CN106337066B - Process for producing sodium gluconate by energy-saving environment-friendly enzyme method - Google Patents
Process for producing sodium gluconate by energy-saving environment-friendly enzyme method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 51
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000176 sodium gluconate Substances 0.000 title claims abstract description 40
- 229940005574 sodium gluconate Drugs 0.000 title claims abstract description 40
- 235000012207 sodium gluconate Nutrition 0.000 title claims abstract description 40
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 19
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 238000000855 fermentation Methods 0.000 claims abstract description 54
- 230000004151 fermentation Effects 0.000 claims abstract description 54
- 229920002472 Starch Polymers 0.000 claims abstract description 38
- 235000019698 starch Nutrition 0.000 claims abstract description 38
- 239000008107 starch Substances 0.000 claims abstract description 38
- 235000013336 milk Nutrition 0.000 claims abstract description 33
- 239000008267 milk Substances 0.000 claims abstract description 33
- 210000004080 milk Anatomy 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims description 33
- 230000008020 evaporation Effects 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229940088598 enzyme Drugs 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 108090000637 alpha-Amylases Proteins 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 102000004139 alpha-Amylases Human genes 0.000 claims description 9
- 229940024171 alpha-amylase Drugs 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 102000016938 Catalase Human genes 0.000 claims description 6
- 108010053835 Catalase Proteins 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004366 Glucose oxidase Substances 0.000 claims description 6
- 108010015776 Glucose oxidase Proteins 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 6
- 229940116332 glucose oxidase Drugs 0.000 claims description 6
- 235000019420 glucose oxidase Nutrition 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000002918 waste heat Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 241000228245 Aspergillus niger Species 0.000 claims description 3
- 108010073178 Glucan 1,4-alpha-Glucosidase Proteins 0.000 claims description 3
- 241000228150 Penicillium chrysogenum Species 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 108010019077 beta-Amylase Proteins 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011344 liquid material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KTCHEMONOXOHMN-UHFFFAOYSA-M sodium 2,2,3,3,4-pentahydroxyhexanoate Chemical compound OC(C(C(C(=O)[O-])(O)O)(O)O)CC.[Na+] KTCHEMONOXOHMN-UHFFFAOYSA-M 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/58—Aldonic, ketoaldonic or saccharic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
the invention belongs to the technical field of sodium gluconate production, and particularly relates to a novel process for producing sodium gluconate by an energy-saving environment-friendly enzyme method. The novel process for producing sodium gluconate by using the energy-saving environment-friendly enzyme method comprises the following steps: (1) liquefying and saccharifying starch milk; c. saccharifying; (2) continuously eliminating; (3) fermenting; b. fermenting the saccharified liquid; (4) decoloring; (5) concentrating; (6) filtering, washing, drying and obtaining the finished product. Compared with the traditional catalysis method and fermentation method, the process has the remarkable advantages of high safety and easiness in extraction and refining of products, greatly improves the quality of sodium gluconate, and can reduce the steam consumption of the products and greatly reduce the cost of the products.
Description
Technical Field
The invention belongs to the technical field of sodium gluconate production, and particularly relates to a process for producing sodium gluconate by an energy-saving environment-friendly enzyme method.
Background
Sodium gluconate is also known as sodium pentahydroxyhexanoate and has a molecular formula of C6H11O7 Na. Due to the characteristics of no toxicity, good thermal stability and the like, the composite material has wide application in the aspects of building industry, food, medicine and the like. Because sodium gluconate has important application and the demand of sodium gluconate in China is more and more increased along with the rapid development of the food industry and the building industry in recent years, the production process, the process research improvement and the like of the sodium gluconate are emphasized.
at present, the production method of sodium gluconate mainly comprises a homogeneous phase chemical oxidation method, an electrolytic oxidation method, a heterogeneous phase catalytic oxidation method and a biological fermentation method. Among them, heterogeneous catalytic oxidation and biological fermentation are most commonly used. The heterogeneous catalytic oxidation method is restricted by the catalytic efficiency of the catalyst, and the production cost is higher. In addition, because heavy metals have certain toxicity, sodium gluconate produced by a multi-phase catalysis method is not suitable for the field of foods, and the application range of products is limited; the fermentation method has the defects of easy bacterial contamination, difficult removal of soluble protein in the fermentation liquor, multiple operation steps and the like, and limits the improvement of the yield, the color degree and the purity of the sodium gluconate product.
