CN103409315A - Reaction separating and coupling apparatus, and technology for preparation of gluconic acid from xylitol crystallization mother liquor - Google Patents
Reaction separating and coupling apparatus, and technology for preparation of gluconic acid from xylitol crystallization mother liquor Download PDFInfo
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- CN103409315A CN103409315A CN2013103124209A CN201310312420A CN103409315A CN 103409315 A CN103409315 A CN 103409315A CN 2013103124209 A CN2013103124209 A CN 2013103124209A CN 201310312420 A CN201310312420 A CN 201310312420A CN 103409315 A CN103409315 A CN 103409315A
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Abstract
The invention provides a reaction separating and coupling apparatus, and a technology for preparation of gluconic acid from xylitol crystallization mother liquor. The reaction separating and coupling apparatus comprises a nanofiltration device, a co-immobilization glucose oxidase and catalase column reactor; a fixed bed chromatography column, a computer control system, a transmission pump, a raw material liquid storage tank, a product liquid storage tank, an eluate storage tank, and valves. Reaction coupling of the co-immobilization glucose oxidase and catalase column reactor and adsorption processes of the fixed bed chromatography column is realized for the first time, so that a gluconic acid solution containing a large amount of impurities is prepared from xylitol crystallization mother liquor by the immobilization enzyme column reactor, and is delivered into the fixed bed chromatography column directly, and production of high purity gluconic acid with selectivity is realized. Production efficiency of gluconic acid from xylitol crystallization mother liquor is increased; feedback inhibition is eliminated; the value of industrial waste is increased; and reaction, solid-liquid separation and purification are combined by the reaction separating and coupling apparatus, and the technology. The obtained gluconic acid is colorless crystals, yield is of 84 to 95%, and purity can reach 94 to 97%.
Description
One, technical field
The invention belongs to technical field of biochemical industry, be specifically related to Reaction Separation coupling device and technique that crystal mother solution of xylitol prepares gluconic acid.
Two, background technology
Xylitol is a kind of natural low caloric value new function sweeting agent and the senior dietotherapy product that extract from the plants such as white birch, Oak Tree, corn cob, bagasse, has to reduce blood fat, anti-ketoboidies, maintain the function such as normal bone density.Chemical hydrolysis hydrogenation crystallization process is the main method of producing at present Xylitol.Usually, when producing wood sugar, can be accompanied by the generation of mass crystallization mother liquor, the total sugar concentration that this crystalline mother solution contains is about 75%.Owing to recycling crystalline mother solution, residue in the assorted sugar in mother liquor, such as glucose, pectinose etc., accumulate gradually, directly affect yield and the quality of Xylitol crystallization.At present, the most of directly discharge of this mother liquor, serious environment pollution, only a small amount of be used to producing caramel colorant or as the glycerol substitute of toothpaste industry, cheap, affected the economic benefit of Xylitol industry.Utilize discarded crystal mother solution of xylitol to produce high value added product, be conducive to improve the Xylitol industrial economy, reduce energy consumption and reduce environmental pollution.
Gluconic acid and derivative thereof, as gluconate, gluconic acid delta-lactone etc., be the multiduty important Organic chemical products of a class, they are as complexing agent, the grease-removing agent of iron and steel, glass surface, foodstuff additive etc. are widely used in the fields such as metal processing, food, daily-use chemical industry.At present, gluconic acid is generally obtained by glucose oxidase, comprises chemical catalytic oxidation, electrochemical oxidation and fermentation method etc.China is mainly by the fermentative Production calglucon, then obtains gluconic acid through acidification, then makes various gluconates.The method equipment is huge, and investment cost is high, and by product is many, and raw material is glucose, and total cost of production is higher.Therefore we intend finding new approach, utilize cheap raw material or trade waste to prepare gluconic acid, and improve related process, thereby reduce production costs.
At present, the method of main crystal mother solution of xylitol recycling is by the monosaccharide component in ion-exchange chromatography separating xylose alcohol crystalline mother solution such as glucose, wood sugar, arabitol etc., as patent CN102924538A: a kind of from wood-sugar fermentation liquid or xylose mother liquid, extracting the method for wood sugar, pectinose and semi-lactosi, but the characteristics of this technique are need separately build biochemical treatment apparatus to purify, and simulation moving-bed investment is large, operational condition is harsh, cause production cost high, product is lacked competitiveness.The method of existing processing xylose mother liquid is also " a kind of method of processing xylose mother liquid " patent of CN102580611A just like publication No., and disclosed is with xylose mother liquid discarded in xylose production and commercially available C
12-14Alkyl glycidyl ether is raw material, is 63～93 ℃ in temperature, and pH is that under 7.2～9.2 condition, dehydrating condensation makes wood sugar C
12-14Acyl hydroxypropyl ether crude product, then through separation and purification, obtain xylose mother liquid-C
12-14Acyl hydroxypropyl ether surfactant product, however this technique need to consume a large amount of commercially available C
12-14Alkyl glycidyl ether (xylose mother liquid and C
12-14The alkyl glycidyl ether volume ratio is 1: 2～5), and C
12-14Alkyl glycidyl ether has toxicity, inflammable and expensive, so this technique is in environmental protection, safety with do not have in price advantage.
