CN102659567A - Method for continuously removing anions from citric acid-containing solution - Google Patents
Method for continuously removing anions from citric acid-containing solution Download PDFInfo
- Publication number
- CN102659567A CN102659567A CN2012101346099A CN201210134609A CN102659567A CN 102659567 A CN102659567 A CN 102659567A CN 2012101346099 A CN2012101346099 A CN 2012101346099A CN 201210134609 A CN201210134609 A CN 201210134609A CN 102659567 A CN102659567 A CN 102659567A
- Authority
- CN
- China
- Prior art keywords
- exchange resin
- resin column
- anion
- post
- column group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a method for continuously removing anions from a citric acid-containing solution. The method is carried out in a mobile separator. Each anion exchange resin column group sequentially and cyclically passes through an adsorption area, a washing area, a regeneration area and a regenerative washing area, and an anion exchange resin column group or a plurality of anion exchange resin column groups connected in series exist in each working area; at least two anion exchange resin column groups connected in series exist in the adsorption area, and the citric acid-containing solution sequentially contacts the anion exchange resin column groups positioned in the adsorption area, so that anions except citric acid radical ions in the citric acid-containing solution are adsorbed to anion exchange resins; and the anion exchange resin column group positioned at the first position of the adsorption area reaches adsorption saturation and enters the washing area. Spare columns are not used, and equipment and the resins can be utilized to the greatest extent; and the consumption of a regenerant and water is low, the waste liquor emission is low, and the yield of citric acid can be improved by about 1 percent.
Description
Technical field
The present invention relates to a kind of anionic method that contains in the citric acid solution that removes continuously.
Background technology
Hydrocerol A is a kind of organic acid that is widely used in industries such as beverage, food and medicine, and China is citric acid production big country, and the process for extracting of domestic Hydrocerol A is mainly calcium salt method.And mostly adopting the fixed bed intermittent type that Hydrocerol A acidolysis liquid is being left friendship from the section of handing over, to remove positively charged ion in the acid hydrolysis solution, negatively charged ion etc.
Particularly,, generally form from the friendship system for a cover fixed bed intermittent type acid hydrolysis solution by principal post, auxilliary post and three posts of stand-by column.During work, principal post, the auxilliary post punishment in advance that is cascaded, another root pillar is subsequent use.
Fixed bed intermittent type to be made up of A post, B post and C post is an example from the friendship system.At first, the series connection of A post and B post contains citric acid solution and flows into the A post, flows into the B post from the A post again, flows out and is collected from the B post then, and at this moment, the A post is as principal post (promptly playing main exchange interaction), and the B post is as auxilliary post (promptly playing auxiliary exchange interaction), and the C post is as stand-by column.After the A post is saturated, the feed liquid in the A post is pressed into the C post, and with B post and the series connection of C post.In ensuing exchange process, the said citric acid solution that contains at first flows into the B post, flows into the C post from the B post again, flows out and is collected from the C post then, and at this moment, the B post is as principal post, and the C post is as auxilliary post.Simultaneously, the A post is washed repeatedly, afterwards the A post is pressed empty with deionized water.The diluted acid content that obtains after with deionized water rinsing A post stops to use deionized water rinsing during less than 0.2 weight %, adds basic soln the A post is regenerated, and uses deionized water rinsing A post near neutral then.To pass through A post after the above-mentioned processing as stand-by column, recycle so repeatedly.
This shows that there is following defective in prior art:
(1) because assist the reason of post, stand-by column, there is a waiting time in resin column, and resin is not fully used, and causes equipment and resin utilization ratio low.
(2) fixed bed batch operation, labor strength is big.
(3) the fixed bed area occupied is bigger, and the quality product fluctuation is big, instability, and yield is lower.
(4) consumption such as deionized water, regenerator is higher, and the discharging of waste liquid amount is big, and production cost is higher.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of anionic method that contains in the citric acid solution that removes continuously is provided.
A kind of anionic method that contains in the citric acid solution that removes continuously; It is characterized in that this method is carried out in moving separating device, said moving separating device comprises many group anion-exchange resin column groups; Every group of anion-exchange resin column group comprises the anion-exchange resin column of one or more parallel connections; Every group of anion-exchange resin column group comprises adsorption zone, washing section, breeding blanket and regeneration rinsing area successively and circularly through four functional zone, and the flushing of adsorbing successively, wash, regenerate and regenerate; Many groups anion-exchange resin column group that there is one group of anion-exchange resin column group in each WS or is connected in series
Wherein, There are two groups of anion-exchange resin column groups that are connected in series at least in said adsorption zone; And said contain citric acid solution successively with the anion-exchange resin column groups of contact that is in adsorption zone; Make the negatively charged ion except that citrate ion that contains in the citric acid solution be adsorbed on the anionite-exchange resin, be in the first anion-exchange resin column group of adsorption zone and reach the saturated back entering of absorption washing section.
