阅读说明：本技术 一种离子液体体系中小分子糖的脱除方法 (A kind of removal methods of ion liquid system small molecular sugar ) 是由 王均凤 李维超 王道广 聂毅 张锁江 于 2019-09-12 设计创作，主要内容包括：本发明提供一种离子液体体系中小分子糖的脱除方法,所述脱除方法为：将待处理样品通过电渗析装置进行电渗析处理,得到纯化离子液体水溶液和小分子糖的水溶液。本发明提供的脱除方法使离子液体和小分子糖的完全分离,得到高纯度的纯化离子液体水溶液,小分子糖脱除率高,离子液体回收率高,不产生大量工业三废,是一种真正高效、环保的脱除工艺；而且所述脱除方法操作简便,能耗低,效率高,可以处理不同种类的离子液体体系以及多种小分子糖,是一种普适性强的脱除方法,易于大规模的工业化推广。(The present invention provides a kind of removal methods of ion liquid system small molecular sugar, the removal methods are as follows: sample to be processed is carried out electrodialysis process by electrodialysis plant, obtains the aqueous solution of purifying ionic liquid aqueous solution and small molecular sugar.Removal methods provided by the invention make being kept completely separate for ionic liquid and small molecular sugar, the purifying ionic liquid aqueous solution of high-purity is obtained, small molecular sugar removal efficiency is high, and the ionic liquid rate of recovery is high, a large amount of three industrial wastes are not generated, are a kind of removing process really efficiently, environmentally friendly；And the removal methods are easy to operate, and low energy consumption, and it is high-efficient, it can handle different types of ion liquid system and a variety of small molecular sugars, be a kind of removal methods that universality is strong, be easy to large-scale industrialization popularization.)

1. a kind of removal methods of ion liquid system small molecular sugar, which is characterized in that the removal methods are as follows: will be to be processed Sample carries out electrodialysis process by electrodialysis plant, obtains the aqueous solution of purifying ionic liquid aqueous solution and small molecular sugar.

2. removal methods according to claim 1, which is characterized in that the electrodialysis process the following steps are included:

(1) concentrate is passed through in the enriched chamber of electrodialysis plant and is recycled；

(2) diluting compartment that sample to be processed is passed through electrodialysis plant is recycled；

(3) pole room that pole liquid is passed through electrodialysis plant is recycled；

(4) electrodialysis plant is powered, until closing power supply when the conductivity in diluting compartment≤100 μ s/cm；Institute is obtained in enriched chamber Purifying ionic liquid aqueous solution is stated, the aqueous solution of the small molecular sugar is obtained in diluting compartment.

3. removal methods according to claim 1 or 2, which is characterized in that step (1) concentrate is ionic liquid Aqueous solution；

Preferably, the concentration of step (1) the concentrate intermediate ion liquid is 0~30g/L；

Preferably, the ionic liquid in step (1) described concentrate is identical as the ionic liquid type in sample to be processed.

4. described in any item removal methods according to claim 1~3, which is characterized in that in step (2) sample to be processed The concentration of ionic liquid is 5~30g/L；

Preferably, the concentration of step (2) the sample small molecular sugar to be processed is 0.5~4g/L.

5. removal methods according to any one of claims 1 to 4, which is characterized in that step (1) concentrate and step (2) volume ratio of the sample to be processed is 1:(1~4).

6. described in any item removal methods according to claim 1~5, which is characterized in that step (3) the pole liquid is ionic liquid The aqueous solution of body；

Preferably, the concentration of step (3) the pole liquid intermediate ion liquid is 10~40g/L；

Preferably, the ionic liquid in step (3) the pole liquid is identical as the ionic liquid type in sample to be processed.

7. described in any item removal methods according to claim 1~6, which is characterized in that the voltage of step (4) described energization is 3~7V.

8. described in any item removal methods according to claim 1~7, which is characterized in that step (1) concentrate, step (2) sample to be processed, step (3) the pole liquid are recycled with identical flow velocity.

9. described in any item removal methods according to claim 1~8, which is characterized in that the ion in the sample to be processed Liquid is alkyl imidazole salt and/or Fixanol；

Preferably, the small molecular sugar in the sample to be processed is selected from glucose, galactolipin, xylose, ribose, fructose or maltose In any a kind or at least two kinds of of combination.

