5us/cm, transparence is greater than 99%, otherwise, can be too much because of the foreign ion that contains in the xylose mother liquid, during through the chromatographic separation resin, make the rapid inactivation of resin, influence the exchange absorption property of resin, cause resolution to reduce, standby in incoming stock then jar, through the xylose mother liquid of handling like this, concentration is about 30%, and specific conductivity is less than 5us/cm, transparence is greater than 99%, galactose content is about 22%, and pectinose content is about 7%, and wood sugar content is about 56%, glucose content is about 6%, and other material accounts for about 9%.
(2) with 1: 1 proportioning mixed solution of the Na CL of the NaOH of deionized water configuration irrigation 0.1mol/l and 0.02mol/l, in this technological operation, we select for use 1: 1 proportioning mixed solution of NaCL of the NaOH of 0.1mol/l and 0.02mol/l as the irrigation to chlorine type basic anion chromatographic separation resin, and its separating effect is best after testing.We also once used the NaOH of deionized water, 0.1mol/l, the NaCL of 0.02mol/l to do irrigation, and its separating effect is not fine, and resolution is lower.Have only 1: 1 proportioning mixed solution of NaCL of the NaOH of 0.1mol/l and 0.02mol/l the highest to the various sugared resolution in the xylose mother liquid, separating effect is best, this is because minor N aOH can replenish the hydroxyl of resin surface owing to other negatively charged ion that is existed in the water replaces the loss that causes, can improve separation efficiency, NaCL then can shorten the residence time of feed liquid in resin, cause the separation efficiency height, resolution increases.
(3) with feedstock pump and eluent pump respectively 1: 1 proportioning mixed solution of the NaCL of the NaOH of raw material xylose mother liquid of having handled well and eluent 0.1mol/l and 0.02mol/l by deoxygenation and microfiltration equipment after, and then be injected in the simulation moving-bed equipment that fills chlorine type basic anion chromatographic separation resin, by the control separation temperature, charging and discharging flow, circular flow, pulling parameters such as valve time makes the various sugar in the xylose mother liquid obtain good separation, last xylose mother liquid is separated into the mixed solution of semi-lactosi and pectinose, mixed solution two portions of wood sugar and glucose, and flow out continuously by rotary distributor at the different sites of chromatographic column, in separating finished product storage tank and separating the byproduct storage tank.In separating finished product storage tank, be mainly the mixed solution of semi-lactosi and pectinose, in separating the byproduct storage tank, be mainly the mixed solution of wood sugar and glucose.
In chromatographic separation process; 1: 1 proportioning mixed solution of the NaOH of raw material xylose mother liquid and eluent 0.1mol/l and the NaCL of 0.02mol/l must be by deoxygenation and microfiltration equipment; to remove oxygen and mechanical impurity wherein; its objective is protection chromatogram separation resin, prolong the work-ing life of separation resin.
In chromatographic separation process, selected resin is a chlorine type basic anion chromatographic separation resin, this resin has special effect to the separation of monose, it can distribute monose such as the semi-lactosi in the xylose mother liquid, pectinose, wood sugar and glucose, be adsorbed on the different sites of chromatographic column, form with single component or two-pack flows out respectively then, separates the purpose of purifying to reach.
In chromatographic separation process, the height of temperature directly has influence on isolating effect, the temperature height, and monose can decompose on hydroxyl surface, causes its rate of recovery to reduce, and resolution reduces; Temperature is low, and the various monose in the xylose mother liquid can not get separating, and inseparable at all, separation temperature scope suitable among the present invention is at 20-60 ℃, and the preferable separation temperature is 40-50 ℃.
In chromatographic separation process, the concentration of xylose mother liquid is 20-40%, excessive concentration can increase the viscosity of feed liquid, and the segregational load of separation resin is increased, surpassed its ability to bear, cause resolution to reduce, concentration is low excessively, then influences production efficiency, move uneconomically, preferred concentration range is 25-35%.
In chromatographic separation process, selected equipment is the simulation moving-bed of 12 posts, it comprises facilities such as rotary distributor, 12 root chromatogram columns, time controlled system, flux monitoring system, temperature controlling system, pressure automatic control system, has realized automatic control, self-regulating DCS time variable control fully.
