CN102030630A - Method for producing industrial grade sodium gluconate or calcium gluconate from yellow ginger starch - Google Patents
Method for producing industrial grade sodium gluconate or calcium gluconate from yellow ginger starch Download PDFInfo
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Abstract
The invention relates to a method for producing industrial grade sodium gluconate or calcium gluconate from yellow ginger starch. The method comprises the following steps: (1) pre-treating the yellow ginger starch; (2) liquefying by an enzyme method to obtain starch liquefied liquid; (3) saccharifying by the enzyme method to obtain starch saccharified liquid; (4) removing impurities from the starch saccharified liquid and decolorizing to obtain a colorless saccharified liquid; (5) adding a Pd/C catalyst to the saccharified liquid to catalytically oxidize the glucose in the saccharified liquid to prepare sodium gluconate or calcium gluconate; (6) vacuum filtering and recovering the catalyst; and (7) decolorizing the filtrate, concentrating by vacuum evaporation, and crystallizing or spray drying to obtain the finished product of the sodium gluconate or the calcium gluconate. The conversion rate of the yellow ginger starch and the yield of the sodium gluconate or the calcium gluconate are high, the purity is higher than 90%, and the sodium gluconate or the calcium gluconate has high quality and lower production cost, and is especially suitable to be used as a cement enhancer.
Description
Technical field
The present invention relates to the production method of Sunmorl N 60S or calglucon, particularly a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon.
Background technology
Yellow ginger claims bitter galingal, duration and degree of heating root again, is the distinctive species of China, formal name used at school be Rhizome of Peltate Yam (
Discover zingiberensisC. H. Wright), be the perennial vine of Dioscoreaceae Wild yam, it is yellow or orange that its rhizome is, contain 1.1%～16.5% the diosgenin (sapogenin) of having an appointment, in addition, the yellow ginger rhizome also contains 45%～50% the starch of having an appointment, 40%～50% Mierocrystalline cellulose and a small amount of tannin, alkaloid, pigment etc.Diosgenin is the raw material of thirties kinds of medicine such as synthesizing steroid hormone medicine and steroid contraception class medicine, and its application is very extensive.Therefore, occupy the yellow ginger of the hat of world's yam as diosgenin content, global demand rises year by year, and its main purposes is used for extracting saponin exactly.Yet, utilize the production technique of yellow ginger extraction diosgenin backward relatively at present, the extraction yield of saponin is low, contains a large amount of starch in the waste after the extraction.Because this starch more or less all contains a certain amount of saponin, can cause infertilely after people and animals are edible, be the starch that a kind of anorexia is used, and directly discharging cause water source eutrophication and water quality deterioration, contaminate environment easily.At present, the development and use of yellow ginger resource mainly are the extractions of saponin, and content abundant starch in the yellow ginger is not had the good comprehensive utilization, and are totally unfavorable to the Sustainable development of yellow ginger industry.Therefore, the starch that by-product contains saponin in how turmeric saponin being extracted is developed new purposes, is to improve the value of exploiting and utilizing of yellow ginger and promote the Sustainable development of yellow ginger industry all to have important environmental benefit and economic worth.
