CN102102116B - Method for preparing high-purity crystalline dextrose from maize peel acid hydrolysis residues - Google Patents
Method for preparing high-purity crystalline dextrose from maize peel acid hydrolysis residues Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity crystalline dextrose from maize peel acid hydrolysis residues, which belongs to the technical field of sugar manufacturing industry. The method for preparing high-purity crystalline dextrose from maize peel acid hydrolysis residues is characterized by comprising the following steps of: hydrolyzing; performing initial concentration; decoloring; purifying; concentrating; and crystallizing. In the method, the maize peel acid hydrolysis residues are taken as a raw material for producing crystalline dextrose, so that the problem of treatment of a large quantity of waste residues produced by the production of xylose and arabinose by a maize peel acid hydrolysis method is solved; and glucose and cello-oligosaccharide are separated and recycled by using cation exchange resin and a simulated moving bed, so that the separating and recycling rate is over 90 percent, a recycling procedure is simplified, and energy consumption is lowered.
Description
Technical field
The present invention relates to a kind of method of utilizing maize peel acid hydrolysis slag to prepare high-purity crystallized glucose, belong to the sugar industry technical field.
Background technology
Maize peel claims again zein fiber, is the crust of corn grain, is the byproduct in the W-Gum industry, accounts for 10% of corn gross weight.Enter 21 century, the fast-developing impetus appears in China's corn deep processing industry, and in 2001/02 year, China's deep processing consumes corn quantity and is about 1,250 ten thousand tons, and in 2008/09 year, it is 3,850 ten thousand tons that China's corn deep processing consumes the corn amount.Wherein will produce 3,850,000 tons of maize peels.Maize peel warp is crossed and also is left about 30% hydrolysis residue after wood sugar, pectinose are extracted in acid hydrolysis.About 70% composition is Mierocrystalline cellulose in the hydrolysis residue, and the Mierocrystalline cellulose of this moment has passed through sour pre-treatment, and being easy to by cellulase hydrolysis is monose and staple fibre.Be that (application number is CN1699389A: Chinese patent 200510082782.9) such as publication number, a kind of method of preparing crystalline xylose by hydrolysis of maize peel is disclosed, may further comprise the steps: with maize peel 0.5-1mL/kg fire resistant alpha-diastase pre-treatment, make starch stripping contained in the maize peel, obtain maize peel liquefaction slag; With the maize peel slag 1.2-2.0%H that liquefies
2SO
4The atmospheric boiling hydrolysis, hydrolysate comprises total reducing sugars 55-75%; With the hydrolysate crystallization, add the wood sugar crystal seed during crystallization, adding crystal seed amount is the 20-40% to total reducing sugar amount in the massecuite.
When using maize peel acidolysis slag to prepare crystalline dextrose, owing to contain the compositions such as glucose, wood sugar, pectinose and staple fibre in the hydrolyzed solution, can be because of the not high final product quality that affects of glucose purity when being directly used in crystallization, realization is further to be separated and common process for purification is difficult to.Be that (application number is: Chinese patent 200610097633.4) discloses a kind of hydrolyzed solution that utilizes maize peel preparation and its preparation method and application to CN1966665A such as publication number.This hydrolyzed solution is to adopt physical method to process maize peel, adopt again chemical process and/or biological method that the maize peel of fragmentation is processed, make and contain the hydrolyzed solution that glucose, wood sugar, pectinose, semi-lactosi and seminose and monose total content account for maize peel dry weight 54～71.9%.This hydrolyzed solution can be used for preparing substratum.Though above-mentioned patent has proposed a kind of application approach of hydrolyzed solution, narrow in view of application surface, can't process a large amount of maize peel acidolysis slags, can't solve the not high problem of maize peel acidolysis slag direct production glucose quality at all.
Simulation moving-bed (SMB) chromatographic separation technology be a kind of new-modernization credit of growing up the sixties in 20th century from technology, in the preparative chromatography technology, be suitable for carrying out the continuity large-scale industrial production most.The rise of SMB technology is considered to the once innovation in the Chemical Engineering Technology, its range of application also constantly enlarges, spread all over a lot of fields such as oil, fine chemistry industry, biological fermentation, medicine, food, especially in the separating of the mixtures such as homologous compound, chiral isomer medicine, carbohydrate, organic acid and amino acid, demonstrate its special performance.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method take maize peel acid hydrolysis slag as the raw material production crystalline dextrose is provided.
