Background technology
Oligofructose (fructooligsacchride, FOS is to call FOS in the following text) has another name called fructooligosaccharide; Oligofructose or kestose family oligose, molecular formula are G-F-Fn (n=1,2; 3, G is a glucose, and F is a fructose); It is by sucrose and 1~3 fructosyl kestose (GF through the fructosyl be combined in β-1,2 glycosidic bond and the sucrose
2), GF3 (GF
3) and GF4 (GF
4) wait one type of glucide general name.Oligofructose mainly is to obtain low-purity oligofructose (oligofructose accounts for dry-matter more than 50%, the G type) through 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 on the basis of G type, eliminating composition be further purified obtains.One 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.With the regular grade oligofructose is raw material, carries out enzyme reaction and membrane sepn through the film enzyme reactor, and 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 the film upkeep cost is high, film leaks easily, and the nanometer film upkeep cost is high, operational requirement is higher, have 40% above dry-matter to lose; One Chinese patent application is the working method that CN200710021605.9 discloses a kind of high-purity fructo oligosaccharides; Know-why is: content is about 55% regular grade oligofructose; Adopt yeast conversion to eliminate the glucose in the regular grade oligofructose, the content of oligofructose is reached more than 75%; Utilize ion-exchange chromatography separation and membrane separation technique to combine again, remove 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 receives cell metabolite, and yield is low, aftertreatment complicacy 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%; One 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 working method of intermittent type or continous way.Promptly utilizing immobilized fructosyltransferase to transform sucrose generates on the 50% oligofructose basis; Utilize P-FAD or Hexose phosphate dehydrogenase 35-45% glucose oxidase nearly again; Glucose generates a large amount of glucono-s and has the strong oxidizing property hydrogen peroxide; The strongly inhibited reaction was regulated pH through adding analogue enztme decomposition of hydrogen peroxide and alkaline matter, used reaction to be able to proceed.This method produces a large amount of gluconates, and the operation desalination is difficult after causing, by-product volume is 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 realizes above-mentioned purpose through following technical scheme: a kind of molecular sieve and traverse baffle bio-reactor that is used to prepare 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, is connected with the first molecular sieve cylinder through stainless steel pipes by first pulse pump, and 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 through diameter, and the first pilot valve D1 the other end is connected with first Cooling or heating jar, and the bottom of first Cooling or heating jar connects first beverage pump through 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, and the bottom of buffering basin connects second pulse pump, and second pulse pump is connected with the second molecular sieve cylinder through 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 through stainless steel pipes, and 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 through stainless steel pipes, the second beverage pump pump and the second traverse baffle bio-reactor, and 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 through stainless steel pipes.
Utilize said 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 through discontinuous pulses; With 120-400min sample introduction pitch time purity is 50% the G type oligofructose opening for feed to the one-level molecular sieve, and 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 mxm.; 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, switch pilot valve when reading value begins to descend to collecting G type oligofructose, reading value switches pilot valve once more when being 0.5 times of mxm. 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, reduce to 0.5% and finish collection when following greater than 0.
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 according to the 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; Through controlling 50% G type oligofructose (I) linear flow speed through molecular sieve; Collection obtains P type oligofructose component (II); Because collect partly oligofructose, obvious variation has taken place component originally, all the other components have all raise except that oligofructose; Uncollected part (III) through the traverse baffle bio-reactor of immobilized fructosyltransferase is housed; Further transform to generate oligofructose to sucrose again, go here and there a molecular sieve again, the same wire 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, through 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, through 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,, reclaim the F42 syrup and make the dry-matter loss few through adopting secondary traverse baffle bio-reactor.
4, used push agent is a 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.
Embodiment
Below through embodiment 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 that is used to prepare 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 that 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, stainless steel consider net ※ and molecular sieve filled thing * * * composition,
and
be baffled reactor internal reaction flow to.
Concrete mode of connection: throw into 50%G type oligofructose 50% G oligofructose basin 1; The bottom of 50% G oligofructose basin 1 connects the first pulse pump C1; Is that the stainless steel pipes of 25-32mm is delivered to the first molecular sieve cylinder 2 by the first pulse pump C1 through 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 through diameter earlier; It is that the stainless steel pipes of 25-32mm connects the first beverage pump F1 through diameter that the first online solid substance automatic-detector E1 reading value reaches bottom that first pilot valve D1 when the highest leads the flow direction to first Cooling or heating jar, 3, the first Cooling or heating jars 3, and 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, and the second pulse pump C2 is that the bottom that the stainless steel pipes of 25-32mm is delivered to the second molecular sieve cylinder, 7, the second molecular sieve cylinders 7 meets the second online solid substance automatic-detector E2 earlier through diameter; 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, the second online solid substance automatic-detector E2 reading values second pilot valve D2 when mxm. begins to descend and led 55 type oligofructose basins, 8, the second online solid substance automatic-detector E2 reading values to the flow direction when being 0.5 times of mxm. through diameter earlier; 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 through diameter, and 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 repeatedly delivering to F42 high fructose syrup basin 11 after the baffling reaction; After the first pulse pump C1 and the completion of the second pulse pump C2 application of sample; 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 through 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 through the 3rd beverage pump F3.
Embodiment 2
An instance 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 through 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 instance 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 through 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 instance 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 through 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 instance 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 through 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 instance 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 through 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 instance 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 through 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 instance 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 through preparing purity after the circulation, and purity is 55.4% 55 type oligofructoses, and fructose content is 42.8% high fructose syrup F4.