10. described in any item removal methods according to claim 1~9, which is characterized in that the removal methods specifically include with Lower step:

(1) concentrate that ionic liquid concentration is 0~30g/L is passed through in the enriched chamber of electrodialysis plant and is recycled；

(2) be 5~30g/L by ionic liquid concentration, the sample to be processed that small molecular sugar concentration is 0.5~4g/L is passed through electrodialysis The diluting compartment of device is recycled；

(3) pole room that the pole liquid that ionic liquid concentration is 10~40g/L is passed through electrodialysis plant is recycled；

(4) electrodialysis plant is powered, voltage is 3~7V, until closing power supply when conductivity≤100 μ s/cm in diluting compartment；It is dense The purifying ionic liquid aqueous solution is obtained in contracting room, obtains the aqueous solution of the small molecular sugar in diluting compartment；

Wherein, the volume ratio of step (1) concentrate and step (2) described sample to be processed is 1:(1~4), step (1) institute State concentrate, step (2) sample to be processed, the ionic liquid in step (3) the pole liquid is same ionic liquid.

Technical field

The invention belongs to ionic liquids to be recycled technical field, and in particular to a kind of ion liquid system small molecular sugar Removal methods.

Background technique

The natural organic polymer compounds such as cellulose are from a wealth of sources, rich reserves, pass through dissolution, regeneration, processing etc. Available multi-products are managed, the fields such as chemical industry, weaving, food, medicine and biomaterial are widely used in.Naturally have at present The production of machine high-molecular compound mainly uses organic examinations such as N-methylmorpholine-N- oxide (NMMO), formaldehyde, acetone, carboxylic acid The inorganic reagents such as agent and sulphite, vulcanized sodium, sulfuric acid, zinc sulfate, carbon disulfide are as solvent and auxiliary agent, however organic reagent With volatility, can have an adverse effect to the health of environment and operator, inorganic reagent has strong corrosive, leads to equipment Depreciation and loss it is serious；In addition, the chemical reagent generated in production is unable to direct emission, subsequent recycling and treatment process are numerous It is trivial, recovery utilization rate is extremely low.

Ionic liquid is the green solvent of the great application prospect of one kind of rising in recent years, unique highly polar, no with its The excellent performances such as volatilization, stable to water and air are widely used in electrochemistry, organic synthesis, chemical separating, material preparation etc. The research in field is acknowledged as that the environmentally friendly solvent of easy volatile solvent can be substituted in many fields.2002, Alabama The equal dissolution that ionic liquid is applied to cellulose first of professor Rogers of university, it was recently reported that native cellulose is in ionic liquid Solubility property, become the direct solvent of another cellulose after NMMO.

In the production technology of the organic high molecular compounds such as ion liquid dissolving cellulose, along with the degradation of cellulose Add water process needed for process and organic matter regeneration, therefore ionic liquid aqueous solution largely containing small molecular sugar can be generated. However the preparation and purification complex process of ionic liquid, high production cost, therefore, the high efficiente callback recycling of ionic liquid are determined Ionic liquid has been determined in the development prospect of organic high molecular compound dissolution regeneration field.Water is dedicated to there are many researcher at present The research of effects of ion liquids recovery method, for example, CN101503866 disclose it is a kind of using ionic liquid as the fiber of solvent The recovery method of solvent is utilized later using the solid granular impurity being first filtered to remove in ionic liquid in cellulose fiber preparation Reverse osmosis membrane carries out film concentration, is then evaporated under reduced pressure, makes containing ionic liquid to the solution containing ionic liquid after concentration Mass content≤2% of water in solution, obtains the ionic liquid of recycling.It is acylated that CN102371078A discloses a kind of cellulose homogeneous-phase The recovery method of ion liquid solvent after reaction, the first decoloration of ionic liquid waste liquid, the filtering by cellulose homogeneous-phase after acylated, then Filtered ionic liquid waste liquid is evaporated under reduced pressure, then the ionic liquid waste liquid after vacuum distillation is added in molecular distillation apparatus Molecular distillation is carried out, collecting gained heavy constituent is ionic liquid after the recovery；The method will be evaporated under reduced pressure and molecular distillation Technology combines, can efficiently remove cellulose homogeneous-phase it is acylated after organic residue and water in ion liquid solvent waste liquid so that The ionic liquid purity arrived is 99% or more.CN102559943A discloses the technique side of a kind of separating glucose and ionic liquid Method, specifically: anti-solvent is added in the mixture solution of glucose and ionic liquid, crystallizes glucose from ionic liquid It is precipitated, by being filtered, washed, obtains pure glucose, and evaporate filtrate and isolate anti-solvent, obtain ionic liquid recovered liquid；Institute Stating anti-solvent includes methanol, ethyl alcohol, isopropanol, 1- propyl alcohol, acetonitrile, methylene chloride, preferred alcohol.

