CA2007126A1 - Process of separating acids from substrates containing salts and carbohydrates - Google Patents
Process of separating acids from substrates containing salts and carbohydratesInfo
- Publication number
- CA2007126A1 CA2007126A1 CA 2007126 CA2007126A CA2007126A1 CA 2007126 A1 CA2007126 A1 CA 2007126A1 CA 2007126 CA2007126 CA 2007126 CA 2007126 A CA2007126 A CA 2007126A CA 2007126 A1 CA2007126 A1 CA 2007126A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- acids
- ion exchange
- exchange resins
- process according
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
ABSTRACT
Proposed is a process of separating acids from substrates containing salts and carbohydrates in which the substrates are made to pass over resins adsorptively removing the acids from the substrate and the acids are subsequently separated from the resins by elution, with the particular feature that basic ion exchange resins are used as the resins.
Proposed is a process of separating acids from substrates containing salts and carbohydrates in which the substrates are made to pass over resins adsorptively removing the acids from the substrate and the acids are subsequently separated from the resins by elution, with the particular feature that basic ion exchange resins are used as the resins.
Description
2nn7~26 The invention relates to a process of separating acids from substrates contain1ng salts and carbohydrates, in which the substrates are made to pass over res1ns adsorptively removing the acids from the substrates and the aclds are subsequently separated from the resins by e1ut10n.
Organ1c and inorganic ac1ds are used in many branches of industry:
1n appl1cat10ns 1n the fields of pharmaceut1cals and foodstuffs, but also when used 1n pur1fying chemicals, these must be of part1cularly h1gh qual1ty.
~ p to now, proposed pur1f1cation methods for ac~ds, ln addltion to prec1p1tat10n as heavy metal salt or alkaline earth metal salt, have been 11qu1d/11quid extract10n and the format10n of volat11e der1vat1ves (for 1nstance methyl esters). All these methods are also used on an 1ndustr1al scale for the process1ng of techn~cally 1mportant u1ds such as lact1c ac1d, mal1c ac1d, succ1n1c ac1d, tartar1c ac1d, c1tr1c ac1d, glucon1c ac1d and phosphoric ac1d. However, the processes ment10ned have ser10us drawbacks. The pur1ficat10n methods provid1ng or the ac1d to be 1solated v1a an 1nsoluble salt consume large amounts ;;
of aux111ary chem1cals. ln most cases, a spar1ng1y soluble calc1um sa1t ~s formed and subsequent1y reacted with sulfur1c ac1d to form the free ac1d and an equ1molar amount of gypsum. ln addit10n to the j expense for 11me and su1fur1c ac1d, the gypsum formed must be d1scarded. Pur~f1cat10n methods based on the d1stribut10n between two mutua11y 1nsoluble phases and processes 1n wh1ch the acid 1s reacted to a more volat11e derivat1ve operate w1th large amounts of organ1c solvents const~tuting a safety and environmenta1 hazard.
The extraction of lactic acid is disclosed in EP O 159 585; DE-OS
':;'':,' '~,
Organ1c and inorganic ac1ds are used in many branches of industry:
1n appl1cat10ns 1n the fields of pharmaceut1cals and foodstuffs, but also when used 1n pur1fying chemicals, these must be of part1cularly h1gh qual1ty.
~ p to now, proposed pur1f1cation methods for ac~ds, ln addltion to prec1p1tat10n as heavy metal salt or alkaline earth metal salt, have been 11qu1d/11quid extract10n and the format10n of volat11e der1vat1ves (for 1nstance methyl esters). All these methods are also used on an 1ndustr1al scale for the process1ng of techn~cally 1mportant u1ds such as lact1c ac1d, mal1c ac1d, succ1n1c ac1d, tartar1c ac1d, c1tr1c ac1d, glucon1c ac1d and phosphoric ac1d. However, the processes ment10ned have ser10us drawbacks. The pur1ficat10n methods provid1ng or the ac1d to be 1solated v1a an 1nsoluble salt consume large amounts ;;
of aux111ary chem1cals. ln most cases, a spar1ng1y soluble calc1um sa1t ~s formed and subsequent1y reacted with sulfur1c ac1d to form the free ac1d and an equ1molar amount of gypsum. ln addit10n to the j expense for 11me and su1fur1c ac1d, the gypsum formed must be d1scarded. Pur~f1cat10n methods based on the d1stribut10n between two mutua11y 1nsoluble phases and processes 1n wh1ch the acid 1s reacted to a more volat11e derivat1ve operate w1th large amounts of organ1c solvents const~tuting a safety and environmenta1 hazard.
The extraction of lactic acid is disclosed in EP O 159 585; DE-OS
':;'':,' '~,
- 2 - :
.~
~ , ~ æ{~7 ~L~2 32 22 837 presents a process in which lactic acid is purified by the formation of methyl lactate.
Methods of the pur1f1cat10n of citrlc acld by means of liquid/liquid extract10n are d1sclosed in US-PS 4 251 671 and 4 334 095 as well as 1n AT-PS 382 364.
A process of 1solat1ng citric acid from fermentat10n broths by the format10n of spar1ngly soluble salts is disclosed in US-PS 2 810 755.
Further processes of extract1ng tartar1c actd,c1tric acid, mal1c ac1d and lact1c ac1d were proposed 1n DE-OS 1 443 538 and EP O 049 429.
