CN109852735B - Refining process method of high fructose corn syrup - Google Patents
Refining process method of high fructose corn syrup Download PDFInfo
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- CN109852735B CN109852735B CN201910197773.6A CN201910197773A CN109852735B CN 109852735 B CN109852735 B CN 109852735B CN 201910197773 A CN201910197773 A CN 201910197773A CN 109852735 B CN109852735 B CN 109852735B
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Abstract
The invention provides a refining process method of high fructose corn syrup, which comprises the following steps: performing membrane clarification treatment on the high fructose corn syrup stock solution to obtain a clarified solution; sequentially carrying out two-stage decoloring treatment on the obtained clarified liquid by adopting a decoloring membrane and a decoloring agent to obtain a decolored liquid; and sequentially carrying out electrodialysis desalination and ion exchange desalination on the obtained decolorized solution to obtain a refined fructose-glucose syrup solution. The process method combines membrane treatment and decolorant treatment to realize the decoloration of the high fructose corn syrup stock solution, combines electrodialysis and ion exchange to realize the desalination of the high fructose corn syrup stock solution, ensures that the color value of the refined high fructose corn syrup is lower than 10IU and the conductivity is lower than 20 mu S/cm, and reaches the quality standard for food; meanwhile, the consumption of the decoloring agent and the ion exchange resin when used independently is greatly reduced, the production cost is reduced, and the discharge of eluent and solid waste is reduced.
Description
Technical Field
The invention belongs to the technical field of sugar refining, and relates to a refining process method of high fructose corn syrup.
Background
The high fructose corn syrup is syrup consisting of fructose and glucose, is popular with consumers due to the advantages of unique flavor, high solubility, easy absorption and utilization and the like, and is widely applied to the industries of food, beverage, medical care and the like. At present, the way of industrially producing the high fructose corn syrup mainly takes starch as a raw material, converts the starch into glucose through liquefaction and saccharification, and isomerizes the glucose into fructose through glucose isomerase. In the process of forming the high fructose corn syrup, pigments and inorganic salts are often generated, and in order to ensure the quality of the high fructose corn syrup, decolorization and desalination are indispensable refining procedures for producing the high fructose corn syrup.
The traditional high fructose corn syrup production process specifically comprises the following steps: starch-size mixing-saccharification-neutralization-active carbon decoloration-ion exchange desalination-evaporation-isomerization-active carbon decoloration-ion exchange desalination-evaporation-finished product. The principle of activated carbon decolorization is to utilize physical adsorption between activated carbon and pigment, the principle of ion exchange desalination is to utilize physical adsorption between anion and cation exchange resin and anion and cation, and because the color value and the salt content of the initial high fructose corn syrup are high, the processing load of the activated carbon decolorization and ion exchange desalination processes is large, the energy consumption required by regeneration of the activated carbon and the ion exchange resin is high, the use amount of acid-base eluent is large, and a large amount of high-salinity wastewater and solid waste are generated. Therefore, the production cost of the two steps accounts for a large proportion of the total production cost of the high fructose corn syrup.
In order to solve the above problems, the refining of high fructose corn syrup needs to be continuously improved. CN 107455732A discloses a method for reducing the consumption of activated carbon in the production process of high fructose corn syrup, in the method, isomerized high fructose corn syrup does not directly enter a decoloring tank, but enters a cationic resin adjusting column, the high fructose corn syrup coming out of the cationic resin adjusting column is mixed with the original isomerized high fructose corn syrup, and then is decolored in the decoloring tank, thereby reducing the consumption of the activated carbon. CN 108251470A discloses a preparation method of high fructose corn syrup, which comprises the steps of starch milk liquefaction, saccharification, ceramic membrane impurity removal, clarification, decolorization, nanofiltration membrane decolorization and desalination, isomerization by isomerization enzyme, adsorbent purification, ceramic membrane impurity removal, decolorization, clarification, nanofiltration membrane desalination, triple-effect evaporation and concentration and refining into syrup.
In summary, the refining process of high fructose corn syrup needs to seek suitable treatment operations and combination thereof, so as to achieve that the refined high fructose corn syrup meets the product standard and can reduce the cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high fructose corn syrup refining process method, which combines membrane treatment and decolorant treatment to realize the decolorization of high fructose corn syrup stock solution, combines electrodialysis and ion exchange to realize the desalination of the high fructose corn syrup stock solution, enables the refined high fructose corn syrup to reach the food grade quality standard, reduces the use amount of decolorant and ion exchange resin, and reduces the cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a refining process method of high fructose corn syrup, which comprises the following steps:
(1) performing membrane clarification treatment on the high fructose corn syrup stock solution to obtain a clarified solution;
(2) sequentially carrying out two-stage decoloring treatment on the clarified liquid obtained in the step (1) by adopting a decoloring membrane and a decoloring agent to obtain a decolored liquid;
(3) and (3) sequentially carrying out electrodialysis desalination and ion exchange desalination on the destaining solution obtained in the step (2) to obtain a refined fructose-glucose syrup solution.
