CN1687139A - Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide - Google Patents

Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide Download PDF

Info

Publication number
CN1687139A
CN1687139A CN 200510049734 CN200510049734A CN1687139A CN 1687139 A CN1687139 A CN 1687139A CN 200510049734 CN200510049734 CN 200510049734 CN 200510049734 A CN200510049734 A CN 200510049734A CN 1687139 A CN1687139 A CN 1687139A
Authority
CN
China
Prior art keywords
chitosan
path
reaction
electrochemical reactor
separator column
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
Application number
CN 200510049734
Other languages
Chinese (zh)
Other versions
CN100488974C (en
Inventor
杨健
王奕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CNB200510049734XA priority Critical patent/CN100488974C/en
Publication of CN1687139A publication Critical patent/CN1687139A/en
Application granted granted Critical
Publication of CN100488974C publication Critical patent/CN100488974C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The present invention discloses an integrated reaction separation method for preparing chitosan oligosaccharide and its equipment. After the chitosan is degraded by electrochemical reaction, said invention adopts analog moving bed to implement integrated separation and extraction of chitosan oligosaccharide. Besides, said invention also provides the electrochemical degradation reaction condition and concrete steps of integrated separation and extraction of said analog moving bed.

Description

The integrated reaction separation method and the device of oligochitosan preparation
Technical field
The present invention relates to carbohydrate, relate in particular to a kind of integrated reaction separation method and device of oligochitosan preparation, it adopts electrochemical reaction degrade chitosan method, simulation moving-bed separating and extracting method and the isolating integrated apparatus technology of integrated reaction.
Background technology
Oligochitosan is meant that by 2~10 glucosamines with β-1, the oligose that the 4-glycosidic link is formed by connecting obtains by the high-molecular weight degradation of chitosan.Oligochitosan has the physiological function of water-soluble and multiple excellence, has wide application field and exploitation value, thereby receives much attention, and Chinese patent CN1126756C, CN1177856C and CN1544479A etc. describe to some extent.In the prior art, mainly contain three class preparation methods:
(1) acid-hydrolysis method;
(2) chemical oxidation edman degradation Edman;
(3) enzyme liberating method.
Wherein, method (1) is reacted bad control, and what mainly obtain is monose, disaccharides, is difficult to obtain required active oligosaccharides; Method (2) needs to consume chemical oxidizing agent, the direct or indirect contaminate environment of meeting; The technical requirements height of method (3), specificity enzyme difficulty obtains, and reaction time is longer.
Summary of the invention
The integrated reaction separation method and the device that the purpose of this invention is to provide a kind of oligochitosan preparation.The method of realization response isolation integral and device thereof are to overcome the deficiencies in the prior art.
Chitosan adopts simulation moving-bed integrated separation and Extraction oligochitosan, wherein after being degraded by electrochemical reaction, the electrochemical degradation reaction conditions is, the chitosan concentration that feeds intake is 10~20g/L, and sodium chloride aqueous solution concentration is 10~30g/L, the pH value of solution value is 1~3, current density 1~3A/dm 2, temperature of reaction is 30~60 ℃; Simulation moving-bed integrated isolating each unit step is: absorption, washing, desorption, regeneration, desorbing agent are the aqueous ethanolic solution of concentration 5~60%, and regenerator is the aqueous sodium hypochlorite solution of 5~10g/L, and the separator column temperature is 50~60 ℃.