However in existing ionic liquid recovery processing technique, it is miscellaneous that major part all lays particular emphasis on solid phase in ion liquid system Matter, the removing of inorganic heavy metal impurity and aqueous solvent evaporation, seldom in view of the degradation of cellulose in ion liquid system produces The removal of object, i.e. small molecular sugar, ionic liquid recycling after recycling can be seriously affected by remaining on the small molecular sugar in ionic liquid When to the solubility property of cellulose.And the separating technology of ionic liquid and small molecular sugar is then filtered or is added a large amount of anti-solvent with film It carries out based on dilution crystallization, low efficiency, complex process can generate a large amount of waste liquids, be unfavorable for environmental protection.

Based on this, develop it is a kind of it is high-efficient, low energy consumption, the removing side of the ion liquid system small molecular sugar of simple process Method realizes that the high efficiente callback of ionic liquid utilizes, is the research emphasis of this field.

Summary of the invention

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of the de- of ion liquid system small molecular sugar Except method, being kept completely separate for ionic liquid and small molecular sugar is made by electrodialysis process process, purifying ionic liquid is obtained, realizes Ionic liquid fast and efficiently purifies concentration, for ionic liquid recycling recycling technical support is provided, have it is high-efficient, Process is simple, low power consumption and other advantages.

In order to achieve that object of the invention, the invention adopts the following technical scheme:

The present invention provides the removal methods of ion liquid system small molecular sugar, the removal methods are as follows: by sample to be processed Product carry out electrodialysis process by electrodialysis plant, obtain the aqueous solution of purifying ionic liquid aqueous solution and small molecular sugar.

The removal methods of ion liquid system small molecular sugar provided by the invention by electrodialysis plant realize, using from Sub- liquid and nonionic compound migratory behaviour difference in the presence of an electric field realize the complete of ionic liquid and small molecular sugar Separation；The removal methods have universality, it can be achieved that the removing of various small molecular sugars and ionic liquid in different kinds of ions liquid Purifying.The method of dilution crystallization is carried out not with the membrane filter methods such as nanofiltration in the prior art, reverse osmosis and addition anti-solvent Together, removal methods of the present invention are carried out under electric field driven, and more efficient, the occupied area of equipment is smaller, more favorably In the application for realizing heavy industrialization；And removal methods of the present invention will not generate useless without consuming a large amount of solvents Liquid, the product after removing are the ionic liquid by concentrating and purifying, and are concentrated by evaporation by simple solvent (water) or no longer need to locate Reason can be reused.Therefore, removal methods provided by the invention have high-efficient, simple process, low energy consumption, applicability The advantages that strong, and treatment process will not generate waste liquid, be a kind of removing process really efficiently, environmentally friendly.

Preferably, the electrodialysis process the following steps are included:

(1) concentrate is passed through in the enriched chamber of electrodialysis plant and is recycled；

(2) diluting compartment that sample to be processed is passed through electrodialysis plant is recycled；

(3) pole room that pole liquid is passed through electrodialysis plant is recycled；

(4) electrodialysis plant is powered, until the conductivity in diluting compartment≤100 μ s/cm (such as the conductivity in diluting compartment For 50 μ s/cm, 55 μ s/cm, 60 μ s/cm, 65 μ s/cm, 70 μ s/cm, 75 μ s/cm, 80 μ s/cm, 85 μ s/cm, 90 μ s/cm, 95 μ S/cm or 100 μ s/cm etc.) when close power supply；The purifying ionic liquid aqueous solution is obtained in enriched chamber, obtains institute in diluting compartment State the aqueous solution of small molecular sugar.