Above-mentioned research is the utilization to the separation between the sugar alcohol component or mixed sugar liquid, and rare specificity reclaims and utilize the report of mother liquor middle and high concentration glucose.Patent CN101538591A: from preparing the method for gluconic acid xylose crystallization mother liquor, reported a kind of method of utilizing xylose crystallization mother liquor to prepare gluconic acid, but reaction process prepared by gluconic acid is separated with sepn process, i.e. reaction could be from separation and purification gluconic acid reaction solution after finishing, step is lengthy and tedious, and power consumption and productive rate are not high.And immobilized enzyme reactor and fixed-bed resin sepn process coupling can be overcome to this shortcoming, on the ion-exchange high-throughput techniques, by glucose oxidase, be gluconic acid and from removing crystal mother solution of xylitol in conjunction with the specificity of enzyme process, can reduce the restraining effect of product gluconic acid to immobilized enzyme, realize the serialization production of gluconic acid, waste resource is recycled simultaneously, the demand that meets national development green chemical industry and recycling economy is the new approaches of innovative technology.
This laboratory has prepared the hydroxyl crosslinked chitosan resin of polylysine modification, and in order to common fixing glucose oxidase (GOD) and catalase (CAT), glucose is generated Gluconolactone and H by the GOD oxidation under oxygen exists
2O
2, the former is converted into gluconic acid automatically in the aqueous solution, and the latter is decomposed and generates water and oxygen by CAT, and oxygen, again by the GOD recycle, can prevent H
2O
2Accumulation, keep enzyme activity, improves inversion rate of glucose.
In xylose crystallization mother liquor, contain 5～15% glucose, 1～5% semi-lactosi and pectinose, the present invention utilizes in xylose crystallization mother liquor and contains the solute that the pigment equimolecular quantity is larger, its molecular weight generally is greater than 2000Da, and the carbohydrate molecule amounts such as wood sugar, semi-lactosi, pectinose, glucose are less, be generally these characteristics of hundreds of Da, select suitable nanofiltration membrane can remove the solute of macromolecule scope, prevent that simultaneously subsequent reactions from separating cylinder and stopping up; Glucose in filtrate obtains gluconic acid after adopting the oxidation of co-immobilization CAT/GOD cross-linked chitosan Methionin Choice of Resin, wood sugar, semi-lactosi, pectinose etc. can be not oxidized, the gluconic acid formation negatively charged ion that dissociates in solution, all the other carbohydrates are not charged, therefore can separate with anionite-exchange resin or absorption with macroporous adsorbent resin, then by the NaOH eluant solution, obtain sodium gluconate solution, this solution finally can obtain the gluconic acid powder-product through acidifying, concentrated, drying.
Three, summary of the invention
The object of the present invention is to provide the Reaction Separation coupling device for preparing gluconic acid from crystal mother solution of xylitol.
A further object of the present invention is to provide utilizes the technique for preparing the Reaction Separation coupling device production gluconic acid of gluconic acid from crystal mother solution of xylitol, to improve the production efficiency for preparing gluconic acid from crystal mother solution of xylitol, remove feedback inhibition, simplify separating step and make reaction carry out continuously, realize the high value utilization of trade waste, and overcome the shortcomings of prior art.
The Reaction Separation coupling device for preparing gluconic acid from crystal mother solution of xylitol of the present invention, comprise nanofiltration device, co-immobilization glucose oxidase and catalase column reactor, fixed bed chromatography post, computerized control system, transmission pump, stock liquid storage tank, product container for storing liquid, the elutriant container for storing liquid, valve, three-way valve, four way valve.As shown in Figure 1.
Described nanofiltration device top is connected with reservoir by pump, bottom liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor bottom, the outlet of the other end trapped fluid is connected with the circulation main pipe rail, and is connected with the raw material container for storing liquid.Co-immobilization glucose oxidase and catalase column reactor top have the circulation fluid outlet.The fixed bed chromatography post of two parallel connections (can be in parallel a plurality of as required) bottom is equipped with the circulation fluid import, and the chromatography column top all has the circulation fluid outlet.
Four ports of the four way valve on the circulation fluid main pipe rail on described fixed bed chromatography post top, respectively by the circulation fluid outlet at pipeline and described chromatography column top, together immobilized glucose oxidase and catalase column reactor UNICOM a main pipe rail, and the pipeline be communicated with between four way valve be connected, an and port of the four way valve on the circulation fluid exit pipeline of the chromatography column of second parallel connection, with the pipeline of a port that is communicated with three-way valve, be connected, a port of this three-way valve is connected with the product container for storing liquid by pipeline.
Four ports of described four way valve on the circulation fluid main pipe rail at place, fixed bed chromatography column bottom, by pipeline, be connected with the circulation fluid import of described fixed bed chromatography column bottom, the circulation fluid outlet of each chromatography column transmission pump separately, the pipeline reached between the connection four-way valve respectively, and a port of the four way valve on the circulation fluid ingress pipeline of second chromatography column, be connected with the pipeline of a port of the above-mentioned three-way valve be communicated with; One port of the four way valve on the circulation fluid ingress pipeline of the fixed bed chromatography post of second parallel connection, a port by the four-way valve on pipeline and the circulation fluid main pipe rail that is connected this chromatography column top circulation fluid export pipeline is connected.