Methods of pur1fytng phosphor1c acid are disclosed 1n DE-OS 23 20 ~77 and 17 67 442 and 1n DE-AS 23 21 751.
for c1tr1c ac1d, EP-A O 151 470 further d1scloses a process where1n f1rst, h1gher molecular compounds are separated from the contam1nated c1tr1c ac1d solut10n by means of ultraf11trat10n; impur1t1es st111 present are subsequently removed by adsorpt10n on non-ionogen1c restns of large spec1f1c surface, the substant1a11y more polar c1tr1c acid rema1n1ng unbound.
As a further pur1ficat10n measure, US-PS 4 720 579 d1scloses the adsorpt10n of citr1c ac1d on neutral, non-10nogen1c, macroret1cular, water-1nsoluble res1ns. The eluant used 1s water or a mixture of water and acetone. The process 1s capable of separating salts and carbohydrates from the citric acid.
The present 1nvention is based on the state of the art represented by US-PS 4 720 579. On principle, the ob~ect is to pass substrates conta1n1ng acids, salts and carbohydrates over resins selectively , ~ .
.i .
. .
:i;
.j .
2~C~7~l26 acting as adsorbers for the acid;, while the other components of the substrates are passed on. The acids whose purification or recovery is intended are subsequently obtained by elution of the charged res1ns.
It was now surprisingly found that basic ion exchange resins are su1table for the chromatographic isolation and/or purification of ac1ds 1n general, 1.e. as well as of organic as of inorganic acids, wlth fru1t ac1ds to be particularly mentioned among the carboxylic ac1ds. Of the typ1cal ac1dic organic edible acids , tartaric acid, c1tr1c acld, mal1c ac1d, fumaric acid and succinic acid are usually des1gnated as fruit ac1ds 1n 11terature.
The ac1ds are adsorbed selectively and reversibly and the ;~
pur1f1cat10n effects obta1ned and the charging capac1ty of the resins are substant1ally h19her than those of the non-ionogen1c resins.
The process accord1ng to the invent10n of chromatographically pur1fy1ng or separat1ng acids is thus ma1nly characterized 1n that bas1c 10n exchange res1ns are used for the separation.
The use of bas1c 10n exchange resins for the purificat10n of fru1t ac1ds 1s known per se 1n processes 1n wh1ch the fru1t ac1ds themse1ves pass through the 10n exchanger bed while impurities in the substrate such as stronger ac1ds or salts are retained on the resin by 10n exchange. The 10n exchange resins are regenerated in this ;-, known process pr10r to the break-through of the impur1ties , the charge be1ng removed. ; DD-PS 203 533 discloses an ion exchange process for the recovery of carboxylic and oxycarboxylic acids from their salt solutions conta1ning foreign salts in which the salts are first converted to ~-~
~., 4 - ;~
~)07~26 ac1ds via cation exchangers in H~-form. The result is a m~xture of carboxylic acids and foreign acids. A fraction of this mixture of low concentrat10n is then used for first charg~ng an anion exchanger present 1n the base or hydroxyl form , thus substantially converting 1t to the carboxylic acid form. A higher concentrated fraction of the ac1d m1xture obtained in the decationization step is then passed over the 10n exchanger charged with acid, with the acid to be recovered pass1ng the res1n bed unhampered and merely the stronger foreign anions (ch10r1de be1ng ment10ned) be1ng bound to the resin by 10n exchange.
DE-OS 29 31 759 relates to the separat10n of citric ac1d from a m1xture w1th oxallc acid and n~tric acid ln wh1ch this mixture is passed over an anion exchanger wh1ch was optionally previously equillbrated w1th c1tr1c ac1d. The 10n exchanger withdraws nitr1c acid and oxal1c ac1d from th1s m1xture by ion echange wh11e the c1tr1c acid passes through the column.
DE-OS 25 43 332 relates to a process of separat1ng maleic acid 1mpur1t1es from synthet1c tartar1c acid wh1ch 1s passed over bas1c an10n exchangers present 1n hydroxyl or tartrate form. The 10n exchanger aga1n w1thdraws the stronger maleic ac1d from the mixture, wh11e the tartarlc acid to be recovered passes through the column.
In the process accord1ng to the invention, the acids to be recovered or pur1f1ed are not recovered by 10n exchange, but instead adsorptively bound to the res1ns and recovered from there by elution.
The bas1c 10n exchange resins are conveniently used for the 1solat10n and /or pur1fication of ac1ds of a PKS value within a range of from 1.2 to 4.8, preferably of from 2.1 to 3.9.
The resins are preferably employed in acid-charged form. According . ':
, . i '~ .
2~ 7 ~L
tQ ~he ~nventiQn~ the resin is conveniently charged by means of an anlon to which the resin has an equal, or higher affinity than, to thè acid to be purif1ed. The charging of the resin does not have to be carr1ed out as an expliclt operat10n, in many cases, it automatically occurs 1n the course of extended use. Particularly used are bas1c 10n exchange res1ns charged wlth hydrochloric acid, nitric acid, phosphoric acid, citric acid or sulfuric ac1d, preferably w1th sulfuric ac1d~
The an10n exchange res1ns according to the invention can be strongly or weakly basic and of gel or macroreticular structure. The ion exchangers may among others contaln a styrene/d1vinyl benzene basis or a cross-linked acrylic resin bas1s.
The elut10n can be carried out with water in a known manner; 1t 1s preferred, however, to use a diluted acid, in particular sulfuric ac1d 1n a concentrat10n range of from 0 to 1 percent. Low pH values known to be beneficial for other processes are also convenient for the process according to the 1nvention. The elution temperature can be selected between room temperature and the stabil~zation threshold temperature of the res1n, the elution is preferably carrled out at a temperature preventing the microbial contamination of the resin The process 1s preferably carried out in a quasi-continuous apparatus (s1mulated mov1ng bed), although fully continuous or batch operation 1s also poss1ble.
