CN105646600A - Method for removing residual acids in biosaccharide preparation technique by electrodialysis - Google Patents

Method for removing residual acids in biosaccharide preparation technique by electrodialysis Download PDF

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Publication number
CN105646600A
CN105646600A CN201610020663.9A CN201610020663A CN105646600A CN 105646600 A CN105646600 A CN 105646600A CN 201610020663 A CN201610020663 A CN 201610020663A CN 105646600 A CN105646600 A CN 105646600A
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China
Prior art keywords
material pot
biological
acid
biological sugar
compartment
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CN201610020663.9A
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Chinese (zh)
Inventor
汪耀明
李为
吴亮
李传润
颜海洋
张勤
徐铜文
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HEFEI CHEMJOY POLYMER MATERIALS SCIENCE AND TECHNOLOGY Co Ltd
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HEFEI CHEMJOY POLYMER MATERIALS SCIENCE AND TECHNOLOGY Co Ltd
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Priority to CN201610020663.9A priority Critical patent/CN105646600A/en
Publication of CN105646600A publication Critical patent/CN105646600A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • C07H1/06Separation; Purification
    • C07H1/08Separation; Purification from natural products

Abstract

The invention discloses a method for removing residual acids in a biosaccharide preparation technique by electrodialysis. The method is characterized in that residual inorganic acids in the biosaccharide hydrolysate are removed by an electrodialysis process. The method comprises the following steps: hydrolyzing agricultural plant chopped fiber waste under the action of dilute acids to obtain the biosaccharide hydrolysate, and adding the hydrolysate into a desalination chamber internal circulation of an electrodialysis plant to carry out electrodialysis, thereby removing the residual acids, wherein the operation temperature is controlled at 35 DEG C or below, and the operating current density is 10-40mA/cm<2>. The method ensures the high yield of the product on the premise of effectively removing residual acids in the biosaccharide hydrolysate, and is a clean, efficient, green and environment-friendly technique.

