CN1049455C - Production of lactone gluconate by using black aspergillus to ferment glucose - Google Patents

Abstract

The present invention comprises the following steps: using aspergillus niger IFF12230 slant strains to ferment glucose under the condition that NaOH solution is added in a flowing mode to control acidity; supplementing glucose to carry out high-concentration glucose fermentation at the later stage of the fermentation; after the fermentation is finished, obtaining food-grade gluconolactone products by the steps of thallus removal, decolorization, ion exchange, concentration, crystallization and drying; concentrating, crystallizing and drying the first crystallized mother liquid again to obtain gluconolactone; adding zinc oxide to the second crystallized mother liquid to produce a side product, namely zinc gluconate. The total yield of the gluconolactone in the method is about 60%, and the yield of the zinc gluconate is more than 0.1 kg/kg gluconolactone. The method of the present invention has the characteristics of simple technological process, low energy consumption and high yield.

Description

Production of lactone gluconate by using black aspergillus to ferment glucose

The present invention relates to a kind of production method of glucolactone, particularly adopt fermentation of Aspergillus niger glucose to produce the method for Gluconolactone again through ion-exchange.

At present production method of glucolactone mainly contains three kinds: a kind of fermentation of Aspergillus niger glucose by lime carbonate as neutralizing agent, condensing crystal generates calglucon then, use sulfuric acid and its reaction with precipitated calcium again, through the anion-cation exchange resin removal of impurity, last condensing crystal drying obtains Gluconolactone, and this method is 62% (in calglucon) to the method yield of calglucon; The 2nd, glucose generates calglucon by the electrocatalysis method, lactonizes through sulfuric acid reaction and zwitterion exchange again, and last condensing crystal drying obtains Gluconolactone, and this method yield is 45% (with glucose meter); The 3rd, the method by immobilized cell generates Gluconolactone by one step of glucose, and this method yield is 50% (with glucose meter).

In above-mentioned three kinds of methods, first method is because calglucon solubleness less (4%), therefore glucose fermentation concentration can not be too high, at most can only 15%, otherwise fermented liquid has crystallization and separates out, glucose concn is too rare in the fermented liquid like this, can't be directly used in the production Gluconolactone, can only generate calglucon earlier, just produce Gluconolactone at last through sulfation regulating YIN and YANG ion exchange resinization again, owing to need through two kinds of resins exchange, the diluted multiple of solution big (about 5～6 times), energy consumption is big when concentrating at last, and this method calglucon and sulfuric acid reaction need to carry out under 100 ℃ of temperature, the energy consumption height is to the equipment requirements height; Second method needs numerous and diverse step of removing catalyzer, and its technical process is long, energy consumption is high, and yield is low; The third method still is in the laboratory study stage, also is not used for industrial production.

Deficiency at above-mentioned Gluconolactone production method, the present invention adopts fermentation of Aspergillus niger glucose, and mend sugared in the fermentation later stage to carry out high sugar-fermenting, again through malaga saccharic acid lactone in next life Zeo-karb transition, thereby reach the purpose that the Gluconolactone production process route is simple, energy consumption is low and yield is high.

For achieving the above object, the present invention adopts aspergillus niger strain IFFI 2230, through seed culture, fermentation, remove thalline, decolouring, ion-exchange, concentrate, crystallization and drying and other steps, glucose fermentation after making the transition, ion-exchange is generated Gluconolactone, fermenting process stream adds NaOH solution with the control pH value, and fermentation later stage benefit sugar makes total reducing sugar reach 400～450g/L and proceeds fermentation again; Concrete fermentation condition is as follows: in the fermentation culture that contains 15% glucose, inserting the employing aspergillus niger IFFI 2230 slant strains cultured seed liquid of 10% (W/W), is that 32 ℃, vapour-liquid ratio are 1.7～2.1m in temperature ³/ m ³.min, mixing speed is 600～800rpm, ventilating fermentation is 48～60 hours under pH2.0～6.5 conditions, fermenting process stream adds 50%NaOH solution with control fermented liquid pH value, when residual sugar is 15～80g/L, add glucose in the fermentation later stage and make total reducing sugar reach 400～450g/L, continue to ferment and when residual sugar is 2.0～2.9g/L, finish fermentation.