The 1nvent10n 1s expla1ned 1n the follow1ng by means of examples The res1ns used are conventional, commerc1ally available products accord1ng to the following table:
~,~
- 6 - `
~,' :::
.~ .
'', . :
~007~26 Des~gnatlon Polymer Basis Active Group Type Manufacturer AMBERLITE XAD-4 polystyrene - O Rohm & Haas AMBERLITE IRA904 styrene/DVB amine --- Rohm & Haas AMBERILTE IRA900 styrene/DVB amine --- Rohm & Haas AMBERLITE IRA958 acrylic/DVB amine --- Rohm & Haas AMBERLITE IRA93 styrene/DVB amlne - Rohm & Haas AMBERLITE IRA67 acrylic amine - Rohm & Haas AMBERLITE IRA35 acrylic/DVB amine - Rohm & Haas LEWATIT MP-64 polystyrene amine - Bayer LEWAtIT MPSOOA polystyrene amine -- Bayer DOWE~ ~GR2 epoxy amine amine - Dow Chemical RELITE MG1 acrylic/DVB polyamine - Tanatex O ..... non-ionogenic - ..... weakly bas~c -- ..... limited strongly basic --- .......... strongly basic Following complete regeneration by means of 4 percent NaOH, the an10n exchange resins were converted to the sulfate form by means of 10 percent sulfuric ac~d and conditioned by means of 0.1 percent sulfuric acid. The resins thus prepared were charged into columns of 25 mm diameter and 800 mm length. Following the inject~on of 5 ml of a solution consisting of 40 percent citric acid and 10 percent maltose ln water, elution was carried out with 15 ml/min 0.1 percent sulfuric acid. The column temperature was ad~usted to 80C by means of a c1rcul~t~on thermost~t. The eluate concentrations were determiend ', ~ 7~L~6 by measuring the refractive index. Under these conditions, maltose and citric acid were completely separated on nearly all the res~ns.
The table shows the retention volumes of maltose and citr~c acid.
Resln Elution Volume Elution Volume Maltose Citric Ac~d (ml) (ml) ;;
AMBERLITE IRA 900 270 911 ~;AMBERLITE IRA 958 270 656 AMBERLITE lRA 93 SP 338 806 AMBERLITE IRA 35 296 544 ;~LEWATIT MP 64 341 731 WWEX WGR 2 no separation possible RELlTE MG 1 no separat1On possible As descr1bed 1n Examp1e 1, a column was packed with AMBERLITE ;~
IRA 67 and equllbrated w1th a flow of 30 ml/m1n of 0.1 percent sulfur1c ac1d. The temperature of the column was ad~usted to 75C. The exctusion volume of the resin was determined by in~ection of 1 ml of a 5 ~'^i percent Dextran T10 solution . It can be assumed that a high molecular, uncharged substance w111 not be retained under these condlt1Ons. ;, The exclusion volume was calculated as follows ;;
,.', ,~ , I - 8 - ~
',,
.~
~ , ~ æ{~7 ~L~2 32 22 837 presents a process in which lactic acid is purified by the formation of methyl lactate.
Methods of the pur1f1cat10n of citrlc acld by means of liquid/liquid extract10n are d1sclosed in US-PS 4 251 671 and 4 334 095 as well as 1n AT-PS 382 364.
A process of 1solat1ng citric acid from fermentat10n broths by the format10n of spar1ngly soluble salts is disclosed in US-PS 2 810 755.
Further processes of extract1ng tartar1c actd,c1tric acid, mal1c ac1d and lact1c ac1d were proposed 1n DE-OS 1 443 538 and EP O 049 429.
Methods of pur1fytng phosphor1c acid are disclosed 1n DE-OS 23 20 ~77 and 17 67 442 and 1n DE-AS 23 21 751.
for c1tr1c ac1d, EP-A O 151 470 further d1scloses a process where1n f1rst, h1gher molecular compounds are separated from the contam1nated c1tr1c ac1d solut10n by means of ultraf11trat10n; impur1t1es st111 present are subsequently removed by adsorpt10n on non-ionogen1c restns of large spec1f1c surface, the substant1a11y more polar c1tr1c acid rema1n1ng unbound.
As a further pur1ficat10n measure, US-PS 4 720 579 d1scloses the adsorpt10n of citr1c ac1d on neutral, non-10nogen1c, macroret1cular, water-1nsoluble res1ns. The eluant used 1s water or a mixture of water and acetone. The process 1s capable of separating salts and carbohydrates from the citric acid.
The present 1nvention is based on the state of the art represented by US-PS 4 720 579. On principle, the ob~ect is to pass substrates conta1n1ng acids, salts and carbohydrates over resins selectively , ~ .
.i .
. .
:i;
.j .
2~C~7~l26 acting as adsorbers for the acid;, while the other components of the substrates are passed on. The acids whose purification or recovery is intended are subsequently obtained by elution of the charged res1ns.
It was now surprisingly found that basic ion exchange resins are su1table for the chromatographic isolation and/or purification of ac1ds 1n general, 1.e. as well as of organic as of inorganic acids, wlth fru1t ac1ds to be particularly mentioned among the carboxylic ac1ds. Of the typ1cal ac1dic organic edible acids , tartaric acid, c1tr1c acld, mal1c ac1d, fumaric acid and succinic acid are usually des1gnated as fruit ac1ds 1n 11terature.
The ac1ds are adsorbed selectively and reversibly and the ;~
pur1f1cat10n effects obta1ned and the charging capac1ty of the resins are substant1ally h19her than those of the non-ionogen1c resins.