Meanwhile, the energy consumption in the production process of sodium gluconate in the prior art is high, the energy utilization rate is low, and the requirements of energy conservation and environmental protection cannot be met.
disclosure of Invention
the invention aims to provide a novel process for producing sodium gluconate by an energy-saving and environment-friendly enzyme method aiming at the defects, and compared with the traditional catalysis method and fermentation method, the process has the remarkable advantages of high safety and easiness in extraction and refining of products, greatly improves the quality of sodium gluconate, and can reduce the steam consumption of the products and greatly reduce the cost of the products.
the technical scheme of the invention is as follows: an energy-saving environment-friendly process for producing sodium gluconate by an enzyme method comprises the following steps:
(1) Starch milk liquefaction and saccharification: a. liquefaction: firstly, in a plate heat exchanger I, adopting 50-60 ℃ high-temperature hot water to carry out heat exchange on raw material starch milk and heat the raw material starch milk to 40-45 ℃, then, mixing the raw material starch milk to 40-44% by mass, conveying the mixed material to a liquefaction ejector, adjusting the pH value to 4.8-5.0, sequentially adding 11-13U/g of high-temperature-resistant alpha-amylase and 0.05-0.08% by mass of anhydrous calcium chloride, liquefying the mixture at 80-95 ℃ for 15-24 minutes, and simultaneously carrying out ultrasonic treatment for 6-10 minutes under the condition of 240W of power; finally, regulating the temperature to be below 100 ℃ and 110 ℃, adding 12-15U/g of high-temperature resistant alpha-amylase to carry out liquefaction for 12-16 minutes to obtain a liquefied solution;
b. Flash evaporation and cooling: the obtained 100-plus-110 ℃ liquefied liquid enters a flash evaporation tank to be subjected to flash evaporation to respectively obtain secondary flash evaporation steam and flash evaporation liquefied liquid at the temperature of 95-99 ℃; the flash evaporation liquefied liquid at the temperature of 95-99 ℃ is firstly cooled to 80-85 ℃ through heat exchange of a plate heat exchanger II, and then is cooled to 58-62 ℃ through heat exchange of a plate heat exchanger III;
c. saccharification: conveying the obtained flash evaporation liquefied liquid at the temperature of 58-62 ℃ into a saccharification tank, regulating the pH value to be 4.0-4.2 at the constant temperature of 60 ℃, sequentially adding 0.331AUSP pullulanase, 218.1U/g beta-amylase and 51.32U/g amyloglucosidase, and carrying out enzymolysis and saccharification for 3.5-5.5 hours to obtain saccharified liquid at the temperature of 58-62 ℃, wherein the saccharified liquid is heated to 75-80 ℃ through heat exchange of a plate heat exchanger II, and the mass fraction of glucose contained in the saccharified liquid is 35-37%;
(2) and (3) continuous elimination: conveying the obtained saccharified liquid at the temperature of 75-80 ℃ to a fermentation continuous-digestion ejector for continuous digestion, and performing heat exchange and cooling on the saccharified liquid subjected to continuous digestion to 37-39 ℃ through a plate heat exchanger IV;
(3) fermentation: a. enzyme preparation: placing the penicillium notatum and the aspergillus niger in a container according to the weight ratio of 1.5:1, adding a phosphate buffer solution with the pH value of 5.1 according to the proportion of 3.0mL of hypha per gram, freezing for 15 minutes at the temperature of minus 25 ℃, melting at room temperature, and repeating twice; performing ultrasonic wall breaking for 5-8 minutes under the ultrasonic power of 400W, performing primary purification by using ethanol with the volume fraction of 70%, and performing secondary purification by using polyethylene glycol with the mass fraction of 14% to obtain purified glucose oxidase liquid; adding catalase into the purified glucose oxidase liquid to obtain a double-enzyme liquid, wherein the enzyme feeding amount of the catalase is 0.05 g/mL; sterilizing hydroxyapatite, and adding into a double-enzyme solution, wherein the solid-to-liquid ratio is 1: 10; standing at 3 deg.C for 2-3.5 hr, naturally settling, and centrifuging at 3500r for 10 min to separate the impregnated carrier from the clear solution to obtain impregnated carrier;