In recent years, Sunmorl N 60S or calglucon are as a kind of important intermediate of industry such as chemical industry, building materials, food, medicine and light industry, purposes is very extensive, as aspect the cement reinforcement agent, Sunmorl N 60S or calglucon are widely used as water reducer and retardant, can delay concrete time of coagulation, reduce slump-loss, improve concrete strength.Along with Sunmorl N 60S or calglucon at home and abroad demand grow with each passing day, output constantly enlarges, and makes that the demand as the glucose of Sunmorl N 60S or calglucon raw materials for production also continues to increase, production cost improves gradually.If the starch that we can extract turmeric saponin in the waste is converted into glucose, and the glucose production Sunmorl N 60S or the calglucon of utilization conversion, though containing a small amount of turmeric saponin should not be in the food and medicine sector application, agent is adaptable fully as cement reinforcement but at building material industry, this not only can either turn waste into wealth, can reduce greatly again and be used to produce the Sunmorl N 60S of cement reinforcement agent or the production cost of calglucon, increase economic efficiency.This product also is adaptable fully in other industry simultaneously,
At present, not a lot of about the report of the development and use of yellow ginger starch, substantially all belong to transforming glucose research, the report that directly utilizes yellow ginger Starch Production Sunmorl N 60S or calglucon is not arranged, the related invention patent does not have substantially yet both at home and abroad.Analyze its reason, may be that the saponin that is contained in the yellow ginger starch has certain toxicity, and saponin has cohesion to materials such as fiber in the yellow ginger starch and protein, make it be difficult to separate with starch, make that the solubleness of yellow ginger starch is lower, and the color of yellow ginger starch is yellow dark, and the quality of its product is had adverse influence.The present invention fully utilizes Starch Production industrial glucose acid sodium or the calglucon in turmeric saponin extraction waste or the yellow ginger powder slurry, to improve the development and use efficient of yellow ginger, can significantly reduce pollution and the influence of yellow ginger production, help promoting the healthy Sustainable development of yellow ginger industry environment.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon, this method is used for the starch of turmeric saponin extraction waste or yellow ginger powder slurry is utilized, and then preparation Sunmorl N 60S or calglucon finished product, production technique is simple, starch transformation efficiency height, product yield and purity height, quality is good, added value of product is higher, and production cost is low.
To achieve these goals, technical scheme of the present invention is: a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 20%～30%, stirring is sized mixing, put it in the high pressure vessel then, under 120 ℃～125 ℃ of pressure 0.1 MPa～0.15 MPa, temperature, boil 20min～30min, after the taking-up, the pH value that adds sodium hydroxide solution or saturated limewater solution adjusting starch milk by 0.1mol/L～1mol/L is 6.0～6.5, at 85 ℃～95 ℃ following ultra-sonic oscillation 30min～60min;
2) enzymatic liquefaction: need enzyme amount 8U～15U by every gram dry starch, in starch milk, add bacterial, stirring 10min～the 30min that sizes mixing, after sizing mixing evenly, under 80 ℃～100 ℃, carry out vapo(u)r blasting liquefaction, after vapo(u)r blasting liquefaction is finished, heat up 20 ℃～30 ℃ again, and insulation 20min～30min enzyme that goes out, obtain liquefied starch;
3) enzyme process saccharification: liquefied starch is cooled to 55 ℃～60 ℃, adding sodium hydroxide solution or saturated limewater solution in the ratio of 0.1mol/L～1mol/L in liquefied starch, to regulate the pH value be 4.0～4.5, and need enzyme amount 150U～200U add saccharifying enzyme by every gram dry starch, insulation saccharification 40h～50h, after checking no dextrin to exist, the pH value of its liquid is transferred to 4.8～5.0, be heated to 80 ℃～85 ℃ simultaneously, insulation 20min～30min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: starch saccharificating liquid is removed insoluble impurities after filtration, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 65 ℃～75 ℃, interpolation quality percentage composition is 1.0%～1.5% activated carbon decolorizing in clarification saccharification liquid, stir 30min～60min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the glucose content of measuring colourless saccharification liquid, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 10:1～50:1, in colourless saccharification liquid, add the Pd/C catalyzer, and feeding pressurized air or oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 45 ℃～48 ℃, and pressurized air or amount of oxygen are 40m
3/ h～50m
3/ h, stirring velocity is 1500 r/min～2000 r/min, ratio in 0.1mol/L～1mol/L in catalytic reaction process adds sodium hydroxide solution or saturated limewater solution to colourless saccharification liquid, the pH value of controlling colourless saccharification liquid is 9.0～9.5, remaining glucose content in the colourless saccharification liquid of sampling and measuring, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, filtrate is Sunmorl N 60S or calcium gluconate solution, the catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter Sunmorl N 60S or calcium gluconate solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 65 ℃～75 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.0%～1.5%, stir 30min～60min, vacuum filtration, elimination gac, get colourless Sunmorl N 60S or calcium gluconate solution, 55 ℃ then～65 ℃ following vacuum concentration evaporations after crystallization or the spraying drying, obtain Sunmorl N 60S or calglucon finished product.