Between described connection transmission pump, on the pipeline of circulation fluid import, four way valve is arranged, two other port of this valve is respectively by pipeline and a circulation fluid main pipe rail that is communicated with co-immobilization glucose oxidase and catalase column reactor bottom, and a main pipe rail of elutriant container for storing liquid is connected.
Described co-immobilization glucose oxidase and catalase column reactor have discharge port and circulation fluid outlet with pH electrode, temperature sensor, top, and the circulation fluid discharge port is connected with the circulation main pipe rail.
The switch of described computerized control system by-pass valve control, three-way valve, four way valve and pump, and controlled circulation liquid is mobile.
Utilization of the present invention prepares the technique of the Reaction Separation coupling device production gluconic acid of gluconic acid from crystal mother solution of xylitol:
At first, in co-immobilization glucose oxidase and catalase column reactor, fill respectively the immobilized enzyme resin, fill anionite-exchange resin in two chromatography columns; Nanofiltration device adds the nanofiltration membrane of certain molecular weight cut-off.
Second step, pass through transmission pump, xylose crystallization mother liquor enters nanofiltration device, nanofiltration device liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor bottom, provide and meet the requirements of xylose crystallization mother liquor, the other end trapped fluid is connected with the circulation main pipe rail, and is connected with the raw material container for storing liquid.
The 3rd step, set suitable enzyme temperature alive in co-immobilization glucose oxidase and catalase column reactor, by computerized control system, regulating the circulation fluid main pipe rail and connect the four way valve on pipeline between transmission pump makes first fixed bed chromatography column top be communicated with the circulation fluid main pipe rail, the coupled transmission pump in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and first fixed bed chromatography post, circulate by realization response liquid, when first fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, regulate and connect the four way valve on pipeline between transmission pump, make elutriant container for storing liquid (leacheate, elutriant, regenerated liquid) with this pump, be communicated with, liquid storage wherein enters first fixed bed chromatography post by this transmission pump, by drip washing, after wash-out and regeneration, first chromatography column enters holding state, simultaneously, four way valve on regulating the circulation fluid main pipe rail and being connected transmission pump, make second fixed bed chromatography column top in parallel be communicated with the circulation fluid main pipe rail, the coupled transmission pump in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and second fixed bed chromatography post, circulate by realization response liquid, realize the reactive separation process of gluconic acid, when second fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, first fixed bed chromatography post that enters holding state enters the working order of circulation coupling, and second fixed bed chromatography post be by drip washing simultaneously, wash-out and regeneration, enter holding state, iterative cycles.
The 4th step, the thick sodium gluconate solution obtained by the 3rd step, through after acidifying, pumping in reverse osmosis machine, carries out reverse osmosis concentration under 1.6～3.0MPa pressure, then, this concentrated solution is pumped in drying machine with centrifugal spray to 125～185 ℃ of lower spraying dryings.Finally just obtain the gluconic acid powder-product.
Described immobilized enzyme resin of filling in co-immobilization glucose oxidase and catalase column reactor can be immobilization GOD cross-linked chitosan Methionin resin, can be also co-immobilization GOD/CAT cross-linked chitosan Methionin resin.
Described nanofiltration device molecular weight cut-off is 2000～7000Da.
In described co-immobilization glucose oxidase and catalase column reactor, suitable CAT/GOD enzyme temperature alive is 40～65 ℃.
Xylose crystallization mother liquor pH in described raw material container for storing liquid is 3～5.
Described leacheate is distilled water, elutriant, the NaOH solution (m/v) of regenerated liquid difference 0.5%～10% and 4%～20% NaOH solution.
Described anionite-exchange resin is the macroporous adsorbent resin with certain grain size distribution, weak base anion-exchange resin, and strongly basic anion exchange resin, can adjust its different strong and weak base numbers, and degree of crosslinking.
In described co-immobilization glucose oxidase and catalase column reactor, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin or fill immobilization GOD cross-linked chitosan Methionin resin.Xylose crystallization mother liquor in container for storing liquid enters from top co-immobilization glucose oxidase and catalase column reactor after the nanofiltration decolouring, computerized control system is controlled co-immobilization CAT/GOD optimal reaction temperature automatically between 40～65 ℃, and pH is between 3～5, coutroi velocity is per hour between 2BV～8BV.The gluconic acid that reacted liquid generates through the absorption reaction of fixed bed chromatography post, the liquid after the absorption fixed bed bed of flowing through turns back in the raw material container for storing liquid.Through the several times circulation, fixedly to wear chromatography column and reach capacity, drip washing bed, leacheate merge in the raw material container for storing liquid, then through the elutriant wash-out, reclaim regenerated liquid regeneration fixed bed chromatography post; Simultaneously, co-immobilization glucose oxidase and catalase column reactor are switched to another fixed bed chromatography post by valve, realize that enzymatic reaction, separation, desorb and reprocessing cycle synchronously carry out.The gluconic acid powder finally obtained is the clear crystal shape, and yield is 84～95%, and purity reaches 94～97%.
