CN114276389B - Method and system for purifying xylose by valve array type continuous chromatography - Google Patents

Method and system for purifying xylose by valve array type continuous chromatography Download PDF

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CN114276389B
CN114276389B CN202111350061.7A CN202111350061A CN114276389B CN 114276389 B CN114276389 B CN 114276389B CN 202111350061 A CN202111350061 A CN 202111350061A CN 114276389 B CN114276389 B CN 114276389B
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chromatographic column
xylose
set position
columns
position chromatographic
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CN114276389A (en
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唐海静
王圣昶
霍洋
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Oushangyuan Intelligent Equipment Co ltd
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Abstract

The invention provides a method and a system for purifying xylose by valve array type continuous chromatography, wherein the purifying method comprises the following steps: the xylose mixed solution is continuously added into a first set position chromatographic column of a plurality of chromatographic columns connected in series, raffinate is continuously extracted from a second set position chromatographic column, eluent is continuously added into a third set position chromatographic column, extracting solution is continuously extracted from the third set position chromatographic column, the rest of the solution is added into the first set position chromatographic column together with the xylose mixed solution after passing through the rest of the chromatographic columns, according to the flowing direction of the xylose mixed solution, the distance between the third set position chromatographic column and the first set position chromatographic column is larger than the distance between the second set position chromatographic column and the first set position chromatographic column, the chromatographic columns are sequentially switched at set interval time, and the switching direction is opposite to the flowing direction of the xylose mixed solution. The method can well separate xylose from impurities, reduce the conductivity of the xylose solution by about 95%, and improve the light transmittance by more than 50%. The invention is characterized by continuous feeding, eluting and collecting, and easy operation.

Description

Method and system for purifying xylose by valve array type continuous chromatography
Technical Field
The invention relates to a xylose processing technology, in particular to a method and a system for purifying xylose by valve array type continuous chromatography.
Background
Xylose is pentose with molecular formula of C 5 H 10 O 5 The crystal is in a fine needle shape, the appearance is white and fine crystal or powder, the sweet taste is equivalent to 0.7 of the sweetness of the sucrose; the melting point is 153-154 ℃. At present, corncob and viscose fiber are mainly used for squeezing alkali liquor to prepare xylose as raw materials in China.
The production process of xylose mainly uses chemical method, and utilizes acid to make poly-pentosan hydrolysis to obtain xylose mixed liquor, then adopts the processes of decoloring, ion-exchange or electrodialysis, evaporation concentration and crystallization separation so as to obtain the xylose finished product. As a certain amount of acid is needed to be added as a catalyst for xylose hydrolysis, the pH value of the xylose mixed solution obtained after hydrolysis is lower, the conductivity is higher, and the color is darker.
The salt and pigment of the hydrolysate are removed in the traditional process, a large amount of activated carbon is required to be used for decoloring, then acid and salt are removed for a plurality of times through the ion exchange process, and chemicals such as acid and alkali are required to be used in the ion exchange regeneration, so that the consumption is high, a large amount of wastewater is generated, and the pollution is serious.
Disclosure of Invention
In order to reduce the pollution problem in xylose processing, the invention adopts a valve array type continuous chromatographic separation system to decolorize and desalt xylose mixed solution, thereby reducing a great amount of sewage discharge.
The technical scheme of the invention is as follows: a method for purifying xylose by valve array continuous chromatography includes such steps as continuously adding xylose mixture to the first set-position chromatographic columns of multiple serially connected chromatographic columns, continuously extracting raffinate from the second set-position chromatographic columns, continuously adding eluent to the third set-position chromatographic columns, continuously extracting extract from the third set-position chromatographic columns, passing the rest of chromatographic columns, adding the rest of liquid to the first set-position chromatographic columns together with xylose mixture, and sequentially switching the chromatographic columns at intervals. The rest liquid passing through the third set chromatographic column passes through the rest chromatographic columns and is mixed with xylose mixed solution to be added into the first set chromatographic column to form circulation. The chromatographic column is switched by opening and closing the valve. Since the xylose and impurities in the xylose mixture differ in flow rate in the chromatographic resin with the liquid carrier, an extract and a raffinate can be obtained at the outlet of a specific chromatographic column. The extracting solution is xylose solution, and the raffinate is rich in salt and pigment.