Consisting of of above-mentioned fermentation culture: 15% glucose, 0.037%KH ₂PO ₄, 0.055% urea, 0.015%MgSO ₄, 0.1%CaCO ₃

Seed culture fluid contains 5% glucose, 0.012%MgSO ₄, 0.2%KCl, 0.015KH ₂PO ₄, 0.06%NH ₄H ₂PO ₄, 0.2% peptone and 0.3% extractum carnis, culture condition is: add a few ring aspergillus niger IFFI2230 slant strains, cultivated 24 hours with the 250rpm shaking table under 30 ℃ of temperature.

Add glucose in the fermentation later stage, can disposablely add, also can add at twice, its total reducing sugar amount is at 400～450g/L, add fashionable at twice, for the first time the sugar that adds fully ferments when residual sugar is lower than 75g/L, adds sugar more for the second time, and the amount summation of twice adding reaches total reducing sugar 400～450g/L.

Add zinc oxide in the secondary crystal mother liquor of production Gluconolactone, also can produce the byproduct Zinc Gluconate.

The present invention utilizes the big characteristic of Sunmorl N 60S solubleness to adopt the fermentation later stage to add the technology of sugar, carry out the high concentration glucose fermentation, the exchange of fermented liquid direct ion can be converted into the target product Gluconolactone, improved plant factor, reduced and generated calisanin crystalline step in the existing technology, reduced the crystals dried step of once concentration, operational path is simple; Simultaneously because only through a cationic exchange, solution dilution multiple low (having only about 2.5 times), energy consumption is low, and production cost is little, the yield height, and also the secondary crystal mother liquor can be used for the byproduct of production high added value---Zinc Gluconate; The inventive method compares to existing manufacturing technique, and under the low prerequisite of shortened process, energy consumption, the method yield still is higher than existing technology substantially.

Following concrete steps of producing for the inventive method:

1. culture of seed liquid:

In the seed culture medium after the following sterilization of several rings addings of aspergillus niger IFFI 2230 slant strains pickings: 5% glucose, 0.012%MgSO ₄, 0.02%KCl, 0.015%KH ₂PO ₄, 0.06%NH ₄H ₂PO ₄, 0.2% peptone and 0.3% extractum carnis, cultivated 24 hours in 30 ℃, 250rpm shaking table, seed liquor;

2. fermentation:

Sterilized 15% glucose, the 0.03%KH of containing packs in 15 liters of mechanical agitating fermentation tanks ₂PO ₄, 0.055% urea, 0.015%MgSO ₄, 0.1%CaCO ₃Fermentation culture, inoculum size with 10% insert cultured seed liquid, at 32 ℃, vapour-liquid ratio 1.7～8.1m ³/ m ³.min, mixing speed is to ventilate under 600～800rpm condition to stirring fermentation, in the fermenting process stream add 50%NaOH solution with control fermented liquid PH at 2.0～8.5, when the fermented liquid residual sugar is 15～80g/L, adding glucose to total reducing sugar is 400～450g/L, continue to ferment to residual sugar be 2.0～2.9g/L when maybe can't stream adding NaOH, finish fermentation.

3. remove thalline:

Put jar and remove thalline with the filter bag filtering fermentating liquid;

4. decolouring:

Adding 2% gac boils and decolours.Gac is removed in centrifugation again;

5. ion-exchange removes sodium ion:

Destainer: remove sodium ion through 732 Zeo-karbs (Φ 150 * 1000) exchange.