Of the present invention above-mentionedly have the following advantages from the process of handing over continuously:
(1) do not have stand-by column, after resin column regeneration is good, carry out work immediately, do not have the waiting time, resin can farthest obtain utilizing.
(2) method of using the plural serial stage mode and preferably using counter-current regeneration in the process of regeneration and regeneration flushing, can obviously reduce the consumption of regenerator and water, and the consumption of regenerator and water all reduces about 30%.
(3) because water practices thrift 30%, so the discharging of waste liquid amount also reduces about 30%, and the yield of Hydrocerol A can improve about 1%.
(4) occupation area of equipment is little, and operation is control automatically, and labour productivity is high, and the utilization ratio of equipment and resin is higher.
Description of drawings
Accompanying drawing is to be used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used to explain the present invention with following embodiment, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the process flow sheet of a kind of preferred implementation of the present invention.
Embodiment
The present invention provides a kind of anionic method that contains in the citric acid solution that removes continuously; It is characterized in that this method is carried out in moving separating device, said moving separating device comprises many group anion-exchange resin column groups; Every group of anion-exchange resin column group comprises the anion-exchange resin column of one or more parallel connections; Every group of anion-exchange resin column group comprises adsorption zone, washing section, breeding blanket and regeneration rinsing area successively and circularly through four functional zone, and the flushing of adsorbing successively, wash, regenerate and regenerate; Many groups anion-exchange resin column group that there is one group of anion-exchange resin column group in each WS or is connected in series
Wherein, There are two groups of anion-exchange resin column groups that are connected in series at least in said adsorption zone; And said contain citric acid solution successively with the anion-exchange resin column groups of contact that is in adsorption zone; Make the negatively charged ion except that citrate ion that contains in the citric acid solution be adsorbed on the anionite-exchange resin, be in the first anion-exchange resin column group of adsorption zone and reach the saturated back entering of absorption washing section.
Among the present invention, the said resin column group that is in the adsorption zone first place is meant and is in the adsorption zone, and is about to leave the resin column group that adsorption zone gets into next WS (being washing section).The implication that is in the first resin column group in other WSs is identical therewith.
The principal feature of moving separating device of the present invention (being ISEP equipment) is that the position that flow is imported and exported does not change; Anionite-exchange resin contacts with liquid; And the anionite-exchange resin separator column continuously regularly changes the position in certain sequence, and the every interval of promptly multistage anionite-exchange resin separator column certain hour moves one-level to next WS; The progression of this device is many more, and moving process is just more approaching evenly, continuously.Like this, thus realize from the solution that contains Hydrocerol A, removing continuously negatively charged ion.
All the time have two phases in the said moving separating device: solid phase is an anionite-exchange resin, and liquid phase (moving phase) is respectively the solution, deionized water (washing composition), basic soln (regenerator), the water that contain Hydrocerol A, contain the waste liquid of impurity such as inorganic salt and from handing over liquid etc.
In said moving separating device; The alkaline reactive group that contains on negatively charged ion such as sulfate ion and cl ions in the solution of Hydrocerol A and the anionite-exchange resin exchanges absorption; And Hydrocerol A is not flowed out by resin absorption, thereby realizes separating of Hydrocerol A and sulfate ion and cl ions.Particularly, at adsorption zone, said contact is preferably carried out under the condition of 0.9-1.6 in the pH value, is to carry out under the condition of 1.2-1.4 in the pH value most preferably.In this scope, Hydrocerol A ionization is less, mainly exists with citric acid molecule, therefore, has only the citrate ion of minute quantity and anionite-exchange resin to exchange absorption.Again because sulfuric acid and hydrochloric acid are inorganic acids; So carrying out along with resins exchange absorption; Sulfate ion again a small amount of citrate ion on the resin column to replacing; The citrate ion of replacing flows out with solution, thereby realizes anionic separation such as Hydrocerol A and sulfate radical and cl ions, reaches the purpose of purifying Hydrocerol A.
According to the present invention, in four WSs, liquid can be introduced from the upper end of resin anion(R.A) post group, also can introduce from the lower end.Preferably, at adsorption zone, the solution that contains Hydrocerol A is introduced from the upper end that is in the first anion-exchange resin column group of adsorption zone, flows out from the lower end that is in adsorption zone omega-anion-exchange resin column group, obtains Hydrocerol A from handing over liquid.
, the absorption of the alkaline reactive group on negatively charged ion in the solution that contains Hydrocerol A and said resin exchange stops exchange (can calculate the upper column quantity of the solution that contains Hydrocerol A) when reaching the work exchange capacity (be resin reaches absorption saturated) of said resin according to anionic concentration such as sulfate ion in the solution that contains Hydrocerol A of the work exchange capacity of anionite-exchange resin and upper prop and cl ionss.