In the invention, the high fructose corn syrup stock solution is clarified by a membrane to remove insoluble impurities such as suspended matters, thalli and the like in the stock solution, so that the subsequent decolorization and desalination processes are facilitated; because the color value and the salt content of the high fructose corn syrup stock solution are higher, the high-quality high fructose corn syrup is obtained by fully intercepting and adsorbing pigments in the solution through two-stage decoloring treatment of a decoloring membrane and a decoloring agent and fully removing inorganic salts through two-stage treatment of electrodialysis and ion exchange, so that the consumption of the decoloring agent and the ion exchange resin when being used independently is greatly reduced, the production cost is reduced, and the discharge of eluent and solid wastes is reduced.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferable technical scheme of the invention, the high fructose corn syrup stock solution in the step (1) is pretreated before membrane clarification treatment.
Preferably, the pretreatment comprises any one of centrifugation, shaking, suspension separation, vacuum drum filtration or plate and frame filtration or a combination of at least two of these, typical but non-limiting examples being: a combination of centrifugal separation and vibratory separation, a combination of suspension separation and plate-and-frame filtration, a combination of centrifugal separation, suspension separation and vacuum drum filtration, and the like.
In the invention, the high fructose corn syrup stock solution is mainly prepared by saccharification of starch or cellulose substances or by isomerization of glucose, and is often accompanied with generation of pigments and inorganic salts in the production process, and the color value of the high fructose corn syrup stock solution used in the invention is 1800-2500 IU, and the conductivity is 5.5-8.0 mS/cm.
Meanwhile, as the high fructose corn syrup stock solution usually has larger solid particles or impurities, the life of the high fructose corn syrup stock solution is shortened and the cost is increased for avoiding the damage of the membrane caused by the larger solid particles or impurities in the stock solution, and the high fructose corn syrup stock solution is pretreated before the membrane clarification treatment to remove the larger solid particles or impurities in the stock solution.
As a preferable technical scheme of the invention, the membrane clarification treatment in the step (1) is carried out by adopting a micro-filtration membrane and/or an ultrafiltration membrane.
Preferably, the membrane has a pore size of 0.005 to 0.45. mu.m, such as 0.005. mu.m, 0.01. mu.m, 0.05. mu.m, 0.10. mu.m, 0.15. mu.m, 0.20. mu.m, 0.25. mu.m, 0.30. mu.m, 0.35. mu.m, 0.40. mu.m, or 0.45. mu.m, but not limited to the values listed, and other values not listed within this range of values are equally applicable, preferably 0.01 to 0.22. mu.m; wherein the aperture range of the micro-filtration membrane is 0.10-0.45 μm, and the aperture range of the ultra-filtration membrane is 0.005-0.10 μm.
Preferably, the module type of the membrane comprises any one of a roll, tube, flat sheet or hollow fiber type or a combination of at least two of the following typical but non-limiting examples: the membrane module comprises a combination of a spiral-wound membrane module and a tubular membrane module, a combination of a tubular membrane module and a hollow fiber membrane module, a combination of a spiral-wound membrane module, a flat-plate membrane module and a hollow fiber membrane module and the like.
Preferably, the material of the membrane comprises synthetic organic matter and/or inorganic oxide.
Preferably, the synthetic organic substance comprises any one of polyamide, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyvinylidene fluoride, polyacrylonitrile or polyarylethersulfone ketone or a combination of at least two of these, typical but non-limiting examples being: combinations of polyamide and polysulfone, combinations of polysulfone and polyethersulfone, combinations of polyethersulfone and polyvinylidene fluoride, combinations of polyamide and polyacrylonitrile, combinations of polysulfone, polyethersulfone and sulfonated polyethersulfone, combinations of polyamide, polyethersulfone and polyarylethersulfone ketone, and the like.
Preferably, the inorganic oxide comprises any one of, or a combination of at least two of, alumina, zirconia, titania or silica, typical but non-limiting examples of which are: combinations of aluminum oxide and zirconium dioxide, combinations of zirconium dioxide and titanium dioxide, combinations of aluminum oxide, titanium dioxide, and silicon dioxide, and the like.
In a preferred embodiment of the present invention, the temperature of the membrane clarification treatment in step (1) is 25 to 85 ℃, for example, 25 ℃, 35 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃ or 85 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 55 to 70 ℃.
Preferably, the pressure of the membrane clarification treatment in step (1) is 0.1 to 0.5MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5MPa, but not limited to the recited values, and other values within the range are also applicable, preferably 0.2 to 0.4 MPa.
In a preferred embodiment of the present invention, the molecular weight cut-off of the decolorizing membrane of step (2) is 150 to 5000Da, for example, 150Da, 300Da, 500Da, 1000Da, 1500Da, 2000Da, 3000Da, 4000Da, 5000Da, etc., but the molecular weight cut-off is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable, preferably 300 to 2000 Da.