Description

A kind of method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology
Technical field
The present invention relates to a kind of method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology.
Background technology
In nature, biological sugar (such as wood sugar, semi-lactosi, seminose and pectinose etc.) is distributed widely in organism, is the nascent product of photosynthesis of plant. Carbohydrate is not only the stored reserves in plant materials, and is the precursor of other organic compound of biosynthesizing. These biological sugar in plant have various biological activity, and toxic side effect is little. As wood sugar in Digestive tract the most stable, not digested enzymic hydrolysis, metabolism does not rely on Regular Insulin, and has the effect of prevention of dental caries, is the desirable sweeting agent preparing the food such as chewing gum, chocolate, hard candy for the patient such as diabetes, hepatitis. Pectinose can suppress to be hydrolyzed the enzyme of disaccharide, therefore has the blood sugar reducing function suppressing the blood sugar caused because taking in sucrose to raise, suppress disaccharide hydrolysis; It is to the restraining effect of disaccharide lytic enzyme simultaneously, the sucrose not being decomposed is decomposed by the microorganisms in large intestine produces a large amount of organic acids in small intestine, and liver synthetic fat is had restraining effect by this kind of organic acid. Therefore can as the desirable feedstock of dieletic foodstuff, diet food, healthy functions food, protective foods.
At present, the main extracting method of biological sugar is acid-hydrolysis method. The disclosed biological sugar extracting method of Chinese patent (application number 200810134456.1) is: first utilize corn cob for raw material, the pentosan hydrolysis in vegetable fibre obtains the hydrolyzed solution of wood sugar and pectinose under the effect of diluted acid; Gained hydrolyzed solution passes through and neutralizes depickling, decolouring, concentrates, ion-exchange obtains comparatively pure Xylitol and pectinose. The disclosed biological sugar extracting method of Chinese patent (application number 200910228993.7) is: take corn cob as raw material, is obtained the Xylitol of high purity by techniques such as hydrolysis, depickling, decolouring, ion-exchange, hydrogenations. In the operational path of this kind of biological sugar of acid-hydrolysis method preparation, lignocellulosic hydrolysate generally contains the diluted acid of 0.6%��0.8%, there is the operational path of a neutralization depickling, it is generally add a large amount of saturated limewaters, after fully stirring neutralization precipitation, remove the residual acid in hydrolyzed solution.There are several significantly shortcomings in the method for this kind of neutralization depickling:
(1) a large amount of industrial chemicals is consumed, and its process observable index relatively big (neutralization process temperature maintains 80 DEG C��85 DEG C).
(2) a large amount of solid slag (CaSO is produced4) and waste water, it is easy to bring secondary pollution.
(3) technological operation is loaded down with trivial details, and labour intensity is big, and a small amount of calcium sulfate residual increases the weight of follow-up decolouring, concentrated technique burden.
Therefore, how selecting a kind of clean and effective more, deacidification that the technology of environmental protection is applied to biological sugar, the residual acid removed in biological sugar technique seems particularly urgent.
Summary of the invention
For overcome in existing biological sugar preparation technology the technique existing for residual acid removal process loaded down with trivial details, easily bring the shortcomings such as secondary pollution, energy consumption are bigger, it is desirable to provide a kind of environmental friendliness, method easy and simple to handle remove the residual acid in biological sugar preparation technology.
Technical solution problem of the present invention, adopts following technical scheme:
The present invention utilizes electrodialytic technique to remove the method for residual acid in biological sugar preparation technology, is utilize electrodialytic technique effectively to remove the residual acid in biological saccharic acid hydrolysis method preparation process, and its feature is:
Arranging electrodialysis unit, described electrodialysis unit is made up of diluting compartment material pot, concentration compartments's material pot, room, pole material pot, membrane module, three recycle pumps, direct supply and pipeline; Described membrane module is made up of anode, negative electrode and the cationic exchange membrane being alternately arranged under the overlay successively, filter, anion-exchange membrane, composition anolyte compartment, diluting compartment, concentration compartments and cathode compartment, and film logarithm is 10��20 right, and membrane area is 100mm �� 200mm; Described anolyte compartment is connected with room, pole material pot by a recycle pump jointly with cathode compartment; Diluting compartment is connected with diluting compartment material pot by recycle pump, and concentration compartments is connected with concentration compartments's material pot by recycle pump; On the positive pole that anode and negative electrode are connected to direct supply by wire respectively and negative pole; Ion-exchange membrane used is homogeneous ion-exchange membrane or heterogeneous ion-exchange membrane.
First biological sugar hydrolyzed solution is introduced the diluting compartment material pot of electrodialysis unit, and adds tap water in concentration compartments's material pot, in the material pot of room, pole, add electrode solution;
Then circulated between diluting compartment and diluting compartment material pot by recycle pump control biological sugar hydrolyzed solution, control tap water circulates between concentration compartments and concentration compartments's material pot, and control electrolytic solution circulates between anolyte compartment, cathode compartment and room, pole material pot;
On the negative electrode of membrane module and anode, 10��40mA/cm is applied finally by direct supply2Constant current, control service temperature below 35 DEG C, and by conductivitimeter monitoring desalination indoor biological sugar hydrolyzed solution specific conductivity; When specific conductivity is at 1000 �� Scm-1Time following, namely complete the removal of residual acid in biological sugar hydrolyzed solution. After electrodialysis, the feed liquid in diluting compartment is used as the material of biological sugar next step decoloration process of preparation.