The process accord1ng to the invent10n of chromatographically pur1fy1ng or separat1ng acids is thus ma1nly characterized 1n that bas1c 10n exchange res1ns are used for the separation.
The use of bas1c 10n exchange resins for the purificat10n of fru1t ac1ds 1s known per se 1n processes 1n wh1ch the fru1t ac1ds themse1ves pass through the 10n exchanger bed while impurities in the substrate such as stronger ac1ds or salts are retained on the resin by 10n exchange. The 10n exchange resins are regenerated in this ;-, known process pr10r to the break-through of the impur1ties , the charge be1ng removed. ; DD-PS 203 533 discloses an ion exchange process for the recovery of carboxylic and oxycarboxylic acids from their salt solutions conta1ning foreign salts in which the salts are first converted to ~-~
~., 4 - ;~
~)07~26 ac1ds via cation exchangers in H~-form. The result is a m~xture of carboxylic acids and foreign acids. A fraction of this mixture of low concentrat10n is then used for first charg~ng an anion exchanger present 1n the base or hydroxyl form , thus substantially converting 1t to the carboxylic acid form. A higher concentrated fraction of the ac1d m1xture obtained in the decationization step is then passed over the 10n exchanger charged with acid, with the acid to be recovered pass1ng the res1n bed unhampered and merely the stronger foreign anions (ch10r1de be1ng ment10ned) be1ng bound to the resin by 10n exchange.
DE-OS 29 31 759 relates to the separat10n of citric ac1d from a m1xture w1th oxallc acid and n~tric acid ln wh1ch this mixture is passed over an anion exchanger wh1ch was optionally previously equillbrated w1th c1tr1c ac1d. The 10n exchanger withdraws nitr1c acid and oxal1c ac1d from th1s m1xture by ion echange wh11e the c1tr1c acid passes through the column.
DE-OS 25 43 332 relates to a process of separat1ng maleic acid 1mpur1t1es from synthet1c tartar1c acid wh1ch 1s passed over bas1c an10n exchangers present 1n hydroxyl or tartrate form. The 10n exchanger aga1n w1thdraws the stronger maleic ac1d from the mixture, wh11e the tartarlc acid to be recovered passes through the column.
In the process accord1ng to the invention, the acids to be recovered or pur1f1ed are not recovered by 10n exchange, but instead adsorptively bound to the res1ns and recovered from there by elution.
The bas1c 10n exchange resins are conveniently used for the 1solat10n and /or pur1fication of ac1ds of a PKS value within a range of from 1.2 to 4.8, preferably of from 2.1 to 3.9.
The resins are preferably employed in acid-charged form. According . ':
, . i '~ .
2~ 7 ~L
tQ ~he ~nventiQn~ the resin is conveniently charged by means of an anlon to which the resin has an equal, or higher affinity than, to thè acid to be purif1ed. The charging of the resin does not have to be carr1ed out as an expliclt operat10n, in many cases, it automatically occurs 1n the course of extended use. Particularly used are bas1c 10n exchange res1ns charged wlth hydrochloric acid, nitric acid, phosphoric acid, citric acid or sulfuric ac1d, preferably w1th sulfuric ac1d~
The an10n exchange res1ns according to the invention can be strongly or weakly basic and of gel or macroreticular structure. The ion exchangers may among others contaln a styrene/d1vinyl benzene basis or a cross-linked acrylic resin bas1s.
The elut10n can be carried out with water in a known manner; 1t 1s preferred, however, to use a diluted acid, in particular sulfuric ac1d 1n a concentrat10n range of from 0 to 1 percent. Low pH values known to be beneficial for other processes are also convenient for the process according to the 1nvention. The elution temperature can be selected between room temperature and the stabil~zation threshold temperature of the res1n, the elution is preferably carrled out at a temperature preventing the microbial contamination of the resin The process 1s preferably carried out in a quasi-continuous apparatus (s1mulated mov1ng bed), although fully continuous or batch operation 1s also poss1ble.
The 1nvent10n 1s expla1ned 1n the follow1ng by means of examples The res1ns used are conventional, commerc1ally available products accord1ng to the following table:
~,~
- 6 - `
~,' :::
.~ .
'', . :
~007~26 Des~gnatlon Polymer Basis Active Group Type Manufacturer AMBERLITE XAD-4 polystyrene - O Rohm & Haas AMBERLITE IRA904 styrene/DVB amine --- Rohm & Haas AMBERILTE IRA900 styrene/DVB amine --- Rohm & Haas AMBERLITE IRA958 acrylic/DVB amine --- Rohm & Haas AMBERLITE IRA93 styrene/DVB amlne - Rohm & Haas AMBERLITE IRA67 acrylic amine - Rohm & Haas AMBERLITE IRA35 acrylic/DVB amine - Rohm & Haas LEWATIT MP-64 polystyrene amine - Bayer LEWAtIT MPSOOA polystyrene amine -- Bayer DOWE~ ~GR2 epoxy amine amine - Dow Chemical RELITE MG1 acrylic/DVB polyamine - Tanatex O ..... non-ionogenic - ..... weakly bas~c -- ..... limited strongly basic --- .......... strongly basic Following complete regeneration by means of 4 percent NaOH, the an10n exchange resins were converted to the sulfate form by means of 10 percent sulfuric ac~d and conditioned by means of 0.1 percent sulfuric acid. The resins thus prepared were charged into columns of 25 mm diameter and 800 mm length. Following the inject~on of 5 ml of a solution consisting of 40 percent citric acid and 10 percent maltose ln water, elution was carried out with 15 ml/min 0.1 percent sulfuric acid. The column temperature was ad~usted to 80C by means of a c1rcul~t~on thermost~t. The eluate concentrations were determiend ', ~ 7~L~6 by measuring the refractive index. Under these conditions, maltose and citric acid were completely separated on nearly all the res~ns.