b. Fermentation of saccharified liquid: adding the saccharified liquid into a fermentation tank, keeping the temperature at 38-39 ℃, introducing oxygen at 0.012m3/min and rotating at 100r/min, and correcting the dissolved oxygen by 100% after the dissolved oxygen is stable; stopping ventilation, relieving pressure, and adding an impregnated carrier, wherein the solid-to-liquid ratio is 1: 20; restoring ventilation, keeping the tank pressure at 0.15MPa, adding 0.3mL of defoaming agent, keeping the pH value at 4.5-5.0, and fermenting at 38-39 ℃ to obtain fermentation liquor; heating the fermentation liquor at 38-39 ℃ to 45-50 ℃ through heat exchange of a plate heat exchanger V;
(4) And (3) decoloring: decoloring the fermentation liquor after heat exchange for 20-35 minutes by using powdered activated carbon AK-220 under the conditions that the temperature is 45-50 ℃ and the pH value is 4.5-5.2;
(5) Concentration: the decolorized fermentation liquor enters an evaporator for evaporation concentration, wherein the fermentation liquor is preheated to 60-75 ℃ by an evaporation preheater, and the evaporation preheater adopts secondary flash steam waste heat;
(6) filtering, washing, drying and obtaining the finished product.
and (2) the high-temperature hot water of the plate heat exchanger I in the step (1) is composed of liquefied liquid heat exchange temperature-rising medium water of a plate heat exchanger III and saccharified liquid heat exchange temperature-rising medium water of a plate heat exchanger IV.
And (2) the heat exchange low-temperature effluent of the plate heat exchanger I in the step (1) enters a plate heat exchanger V to exchange heat with the fermentation liquor.
And (3) the solid-to-liquid ratio of the powdered activated carbon AK-220 in the decolorization in the step (4) to the fermentation liquor after heat exchange is 1: 15.
The temperature of the secondary flash steam in the step (1) is more than 100 ℃.
The ultrasonic treatment in the step (1) is specifically to insert an ultrasonic amplitude transformer 2.5-3cm below the liquid level of the starch milk, and the rotating speed of magnetic stirring is 50%.
the invention has the beneficial effects that: the process for producing sodium gluconate by using the energy-saving environment-friendly enzyme method takes the starch milk as a raw material to produce the sodium gluconate by using the enzyme method, and the novel process carries out scientific and reasonable matching design on the matching among the steps and the matching of process reagents, parameters and conditions in the steps, so that the yield of the sodium gluconate is improved by 37.3-43.8%. The following is specifically described:
(1) the starch milk is liquefied to be mixed to 40-44% in mass fraction, the starch milk concentration is improved, the energy consumption and the water consumption in the production process are reduced, and through production practices, the starch milk with the concentration enables the energy consumption to be reduced by 23.7-26.1% and the water consumption to be reduced by 34.8-41.6% in the production process of sodium gluconate.
(2) The high-temperature resistant alpha-amylase and the anhydrous calcium chloride are compounded for use, the dosage, the adding sequence and the adding temperature of the high-temperature resistant alpha-amylase and the anhydrous calcium chloride are cooperatively designed, especially the high-temperature resistant alpha-amylase adopts the adding mode of different dosages under two conditions, and ultrasonic treatment is cooperatively matched, so that the liquefaction of the adopted high-concentration starch milk is facilitated, the viscosity in the liquefaction process is reduced, and the DE value in the liquefaction process is improved; the liquefaction value is increased by 12.3-14.8%, the peak viscosity is reduced by 38.1-40.1%, and the DE value is increased by 63.1-67.4%.
(3) The yield of the starch sugar obtained by saccharification is 109.3-112.5%, wherein the yield of the glucose reaches 96.81-97.69%.
(4) the light transmittance reaches 95.8 to 97.1 percent after the powdered activated carbon AK-220 is adopted for decolorization.
