Utilize molecular sieve and traverse baffle bio-reactor to prepare the method for oligofructose
Technical field
The present invention relates to a kind of method for preparing high-purity oligomer fructose, particularly utilize molecular sieve and traverse baffle bio-reactor to prepare the method for oligofructose.
Background technology
Oligofructose (fructooligsacchride, FOS, to call FOS in the following text) have another name called fructooligosaccharide, oligofructose or kestose family oligose, molecular formula is G-F-Fn (n=1,2,3, G is glucose, and F is fructose), it is by sucrose and 1~3 fructosyl kestose (GF by the fructosyl be combined in β-1,2 glycosidic bond and the sucrose
2), GF3 (GF
3) and GF4 (GF
4) wait a class carbohydrate general name.Oligofructose mainly is to obtain low-purity oligofructose (oligofructose accounts for dry-matter more than 50%, the G type) by fructosyl transferase conversion sucrose or hydrolytic inulin.And high-purity fructo oligosaccharides (oligofructose accounts for dry-matter more than 90%, the P type) to be glucose, fructose and the sucrose of eliminating composition on the basis of G type be further purified obtains.Chinese patent application number discloses a kind of preparation method of high-purity fructo oligosaccharides for CN200810156870.2, technical essential is the technical field that nanometer film separation and enzyme reaction organically combine the purification oligofructose, utilize nanometer film dam disaccharide, oligose, reach the separation purpose.Be raw material with the regular grade oligofructose, carry out enzyme reaction and membrane sepn by the film enzyme reactor, the content of monose and sucrose obtains highly purified oligofructose thereby reduce wherein.This method shortcoming is that facility investment is big, working pressure is up to 50-80bar, and film upkeep cost height, film leak easily, and nanometer film upkeep cost height, operational requirement be higher, have 40% above dry-matter to lose; Chinese patent application is the production method that CN200710021605.9 discloses a kind of high-purity fructo oligosaccharides, know-why is: content is about 55% regular grade oligofructose, adopt the glucose in the yeast conversion elimination regular grade oligofructose, the content of oligofructose is reached more than 75%; The recycling ion-exchange chromatography separates and membrane separation technique combines, and removes wherein other composition.This method shortcoming is for directly pouring into a large amount of yeast cell in the liquid glucose after the liquid glucose dilution, and in the time of yeast digestion 40-45% monose, it is seriously polluted that this method production cycle is long, output is subjected to cell metabolite, and yield is low, aftertreatment complexity etc.; Produce a large amount of metabolites, cause product separation, difficulty such as refining, product color is dark, specific conductivity is high, productive rate is low, dry-matter loses about 40%; Chinese patent application is the preparation method that CN200810030332.9 discloses a kind of high-purity fructo oligosaccharides, and know-why is preparation immobilized fructosyltransferase, immobilized glucose oxidase and immobilization hydrogen peroxide analogue enztme earlier; The enzyme that utilizes above-mentioned preparation then prepares high-purity fructo oligosaccharides with the production method of intermittent type or continous way.Namely utilizing immobilized fructosyltransferase to transform sucrose generates on the 50% oligofructose basis, recycling glucose oxidase or Hexose phosphate dehydrogenase be the 35-45% glucose oxidase nearly, glucose generates a large amount of gluconic acids and has the strong oxidizing property hydrogen peroxide, the strongly inhibited reaction, regulate pH by adding analogue enztme decomposition of hydrogen peroxide and alkaline matter, and used reaction to be proceeded.This method produces a large amount of gluconates, causes back operation desalination difficulty, by-product volume big, and same dry-matter loses about 40%.
Other relevant method for preparing high-purity oligomer fructose is published in " Guangxi light industry " the 2nd phase in 2007 " high-purity fructo oligosaccharides development progress " and has stated the preparation method of several each high-purity fructo oligosaccharides at treatises such as Mi Yunhong.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing molecular sieve and traverse baffle bio-reactor to prepare oligofructose, can obtain the high fructose syrup of F42 when can access high-purity fructo oligosaccharides again.And the dry-matter loss less, the facility investment expense is low, easy and simple to handle, energy consumption is low, product is pure, aftertreatment is simple.
