CN107814849B - Method for removing sodium chloride in cassava starch polysaccharide iron compound liquid - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/716—Glucans
- A61K31/718—Starch or degraded starch, e.g. amylose, amylopectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/26—Iron; Compounds thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
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Abstract
A method for removing sodium chloride in cassava starch polysaccharide iron compound liquid comprises the following steps: adding cassava starch and water into a reaction kettle, heating and adjusting the pH value, adding a hydrogen peroxide solution to degrade the cassava starch to obtain an oligosaccharide solution with the weight-average molecular weight of 3K-27 KDa, and then adding a ferric trichloride solution and alkali to perform a complex reaction to obtain a cassava starch polysaccharide iron liquid; b, carrying out ultrafiltration on the cassava starch polysaccharide iron liquid prepared in the step A, intercepting a small molecular cassava starch polysaccharide iron compound with the molecular weight of 2.5K-200KDa, removing part of sodium chloride and C, carrying out nanofiltration on the permeate liquid obtained in the step B, intercepting a small molecular cassava starch polysaccharide iron compound with the molecular weight of 200Da by using a nanofiltration membrane, removing the sodium chloride and D, combining the intercepted liquids obtained in the step B and the step C, carrying out spray drying to obtain a solid cassava starch polysaccharide iron compound, and directly discharging the nanofiltration permeate liquid. The method has the advantages of simple process, energy conservation, environmental protection, mild condition and easy continuous production; the concentration of sodium chloride in the cassava starch polysaccharide iron compound liquid can be reduced; the recovery rate of the cassava starch polysaccharide-iron compound is more than 99%, and the removal rate of sodium chloride is more than 98%.
Description
Technical Field
The invention relates to a method for removing sodium chloride from a cassava starch polysaccharide iron compound liquid, in particular to a method for removing and concentrating sodium chloride from a cassava starch polysaccharide iron compound liquid by applying an ultrafiltration and nanofiltration membrane combined technology.
Background
The polyferose compound as an iron supplement has the characteristics of good stability, small irritation to intestines and stomachs, multi-aspect bioactivity of polysaccharide, easy absorption and utilization by human and animals, obvious effect of treating iron deficiency anemia of human and animals, and wide clinical application of certain polyferose such as iron dextran. The iron polysaccharide complex consists of two parts, namely glycosyl and glycoFe, wherein the glycosyl can be glucan (dextran), cassava starch sugar, chitosan, cane sugar, plant polysaccharide and the like, the plant iron polysaccharide complex taking plant extract polysaccharide as a ligand becomes a hot point of attention in the pharmaceutical industry because of having a unique health care function, and the cassava starch polysaccharide iron complex taking cassava starch degradation product cassava starch polysaccharide as a ligand is of great and cheap raw material source amount and simple preparation process, has an obvious iron supplementing effect on animals, and is of interest in the breeding industry. The polyferose complex is a general name of a macromolecular polyferose complex with a wide molecular weight distribution range, and is prepared by reacting polysaccharide and ferric trichloride, wherein the prepared polyferose complex synthesis reaction finished solution contains a large amount of sodium chloride (10-20 wt%), and if a polyferose dry product is prepared by direct concentration and drying, the large amount of sodium chloride does not meet the use requirement, so the polyferose dry product is particularly not suitable for preparation of injection, and the sodium chloride is easy to absorb moisture, so that the product is easy to agglomerate and is not beneficial to storage, and therefore, the sodium chloride in the polyferose complex must be removed.
In the traditional process, alcohols such as ethanol can be used as a precipitator to separate sodium chloride in the polyferose complex, the method has complex operation process, ethanol is a flammable and explosive substance, potential safety hazards exist in production, a large amount of steam is consumed for recovering ethanol, and the production cost is high.