(5) the whole process utilizes heat energy to the maximum extent: feeding and preheating the evaporator by using the waste heat of the secondary steam after flash evaporation in the starch sugar preparation stage; heating the saccharified discharged material by partially utilizing the heat energy of the high-temperature liquefied liquid material; sequentially heating the starch milk and the fermentation liquor by using liquefied cooling hot water; the starch milk and the fermentation liquor are sequentially heated by continuous-digestion cooling hot water. At first, in the starch sugar-making stage of sodium gluconate production, the waste heat of flash-evaporated secondary steam is used for preheating the feeding material of a fermentation liquor evaporator, the vacuum of the evaporator is used for absorbing the liquefied secondary steam to an evaporation preheater, and the parameters are set as follows: the secondary steam is more than or equal to 100 ℃, the feeding temperature of the evaporator is 60-75 ℃, and the feeding concentration is 30-35%. According to the heat balance of the materials, the feeding temperature of the evaporator is raised by 8-15 ℃, which is equivalent to reducing the use amount of steam for raising the temperature of the materials by 8-15 ℃; in the starch sugar preparation stage in sodium gluconate production, a liquefied liquid material at 95-99 ℃ and a saccharified liquid material at 60 +/-3 ℃ are subjected to plate heat exchange, the material flow rate is equal to heat exchange, the area of the heat exchanger is mixed with 2.5 square meters of a plate heat exchanger according to the sugar liquid flow rate of 1m3/h, the temperature of the liquefied liquid material after heat exchange is reduced to 80-85 ℃ from 95-99 ℃, the temperature of the sugar liquid is increased to 75-80 ℃ from 60 +/-2 ℃, the saccharified liquid material is finally increased by 15-20 ℃, and the steam quantity for fermentation and continuous elimination is saved; in the starch sugar preparation stage of sodium gluconate production again, the liquefied starch milk is subjected to plate heat exchange and heating by using liquefied liquid cooling hot water at 50-60 ℃, then the liquefied cooling hot water is subjected to plate heat exchange with fermentation liquor at 37-39 ℃ in series, two heat exchange steps are integrated, and the final accumulated temperature rise of the starch milk and the fermentation liquor is more than or equal to 12 ℃; and finally, in the production of sodium gluconate, the starch milk before liquefaction is subjected to plate heat exchange and heating by continuously eliminating and cooling hot water at 50-60 ℃ in a fermentation stage, then the continuously eliminating and cooling hot water is subjected to plate heat exchange with the fermentation liquor at 37-39 ℃ in series, two plate heat exchange are integrated, and the final accumulated temperature rise of the starch milk and the fermentation liquor is more than or equal to 10 ℃.
in conclusion, compared with the traditional catalytic method and fermentation method, the novel process for producing sodium gluconate by using the energy-saving and environment-friendly enzyme method has the obvious advantages of high safety and easiness in extraction and refining of products, greatly improves the quality of sodium gluconate, comprehensively utilizes liquefied flash-evaporation secondary steam, high-temperature liquefied liquid, liquefied cooling hot water and heat generated by continuous fermentation in the production of sodium gluconate, can reduce the steam consumption of the products, and greatly reduces the cost of the products. By adopting the new process to produce the sodium gluconate, the steam consumption of finished products per ton is reduced by 0.28 ton, 28000 tons of steam are saved per year according to the annual capacity of 10 ten thousand tons, the enterprise cost is reduced, and the carbon emission is reduced, so that the environment is protected, and the effect is obvious.
Drawings
FIG. 1 is a process route diagram for heat energy utilization in a new process for producing sodium gluconate by an energy-saving and environment-friendly enzymatic method according to a specific embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to embodiments.