Therefore; The effect of adsorption zone is to be adsorbed on the negatively charged ion except that citrate ion in the solution that contains Hydrocerol A on the resin anion(R.A) as much as possible; Thereby purification Hydrocerol A; Those skilled in the art can select the number of the loadings and the resin column group of every group of resin in the resin column group as required, and the anionic content except that citrate ion is below the 10ppm, further to be preferably below the 4ppm in the liquid from handing over preferably to make said Hydrocerol A.
Continuous from the friendship method through many post tandem workings, thereby can suitably improve the charging flow velocity.At adsorption zone, the flow velocity of the said solution that contains Hydrocerol A can for 0.5-8.0 times of column volume/hour, be preferably 3-5 times of column volume/hour.In the method for prior art, owing to have only a principal post and an auxilliary post, therefore, the flow velocity that contains the solution of Hydrocerol A can't reach above-mentioned preferred flow velocity.Therefore, method of the present invention has improved the treatment capacity of resin unit time than prior art.
According to the present invention; Preferably there are two groups of anion-exchange resin column groups at least in washing section, at washing section, preferably; Deionized water is introduced from the upper end that is in the first resin column group of washing section; Flow through successively and respectively organize the anion-exchange resin column group in this washing section, flow out, obtain the scrub stream fluid from the lower end that is in washing section omega-resin column group.
Owing to also contain the Hydrocerol A of some amount in the scrub stream fluid; Therefore, preferably, said scrub stream fluid is introduced adsorption zone from the upper end that is in the first resin anion(R.A) post group of adsorption zone; Because plural serial stage washs; The water yield that consumes is less, guarantees that the washing effluent volume is less, and less scrub stream fluid gets into adsorption zone again and adsorbs.So not only can the Hydrocerol A in the scrub stream fluid also all be reclaimed, and can guarantee that Hydrocerol A leaves the acidity of handing over liquid, thereby further improve the yield of Hydrocerol A.
At washing section; The flow velocity of deionized water can be the conventional flow velocity in this area, and can adjust according to actual needs, so that Hydrocerol A residual in the resin column is as far as possible all washed out; Simultaneously; Take all factors into consideration the concentration of the citric acid solution that final purifying obtains, preferably, the flow velocity of deionized water be 0.4-5.0 times of column volume/hour.
According to the present invention; Preferably there are two groups of anion-exchange resin column groups at least in the breeding blanket, in the breeding blanket, preferably; Basic soln is introduced from the lower end that is in the first resin column group in breeding blanket; Flow through successively and respectively organize the anion-exchange resin column group in this breeding blanket, flow out, obtain the recovery stream fluid from the upper end that is in breeding blanket omega-resin column group.Through counter-current regeneration, the resin that can loosen makes between regenerator (being basic soln) and the resin and fully contacts the regenerated better effects if.
Wherein, said basic soln can be preferably sodium hydroxide solution for the conventional basic soln as regenerator in this area.The concentration of said basic soln is preferably 3-10%.Hydroxide ion in the basic soln makes negatively charged ion desorbs such as sulfate ion and the cl ions on the said resin so that said resin returns to alkaline state.
In the breeding blanket, the flow velocity of basic soln can be that the routine of this area selects, and as far as possible all exchanges and is as the criterion will be adsorbed on negatively charged ion on the resin column.Preferably, the flow velocity of said basic soln be 1-4 times of column volume/hour.
According to the present invention; Preferably there are two groups of anion-exchange resin column groups at least in the regeneration rinsing area, at the regeneration rinsing area, preferably; Water is introduced from the upper end that is in the first resin column group of regeneration rinsing area; Flow through successively and respectively organize the anion-exchange resin column group in this regeneration rinsing area, flow out from the lower end that is in regeneration rinsing area omega-anion-exchange resin column group, the flushing flow fluid obtains regenerating.
At the regeneration rinsing area, the resin after the water flushing regeneration is near neutral, and the resin anion(R.A) post that flushing is good need not waited for regard to getting into adsorption zone again and carry out the absorption exchange of next round.
Said water can be considered cost factor for deionized water or tap water, preferably uses tap water.
At the regeneration rinsing area, the flow velocity of water can be that the routine of this area selects, preferably, the flow velocity of water be 2-8 times of column volume/hour.
Contriver of the present invention finds, said regeneration flushing flow fluid is introduced the breeding blanket from the lower end that is in the first anion-exchange resin column group in breeding blanket, can recycle said regeneration flushing flow fluid, saves the consumption of water and regenerator.Reduce the discharging of waste water simultaneously, reduced the environmental protection treatment cost.
Those skilled in the art can select the number of the anion-exchange resin column group of each WS as required, and the number of selecting every group of resin column in the resin column group.Preferably, the number that is in the anion-exchange resin column group of each WS is 2-8, further is preferably 2-4, and the number of the resin column in every group of resin column group is 1-4, further is preferably 1-2.