Described biological sugar hydrolyzed solution is by pentosan hydrolysis being obtained under the effect of diluted acid by agricultural plants staple fibre waste material; Described agricultural plants staple fibre waste material is corn cob, bagasse or plants shell, described diluted acid to be concentration be 1%��10% sulfuric acid, hydrochloric acid or oxalic acid.
If the solid content of described biological sugar hydrolyzed solution is higher than 20%, then carry out electrodialysis by water or ethanol after being diluted again.
After being processed by biological syrup solution solution electrodialysis, the relative removal efficiency of residual acid reaches more than 99%, and the receipts rate of biological sugar can reach 84.8%.
The invention has the beneficial effects as follows:
(1) the present invention achieves the selective removal of residual acid in biological sugar hydrolyzed solution by electrodialysis process, and whole process does not add extra chemical reagent, does not produce solid slag, alleviates the technique burden in downstream.
(2) clearance of residual acid in biological sugar hydrolyzed solution is greater than 99% by the electrodialysis process of the present invention, and the receipts rate of its biological sugar can reach 84.8%.
(3) the present invention is lower by the energy consumption of electrodialysis process process biological sugar hydrolyzed solution.
(4) the method technique removing residual acid in the present invention's this kind of removal biological sugar preparation process is simple, operates control easily, can not destroy the original structure of biology sugar, can not cause environmental pollution, is a kind of desirable processing method being suitable for applying.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the present invention;
Number in the figure: 1 is concentration compartments's material pot; 2 is diluting compartment material pot; 3 is room, pole material pot; 4 is membrane module; 5 is direct supply; 6 is recycle pump.
Embodiment
Embodiment 1
As shown in Figure 1, the present embodiment removes the residual acid in biological sugar hydrolyzed solution as follows:
Pentosan in vegetable fibre is hydrolyzed by agricultural plants staple fibre waste material (corn cob) under 8% effect of sulfuric acid, obtain biological sugar hydrolyzed solution 500ml (main containing wood sugar and a small amount of sulfuric acid and colloid, albumen, pigment, its pH value is about 1.0, specific conductivity is about 13.5mS/cm, sugar content is 6.5%, and sulfuric acid content is 0.76%);
Arranging electrodialysis unit, as shown in Figure 1, electrodialysis unit is made up of diluting compartment material pot 2, concentration compartments's material pot 1, room, pole material pot 3, membrane module 4, three recycle pumps 6, direct supply 5 and pipeline; Membrane module is made up of anode, negative electrode and the cationic exchange membrane being alternately arranged under the overlay successively, filter, anion-exchange membrane, composition anolyte compartment, diluting compartment, concentration compartments and cathode compartment, film logarithm be 10 to (selected homogeneous phase ionic membrane be Hefei Ke Jia macromolecular material Science and Technology Ltd. produce, cationic membrane is model is CJMC-2, anionic membrane model is CJMA-2, and membrane area is 100mm �� 200mm); Anolyte compartment is connected with room, pole material pot by a recycle pump jointly with cathode compartment; Diluting compartment is connected with diluting compartment material pot by recycle pump, and concentration compartments is connected with concentration compartments's material pot by recycle pump; Anode and negative electrode are connected to positive pole and the negative pole of direct supply respectively by wire;
500ml biological sugar hydrolyzed solution is introduced the diluting compartment material pot of electrodialysis unit, and in concentration compartments's material pot, adds 500ml deionized water, in the material pot of room, pole, add 500ml0.3M metabisulfite solution;
Then circulated between diluting compartment and diluting compartment material pot by recycle pump control biological sugar hydrolyzed solution, control tap water circulates between concentration compartments and concentration compartments's material pot, and control electrolytic solution circulates between anolyte compartment, cathode compartment and room, pole material pot;
Finally connecting direct supply, control actuating current density is at 10mA/cm2, control service temperature, below 35 DEG C, starts electroosmose process and removes the residual acid in biological sugar hydrolyzed solution, by the conductivity value of conductivitimeter monitoring desalination indoor biological sugar hydrolyzed solution, and time recording actuating current and voltage. When specific conductivity is at 1000 �� Scm-1Time following, namely complete the removal of residual acid in biological sugar hydrolyzed solution.
The operating time of the whole electrodialysis process of the present embodiment is 80min, and the clearance of residual acid is 99.0%, and the rate of recovery of biological sugar is 84.8%.
Embodiment 2
The present embodiment is identical with embodiment 1, and difference is only: when carrying out electrodialysis, and control actuating current density is at 20mA/cm2��
The operating time of the whole process of the present embodiment is 75min, and the clearance of residual acid is 99.2%, and the rate of recovery of biological sugar is 83.2%.
Embodiment 3
The present embodiment is identical with embodiment 1, and difference is only: when carrying out electrodialysis, and control actuating current density is at 30mA/cm2��
The operating time of the whole process of the present embodiment is 73min, and the clearance of residual acid is 99.3%, and the rate of recovery of biological sugar is 81.6%.
Embodiment 4
The present embodiment is identical with embodiment 1, and difference is only: when carrying out electrodialysis, and control actuating current density is at 40mA/cm2��
The operating time of the whole process of the present embodiment is 70min, and the clearance of residual acid is 99.4%, and the rate of recovery of biological sugar is 78.4%.