The present invention is achieved through the following technical solutions above-mentioned purpose: a kind of molecular sieve and traverse baffle bio-reactor for the preparation of oligofructose, G oligofructose basin by 50%, the first molecular sieve cylinder, the second molecular sieve cylinder, first Cooling or heating jar, second Cooling or heating jar, P type oligofructose basin, the first traverse baffle bio-reactor, the second traverse baffle bio-reactor, the buffering basin, 55 type oligofructose basins, F42 high fructose syrup basin, the purified water basin, motor, stirring arm, first pulse pump, second pulse pump, first pilot valve, second pilot valve, the first online solid substance automatic-detector, the second online solid substance automatic-detector, first beverage pump, second beverage pump, the 3rd beverage pump, net considered by stainless steel and molecular sieve filled thing is formed
Concrete mode of connection: the bottom of 50% G oligofructose basin connects first pulse pump, be connected with the first molecular sieve cylinder by stainless steel pipes by first pulse pump, the bottom of the first molecular sieve cylinder connects the first online solid substance automatic-detector earlier, connect first pilot valve again, first pilot valve, one end is that the stainless steel pipes of 25-32mm is connected with P type oligofructose basin by diameter, the first pilot valve D1 the other end is connected with first Cooling or heating jar, the bottom of first Cooling or heating jar connects first beverage pump by stainless steel pipes, first beverage pump is connected with the first traverse baffle bio-reactor, the first traverse baffle bio-reactor is connected with the buffering basin, the bottom of buffering basin connects second pulse pump, second pulse pump is connected with the second molecular sieve cylinder by stainless steel pipes, the bottom of the second molecular sieve cylinder connects the second online solid substance automatic-detector earlier, connect second pilot valve again, port of second pilot valve is connected with P type oligofructose basin by stainless steel pipes, the second pilot valve another port is connected with 55 type oligofructose basins, second pilot valve port again is connected with second Cooling or heating jar, the bottom of second Cooling or heating jar connects second beverage pump by stainless steel pipes, the second beverage pump pump and the second traverse baffle bio-reactor, the second traverse baffle bio-reactor is connected with F42 high fructose syrup basin, the purified water basin connects the 3rd beverage pump, and the 3rd beverage pump connects the first molecular sieve cylinder and the first traverse baffle bio-reactor by stainless steel pipes.
Utilize described molecular sieve and traverse baffle bio-reactor to prepare the method for high-purity oligofructose, comprise the steps:
(1) adds sample loading mode and add the purified water push agent continuously by discontinuous pulses; With 120-400min sample introduction pitch time purity be 50% G type oligofructose to the opening for feed of one-level molecular sieve, each inlet amount is for accounting for molecular sieve volume 15-35% (V/V), with 0.2-1.0m
3The speed of/h adds the purified water push agent continuously;
(2) when the online solid substance automatic-detector reading value of molecular sieve outlet greater than 0 the time, begin to switch pilot valve and collect P type oligofructose, reading value switches pilot valve and flows to one-level traverse baffle bio-reactor when maximum, when the secondary molecular sieve with one-level traverse baffle bio-reactor exports online solid substance automatic-detector reading value greater than 0 the time, begin to switch pilot valve and receive P type oligofructose, when beginning to descend, reading value switches pilot valve to collecting G type oligofructose, reading value switches pilot valve again when being 0.5 times of maximum and flows to secondary traverse baffle bio-reactor, collect F42 when the online solid substance automatic-detector reading value of secondary traverse baffle bio-reactor outlet from opening greater than 0, be down to 0.5% and finish collection when following.
Prepare 90 types~95 type oligofructoses after the circulation, 55 type oligofructoses, high fructose syrup F42.Repeating step 1-2 can realize continuous preparation.
2 same control flows set by step, purified water push agent linear flow speed is at 1.2-1.5m
3During/h, can be prepared into the oligofructose product of 70 types, 75 types, 80 types.
The molecular sieve that utilizes of the present invention with the know-why that the traverse baffle bio-reactor prepares the method for oligofructose is: the glucide that utilizes different molecular weight in fluid medium movement rate difference and molecular sieve to different glucide retardations, by controlling 50% G type oligofructose (I) by the linear flow speed of molecular sieve, collection obtains P type oligofructose component (II), owing to collect partly oligofructose, obvious variation has taken place in component originally, all the other components have all raise except oligofructose, uncollected part (III) by the traverse baffle bio-reactor of immobilized fructosyltransferase is housed, sucrose is further transformed the generation oligofructose again, go here and there a molecular sieve again, the same control line flow velocity degree with one-level obtains P type oligofructose (IV) and 55 type oligofructoses, remaining component switches to the traverse baffle bio-reactor that another is equipped with fixed glucose isomerase and immobilized glucoamylase preparation, by obtaining F42 fruit glucose after the isomery hydrolysis.This method major advantage is that P type oligofructose yield is higher, production process keeps the component components unchanged, only changes the content ratio of component composition, can obtain the high fructose syrup product of F42 when obtaining P oligofructose and 55 type oligofructoses so again.