The present invention is first by co-immobilization glucose oxidase and catalase column reactor and fixed bed chromatography post adsorption process realization response coupling, make through the gluconic acid solution that contains a large amount of impurity that co-immobilization glucose oxidase and catalase column reactor make, directly to enter fixed bed chromatography post by xylose crystallization mother liquor, specificity is produced highly purified gluconic acid.This invention can improve the production efficiency for preparing gluconic acid from crystal mother solution of xylitol, remove feedback inhibition, simplify separating step and make reaction carry out continuously, realize the high value utilization of trade waste, it is a kind of equipment and process that integrates reaction, solid-liquid separation, preliminary purification, can reduce the downstream purification step, not affect reaction process simultaneously.
The accompanying drawing explanation
Fig. 1 is the Reaction Separation coupling device schematic diagram that crystal mother solution of xylitol of the present invention prepares gluconic acid.
Wherein 1. stock liquid storage tanks, 2. transmission pump, 3. nanofiltration device, 4. valve, 5. three-way valve, 6. four way valve, 7. co-immobilization glucose oxidase and catalase column reactor, 8. fixed bed chromatography post, 9. product container for storing liquid, 10. elutriant container for storing liquid, 11. computerized control systems.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, processing condition and result thereof only illustrate the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1:
Fig. 1 is a specific embodiment of the present invention, as can be seen from the figure, should prepare from crystal mother solution of xylitol the Reaction Separation coupling device of gluconic acid, comprise co-immobilization glucose oxidase and catalase column reactor 7,3, two fixed bed chromatography posts 8 of nanofiltration device, computerized control system 11, three transmission pumps 2, stock liquid storage tank 1, product container for storing liquid 9, elutriant container for storing liquid 10,5, five four way valves 6 of 4, three three-way valves of five valves.As shown in Figure 1.
Described nanofiltration device 3 tops are connected with reservoir by pump 2a, bottom liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor 7 bottoms, the outlet of the other end trapped fluid is connected with the circulation main pipe rail, and is connected with raw material container for storing liquid 1.Co-immobilization glucose oxidase and catalase column reactor 7 tops have the circulation fluid outlet.The fixed bed chromatography post 8 of two parallel connections (can be in parallel a plurality of as required) bottom is equipped with the circulation fluid import, and chromatography column 8 tops all have the circulation fluid outlet.
Four ports of four way valve 6a on the circulation fluid main pipe rail at place, described first fixed bed chromatography post 8a top, respectively by the circulation fluid outlet at pipeline and described chromatography column 8a top, a main pipe rail of immobilized glucose oxidase and catalase column reactor 7 UNICOMs together, and the pipeline be communicated with between four way valve 6c is connected, and the port of the four way valve 6b on the circulation fluid exit pipeline of the chromatography column 8b of second parallel connection, with the pipeline of a port that is communicated with three-way valve 5b, be connected, one port of this three-way valve is connected with product container for storing liquid 9 by pipeline.
Four ports of described four way valve 6 on the circulation fluid main pipe rail at fixed bed chromatography post 8 places, bottom, by pipeline, be connected with the circulation fluid import of described fixed bed chromatography post 8 bottoms, the circulation fluid outlet of each chromatography column transmission pump 6c, 6d separately, the pipeline reached between connection four-way valve 6e respectively, and the port of the four way valve 6d on the circulation fluid ingress pipeline of second chromatography column 8b, be connected with the pipeline of the port of the above-mentioned three-way valve 5b be communicated with; The port of four way valve 6c on the circulation fluid ingress pipeline of the fixed bed chromatography post 8a that first is in parallel, a port by the four-way valve 6a on pipeline and the circulation fluid main pipe rail that is connected this chromatography column 8a top circulation fluid export pipeline is connected.
Between described connection transmission pump, on the pipeline of circulation fluid import, four way valve 6e is arranged, two other port of this valve is respectively by pipeline and a circulation fluid main pipe rail that is communicated with co-immobilization glucose oxidase and catalase column reactor 7 bottoms, and a main pipe rail of elutriant container for storing liquid 10 is connected.
Described co-immobilization glucose oxidase and catalase column reactor 7 have discharge port and circulation fluid outlet with pH electrode, temperature sensor, top, and the circulation fluid discharge port is connected with the circulation main pipe rail.
The switch of described computerized control system 11 by-pass valve controls, three-way valve, four way valve and pump, and controlled circulation liquid is mobile.
At first, device according to Fig. 1, the nanofiltration membrane that is 3000Da by molecular weight cut-off is placed in nanofiltration device 3, in co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin, in two chromatography columns 8, fill anionite-exchange resin D239.
Second step, by transmission pump 2a, xylose crystallization mother liquor enters nanofiltration device 3, nanofiltration device liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor 7 bottoms, provide and meet the requirements of xylose crystallization mother liquor, the other end trapped fluid is connected with the circulation main pipe rail, and is connected with raw material container for storing liquid 1.