The used anionite-exchange resin of the present invention can for this area conventional be used for removing the anionic anionite-exchange resin that contains citric acid solution, preferably, the total exchange capacity of said anionite-exchange resin is greater than 6.5mmol/g.Particularly, said anionite-exchange resin is preferably the acrylic acid series weakly basic anion exchange resin.In use, can carry out activation to this resin, the activatory method has been as well known to those skilled in the art.
Method of the present invention is specially adapted to the higher solution that contains Hydrocerol A of citric acid content, preferably, is benchmark with the gross weight of the solution that contains Hydrocerol A, and the content of Hydrocerol A is 20-60 weight % in the said solution that contains Hydrocerol A.The solution that contains Hydrocerol A that satisfies above-mentioned content for example can be Hydrocerol A destainer (or Hydrocerol A acidolysis liquid; Hydrocerol A acidolysis liquid is the middle article when producing Hydrocerol A with calcium salt method; Be that citric acid fermentation broth obtains Hydrocerol A press filtration clear liquid through filter press; Press filtration clear liquid and lime carbonate or calcium hydroxide etc. carry out neutralization reaction, remove impurity such as Deproteinization, colloid, sugar and salt, obtain more purified citrate of lime or hydrogen citrate calcium; Citrate of lime or hydrogen citrate calcium and vitriol oil generation acidolysis reaction generate Hydrocerol A acidolysis liquid and calcium sulphate solid, remove by filter calcium sulphate solid, promptly obtain purified Hydrocerol A acidolysis liquid).More preferably remove the Hydrocerol A destainer behind the positively charged ion.
Among the present invention, the working temperature of said four WSs can be identical with the normal condition of this area, for example all can be 20-50 ℃.
Be elaborated below in conjunction with the accompanying drawing specific embodiments of the invention.Should be understood that embodiment described herein only is used for explanation and explains the present invention, is not limited to the present invention.
The technology stringing figure of the complete assembly that the present invention is used is as shown in Figure 1, is divided into adsorption zone, washing section, breeding blanket and four WSs of regeneration rinsing area, imports and exports the position through continuously changing flow, and anionite-exchange resin is contacted with various liquid.In each WS and between the WS, the flow direction of various liquid realizes through the start or stop state that regularly switches the terminal valve on the resin column group.This device is equipped with flow switching valve (or adopting the hyperchannel reversing valve) in the import and export of every group of resin column group, every interval certain hour, and the resin column group is whole to move one-level relative to flow import and export position.
As shown in Figure 1; Having 10 anion-exchange resin columns according to ISEP equipment carries out the technology stringing and arranges; Wherein, adsorption zone has 3 posts (post 8, post 9 and post 10), and washing section has 3 posts (post 5, post 6 and post 7); There are 2 posts (post 3 and post 4) breeding blanket, and the regeneration rinsing area has 2 posts (post 1 and post 2).
Below, in conjunction with Fig. 1, relatively move before the one-level with resin column and moving phase the running condition of equipment therefor of the present invention is described with latter two state of one-level that relatively moves.
At adsorption zone, the solution that contains Hydrocerol A is introduced from the upper end of post 8, behind the post 9 of flowing through, flows out from the lower end of post 10; At washing section, deionized water is introduced from the upper end of post 5, behind the post 6 of flowing through, flows out from the lower end of post 7, and introduces adsorption zone from the upper end of post 8; In the breeding blanket, basic soln is introduced from the lower end of post 3, flows out from the upper end of post 4; At the regeneration rinsing area, water is introduced from the upper end of post 1, flows out from the lower end of post 2, and introduces the breeding blanket from the lower end of post 3.
Treat post 8 reach absorption saturated after, one-level is moved in the whole flow relatively of resin column group import and export position, promptly; Post 1 breaks off with post 2 and is connected and is connected with post 10, and post 8 breaks off with post 9 and being connected, therefore; At adsorption zone; The solution that contains Hydrocerol A is introduced from the upper end of post 9, behind the post 10 of flowing through, flows out from the lower end of post 1; Post 8 breaks off with post 9 and is connected and is connected with post 7, and post 5 breaks off with post 6 and being connected, and therefore, at washing section, deionized water is introduced from the upper end of post 6, behind the post 7 of flowing through, flows out from the lower end of post 8, and introduces adsorption zone from the upper end of post 9; Post 5 breaks off with post 6 and is connected and is connected with post 4, and post 3 breaks off with post 4 and being connected, and therefore, in the breeding blanket, basic soln is introduced from the lower end of post 4, flows out from the upper end of post 5; Post 3 breaks off with post 4 and is connected and is connected with post 2, and post 1 breaks off with post 2 and being connected, and therefore, at the regeneration rinsing area, water is introduced from the upper end of post 2, flows out from the lower end of post 3, and introduces the breeding blanket from the lower end of post 4.
Required timing definition is an one-period through each position of No. 1 resin column to 10 resin column of associating successively with (also being every) resin column in the system in the present invention.