Outstanding advantage of the present invention is:
1, by adopting secondary molecular sieve and secondary traverse baffle bio-reactor, a production process can access 90 types and 95 type oligofructoses, 55 type oligofructoses, high fructose syrup F42.
2, production process keeps the G type oligofructose component components unchanged of raw material 50%, only changes the content ratio of component composition, keeps product stability.
3, by adopting secondary traverse baffle bio-reactor, reclaim the F42 syrup and make the dry-matter loss few.
4, used push agent is purified water, does not add other chemical organic solvent, and product is pure, aftertreatment is simple.
5, adopt secondary molecular sieve and two traverse baffle bio-reactors, the device fabrication expense is low, easy and simple to handle, energy consumption is low.
Description of drawings
Fig. 1 is the structural representation of the molecular sieve for the preparation of oligofructose of the present invention and traverse baffle bio-reactor.
Embodiment
By the following examples technical scheme of the present invention is described further.
Embodiment 1
As shown in Figure 1, a kind of molecular sieve and traverse baffle bio-reactor for the preparation of oligofructose, G oligofructose basin 1 by 50%, the first molecular sieve cylinder 2, the second molecular sieve cylinder 7, first Cooling or heating jar 3, second Cooling or heating jar 9, P type oligofructose basin 4, the first traverse baffle bio-reactor 5, the second traverse baffle bio-reactor 10, buffering basin 6,55 type oligofructose basins 8, F42 high fructose syrup basin 11, purified
water basin 12, motor A1-A12, be stirring arm B1-B7, the first pulse pump C1, the second pulse pump C2, the first pilot valve D1, the second pilot valve D2, the first online solid substance automatic-detector E1, the second online solid substance automatic-detector E2, the first beverage pump F1, the second beverage pump F2, the 3rd beverage pump F3, net ※ considered by stainless steel and molecular sieve filled thing * * * forms
With
For baffled reactor internal reaction liquid flows to.
Concrete mode of connection: 50%G type oligofructose thrown into 50% G oligofructose basin 1, the bottom of 50% G oligofructose basin 1 connects the first pulse pump C1, be that the stainless steel pipes of 25-32mm is delivered to the first molecular sieve cylinder 2 by the first pulse pump C1 by diameter, the bottom of the first molecular sieve cylinder 2 meets the first online solid substance automatic-detector E1 earlier, meet the first pilot valve D1 again, the first pilot valve D1 is P type oligofructose that the stainless steel pipes of 25-32mm is delivered to P type oligofructose basin 4 by diameter earlier, the first online solid substance automatic-detector E1 reading value reaches that the first pilot valve D1 leads first Cooling or heating jar 3 to the flow direction when the highest, the bottom of first Cooling or heating jar 3 is that the stainless steel pipes of 25-32mm connects the first beverage pump F1 by diameter, the first beverage pump F1 is pumped into the first traverse baffle bio-reactor 5, component is delivered to buffering basin 6 through after repeatedly baffling reacts in the first traverse baffle bio-reactor 5, the bottom of buffering basin 6 connects the second pulse pump C2, the second pulse pump C2 is that the stainless steel pipes of 25-32mm is delivered to the second molecular sieve cylinder 7 by diameter, the bottom of the second molecular sieve cylinder 7 meets the second online solid substance automatic-detector E2 earlier, meet the second pilot valve D2 again, the second pilot valve D2 is P type oligofructose that the stainless steel pipes of 25-32mm is delivered to P type oligofructose basin 4 by diameter earlier, the second pilot valve D2 led 55 type oligofructose basins 8 to the flow direction when the second online solid substance automatic-detector E2 reading value began to descend from maximum, when the second online solid substance automatic-detector E2 reading value is 0.5 times of maximum, D2 leads second Cooling or heating jar 9 to the flow direction, the bottom of second Cooling or heating jar 9 is that the stainless steel pipes of 25-32mm connects the second beverage pump F2 by diameter, the second beverage pump F2 is pumped into the second traverse baffle bio-reactor 10, component in the second traverse baffle bio-reactor 10 through delivering to F42 high fructose syrup basin 11 after the reaction of baffling repeatedly, after the first pulse pump C1 and the second pulse pump C2 application of sample are finished, connect the 3rd beverage pump F3 by purified water basin 12, the 3rd beverage pump F3 is that the stainless steel pipes of 25-32mm connects the first molecular sieve cylinder 2 and the first traverse baffle bio-reactor 5 by diameter, and the purified water push agent is delivered to the first molecular sieve cylinder 2 and the first traverse baffle bio-reactor 5 by purified water basin 12 by the 3rd beverage pump F3.