The 3rd step, set suitable CAT/GOD enzyme temperature alive in co-immobilization glucose oxidase and catalase column reactor 7, by computerized control system 11, regulating the circulation fluid main pipe rail and connect the four way valve 6e on pipeline between transmission pump 2b makes first fixed bed chromatography post 8a top be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2b in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor 7 and first fixed bed chromatography post 8a, circulate by realization response liquid, when first fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, regulate and connect the four way valve 6e on pipeline between transmission pump, make container for storing liquid 10 (elutriants, leacheate, regenerated liquid) with this pump, be communicated with, liquid storage wherein enters first fixed bed chromatography post 8a by this transmission pump, by drip washing, after wash-out and regeneration, first chromatography column enters holding state, simultaneously, four way valve 6e on regulating the circulation fluid main pipe rail and being connected transmission pump, make second fixed bed chromatography post 8b top in parallel be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2d in bottom is connected, transmission pump 2d is immobilized glucose oxidase and 7 connections of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and second fixed bed chromatography post, circulate by realization response liquid, realize the reactive separation process of gluconic acid, when second fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, first fixed bed chromatography post that enters holding state enters the working order of circulation coupling, and second fixed bed chromatography post be by drip washing simultaneously, wash-out and regeneration, enter holding state, iterative cycles.
The 4th step, the thick sodium gluconate solution obtained by the 3rd step, through after acidifying, pumping in reverse osmosis machine, carries out reverse osmosis concentration under 1.6MPa pressure, then, this concentrated solution is pumped in drying machine with centrifugal spray to 125 ℃ of lower spraying dryings.Finally just obtain the gluconic acid powder-product.
Described nanofiltration device molecular weight cut-off is 2000Da.
In described co-immobilization glucose oxidase and catalase column reactor, temperature is 40 ℃.
Xylose crystallization mother liquor pH in described raw material container for storing liquid is 3.
Described leacheate is distilled water, elutriant, the NaOH solution (m/v) of regenerated liquid difference 1% and 5% NaOH solution.
In described co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin.Xylose crystallization mother liquor in container for storing liquid 1 enters from top co-immobilization glucose oxidase and catalase column reactor 7 after the nanofiltration decolouring, it is 40 ℃ that computerized control system 11 is controlled co-immobilization CAT/GOD temperature of reaction automatically, and pH is 3, coutroi velocity is at 2BV/h.The gluconic acid that reacted liquid generates through 8 absorption reactions of fixed bed chromatography post, the liquid after the absorption fixed bed bed of flowing through turns back in raw material container for storing liquid 1.Through the several times circulation, with pH meter, detect the pH value of circulation fluid, when the pH value continuous decrease of the circulation fluid after first fixed bed chromatography post absorption gluconic acid, illustrate that this chromatography column reaches capacity, drip washing bed, leacheate merge in the raw material container for storing liquid, then through the elutriant wash-out, reclaim regenerated liquid regeneration fixed bed chromatography post; Simultaneously, co-immobilization glucose oxidase and catalase column reactor are switched to another fixed bed chromatography post by valve, realize that enzymatic reaction, separation, desorb and reprocessing cycle synchronously carry out.The gluconic acid crystal obtained thus, its yield is 92%, purity reaches 95%.
Following examples are all used the device in the present embodiment.
Embodiment 2:
At first, device according to Fig. 1, the nanofiltration membrane that is 4000Da by molecular weight cut-off is placed in nanofiltration device 3, in co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin, in two chromatography columns 8, fill anionite-exchange resin D239.
Second step, by transmission pump 2a, xylose crystallization mother liquor enters nanofiltration device 3, nanofiltration device liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor 7 bottoms, provide and meet the requirements of xylose crystallization mother liquor, the other end trapped fluid is connected with the circulation main pipe rail, and is connected with raw material container for storing liquid 1.
The 3rd step, set suitable CAT/GOD enzyme temperature alive in co-immobilization glucose oxidase and catalase column reactor 7, by computerized control system 11, regulating the circulation fluid main pipe rail and connect the four way valve 6e on pipeline between transmission pump 2b makes first fixed bed chromatography post 8a top be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2b in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor 7 and first fixed bed chromatography post 8a, circulate by realization response liquid, when first fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, regulate and connect the four way valve 6e on pipeline between transmission pump, make container for storing liquid 10 (elutriants, leacheate, regenerated liquid) with this pump, be communicated with, liquid storage wherein enters first fixed bed chromatography post 8a by this transmission pump, by drip washing, after wash-out and regeneration, first chromatography column enters holding state, simultaneously, four way valve 6e on regulating the circulation fluid main pipe rail and being connected transmission pump, make second fixed bed chromatography post 8b top in parallel be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2d in bottom is connected, transmission pump 2d is immobilized glucose oxidase and 7 connections of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and second fixed bed chromatography post, circulate by realization response liquid, realize the reactive separation process of gluconic acid, when second fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, first fixed bed chromatography post that enters holding state enters the working order of circulation coupling, and second fixed bed chromatography post be by drip washing simultaneously, wash-out and regeneration, enter holding state, iterative cycles.