Chinese patent CN 1015887 discloses a method for desalting and concentrating iron dextran complex water solution by using nanofiltration technology, which comprises pretreating with microfiltration membrane and concentrating with nanofiltration membrane, wherein the method comprises removing sodium chloride and concentrating with original solution of iron dextran complex reaction completion solution with molecular weight of 5000-: 1. the cassava starch polysaccharide degraded by hydrogen peroxide has wide molecular weight distribution, and the molecular weight distribution range is between thousands and hundreds of thousands according to different degradation processes; 2. the aperture of the microfiltration membrane is generally 0.1-1 μm, only particles with the particle size larger than 0.1 μm in the solution can be intercepted, and impurities such as vegetable protein and the like brought by cassava starch polysaccharide iron compound molecules and cassava starch raw materials cannot be intercepted. When the reaction completion liquid of the cassava starch polysaccharide iron compound treated by the microfiltration membrane adopts a nanofiltration membrane with low permeation flux for nanofiltration desalination, the permeation pressure is very high, impurities in the solution easily cause the blockage of the nanofiltration membrane, so that the nanofiltration operation pressure is very high, the nanofiltration operation is difficult to smoothly perform, and the nanofiltration efficiency is very low. Chinese patent CN103224571B discloses a method for desalting and concentrating crude polysaccharide-iron complex aqueous solution by adopting ultrafiltration membrane separation technology with molecular weight cutoff of 5K-150 KDa. The method is also not suitable for removing sodium chloride and concentrating the reaction completion liquid of the cassava starch polysaccharide iron compound prepared by the reaction of cassava starch polysaccharide prepared by hydrogen oxidation degradation and ferric trichloride, because the molecular weight of polysaccharide iron intercepted by the method is more than 5KDa, while the molecular weight distribution range of the cassava starch polysaccharide iron compound prepared by the reaction of cassava starch polysaccharide prepared by acid degradation and ferric trichloride is wider, according to different preparation processes, the distribution of the weight average molecular weight of the obtained polysaccharide iron is generally between 3K and 27KDa, even wider, and part of the molecular weight of the cassava starch polysaccharide iron compound is less than 5KDa, if the method is adopted for desalting and concentrating, two adverse consequences can be generated: 1. the cassava starch polysaccharide iron compound with the molecular weight less than 5KDa permeates an ultrafiltration membrane, so that the yield of the cassava starch polysaccharide iron compound is reduced, and the recovery rate of the polysaccharide iron is only more than 95 percent; 2. as the permeated cassava starch polysaccharide iron compound contains a higher carbon source, the COD content in the permeated liquid is higher, and the permeated liquid cannot be directly discharged, and the COD in the solution can be discharged only after the solution is further treated to reach the discharge standard. Therefore, no ideal process method exists for removing sodium chloride and concentrating the reaction completion liquid of the cassava starch polysaccharide iron complex synthesized by the reaction of cassava starch polysaccharide prepared by using cassava starch as a raw material and carrying out hydrogen oxide degradation and iron. The invention provides a combined technology of ultrafiltration and nanofiltration, which can better solve the problems, and has the advantages of good sodium chloride removal and concentration effects on a cassava starch polysaccharide iron compound reaction completion liquid synthesized by reacting cassava starch polysaccharide which is prepared by taking cassava starch as a raw material through acid degradation and ferric trichloride, simple and safe operation process, energy conservation, environmental protection, mild conditions, easy continuous production, high recovery rate of the cassava starch polysaccharide iron compound of more than 99 percent, high removal rate of sodium chloride of more than 98 percent, direct discharge of nanofiltration permeate liquid, and no similar report at home and abroad.
