CN101108194B - Method of eliminating sodium chloride in iron-dextran complex compound water solution and device thereof - Google Patents

Method of eliminating sodium chloride in iron-dextran complex compound water solution and device thereof Download PDF

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CN101108194B
CN101108194B CN2007101293014A CN200710129301A CN101108194B CN 101108194 B CN101108194 B CN 101108194B CN 2007101293014 A CN2007101293014 A CN 2007101293014A CN 200710129301 A CN200710129301 A CN 200710129301A CN 101108194 B CN101108194 B CN 101108194B
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sodium chloride
iron
solution
electrode
dextran
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CN101108194A (en
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翁德洪
李广
梁艳玲
韦少平
柯敏
韦宏
张丽娟
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Guangxi Research Institute of Chemical Industry
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Abstract

The invention relates to a method and device for eliminating sodium chloride in the aqueous solution for the complex of ferrodextran, which is characterized in that: the ferrodextran is prepared with dextran and ferric trichloride. The sodium chloride in the ferrodextran is eliminated with an electrodialysis film, that is, eliminating the sodium chloride of the solvent by electrodialysis process in the ferrodextran complex solvent with iron content is more than or equal to 40mg/ml, sodium chloride content is more than or equal to 5.0 per cent wt and viscosity of 3.0mpa is multiplied by s (20 DEG C.) under the temperature of 10 to 90 DEG C. Compared with the technique of eliminating sodium chloride with alcohol precipitation, the invention prevents the safety hazard from flammable and combustible alcohol and reduces the production cost.

Description

A kind of method and device of removing sodium chloride in the iron-dextran complex compound water solution
Technical field
The present invention relates to a kind of method and device of producing the impurity in the iron-dextran complex compound process of removing, particularly remove the method and the device of sodium chloride in the iron-dextran complex compound water solution.
Background technology
Iron dextran is the iron supplement agent of a kind of humans and animals, by iron deficiency anemia oral or that the injection iron dextran can be treated the human or animal.Iron dextran is a kind of macromole complex, degrade under alkali condition by dextran (about weight average molecular weight 20000), carrying out complex reaction with ferric chloride again after the acid neutralization makes, contain a large amount of inorganic salts---sodium chloride in prepared iron-dextran complex compound stock solution, its weight percentage is generally greater than 10%.The iron dextran injection requires the concentration expressed in percentage by weight of iron dextran solution chlorination sodium less than 2%, so excessive sodium chloride must be removed in the solution, just can make the dextran ferrous solution as the injection raw material.Chinese patent CN1041762A and CN00130269.8 have reported the method that removes sodium chloride in the iron-dextran complex compound water solution, ethanol with 2~3 times of volumes of iron-dextran complex compound solution that contain sodium chloride that are equivalent to prepare carries out precipitate and separate, utilize iron dextran to be insoluble to the characteristic of ethanol, make iron dextran from solution, be precipitated out, salt is then stayed in the alcoholic aqueous solution, thereby salt is removed.The iron dextran that is precipitated out is dissolved in distilled water after dried, crushed, is mixed with iron dextran inj, and alcohol water blend recycles through recovery of alcohol distillation, the salt bearing liquid wastes discharging.
Above-mentioned desalination method technological process is long, uses organic precipitant ethanol, and ethanol is inflammable and explosive organic compound, there is potential safety hazard in the production process, simultaneously in the ethanol removal process, need to consume a large amount of steam, add the loss of ethanol in the removal process, cause production cost to improve.