Xylose mother liquid is after above-mentioned steps is separated, and the separation finished product mixed liquid concentration of gained is between 3-10%, and wherein galactose content accounts for 30-60%, and pectinose content accounts for 25-40%; Separate the byproduct mixed liquid concentration between 10-30%, wherein wood sugar content accounts for 60-90%, and glucose content accounts for 5-20%.
When (4) the above-mentioned separation finished product mixed solution that obtains being concentrated into concentration and being 25% left and right sides with the thin plate vaporizer, the pH value of the Na OH regulator solution with 30% is 7.5～8.0, squeeze in the autoclave, press 2～5% of dry matter content and add radium niobium nickel catalyzator, 100～180 ℃ of controlled temperature, pressure 8.0～15.0MPa, 200～700 rev/mins of mixing speed, carry out hydrogenation, make the semi-lactosi in the mixed solution be converted into melampyrin, pectinose is converted into arabitol, obtain the mixed solution of melampyrin and arabitol, the concentration of this solution is 22-26%, melampyrin ingredients constitute 30-60% wherein, arabitol ingredients constitute 25-40%.
(5) with above-mentioned melampyrin and arabitol mixed solution, method according to the first step is decoloured, ion-exchange, import in the crystallizer when being concentrated into finite concentration with triple-effect evaporator then and carry out decrease temperature crystalline, make it to separate out the melampyrin crystal, here the concentration of alcohol mixture liquid can not be steamed too highly, otherwise can separate out prematurely because the solubleness of melampyrin in water is very low, and not have the crystalline purpose, the concentration of preferably evaporating pure cream is 30-45%.
(6) the melampyrin alcohol cream of advantages of good crystallization is put into whizzer, rely on centrifugal force that wherein arabitol and other fusel are separated with melampyrin, reach the purpose of purification melampyrin, and then the drying operation, the melampyrin crystal product can be obtained.
Advantage of the present invention is: the mother liquor of producing the wood sugar generation of making has on the one hand obtained utilizing again as waste, has promptly improved the utility value of xylose mother liquid, for enterprise has created remarkable economic efficiency; Adopt chromatographic separation technology to separate four kinds of components simultaneously on the other hand the scientific-technical progress of industry is had far-reaching social effect.
Embodiment
With specific embodiment the present invention is further described below:
Embodiment 1: get concentration and be 65% xylose mother liquid 60kg, add deionized water 58kg and dilute, make concentration and be 33% xylose mother liquid 118kg, press 5% of dry matter content then and add Powdered Activated Carbon 1.95kg, regulating agitator speed is 300 rev/mins, and under 80 ℃ of temperature, insulated and stirred is after 40 minutes, filter, obtain the destainer of xylose mother liquid, index is: refractive power concentration 33%, transparence 93%, total acid 0.0098%, mineral acid 0.0049%; This destainer is carried out ion-exchange through cloudy (D301 resin) → sun (001 * 7 resin) → cloudy (D296 resin) exchange column, the xylose mother liquid that is purified, index is: refractive power concentration 30%, transparence 100%, total acid 0.00245%, mineral acid 0, specific conductivity 2us/cm, galactose content are 22.03%, and pectinose content is 6.97%, wood sugar content is 55.98%, and glucose content is 6.21%.
12 root chromatogram columns of simulation moving-bed equipment are filled chlorine type basic anion chromatographic separation resin, under temperature controlling system, make this system be constant at 45 ℃, with feedstock pump and eluent pump respectively 1: 1 proportioning mixed solution of the NaCL of the NaOH of standby raw material xylose mother liquid and eluent 0.1mol/l and 0.02mol/l by deoxygenation and microfiltration equipment after, and then be injected in the chromatographic column, the control feed rate is 1.2l/h, advancing the eluent flow is 3.4l/h, separating the finished product flow is 0.9l/h, separating the byproduct flow is 2.4l/h, circular flow is 8l/h, pulling the valve time is 560-580 second, xylose mother liquid repeated multiple times ground in simulated moving bed system is separated, wash-out, semi-lactosi and the pectinose mixed liquid concentration collected after separating are 5.8%, obtain 78.95kg altogether and separate the finished product mixed solution, and separation yield is 13.04%, wherein semi-lactosi accounts for 53.4%, pectinose accounts for 34.3%, and wood sugar accounts for 2.1%, and glucose accounts for 5.4%.