In the invention, the principle of membrane decolorization mainly depends on electrostatic interaction and/or size screening, namely, the decolorization membrane can physically intercept pigments with the same charges as the decolorization membrane and pigments with the size larger than the pore diameter of the membrane, fructose and glucose can completely permeate the membrane, so that the removal of the pigments in the fructose-glucose syrup is realized, and the removal rate of the pigments after the decolorization membrane treatment can reach more than 80%.
Preferably, the component type of the decolorizing membrane of step (2) includes any one of roll type, tube type, flat plate type or hollow fiber type or a combination of at least two of them, and the combination is exemplified by typical but non-limiting examples: the membrane module comprises a combination of a spiral-wound membrane module and a tubular membrane module, a combination of a tubular membrane module and a hollow fiber membrane module, a combination of a spiral-wound membrane module, a flat-plate membrane module and a hollow fiber membrane module and the like.
Preferably, the material of the decolorizing membrane in step (2) comprises any one or a combination of at least two of polypiperazine, polyamide, polysulfone, polyethersulfone or sulfonated polyethersulfone, and typical but non-limiting examples of the combination are as follows: combinations of polypiperazine and polysulfone, polysulfones and polyethersulfones, polyamides and sulfonated polyethersulfones, polysulfones, polyethersulfones and sulfonated polyethersulfones, polypiperazines, polyamides and polyethersulfones, and the like.
Preferably, the temperature for the decoloring treatment with the decoloring membrane in the step (2) is 25 to 85 ℃, for example, 25 ℃, 35 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃ or 85 ℃, but not limited to the enumerated values, and other values not enumerated within the range of the enumerated values are also applicable, preferably 55 to 70 ℃.
Preferably, the pressure for decoloring in the step (2) with the decoloring membrane is 0.1 to 4.0MPa, such as 0.1MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, or 4.0MPa, but is not limited to the above-mentioned values, and other values within the above-mentioned range are also applicable, and preferably 0.5 to 2.0 MPa.
As a preferred technical scheme of the invention, the decolorizing agent in the step (2) comprises activated carbon.
Preferably, the activated carbon comprises powdered carbon and/or granular carbon.
Preferably, the temperature for decoloring with the decoloring agent in the step (2) is 50 to 90 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the enumerated values, and other values not enumerated within the range of the enumerated values are also applicable, preferably 60 to 80 ℃.
In the invention, after the decoloration treatment of the decolorizing membrane, in order to further remove the residual pigment, the activated carbon is used as a decolorizing agent, so that the color value reaches the food grade standard, and compared with the decoloration by completely using the activated carbon, the consumption of the activated carbon is reduced by more than 80 percent.
In a preferred embodiment of the present invention, the electrodialysis in step (3) is performed using an electrodialysis apparatus.
Preferably, the current density of the electrodialysis treatment in the step (3) is 5-30 mA/cm2E.g. 5mA/cm2、10mA/cm2、15mA/cm2、20mA/cm2、25mA/cm2Or 30mA/cm2And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
In the invention, the current density during the electrodialysis treatment is an important factor influencing the treatment effect, and if the current density is too high, the energy consumption is increased, and the treatment cost is higher; if the current density is too small, the processing efficiency is lowered.
Preferably, in the electrodialysis treatment in step (3), the linear velocity of the liquid flow is 1-6 cm/s, such as 1cm/s, 2cm/s, 3cm/s, 4cm/s, 5cm/s or 6cm/s, but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the cathode membranes of the electrodialysis unit comprise any one of, or a combination of at least two of, polyethylene cathode membranes, polysulfone-type cathode membranes, or polyfluoroethylene-polyamine-type cathode membranes, typical but non-limiting examples of which are: a combination of a polyethylene cathode film and a polysulfone-type cathode film, a combination of a polysulfone-type cathode film and a polyvinyl fluoride-polyamine-type cathode film, a combination of a polyethylene cathode film, a polysulfone-type cathode film and a polyvinyl fluoride-polyamine-type cathode film, and the like.
Preferably, the positive membrane of the electrodialysis device comprises any one of or a combination of at least two of polyethylene positive membrane, polyphenylene ether positive membrane, polyvinylidene fluoride positive membrane, polymethacrylic acid positive membrane or polychlorotrifluoroethylene positive membrane, typical but non-limiting examples of which are: a combination of a polyethylene positive film and a polyphenylene ether positive film, a combination of a polyphenylene ether positive film and a polyvinylidene fluoride positive film, a combination of a polyphenylene ether positive film and a polymethacrylic acid positive film, a combination of a polyphenylene ether positive film, a polyvinylidene fluoride positive film and a polychlorotrifluoroethylene positive film, and the like.
In the invention, during electrodialysis treatment, ions move and migrate under the action of an electric field, the desalination process is accurately regulated and controlled, the content of inorganic salt in the fructose-glucose syrup is reduced by more than 90 percent through the selective permeation and interception functions of the membrane, the electrodialysis membrane does not need to be regenerated, the discharge of waste water can be reduced, and the energy consumption and the production cost are reduced.