Summary of the invention
The purpose of this invention is to provide a kind of method and device of removing sodium chloride in the iron-dextran complex compound water solution, particularly overcome the weak point of prior art alcohol precipitation, adopt removal method and the device of electrodialysis sodium chloride in the iron-dextran complex compound water solution.The electrodialysis methods that the present invention adopts is compiled " ion exchange membrane-preparation, performance and application " Chemical Industry Press referring to the Wang Zhen Kun, Beijing, 1986 principle and technology, (principle schematic of concrete electrodialysis arrangement is seen accompanying drawing 1).There is complete electrodialysis plant to can be used for electrodialysis desalination in the market, but since iron-dextran complex compound water solution involved in the present invention be a kind of high solids content (〉=40%wt), high content of salt (〉=5.0%wt), viscosity higher 〉=3.0mpas.20 ℃) the macromolecule aqueous solution and solution in contain the charged colloidal particle granule, the precipitation of reuniting takes place because of removing electric charge in energising back colloidal particles, simultaneously because the viscosity of solution is bigger, very easily cause the resistance of obstruction of electrodialysis plant closed circuit and ion exchange membrane to increase, electrodialysis operation can't be carried out smoothly.Therefore, directly the desalination that adopts the electrodialysis plant of finalizing the design on the market to be used for the macromolecule aqueous solution of high solids content, high salinity and viscosity higher does not see that report is arranged, and the invention solves the technological problems that than colloidal particles generation precipitation in big and the electrodialytic process electrodialysis operation can't be carried out because of material viscosity.
Method and the device of removing sodium chloride in the iron-dextran complex compound water solution of the present invention, be greater than 40mg/ml with iron-holder, sodium chloride-containing feeds down by electrode at 10 ℃~90 ℃ greater than the iron dextran complex liquid of 5.0%wt, the electrodialyzer that cationic membrane and anionic membrane alternately rearrange, the Na of energising back sodium chloride under effect of electric field +Ion arrives the salt chamber by cationic membrane, and Cl -Arrive the salt chamber of another side by anionic membrane, iron-dextran complex compound water solution is then stayed feed chamber, to arrive the purpose of removing sodium chloride, sodium chloride concentration is reduced to below the 1.0%wt, the substituted alcohol sedimentation method are removed the method for sodium chloride in the iron-dextran complex compound solution, eliminate in the production process because of using the safety in production hidden danger that inflammable and explosive ethanol brings and reducing production costs.
The method of sodium chloride in the iron-dextran complex compound water solution is removed in above-described electrodialysis; be with catholyte and anode mixture; a shared circulation receiver and circulating pump can make the electrodialysis process operation easier, and help the protection to ion exchange membrane and electrode.
The method of sodium chloride in the iron-dextran complex compound water solution is removed in above-described electrodialysis, the dextran complex is made by dextran and ferric chloride reaction, total iron content 〉=40mg/ml in the iron-dextran complex compound ferrous solution, sodium chloride content 〉=5.0%wt, solution viscosity 〉=3.0mpas (20 ℃).
The method of sodium chloride in the iron-dextran complex compound water solution is removed in above-described electrodialysis, 10 ℃~90 ℃ of operative temperatures, be preferably 15 ℃~70 ℃, electric current density is 5mA/cm2~60mA/cm2, be preferably 10mA/cm2~50mA/cm2, electrodialysis jar chamber inner fluid speed is 1cm/s~10cm/s.
The device characteristic that uses in this electrodialysis methods is to have large-area positive pole (anode (+)) and negative pole (negative electrode ()), space between positive pole and the negative pole is separated into a large amount of narrow chambers by a large amount of cation exchange membranes of alternately arranging and anion exchange membrane, these chambers are separated from each other by these films, are also referred to as raw material circular chamber and salt circular chamber.In order to implement the present invention, be filled in rare salt circular chamber with the iron-dextran complex compound water solution for the treatment of desalination, and in other dense salt circular chamber, fill electrolyte aqueous solution, normally sodium chloride, also fill in two electrode chambers and contain electrolytical aqueous solution, normally alkali or inorganic salt; Solution in rare salt chamber, dense salt chamber and the electrode chamber circulates with pump respectively in electrodialytic process.