It is 25% that the separation finished product mixed solution that obtains is concentrated into concentration, after the NaOH adjusting pH value with 30% is 7.7, joins in the autoclave, press 4% of dry matter weight and add radium niobium nickel catalyzator 180g, be heated to 115 ℃, control pressure is 10.0MPa, mixing speed is 450 rev/mins, carry out hydrogenation, hydrogenation finished in about 2.5 hours, and sampling detects with gas chromatograph, melampyrin ingredients constitute 50.8%, arabitol ingredients constitute 31.97%, Xylitol ingredients constitute 1.8%, sorbyl alcohol ingredients constitute 5%.Refractive power concentration is 24%.
With above-mentioned hydride decolour, ion-exchange, being concentrated into concentration with triple-effect evaporator is 35%, import in the crystallizer and carry out decrease temperature crystalline, put into whizzer after finishing, the adjusting centrifugal rotational speed is 4080 rev/mins and carries out centrifugal, 70 ℃ of following vacuum-dryings, obtain 3.45kg melampyrin crystal at last, crystallization yield is 27.2%.
Claims (7)
1, a kind of preparation method of dulcose crystal is characterized in that being finished by following method:
(1) get concentration be the xylose mother liquid thin up of 50-70% to 20-40%, decolour, ion-exchange, change in the head tank.
(2) water configuration eluent changes in the eluent jar.
(3) in simulation moving-bed equipment, fill separating agent, and this system is constant at suitable separation temperature scope at 20-60 ℃ with thermostatic control system, with feedstock pump and eluent pump respectively the xylose mother liquid through purifying and the eluent that configures by deoxygenation and microfiltration equipment after, and then be injected into the different sites of chromatographic column by simulation moving-bed rotary distributor, adsorb repeatedly continuously, separate, after separating purification, the mixed solution of the mixed solution of semi-lactosi and pectinose and wood sugar and glucose flows out by rotary distributor continuously from the different sites of chromatographic column respectively, in separating finished product storage tank and separating the byproduct storage tank.
(4) semi-lactosi in the separation finished product storage tank and the mixed solution of pectinose are concentrated, when concentration is 15-35%, the pH value of regulator solution is 7.5～8.0, controlled temperature is 100～180 ℃, and pressure is 8.0～15.0MPa, and mixing speed is 200～700 rev/mins, with radium niobium nickel is that catalyzer carries out hydrogenation reaction, make the semi-lactosi in the mixed solution be converted into melampyrin, pectinose is converted into arabitol, obtains the mixed solution of melampyrin and arabitol.
(5) mixed solution to melampyrin and arabitol decolour, after the ion-exchange, evaporation concentration imports in the crystallizer and carries out decrease temperature crystalline during to 30-45%, makes it to separate out the melampyrin crystal.
(6) through operations such as centrifugal, dryings, obtain the melampyrin crystal product.
2, the preparation method of a kind of dulcose crystal according to claim 1 is characterized in that described water is deionized water.
3, the preparation method of a kind of dulcose crystal according to claim 1, it is characterized in that preferably being constant at suitable separation temperature scope is 40-50 ℃.
4, the preparation method of a kind of dulcose crystal according to claim 1, the concentration range that it is characterized in that preferred xylose mother liquid is 25-40%.
5, the preparation method of a kind of dulcose crystal according to claim 1, it is characterized in that described simulation moving-bed be the simulation moving-bed equipment of 12 posts.
6, the preparation method of a kind of dulcose crystal according to claim 1 is characterized in that used separating agent is a chlorine type basic anion chromatographic separation resin.