As a preferred technical scheme of the invention, the ion exchange desalination of the step (3) is carried out by adopting an ion exchange resin bed.
Preferably, the ion exchange resin bed is packed with a mixture of cation exchange resin and anion exchange resin.
Preferably, the cation exchange resin comprises a sulfonic acid group-containing cation exchange resin.
Preferably, the anion exchange resin comprises a resin containing-N+(CH3)3Radical anion exchange resins.
In the present invention, after the electrodialysis desalination, the ion exchange resin is used for further desalination, and the usage amount of the ion exchange resin is reduced by 90% or more compared with the case of using the ion exchange resin completely for desalination.
As a preferred embodiment of the present invention, the color value of the refined fructose-glucose syrup solution in step (3) is less than 10IU, such as 10IU, 8IU, 6IU, 4IU, 2IU, etc., but not limited to the values listed, other values not listed in the range of the values are also applicable, and the conductivity is less than 20. mu.S/cm, such as 20. mu.S/cm, 18. mu.S/cm, 15. mu.S/cm, 12. mu.S/cm, 10. mu.S/cm or 8. mu.S/cm, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) pretreating a high fructose corn syrup stock solution, and then performing membrane clarification treatment by adopting a microfiltration membrane and/or an ultrafiltration membrane, wherein the pore diameter of the membrane is 0.005-0.45 mu m, the membrane clarification treatment temperature is 25-85 ℃, and the treatment pressure is 0.1-0.5 MPa, so as to obtain a clarified solution;
(2) sequentially carrying out two-stage decoloring treatment on the clarified liquid obtained in the step (1) by adopting a decoloring membrane and activated carbon, wherein the molecular weight cut-off of the decoloring membrane is 150-5000 Da, the temperature for decoloring treatment by adopting the decoloring membrane is 25-85 ℃, the treatment pressure is 0.1-4.0 MPa, and the temperature for decoloring treatment by adopting the activated carbon is 50-90 ℃ to obtain a decoloring liquid;
(3) sequentially carrying out electrodialysis desalination and ion exchange desalination on the destaining solution obtained in the step (2), wherein the current density of the electrodialysis treatment is 5-30 mA/cm2And (3) carrying out ion exchange desalting in an ion exchange resin bed filled with cation exchange resin and anion exchange resin in a mixed manner at a liquid flow linear velocity of 1-6 cm/s to obtain the refined high fructose corn syrup solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts membrane decolorization firstly, so that the decolorization rate of the fructose-glucose syrup reaches over 80 percent based on the physical interception effect of a decolorizing membrane on pigments, and then decolorizer is used for decolorization, so that the use amount of the decolorizer is greatly reduced, the cost is reduced, and finally the color value of the fructose-glucose syrup is lower than 10 IU;
(2) the method firstly carries out electrodialysis desalination, and leads the desalination rate of the high fructose corn syrup to reach more than 90 percent based on the selective permeation and interception effects of an electrodialysis membrane, thereby greatly reducing the dosage of subsequent ion exchange resin and finally leading the conductivity of the high fructose corn syrup to be lower than 20 mu S/cm;
(3) when the electrodialysis treatment is adopted, the method can realize the accurate regulation and control of the desalting process; meanwhile, the use of the electrodialysis membrane reduces the discharge of a large amount of waste liquid generated by resin regeneration.
Drawings
FIG. 1 is a schematic flow chart of a refining process of high fructose corn syrup provided in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a refining process method of high fructose corn syrup in part, which comprises the following steps:
(1) performing membrane clarification treatment on the high fructose corn syrup stock solution membrane to obtain a clarified solution;
(2) sequentially carrying out two-stage decoloring treatment on the clarified liquid obtained in the step (1) by adopting a decoloring membrane and a decoloring agent to obtain a decolored liquid;
(3) and (3) sequentially carrying out electrodialysis desalination and ion exchange desalination on the destaining solution obtained in the step (2) to obtain a refined fructose-glucose syrup solution.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a refining process method of high fructose corn syrup, the flow schematic diagram of the process method is shown in figure 1, and the refining process method comprises the following steps:
(1) centrifuging the high fructose corn syrup stock solution (color value: 2470IU, conductance: 7.78mS/cm), and clarifying with polyvinylidene fluoride tubular membrane with aperture of 0.1 μm at 55 deg.C under operation pressure of 0.3MPa to obtain clarified solution;
(2) decolorizing the clarified liquid obtained in the step (1) by adopting a decolorizing membrane, wherein the decolorizing membrane is a polyamide roll-type membrane, the molecular weight cutoff is 500Da, the operating temperature is 55 ℃, the pressure is 1.0MPa, and then decolorizing is carried out again by adopting granular activated carbon at the decolorizing temperature of 55 ℃ to obtain a decolorizing liquid;
(3) performing electrodialysis on the decolorized solution obtained in the step (2), wherein the positive membrane used in the electrodialysis is a polyphenyl ether homogeneous positive membrane, the negative membrane used in the electrodialysis is a polysulfone homogeneous negative membrane, and the current density is 10mA/cm2The liquid flow linear velocity is 2cm/s, and then the electrodialysis solution is led into the tank for separationA bed of a mixed anion exchange resin containing-N+(CH3)3The group acrylic resin and the cation exchange resin are sulfonic acid group-containing acrylic resins, and the refined fructose-glucose syrup solution is obtained.