In general, any film that is usually used in electrodialysis methods can be used to carry out the present invention, normally commercially available cation exchange membrane and anion exchange membrane are arranged and be used in the electrodialysis that the inventive method carries out, negative electrode can adopt rustless steel and nickel plate, and anode can adopt nickel plate, graphite, titanium ruthenium or titanium according to ruthenium electrode.
Under the effect of DC electric field, with the potential difference is motive force, anion in the iron-dextran complex compound solution sees through anionic membrane and moves to the salt chamber, the cation permeation cation exchange membrane moves to another side salt chamber, iron-dextran complex compound is owing to be nonionic, can not see through ionic membrane moves, after energising a period of time, along with the inorganic the moon in the dextran ferrous solution, cation constantly sees through cloudy, cationic membrane moves to the salt chamber, sodium chloride concentration in the dextran solution constantly descends, when the sodium chloride concentration in the solution dropped to certain value, discharging promptly obtained the iron dextran inj raw material that sodium chloride concentration can meet the injection requirement.
The present invention also reforms electrodialysis process, and in common electrodialysis process operation, catholyte and anolyte are to separate circulation respectively.In electrodialytic process, along with the carrying out of electrochemical reaction on the electrode, releasing hydrogen gas and produce OH on the negative electrode -Ion is emitted oxygen and is produced H on the anode +Ion, therefore along with the carrying out of electrodialytic process, the alkali concn of catholyte is increasing, acid concentration in the anolyte is increasing, when bronsted lowry acids and bases bronsted lowry concentration is big, can reduce the performance of electrode and ionic membrane, when alkali concn in the catholyte and the acid concentration in the anolyte are big simultaneously, because concentration polarization, can produce osmosis, make OH -To the migration of dextran ferrous solution, the H in the anolyte +Also can move to the salt chamber through cationic membrane by part substituted metal ion, thereby make the current efficiency of desalination reduce, therefore in practical operation, want frequent discharge unit catholyte and anolyte, add the part distilled water simultaneously, with the acid concentration of the alkali concn of control cathode chamber and anode chamber within the specific limits, guarantee carrying out smoothly of electrodialytic process.Consequently carry out along with electrodialytic, discharge a large amount of diluted acid and dilute alkaline soln, this has caused certain difficulty to post processing.
Device characteristic of the present invention is that in electrodialytic process catholyte and anolyte to be mixed be the shared circulation receiver of catholyte and anolyte, a shared circulating pump (when electrodialytic voltage is low, can't produce short circuit current), after neutralization, send cathode chamber and anode chamber back to through circulating pump by the acid of anode chamber's generation and the alkali of cathode chamber generation again like this, thereby the acid-base value of holding anode liquid and catholyte remains unchanged basically, catholyte and anolyte have only played the effect of ion migration, reduce the discharging and the processing of utmost point liquid, thereby made electrodialysis operation easier.
In order to implement the present invention better, operating parameter should carefully be controlled, and the major parameter of controlling in the operating process comprises: the flowing velocity and the temperature of electric current density, circulation indoor liquid.The electric current density increase helps improving ion migration amount in the unit interval, shorten the electrodialysis operation time, but the selection of electric current density should be taken into account the ability to bear of ion exchange membrane, electric current density is crossed conference and is made the heat effect increase simultaneously, increase the load of heat exchanger, general electric current density should be at 5~60mA/cm 2Be advisable in the scope.Each circular chamber liquid circulation amount increase helps increasing the flowing velocity of circulating fluid in chamber, reduce resistance to mass tranfer and polarization phenomena, so liquid flow velocity is generally 1~10cm/s in the chamber.Operative temperature suitably raising helps accelerating ion migration speed, and electrodialytic process is accelerated, but the selection of operative temperature also will be considered the ability to bear and the heat exchanger load of the ion exchange membrane that uses, and general temperature should be between 15~90 ℃.
Compare with alcohol precipitation desalination method, adopt the electroosmose process desalination to have following advantage:
1, desalting process does not adopt inflammable and explosive ethanol to make precipitant, has eliminated the hidden danger that produces burning, blast in the production process.