The integrated reaction separation device of oligochitosan preparation: direct supply is powered respectively to degradation of chitosan electrochemical reactor and the synthetic electrochemical reactor of regenerator, the inlet pipe of the synthetic electrochemical reactor of degradation of chitosan electrochemical reactor and regenerator connects into switchable shared feed-pipe by switching valve separately, its shared feed-pipe joins by the outlet pipe of switch-valve and transferpump, the switching valve of the outlet pipe of chitosan aqueous solution dosing vessel and sodium chloride aqueous solution dosing vessel by separately joins with the inlet pipe of transferpump respectively, the return line of chitosan aqueous solution dosing vessel and sodium chloride aqueous solution dosing vessel by separately switching valve and the outlet pipe of transferpump join, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor and constant flow pump joins, respectively with internally piloted valve F1, F2, Fn and separator column X1, X2, the feed passageway serial connection of Xn, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor and constant flow pump joins, return line by backflow switching valve and chitosan aqueous solution dosing vessel joins again, the discharge nozzle and the internally piloted valve T0 of the synthetic electrochemical reactor of regenerator, after the path P2 of constant flow pump joins, respectively with internally piloted valve T1, T2, Tn and separator column X1, X2, the feed passageway serial connection of Xn, after the discharge nozzle of the synthetic electrochemical reactor of regenerator and the path P2 of constant flow pump join, be connected by the return line of backflow switching valve again with the sodium chloride aqueous solution dosing vessel, first discharge nozzle of pure water header tank and internally piloted valve S0, the path P2 serial connection of constant flow pump, after second discharge nozzle of pure water header tank and the path P3 of constant flow pump join, respectively with internally piloted valve S1, S2, Sn and separator column X1, X2, the feed passageway serial connection of Xn, after the path P4 of the discharge nozzle of desorbing agent header tank and constant flow pump joins, respectively with internally piloted valve D1, D2, Dn and separator column X1, X2, the feed passageway of Xn connects, the inlet pipe of oligochitosan extracting solution storage tank respectively with internally piloted valve A1, A2, An and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column X1, X2, the discharging path of Xn connects, the inlet pipe of residuum storage tank respectively with internally piloted valve B1, B2, Bn and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column X1, X2, the discharging path of Xn connects, the inlet pipe of oligochitosan extracting solution storage tank and the inlet pipe of residuum storage tank are connected with separately blow-off valve and blowdown piping respectively, separator column X1, X2, Xn respectively advances, the discharging path is priority and internally piloted valve V1 also, V2, Vn is connected in series successively, constitutes separator column X1, X2, series loop between the Xn.
Advantage of the present invention:
1) adopts electrochemical process degrade chitosan mild condition, be easy to control, do not consume oxygenant, can improve the quality of products;
2) lack reaction time, dna purity and efficient height directly improve productive rate;
3) filler can be regenerated, and the extracting solution loss is little, good economy performance;
4) process is simple and direct, is easy to integratedly, and device can be realized integrated continuous production.
Description of drawings
The integrated reaction separation process scheme and the apparatus structure synoptic diagram of the preparation of Fig. 1 oligochitosan;
The integrated reaction separation device structural representation of the oligochitosan preparation of Fig. 2 four separator columns;
The integrated reaction separation device structural representation of the oligochitosan preparation of Fig. 3 eight separator columns;
Fig. 4 electrochemical reactor structural shape synoptic diagram;
The electricity of Fig. 5 parting liquid is led and is concerned over time and control graphic representation.
Embodiment