Technical scheme of the present invention is as follows:
A kind of method of utilizing maize peel acid hydrolysis slag to prepare high-purity crystallized glucose is characterized in that step is as follows, is mass ratio:
(1) maize peel acidolysis slag is added water in 1: 5～1: 10 by solid-to-liquid ratio, add again the cellulose complex enzyme of acidolysis slag dry weight 1～3%, at 45～60 ℃, under the condition of pH4～6, at the uniform velocity stir 24～36h, namely get hydrolyzed solution; Cellulose complex enzyme is common commercially available prod, can be glucose, wood sugar, pectinose and cell-oligosaccharide with cellulose hydrolysis.45～60wt% of hydrolyzed solution stripping total solid, glucose purity is 60～75wt%;
(2) hydrolyzed solution that step (1) is made filters, and removes hydrolysis residue, and the hydrolyzed solution after then will filtering is concentrated into sugared content 25～35wt%, gets concentrating hydrolysate;
(3) add gac in the concentrating hydrolysate that makes to step (2), stir, get the decolouring liquid glucose; Preferably, bleaching temperature is 75～80 ℃; The gac add-on is 3～5% of concentrating hydrolysate weight; Bleaching time 0.5～1.5 hour;
(4) the decolouring liquid glucose that step (3) is made gets raw sugar liquid after implementing the continuous ionic exchange by cationic, anionic exchange resin; Then, utilize simulation moving-bed device to separate, separation temperature 45-80 ℃, as sorbent material, take purified water as eluent, obtain Glucose Liquid with the cation separation resin;
(5) the Glucose Liquid simmer down to concentration 72～75wt% that step (4) is made, then purity put into crystallizer with dense liquid glucose greater than the dense liquid glucose of 95wt%, is cooled to 23 ℃ by 55～65 ℃ of temperature, rate of temperature fall is 1 ℃/h, and centrifugal, washing, drying obtain crystalline dextrose.
The water ratio of the maize peel acidolysis slag in the described step (1) is 5.7wt%.
Concentrated in the described step (2) is to adopt Anhui Pu Lang membrane concentration system (the multi-functional pilot plant of 4040 types) to concentrate;
The specific conductivity of the raw sugar liquid in the described step (4)≤10 μ s/cm.
Concentrated employing triple-effect evaporator in the described step (5) concentrates, and the first step is concentrated into 40～50wt%, and second step is concentrated into 72～75wt%.The cell-oligosaccharide that separates reclaims with spray-dired method.
Crystallizer in the described step (5) is the crystallizer that contains 1/3 crystal seed.
Cationic, anionic exchange resin is implemented the Step By Condition in the continuous ionic exchange in the above-mentioned steps (4), can be that (application number is CN1390845A: Chinese patent 02135121.X) with reference to publication number; Simulation moving-bed device in the step (4) is comprised of the chromatographic column more than 4,6,8,9,12 or 12; Chromatographic column more than 1 or 1 forms 1 tower.Simulation moving-bed device is comprised of the tower more than 2,3 or 4; Chromatographic column in the same tower communicates through divider, and the separator column between different towers joins end to end through pump or pipeline; Separation temperature is 45-80 ℃; The raw material sugar concentration is 30%, and wherein glucose concn is 18～22.5%.Moving bed imitation chromatogram separation facility separating glucose, cell-oligosaccharide, wood sugar pectinose, as sorbent material, sorbent material fills in the post with the cation separation resin; Take purified water as eluent; The continuously feeding continuous discharge, obtain simultaneously three kinds of materials, the first is cell-oligosaccharide concentration 4%, the material of the fiber-enriched oligosaccharides of purity＞85%, the second is glucose concn 13%, the material that is rich in glucose of purity＞90%, the third is the mixed solution of wood sugar pectinose, sugared concentration is lower.
Beneficial effect of the present invention is as follows:
1, the present invention is take maize peel acidolysis slag as the raw material production crystalline dextrose, solved the processing problem that the maize peel acid-hydrolysis method is produced a large amount of waste residues that wood sugar, pectinose produce;
2, the present invention adopts Zeo-karb and simulation moving-bed Separation and Recovery glucose and cell-oligosaccharide, and the Separation and Recovery rate has been simplified recovery process greater than 90%, has reduced energy consumption;
3, the present invention adopts enzymatic hydrolysis in about 50 ℃, greatly reduces energy consumption, has reduced the pollution of other medicines.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Describe the present invention in detail below in conjunction with Figure of description and embodiment, be mass percent among the embodiment, cellulose complex enzyme is available from the outstanding promise biological enzyme in Zaozhuang company limited, and LZJZ type triple-effect evaporator is available from Shandong Hongzhou Chemical Machinery Co., Ltd..The acidolysis of maize peel described in embodiment slag is maize peel according to publication number is that the Chinese patent method of CN101029060A is extracted the maize peel waste residue that obtains behind the wood sugar, water ratio is 5.7%, simulation moving-bed available from company limited of Wuxi green separation technical institute, the cation separation resin is available from the long-range development in science and technology chemical industry in Wuhan company limited, model DIAION UBK530.