Disclosure of Invention
The invention aims to provide a method for removing sodium chloride and concentrating cassava starch polysaccharide iron compound liquid by applying an ultrafiltration and nanofiltration membrane combined technology, the method can reduce the concentration of sodium chloride in the cassava starch polysaccharide iron compound synthesis reaction finished liquid, simultaneously improve the concentration of the cassava starch polysaccharide iron compound, and the nanofiltration permeate liquid has low COD concentration and can be directly discharged. The method has the advantages of simple and safe operation process, energy conservation, environmental protection, mild conditions, easy continuous production, high recovery rate of the cassava starch polysaccharide-iron compound and direct discharge of nanofiltration permeate. The specific technical scheme is as follows:
a method for removing sodium chloride in a cassava starch polysaccharide iron compound liquid relates to the removal and concentration of sodium chloride in the cassava starch polysaccharide iron compound liquid by applying an ultrafiltration and nanofiltration membrane combined technology, and comprises the following steps:
step A, adding cassava starch and water into a reaction kettle, heating to 50-80 ℃, adding alkali to adjust the pH value to be neutral, adding a hydrogen peroxide solution to degrade the cassava starch at constant temperature to obtain a cassava starch oligosaccharide solution with the weight-average molecular weight of 3K-27 KDa, then simultaneously adding a ferric trichloride solution and a sodium hydroxide solution to perform a complex reaction to obtain a cassava starch polysaccharide-iron compound synthesis reaction completion solution; the ratio of the cassava starch, the hydrogen peroxide and the water is 0.25-0.30: 0.05-0.12: 1;
b, performing ultrafiltration on the cassava starch polysaccharide iron compound liquid prepared in the step A by using an ultrafiltration membrane component, wherein the molecular weight cut-off of the ultrafiltration membrane component is 2.5K-200KDa, the cassava starch polysaccharide iron compound is cut off by the ultrafiltration membrane, the permeate liquid is an aqueous solution containing small molecular cassava starch polysaccharide iron compound and sodium chloride, and the concentration and purity of the cassava starch polysaccharide iron compound in the cut-off liquid are improved; the temperature of the feed liquid in the ultrafiltration process is 10-60 ℃, and the pressure is 0.1-1.0 MPa;
c, nanofiltration is carried out on the permeate liquid obtained in the step B by using a nanofiltration membrane component, the molecular weight of the nanofiltration membrane is 200Da, the nanofiltration cut-off liquid is a micromolecule cassava starch polysaccharide iron compound, the nanofiltration permeate liquid is a sodium chloride aqueous solution, and the concentration and the purity of the micromolecule cassava starch polysaccharide iron compound in the cut-off liquid are improved; and D, combining the interception liquid obtained in the step B and the interception liquid obtained in the step C, and performing spray drying to obtain a solid cassava starch polysaccharide iron compound, wherein the nanofiltration permeating liquid can be directly discharged. The temperature of the feed liquid in the nanofiltration process is 10-60 ℃, and the pressure is 0.1-3.0 MPa.
In the synthesis process of the cassava starch polysaccharide iron compound, the cassava starch polysaccharide is prepared by degrading cassava starch through hydrogen oxide, the cassava starch polysaccharide with a wide molecular weight distribution range can be generated in the cassava starch degradation process, the weight average molecular weight distribution of the cassava starch polysaccharide is generally between thousands and hundreds of thousands, and the microfiltration membrane has no interception effect on the cassava starch polysaccharide iron compound molecules due to large pore size, so that the cassava starch polysaccharide iron compound molecules cannot be separated from sodium chloride by adopting a microfiltration process. Although the cassava starch polyferose compound molecules can be separated from sodium chloride by adopting the nanofiltration process, compared with a microfiltration membrane and an ultrafiltration membrane, the nanofiltration membrane has low water flux and high operating pressure, and when the cassava starch polyferose compound has high concentration and the cassava starch raw material contains impurities such as vegetable protein, the solution has high osmotic pressure and high operating pressure, and the phenomenon of membrane blockage can occur inevitably, so that the conditions of high operating pressure, low separation efficiency and even unsmooth nanofiltration operation can occur when the nanofiltration separation process is only adopted to carry out nanofiltration separation and concentration on the cassava starch polyferose compound synthetic reaction finished liquid.