As shown in Figure 1, the integrated reaction separation device of oligochitosan preparation has direct supply 2 and powers respectively to degradation of chitosan electrochemical reactor 1 and the synthetic electrochemical reactor 3 of regenerator, the inlet pipe of the synthetic electrochemical reactor 3 of degradation of chitosan electrochemical reactor 1 and regenerator connects into switchable shared feed-pipe by switching valve separately, its shared feed-pipe joins by the outlet pipe of switch-valve and transferpump 13, the switching valve of the outlet pipe of chitosan aqueous solution dosing vessel 14 and sodium chloride aqueous solution dosing vessel 12 by separately joins with the inlet pipe of transferpump 13 respectively, the return line of chitosan aqueous solution dosing vessel 14 and sodium chloride aqueous solution dosing vessel 12 by separately switching valve and the outlet pipe of transferpump 13 join, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor 1 and constant flow pump 6 joins, respectively with internally piloted valve F1, F2, X1 in Fn and the separator column 8, X2, the feed passageway serial connection of Xn post, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor 1 and constant flow pump 6 joins, return line by backflow switching valve and chitosan aqueous solution dosing vessel 14 joins again, the discharge nozzle and the internally piloted valve T0 of the synthetic electrochemical reactor 3 of regenerator, after the path P2 of constant flow pump 6 joins, respectively with internally piloted valve T1, T2, X1 in Tn and the separator column 8, X2, the feed passageway serial connection of Xn post, after the discharge nozzle of the synthetic electrochemical reactor 3 of regenerator and the path P2 of constant flow pump 6 join, be connected by the return line of backflow switching valve again with sodium chloride aqueous solution dosing vessel 12, first discharge nozzle of pure water header tank 4 and internally piloted valve S0, the path P2 serial connection of constant flow pump 6, after second discharge nozzle of pure water header tank 4 and the path P3 of constant flow pump 6 join, respectively with internally piloted valve S1, S2, X1 in Sn and the separator column 8, X2, the feed passageway serial connection of Xn post, after the path P4 of the discharge nozzle of desorbing agent header tank 5 and constant flow pump 6 joins, respectively with internally piloted valve D1, D2, X1 in Dn and the separator column 8, X2, the feed passageway of Xn post connects, the inlet pipe of oligochitosan extracting solution storage tank 10 respectively with internally piloted valve A1, A2, An and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column 8 in X1, X2, the discharging path of Xn post connects, the inlet pipe of residuum storage tank 11 respectively with internally piloted valve B1, B2, Bn and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column 8 in X1, X2, the discharging path of Xn post connects, the inlet pipe of oligochitosan extracting solution storage tank 10 and the inlet pipe of residuum storage tank 11 are connected with separately blow-off valve and blowdown piping respectively, X1 in the separator column 8, X2, respectively advancing of Xn post, the discharging path is priority and internally piloted valve V1 also, V2, Vn is connected in series successively, constitutes the X1 in the separator column 8, X2, series loop between the Xn post.
The integrated reaction separation method operating process of oligochitosan preparation: open direct supply 2 and give degradation of chitosan electrochemical reactor 1 and regenerator synthetic electrochemical reactor 3 power supplies respectively; In chitosan aqueous solution dosing vessel 14 and sodium chloride aqueous solution dosing vessel 12, be respectively charged into the sodium chloride aqueous solution SE that chitosan aqueous solution SG that concentration is 10~20g/L and concentration are 10~30g/L, reaching separately by transferpump 13, switching valve inputs to degradation of chitosan electrochemical reactor 1 and the synthetic electrochemical reactor 3 of regenerator respectively, in degradation of chitosan electrochemical reactor 1, reaction conditions is: the pH value of solution value is 1~3, current density 1~3A/dm 2, temperature of reaction is 30~60 ℃, obtains degradation of chitosan reaction residual liquor F by electrochemical reaction, in the synthetic electrochemical reactor 3 of regenerator, reaction conditions is: the pH value of solution value is 7, current density 1~3A/dm 2Temperature of reaction is under 30~50 ℃, obtain filler regenerator T by electrochemical reaction, in pure water header tank 4 and desorbing agent header tank 5, be respectively charged into pure water S and desorbing agent D, four kinds of logistics such as F, T, S and D inputed to simulation moving-bed SMB by the multiple constant current pump 6 that links respectively carry out separation and Extraction; The main equipment of SMB system is one group of separator column that is equal to 8, be designated X1 respectively, X2, Xn, fill gac in the separator column as