Below, the present invention will be described in more detail through embodiment.
Following examples of the present invention all adopt the ISEP chromatographic fractionation system of 10 resin columns shown in Figure 1, and the post height is 1.0 meters, and the sectional area of every pillar is 0.000962 square metre; Every resin column independently is one group of resin column group; Therefore, when explanation embodiment of the present invention, only relate to resin column; But those skilled in the art can understand, and can realize the present invention fully with the resin column in the resin column group replacement specific embodiment of the invention of a plurality of parallel connections; 100g pack in every resin column into available from the D318 type anionite-exchange resin of Jiangsu Su Qing board, and total exchange capacity>=6.5mmol/g carries out activation by this resin of alkali acid base pair, and water dashes to neutral subsequent use; The used solution that contains Hydrocerol A is the qualified Hydrocerol A destainer of transmittance, wherein, citric acid content be 50% (m/v, g/mL), SO
4 2-Content is 3500ppm, Cl
-Content is 30ppm, rolls over to be univalent anion the about 74mmol/kg of content.
Wherein, the concentration of Hydrocerol A detects according to GB 1987-2007 standard; Various anionic content detect through the conventional negatively charged ion detection method in the chemical analysis method.Among the present invention, the ppm of unit all refers to weight content.
Embodiment 1
At adsorption zone; The Hydrocerol A destainer with 3 times of column volumes/hour flow velocity introduce from the upper end of post 8; Make negatively charged ion except that citrate ion and resin generation exchange absorption in the citric acid solution; The absorption effluent flows out from the lower end of post 10, and said exchange is adsorbed on pH and carries out under 1.2 the condition.
At washing section; Deionized water with 1 times of column volume/hour flow velocity introduce from the upper end of post 5; The resin that washing absorption is saturated, and the scrub stream fluid is flowed out from the lower end of post 7, scrub stream fluid that obtains and Hydrocerol A destainer mix; Introduce from the upper end of post 8 again, contact with resin again and remove negatively charged ion.
In the breeding blanket, the sodium hydroxide solution of 4 weight % with 2 times of column volumes/hour flow velocity introduce from the upper end of post 3, the good resin of regeneration washing, the recovery stream fluid flows out from the lower end of post 4.
At the regeneration rinsing area; Flow velocity be 3 times of column volumes/hour tap water introduce from the upper end of post 1; The flushing resin is near neutral, and the regeneration flushing flow fluid that obtains flows out from the lower end of post 2, and mixes with dilute sodium hydroxide; Get into the breeding blanket from the upper end of post 3, and the resin column after the regeneration flushing carries out the absorption exchange of next round.
The working temperature of each WS is 30 ℃.
Through one-period (26.67 hours), co-processing 80000ml Hydrocerol A destainer, obtain the 84708ml Hydrocerol A altogether from handing over liquid, said Hydrocerol A is from handing in the liquid, and citric acid content is 47.15% (m/v), SO
4 2-Content is 0.5ppm, Cl
-Content is 0.3ppm.Through calculating, the Hydrocerol A yield is 99.85%.
With respect to every ml Hydrocerol A destainer of handling, the amount of the sodium hydroxide solution of consumption is 0.67ml, and the consumption of deionized water is 0.33ml, and the consumption of tap water is 1ml.
Embodiment 2
At adsorption zone; The Hydrocerol A destainer with 5 times of column volumes/hour flow velocity introduce from the upper end of post 8; Make negatively charged ion except that citrate ion and resin generation exchange absorption in the citric acid solution; The absorption effluent flows out from the lower end of post 10, and said exchange is adsorbed on pH and carries out under 1.2 the condition.
At washing section; Deionized water with 3 times of column volumes/hour flow velocity introduce from the upper end of post 5; The resin that washing absorption is saturated, and the scrub stream fluid is flowed out from the lower end of post 7, scrub stream fluid that obtains and Hydrocerol A destainer mix; Introduce from the upper end of post 8 again, contact with resin again and remove negatively charged ion.
In the breeding blanket, the sodium hydroxide solution of 4 weight % with 3 times of column volumes/hour flow velocity introduce from the upper end of post 3, the good resin of regeneration washing, the recovery stream fluid flows out from the lower end of post 4.
At the regeneration rinsing area; Flow velocity be 6 times of column volumes/hour tap water introduce from the upper end of post 1; The flushing resin is near neutral, and the regeneration flushing flow fluid that obtains flows out from the lower end of post 2, and mixes with dilute sodium hydroxide; Get into the breeding blanket from the upper end of post 3, and the resin column after the regeneration flushing carries out the absorption exchange of next round.
The working temperature of each WS is 30 ℃.
Through one-period (16 hours), co-processing 80000ml Hydrocerol A destainer, obtain the 85000ml Hydrocerol A altogether from handing over liquid, said Hydrocerol A is from handing in the liquid, and citric acid content is 47.0% (m/v), SO
4 2-Content is 0.7ppm, Cl
-Content is 0.5ppm.Through calculating, the Hydrocerol A yield is 99.88%.