In the step 1), described yellow ginger starch extracts waste or yellow ginger powder slurry from turmeric saponin, and the mass percentage content that described turmeric saponin extracts starch in waste or the yellow ginger powder slurry is 20%～50%.
In the step 1), the time that described stirring is sized mixing is 10min～30min, and described frequency of ultrasonic is 20 KHz～25 KHz.
Step 2) in, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction.
In the step 3), with having or not dextrin to exist in the raw spirit detection liquefied starch.
In the step 4), described starch saccharificating liquid filters through filter paper or 100 orders～200 mesh filter screens, obtains clarifying saccharification liquid.
In the step 5), before the glucose catalyticing oxidation reaction, the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in the glucose catalyticing oxidation reaction process, adopt the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, be lower than 1% until remaining glucose content.
In the step 5), described Pd/C catalyzer is that load has the gac of palladium and the gac that load has bismuth or tin, and in the described Pd/C catalyzer, the quality percentage composition of palladium is 3%～5%, the quality percentage composition of bismuth or tin is 3%～5%, and granularity of activated carbon is 100 orders～200 orders.
In the step 6), adopt rotation concentration and evaporation instrument 55 ℃～65 ℃ following vacuum concentration evaporations.
The invention has the beneficial effects as follows:
1. present method adopts the method for high pressure, high-temperature boiling yellow ginger starch milk and ultra-sonic oscillation that yellow ginger starch is carried out pre-treatment, solved preferably in the yellow ginger starch starch and fiber and protein not easily separated with the lower difficult problem of solubleness.And in processing step thereafter, repeat to remove insoluble impurities and adopt the activated carbon decolorizing step, the impurity such as fiber, protein and turmeric saponin that contained in the yellow ginger starch have been removed effectively, the color and luster and the quality of Sunmorl N 60S or calglucon finished product have not only been guaranteed, also help improving the yield and the purity of Sunmorl N 60S or calglucon, also reduce the content of toxin such as turmeric saponin, even all removed turmeric saponin.
2. present method uses double-enzyme method that yellow ginger starch is converted into glucose, just be a bacterial hydrolyzed starch with the sharpest edges of traditional acidic process, help starch and other separate impurities, saccharifying enzyme is good to amylatic saccharification result, starch transformation efficiency height, saccharification liquid can easily be removed other impurity such as Mierocrystalline cellulose that exist in the yellow ginger starch material through filtering.
3. the Pd/C catalyst of present method use is active high, the efficient height of catalyzed reaction, improved the yield of Sunmorl N 60S or calglucon effectively, and the Pd/C catalyzer is longer work-ing life, recyclable back is reused, help improving the production efficiency of the inventive method, reduce production costs.
4. the yellow ginger starch transformation efficiency of the inventive method is more than 95%, and Sunmorl N 60S or calglucon yield are more than 80%, and Sunmorl N 60S or calglucon purity are more than 90%, the quality height, and quality is good.The industrial glucose acid sodium finished product that the inventive method is produced can be widely used in oil, chemical industry is used as water treatment agent, and industrial glucose acid sodium or calglucon finished product that the inventive method is produced are particularly suitable for using as the cement reinforcement agent of building material industry.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
A kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 20%～30%, stirring is sized mixing, put it in the high pressure vessel then, under 120 ℃～125 ℃ of pressure 0.1 MPa～0.15 MPa, temperature, boil 20min～30min, after the taking-up, the pH value that adds sodium hydroxide solution or saturated limewater solution adjusting starch milk by 0.1mol/L～1mol/L is 6.0～6.5, at 85 ℃～95 ℃ following ultra-sonic oscillation 30min～60min;
2) enzymatic liquefaction: need enzyme amount 8U～15U by every gram dry starch, in starch milk, add bacterial, stirring 10min～the 30min that sizes mixing, after sizing mixing evenly, under 80 ℃～100 ℃, carry out vapo(u)r blasting liquefaction, after vapo(u)r blasting liquefaction is finished, heat up 20 ℃～30 ℃ again, and insulation 20min～30min enzyme that goes out, obtain liquefied starch;