adsorption stuffing, integrated isolating each unit step is: absorption, washing, desorption, regeneration, desorbing agent D is the aqueous ethanolic solution of concentration 5~60%, regenerator T is the aqueous sodium hypochlorite solution of 5~10g/L, the separator column temperature is 50~60 ℃, SMB separation-extraction technology process is subjected to computer system 7 controls, its upper computer is industrial computer IPC operation SMB software, carry out the real time data communication by RS232 or RS485 agreement and lower computer programmable logic controller PLC, measured signal according to the conductivity meter 9 in separator column exit, install in the automatic switchover separator column inlet ductwork, correspond respectively to F, T, four groups of feeding pipe magnetic valve: F1 of four kinds of logistics such as S and D, F2, Fn, T1, T2, Tn, S1, S2, Sn and D1, D2, Dn; And switch synchronously and install in the separator column export pipeline, correspond respectively to separated product oligochitosan extracting solution DA and residuum and non-target product SB etc. two groups of discharge nozzle way solenoid valve: A1, A2 ..., An and B1, B2 ..., Bn; And one group of circuit electromagnetic valve: V1, V2 in the separator column inter-stage series pipe ..., Vn; Finally, from DA storage tank 10, collect serially and obtain the oligochitosan extracting solution, simultaneously residuum and non-target product are sent into SB storage tank 11, and enter the product postprocessing working procedures respectively, obtain final oligochitosan product and reclaim eluent by technique known.
Following examples are described respectively step by step by electrochemical reaction degrade chitosan, electrochemical reaction synthetic separating column packing regenerator, oligochitosan separation and Extraction and the integrated separating reaction of oligochitosan etc.
Embodiment 1
As Fig. 1, Fig. 2 and electrochemical degradation reactive moieties shown in Figure 3, direct supply 2 output voltages are 0~12V, and electric current is 0~20A.
Adopt electrochemical reactor 1 to carry out the degradation of chitosan reaction, its structural shape as shown in Figure 4, box-type shell 15 is made for non-metallic material among the figure, battery lead plate 16 is made up of 4 blocks of synthetic graphite plates, and width is 380mm, highly is 180mm, mean thickness is 18mm, parallel arrangement constitutes the placed in-line non-diaphragm electrochemical reactor of multipole type three joints, and the interpolar mean distance is 20mm, single electrode area 6.8dm 2, effecting reaction liquid volume 5L.
The chitosan concentration that drops into is 10g/L, and NaCl concentration is 20g/L, and pH value of solution value 1~3, temperature of reaction are 40~50 ℃, and current density is 2~3A/dm 2
In reaction process, judge reaction process to measure soltion viscosity.Under constant temperature, pass through the required time of calibrated scale line by determination of ubbelohde viscometer specified rate solution.If before the reaction is t0, the reaction back is t, and then 1-t/t0 is exactly that viscosity reduces the branch rate.Get viscosity degradation 90% in the present embodiment and be controlled target.
Finally, the reaction times is 70min, and assaying reaction is finished liquid, and the oligochitosan production rate is 85%, and it is colourless that reaction residual liquor is.
Embodiment 2
Used DeR device is identical with example 1.
The chitosan concentration that drops into is 20g/L, and NaCl concentration is 20g/L, and pH value of solution value 1~3, temperature of reaction are 50~60 ℃, and current density is 2~3A/dm 2
Reaction control method is identical with example 1, still gets viscosity degradation 90% and is controlled target.
Finally, the reaction times is 130min, and assaying reaction is finished liquid, and the oligochitosan production rate is 84.5%, and reaction residual liquor is oyster.
Embodiment 3
Used DeR device is identical with example 1.
The chitosan concentration that drops into is 20g/L, and NaCl concentration is 20g/L, and pH value of solution value 1~3, temperature of reaction are 60~70 ℃, and current density is 2~3A/dm 2
Reaction control method is identical with example 1.Still get viscosity degradation 90% and be controlled target.
Finally, the reaction times is 120min, and assaying reaction is finished liquid, and the oligochitosan production rate is 81.7%, and reaction residual liquor is light brown.Show that the anode surface side reaction increases, the oligochitosan production rate descends to some extent.