Embodiment 2
An example that utilizes the method that molecular sieve and traverse baffle bio-reactor prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 40 (cm/cm), weighting material is the sodium type resin of particle diameter 0.3mm, secondary molecular sieve diameter/highly be 1: 15 (cm/cm), the weighting material particle diameter is the sodium type resin of 0.2mm; One-level traverse baffle bio-reactor is 1.0m by each volume
33 baffled reactors and connect a 6m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 15% (V/V), temperature of reaction is 35 ℃, pH is 4.5; Secondary traverse baffle bio-reactor is 0.2m by each volume
35 baffled reactors and connect a 4m
3Cooling or heating jar form, 1-4 baffled reactor adds glucose isomerase zymin 20% (V/V), the 5th baffled reactor interpolation immobilized glucoamylase preparation 10% (V/V), temperature of reaction is 70 ℃, pH is 3.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 15% (V/V), and the interpulse break time is 120min, and purified water push agent linear flow speed is 1.0m
3/ h is 96.4% P type oligofructose by preparing purity after the circulation, and purity is 58.3% 55 type oligofructoses, and fructose content is 44.5% high fructose syrup F42 type.
Embodiment 3
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 12 (cm/cm), weighting material is the calcium type resin of particle diameter 0.1mm, secondary molecular sieve diameter/highly be 1: 30 (cm/cm), the weighting material particle diameter is the sodium type resin of 0.4mm; One-level traverse baffle bio-reactor is 0.2m by each volume
35 baffled reactors and connect a 4m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 30% (V/V), temperature of reaction is 55 ℃, pH is 6.0; Secondary traverse baffle bio-reactor is 1.0m by each volume
33 baffled reactors and connect a 6m
3Cooling or heating jar form, 1-2 baffled reactor adds glucose isomerase zymin 20% (V/V), the 3rd baffled reactor interpolation immobilized glucoamylase preparation 20% (V/V), temperature of reaction is 55 ℃, pH is 5.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 35% (V/V), and the interpulse break time is 400min, and purified water push agent linear flow speed is 0.2m
3/ h is 92.3% P type oligofructose by preparing purity after the circulation, and purity is 56.8% 55 type oligofructoses, and fructose content is 43.6% high fructose syrup F42 type.
Embodiment 4
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 20 (cm/cm), weighting material is the calcium type resin of particle diameter 0.2mm, secondary molecular sieve diameter/highly be 1: 20 (cm/cm), the weighting material particle diameter is the calcium type resin of 0.3mm; One-level traverse baffle bio-reactor is 0.5m by each volume
34 baffled reactors and connect a 6m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 20% (V/V), temperature of reaction is 45 ℃, pH is 5.0; Secondary traverse baffle bio-reactor is 0.5m by each volume
33 baffled reactors and connect a 6m
3Cooling or heating jar form, 1-2 baffled reactor adds glucose isomerase zymin 25% (V/V), the 3rd baffled reactor interpolation immobilized glucoamylase preparation 15% (V/V), temperature of reaction is 60 ℃, pH is 4.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 20% (V/V), and the interpulse break time is 250min, and purified water push agent linear flow speed is 0.5m
3/ h is 95.4% P type oligofructose by preparing purity after the circulation, and purity is 57.1% 55 type oligofructoses, and fructose content is 45.2% high fructose syrup F42 type.