The process for producing the sodium gluconate by the energy-saving environment-friendly enzyme method comprises the following steps:
(1) starch milk liquefaction and saccharification: a. liquefaction: firstly, in a plate heat exchanger I, adopting 50-60 ℃ high-temperature hot water to carry out heat exchange on raw material starch milk and heat the raw material starch milk to 40-45 ℃, then, mixing the raw material starch milk to 40-44% by mass, conveying the mixed material to a liquefaction ejector, adjusting the pH value to 4.8-5.0, sequentially adding 11-13U/g of high-temperature-resistant alpha-amylase and 0.05-0.08% by mass of anhydrous calcium chloride, liquefying the mixture at 80-95 ℃ for 15-24 minutes, and simultaneously carrying out ultrasonic treatment for 6-10 minutes under the condition of 240W of power; finally, regulating the temperature to be below 100 ℃ and 110 ℃, adding 12-15U/g of high-temperature resistant alpha-amylase to carry out liquefaction for 12-16 minutes to obtain a liquefied solution;
b. Flash evaporation and cooling: the obtained 100-plus-110 ℃ liquefied liquid enters a flash evaporation tank to be subjected to flash evaporation to respectively obtain secondary flash evaporation steam and flash evaporation liquefied liquid at the temperature of 95-99 ℃; the flash evaporation liquefied liquid at the temperature of 95-99 ℃ is firstly cooled to 80-85 ℃ through heat exchange of a plate heat exchanger II, and then is cooled to 58-62 ℃ through heat exchange of a plate heat exchanger III;
c. Saccharification: conveying the obtained flash evaporation liquefied liquid at the temperature of 58-62 ℃ into a saccharification tank, regulating the pH value to be 4.0-4.2 at the constant temperature of 60 ℃, sequentially adding 0.331AUSP pullulanase, 218.1U/g beta-amylase and 51.32U/g amyloglucosidase, and carrying out enzymolysis and saccharification for 3.5-5.5 hours to obtain saccharified liquid at the temperature of 58-62 ℃, wherein the saccharified liquid is heated to 75-80 ℃ through heat exchange of a plate heat exchanger II, and the mass fraction of glucose contained in the saccharified liquid is 35-37%;
(2) And (3) continuous elimination: conveying the obtained saccharified liquid at the temperature of 75-80 ℃ to a fermentation continuous-digestion ejector for continuous digestion, and performing heat exchange and cooling on the saccharified liquid subjected to continuous digestion to 37-39 ℃ through a plate heat exchanger IV;
(3) Fermentation: a. enzyme preparation: placing the penicillium notatum and the aspergillus niger in a container according to the weight ratio of 1.5:1, adding a phosphate buffer solution with the pH value of 5.1 according to the proportion of 3.0mL of hypha per gram, freezing for 15 minutes at the temperature of minus 25 ℃, melting at room temperature, and repeating twice; performing ultrasonic wall breaking for 5-8 minutes under the ultrasonic power of 400W, performing primary purification by using ethanol with the volume fraction of 70%, and performing secondary purification by using polyethylene glycol with the mass fraction of 14% to obtain purified glucose oxidase liquid; adding catalase into the purified glucose oxidase liquid to obtain a double-enzyme liquid, wherein the enzyme feeding amount of the catalase is 0.05 g/mL; sterilizing hydroxyapatite, and adding into a double-enzyme solution, wherein the solid-to-liquid ratio is 1: 10; standing at 3 deg.C for 2-3.5 hr, naturally settling, and centrifuging at 3500r for 10 min to separate the impregnated carrier from the clear solution to obtain impregnated carrier;
b. Fermentation of saccharified liquid: adding the saccharified liquid into a fermentation tank, keeping the temperature at 38-39 ℃, introducing oxygen at 0.012m3/min and rotating at 100r/min, and correcting the dissolved oxygen by 100% after the dissolved oxygen is stable; stopping ventilation, relieving pressure, and adding an impregnated carrier, wherein the solid-to-liquid ratio is 1: 20; restoring ventilation, keeping the tank pressure at 0.15MPa, adding 0.3mL of defoaming agent, keeping the pH value at 4.5-5.0, and fermenting at 38-39 ℃ to obtain fermentation liquor; heating the fermentation liquor at 38-39 ℃ to 45-50 ℃ through heat exchange of a plate heat exchanger V;
(4) and (3) decoloring: decoloring the fermentation liquor after heat exchange for 20-35 minutes by using powdered activated carbon AK-220 under the conditions that the temperature is 45-50 ℃ and the pH value is 4.5-5.2;
(5) Concentration: the decolorized fermentation liquor enters an evaporator for evaporation concentration, wherein the fermentation liquor is preheated to 60-75 ℃ by an evaporation preheater, and the evaporation preheater adopts secondary flash steam waste heat;
(6) Filtering, washing, drying and obtaining the finished product.
and (2) the high-temperature hot water of the plate heat exchanger I in the step (1) is composed of liquefied liquid heat exchange temperature-rising medium water of a plate heat exchanger III and saccharified liquid heat exchange temperature-rising medium water of a plate heat exchanger IV.
And (2) the heat exchange low-temperature effluent of the plate heat exchanger I in the step (1) enters a plate heat exchanger V to exchange heat with the fermentation liquor.