3) enzyme process saccharification: liquefied starch is cooled to 55 ℃～60 ℃, adding sodium hydroxide solution or saturated limewater solution in the ratio of 0.1mol/L～1mol/L in liquefied starch, to regulate the pH value be 4.0～4.5, and need enzyme amount 150U～200U add saccharifying enzyme by every gram dry starch, insulation saccharification 40h～50h, after checking no dextrin to exist, the pH value of its liquid is transferred to 4.8～5.0, be heated to 80 ℃～85 ℃ simultaneously, insulation 20min～30min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: starch saccharificating liquid is removed insoluble impurities after filtration, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 65 ℃～75 ℃, interpolation quality percentage composition is 1.0%～1.5% activated carbon decolorizing in clarification saccharification liquid, stir 30min～60min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the glucose content of measuring colourless saccharification liquid, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 10:1～50:1, in colourless saccharification liquid, add the Pd/C catalyzer, and feeding pressurized air or oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 45 ℃～48 ℃, and pressurized air or amount of oxygen are 40m
3/ h～50m
3/ h, stirring velocity is 1500 r/min～2000 r/min, ratio in 0.1mol/L～1mol/L in catalytic reaction process adds sodium hydroxide solution or saturated limewater solution to colourless saccharification liquid, the pH value of controlling colourless saccharification liquid is 9.0～9.5, remaining glucose content in the colourless saccharification liquid of sampling and measuring, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, filtrate is Sunmorl N 60S or calcium gluconate solution, the catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter Sunmorl N 60S or calcium gluconate solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 65 ℃～75 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.0%～1.5%, stir 30min～60min, vacuum filtration, the elimination gac, obtain water white transparency Sunmorl N 60S or calcium gluconate solution, 55 ℃ then～65 ℃ following vacuum concentration evaporations after crystallization or the spraying drying, obtain white crystals or powdery Sunmorl N 60S or calglucon finished product.
Embodiment 1:
A kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 30%, the stirring 30min that sizes mixing, put it in the high pressure vessel then, at pressure 0.1MPa, boil 20min under 120 ℃ of the temperature, after the taking-up, the pH value that adds sodium hydroxide solution adjusting starch milk by 0.5mol/L is 6.0, at 90 ℃ of following ultra-sonic oscillation 30min, ultrasonic frequency is 23KHz, and ultra-sonic oscillation can make the starch in the starch milk be uniformly dispersed, overcome clustering phenomena, improve its solubleness, can also quicken starch and fiber in the starch milk, separate impurities such as protein are to improve the filter effect of insoluble impurities in the step thereafter;
2) enzymatic liquefaction: need enzyme amount 12U by every gram dry starch, in starch milk, add bacterial, stir 30 min that size mixing, size mixing evenly after, under 85 ℃, carry out vapo(u)r blasting liquefaction, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction, after vapo(u)r blasting liquefaction is finished, heats up 25 ℃ again, and the insulation 30min enzyme that goes out, obtain liquefied starch, in present method, described U represents enzyme activity unit;
3) enzyme process saccharification: liquefied starch is cooled to 55 ℃, adding sodium hydroxide solution in the ratio of 0.5mol/L in liquefied starch, to regulate the pH value be 4.0, and by every gram dry starch need enzyme amount 180U adding saccharifying enzyme, insulation saccharification 45h, after detecting no dextrin existence with raw spirit, the pH value of its liquid is transferred to 4.8, be heated to 85 ℃ simultaneously, the insulation 20min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: described starch saccharificating liquid is through filter paper filtering, remove insoluble impurities, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 65 ℃, interpolation quality percentage composition is 1.0% activated carbon decolorizing in clarification saccharification liquid, stirs 60 min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 10:1, in colourless saccharification liquid, add Pd-Bi/C catalyzer, the mass percentage content of palladium in the Pd-Bi/C catalyzer (Pd) and bismuth (Bi) is 3%, and in colourless saccharification liquid, feed pressurized air or oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 47 ℃, and the pressurized air add-on is 45m
3/ h, stirring velocity is 1800 r/min, ratio in 0.5mol/L in catalytic reaction process adds the sodium hydroxide solution neutralization to colourless saccharification liquid, and the pH value of controlling colourless saccharification liquid is 9.2, adopts the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, behind the 4h, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, and filtrate is sodium gluconate solution, Pd-Bi/C the catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter sodium gluconate solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 65 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.0%, stir 60min, vacuum filtration, elimination gac, obtain the water white transparency sodium gluconate solution, adopt rotation concentration and evaporation instrument 60 ℃ of following vacuum concentration evaporations then, after crystallization or the spraying drying, obtain white crystals or powdery Sunmorl N 60S finished product.