Embodiment 5
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 20 (cm/cm), weighting material is the sodium type resin of particle diameter 0.15mm, secondary molecular sieve diameter/highly be 1: 20 (cm/cm), the weighting material particle diameter is the calcium type resin of 0.35mm; One-level traverse baffle bio-reactor is 1.0m by each volume
34 baffled reactors and connect a 8m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 25% (V/V), temperature of reaction is 42 ℃, pH is 5.5; Secondary traverse baffle bio-reactor is 0.5m by each volume
34 baffled reactors and connect a 8m
3Cooling or heating jar form, 1-3 baffled reactor adds glucose isomerase zymin 30% (V/V), the 4th baffled reactor interpolation immobilized glucoamylase preparation 20% (V/V), temperature of reaction is 65 ℃, pH is 4.0; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 30% (V/V), and the interpulse break time is 300min, and purified water push agent linear flow speed is 1.0m
3/ h is 94.2% P type oligofructose by preparing purity after the circulation, and purity is 55.8% 55 type oligofructoses, and fructose content is 42.6% high fructose syrup F42 type.
Embodiment 6
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 40 (cm/cm), weighting material is the sodium type resin of particle diameter 0.2mm, secondary molecular sieve diameter/highly be 1: 30 (cm/cm), the weighting material particle diameter is the calcium type resin of 0.4mm; One-level traverse baffle bio-reactor is 1.0m by each volume
34 baffled reactors and connect a 8m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 20% (V/V), temperature of reaction is 50 ℃, pH is 4.8; Secondary traverse baffle bio-reactor is 0.5m by each volume
34 baffled reactors and connect a 8m
3Cooling or heating jar form, 1-3 baffled reactor adds glucose isomerase zymin 20% (V/V), the 4th baffled reactor interpolation immobilized glucoamylase preparation 20% (V/V), temperature of reaction is 60 ℃, pH is 4.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 30% (V/V), and the interpulse break time is 300min, and purified water push agent linear flow speed is 1.2m
3/ h is 76% 75 type oligofructoses by preparing purity after the circulation, and purity is 56.9% 55 type oligofructoses, and fructose content is 43.2% high fructose syrup F42 type.
Embodiment 7
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 25 (cm/cm), weighting material is the calcium type resin of particle diameter 0.15mm, secondary molecular sieve diameter/highly be 1: 15 (cm/cm), the weighting material particle diameter is the sodium type resin of 0.2mm; One-level traverse baffle bio-reactor is 0.2m by each volume
35 baffled reactors and connect a 3m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 25% (V/V), temperature of reaction is 44 ℃, pH is 5.0; Secondary traverse baffle bio-reactor is 0.5m by each volume
34 baffled reactors and connect a 4m
3Cooling or heating jar form, 1-3 baffled reactor adds glucose isomerase zymin 25% (V/V), the 4th baffled reactor interpolation immobilized glucoamylase preparation 15% (V/V), temperature of reaction is 70 ℃, pH is 5.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 35% (V/V), and the interpulse break time is 150min, and purified water push agent linear flow speed is 1.5m
3/ h is 71.3% P type oligofructose by preparing purity after the circulation, and purity is 56.2% 55 type oligofructoses, and fructose content is 43.3% high fructose syrup F42 type.
Embodiment 8
Another example of method that utilizes molecular sieve and traverse baffle bio-reactor to prepare oligofructose of the present invention comprises the steps:
One-level molecular sieve diameter/highly be 1: 35 (cm/cm), weighting material is the sodium type resin of particle diameter 0.2mm, secondary molecular sieve diameter/highly be 1: 25 (cm/cm), the weighting material particle diameter is the sodium type resin of 0.3mm; One-level traverse baffle bio-reactor is 0.5m by each volume
34 baffled reactors and connect a 8m
3Cooling or heating jar form, each baffled reactor adds fructosyl transferase preparation 25% (V/V), temperature of reaction is 42 ℃, pH is 5.4; Secondary traverse baffle bio-reactor is 1.0m by each volume
33 baffled reactors and connect a 6m
3Cooling or heating jar form, 1-2 baffled reactor adds glucose isomerase zymin 30% (V/V), the 3rd baffled reactor interpolation immobilized glucoamylase preparation 20% (V/V), temperature of reaction is 65 ℃, pH is 4.5; By the string mode of one-level molecular sieve → one-level traverse baffle bio-reactor → secondary molecular sieve → secondary traverse baffle bio-reactor, inlet amount is by accounting for molecular sieve volume 32% (V/V), and the interpulse break time is 270min, and purified water push agent linear flow speed is 1.3m
3/ h is 84.3% 80 type oligofructoses by preparing purity after the circulation, and purity is 55.4% 55 type oligofructoses, and fructose content is 42.8% high fructose syrup F4.