And (3) the solid-to-liquid ratio of the powdered activated carbon AK-220 in the decolorization in the step (4) to the fermentation liquor after heat exchange is 1: 15.
The temperature of the secondary flash steam in the step (1) is more than 100 ℃.
The ultrasonic treatment in the step (1) is specifically to insert an ultrasonic amplitude transformer 2.5-3cm below the liquid level of the starch milk, and the rotating speed of magnetic stirring is 50%.
the detailed heat energy utilization condition is as follows:
(1) the prepared starch milk is preheated by a plate heat exchanger I, the temperature rises to 12-18 ℃, the starch milk is heated to 125 ℃ by a liquefaction ejector, then the starch milk enters a flash tank to be liquefied and instantly cooled to 95-99 ℃, flashed secondary steam is sent to an evaporator to preheat the sodium gluconate solution, and the sodium gluconate solution is heated to 15 ℃.
(2) After passing through a flash tank, the liquefied liquid at the temperature of 95-99 ℃ enters a plate heat exchanger II to exchange heat with the saccharified liquid at the temperature of 60 +/-2 ℃, the material flow rate is equal to the heat exchange, the temperature of the liquefied liquid is reduced from 95-99 ℃ to 80-85 ℃ after the heat exchange, the temperature of the sugar liquid is increased from 60 +/-3 ℃ to 75-80 ℃, and the saccharified liquid is finally increased by 15-20 ℃.
(3) And (3) cooling the liquefied liquid at the temperature of 80-85 ℃ to 60 +/-3 ℃ by cold water through a plate heat exchanger III, feeding the liquefied liquid into a saccharification tank, heating the cold water to 50-60 ℃ after heat exchange, concentrating hot water, feeding all the hot water into a plate heat exchanger I, discharging the hot water from the plate heat exchanger I into a plate heat exchanger V, and heating the starch milk and the fermentation liquid.
(4) And the sugar liquor is initially heated by the plate heat exchanger II, enters a fermentation continuous-elimination ejector, is continuously eliminated to 110 ℃, enters the plate heat exchanger IV to be cooled after sterilization is finished, enters a fermentation tank after being cooled, is heated to 50-60 ℃ after cold water enters the plate heat exchanger IV, and sequentially enters the plate heat exchanger I and the plate heat exchanger V. Finally, the cumulative temperature rise of the starch milk and the fermentation liquor is more than or equal to 22 ℃.
When the device and the production method are used for producing the sodium gluconate, the steam consumption of finished products per ton is reduced by 0.28 ton, and 28000 tons of steam are saved for one year according to the annual capacity of 10 ten thousand tons, so that the effect is obvious.
Claims (4)
1. an energy-saving environment-friendly process for producing sodium gluconate by an enzyme method comprises the following steps:
(1) Starch milk liquefaction and saccharification: a. liquefaction: firstly, in a plate heat exchanger I, adopting 50-60 ℃ high-temperature hot water to carry out heat exchange on raw material starch milk and heat the raw material starch milk to 40-45 ℃, then, mixing the raw material starch milk to 40-44% by mass, conveying the mixed material to a liquefaction ejector, adjusting the pH value to 4.8-5.0, sequentially adding 11-13U/g of high-temperature-resistant alpha-amylase and 0.05-0.08% by mass of anhydrous calcium chloride, liquefying the mixture at 80-95 ℃ for 15-24 minutes, and simultaneously carrying out ultrasonic treatment for 6-10 minutes under the condition of 240W of power; finally, regulating the temperature to be below 100 ℃ and 110 ℃, adding 12-15U/g of high-temperature resistant alpha-amylase to carry out liquefaction for 12-16 minutes to obtain a liquefied solution;
b. Flash evaporation and cooling: the obtained 100-plus-110 ℃ liquefied liquid enters a flash evaporation tank to be subjected to flash evaporation to respectively obtain secondary flash evaporation steam and flash evaporation liquefied liquid at the temperature of 95-99 ℃; the flash evaporation liquefied liquid at the temperature of 95-99 ℃ is firstly cooled to 80-85 ℃ through heat exchange of a plate heat exchanger II, and then is cooled to 58-62 ℃ through heat exchange of a plate heat exchanger III;