With respect to every ml Hydrocerol A destainer of handling, the amount of the sodium hydroxide solution of consumption is 0.6ml, and the consumption of deionized water is 0.6ml, and the consumption of tap water is 1.2ml.
Embodiment 3
At adsorption zone; The Hydrocerol A destainer with 4 times of column volumes/hour flow velocity introduce from the upper end of post 8; Make negatively charged ion except that citrate ion and resin generation exchange absorption in the citric acid solution; The absorption effluent flows out from the lower end of post 10, and said exchange is adsorbed on pH and carries out under 1.2 the condition.
At washing section; Deionized water with 2 times of column volumes/hour flow velocity introduce from the upper end of post 5; The resin that washing absorption is saturated, and the scrub stream fluid is flowed out from the lower end of post 7, scrub stream fluid that obtains and Hydrocerol A destainer mix; Introduce from the upper end of post 8 again, contact with resin again and remove negatively charged ion.
In the breeding blanket, the sodium hydroxide solution of 4 weight % with 2.5 times of column volumes/hour flow velocity introduce from the upper end of post 3, the good resin of regeneration washing, the recovery stream fluid flows out from the lower end of post 4.
At the regeneration rinsing area; Flow velocity be 4 times of column volumes/hour tap water introduce from the upper end of post 1; The flushing resin is near neutral, and the regeneration flushing flow fluid that obtains flows out from the lower end of post 2, and mixes with Hydrogen chloride; Get into the breeding blanket from the upper end of post 3, and the resin column after the regeneration flushing carries out the absorption exchange of next round.
The working temperature of each WS is 30 ℃.
Through one-period (20 hours), co-processing 80000ml Hydrocerol A destainer, obtain the 84800ml Hydrocerol A altogether from handing over liquid, said Hydrocerol A is from handing in the liquid, and citric acid content is 47.1% (m/v), SO
4 2-Content is 0.6ppm, Cl
-Content is 0.4ppm.Through calculating, the Hydrocerol A yield is 99.85%.
With respect to every ml Hydrocerol A destainer of handling, the amount of the sodium hydroxide solution of consumption is 0.625ml, and the consumption of deionized water is 0.5ml, and the consumption of tap water is 1ml.
Comparative Examples 1
With an operational cycle be example,
With 50000ml Hydrocerol A destainer with 2 column volumes/hour flow velocity and 1800g anionite-exchange resin (because intermittent type has principal post, auxilliary post and stand-by column from the skill of handing over; So play the principal post that has only of exchange interaction; Be the 600g resin) carried out Continuous Contact 25 hours; Make negatively charged ion except that citrate ion and resin generation exchange absorption in the citric acid solution, obtain Hydrocerol A from handing over liquid.Then with the saturated resin of 40000ml deionized water wash absorption, wherein the 4600ml effluent removes negatively charged ion, remaining 45400ml effluent conduct backfill next time usefulness with contact with resin again after the Hydrocerol A destainer mixes again.With the good resin of sodium hydroxide solution regeneration washing of 40000ml, 4 weight %, water rinse resin is extremely near neutral from the beginning with 70000ml in the back, carries out the absorption exchange of next round again.The working temperature of wherein, absorption, washing, regeneration and regeneration flushing is 30 ℃.
Obtain Hydrocerol A altogether from handing over liquid 54600ml, wherein, the content of Hydrocerol A is 45.1% (m/v), SO
4 2-Content is 1.0ppm, Cl
-Content is 0.8ppm.Through calculating, the Hydrocerol A yield is 98.5%.
Through 25 hours, can handle Hydrocerol A destainer 50L.
With respect to every ml Hydrocerol A destainer, the amount of the sodium hydroxide solution of consumption is 0.8ml, and the consumption of deionized water is 0.8ml, and the consumption of tap water is 1.4ml.
Result by embodiment 1-3 and Comparative Examples 1 can find out, uses of the present invention continuously in the friendship method, and the amount of the Hydrocerol A that unit time unit's resin obtains (total acid content) is 2.43 times of prior art, and the yield of Hydrocerol A has improved 1.35%; With respect to handling every ml Hydrocerol A destainer, the amount of the sodium hydroxide solution that Comparative Examples 1 consumes Duo 26.7% than embodiment 1-3, and the consumption of deionized water is many 67.7%, more than the consumption of tap water 30.8%; Above numerical value is MV and Comparative Examples 1 result relatively of embodiment 1-3.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be regarded as the disclosed content of the present invention equally.