Embodiment 4
Used DeR device is identical with example 1.
The chitosan concentration that drops into is 10g/L, and NaCl concentration is 10g/L, and pH value of solution value 1~3, temperature of reaction are 30~40 ℃, and current density is 1~2A/dm 2
Reaction control method is identical with example 1.Still get viscosity degradation 90% and be controlled target.
Finally, the reaction times is 90min, and assaying reaction is finished liquid, and the oligochitosan production rate is 83%, and reaction residual liquor is colourless.
Embodiment 5
As Fig. 1, Fig. 2 and the synthetic separating column packing regenerator part of electrochemical reaction shown in Figure 3, direct supply 2 output voltages are 0~12V, and electric current is 0~20A.
Adopt electrochemical reactor 3 to carry out the regenerator building-up reactions, its structural shape as shown in Figure 4.
The NaCl concentration that drops into is 30g/L, and the pH value of solution value is 7, and temperature of reaction is 30~50 ℃, and current density is 1~3A/dm 2
Finally, it is separating column packing regenerator NaClO that assaying reaction is finished liquid, and its concentration is 5~10g/L.
Embodiment 6
Simulation moving-bed separation and Extraction part as shown in Figure 2, its separator column is 4, be of a size of 50mm * 500mm, every filling gac 100g, solution flow rate is 30mL/min, column temperature is 50~60 ℃, and desorbing agent D is 5~60% aqueous ethanolic solution, and filler regenerator T is 1~3% aqueous sodium hypochlorite solution.
The unit step of sepn process is followed successively by:
1) reaction residual liquor F supplies with separator column 8:X1~X4 from electrochemical reactor 1 by constant flow pump 6 and F group magnetic valve F1~F4;
2) filler regenerator T is supplied with separator column 8:X1~X4 from electrochemical reactor 3 by constant flow pump 6 and T group magnetic valve T1~T4;
3) pure water S is supplied with separator column 8:X1~X4 from pure water header tank 4 by constant flow pump 6 and S group magnetic valve S1~S4;
4) desorbing agent D is supplied with separator column 8:X1~X4 from desorbing agent header tank 5 by constant flow pump 6 and D group magnetic valve D1~D4;
More than 4 the step abbreviate as respectively: absorption, washing, desorption and regeneration; Go round and begin again, by the SMB time variable control switching that circulates.
Conductance measurement device 9 is installed, in order to the separation and Extraction process is monitored in real time in the export pipeline of separator column.Fig. 5 has provided the corresponding relation that actual conductivity changes and control curve and separation and Extraction process in time.Electricity according to conductivitimeter 9 is led variation, and all detect and control signal is focused on by upper computer IPC, by SMB software control lower computer PLC to realize continuous integrated separation and Extraction.Be about 6min above switching time, final oligochitosan separation rate is 95%.
Embodiment 7
Used simulation moving-bed separating extraction device is identical with example 6.Wherein, solution flow rate is 20mL/min, is about 9min switching time, and final oligochitosan separation rate is 95%.
Embodiment 8
In the simulation moving-bed separation and Extraction part as shown in Figure 3, separator column increases to 8, and its separator column scantlings of the structure, schedule of operation are identical with example 6.Wherein, solution flow rate is 35mL/min, is about 5min switching time, and final oligochitosan separation rate is 97%.
Embodiment 9
The simulated moving bed system that adopts, its separator column increase to 12, and its separator column scantlings of the structure, schedule of operation are identical with example 6.Wherein, solution flow rate is 40mL/min, is about 5min switching time, and final oligochitosan separation rate is 99%.
Embodiment 10
The integrated tripping device of oligochitosan preparation as shown in Figure 3.Adopt the chitosan electrochemical degradation reaction identical with example 1, the identical filler regenerator electrochemical synthesis reaction with example 5, the simulation moving-bed separation and Extraction process identical with example 8 be coupled.
Finally, the reaction production rate of oligochitosan is 85%, and oligochitosan separation and Extraction rate is 97%.