In the embodiment, after the decolorizing membrane is decolorized in the step (2), the decolorizing rate of the high fructose corn syrup can reach 85%, the desalting rate of the solution subjected to electrodialysis in the step (3) can reach about 98%, and finally the conductivity of the refined high fructose corn syrup solution is reduced to 20 mus/cm, and the color value is 10 IU.
Example 2:
the embodiment provides a refining process method of high fructose corn syrup, which comprises the following steps:
(1) performing plate-frame filtration on a high fructose corn syrup stock solution (color value: 2200IU, electric conductivity: 7.56mS/cm), and then performing clarification treatment by adopting an alumina ceramic membrane with the aperture of 0.22 mu m at the temperature of 70 ℃, wherein the operating pressure of the ceramic membrane is 0.2MPa, so as to obtain a clarified solution;
(2) decolorizing the clarified liquid obtained in the step (1) by adopting a decolorizing membrane, wherein the decolorizing membrane is a polyether sulfone hollow fiber membrane, the molecular weight cutoff is 1000Da, the operation temperature is 60 ℃, the pressure is 0.5MPa, and then decolorizing is carried out again by adopting granular activated carbon at the decolorizing temperature of 70 ℃ to obtain a decolorized liquid;
(3) performing electrodialysis on the decolorized solution obtained in the step (2), wherein the positive membrane used by the electrodialysis is a polyvinylidene fluoride positive membrane, the negative membrane used by the electrodialysis is a polysulfone type homogeneous negative membrane, and the current density is 20mA/cm2The liquid flow line speed is 4cm/s, and then the electrodialysis solution is introduced into an ion exchange mixed resin bed, wherein the anion exchange resin is a mixed resin containing-N+(CH3)3The group acrylic resin and the cation exchange resin are sulfonic acid group-containing acrylic resins, and the refined fructose-glucose syrup solution is obtained.
In the embodiment, after the decolorizing membrane is decolorized in the step (2), the decolorizing rate of the high fructose corn syrup can reach 81%, the desalting rate of the solution subjected to electrodialysis in the step (3) can reach about 95%, and finally the conductivity of the refined high fructose corn syrup solution is reduced to 19 muS/cm, and the color value is 9.8 IU.
Example 3:
the embodiment provides a refining process method of high fructose corn syrup, which comprises the following steps:
(1) separating the high fructose corn syrup stock solution (color value: 1930IU, conductance: 6.75mS/cm) by a vibrating screen, and clarifying by adopting a polyethersulfone roll-type membrane with the pore diameter of 0.01 mu m at 40 ℃, wherein the operating pressure of the roll-type membrane is 0.4MPa to obtain a clarified solution;
(2) decolorizing the clarified liquid obtained in the step (1) by adopting a decolorizing membrane, wherein the decolorizing membrane is a polypiperazine roll-type membrane, the molecular weight cutoff is 300Da, the operation temperature is 70 ℃, the pressure is 4.0MPa, and then decolorizing is carried out again by adopting powdered activated carbon at the decolorizing temperature of 80 ℃ to obtain a decolorized liquid;
(3) performing electrodialysis on the decolorized solution obtained in the step (2), wherein the positive membrane used in the electrodialysis is a polytrifluorochloroethylene positive membrane, the negative membrane used in the electrodialysis is a polyvinyl fluoride-polyamine negative membrane, and the current density is 30mA/cm2The liquid flow line speed is 6cm/s, and then the electrodialysis solution is introduced into an ion exchange mixed resin bed, wherein the anion exchange resin is a mixed resin containing-N+(CH3)3The group acrylic resin and the cation exchange resin are sulfonic acid group-containing acrylic resins, and the refined fructose-glucose syrup solution is obtained.
In the embodiment, after the decolorizing membrane in the step (2) is decolorized, the decolorizing rate of the high fructose corn syrup can reach 90%, the desalting rate of the solution after electrodialysis in the step (3) can reach about 97%, and finally the conductivity of the refined high fructose corn syrup solution is reduced to below 18.3 muS/cm, and the color value is lower than 8.4 IU.