Claims (14)
1. one kind removes the anionic method that contains in the citric acid solution continuously; It is characterized in that this method is carried out in moving separating device, said moving separating device comprises many group anion-exchange resin column groups; Every group of anion-exchange resin column group comprises the anion-exchange resin column of one or more parallel connections; Every group of anion-exchange resin column group comprises adsorption zone, washing section, breeding blanket and regeneration rinsing area successively and circularly through four functional zone, and the flushing of adsorbing successively, wash, regenerate and regenerate; Many groups anion-exchange resin column group that there is one group of anion-exchange resin column group in each WS or is connected in series
Wherein, There are two groups of anion-exchange resin column groups that are connected in series at least in said adsorption zone; And said contain citric acid solution successively with the anion-exchange resin column groups of contact that is in adsorption zone; Make the negatively charged ion except that citrate ion that contains in the citric acid solution be adsorbed on the anionite-exchange resin, be in the first anion-exchange resin column group of adsorption zone and reach the saturated back entering of absorption washing section.
2. method according to claim 1, wherein, at adsorption zone, said contact is carried out under the condition of 0.9-1.6 in the pH value.
3. method according to claim 1; Wherein, at adsorption zone, contain citric acid solution and introduce from the upper end that is in the first anion-exchange resin column group of adsorption zone; Flow out from the lower end that is in adsorption zone omega-anion-exchange resin column group, obtain Hydrocerol A from handing over liquid.
4. method according to claim 3, wherein, the anionic content except that citrate ion is below the 10ppm to said Hydrocerol A in the liquid from handing over.
5. method according to claim 1, wherein, at adsorption zone, the said flow velocity that contains citric acid solution be 0.5-8 times of column volume/hour.
6. method according to claim 1; Wherein, there are two groups of anion-exchange resin column groups that are connected in series at least in washing section, at washing section; Deionized water is introduced from the upper end that is in the first resin column group of washing section; Flow through successively and respectively organize the anion-exchange resin column group in this washing section, flow out, obtain the scrub stream fluid from the lower end that is in washing section omega-resin column group.
7. method according to claim 6 wherein, is introduced adsorption zone with said scrub stream fluid from the upper end that is in the first resin anion(R.A) post group of adsorption zone.
8. method according to claim 1; Wherein, there are two groups of anion-exchange resin column groups that are connected in series at least in the breeding blanket, in the breeding blanket; Basic soln is introduced from the lower end that is in the first resin column group in breeding blanket; Flow through successively and respectively organize the anion-exchange resin column group in this breeding blanket, flow out, obtain the recovery stream fluid from the upper end that is in breeding blanket omega-resin column group.
9. method according to claim 1; Wherein, there are two groups of anion-exchange resin column groups that are connected in series at least in the regeneration rinsing area, at the regeneration rinsing area; Deionized water is introduced from the upper end that is in the first resin column group of regeneration rinsing area; Flow through successively and respectively organize the anion-exchange resin column group in this regeneration rinsing area, flow out from the lower end that is in regeneration rinsing area omega-anion-exchange resin column group, the flushing flow fluid obtains regenerating.
10. method according to claim 9 wherein, is introduced the breeding blanket with said regeneration flushing flow fluid from the lower end that is in the first anion-exchange resin column group in breeding blanket.
11. according to any described method among the claim 1-10, wherein, the number that is in the anion-exchange resin column group of each functional zone is 2-8, the number of the anion-exchange resin column in every group of anion-exchange resin column group is 1-4.
12. according to any described method among the claim 1-10, wherein, the total exchange capacity of said anionite-exchange resin is more than or equal to 6.5mmol/g.
13. according to any described method among the claim 1-10, wherein, said anionite-exchange resin is the acrylic acid series weakly basic anion exchange resin.