The described yellow ginger starch of present embodiment transformation efficiency is 97.3%, and the Sunmorl N 60S yield is 85.4%, and Sunmorl N 60S purity is 91.7%.
Embodiment 2:
A kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 25%, the stirring 30min that sizes mixing, put it in the high pressure vessel then, under 122 ℃ of pressure 0.12MPa, temperature, boil 30min, after the taking-up, the pH value that adds sodium hydroxide solution adjusting starch milk by 0.1mol/L is 6.5, at 92 ℃ of following ultra-sonic oscillation 30min, ultrasonic frequency is 20KHz, starch in the starch milk is uniformly dispersed, and quickens separate impurities such as starch and fiber in the starch milk, protein;
2) enzymatic liquefaction: need enzyme amount 10U by every gram dry starch, in starch milk, add bacterial, stirring 20 min that size mixing, after sizing mixing evenly, carry out vapo(u)r blasting liquefaction under 95 ℃, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction, after vapo(u)r blasting liquefaction is finished, heat up 20 ℃ again, and the insulation 25min enzyme that goes out, liquefied starch obtained;
3) enzyme process saccharification: liquefied starch is cooled to 60 ℃, adding sodium hydroxide solution in the ratio of 1.0mol/L in liquefied starch, to regulate the pH value be 4.5, and by every gram dry starch need enzyme amount 180U adding saccharifying enzyme, insulation saccharification 48h, after detecting no dextrin existence with raw spirit, the pH value of its liquid is transferred to 5.0, be heated to 80 ℃ simultaneously, the insulation 30min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: described starch saccharificating liquid is through 100 strainer filterings, remove insoluble impurities, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 65 ℃, interpolation quality percentage composition is 1.5% activated carbon decolorizing in clarification saccharification liquid, stirs 30min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 50:1, in colourless saccharification liquid, add the Pd-Sn/C catalyzer, the mass percentage content of palladium in the Pd-Sn/C catalyzer (Pd) and tin (Sn) is 5%, and in colourless saccharification liquid, feed pressurized air or oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 45 ℃, and the pressurized air add-on is 40m
3/ h, stirring velocity is 1500 r/min, ratio in 1.0mol/L in catalytic reaction process adds the sodium hydroxide solution neutralization to colourless saccharification liquid, and the pH value of controlling colourless saccharification liquid is 9.5, adopts the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, behind the 7h, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, and filtrate is sodium gluconate solution, the Pd-Sn/C catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter sodium gluconate solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 65 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.5%, stir 30min, vacuum filtration, elimination gac, obtain the water white transparency sodium gluconate solution, adopt rotation concentration and evaporation instrument 65 ℃ of following vacuum concentration evaporations then, after crystallization or the spraying drying, obtain white crystals or powdery Sunmorl N 60S finished product.
The described yellow ginger starch of present embodiment transformation efficiency is 98.5%, and the Sunmorl N 60S yield is 80.7%, and Sunmorl N 60S purity is 90.8%.