The 4th step, the thick sodium gluconate solution obtained by the 3rd step, through after acidifying, pumping in reverse osmosis machine, carries out reverse osmosis concentration under 2.0MPa pressure, then, this concentrated solution is pumped in drying machine with centrifugal spray to 145 ℃ of lower spraying dryings.Finally just obtain the gluconic acid powder-product.
Described nanofiltration device molecular weight cut-off is 4000Da.
In described co-immobilization glucose oxidase and catalase column reactor, temperature is 50 ℃.
Xylose crystallization mother liquor pH in described raw material container for storing liquid is 4.
Described leacheate is distilled water, elutriant, the NaOH solution (m/v) of regenerated liquid difference 2% and 6% NaOH solution.
In described co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin.Xylose crystallization mother liquor in container for storing liquid 1 enters from top co-immobilization glucose oxidase and catalase column reactor 7 after the nanofiltration decolouring, it is 50 ℃ that computerized control system 11 is controlled co-immobilization CAT/GOD temperature of reaction automatically, and pH is 4, coutroi velocity is at 6BV/h.The gluconic acid that reacted liquid generates through 8 absorption reactions of fixed bed chromatography post, the liquid after the absorption fixed bed bed of flowing through turns back in raw material container for storing liquid 1.Through the several times circulation, with pH meter, detect the pH value of circulation fluid, when the pH value continuous decrease of the circulation fluid after first fixed bed chromatography post absorption gluconic acid, illustrate that this chromatography column reaches capacity, drip washing bed, leacheate merge in the raw material container for storing liquid, then through the elutriant wash-out, reclaim regenerated liquid regeneration fixed bed chromatography post; Simultaneously, co-immobilization glucose oxidase and catalase column reactor are switched to another fixed bed chromatography post by valve, realize that fermentation, separation, desorb and reprocessing cycle synchronously carry out.The gluconic acid crystal obtained thus, its yield is 88%, purity reaches 97%.
Embodiment 3:
At first, device according to Fig. 1, the nanofiltration membrane that is 5000Da by molecular weight cut-off is placed in nanofiltration device 3, in co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin, in two chromatography columns 8, fill anionite-exchange resin D239.
Second step, by transmission pump 2a, xylose crystallization mother liquor enters nanofiltration device 3, nanofiltration device liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor 7 bottoms, provide and meet the requirements of xylose crystallization mother liquor, the other end trapped fluid is connected with the circulation main pipe rail, and is connected with raw material container for storing liquid 1.
The 3rd step, set suitable CAT/GOD enzyme temperature alive in co-immobilization glucose oxidase and catalase column reactor 7, by computerized control system 11, regulating the circulation fluid main pipe rail and connect the four way valve 6e on pipeline between transmission pump 2b makes first fixed bed chromatography post 8a top be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2b in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor 7 and first fixed bed chromatography post 8a, circulate by realization response liquid, when first fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, regulate and connect the four way valve 6e on pipeline between transmission pump, make container for storing liquid 10 (elutriants, leacheate, regenerated liquid) with this pump, be communicated with, liquid storage wherein enters first fixed bed chromatography post 8a by this transmission pump, by drip washing, after wash-out and regeneration, first chromatography column enters holding state, simultaneously, four way valve 6e on regulating the circulation fluid main pipe rail and being connected transmission pump, make second fixed bed chromatography post 8b top in parallel be communicated with the circulation fluid main pipe rail, the coupled transmission pump 2d in bottom is connected, transmission pump 2d is immobilized glucose oxidase and 7 connections of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and second fixed bed chromatography post, circulate by realization response liquid, realize the reactive separation process of gluconic acid, when second fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, first fixed bed chromatography post that enters holding state enters the working order of circulation coupling, and second fixed bed chromatography post be by drip washing simultaneously, wash-out and regeneration, enter holding state, iterative cycles.
The 4th step, the thick sodium gluconate solution obtained by the 3rd step, through after acidifying, pumping in reverse osmosis machine, carries out reverse osmosis concentration under 3.0MPa pressure, then, this concentrated solution is pumped in drying machine with centrifugal spray to 185 ℃ of lower spraying dryings.Finally just obtain the gluconic acid powder-product.
Described nanofiltration device molecular weight cut-off is 5000Da.
In described co-immobilization glucose oxidase and catalase column reactor, temperature is 60 ℃.
Xylose crystallization mother liquor pH in described raw material container for storing liquid is 5.
Described leacheate is distilled water, elutriant, the NaOH solution (m/v) of regenerated liquid difference 4% and 10% NaOH solution.