Preferably, step (1) concentrate is the aqueous solution of ionic liquid.

Preferably, the concentration of step (1) the concentrate intermediate ion liquid is 0~30g/L, such as 0g/L, 1g/L, 3g/ L, 5g/L, 7g/L, 10g/L, 12g/L, 15g/L, 18g/L, 20g/L, 23g/L, 25g/L, 27g/L or 29g/L and above-mentioned point Specific point value between value, as space is limited and for concise consideration, the tool that range described in the present invention no longer exclusive list includes Body point value.

As the preferred technical solution of the present invention, when the concentration of the concentrate is within the scope of above-mentioned restriction, just it is able to achieve The maximization of energy consumption minimumization and the ionic liquid rate of recovery of processing step.If the concentration of concentrate intermediate ion liquid is higher than 30g/L, then the rate of recovery of ionic liquid is declined after will lead to electrodialysis process removing small molecular sugar.

Preferably, the ionic liquid in step (1) described concentrate is identical as the ionic liquid type in sample to be processed.

Preferably, the concentration of step (2) the sample intermediate ion liquid to be processed be 5~30g/L, such as 6g/L, 8g/L, It is specific between 10g/L, 12g/L, 15g/L, 18g/L, 20g/L, 23g/L, 25g/L, 27g/L or 29g/L and above-mentioned point value Point value, as space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.

As the preferred technical solution of the present invention, the concentration of the sample intermediate ion liquid to be processed is 5~30g/L.Such as The concentration of fruit sample intermediate ion liquid to be processed is lower than 5g/L, then removes the ratio of water in the purifying ionic liquid obtained after processing It is excessively high, increase the subsequent process and energy consumption for steaming solvent (water)；If the concentration of sample intermediate ion liquid to be processed is higher than 30g/ L, then small molecular sugar will increase by the amount that electrodialysis enters enriched chamber, and the removal efficiency of small molecular sugar is caused to reduce；And it handles The water into enriched chamber also will increase afterwards, and ionic liquid diluting effect after purification is caused to increase.

Preferably, the concentration of step (2) the sample small molecular sugar to be processed be 0.5~4g/L, such as 0.6g/L, 0.8g/L、1g/L、1.2g/L、1.5g/L、1.8g/L、2g/L、2.3g/L、2.5g/L、2.8g/L、3g/L、3.3g/L、3.5g/ L, the specific point value between 3.7g/L or 3.9g/L and above-mentioned point value, as space is limited and for concise consideration, the present invention is not The specific point value that range described in exclusive list includes again.

Preferably, the volume ratio of step (1) concentrate and step (2) described sample to be processed is 1:(1~4), example Such as 1:1.1,1:1.3,1:1.5,1:1.7,1:1.9,1:2,1:2.2,1:2.5,1:2.8,1:3,1:3.2,1:3.5,1:3.7 or 1:3.9 waiting.

As the preferred technical solution of the present invention, the volume ratio of concentrate and sample to be processed is in 1:(1~4) in range When, just it is able to achieve the maximization of energy consumption minimumization and the ionic liquid rate of recovery of processing step.If the volume ratio of the two is super Above-mentioned restriction range out then will lead to the reduction of the ionic liquid rate of recovery, or cost is evaporated in purifying ion liquid solvent (water) Increase.

Preferably, step (3) the pole liquid is the aqueous solution of ionic liquid.

Preferably, the concentration of step (3) the pole liquid intermediate ion liquid be 10~40g/L, such as 11g/L, 13g/L, 15g/L, 18g/L, 20g/L, 23g/L, 25g/L, 27g/L, 30g/L, 32g/L, 35g/L, 37g/L or 39g/L and above-mentioned point Specific point value between value, as space is limited and for concise consideration, the tool that range described in the present invention no longer exclusive list includes Body point value.

Preferably, the ionic liquid in step (3) the pole liquid is identical as the ionic liquid type in sample to be processed.