Example 4:
the embodiment provides a refining process method of high fructose corn syrup, which comprises the following steps:
(1) separating the high fructose syrup stock solution (color value: 1850IU, conductance: 7.08mS/cm), clarifying with polyamide hollow fiber membrane with pore diameter of 0.45 μm at 85 deg.C under operation pressure of 0.1MPa to obtain clarified solution;
(2) decolorizing the clear liquid obtained in the step (1) by adopting a decolorizing membrane, wherein the decolorizing membrane is a polysulfone and polyether sulfone plate type membrane, the molecular weight cutoff is 5000Da, the operation temperature is 85 ℃, the pressure is 0.1MPa, and then decolorizing is carried out again by adopting powdered activated carbon at the decolorizing temperature of 90 ℃ to obtain the decolorizing liquid;
(3) performing electrodialysis on the decolorized solution obtained in the step (2), wherein a positive membrane used by the electrodialysis is a polymethacrylic acid positive membrane, a negative membrane used by the electrodialysis is a polysulfone type homogeneous phase negative membrane, and the current density is 5mA/cm2The liquid flow line speed is 1cm/s, and then the electrodialysis solution is introduced into an ion exchange mixed resin bed, wherein the anion exchange resin is a mixed resin containing-N+(CH3)3The group styrene type resin and the cation exchange resin are sulfonic group-containing styrene type resins, and a purified fructose syrup solution is obtained.
In the embodiment, after the decolorizing membrane in the step (2) is decolorized, the decolorizing rate of the high fructose corn syrup can reach 80%, the desalting rate of the solution after electrodialysis in the step (3) can reach about 92%, and finally the conductivity of the refined high fructose corn syrup solution is reduced to 19.3 muS/cm, and the color value is 9.8 IU.
Example 5:
the embodiment provides a refining process method of high fructose corn syrup, which comprises the following steps:
(1) performing vacuum drum filtration on a high fructose corn syrup stock solution (color value: 2350IU, electric conductivity: 5.63mS/cm), and then performing clarification treatment by adopting a titanium dioxide and silicon dioxide ceramic membrane with the aperture of 0.3 mu m at the temperature of 25 ℃, wherein the operating pressure of the ceramic membrane is 0.5MPa, so as to obtain a clarified solution;
(2) decolorizing the clarified liquid obtained in the step (1) by adopting a decolorizing membrane, wherein the decolorizing membrane is a polyamide and polysulfone hollow fiber membrane, the molecular weight cutoff is 2000Da, the operation temperature is 25 ℃, the pressure is 2.0MPa, and then decolorizing is carried out again by adopting granular activated carbon at the decolorizing temperature of 50 ℃ to obtain a decolorized liquid;
(3) decolorizing the obtained product in the step (2)Performing electrodialysis with positive membrane of polychlorotrifluoroethylene and negative membrane of polyvinyl fluoride-polyamine type at current density of 15mA/cm2The liquid flow line speed is 5cm/s, and then the electrodialysis solution is introduced into an ion exchange mixed resin bed, wherein the anion exchange resin is a mixed resin containing-N+(CH3)3The group styrene type resin and the cation exchange resin are sulfonic group-containing styrene type resins, and a purified fructose syrup solution is obtained.
In the embodiment, after the decolorizing membrane in the step (2) is decolorized, the decolorizing rate of the high fructose corn syrup can reach 83%, the desalting rate of the solution after electrodialysis in the step (3) can reach about 94%, and finally the conductivity of the refined high fructose corn syrup solution is reduced to 16.4 muS/cm, and the color value is 7.4 IU.
Example 6:
this example provides a refining process of high fructose corn syrup, which is referred to the method in example 1, except that: the current density in the step (3) is 32mA/cm2。
In this example, the current density was large, and the power consumption required to achieve the same conductivity as in example 1 was 1.5 times that of example 1 under the same other conditions.
Example 7:
this example provides a refining process of high fructose corn syrup, which is referred to the method in example 1, except that: the current density in the step (3) is 4mA/cm2。
In this example, the current density was low, the electrodialysis process was slow, and the time required to achieve the same conductivity as in example 1 was 3 times longer than that of example 1 under the same other conditions.
Comparative example 1:
this comparative example provides a process for refining high fructose corn syrup, which is referred to in example 1, with the only difference that: in the step (2), the decoloring membrane treatment is not adopted, and only activated carbon decoloring is carried out.
In the comparative example, the high fructose corn syrup solution is decolorized only by using activated carbon, the using amount of the activated carbon is 4.5 times that of the activated carbon in example 1, the cost of raw materials is greatly increased, and the activated carbon needs to be regenerated frequently, so that the required energy consumption is high, and the using amount of eluent is large.
Comparative example 2:
this comparative example provides a process for refining high fructose corn syrup, which is referred to in example 1, with the only difference that: step (3) does not carry out electrodialysis desalination, and only adopts ion exchange desalination.
In the comparative example, the salt content of the high fructose corn syrup solution is high, the dosage of the ion exchange resin can be greatly increased by 9.1 times compared with that of example 1 only by adopting ion exchange for desalting, a large amount of acid-base eluent is required during regeneration of the used ion exchange resin, and a large amount of high-salt wastewater can be generated.