The chromatographic column adopts macroporous strong acid cation separation resin.
The particle size of the resin is 0.20-0.35mm.
The xylose mixed solution is prepared by hydrolyzing corncob with acid, adjusting pH value with lime, filtering to obtain xylose filtrate, and evaporating and concentrating the xylose filtrate.
The eluent is water, preferably deionized water, more preferably evaporative condensate or steam condensate.
The feed liquid ratio is 1:1.2-2. The feed-to-liquid ratio refers to the ratio of the added xylose mixture to the eluent.
The flow rate of the eluent is 1m/h-3m/h.
And adding sulfuric acid to the corncob for hydrolysis.
The conductivity of the xylose mixture is preferably 30000. Mu.m/cm or less, more preferably 20000. Mu.m/cm or less, still more preferably 10000. Mu.m/cm or less.
The dry matter content in the extract is 1-40wt%. The dry matter is mainly xylose.
The dry solids (dry matter) content of the xylose mixture is 1-70wt%. The dry solids (dry matter) include xylose and a portion of the impurities.
The extract is evaporated and/or membrane concentrated to obtain xylose.
The raffinate is subjected to evaporation and/or membrane concentration treatment to obtain xylose byproducts.
The temperature of the xylose mixture is 0-100 ℃, preferably 20-80 ℃.
The temperature of the eluent is 0-100deg.C, preferably 20-80deg.C.
The invention provides a system for purifying xylose by valve array type continuous chromatography, which comprises a plurality of chromatographic columns which are arranged in series and connected end to end, wherein the system comprises
A first set-position chromatographic column, wherein xylose mixed liquor continuously enters from the first set-position chromatographic column;
a second set-point chromatographic column, the raffinate being continuously withdrawn from an outlet of the second set-point chromatographic column;
a third setting chromatographic column, eluent continuously enters from the third setting chromatographic column, and extracting solution is continuously extracted from an outlet of the third setting chromatographic column;
the third set point chromatographic column is positioned downstream of the second set point chromatographic column in the xylose mixture flow direction.
The chromatographic columns are sequentially switched at set interval time, and the switching direction is opposite to the flowing direction of the xylose mixture. The chromatographic column is switched by the valve.
The number of the chromatographic columns is 36 columns or less, preferably 30 columns, 24 columns, 20 columns, 16 columns, 12 columns or 8 columns.
The chromatographic column adopts macroporous strong acid cation separation resin.
The particle size of the resin is 0.20-0.35mm. The particle size of the resin has key influence on separation, the particle size is large, the separation and uniform distribution of feed liquid in the column are not facilitated, the separation purity is low, the particle size is small, the density of a stationary phase of a chromatographic separation column is increased, the passing of the separation feed liquid is not facilitated, the separation speed and the separation effect are influenced, the column pressure is increased, and the resin is crushed.
The system for separating xylose by valve array type continuous chromatography automatically controls continuous feeding, continuous elution and continuous extraction through a PLC.
Since the salt contained in the xylose solution is mainly generated by the processes of hydrolyzing, adding acid and adjusting pH value, the xylose solution mainly consists of cations and anions, and the ions can be single-charge ions or multi-charge ions. The present invention relates to different retention times or elution volumes of xylose on a chromatographic column compared to salts, pigments. Xylose is mainly enriched in an extraction liquid phase, and salt and pigment are enriched in a raffinate liquid phase.
According to the invention, the separation and purification of the xylose mixed solution are carried out by adopting a valve array type continuous chromatographic separation method and a valve array type continuous chromatographic separation system, the eluent can be recycled, the chromatographic column can realize regeneration through the eluent, other regeneration liquid is not required to be added, the cost can be reduced, the use of acid and alkali is reduced, and the method is energy-saving and environment-friendly.