2, operation is carried out at normal temperatures and pressures, and process does not have phase transformation, and production process is easy to control.
3, owing to do not adopt ethanol to make precipitant, save the ethanol recycle section, reduced running cost and energy consumption.
Description of drawings
Fig. 1 is the principle schematic that electrodialysis of the present invention is arranged.
The parts sequence number of Fig. 1: 1, anode 2, negative electrode 3, cationic membrane 4, anionic membrane 5, salt water cycle basin 6, brine flow meter 7, brine pump 8, raw material circulation basin 9, material flow meter 10, feedstock pump 11, electrode solution circulation basin 12, electrode solution effusion meter 13, electrode liquid pump
Negative electrode can adopt stainless steel and nickel plate, and anode can adopt nickel plate, graphite, titanium ruthenium or titanium according to ruthenium electrode.
From figure, see: be catholyte and a shared circulation receiver of anolyte between anode 1 and the negative electrode 2, the alkali that the acid that is produced by the anode chamber and cathode chamber produce through neutralization by common recycle pumped back cathode chamber and anode chamber, the circulation receiver is separated into a large amount of narrow chamber, constitutive material circular chamber and salt circular chambers by cation-exchange membrane 3 and the anion-exchange membrane 4 of a large amount of alternative arrangements. Raw material circular chamber and raw material circulation basin 8, material flow meter 9 and the feedstock pump 10 constitutive material circulatory systems; Salt circular chamber and brine recycling basin 5, brine flow meter 6 and brine pump 7 form brine circulation system; Electrode solution in the circulation receiver and electrode solution circulation basin 11, electrode solution flowmeter 12, electrode liquid pump 13 form the electrode solution circulatory system.
Concrete embodiment
Illustrate embodiments of the invention to be described the electrodialysis plant that assembles, but to be not limited to following embodiment according to Fig. 1 below.
Embodiment 1:
In raw material circulation basin, salt water cycle basin, electrode solution circulation basin, adding the saliferous percent by weight respectively is 15% (w/w, down together) iron-dextran complex compound water solution of iron-holder 50mg/mL is 40 liters, 0.5% sodium chloride solution, 0.5% metabisulfite solution, wherein the amount of sodium chloride solution and metabisulfite solution is advisable can satisfy the electrodialytic process circulation.Start the feed liquid circulating pump, treat the material stable circulation after, apply unidirectional current, to electric current density be 50mA/cm 2, it is constant to keep voltage, carries out the constant voltage electrodialysis.In electrodialytic process, constantly add distilled water, keep the iron dextran solution amount and be always 40 liters, in electrodialytic process, 15 ℃ of control solution temperatures.Along with the carrying out of electrodialytic process, when the energising amount reaches 3298 ampere-hours, stop electrodialysis, discharging obtains sodium chloride content less than 0.8%, and iron content is greater than the dextran ferrous solution of 50mg/mL.
Embodiment 2:
At raw material circulation basin, salt water cycle basin, in the electrode solution circulation basin, add iron-holder 〉=50mg/mL respectively, salinity is 15% dextran ferrous solution 80kg, 0.5% sodium chloride solution, 0.5% metabisulfite solution, wherein the amount of sodium chloride solution and metabisulfite solution is advisable can satisfy the electrodialytic process circulation.Start the feed liquid circulating pump, treat the material stable circulation after, apply unidirectional current, to electric current density be 55mA/cm 2, it is constant to keep voltage, carries out the constant voltage electrodialysis and controls 55 ℃ of solution temperatures.Along with the carrying out of electrodialytic process, electric current constantly descends, and when the energising amount reaches 5497 ampere-hours, stops electrodialysis, and discharging obtains sodium chloride content less than 1.0%, and iron content is greater than the dextran ferrous solution 45kg of 100mg/mL.