When the cassava starch polysaccharide iron compound synthesis reaction finished liquid is filtered only by adopting the ultrafiltration membrane, although sodium chloride can permeate the ultrafiltration membrane to realize the separation of the cassava starch polysaccharide iron compound and the sodium chloride, part of micromolecule cassava starch polysaccharide iron compound can permeate the ultrafiltration membrane to enter one side of the permeate liquid along with the sodium chloride due to the fact that the molecular weight intercepted by the ultrafiltration membrane is large, so that the cassava starch polysaccharide iron compound loss is caused, and the recovery rate is reduced; on the other hand, the part of the penetrated micromolecular cassava starch polysaccharide iron complex has high COD concentration and deep color, is easy to deteriorate and decay, cannot be directly discharged, and must be treated firstly to ensure that the COD content is lower than the discharge standard of wastewater and then can be discharged, thus generating extra treatment cost.
The combined technology of ultrafiltration and nanofiltration membrane is adopted to just solve the problems and exert the respective advantages of ultrafiltration and nanofiltration. The sodium chloride is removed by the ultrafiltration membrane, most of the cassava starch polysaccharide-iron compound is intercepted, the efficiency of separating and removing the sodium chloride is very high due to the large flux and the low operation pressure of the ultrafiltration membrane, and other impurities brought by the cassava starch raw material, such as plant protein and the like, are intercepted by the ultrafiltration membrane while the sodium chloride is separated, so that the subsequent nanofiltration separation operation is very favorable. The sodium chloride and low-concentration micromolecular cassava starch polysaccharide iron compound penetrating through the ultrafiltration membrane have lower osmotic pressure, meanwhile, impurities which can cause membrane blockage in nanofiltration operation are intercepted by the front ultrafiltration membrane, when the nanofiltration membrane with lower flux is used for nanofiltration separation of the sodium chloride and the micromolecular cassava starch polysaccharide iron compound, the nanofiltration operation can be efficiently and smoothly carried out due to lower operation pressure, nanofiltration penetrating liquid is sodium chloride aqueous solution which almost does not contain the cassava starch polysaccharide iron compound, the COD concentration is very low, the discharging can be directly carried out, and nanofiltration intercepting liquid is concentrated micromolecular cassava starch polysaccharide iron compound aqueous solution. The advantages of the ultrafiltration and the nanofiltration are fully exerted, so that the operation of separating sodium chloride from the liquid of the cassava starch polyferose compound can be efficiently carried out, the recovery rate of the cassava starch polyferose compound is high and can reach more than 99%, and the removal rate of the sodium chloride is more than 98%.
The ultrafiltration membrane is an inorganic ceramic membrane and an organic polymer membrane, and the membrane material comprises but is not limited to alumina, titanium oxide, zirconia, cellulose acetate, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyamide, polyimide, polypiperazine and polyvinyl alcohol; the component of the ultrafiltration membrane is tubular, roll-type or hollow fiber type, and the cut-off molecular weight of the ultrafiltration membrane is 2.5K-200 KDa;
the nanofiltration membrane is an organic composite membrane, and the membrane material is cellulose acetate, sulfonated polysulfone, polyamide, polyether sulfone, sulfonated polyether sulfone, polypiperazine or polyvinyl alcohol; the nanofiltration membrane component is in a roll type or a tube type, and the intercepted molecular weight of the nanofiltration membrane is 200-800 Da;
wherein the ultrafiltration and nanofiltration can be in cross-flow filtration mode.
The outstanding substantive features and remarkable progress of the invention are as follows:
1. the method for removing sodium chloride from the cassava starch polysaccharide iron compound liquid has the advantages of simple and safe operation process, energy conservation, environmental protection, mild conditions and easy continuous production. The prepared cassava polysaccharide iron can be used as an iron supplement for cattle, sheep, pigs or poultry in the breeding industry, can be an injection for injection, or can be used as a feed additive to be an oral liquid for cattle, sheep and pigs, or can be added into a feed to promote the iron source of the poultry and livestock, and is safe and reliable without any side effect.