Embodiment 3:
A kind of method of utilizing yellow ginger Starch Production industrial glucose acid calcium comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 25%, the stirring 25min that sizes mixing, put it in the high pressure vessel then, under 125 ℃ of pressure 0.15MPa, temperature, boil 20min, after the taking-up, the pH value that adds saturated limewater solution adjusting starch milk by 0.1mol/L is 6.2, at 90 ℃ of following ultra-sonic oscillation 25min, ultrasonic frequency is 24KHz, starch in the starch milk is uniformly dispersed, and quickens separate impurities such as starch and fiber in the starch milk, protein;
2) enzymatic liquefaction: need enzyme amount 15U by every gram dry starch, in starch milk, add bacterial, the stirring 25min that sizes mixing, after sizing mixing evenly, carry out vapo(u)r blasting liquefaction under 90 ℃, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction, after vapo(u)r blasting liquefaction is finished, heat up 30 ℃ again, and the insulation 20min enzyme that goes out, liquefied starch obtained;
3) enzyme process saccharification: liquefied starch is cooled to 58 ℃, adding saturated limewater solution in the ratio of 1.0mol/L in liquefied starch, to regulate the pH value be 4.2, and by every gram dry starch need enzyme amount 200U adding saccharifying enzyme, insulation saccharification 45h, after detecting no dextrin existence with raw spirit, the pH value of its liquid is transferred to 4.9, be heated to 85 ℃ simultaneously, the insulation 25min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: described starch saccharificating liquid is through 200 strainer filterings, remove insoluble impurities, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 70 ℃, interpolation quality percentage composition is 1.2% activated carbon decolorizing in clarification saccharification liquid, stirs 20min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 30:1, in colourless saccharification liquid, add the Pd-Sn/C catalyzer, the mass percentage content of palladium in the Pd-Sn/C catalyzer (Pd) and tin (Sn) is 4%, and in colourless saccharification liquid aerating oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 48 ℃, and the oxygen add-on is 40m
3/ h, stirring velocity is 1700 r/min, ratio in 1.2mol/L in catalytic reaction process adds the neutralization of saturated limewater solution to colourless saccharification liquid, and the pH value of controlling colourless saccharification liquid is 9.3, adopts the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, behind the 5h, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, and filtrate is calcium gluconate solution, the Pd-Sn/C catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter the calglucon sodium solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 70 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.2%, stir 20min, vacuum filtration, elimination gac, obtain the water white transparency calcium gluconate solution, adopt rotation concentration and evaporation instrument 58 ℃ of following vacuum concentration evaporations then, after crystallization or the spraying drying, obtain white crystals or powdery calglucon finished product.
The described yellow ginger starch of present embodiment transformation efficiency is 98.1%, and the calglucon yield is 83.8%, and calglucon purity is 92.2%.
Embodiment 4:
A kind of method of utilizing yellow ginger Starch Production industrial glucose acid calcium comprises the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 30%, the stirring 30min that sizes mixing, put it in the high pressure vessel then, under 123 ℃ of pressure 0.13MPa, temperature, boil 25min, after the taking-up, the pH value that adds saturated limewater solution adjusting starch milk by 1.0mol/L is 6.5, at 90 ℃ of following ultra-sonic oscillation 20min, ultrasonic frequency is 22KHz, starch in the starch milk is uniformly dispersed, and quickens separate impurities such as starch and fiber in the starch milk, protein;
2) enzymatic liquefaction: need enzyme amount 18U by every gram dry starch, in starch milk, add bacterial, the stirring 30min that sizes mixing, after sizing mixing evenly, carry out vapo(u)r blasting liquefaction under 85 ℃, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction, after vapo(u)r blasting liquefaction is finished, heat up 30 ℃ again, and the insulation 20min enzyme that goes out, liquefied starch obtained;
3) enzyme process saccharification: liquefied starch is cooled to 55 ℃, adding saturated limewater solution in the ratio of 0.1mol/L in liquefied starch, to regulate the pH value be 4.5, and by every gram dry starch need enzyme amount 180U adding saccharifying enzyme, insulation saccharification 48h, after detecting no dextrin existence with raw spirit, the pH value of its liquid is transferred to 4.8, be heated to 90 ℃ simultaneously, the insulation 20min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: described starch saccharificating liquid is through 150 strainer filterings, remove insoluble impurities, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 75 ℃, interpolation quality percentage composition is 1.0% activated carbon decolorizing in clarification saccharification liquid, stirs 25min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 40:1, in colourless saccharification liquid, add Pd-Bi/C catalyzer, the mass percentage content of palladium (Pd) is 5% in the Pd-Bi/C catalyzer, the mass percentage content of bismuth (Bi) is 3%, and in colourless saccharification liquid aerating oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 48 ℃, and the pressurized air add-on is 50m
3/ h, stirring velocity is 2000 r/min, ratio in 1.0mol/L in catalytic reaction process adds the neutralization of saturated limewater solution to colourless saccharification liquid, and the pH value of controlling colourless saccharification liquid is 9.0, adopts the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, behind the 5h, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, and filtrate is calcium gluconate solution, Pd-Bi/C the catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter the calglucon sodium solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 75 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.0%, stir 25min, vacuum filtration, elimination gac, obtain the water white transparency calcium gluconate solution, adopt rotation concentration and evaporation instrument 55 ℃ of following vacuum concentration evaporations then, after crystallization or the spraying drying, obtain white crystals or powdery calglucon finished product.