In described co-immobilization glucose oxidase and catalase column reactor 7, fill co-immobilization CAT/GOD cross-linked chitosan Methionin resin.Xylose crystallization mother liquor in container for storing liquid 1 enters from top co-immobilization glucose oxidase and catalase column reactor 7 after the nanofiltration decolouring, it is 60 ℃ that computerized control system 11 is controlled co-immobilization CAT/GOD temperature of reaction automatically, and pH is 5, coutroi velocity is at 10BV/h.The gluconic acid that reacted liquid generates through 8 absorption reactions of fixed bed chromatography post, the liquid after the absorption fixed bed bed of flowing through turns back in raw material container for storing liquid 1.Through the several times circulation, with pH meter, detect the pH value of circulation fluid, when the pH value continuous decrease of the circulation fluid after first fixed bed chromatography post absorption gluconic acid, illustrate that this chromatography column reaches capacity, drip washing bed, leacheate merge in the raw material container for storing liquid, then through the elutriant wash-out, reclaim regenerated liquid regeneration fixed bed chromatography post; Simultaneously, co-immobilization glucose oxidase and catalase column reactor are switched to another fixed bed chromatography post by valve, realize that enzymatic reaction, separation, desorb and reprocessing cycle synchronously carry out.The gluconic acid crystal obtained thus, its yield is 84%, purity reaches 94%.
Embodiment 4:
Adopt the system of embodiment 1.
Fixed bed chromatography column packed resin is selected the anionite-exchange resin in Nankai chemical plant: NK-D201, NK-D241, NK-D293, NK-D296, the anionite-exchange resin of DOW Chemical: XUS40258, XFS-40422.
Resin first uses 45～60 ℃ of hot water repetitive scrubbings to free from extraneous odour, then spends the night by 95% alcohol immersion of 4BV; Inferior daily cold water washing 4 times, add 4%HC1 immersion 3～4h of 4BV filter and use the deionized water repetitive scrubbing to neutral; Add NaOH immersion 3～4h of 4BV4% filter and use the deionized water repetitive scrubbing to neutral, the dress post is standby again.After the adsorptive capacity that reaches capacity, first use distilled water drip washing, then select 3%NaOH as the eluent wash-out, with 5%NaOH solution, regenerate afterwards, finally be washed with distilled water to again neutrality.Selected resin sees the following form 1 in the effect after primary sorption, wash-out, reprocessing cycle in fixed bed.
Table 1
Claims (9)
1. crystal mother solution of xylitol prepares the Reaction Separation coupling device of gluconic acid, comprise nanofiltration device, co-immobilization glucose oxidase and catalase column reactor, fixed bed chromatography post, computerized control system, transmission pump, stock liquid storage tank, product container for storing liquid, the elutriant container for storing liquid, valve, three-way valve, four way valve.It is characterized in that:
Described nanofiltration device top is connected with reservoir by pump, bottom liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor bottom, the outlet of the other end trapped fluid is connected with the circulation main pipe rail, and is connected with the raw material container for storing liquid.Co-immobilization glucose oxidase and catalase column reactor top have the circulation fluid outlet.The fixed bed chromatography post of two parallel connections (can be in parallel a plurality of as required) bottom is equipped with the circulation fluid import, and the chromatography column top all has the circulation fluid outlet.
Four ports of the four way valve on the circulation fluid main pipe rail on described fixed bed chromatography post top, respectively by the circulation fluid outlet at pipeline and described chromatography column top, together immobilized glucose oxidase and catalase column reactor UNICOM a main pipe rail, and the pipeline be communicated with between four way valve be connected, an and port of the four way valve on the circulation fluid exit pipeline of the chromatography column of second parallel connection, with the pipeline of a port that is communicated with three-way valve, be connected, a port of this three-way valve is connected with the product container for storing liquid by pipeline.
Four ports of described four way valve on the circulation fluid main pipe rail at place, fixed bed chromatography column bottom, by pipeline, be connected with the circulation fluid import of described fixed bed chromatography column bottom, the circulation fluid outlet of each chromatography column transmission pump separately, the pipeline reached between the connection four-way valve respectively, and a port of the four way valve on the circulation fluid ingress pipeline of second chromatography column, be connected with the pipeline of a port of the above-mentioned three-way valve be communicated with; One port of the four way valve on the circulation fluid ingress pipeline of the fixed bed chromatography post of second parallel connection, a port by the four-way valve on pipeline and the circulation fluid main pipe rail that is connected this chromatography column top circulation fluid export pipeline is connected.
Between described connection transmission pump, on the pipeline of circulation fluid import, four way valve is arranged, two other port of this valve is respectively by pipeline and a circulation fluid main pipe rail that is communicated with co-immobilization glucose oxidase and catalase column reactor bottom, and a main pipe rail of elutriant container for storing liquid is connected.
2. the Reaction Separation coupling device for preparing gluconic acid from crystal mother solution of xylitol according to claim 1, it is characterized in that described co-immobilization glucose oxidase and catalase column reactor have discharge port and circulation fluid outlet with pH electrode, temperature sensor, top, the circulation fluid discharge port is connected with the circulation main pipe rail.
3. according to the described device of claim 1～2 any one, carry out preparing from crystal mother solution of xylitol the technique of gluconic acid, it is characterized in that:
At first, in co-immobilization glucose oxidase and catalase column reactor, fill respectively the immobilized enzyme resin, fill anionite-exchange resin in two chromatography columns; Nanofiltration device adds the nanofiltration membrane of certain molecular weight cut-off.