2. The method can reduce the concentration of sodium chloride in the cassava starch polysaccharide iron compound liquid and improve the concentration of the cassava starch polysaccharide iron compound, the total recovery rate of the cassava starch polysaccharide iron compound is more than 99%, the removal rate of sodium chloride is more than 98%, the total amount of COD in the nanofiltration permeate is small, the concentration is low, the cassava starch polysaccharide iron compound can be directly discharged, and the environment can not be polluted.
3. The inventor researches that the chemical starch of cassava starch belongs to carbohydrate, and can also be regarded as a high molecular compound formed by connecting α -D glucose through α -1, 4 and α -1, 6-glycosidic bonds, the starch is mainly structurally characterized in that 1.4-glycosidic bonds are formed among glucose units, almost every glucose unit has a C6 primary hydroxyl group and two C2 and C3 secondary hydroxyl groups, cassava starch molecules contain a large number of hydroxyl groups and are active in chemical properties, so that the applicable oligosaccharide with the weight-average molecular weight of 4000-27000 Da is not easy to obtain by acid hydrolysis or enzymolysis, sodium chloride in an cassava polysaccharide iron solution is removed by applying an ultrafiltration and nanofiltration membrane combination technology, the sodium chloride is removed by replacing the prior ethanol or methanol solvent method, flammable and explosive articles such as ethanol or methanol are avoided, and potential safety hazards in production are eliminated.
4. The cassava which can be planted in a large amount in the south is utilized, the resource is rich, a new product is developed, and the comprehensive utilization capacity of the cassava is improved.
Drawings
FIG. 1 is a schematic process flow diagram of the sodium chloride removal and concentration of cassava starch polysaccharide iron complex liquid by using a combination of ultrafiltration and nanofiltration. 1. The device comprises a material liquid tank, 2, a material inlet valve A, 3, a material inlet pump A, 4, an ultrafiltration membrane component, 5, a check valve A,6, the material liquid tank, 7, a material inlet valve B, 8, a material inlet pump B, 9, a nanofiltration membrane component and 10, a check valve B.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the subject matter of the present invention.
Description of the embodiments of the figures:
putting the cassava starch polysaccharide iron compound synthesis reaction completion liquid into a feed liquid tank 1, wherein a feed valve 2A is arranged at an outlet below the feed liquid tank 1 and is connected with a feed pump 3A, the feed pump 3A pumps the cassava starch polysaccharide iron compound synthesis reaction completion liquid into an ultrafiltration membrane component 4 for ultrafiltration, ultrafiltrate enters an ultrafiltration feed liquid tank 6, a feed valve 7B is arranged below the ultrafiltration feed liquid tank 6 and is connected with a feed pump 8B to be pumped into a nanofiltration membrane component 9, a reflux valve 5A is arranged above the ultrafiltration membrane component 4, and ultrafiltration water is pumped back to the feed liquid tank 1; a return valve 10B is also arranged above the nanofiltration membrane component 9 to return the nanofiltration water to the ultrafiltration feed liquid tank 6.
Example 1
And (2) stirring in an enamel reaction kettle, respectively adding 750 kg of water and 220 kg of cassava starch, heating to 60 ℃, adding 75 kg of 27.5% hydrogen peroxide solution, heating to 60 ℃, keeping the temperature constant, carrying out oxidation reaction for 60 minutes, adding 29% of sodium hydroxide to adjust the pH value of the feed liquid to be 7.6 to obtain a cassava starch polysaccharide solution with the weight-average molecular weight of 3K-27 KDa, continuously heating to 90 ℃, keeping the temperature constant, adding 520 liters of 39.0% of ferric trichloride solution and 560 liters of 29.0% of sodium hydroxide solution within 3 hours, adjusting the pH value of the complexing reaction liquid to be 7.3 by using 20% hydrochloric acid after the feeding is finished, and obtaining the cassava starch polysaccharide iron compound synthesis reaction completion liquid.