Claims (6)

1. one kind utilizes the method for residual acid in electrodialytic technique removal biological sugar preparation technology, it is characterised in that: utilize electrodialytic technique effectively to remove the residual acid in biological saccharic acid hydrolysis method preparation process.
2. the method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology according to claim 1, it is characterised in that:
Arranging electrodialysis unit, described electrodialysis unit is made up of diluting compartment material pot, concentration compartments's material pot, room, pole material pot, membrane module, three recycle pumps, direct supply and pipeline; Described membrane module is made up of anode, negative electrode and the cationic exchange membrane being alternately arranged under the overlay successively, filter, anion-exchange membrane, composition anolyte compartment, diluting compartment, concentration compartments and cathode compartment, and film logarithm is 10��20 right, and membrane area is 100mm �� 200mm; Described anolyte compartment is connected with room, pole material pot by a recycle pump jointly with cathode compartment; Diluting compartment is connected with diluting compartment material pot by recycle pump, and concentration compartments is connected with concentration compartments's material pot by recycle pump; On the positive pole that anode and negative electrode are connected to direct supply by wire respectively and negative pole;
First biological sugar hydrolyzed solution is introduced the diluting compartment material pot of electrodialysis unit, and adds tap water in concentration compartments's material pot, in the material pot of room, pole, add electrode solution;
Then circulated between diluting compartment and diluting compartment material pot by recycle pump control biological sugar hydrolyzed solution, control tap water circulates between concentration compartments and concentration compartments's material pot, and control electrolytic solution circulates between anolyte compartment, cathode compartment and room, pole material pot;
On the negative electrode of membrane module and anode, 10��40mA/cm is applied finally by direct supply2Constant current, control service temperature below 35 DEG C, and by conductivitimeter monitoring desalination indoor biological sugar hydrolyzed solution specific conductivity; When specific conductivity is at 1000 �� Scm-1Time following, namely complete the removal of residual acid in biological sugar hydrolyzed solution.
3. the method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology according to claim 2, it is characterised in that: ion-exchange membrane used is homogeneous ion-exchange membrane or heterogeneous ion-exchange membrane.
4. the method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology according to claim 2, it is characterised in that: described biological sugar hydrolyzed solution is by agricultural plants staple fibre waste material is hydrolyzed acquisition under the effect of diluted acid; Described agricultural plants staple fibre waste material is corn cob, bagasse or plants shell, described diluted acid be concentration 1%��10% sulfuric acid, hydrochloric acid or oxalic acid.
5. the method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology according to claim 2, it is characterised in that: if the solid content of described biological sugar hydrolyzed solution is higher than 20%, then carry out electrodialysis by water or ethanol after being diluted again.
6. the method utilizing electrodialytic technique to remove residual acid in biological sugar preparation technology according to claim 2, it is characterized in that: after biological syrup solution solution electrodialysis is processed, the relative removal efficiency of residual acid reaches more than 99%, and the receipts rate of biological sugar can reach 84.8%.
CN201610020663.9A 2016-01-11 2016-01-11 Method for removing residual acids in biosaccharide preparation technique by electrodialysis Pending CN105646600A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002604A (en) * 2017-07-21 2018-05-08 义乌赛蓝膜科技有限公司 A kind of method of concentrated seawater recycling
CN109105586A (en) * 2018-09-05 2019-01-01 安徽农业大学 A method of preparing low fluorine instant tea powder

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US5244553A (en) * 1991-10-31 1993-09-14 North Carolina State University Method for recovering acid from an acid-sugar hydrolyzate
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CN104498640A (en) * 2014-12-19 2015-04-08 成都连接流体分离科技有限公司 Process of co-producing xylose, microcrystalline cellulose and sodium lignin sulfonate by taking plant waste as raw material
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Publication number Priority date Publication date Assignee Title
US5244553A (en) * 1991-10-31 1993-09-14 North Carolina State University Method for recovering acid from an acid-sugar hydrolyzate
CN101086025A (en) * 2007-04-18 2007-12-12 清华大学 Plant fiber material acidolysis solution electrodialysis detoxification process and device
CN104498640A (en) * 2014-12-19 2015-04-08 成都连接流体分离科技有限公司 Process of co-producing xylose, microcrystalline cellulose and sodium lignin sulfonate by taking plant waste as raw material
CN105219892A (en) * 2015-11-19 2016-01-06 山东福田药业有限公司 A kind of xylose production process

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002604A (en) * 2017-07-21 2018-05-08 义乌赛蓝膜科技有限公司 A kind of method of concentrated seawater recycling
CN109105586A (en) * 2018-09-05 2019-01-01 安徽农业大学 A method of preparing low fluorine instant tea powder

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