14. according to any described method among the claim 1-10, wherein, be benchmark with the gross weight that contains citric acid solution, the said content that contains Hydrocerol A in the citric acid solution is 20-60 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210134609.9A CN102659567B (en) | 2012-05-03 | 2012-05-03 | Method for continuously removing anions from citric acid-containing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210134609.9A CN102659567B (en) | 2012-05-03 | 2012-05-03 | Method for continuously removing anions from citric acid-containing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659567A true CN102659567A (en) | 2012-09-12 |
| CN102659567B CN102659567B (en) | 2014-04-16 |
Family
ID=46769180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210134609.9A Active CN102659567B (en) | 2012-05-03 | 2012-05-03 | Method for continuously removing anions from citric acid-containing solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659567B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755756A (en) * | 2014-02-11 | 2014-04-30 | 江苏诚信制药有限公司 | Process system and process method for preparation of vitamin C ascorbyl glucoside |
| CN106904761A (en) * | 2017-04-14 | 2017-06-30 | 中冶赛迪工程技术股份有限公司 | A kind of absorption processing system and method |
| CN107628944A (en) * | 2017-11-02 | 2018-01-26 | 厦门福美科技有限公司 | The method and system of low-ester pectin and calcium citrate is extracted from passion fruit shell |
| CN111268757A (en) * | 2020-02-10 | 2020-06-12 | 西安蓝晓科技新材料股份有限公司 | Novel method for treating wastewater generated in caprolactam ammoximation process |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
| CN114314753A (en) * | 2021-12-27 | 2022-04-12 | 湖南金牛化工有限公司 | Alkali-saving type anion bed regeneration treatment method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190579A (en) * | 2011-03-21 | 2011-09-21 | 安徽丰原生物化学股份有限公司 | Method for treating citric acid-containing solution |
-
2012
- 2012-05-03 CN CN201210134609.9A patent/CN102659567B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190579A (en) * | 2011-03-21 | 2011-09-21 | 安徽丰原生物化学股份有限公司 | Method for treating citric acid-containing solution |
Non-Patent Citations (1)
| Title |
|---|
| 周勇: "柠檬酸(钠)清洁生产工艺的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755756A (en) * | 2014-02-11 | 2014-04-30 | 江苏诚信制药有限公司 | Process system and process method for preparation of vitamin C ascorbyl glucoside |
| CN103755756B (en) * | 2014-02-11 | 2015-07-08 | 江苏诚信药业有限公司 | Process system and process method for preparation of vitamin C ascorbyl glucoside |
| CN106904761A (en) * | 2017-04-14 | 2017-06-30 | 中冶赛迪工程技术股份有限公司 | A kind of absorption processing system and method |
| CN107628944A (en) * | 2017-11-02 | 2018-01-26 | 厦门福美科技有限公司 | The method and system of low-ester pectin and calcium citrate is extracted from passion fruit shell |
| CN107628944B (en) * | 2017-11-02 | 2023-10-24 | 厦门福美科技有限公司 | Method and system for extracting low-ester pectin and calcium citrate from passion fruit shells |
| CN111268757A (en) * | 2020-02-10 | 2020-06-12 | 西安蓝晓科技新材料股份有限公司 | Novel method for treating wastewater generated in caprolactam ammoximation process |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
| CN114314753A (en) * | 2021-12-27 | 2022-04-12 | 湖南金牛化工有限公司 | Alkali-saving type anion bed regeneration treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659567B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659568B (en) | Method for continuously removing cations out of solution containing citric acid | |
| CN102659567B (en) | Method for continuously removing anions from citric acid-containing solution | |
| US9233906B2 (en) | Purification of succinic acid from the fermentation broth containing ammonium succinate | |
| CN202516562U (en) | Continuous ion exchange device for production of decoloring and deacidifying fruit juice | |
| CN111039832B (en) | Method for producing taurine and method for removing impurities from reaction system for preparing taurine | |
| CN101224436A (en) | Ion exchange resin regeneration method | |
| LU505449B1 (en) | Sucrose decoloring method and system | |
| CN103374047A (en) | Method for separating and purifying high-purity 3,2'',6''-tri-N-acetyl-gentamicin C1a alkali (P1) | |
| CN105080624B (en) | A kind of ion exchange resin regeneration method | |
| CN103896762B (en) | A kind of purification process containing citric acid solution | |
| CN112174856B (en) | Purification production process of organic sulfonic acid | |
| CN104447909A (en) | Continuous-chromatography separating and purifying method of etimicin sulfate | |
| CN104098495A (en) | Method for improving caprolactam refining process | |
| CN104193663B (en) | A kind of process for refining of caprolactam | |
| CN111961856B (en) | Device for separating vanadium and rare earth elements from waste FCC catalyst | |
| CN102516065B (en) | Treatment method of solution containing citric acid | |
| CN102190579B (en) | Method for treating citric acid-containing solution | |
| CN211585316U (en) | System for continuously removing anions in 3-hydroxy-1, 3, 5-pentanedioic acid | |
| CN102260167A (en) | Treatment method of citric acid contained solution | |
| US2528047A (en) | Recovery of glutamic compounds from glutamine contained in an impure solution thereof | |
| CN114699801B (en) | Valve array type continuous ion exchange system for purification of red lactic acid | |
| CN100425618C (en) | Method for separating 5' nucleoside triphosphate continuously | |
| JPH0577400B2 (en) | ||
| CN100395252C (en) | Method for continuous separation of fructose-1,6-diphosphate | |
| CN107417514A (en) | A kind of method that citric acid is purified from citric acid solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tong Yi Inventor after: Zhang Junhua Inventor after: Xiong Jieqing Inventor after: Wang Jianguo Inventor after: Wang Hao Inventor after: Hu Fugui Inventor before: Zhang Junhua Inventor before: Xiong Jieqing Inventor before: Wang Jianguo Inventor before: Wang Hao Inventor before: Hu Fugui |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 233010 No. 1 COFCO Avenue, Anhui, Bengbu Patentee after: COFCO Biotechnology Co., Ltd Address before: 233010 No. 73, Daqing Road, Bengbu, Anhui Patentee before: COFCO Biochemistry (Anhui) Co., Ltd. |