Stirring in an enamel reaction kettle, respectively adding water, tapioca starch and hydrogen peroxide solution, heating to 60 ℃, keeping constant temperature for reaction for a period of time to obtain tapioca starch polysaccharide solution with weight average molecular weight of 3K-27 KDa, continuously preserving heat, and simultaneously adding ferric trichloride solution and sodium hydroxide solution for reaction to obtain cassava starch polysaccharide iron compound synthesis reaction completion solution.
The device shown in fig. 1 is adopted to treat cassava starch polysaccharide iron compound liquid, an ultrafiltration membrane component arranged on the device is a multi-channel tubular ceramic ultrafiltration membrane component, a membrane supporting layer is made of alumina, a membrane layer is made of zirconia, the membrane interception molecular weight is 2500Da, and the operation mode is cross-flow filtration. Carrying out ultrafiltration operation on 1000kg of synthetic reaction finished liquid (the sodium chloride content is 15.0 wt%, the iron content is 45.0mg/ml, and the solution density is 1.21 g/ml) at 45 ℃ under the pressure of 0.40MPa, adding 500kg of deionized water into the concentrated solution when the permeate reaches 500kg, continuing ultrafiltration, continuously adding deionized water into the feed tank when the permeate reaches 1000kg, controlling the water adding rate to be equal to the ultrafiltration permeate amount until the permeate reaches 4000kg, and stopping ultrafiltration operation. 500kg of ultrafiltration cut-off (concentrate) (solution density 1.17 g/ml) was obtained, wherein the sodium chloride concentration was 0.25wt%, the iron content was 78.30mg/ml, and the iron recovery was 89.90%. The color of the permeation solution is dark brown, the iron content is 1.10mg/ml, the sodium chloride content is 3.72 wt%, and the COD concentration is 25500 mg/kg.
Placing 4000kg of ultrafiltration permeate containing the sodium chloride and micromolecule cassava starch polysaccharide iron compound in a nanofiltration membrane device shown in figure 1 for nanofiltration operation, wherein the intercepted molecular weight of the nanofiltration membrane is 200Da, the nanofiltration membrane component is a roll type, the nanofiltration membrane material is sulfonated polyether sulfone, the temperature is controlled to be not higher than 50 ℃, the operation pressure is controlled to be not more than 2.0MPa, when the permeate reaches 3500kg, 3500kg of deionized water is added into a feed liquid tank, the nanofiltration operation is continued, and when the total amount of the permeate reaches 7150kg, the nanofiltration is stopped. 50kg of nanofiltration interception concentrated solution (solution density is 1.17 g/ml) is obtained, wherein the iron content is 87.20mg/ml, the sodium chloride concentration is 0.046 wt%, the recovery rate of the cassava starch polysaccharide-iron compound is 99.9% by weight of the ultrafiltration and nanofiltration interception concentrated solution, and the removal rate of the sodium chloride is 99.0%. The iron content in the permeate liquid is zero, the COD concentration is 60 mg/kg, and the permeate liquid can be directly discharged.