The table shows the retention volumes of maltose and citr~c acid.
Resln Elution Volume Elution Volume Maltose Citric Ac~d (ml) (ml) ;;
AMBERLITE IRA 900 270 911 ~;AMBERLITE IRA 958 270 656 AMBERLITE lRA 93 SP 338 806 AMBERLITE IRA 35 296 544 ;~LEWATIT MP 64 341 731 WWEX WGR 2 no separation possible RELlTE MG 1 no separat1On possible As descr1bed 1n Examp1e 1, a column was packed with AMBERLITE ;~
IRA 67 and equllbrated w1th a flow of 30 ml/m1n of 0.1 percent sulfur1c ac1d. The temperature of the column was ad~usted to 75C. The exctusion volume of the resin was determined by in~ection of 1 ml of a 5 ~'^i percent Dextran T10 solution . It can be assumed that a high molecular, uncharged substance w111 not be retained under these condlt1Ons. ;, The exclusion volume was calculated as follows ;;
,.', ,~ , I - 8 - ~
',,
3 :
.. .
' :~
.; ...... , .. ,., .. ,,,., .. ,.- ,.. . .. , ., ,'~
7~L26 T.
e - ~--V
Fl Ttr ........... retention time of Dextran in seconds V ............. column volume in ml Fl ............ f10w ~n ml . s 1 F'rec~sely 1 ml of var~ous substrates was now ~ntroduced ~nto the medlum flow by means of a "drag" in~ector and detected at the column exit v~a the refractive index. The time up to the occurrence of the maxlmum concentration in the eluate and the width of the peak at half he1ght were measured. These data were used for calculat~ng the separation stage number and the distribution coefficient:
Tm~u--T--T
T~
n-16~ In ~ 2) d2 u1~ Tm~
K- --------_-_______ (1-e) ~ z T ...... retent~on time of substance in seconds n ...... separatlon stage number of column d ...... w1dth of substance peak at half height in seconds u ...... area-related flow ~n mlts . crn2 z ...... column length in cm K ...... distribution coefficient of substance 7~6 :, The follow1ng table shows the results obtained:
Substance Concentrat~on Separat1On Stage D~str1but1On ( % by we~ght) Number Coeff1cient n K .:
Sod1um sulfate 10 9.09 0.219 ..
10.11 0.262 ~.:
Maltose 10 2.25 0.149 2.17 0.146 `
2.25 0.149 ~
2.25 0.149 ;;
Glucose 10 6.24 0.362 6.02 0.356 5.81 0.349 Glucon1c Ac1d 10 6.46 0.541 ~
6.22 0.514 ;.
6.22 0.514 ~
Lact1c Ac1d 10 15.11 0.673 ~;.
14.07 0.663 C1tr1c Acid 10 17.50 1.864 18.06 1.815 16.48 1.748 17.25 1.775 ;.~
,'.,"
These values clearly show that a purif~cat~on of c1tric acid under ~.
the selected conditions is poss1ble. The data also show a separat1On of c1tric ac1d - glucon1c ac~d and between c1tric ac~d - lact~c "
ac1d. .
. ~' ~ - 10 -'".', :i ;
!~
~ ~007~26 Example 2 was repeated at a temperature of 60C.
Substance Concentrat1OnSeparat1On Stage D1str1but1On (% by weight) Number Coeff1cient n K
Sodlum Sulfate 10 7.70 0.192 8.71 0.242 Maltose 10 1.62 0.110 1.70 0.112 Glucose 10 4.93 0.322
.. .
' :~
.; ...... , .. ,., .. ,,,., .. ,.- ,.. . .. , ., ,'~
7~L26 T.
e - ~--V
Fl Ttr ........... retention time of Dextran in seconds V ............. column volume in ml Fl ............ f10w ~n ml . s 1 F'rec~sely 1 ml of var~ous substrates was now ~ntroduced ~nto the medlum flow by means of a "drag" in~ector and detected at the column exit v~a the refractive index. The time up to the occurrence of the maxlmum concentration in the eluate and the width of the peak at half he1ght were measured. These data were used for calculat~ng the separation stage number and the distribution coefficient:
Tm~u--T--T
T~
n-16~ In ~ 2) d2 u1~ Tm~
K- --------_-_______ (1-e) ~ z T ...... retent~on time of substance in seconds n ...... separatlon stage number of column d ...... w1dth of substance peak at half height in seconds u ...... area-related flow ~n mlts . crn2 z ...... column length in cm K ...... distribution coefficient of substance 7~6 :, The follow1ng table shows the results obtained:
Substance Concentrat~on Separat1On Stage D~str1but1On ( % by we~ght) Number Coeff1cient n K .:
Sod1um sulfate 10 9.09 0.219 ..
10.11 0.262 ~.:
Maltose 10 2.25 0.149 2.17 0.146 `
2.25 0.149 ~
2.25 0.149 ;;
Glucose 10 6.24 0.362 6.02 0.356 5.81 0.349 Glucon1c Ac1d 10 6.46 0.541 ~
6.22 0.514 ;.
6.22 0.514 ~
Lact1c Ac1d 10 15.11 0.673 ~;.