Embodiment 1
The flow process maize peel acid hydrolysis slag that utilizes as shown in Figure 1 prepares the method for high-purity crystallized glucose, and concrete steps are:
(1) maize peel acidolysis slag 1kg adds water by solid-to-liquid ratio at 1: 8, adds the 0.02kg cellulose complex enzyme again, and 50 ℃, pH5.0 at the uniform velocity stirs 24h, obtains hydrolyzed solution.Sugared concentration is 5.56wt% in this hydrolyzed solution, and wherein the purity of glucose is 65.5wt%;
(2) hydrolyzed solution filter is removed hydrolysis residue and will filter after hydrolyzed solution pass into Anhui Pu Lang membrane concentration system (the multi-functional pilot plant of 4040 types) and concentrate, sugared concentration is concentrated into 30.2wt%, get concentrating hydrolysate;
(3) concentrating hydrolysate is warming up to 78 ℃, adds the activated carbon decolorizing 50min of concentrating hydrolysate quality 3.5%, get the decolouring liquid glucose;
(4) will decolour liquid glucose by the exchange of cationic, anionic exchange resin enforcement continuous ionic, and make the liquid glucose specific conductivity at 9.1 μ s/cm, get raw sugar liquid; Then above-mentioned raw sugar liquid is passed through simulation moving-bed separating glucose and a small amount of cell-oligosaccharide, wood sugar, pectinose, 60 ℃ of separation temperatures, with the cation separation resin as sorbent material, take purified water as eluent, glucose purity is 96.8wt% after separating, and gets Glucose Liquid;
(5) Glucose Liquid is concentrated with triple-effect evaporator, the first step is concentrated into concentration 45wt%, and second step is concentrated into 74.5wt%, gets dense liquid glucose; Wood sugar, pectinose, cell-oligosaccharide reclaim with spray-dired method; Then, dense liquid glucose is put into the crystallizer that contains 1/3 crystal seed, utilize chuck water of condensation cooling, be cooled to 23 ℃ by 60 ℃, rate of temperature fall is 1 ℃/h, and then centrifugal, washing, drying obtain crystalline dextrose.
Through adopting the method measuring and calculating of amplifying in proportion, the recyclable purity of maize peel acidolysis slag per ton is 605 kilograms of the glucose crystallizations of 96.8wt%, and the present invention utilizes the maize peel acidolysis residue to produce glucose, has greatly reduced discharging, has improved simultaneously the added value of maize peel.
Embodiment 2
Flow process utilizes maize peel acid hydrolysis slag to prepare the method for high-purity crystallized glucose as shown in Figure 1, and concrete steps are:
(1) maize peel acidolysis slag 1kg adds water by solid-to-liquid ratio at 1: 10, adds the 0.03kg cellulose complex enzyme again, and 53 ℃, pH4.8 at the uniform velocity stirs 36h, obtains hydrolyzed solution.Sugared concentration is 4.82wt% in this hydrolyzed solution, and wherein the purity of glucose is 66.3wt%;
(2) hydrolyzed solution filter is removed hydrolysis residue and will filter after hydrolyzed solution pass into Anhui Pu Lang membrane concentration system (the multi-functional pilot plant of 4040 types) and concentrate, sugared concentration is concentrated into 29.5wt%, get concentrating hydrolysate;
(3) concentrating hydrolysate is warming up to 80 ℃, adds the activated carbon decolorizing 60min of concentrating hydrolysate quality 3%, get the decolouring liquid glucose;
(4) will decolour liquid glucose by the exchange of cationic, anionic exchange resin enforcement continuous ionic, and make the liquid glucose specific conductivity at 8.7 μ s/cm, get raw sugar liquid; Then above-mentioned raw sugar liquid is passed through simulation moving-bed separating glucose and a small amount of cell-oligosaccharide, wood sugar, pectinose, 70 ℃ of separation temperatures, with the cation separation resin as sorbent material, take purified water as eluent, glucose purity is 97.3wt% after separating, and gets Glucose Liquid;
(5) Glucose Liquid is concentrated with triple-effect evaporator, the first step is concentrated into concentration 45.4wt%, and second step is concentrated into 75.7wt%, gets dense liquid glucose; Wood sugar, pectinose, cell-oligosaccharide reclaim with spray-dired method; Then, dense liquid glucose is put into the crystallizer that contains 1/3 crystal seed, utilize chuck water of condensation cooling, be cooled to 23 ℃ by 55 ℃, rate of temperature fall is 1 ℃/h, and then centrifugal, washing, drying obtain crystalline dextrose.