Preferably, the voltage of step (4) described energization be 3~7V, such as 3.1V, 3.3V, 3.5V, 3.8V, 4V, 4.3V, It is specific between 4.5V, 4.8V, 5V, 5.2V, 5.5V, 5.8V, 6V, 6.2V, 6.5V, 6.7V or 6.9V and above-mentioned point value Value, as space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.

As the preferred technical solution of the present invention, when the voltage of step (4) described energization is 3~7V, can efficiently divide With suitable energy consumption while from ionic liquid and small molecular sugar；If voltage setting is higher than 7V, can make entirely to remove The energy consumption of journey is excessively high, is unfavorable for large-scale industrialization popularization；If voltage is set lower than above-mentioned restriction range, will affect from The separative efficiency of sub- liquid and small molecular sugar makes the removing overlong time of small molecular sugar.

Preferably, step (1) concentrate, step (2) sample to be processed, step (3) the pole liquid are with identical Flow velocity recycled.

Preferably, the ionic liquid in the sample to be processed is alkyl imidazole salt and/or Fixanol.

In the present invention, the alkyl imidazole salt illustratively includes but is not limited to: 1- ethyl-3-methylimidazole p diethylaminobenzoic acid Ester salt, 1- ethyl-3-methylimidazole acetate and 1- ethyl-3-methylimidazole villaumite etc.；The Fixanol is illustratively Including but not limited to: 1- allyl -3- picoline villaumite and N- allyl pyridine villaumite etc..

Preferably, the small molecular sugar in the sample to be processed is selected from glucose, galactolipin, xylose, ribose, fructose or wheat Any a kind or at least two kinds of of combination in bud sugar.

Preferably, the removal methods specifically includes the following steps:

(1) concentrate that ionic liquid concentration is 0~30g/L is passed through in the enriched chamber of electrodialysis plant and is recycled.

(2) be 5~30g/L by ionic liquid concentration, the sample to be processed that small molecular sugar concentration is 0.5~4g/L is passed through electricity The diluting compartment of electrodialysis apparatus is recycled.

(3) pole room that the pole liquid that ionic liquid concentration is 10~40g/L is passed through electrodialysis plant is recycled.

(4) electrodialysis plant is powered, voltage is 3~7V, until closing electricity when conductivity≤100 μ s/cm in diluting compartment Source；The purifying ionic liquid aqueous solution is obtained in enriched chamber, obtains the aqueous solution of the small molecular sugar in diluting compartment.

Wherein, the volume ratio of step (1) concentrate and step (2) described sample to be processed is 1:(1~4), step (1) concentrate, step (2) sample to be processed, the ionic liquid in step (3) the pole liquid are same ionic liquid Body.

Compared with the existing technology, the invention has the following advantages:

(1) removal methods of ion liquid system small molecular sugar provided by the invention by electrodialysis process process make from Being kept completely separate for sub- liquid and small molecular sugar, obtains the purifying ionic liquid aqueous solution of high-purity, the removal efficiency of small molecular sugar can To reach 99.6%, the rate of recovery of ionic liquid can reach 98.6%；Therefore, the small molecular sugar of removal methods of the present invention is de- Except rate height, the ionic liquid rate of recovery is high, does not generate a large amount of three industrial wastes, is a kind of removing process really efficiently, environmentally friendly.

(2) removal methods of ion liquid system small molecular sugar provided by the invention are easy to operate, and low energy consumption, efficiency Height can complete the removing of small molecular sugar and the purifying of ionic liquid, concentration within 25min, be easy to large-scale industry Change and promotes.

(3) removal methods of ion liquid system small molecular sugar provided by the invention can handle different types of ion Liquid system and a variety of small molecular sugars are a kind of removal methods that universality is strong, have a good application prospect.

Detailed description of the invention

Fig. 1 is the process flow chart of the removal methods of ion liquid system small molecular sugar of the present invention.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.

Experimental material used in following embodiment of the present invention includes:

Sample source to be processed is in Xinxiang City, Henan Province chemical fibre factory；Electrodialysis plant is Hefei Ke Jia high molecular material section The electrodialysis plant of the model CJ-ED-1020 of skill Co., Ltd production.