Claims (4)

1, a kind of integrated reaction separation method of oligochitosan preparation, it is characterized in that: after chitosan is degraded by electrochemical reaction, adopt simulation moving-bed integrated separation and Extraction oligochitosan, wherein, the electrochemical degradation reaction conditions is, the chitosan concentration that feeds intake is 10~20g/L, and sodium chloride aqueous solution concentration is 10~30g/L, the pH value of solution value is 1~3, current density 1~3A/dm 2, temperature of reaction is 30~60 ℃; Simulation moving-bed integrated isolating each unit step is: absorption, washing, desorption, regeneration, desorbing agent are the aqueous ethanolic solution of concentration 5~60%, and regenerator is the aqueous sodium hypochlorite solution of 5~10g/L, and the separator column temperature is 50~60 ℃.
2, the integrated reaction separation method of a kind of oligochitosan preparation according to claim 1, it is characterized in that: electrochemical reactor is adopted in described electrochemical degradation reaction, electrochemical reactor is an electrode materials with the synthetic graphite plate, structure formation is no barrier film multipole type, and pole distance is 1~2cm.
3, the integrated reaction separation method of a kind of oligochitosan preparation according to claim 1, it is characterized in that: described simulation moving-bed be the separator columns combination that is equal to by 4~12, the packed bed layer material is a gac in the separator column, and filler can be regenerated by electrochemical reactor synthetic clorox.
4. the integrated reaction separation device of oligochitosan preparation, it is characterized in that, direct supply (2) is powered respectively and is given degradation of chitosan electrochemical reactor (1) and the synthetic electrochemical reactor (3) of regenerator, the inlet pipe of the synthetic electrochemical reactor (3) of degradation of chitosan electrochemical reactor (1) and regenerator connects into switchable shared feed-pipe by switching valve separately, its shared feed-pipe joins by the outlet pipe of switch-valve and transferpump (13), the switching valve of the outlet pipe of chitosan aqueous solution dosing vessel (14) and sodium chloride aqueous solution dosing vessel (12) by separately joins with the inlet pipe of transferpump (13) respectively, the return line of chitosan aqueous solution dosing vessel (14) and sodium chloride aqueous solution dosing vessel (12) by separately switching valve and the outlet pipe of transferpump (13) join, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor (1) and constant flow pump (6) joins, respectively with internally piloted valve F1, F2, X1 in Fn and the separator column (8), X2, the feed passageway serial connection of Xn post, after the path P1 of the discharge nozzle of degradation of chitosan electrochemical reactor (1) and constant flow pump (6) joins, return line by backflow switching valve and chitosan aqueous solution dosing vessel (14) joins again, regenerator synthesizes the discharge nozzle and the internally piloted valve T0 of electrochemical reactor (3), after the path P2 of constant flow pump (6) joins, respectively with internally piloted valve T1, T2, X1 in Tn and the separator column (8), X2, the feed passageway serial connection of Xn post, after the path P2 that regenerator synthesizes the discharge nozzle of electrochemical reactor (3) and constant flow pump (6) joins, be connected by the return line of backflow switching valve again with sodium chloride aqueous solution dosing vessel (12), first discharge nozzle of pure water header tank (4) and internally piloted valve S0, the path P2 serial connection of constant flow pump (6), after the path P3 of second discharge nozzle of pure water header tank (4) and constant flow pump (6) joins, respectively with internally piloted valve S1, S2, X1 in Sn and the separator column (8), X2, the feed passageway serial connection of Xn post, after the path P4 of the discharge nozzle of desorbing agent header tank (5) and constant flow pump (6) joins, respectively with internally piloted valve D1, D2, X1 in Dn and the separator column (8), X2, the feed passageway of Xn post connects, the inlet pipe of oligochitosan extracting solution storage tank (10) respectively with internally piloted valve A1, A2, An and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column (8) in X1, X2, the discharging path of Xn post connects, the inlet pipe of residuum storage tank (11) respectively with internally piloted valve B1, B2, Bn and electricity are led the path C1 of detector, C2, after the Cn serial connection, separately with separator column (8) in X1, X2, the discharging path of Xn post connects, the inlet pipe of the inlet pipe of oligochitosan extracting solution storage tank (10) and residuum storage tank (11) is connected with separately blow-off valve and blowdown piping respectively, X1 in the separator column (8), X2, respectively advancing of Xn post, the discharging path is priority and internally piloted valve V1 also, V2, Vn is connected in series successively, constitutes the X1 in the separator column (8), X2, series loop between the Xn post.
CNB200510049734XA 2005-04-30 2005-04-30 Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide Expired - Fee Related CN100488974C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200510049734XA CN100488974C (en) 2005-04-30 2005-04-30 Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200510049734XA CN100488974C (en) 2005-04-30 2005-04-30 Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100768647A Division CN100455603C (en) 2005-04-30 2005-04-30 Integrated reaction separation device for preparing chitin