14.07 0.663 C1tr1c Acid 10 17.50 1.864 18.06 1.815 16.48 1.748 17.25 1.775 ;.~
,'.,"
These values clearly show that a purif~cat~on of c1tric acid under ~.
the selected conditions is poss1ble. The data also show a separat1On of c1tric ac1d - glucon1c ac~d and between c1tric ac~d - lact~c "
ac1d. .
. ~' ~ - 10 -'".', :i ;
!~
~ ~007~26 Example 2 was repeated at a temperature of 60C.
Substance Concentrat1OnSeparat1On Stage D1str1but1On (% by weight) Number Coeff1cient n K
Sodlum Sulfate 10 7.70 0.192 8.71 0.242 Maltose 10 1.62 0.110 1.70 0.112 Glucose 10 4.93 0.322
4.57 0.312 G1ucon1c Ac1d 10 5.33 0.489 4.85 0.483 C1tr1c Ac1d 10 13.83 1.743 12.69 1.617 Example 2 was repeated at a temperature of 90C.
~ 2 6 Substance Concentration Separation Stage Distribution (% by we~ght) Number Coeffic~ent n K
Sod1um Sulfate 10 11.09 0.227 12.39 0.280 Ma1tose 10 2.97 0.183 3.06 0.186 Glucose 10 8.76 0.404 8.22 0.392 Glucon1c Acid 10 10.96 0.628 9.80 0.594 Lact1c Ac1d 10 18.99 0.776 17.77 0.752 C1tr1c Ac1d 10 30.00 2.514 25.10 2.147 A compar1son of the results of Examples 3 and 4 shows the favorable 1nfluence of the temperature on the separation.
.
A polypropylene column with a d1ameter of 27 mm and a length of 146 mm was packed with AMBERLITE IRA-67 in the sulfate form. At a temperature of 28C, 4.97 ml/min 0.1 percent sulfuric acid were pumped over the column. Then, 0.5 ml hydrofluoric ac~d or phosphoric acid were ln~ected 1nto the med1um flow. The discharge of the substances from the column was detected by means of a conduct1vity detector.
~, ,, , .~
x~n7l26 Substance ConcentrationSeparation Stage Distribution (X by weight)Number Coefficient n K
Hydrofluor1c Ac1d 10 15.45 1.06 Phosphor1c Ac1d 40 15.01 3.14 Th1s example demonstrates the possibility to purify inorganic acids as we11.
Example 2 was repeated w1th 0.1 percent sulfurlc acid as flow med~um and IRA900 as 1On exchanger at a temperature of 75C.
Substance ConcentrationSeparat1On Stage Distribut1On (% by we19ht) Number Coefflcient n K
Sod1um Sulfate 10 6.80 0.319 8.01 0.358 Maltose 10 2.77 0.316 2.77 0.309 61ucose 10 6.24 0.485 6.24 0.485 Glucon1c Ac1d 10 7.02 0.726 6.43 0.717 Lact1c Ac1d 10 16.73 1.036 16.41 1.043 Tartar1c Acid 10 19.47 2.909 Mal1c Ac1d 10 16.86 2.212 Itacon1c Ac1d 10 15.96 3.095 r` ~ 13 ~ .
.~ , . . .
7~26 Example 7 Example 2 was repeated with water as the flow medium and IRA900 as lon exchanger at a temperature of 75C.
Substance Concentrat~on Separat~on Stage D~str~but~on (X by we19ht) Number Coeff~cient n K
Sod1um Sulfate 10 7.70 0.343 7.90 0.370 Maltose 10 3.09 0.340 2.96 0.340 Glucose 10 7.62 0.545 7.03 0.53 Lact1c Ac1d 40 35.47 2.549 EXAMPLE 8: ~
.:
A sem1cont~nuous chromatography plant cons1sting of ten columns ~d1ameter 25 mm, length 1600 mm) was f111ed w~th AMBERLITE IRA900 ln the sulfate form. The plant ~s layed out ~n such a manner that the columns are connected by means of p1pe condu~ts to form a rlng. Th~s r1ng 11ne is connected between the columns to four supply 11nes v1a valves. These supply 11nes are crude product ~nlet, eluant inlet, product outlet and raff1nate outlet. The flows ~n the plant are kept constant by means of adjustable rec~procating pumps. In th1s process, there are always exactly four valves open and div~de the ring formed of columns into four zones. These zones are advanced ~n flow d~rect~on by one column after predeterm~ned per~ods by an ~n-process computer.
~", .', .
,, , .. , ., .
2~)7~26 ,, These sw1tch1ng operations simulate a resin flow counter to the flow direct10n, thls is why it is designated as "simulated moving bed"
process 1n 11terature.
.
~ :::
The dtv1sion 1nto zone was effected according to the fo110w1ng scheme:
Zone 1 2 columns Zone 2 3 columns Zone 3 4 columns I Zone 4 1 column ¦ 8 ml of crude product and 32 ml of water per m1nute were 1ntroduced and 16 ml of product or 24 ml of raffinate were withdrawn during th1s t1me. The temperature of the plant was kept constant at 70C. The 1nternal c1rculat10n volume in the column r1ng was ad~usted to 4 ml/min. The valves were sw1tched every 1550 seconds. A lactic ac1d fermentat10n mash concentrated to approximately 40 percent was _ 1 5 ." ., . ~
:
1ntroduced 1nto this plant. A purified lactic acid with a yield of more than 95 percent was recovered. The raffinate contained, ~n addition to lact1c ac1d traces, colorants, carbohydrates and salts, above all polymers which can cons~derably 1nterfere with lactic ac1d production.