Through adopting the method measuring and calculating of amplifying in proportion, the recyclable purity of maize peel acidolysis slag per ton is 610 kilograms of the glucose crystallizations of 96.8wt%.
The present invention is not limited to above-mentioned specific embodiment; anyone can draw other various forms of concrete schemes under enlightenment of the present invention; no matter substitute and conversion but what kind of is done, the every and same or analogous technical scheme of the application is all within protection scope of the present invention.
Claims (2)
1. a method of utilizing maize peel acid hydrolysis slag to prepare high-purity crystallized glucose is characterized in that step is as follows, is mass ratio:
(1) maize peel acidolysis slag is added water by solid-to-liquid ratio 1:5～1:10, add again the cellulose complex enzyme of acidolysis slag dry weight 1～3wt%, at 45～60 ℃, under the condition of pH4～6, at the uniform velocity stir 24～36h, namely get hydrolyzed solution;
(2) hydrolyzed solution after hydrolysis is filtered, remove hydrolysis residue, the hydrolyzed solution after then will filtering is concentrated into sugared content 25～35wt%, gets concentrating hydrolysate;
(3) in concentrating hydrolysate, add gac, stir, get the decolouring liquid glucose;
(4) will decolour after liquid glucose implements the continuous ionic exchange by cationic, anionic exchange resin, get raw sugar liquid; Then, utilize simulation moving-bed device to separate, separation temperature 45-80 ℃, as sorbent material, take purified water as eluent, obtain Glucose Liquid with the cation separation resin;
(5) with Glucose Liquid simmer down to concentration 72～75wt%, then purity put into crystallizer with dense liquid glucose greater than the dense liquid glucose of 95wt%, is cooled to 23 ℃ by 55～65 ℃ of temperature, and rate of temperature fall is 1 ℃/h, and centrifugal, washing, drying obtain crystalline dextrose;
The specific conductivity of the raw sugar liquid in the described step (4)≤10 μ s/cm.
2. the method for claim 1 is characterized in that, the water ratio of the maize peel acidolysis slag in the described step (1) is 5.7wt%.
3, the method for claim 1 is characterized in that, the bleaching temperature in the described step (3) is 75～80 ℃; The gac add-on is 3%～5% of concentrating hydrolysate weight; Bleaching time 0.5～1.5 hour.
4, the method for claim 1 is characterized in that, the concentrated employing triple-effect evaporator in the described step (5) concentrates, and the first step is concentrated into 40～50wt%, and second step is concentrated into 72～75wt%.
5, the method for claim 1 is characterized in that, the crystallizer in the described step (5) is the crystallizer that contains 1/3 crystal seed.
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| CN102391065B (en) * | 2011-08-09 | 2014-02-05 | 山东省鲁洲食品集团有限公司 | Method for producing dihydric alcohol and low molecular polyalcohol by taking corn husk as raw material |
| CN102559940B (en) * | 2011-12-31 | 2014-08-06 | 三达膜科技（厦门）有限公司 | Separation and purification method of glucose |
| CN105669419B (en) * | 2016-01-09 | 2018-01-26 | 黑龙江八一农垦大学 | The method of saccharic acid in sequential simulated moving bed separating corn stalk acid hydrolysis solution |
| CN112375794A (en) * | 2020-11-27 | 2021-02-19 | 鲁洲生物科技（山东）有限公司 | Method for preparing mixed functional syrup by using corn bran |
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Owner name: LUZHOU BIO-CHEM TECHNOLOGY(SHANGDONG) CO., LTD. Free format text: FORMER OWNER: LUZHOU FOOD PRODUCT GROUP CORP., LTD., SHANDONG PROV. Effective date: 20140212 |
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