Example 2-example 9, except the process steps are the same as example 1. Under the conditions that the sodium chloride content in the cassava starch polysaccharide iron compound synthesis reaction finished solution is kept at 15.0 wt%, and the ultrafiltration membrane module and the nanofiltration membrane module are the same as those in example 1, the temperature and the operating pressure of the treatment solution are changed, and the obtained data are as follows:
Claims (7)
1. the method for removing sodium chloride in the cassava starch polysaccharide iron compound liquid is characterized by comprising the following steps:
adding cassava starch and water into a reaction kettle, heating to 50-80 ℃, adding alkali to adjust the pH value to be neutral, adding a hydrogen peroxide solution to degrade the cassava starch at constant temperature to obtain a cassava starch oligosaccharide solution with the weight-average molecular weight of 3K-27 KDa, then simultaneously adding a ferric trichloride solution and a sodium hydroxide solution to perform a complex reaction to obtain a cassava starch polysaccharide-iron compound synthesis reaction completion solution; the mass ratio of the cassava starch, the hydrogen peroxide and the water is 0.25-0.30: 0.05-0.12: 1;
b, performing ultrafiltration on the cassava starch polysaccharide iron compound synthesis reaction finished liquid prepared in the step A by using an ultrafiltration membrane component, wherein the cassava starch polysaccharide iron compound is intercepted by an ultrafiltration membrane, water can be simultaneously added for ultrafiltration and concentration, and the permeate liquid is an aqueous solution containing small molecular cassava starch polysaccharide iron compound and sodium chloride; the cutoff molecular weight of the ultrafiltration membrane is 2.5K-200 KDa; the operating temperature in the ultrafiltration operating step is 10-60 ℃, and the operating pressure is 0.1-1.0 MPa;
c, nanofiltration is carried out on the permeate liquid obtained in the step B by using a nanofiltration membrane component, nanofiltration cut-off liquid is a micromolecule cassava starch polysaccharide iron compound, water can be added simultaneously for nanofiltration and concentration, and the nanofiltration permeate liquid is a sodium chloride aqueous solution; the molecular weight cut-off of the nanofiltration membrane is 200-800 Da; the operating temperature in the nanofiltration operating step is 10-60 ℃, and the operating pressure is 0.1-3.0 MPa;
d, combining the interception liquid obtained in the step B and the interception liquid obtained in the step C, and performing spray drying to obtain a solid cassava starch polysaccharide iron compound, wherein nanofiltration permeate can be directly discharged; the combination of ultrafiltration and nanofiltration membrane can ensure that the removal rate of sodium chloride is more than 98 percent and the recovery rate of the cassava starch polysaccharide iron compound is more than 99 percent;
the iron content of the liquid after the synthesis reaction of the cassava starch polysaccharide iron compound is 20-60 mg/ml, and the sodium chloride concentration is 8-25 wt%.
2. The method for removing sodium chloride from a cassava starch polysaccharide iron complex liquid according to claim 1, wherein the cassava starch polysaccharide iron complex is prepared by using cassava starch as a raw material, degrading the cassava starch polysaccharide with hydrogen peroxide, and then reacting the cassava starch polysaccharide iron complex with ferric chloride.
3. The method for removing sodium chloride in cassava starch polysaccharide iron compound liquid according to claim 1, wherein the ultrafiltration membrane is an inorganic ceramic membrane and an organic polymer membrane, and the membrane material comprises alumina, titanium oxide, zirconium oxide, cellulose acetate, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyamide, polyimide, polypiperazine and polyvinyl alcohol.
4. The method for removing sodium chloride in cassava starch polysaccharide iron compound liquid according to claim 3, wherein the ultrafiltration membrane is tubular, roll-type or hollow fiber type, and the filtration mode is cross-flow filtration.
5. The method for removing sodium chloride from cassava starch polysaccharide iron compound liquid according to claim 1, wherein the nanofiltration membrane is an organic composite membrane, and the membrane material is cellulose acetate, sulfonated polysulfone, polyamide, polyethersulfone, sulfonated polyethersulfone, polypiperazine or polyvinyl alcohol.
6. The method for removing sodium chloride in cassava starch polysaccharide iron compound liquid according to claim 5, wherein the nanofiltration membrane module is roll-type or tube-type, and the filtration mode is cross-flow filtration.
7. The method for removing sodium chloride from liquid of tapioca starch polysaccharide-iron complex as claimed in claim 1, wherein the prepared tapioca starch polysaccharide-iron complex can be used as iron supplement for livestock in livestock breeding industry.
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