A valve array type continuous chromatographic separation method and system is an industrial method for separating two compounds or ions in a liquid phase in a continuous manner, which takes advantage of different molecular properties (e.g., ion exclusion, hydrogen bonding, or molecular size) to provide a wide range of applications. Compared with the existing purification and desalination methods (such as distillation, crystallization or membrane separation and ion exchange), the method does not need an organic solvent, acid-base or ammonia water solution, and the level and energy consumption of chemical additives are obviously reduced. The chromatographic method can well separate xylose from impurities, reduce the conductivity of the xylose solution by about 95%, and improve the light transmittance by more than 50%. In particular, since the continuous chromatography system of the invention is a continuous process of continuous feeding, elution and collection, it is easy to operate.
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FIG. 1 is a schematic flow diagram of a system for extracting xylose by valve array continuous chromatography of example 1.
FIG. 2 is a schematic diagram of the structure of the system for extracting xylose by valve array continuous chromatography of example 1.
Detailed Description
The present invention will be described in detail with reference to examples.
A method for separating and purifying xylose by valve array type continuous chromatography includes such steps as adding xylose mixture to the first set-position chromatographic columns of multiple serially connected chromatographic columns, extracting raffinate from the second set-position chromatographic columns in the flowing direction of xylose mixture, adding eluent to the third set-position chromatographic columns in the flowing direction of xylose mixture, extracting extract from the third set-position chromatographic columns, circulating the rest liquid with xylose mixture, and sequentially switching the chromatographic columns at intervals opposite to the flowing direction of xylose mixture.
The xylose mixed solution is prepared by hydrolyzing corncob with acid, adjusting pH value with lime, filtering to obtain xylose filtrate, and evaporating and concentrating the xylose filtrate. The dry solids content of the xylose mixture was 1-70wt%. The corn cob is hydrolyzed by adding acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc., preferably sulfuric acid. If sulfuric acid is used as the hydrolysate in the xylose mixture, the major salt in the xylose mixture is sulfate. The electrical conductivity of the xylose mixture is very high, usually in the range of 30000-10000 mu/cm.
Water is used as eluent, preferably deionized water, more preferably evaporative condensate or steam condensate. The flow rate of the eluent is 1m/h-3m/h.
The feed liquid ratio is 1:1.2-2. The feed-to-liquid ratio refers to the ratio of the added xylose mixture to the eluent.
The xylose separating and purifying process of the present invention adopts valve array type continuous chromatographic xylose separating system comprising several chromatographic columns connected serially and with connected ends
A first set-up chromatographic column from which xylose mixed solution enters;
a second set-point chromatographic column from which raffinate is withdrawn from an outlet;
a third setting chromatographic column, eluent enters from the third setting chromatographic column, and extracting solution is extracted from an outlet of the third setting chromatographic column;
in the flow direction of the xylose mixture, a second setting chromatographic column is arranged at the downstream of the first setting chromatographic column, and a third setting chromatographic column is arranged at the downstream of the second setting chromatographic column;
the chromatographic columns are sequentially switched at set interval time, and the switching direction is opposite to the flowing direction of the xylose mixture.
The number of the chromatographic columns is 36 columns or less, preferably 30 columns, 24 columns, 20 columns, 16 columns, 12 columns or 8 columns.
The chromatographic column adopts macroporous strong acid cation separation resin.
The particle size of the resin is 0.20-0.35mm.
The system for separating xylose by valve array type continuous chromatography automatically controls continuous feeding, continuous elution and continuous extraction through a PLC.
Example 1
As shown in fig. 1-2, the system for separating xylose by valve array continuous chromatography comprises 8 chromatographic columns Z1-Z8 connected end to end, wherein the chromatographic column Z5 is a first setting chromatographic column, the chromatographic column Z7 is a second setting chromatographic column, and the chromatographic column Z1 is a third setting chromatographic column.