Second step, pass through transmission pump, xylose crystallization mother liquor enters nanofiltration device, nanofiltration device liquid outlet (nanofiltration destainer) end immobilized glucose oxidase together is connected with catalase column reactor bottom, provide and meet the requirements of xylose crystallization mother liquor, the other end trapped fluid is connected with the circulation main pipe rail, and is connected with the raw material container for storing liquid.
The 3rd step, set suitable enzyme temperature alive in co-immobilization glucose oxidase and catalase column reactor, by computerized control system, regulating the circulation fluid main pipe rail and connect the four way valve on pipeline between transmission pump makes first fixed bed chromatography column top be communicated with the circulation fluid main pipe rail, the coupled transmission pump in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and first fixed bed chromatography post, circulate by realization response liquid, when first fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, regulate and connect the four way valve on pipeline between transmission pump, make elutriant container for storing liquid (leacheate, elutriant, regenerated liquid) with this pump, be communicated with, liquid storage wherein enters first fixed bed chromatography post by this transmission pump, by drip washing, after wash-out and regeneration, first chromatography column enters holding state, simultaneously, four way valve on regulating the circulation fluid main pipe rail and being connected transmission pump, make second fixed bed chromatography column top in parallel be communicated with the circulation fluid main pipe rail, the coupled transmission pump in bottom is connected, transmission pump is immobilized glucose oxidase and the connection of catalase column reactor together, by this transmission pump, can between co-immobilization glucose oxidase and catalase column reactor and second fixed bed chromatography post, circulate by realization response liquid, realize the reactive separation process of gluconic acid, when second fixed bed chromatography post absorption gluconic acid reaches capacity adsorptive capacity, first fixed bed chromatography post that enters holding state enters the working order of circulation coupling, and second fixed bed chromatography post be by drip washing simultaneously, wash-out and regeneration, enter holding state, iterative cycles.
The 4th step, the thick sodium gluconate solution obtained by the 3rd step, through after acidifying, pumping in reverse osmosis machine, carries out reverse osmosis concentration under 1.6～3.0MPa pressure, then, this concentrated solution is pumped in drying machine with centrifugal spray to 125～185 ℃ of lower spraying dryings.Finally just obtain the gluconic acid powder-product.
4. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, it is characterized in that described immobilized enzyme resin of filling in immobilized enzyme pillar reactor can be immobilization GOD cross-linked chitosan Methionin resin, can be also co-immobilization GOD/CAT cross-linked chitosan Methionin resin.
5. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, is characterized in that described nanofiltration device molecular weight cut-off is 2000～7000Da.
6. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, is characterized in that in described immobilized enzyme pillar reactor, suitable CAT/GOD enzyme temperature alive is 40～65 ℃.
7. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, is characterized in that the xylose crystallization mother liquor pH in described raw material container for storing liquid is 3～5.
8. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, is characterized in that described leacheate is distilled water, elutriant, the NaOH solution (m/v) of regenerated liquid difference 0.5%～10% and 4%～20% NaOH solution.
9. the technique for preparing gluconic acid from crystal mother solution of xylitol according to claim 3, it is characterized in that described anionite-exchange resin is the macroporous adsorbent resin with certain grain size distribution, weak base anion-exchange resin, strongly basic anion exchange resin, can adjust its different strong and weak base numbers, and degree of crosslinking.
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| CN104450806A (en) * | 2014-11-27 | 2015-03-25 | 江南大学 | Method for preparing sodium gluconate with enzymatic method |
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| JP2021512640A (en) * | 2018-12-04 | 2021-05-20 | 浙江▲華▼康葯▲業▼股▲フン▼有限公司Ｚｈｅｊｉａｎｇ Ｈｕａｋａｎｇ Ｐｈａｒｍａｃｅｕｔｉｃａｌ Ｃｏ．， Ｌｔｄ． | Systems and methods for continuously hydrolyzing hemicellulose to prepare a xylose solution |
| JP2021512639A (en) * | 2018-12-18 | 2021-05-20 | 浙江▲華▼康葯▲業▼股▲フン▼有限公司Ｚｈｅｊｉａｎｇ Ｈｕａｋａｎｇ Ｐｈａｒｍａｃｅｕｔｉｃａｌ Ｃｏ．， Ｌｔｄ． | Equipment and methods for continuously saturate-filling xylose mother liquor to remove impurities |
| CN113499608A (en) * | 2021-06-29 | 2021-10-15 | 贵州卡本嘉泰生物科技产业发展有限公司 | Chromatographic system for enzymatic reaction and control method thereof |
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| CN114213215A (en) * | 2021-12-29 | 2022-03-22 | 浙江华康药业股份有限公司 | System and method for co-producing xylitol and caramel pigment by using xylose mother liquor |
| WO2023124395A1 (en) * | 2021-12-29 | 2023-07-06 | 浙江华康药业股份有限公司 | System and method for co-producing xylitol and caramel color by using xylose mother liquor |
| CN114213215B (en) * | 2021-12-29 | 2023-11-10 | 浙江华康药业股份有限公司 | System and method for co-producing xylitol and caramel pigment by utilizing xylose mother liquor |
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