c. saccharification: conveying the obtained flash evaporation liquefied liquid at the temperature of 58-62 ℃ into a saccharification tank, regulating the pH value to be 4.0-4.2 at the constant temperature of 60 ℃, sequentially adding 0.331AUSP pullulanase, 218.1U/g beta-amylase and 51.32U/g amyloglucosidase, and carrying out enzymolysis and saccharification for 3.5-5.5 hours to obtain saccharified liquid at the temperature of 58-62 ℃, wherein the saccharified liquid is heated to 75-80 ℃ through heat exchange of a plate heat exchanger II, and the mass fraction of glucose contained in the saccharified liquid is 35-37%;
the temperature of the secondary flash steam in the step (1) is more than 100 ℃;
(2) And (3) continuous elimination: conveying the obtained saccharified liquid at the temperature of 75-80 ℃ to a fermentation continuous-digestion ejector for continuous digestion, and performing heat exchange and cooling on the saccharified liquid subjected to continuous digestion to 37-39 ℃ through a plate heat exchanger IV;
(3) Fermentation: a. enzyme preparation: placing the penicillium notatum and the aspergillus niger in a container according to the weight ratio of 1.5:1, adding a phosphate buffer solution with the pH value of 5.1 according to the proportion of 3.0mL per gram of hypha, placing the mixture at the temperature of minus 25 ℃ for freezing for 15 minutes, melting at room temperature, and repeating the steps twice; performing ultrasonic wall breaking for 5-8 minutes under the ultrasonic power of 400W, performing primary purification by using ethanol with the volume fraction of 70%, and performing secondary purification by using polyethylene glycol with the mass fraction of 14% to obtain purified glucose oxidase liquid; adding catalase into the purified glucose oxidase liquid to obtain a double-enzyme liquid, wherein the enzyme feeding amount of the catalase is 0.05 g/mL; sterilizing hydroxyapatite, and adding into a double-enzyme solution, wherein the solid-to-liquid ratio is 1: 10; standing for 2-3.5 hours at 3 ℃, naturally settling, and centrifuging for 10 minutes at 3500r/min to separate the impregnated carrier from the clear liquid to obtain the impregnated carrier;
b. Fermentation of saccharified liquid: adding the saccharified liquid into a fermentation tank, keeping the temperature at 38-39 ℃, introducing oxygen at 0.012m3/min and rotating at 100r/min, and correcting the dissolved oxygen by 100% after the dissolved oxygen is stable; stopping ventilation, relieving pressure, and adding an impregnated carrier, wherein the solid-to-liquid ratio is 1: 20; restoring ventilation, keeping the tank pressure at 0.15MPa, adding 0.3mL of defoaming agent, keeping the pH value at 4.5-5.0, and fermenting at 38-39 ℃ to obtain fermentation liquor; heating the fermentation liquor at 38-39 ℃ to 45-50 ℃ through heat exchange of a plate heat exchanger V;
(4) and (3) decoloring: decoloring the fermentation liquor after heat exchange for 20-35 minutes by using powdered activated carbon AK-220 under the conditions that the temperature is 45-50 ℃ and the pH value is 4.5-5.2; the solid-liquid ratio of the powdered activated carbon AK-220 in the decolorization in the step (4) to the fermentation liquor after heat exchange is 1: 15;
(5) Concentration: the decolorized fermentation liquor enters an evaporator for evaporation concentration, wherein the fermentation liquor is preheated to 60-75 ℃ by an evaporation preheater, and the evaporation preheater adopts secondary flash steam waste heat;
(6) Filtering, washing, drying and obtaining the finished product.
2. the process for producing sodium gluconate according to claim 1, wherein the high-temperature hot water in plate heat exchanger I in step (1) is composed of liquefied fluid heat exchange temperature-raising medium water in plate heat exchanger III and saccharified fluid heat exchange temperature-raising medium water in plate heat exchanger IV.
3. the process for producing sodium gluconate according to claim 2, wherein the heat-exchanged low-temperature effluent of the plate heat exchanger I in step (1) enters a plate heat exchanger V to exchange heat with the fermentation broth.
4. the process for producing sodium gluconate by using the energy-saving and environment-friendly enzyme method according to claim 1, wherein the ultrasonic treatment in the step (1) is specifically to insert an ultrasonic horn 2.5-3cm below the liquid level of the starch milk and stir the starch milk by magnetic force at a rotation speed of 50%.
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