Embodiment 3:
At raw material circulation basin, salt water cycle basin, in the electrode solution circulation basin, add iron-holder 〉=50mg/mL respectively, salinity is 15% dextran ferrous solution 130kg, 0.5% sodium chloride solution, 0.5% metabisulfite solution, wherein the amount of sodium chloride solution and metabisulfite solution is advisable can satisfy the electrodialytic process circulation.Start the feed liquid circulating pump, treat the material stable circulation after, apply unidirectional current, to electric current density be 55mA/cm 2, it is constant to keep voltage, carries out the constant voltage electrodialysis and control solution temperature not being higher than 90 ℃.Along with the carrying out of electrodialytic process, electric current constantly descends, and when the energising amount reaches 8932 ampere-hours, stops electrodialysis, and discharging obtains sodium chloride content less than 2.0%, and iron content is greater than the dextran ferrous solution 43kg of 140mg/mL.
Embodiment 4-embodiment 9:
The data that obtain according to the condition that as above implementation variations is different are as follows:
Temperature ℃ Electric current density mA/cm 2 Rate of flow of fluid cm/s Handle the afterchlorinate sodium content
Implement
4 10 5 1 1.6%
Implement 5 10 60 5 0.9%
Implement 6 50 60 10 1.0%
Implement 7 50 30 1 0.6%
Implement 8 90 30 5 0.7%
Implement 9 90 5 10 1.2%

Claims (2)

1. method of removing sodium chloride in the iron-dextran complex compound water solution, it is characterized in that: be greater than 40mg/ml with iron-holder, sodium chloride-containing feeds down by electrode at 10 ℃~90 ℃ greater than the iron dextran complex liquid of 5.0%wt, the electrodialyzer that cationic membrane and anionic membrane alternately rearrange, the Na of energising back sodium chloride under effect of electric field +Ion arrives the salt chamber by cationic membrane, and Cl -By the salt chamber of anionic membrane arrival another side, iron-dextran complex compound water solution is then stayed feed chamber, to arrive the purpose of removing sodium chloride, sodium chloride concentration is reduced to below the 1.0%wt;
Described dextran complex is made by dextran and ferric chloride reaction, total iron content 〉=40mg/ml in the iron-dextran complex compound ferrous solution, sodium chloride content 〉=5.0%wt, solution viscosity 〉=3.0mpas in the time of 20 ℃;
Described electrodialytic process operative temperature is 10 ℃~90 ℃, and electric current density is 5mA/cm 2~60mA/cm 2, electrodialysis jar chamber inner fluid speed is 1cm/s~10cm/s;
When carrying out electrodialysis operation, catholyte is mixed with anolyte, a shared electrode circulation receiver and circulating pump, the alkali that acid that is produced by the anode chamber and cathode chamber produce through neutralization after circulating pump is sent cathode chamber and anode chamber back to;
The shared electrode circulation receiver of described catholyte and anolyte, the circulation receiver is separated into a large amount of narrow chambers by a large amount of cation exchange membranes of alternately arranging and anion exchange membrane;
The device that described method of removing sodium chloride in the iron-dextran complex compound water solution is used has three blood circulation, is respectively raw material blood circulation, brine circulation system and electrode solution blood circulation;
Described negative electrode adopts rustless steel or nickel plate, and anode adopts nickel plate, graphite, titanium ruthenium or titanium according to ruthenium electrode.
2. device that method of removing sodium chloride in the iron-dextran complex compound water solution as claimed in claim 1 adopts, it is characterized in that: this device has three blood circulation, is respectively raw material blood circulation, brine circulation system and electrode solution blood circulation; The shared electrode circulation receiver of the catholyte of this device and anolyte, the circulation receiver is separated into a large amount of narrow chambers by a large amount of cation exchange membranes of alternately arranging and anion exchange membrane; The negative electrode of this device adopts rustless steel or nickel plate, and anode adopts nickel plate, graphite, titanium ruthenium or titanium according to ruthenium electrode.
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