The purlfy~ng effect 1s also shown by the h~gh chemlcal oxygen consumpt10n of the raffinate of 13.5 9/l. The follow1ng table shows a compar1son of lact1c ac1d before and after chromatograph1c separat10n:
before after ,, - .
Lact1c Ac1d (%) 40.52 19.53 Color (405 nm, 1 cm) 1.94 0.43 Sulfate (X) 1.78 0.03 Chlor1de (mg/kg) 330 23 Sod1um (mg/kg) 7820 330 Magnes1um (mg/kg) 7 0 Iron (mg/kg) 27 5 EXAMPLE 9:
"
A sem1-1ndustr1al chromatography plant cons1st1ng of twelve columns (d1ameter 0.5 m, length 2.0 m) was f111ed w1th AMBERLITE IRA-67. The res1n was converted to the sulfate form by flush~ng with 0.1 percent sulfuric ac1d. The columns were connected as shown 1n the followlng ~ d1agram:
,1 - 16 -f ~ :
,1 ' ~, .
Z007~Z6 contaminated solution -- _ eluant ~ _ purified ~ contamina~s ~
' ~
At a temperature of 75C, 215 l/h of a citric acid fermentation broth concentrated to approx1mately 45 perent by weight were 1ntroduced and 825 l/h of 0.1 percent sulfuric acid were added as eluant. At the same t1me, 500 l/h of pur1f1ed citr k ac1d solution (product) and 533 l/h of a solut1On containing the impurities (raff1nate) were w1thdrawn. 192 1/h were c1rculated in the column r1ng, the 1nlet and outlet s1tes were sw1tched by one column in flow direction every 1800 seconds.
An analys1s of the so1utions added and withdrawn yielded the follow1ng values:
' .~ ' ,. .:
.~. ~,.
20~7~ 6 Fermentation Broth Product Rafffinate Cltr~c Acid 43.45 ~ 22.36 X 0.02 %
Glucose 0.25 % 0.00 % 0.16 X
Fructose 0.10 X 0.00 % 0.11 %
Ma1tose ~
Isomaltose 1.40 % 0.00 % 0.80 %
Total Sugar 4.60 X 0.03 % 2.35 %
Sulfate 0.98 % 0.27 % 0.43 %
Chlor~de 110 ppm 16 ppm 42 ppm Iron 8 ppm 2 ppm 2 ppm Potassium 370 ppm 0 ppm 190 ppm Sodlum 55 ppm 0 ppm 29 ppm Ca1c1um 20 ppm 1 ppm 8 ppm Magneslum 120 ppm 0 ppm 60 ppm Density 1.27 g/ml 1.07 g/ml1.00 g/ml The productivity of the plant amounts to 2.87 tons (metr~c) of citric acld anhydrate per day, the yield of 99.9 percent is substantially better than those of the known purificat~on processes for citric ac1d. It is evident that virtually all impurities, whether cationic, I anionlc or uncharged, are separated.
' EXAMPLE 10:
!: Example 9 was repeated with crude phosphoric acid. A prefiltered ~ wet phosphoric acid (green acid) of a concentration of 37 percent¦ of P205 was introduced. The columns were switched in flow direction ':
d ''~
.
2007~26 every 1500 seconds. An analysis of the samples of product and raffinate in the equilibrated state showed the following values:
Product Raff~nate t1trable ac1d as P205 15.60 1.90 X
color (405 nm, 1 cm) 0.047 1.486 The y1eld of phosphor1c ac1d amounted to 89.9 percent, a comparison of cat1On charge before and after chromatographic separat1On shows the h1gh pur~f1cat1On performance of the system (all concentrat~ons based on 100 percent P205).
beforeafter Magnes1um 20800 42 mg/kg Calc1um 358 9 mg/kg Alum1num 3390 410 mg/kg Iron 4620 1200 mg/kg ;.
Z1nc 855 15 mg/kg . :
Chrom1um 614 102 mg/kg .
Copper 29 0 mg/kg N1ckel 56 0 mg/kg Manganese 21 0 mg/kg Cadm1um 23 0 mg/kg ~ .,, ~ - 19 -,~ I ...
.'~ ~, .
~ 2 6 Substance Concentration Separation Stage Distribution (% by we~ght) Number Coeffic~ent n K
Sod1um Sulfate 10 11.09 0.227 12.39 0.280 Ma1tose 10 2.97 0.183 3.06 0.186 Glucose 10 8.76 0.404 8.22 0.392 Glucon1c Acid 10 10.96 0.628 9.80 0.594 Lact1c Ac1d 10 18.99 0.776 17.77 0.752 C1tr1c Ac1d 10 30.00 2.514 25.10 2.147 A compar1son of the results of Examples 3 and 4 shows the favorable 1nfluence of the temperature on the separation.
.
A polypropylene column with a d1ameter of 27 mm and a length of 146 mm was packed with AMBERLITE IRA-67 in the sulfate form. At a temperature of 28C, 4.97 ml/min 0.1 percent sulfuric acid were pumped over the column. Then, 0.5 ml hydrofluoric ac~d or phosphoric acid were ln~ected 1nto the med1um flow. The discharge of the substances from the column was detected by means of a conduct1vity detector.
~, ,, , .~
x~n7l26 Substance ConcentrationSeparation Stage Distribution (X by weight)Number Coefficient n K
Hydrofluor1c Ac1d 10 15.45 1.06 Phosphor1c Ac1d 40 15.01 3.14 Th1s example demonstrates the possibility to purify inorganic acids as we11.
Example 2 was repeated w1th 0.1 percent sulfurlc acid as flow med~um and IRA900 as 1On exchanger at a temperature of 75C.