7, the preparation method of a kind of dulcose crystal according to claim 1 is characterized in that used eluent is 1: 1 proportioning mixed solution of the sodium-chlor of the sodium hydroxide of 0.1mol/l and 0.02mol/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100424432A CN100534996C (en) | 2006-02-28 | 2006-02-28 | Preparation of dulcose crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100424432A CN100534996C (en) | 2006-02-28 | 2006-02-28 | Preparation of dulcose crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101029059A true CN101029059A (en) | 2007-09-05 |
| CN100534996C CN100534996C (en) | 2009-09-02 |
Family
ID=38714627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100424432A Expired - Fee Related CN100534996C (en) | 2006-02-28 | 2006-02-28 | Preparation of dulcose crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100534996C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226223A (en) * | 2011-03-29 | 2011-10-26 | 河南永昌飞天淀粉糖有限公司 | Novel starch sugar mother liquor pretreatment technology |
| CN101502308B (en) * | 2009-02-20 | 2011-11-30 | 山东福田药业有限公司 | Method for preparing L-arabinose |
| CN102295528A (en) * | 2010-06-22 | 2011-12-28 | 天津市金圭谷木糖醇有限公司 | Method for extracting dulcite from xylitol mother liquid |
| CN107954836A (en) * | 2017-11-17 | 2018-04-24 | 山东福田药业有限公司 | A kind of method that melampyrin is extracted from Xylitol mother liquor |
-
2006
- 2006-02-28 CN CNB2006100424432A patent/CN100534996C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502308B (en) * | 2009-02-20 | 2011-11-30 | 山东福田药业有限公司 | Method for preparing L-arabinose |
| CN102295528A (en) * | 2010-06-22 | 2011-12-28 | 天津市金圭谷木糖醇有限公司 | Method for extracting dulcite from xylitol mother liquid |
| CN102226223A (en) * | 2011-03-29 | 2011-10-26 | 河南永昌飞天淀粉糖有限公司 | Novel starch sugar mother liquor pretreatment technology |
| CN102226223B (en) * | 2011-03-29 | 2013-07-10 | 河南飞天农业开发股份有限公司 | Novel starch sugar mother liquor pretreatment technology |
| CN107954836A (en) * | 2017-11-17 | 2018-04-24 | 山东福田药业有限公司 | A kind of method that melampyrin is extracted from Xylitol mother liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100534996C (en) | 2009-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109503676B (en) | Method for preparing xylitol and mixed syrup from xylose mother liquor | |
| CN101565762B (en) | Production process for starch sugar | |
| CN101497904B (en) | Method for producing xylitol and arabinose at the same time | |
| CN102912043B (en) | Method for producing purified fructose | |
| JP2008506370A (en) | Method for obtaining a sugar product stream from cellulosic biomass | |
| WO2018105934A2 (en) | Method for efficient production of psicose | |
| PL111348B1 (en) | Method for manufacturing crystalline xylitol | |
| CN111747997B (en) | Method for simultaneously preparing xylose, arabinose and galactose by using intermittent simulated moving bed chromatography | |
| CN103113422B (en) | Method for separating and refining high-purity L-arabinose and D-xylose with simulated moving bed | |
| WO2018105933A1 (en) | Method for producing psicose | |
| CN103981241A (en) | Method for preparing high fructose corn syrup from crystallized sugar mother solution as raw material | |
| WO2014025560A1 (en) | Mannose production from palm kernel meal using simulated moving bed separation | |
| CN107058428B (en) | Fructose and maltose online production process | |
| MX2013003870A (en) | Method for manufacturing high-purity sorbitol syrups from sucrose and uses thereof. | |
| CN100534996C (en) | Preparation of dulcose crystal | |
| CN112708702A (en) | Method for producing plant source D-tagatose | |
| CN114671919B (en) | Method for producing crystalline psicose based on chromatographic separation | |
| CN103409315A (en) | Reaction separating and coupling apparatus, and technology for preparation of gluconic acid from xylitol crystallization mother liquor | |
| CN101497903B (en) | Method for selectively converting and shunting biological products | |
| JP2024507212A (en) | Xylitol/caramel color co-production system and method using xylose mother liquor | |
| CN101554540B (en) | Method for separating glucose, seminose and oligosaccharide by simulated moving bed | |
| CN100347310C (en) | Process for producing nucleotide by enzyme method | |
| CN102102116B (en) | Method for preparing high-purity crystalline dextrose from maize peel acid hydrolysis residues | |
| CN1328386C (en) | Method for preparing mannitol from raw material of cane sugar | |
| CN1219782C (en) | Cane sugar material high-yield joint production process of crystalline fructose and manna sugar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090902 Termination date: 20120228 |