By combining the above examples and comparative examples, the process of the present invention combines membrane treatment and decolorant treatment to achieve decolorization of high fructose corn syrup stock solution, and combines electrodialysis and ion exchange to achieve desalination of high fructose corn syrup stock solution, such that the color value of refined high fructose corn syrup is lower than 10IU, the conductivity is lower than 20 muS/cm, and the refined high fructose corn syrup reaches the food quality standard; meanwhile, the consumption of the decoloring agent and the ion exchange resin when used independently is greatly reduced, the production cost is reduced, and the discharge of eluent and solid waste is reduced.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above process, i.e. it is not meant that the present invention must rely on the above process to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (34)
1. A refining process method of high fructose corn syrup is characterized by comprising the following steps:
(1) performing membrane clarification treatment on the high fructose corn syrup stock solution to obtain a clarified solution;
(2) sequentially carrying out two-stage decoloring treatment on the clarified liquid obtained in the step (1) by adopting a decoloring membrane and a decoloring agent, wherein the molecular weight cutoff of the decoloring membrane is 150-5000 Da, so as to obtain a decoloring liquid;
(3) sequentially carrying out electrodialysis desalination and ion exchange desalination on the destaining solution obtained in the step (2), wherein the current density of the electrodialysis treatment is 5-30 mA/cm2And the linear velocity of the liquid flow is 1-6 cm/s, so as to obtain the refined high fructose corn syrup solution.
2. The method according to claim 1, wherein the high fructose corn syrup stock solution of step (1) is pretreated before being subjected to membrane clarification.
3. The method of claim 2, wherein the pre-treatment comprises any one or a combination of at least two of centrifugation, shaking, suspension separation, vacuum drum filtration, or plate and frame filtration.
4. The method according to claim 1, wherein the membrane clarification treatment in step (1) is performed using a microfiltration membrane and/or an ultrafiltration membrane.
5. The method according to claim 4, wherein the membrane has a pore size of 0.005 to 0.45 μm.
6. The method according to claim 5, wherein the membrane has a pore size of 0.01 to 0.22 μm.
7. The method of claim 4, wherein the module type of the membrane comprises any one of a roll type, a tube type, a flat plate type, or a hollow fiber type, or a combination of at least two of them.
8. The method of claim 4, wherein the material of the membrane comprises synthetic organic and/or inorganic oxide.
9. The method of claim 8, wherein the synthetic organic material comprises one or a combination of at least two of polyamide, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, or polyarylethersulfone ketone.
10. The method of claim 8, wherein the inorganic oxide comprises any one of alumina, zirconia, titania, or silica, or a combination of at least two thereof.
11. The method according to claim 1, wherein the temperature of the membrane clarification treatment in the step (1) is 25-85 ℃.
12. The method according to claim 11, wherein the temperature of the membrane clarification treatment in the step (1) is 55-70 ℃.
13. The method according to claim 1, wherein the pressure of the membrane clarification treatment in the step (1) is 0.1-0.5 MPa.
14. The method according to claim 13, wherein the pressure of the membrane clarification treatment in the step (1) is 0.2-0.4 MPa.
15. The method according to claim 1, wherein the molecular weight cut-off of the decolorizing membrane of step (2) is 300-2000 Da.
16. The method according to claim 1, wherein the component type of the decolorizing membrane of step (2) comprises any one of roll type, tube type, flat plate type or hollow fiber type or a combination of at least two thereof.
17. The method according to claim 1, wherein the material of the decolorizing membrane of step (2) comprises any one or a combination of at least two of polypiperazine, polyamide, polysulfone, polyethersulfone or sulfonated polyethersulfone.
18. The method according to claim 1, wherein the temperature for decoloring in the step (2) by using the decoloring membrane is 25 to 85 ℃.
19. The method according to claim 18, wherein the temperature for decoloring in the step (2) by using the decoloring membrane is 55 to 70 ℃.
20. The method according to claim 1, wherein the pressure for decoloring with a decoloring membrane in the step (2) is 0.1 to 4.0 MPa.
21. The method as claimed in claim 20, wherein the pressure for decoloring in the step (2) with the decoloring membrane is 0.5 to 2.0 MPa.
22. The method of claim 1, wherein the decolorizing agent of step (2) comprises activated carbon.
23. The method of claim 22, wherein the activated carbon comprises powdered carbon and/or granular carbon.
24. The method as claimed in claim 1, wherein the temperature for decoloring in the step (2) by using the decoloring agent is 50-90 ℃.
25. The method as claimed in claim 24, wherein the temperature for decoloring in the step (2) by using the decoloring agent is 60-80 ℃.
26. The process of claim 1, wherein the electrodialysis of step (3) is carried out using an electrodialysis device.
27. The method according to claim 26, wherein the cathode membranes of the electrodialysis device comprise any one of polyethylene cathode membranes, polysulfone-type cathode membranes or polyfluoroethylene-polyamine-type cathode membranes or a combination of at least two thereof.