Xylose mixed liquor (material) enters from a chromatographic column Z5, sequentially flows through chromatographic columns Z6 and Z7, raffinate is extracted from an outlet of the chromatographic column Z7, the rest of the liquid continuously flows through chromatographic columns Z8 and Z9, and as the chromatographic column Z9 is connected with the chromatographic column Z1 in series, eluent-water is added into the chromatographic column Z1, extracting solution is adopted from an outlet of the chromatographic column Z1, the rest of the liquid continuously flows through chromatographic columns Z2, Z3 and Z4, and then enters the chromatographic column Z5 together with the xylose mixed liquor to form circulation. In the process, the xylose feeding mixed solution (feeding) valve of the chromatographic column Z5 is opened, the raffinate valve of the chromatographic column Z7 is opened, the eluent feeding (water feeding) valve and the extracting solution valve of the chromatographic column Z1 are opened, and the rest valves are closed.
Every interval set time, the chromatographic column is sequentially switched by opening and closing the valve, and the switching direction is opposite to the flowing direction of the xylose mixed solution. Specifically, the xylose feeding mixed liquor (feeding) valve of the chromatographic column Z5 is closed, the raffinate valve of the chromatographic column Z7 is closed, the eluent feeding (water feeding) valve and the extracting liquor valve of the chromatographic column Z1 are closed, the xylose feeding mixed liquor (feeding) valve of the chromatographic column Z4 is opened, the raffinate valve of the chromatographic column Z6 is opened, the eluent feeding (water feeding) valve and the extracting liquor valve of the chromatographic column Z8 are opened, and one column is switched to the direction opposite to the xylose mixing liquor flowing direction each time, so that the distance among the chromatographic columns in the first setting position, the chromatographic column in the second setting position and the chromatographic column in the third setting position is unchanged.
As shown in fig. 2, a feed valve and a water inlet valve are arranged at the upper opening of each chromatographic column, and a raffinate valve and an extract valve are arranged at the lower outlet.
Example 2
The system of example 2 is similar to the structure of example 1, but the number of columns may be 30, 24, 20, 16 or 12 columns.
Setting a first setting position chromatographic column, a second setting position chromatographic column and a third setting position chromatographic column according to the number of the chromatographic columns and the material separation condition, namely determining the distances among the first setting position chromatographic column, the second setting position chromatographic column and the third setting position chromatographic column, and carrying out corresponding feeding and discharging.
Then, the chromatographic column is switched according to the set interval time.
Example 3
The system for separating xylose by valve array continuous chromatography in example 1 is adopted to separate and purify xylose mixed liquor, and the specific steps are as follows: adjusting the pH value of the corncob hydrolysate by lime, flocculating and filtering to obtain xylose filtrate, wherein each parameter index of the filtrate after evaporation and concentration is 50-60 wt% of dry matter content, and xylose accounts for 57-67% of dry matter content; xylose content is more than or equal to 90% after chromatographic separation; the temperature is 50-60 ℃, the conductivity is 10000-30000us/cm, the pH value is 5.0-6.0, the light transmittance is 10-30%, the xylose mixed solution enters from the upper part of the chromatographic column Z5, then raffinate is extracted from the chromatographic column Z7, eluent-water enters from the upper part of the chromatographic column Z1, and extract is extracted from the outlet of the chromatographic column Z1. Continuously feeding, eluting and extracting through a circulating pump, wherein indexes of an extracting solution and a raffinate are shown in the following table:
the xylose solution passes through macroporous strong acid cation chromatographic separation resin in a valve array chromatographic separation device, and the operating parameters in the system are as follows: feed liquid ratio 1:1.2-2, extracting solution: raffinate ratio 5:4, switching time is 15min.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. A method for purifying xylose by valve array continuous chromatography is characterized in that xylose mixed liquid is continuously added into a first set position chromatographic column of a plurality of chromatographic columns connected in series, raffinate is continuously extracted from a second set position chromatographic column, eluent is continuously added into a third set position chromatographic column, extracting liquid is continuously extracted from the third set position chromatographic column, the rest liquid is added into the first set position chromatographic column together with xylose mixed liquid after passing through the rest chromatographic column, a feed valve of the first set position chromatographic column is opened, a raffinate valve of the second set position chromatographic column is opened, an eluent inlet valve and an extracting liquid valve of the third set position chromatographic column are opened, the rest valves are closed, according to the flowing direction of xylose mixed liquid, the distance between the third set position chromatographic column and the first set position chromatographic column is larger than the distance between the second set position chromatographic column and the first set position chromatographic column, the chromatographic column is sequentially switched at a set interval time, the switching direction is opposite to the flowing direction of xylose mixed liquid, the distance between the first set position chromatographic column, the second set position chromatographic column and the third set position chromatographic column is ensured not to be changed, and the number of cation separation columns is equal to 16, and the number of cation separation columns is equal to 20 columns.