Publications (2)

Publication Number Publication Date
CN1687139A true CN1687139A (en) 2005-10-26
CN100488974C CN100488974C (en) 2009-05-20

Family

ID=35305181

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200510049734XA Expired - Fee Related CN100488974C (en) 2005-04-30 2005-04-30 Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide

Country Status (1)

Country Link
CN (1) CN100488974C (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755832A (en) * 2013-12-20 2014-04-30 广西科技大学 Chitosan degradation method
CN103772448A (en) * 2013-12-20 2014-05-07 广西科技大学 Degradation method of chitosan
CN103820808A (en) * 2013-12-20 2014-05-28 广西科技大学 Degradation method of chitosan
CN103819580A (en) * 2013-12-20 2014-05-28 广西科技大学 Degradation method of chitosan
CN104233365A (en) * 2014-10-08 2014-12-24 林海波 Electrochemical reactor for preparing oligosaccharide from marine biology functional sugars and preparation method
CN107694150A (en) * 2017-11-06 2018-02-16 南通中国科学院海洋研究所海洋科学与技术研究发展中心 The solid phase extraction method of chitosan oligosaccharide in a kind of solution
CN112679629A (en) * 2020-12-24 2021-04-20 江苏大学 Low-molecular chitosan and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755832A (en) * 2013-12-20 2014-04-30 广西科技大学 Chitosan degradation method
CN103772448A (en) * 2013-12-20 2014-05-07 广西科技大学 Degradation method of chitosan
CN103820808A (en) * 2013-12-20 2014-05-28 广西科技大学 Degradation method of chitosan
CN103819580A (en) * 2013-12-20 2014-05-28 广西科技大学 Degradation method of chitosan
CN104233365A (en) * 2014-10-08 2014-12-24 林海波 Electrochemical reactor for preparing oligosaccharide from marine biology functional sugars and preparation method
CN104233365B (en) * 2014-10-08 2017-06-16 林海波 The electrochemical reactor and preparation method of oligosaccharides are prepared from marine organisms functional sugar
CN107694150A (en) * 2017-11-06 2018-02-16 南通中国科学院海洋研究所海洋科学与技术研究发展中心 The solid phase extraction method of chitosan oligosaccharide in a kind of solution
CN112679629A (en) * 2020-12-24 2021-04-20 江苏大学 Low-molecular chitosan and preparation method thereof

Also Published As

Publication number Publication date
CN100488974C (en) 2009-05-20

Similar Documents

Publication Publication Date Title
CN1687139A (en) Method and equipment of integrated reaction and separation for preparing chitosan oligosaccharide
CN1223520C (en) Water-softening apparatus and regeneration control method
CN86101606A (en) Fluid treatment method and equipment
CN106669867A (en) Continuous and automatic ion exchange device
CN2784413Y (en) Integrated reactive separation plant for preparation of chitosan oligosaccharide
CN1090040C (en) Apparatus for pressure equalisation and flushing in vessel
CN1869076A (en) Integrated reaction separation device for preparing chitin
CN212732180U (en) Continuous ion exchange system for xylose production
CN207221944U (en) Continuous automatic ion exchanging device
CN203922801U (en) A kind of real bed and multiple bed
CN104743639A (en) High-efficiency sodium ion exchanger
CN113769794B (en) Ion exchange system and method for continuously removing impurities in citicoline sodium
CN1051725C (en) Fixed double bunk ion exchange resin regeneration method and device
CN101037242A (en) Disk type electrical ion-removing water softening apparatus
CN110643831B (en) Diaphragm-free electrochemical lithium extraction system and lithium extraction method thereof
CN103910411B (en) Real bed, multiple bed and the industrial de-mineralized water production method as terminal demineralization plant thereof
US10435426B2 (en) Method for separation of acids and sugars to reduce energy consumption
CN2525079Y (en) Uniform resin alternative filling electric deionizing water purifying device
CN207204121U (en) A kind of mixed ion exchanger
CN101992134A (en) Regeneration method of ion exchange resin for desalination
CN206553246U (en) A kind of efficient light electrolysis suspension bed apparatus
CN216273645U (en) Sludge reduction photocatalytic oxidation reactor
CN201907986U (en) Device for processing nickel-containing wastewater generated in preparation process of chemical hydrogenation catalyst by continuous adsorption and regenerative coupling
CN101244853A (en) Technique for water treatment with sodium-ion exchanger
CN108751389A (en) A kind of synchronous nitrogen and phosphorus recovery device of urine purification from driving

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: 20090520

Termination date: 20140430