The described yellow ginger starch of present embodiment transformation efficiency is 97.5%, and the calglucon yield is 82.7%, and calglucon purity is 93.2%.
The industrial glucose acid sodium finished product that the inventive method is produced can be widely used in oil, chemical industry is used as water treatment agent, and industrial glucose acid sodium or calglucon finished product that the inventive method is produced are particularly suitable for using as the cement reinforcement agent in the building material industry.
Claims (9)
1. a method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon is characterized in that comprising the steps:
1) yellow ginger starch pre-treatment: yellow ginger starch and water are mixed, the quality percentage composition that makes starch in the starch milk is 20%～30%, stirring is sized mixing, put it in the high pressure vessel then, under 120 ℃～125 ℃ of pressure 0.1 MPa～0.15 MPa, temperature, boil 20min～30min, after the taking-up, the pH value that adds sodium hydroxide solution or saturated limewater solution adjusting starch milk by 0.1mol/L～1mol/L is 6.0～6.5, at 85 ℃～95 ℃ following ultra-sonic oscillation 30min～60min;
2) enzymatic liquefaction: need enzyme amount 8U～15U by every gram dry starch, in starch milk, add bacterial, stirring 10min～the 30min that sizes mixing, after sizing mixing evenly, under 80 ℃～100 ℃, carry out vapo(u)r blasting liquefaction, after vapo(u)r blasting liquefaction is finished, heat up 20 ℃～30 ℃ again, and insulation 20min～30min enzyme that goes out, obtain liquefied starch;
3) enzyme process saccharification: liquefied starch is cooled to 55 ℃～60 ℃, adding sodium hydroxide solution or saturated limewater solution in the ratio of 0.1mol/L～1mol/L in liquefied starch, to regulate the pH value be 4.0～4.5, and need enzyme amount 150U～200U add saccharifying enzyme by every gram dry starch, insulation saccharification 40h～50h, after checking no dextrin to exist, the pH value of its liquid is transferred to 4.8～5.0, be heated to 80 ℃～85 ℃ simultaneously, insulation 20min～30min enzyme that goes out obtains starch saccharificating liquid;
4) removal of impurities of saccharification liquid, decolouring: starch saccharificating liquid is removed insoluble impurities after filtration, obtain clarifying saccharification liquid, control clarification saccharification liquid temp is at 65 ℃～75 ℃, interpolation quality percentage composition is 1.0%～1.5% activated carbon decolorizing in clarification saccharification liquid, stir 30min～60min, vacuum filtration, the elimination gac gets colourless saccharification liquid;
5) glucose catalyticing oxidation: the glucose content of measuring colourless saccharification liquid, in glucose and catalyst quality in the colourless saccharification liquid than the ratio of 10:1～50:1, in colourless saccharification liquid, add the Pd/C catalyzer, and feeding pressurized air or oxygen, carry out stirring in water bath, the catalyzed reaction temperature is controlled at 45 ℃～48 ℃, and pressurized air or amount of oxygen are 40m
3/ h～50m
3/ h, stirring velocity is 1500 r/min～2000 r/min, ratio in 0.1mol/L～1mol/L in catalytic reaction process adds sodium hydroxide solution or saturated limewater solution to colourless saccharification liquid, the pH value of controlling colourless saccharification liquid is 9.0～9.5, remaining glucose content in the colourless saccharification liquid of sampling and measuring, when being lower than 1%, remaining glucose content stops catalyzed reaction, vacuum filtration, filtrate is Sunmorl N 60S or calcium gluconate solution, the catalyzer of filter residue for reclaiming, dry back is for using next time;
6) product purification: filter Sunmorl N 60S or calcium gluconate solution, remove insoluble impurities, obtain settled solution, control settled solution temperature is at 65 ℃～75 ℃, in settled solution, add the activated carbon decolorizing of massfraction 1.0%～1.5%, stir 30min～60min, vacuum filtration, elimination gac, get colourless Sunmorl N 60S or calcium gluconate solution, 55 ℃ then～65 ℃ following vacuum concentration evaporations after crystallization or the spraying drying, obtain Sunmorl N 60S or calglucon finished product.
2. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: in the step 1), described yellow ginger starch extracts waste or yellow ginger powder slurry from turmeric saponin, and the mass percentage content that described turmeric saponin extracts starch in waste or the yellow ginger powder slurry is 20%～50%.
3. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: in the step 1), the time that described stirring is sized mixing is 10min～30min, and described frequency of ultrasonic is 20 KHz～25 KHz.
4. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: step 2) in, it is the index that vapo(u)r blasting liquefaction is finished that described vapo(u)r blasting liquefaction is faint yellow with iodine liquid color reaction.
5. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1 is characterized in that: in the step 3), with having or not dextrin to exist in the raw spirit detection liquefied starch.
6. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: in the step 4), described starch saccharificating liquid filters through filter paper or 100 orders～200 mesh filter screens, obtains clarifying saccharification liquid.
7. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: in the step 5), before the glucose catalyticing oxidation reaction, the employing Fehlings reagent is measured the glucose content in the colourless saccharification liquid earlier, in the glucose catalyticing oxidation reaction process, adopt the once remaining glucose content of the every 1h sampling and measuring of Fehlings reagent, be lower than 1% until remaining glucose content.
8. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1, it is characterized in that: in the step 5), described Pd/C catalyzer is that load has the gac of palladium and the gac that load has bismuth or tin, in the described Pd/C catalyzer, the quality percentage composition of palladium is 3%～5%, the quality percentage composition of bismuth or tin is 3%～5%, and granularity of activated carbon is 100 orders～200 orders.
9. a kind of method of utilizing yellow ginger Starch Production industrial glucose acid sodium or calglucon according to claim 1 is characterized in that: in the step 6), adopt rotation concentration and evaporation instrument 55 ℃～65 ℃ following vacuum concentration evaporations.
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| CN103923953A (en) * | 2014-04-11 | 2014-07-16 | 山东省食品发酵工业研究设计院 | Method for solidifying sodium gluconate mother liquor produced by fermentation method |
| CN104263781A (en) * | 2014-09-29 | 2015-01-07 | 江苏大学 | Ultrasonic-assisted double-enzyme hydrolysis technology of starch |
| CN105000817A (en) * | 2015-05-21 | 2015-10-28 | 苏州市湘园特种精细化工有限公司 | Concrete retarder and preparation method thereof |
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| CN102643040A (en) * | 2012-03-23 | 2012-08-22 | 辽宁岩砂晶建材有限公司 | Preparation method of retarder for concrete and equipment adopted by preparation method |
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| CN103923953B (en) * | 2014-04-11 | 2016-08-17 | 山东省食品发酵工业研究设计院 | A kind of by the solidified method of gluconic acid mother liquid of sodium of fermentative Production |
| CN104263781A (en) * | 2014-09-29 | 2015-01-07 | 江苏大学 | Ultrasonic-assisted double-enzyme hydrolysis technology of starch |
| CN105000817A (en) * | 2015-05-21 | 2015-10-28 | 苏州市湘园特种精细化工有限公司 | Concrete retarder and preparation method thereof |
| CN108911390A (en) * | 2018-07-18 | 2018-11-30 | 荆楚理工学院 | A kind of processing method of turmeric saponin wastewater comprehensive utilization |
| CN108911390B (en) * | 2018-07-18 | 2021-10-15 | 荆楚理工学院 | Treatment method for comprehensive utilization of diosgenin wastewater |
| CN109944169A (en) * | 2019-04-18 | 2019-06-28 | 联建建设工程有限公司 | Large span cantilever box girder construction method |
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