2. The method of claim 1, wherein the xylose mixed solution is prepared by hydrolyzing corncob with acid, adjusting pH value with lime, filtering to obtain xylose filtrate, and evaporating and concentrating the xylose filtrate.
3. The method of claim 1, wherein the eluent is deionized water or evaporative condensate or steam condensate.
4. The method of claim 1, wherein the eluent flow rate is 1m/h to 3m/h.
5. The method of claim 1, wherein the feed liquid ratio is 1:1.2-2.
6. The method according to claim 1, characterized in that the dry solids content of the xylose mixture is 1-70wt%.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6239274B1 (en) * 1997-12-23 2001-05-29 Xyrofin Oy Method of producing xylose
CN101284849A (en) * 2007-04-13 2008-10-15 山东福田药业有限公司 Process for purifying xylose mother liquor by sequential simulated moving bed
CN105001272A (en) * 2015-06-24 2015-10-28 济南圣泉集团股份有限公司 Treating method for xylose mother liquor
CN107158747A (en) * 2017-05-19 2017-09-15 南京凯通粮食生化研究设计有限公司 A kind of decolouring deionization and separating mixture device and operation method
CN109503676A (en) * 2018-11-27 2019-03-22 浙江华康药业股份有限公司 A method of preparing xylitol and mixing molasses from xylose mother liquid
CN111705168A (en) * 2020-07-08 2020-09-25 江南大学 Method for purifying xylose hydrolysate by desalting with three zones with simulated moving bed
CN111747998A (en) * 2020-07-08 2020-10-09 江南大学 Method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography
AU2021102454A4 (en) * 2021-05-11 2021-07-22 Heilongjiang Bayi Agricultural University Decolorization and Desalination Method of Xylose Hydrolysate Based on Simulated Moving Bed Chromatography

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6239274B1 (en) * 1997-12-23 2001-05-29 Xyrofin Oy Method of producing xylose
CN101284849A (en) * 2007-04-13 2008-10-15 山东福田药业有限公司 Process for purifying xylose mother liquor by sequential simulated moving bed
CN105001272A (en) * 2015-06-24 2015-10-28 济南圣泉集团股份有限公司 Treating method for xylose mother liquor
CN107158747A (en) * 2017-05-19 2017-09-15 南京凯通粮食生化研究设计有限公司 A kind of decolouring deionization and separating mixture device and operation method
CN109503676A (en) * 2018-11-27 2019-03-22 浙江华康药业股份有限公司 A method of preparing xylitol and mixing molasses from xylose mother liquid
CN111705168A (en) * 2020-07-08 2020-09-25 江南大学 Method for purifying xylose hydrolysate by desalting with three zones with simulated moving bed
CN111747998A (en) * 2020-07-08 2020-10-09 江南大学 Method for removing inorganic acid and acetic acid in xylose hydrolysate by using intermittent simulated moving bed chromatography
AU2021102454A4 (en) * 2021-05-11 2021-07-22 Heilongjiang Bayi Agricultural University Decolorization and Desalination Method of Xylose Hydrolysate Based on Simulated Moving Bed Chromatography

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