28. The method of claim 26, wherein the anode membrane of the electrodialysis device comprises any one of polyethylene anode membrane, polyphenylene oxide anode membrane, polyvinylidene fluoride anode membrane, polymethacrylic acid anode membrane or polychlorotrifluoroethylene anode membrane or a combination of at least two of them.
29. The method of claim 1, wherein the ion exchange desalination of step (3) is performed using an ion exchange resin bed.
30. The process of claim 29 wherein the ion exchange resin bed is packed with a mixture of cation exchange resin and anion exchange resin.
31. The method of claim 30, wherein the cation exchange resin comprises a sulfonic acid group-containing cation exchange resin.
32. The method of claim 30, wherein the anion exchange resin comprises a N-containing anion exchange resin+(CH3)3Radical anion exchange resins.
33. The method as claimed in claim 1, wherein the color value of the refined fructose syrup solution in the step (3) is less than 10IU, and the conductivity is less than 20 μ S/cm.
34. Method according to claim 1, characterized in that it comprises the following steps:
(1) pretreating a high fructose corn syrup stock solution, and then performing membrane clarification treatment by adopting a microfiltration membrane and/or an ultrafiltration membrane, wherein the pore diameter of the membrane is 0.005-0.45 mu m, the membrane clarification treatment temperature is 25-85 ℃, and the treatment pressure is 0.1-0.5 MPa, so as to obtain a clarified solution;
(2) sequentially carrying out two-stage decoloring treatment on the clarified liquid obtained in the step (1) by adopting a decoloring membrane and activated carbon, wherein the molecular weight cut-off of the decoloring membrane is 150-5000 Da, the temperature for decoloring treatment by adopting the decoloring membrane is 25-85 ℃, the treatment pressure is 0.1-4.0 MPa, and the temperature for decoloring treatment by adopting the activated carbon is 50-90 ℃ to obtain a decoloring liquid;
(3) sequentially carrying out electrodialysis desalination and ion exchange desalination on the destaining solution obtained in the step (2), wherein the current density of the electrodialysis treatment is 5-30 mA/cm2And (3) carrying out ion exchange desalting in an ion exchange resin bed filled with cation exchange resin and anion exchange resin in a mixed manner at a liquid flow linear velocity of 1-6 cm/s to obtain the refined high fructose corn syrup solution.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102493251A (en) * | 2011-12-01 | 2012-06-13 | 中国科学院过程工程研究所 | Papermaking red liquor sugar component using method |
| CN102492782A (en) * | 2011-12-16 | 2012-06-13 | 长春大成新资源集团有限公司 | Desalting method for syrup and production method for glucose syrup |
| CN107937628A (en) * | 2017-05-23 | 2018-04-20 | 中国科学院过程工程研究所 | The cane sugar manufacture system and its processing method that a kind of full constituent utilizes |
| CN108251470A (en) * | 2017-11-03 | 2018-07-06 | 毛强平 | A kind of preparation method of fructose syrup |
| CN108588290A (en) * | 2018-05-10 | 2018-09-28 | 中国科学院过程工程研究所 | The system and its processing method of pigment and sugar in molasses are recycled in a kind of classification |
| CN109234467A (en) * | 2018-09-30 | 2019-01-18 | 飞潮（无锡）过滤技术有限公司 | The ceramic membrane treatment process of saccharified liquid in a kind of fructose syrup production process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CU22292A1 (en) * | 1991-05-07 | 1995-01-31 | Cigb | Procedure for obtaining fructose-glucose liquors on an industrial scale from saccharose, and the installations for carrying out the process. |
| JP3380092B2 (en) * | 1995-08-14 | 2003-02-24 | オルガノ株式会社 | Method for producing sucrose-type liquid sugar |
| JP4701539B2 (en) * | 2001-05-21 | 2011-06-15 | 栗田工業株式会社 | Sugar liquid purification equipment |
-
2019
- 2019-03-15 CN CN201910197773.6A patent/CN109852735B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102493251A (en) * | 2011-12-01 | 2012-06-13 | 中国科学院过程工程研究所 | Papermaking red liquor sugar component using method |
| CN102492782A (en) * | 2011-12-16 | 2012-06-13 | 长春大成新资源集团有限公司 | Desalting method for syrup and production method for glucose syrup |
| CN107937628A (en) * | 2017-05-23 | 2018-04-20 | 中国科学院过程工程研究所 | The cane sugar manufacture system and its processing method that a kind of full constituent utilizes |
| CN108251470A (en) * | 2017-11-03 | 2018-07-06 | 毛强平 | A kind of preparation method of fructose syrup |
| CN108588290A (en) * | 2018-05-10 | 2018-09-28 | 中国科学院过程工程研究所 | The system and its processing method of pigment and sugar in molasses are recycled in a kind of classification |
| CN109234467A (en) * | 2018-09-30 | 2019-01-18 | 飞潮（无锡）过滤技术有限公司 | The ceramic membrane treatment process of saccharified liquid in a kind of fructose syrup production process |
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