6. condensing crystal:

Exchange liquid is at 70 ℃ of following vacuum concentration to 80～90% (Gluconolactone meter), and proportion 1.4～1.5 is put into crystallizer tank and added 0.1～0.2% glucose sugar lactone as crystal seed, stirred crystallization under 48～54 ℃ of temperature;

7. washing is dry: after the whizzer centrifugation is put in the gained crystallization, add 10～40% (concentrated solution Gluconolactone meter) frozen water or a small amount of edible ethanol washing, in 50 ℃ of oven dry, promptly get Gluconolactone then.

But Gluconolactone is produced in mother liquor reconcentration, crystallization.

8. the production of Zinc Gluconate:

Add ZnO stirring reaction under room temperature by theoretical amount in the secondary mother liquid and remove by filter unnecessary ZnO to neutral, the condensing crystal drying gets the byproduct Zinc Gluconate then.

Embodiment: by 5 enforcements of the present invention that above step and condition are implemented, its concrete implementation condition is listed as follows:

Embodiment	1	2	3	4	5
						Vapour-liquid ratio (M 3/M 3·min)	2.05	1.90	1.75	1.74	1.92
Mixing speed (rpm)	800	600	800	700	800
						Fermentation time (hr.)	48	49	50	48	60
Fermented liquid acidity (PH)	6.3	6.2	2.5	4.5	6.3
						Residual sugar value (g/L) is mended sugar amount (g) for the first time when mending sugar	50	25	45	37	46
2500	1600	2500	2500	1500
					Residual sugar value (g/L) is mended sugar amount (g) for the second time when mending sugar for the second time			17			72
	1350			1500
						Mend sugared secondary fermentation liquid total reducing sugar (g/L)	400	435	400	400	450
Tc (℃)	50	52	48	52	54
						Wash crystallization is with frozen water amount (% Gluconolactone)	15	30	20	40	10
Gluconolactone total recovery (%)	64.4	53	57.2	50.5	58.8
						Zinc Gluconate yield (Kg/Kg Gluconolactone)	0.15	0.16	0.17	0.20	0.12

Claims (5)

1, a kind of method of production of lactone gluconate by using black aspergillus to ferment glucose, through seed culture, fermentation remove thalline, decolouring, ion-exchange, concentrate, crystallization and drying step, glucose fermentation after making the transition, ion-exchange is generated Gluconolactone, it is characterized in that: adopt aspergillus niger IFFI 2230 slant strains, in the fermentation culture that contains 15% glucose, inserting the liquid of cultured seed of 10% (W/W), is 32 ℃ in temperature, and vapour-liquid ratio is 1.7～2.1M ³/ M ³Min, mixing speed is 600～800rpm, ventilating fermentation 48～60hr under pH2.0～6.5 conditions, fermenting process stream adds 50% NaOH solution control fermented liquid pH value, and in the fermentation later stage, when residual sugar was 15～80g/L, adding glucose, to make total reducing sugar be 400～450g/L, continues to ferment and finish fermentation when residual sugar is 2.0～2.9g/L.

2,, it is characterized in that the seed liquor of said seed liquor: at sterilized 5% glucose, the 0.012%MgSO of containing for cultivating by following condition by the described method of claim 1 ₄, 0.2%KCl, 0.015%KH ₂PO ₄, 0.06NH ₄H ₂PO ₄, 0.2% peptone and 0.3% extractum carnis seed culture medium in add aspergillus niger IFFI2230 slant strains after several rings activation, shaking table was cultivated 24 hours under 30 ℃, 250rpm condition.

3, by the described method of claim 1, it is characterized in that said fermented liquid is the fermented liquid of following composition: 15% glucose, 0.037%KH ₂PO ₄, 0.055% urea, 0.015%MgSO ₄, 0.1%CaCO ₃

4, by the described method of claim 1, it is characterized in that adding ZnO in the secondary crystal mother liquor of said Gluconolactone, reaction can obtain the byproduct Zinc Gluconate through the condensing crystal drying.

5, by the described method of claim 1, it is characterized in that the said fermentation later stage adds glucose to total reducing sugar 400～450g/L, once add or adding at twice.