Substance ConcentrationSeparat1On Stage Distribut1On (% by we19ht) Number Coefflcient n K
Sod1um Sulfate 10 6.80 0.319 8.01 0.358 Maltose 10 2.77 0.316 2.77 0.309 61ucose 10 6.24 0.485 6.24 0.485 Glucon1c Ac1d 10 7.02 0.726 6.43 0.717 Lact1c Ac1d 10 16.73 1.036 16.41 1.043 Tartar1c Acid 10 19.47 2.909 Mal1c Ac1d 10 16.86 2.212 Itacon1c Ac1d 10 15.96 3.095 r` ~ 13 ~ .
.~ , . . .
7~26 Example 7 Example 2 was repeated with water as the flow medium and IRA900 as lon exchanger at a temperature of 75C.
Substance Concentrat~on Separat~on Stage D~str~but~on (X by we19ht) Number Coeff~cient n K
Sod1um Sulfate 10 7.70 0.343 7.90 0.370 Maltose 10 3.09 0.340 2.96 0.340 Glucose 10 7.62 0.545 7.03 0.53 Lact1c Ac1d 40 35.47 2.549 EXAMPLE 8: ~
.:
A sem1cont~nuous chromatography plant cons1sting of ten columns ~d1ameter 25 mm, length 1600 mm) was f111ed w~th AMBERLITE IRA900 ln the sulfate form. The plant ~s layed out ~n such a manner that the columns are connected by means of p1pe condu~ts to form a rlng. Th~s r1ng 11ne is connected between the columns to four supply 11nes v1a valves. These supply 11nes are crude product ~nlet, eluant inlet, product outlet and raff1nate outlet. The flows ~n the plant are kept constant by means of adjustable rec~procating pumps. In th1s process, there are always exactly four valves open and div~de the ring formed of columns into four zones. These zones are advanced ~n flow d~rect~on by one column after predeterm~ned per~ods by an ~n-process computer.
~", .', .
,, , .. , ., .
2~)7~26 ,, These sw1tch1ng operations simulate a resin flow counter to the flow direct10n, thls is why it is designated as "simulated moving bed"
process 1n 11terature.
.
~ :::
The dtv1sion 1nto zone was effected according to the fo110w1ng scheme:
Zone 1 2 columns Zone 2 3 columns Zone 3 4 columns I Zone 4 1 column ¦ 8 ml of crude product and 32 ml of water per m1nute were 1ntroduced and 16 ml of product or 24 ml of raffinate were withdrawn during th1s t1me. The temperature of the plant was kept constant at 70C. The 1nternal c1rculat10n volume in the column r1ng was ad~usted to 4 ml/min. The valves were sw1tched every 1550 seconds. A lactic ac1d fermentat10n mash concentrated to approximately 40 percent was _ 1 5 ." ., . ~
:
1ntroduced 1nto this plant. A purified lactic acid with a yield of more than 95 percent was recovered. The raffinate contained, ~n addition to lact1c ac1d traces, colorants, carbohydrates and salts, above all polymers which can cons~derably 1nterfere with lactic ac1d production.
The purlfy~ng effect 1s also shown by the h~gh chemlcal oxygen consumpt10n of the raffinate of 13.5 9/l. The follow1ng table shows a compar1son of lact1c ac1d before and after chromatograph1c separat10n:
before after ,, - .
Lact1c Ac1d (%) 40.52 19.53 Color (405 nm, 1 cm) 1.94 0.43 Sulfate (X) 1.78 0.03 Chlor1de (mg/kg) 330 23 Sod1um (mg/kg) 7820 330 Magnes1um (mg/kg) 7 0 Iron (mg/kg) 27 5 EXAMPLE 9:
"
A sem1-1ndustr1al chromatography plant cons1st1ng of twelve columns (d1ameter 0.5 m, length 2.0 m) was f111ed w1th AMBERLITE IRA-67. The res1n was converted to the sulfate form by flush~ng with 0.1 percent sulfuric ac1d. The columns were connected as shown 1n the followlng ~ d1agram:
,1 - 16 -f ~ :
,1 ' ~, .
Z007~Z6 contaminated solution -- _ eluant ~ _ purified ~ contamina~s ~
' ~
At a temperature of 75C, 215 l/h of a citric acid fermentation broth concentrated to approx1mately 45 perent by weight were 1ntroduced and 825 l/h of 0.1 percent sulfuric acid were added as eluant. At the same t1me, 500 l/h of pur1f1ed citr k ac1d solution (product) and 533 l/h of a solut1On containing the impurities (raff1nate) were w1thdrawn. 192 1/h were c1rculated in the column r1ng, the 1nlet and outlet s1tes were sw1tched by one column in flow direction every 1800 seconds.
An analys1s of the so1utions added and withdrawn yielded the follow1ng values:
' .~ ' ,. .:
.~. ~,.
20~7~ 6 Fermentation Broth Product Rafffinate Cltr~c Acid 43.45 ~ 22.36 X 0.02 %
Glucose 0.25 % 0.00 % 0.16 X
Fructose 0.10 X 0.00 % 0.11 %
Ma1tose ~
Isomaltose 1.40 % 0.00 % 0.80 %
Total Sugar 4.60 X 0.03 % 2.35 %
Sulfate 0.98 % 0.27 % 0.43 %
Chlor~de 110 ppm 16 ppm 42 ppm Iron 8 ppm 2 ppm 2 ppm Potassium 370 ppm 0 ppm 190 ppm Sodlum 55 ppm 0 ppm 29 ppm Ca1c1um 20 ppm 1 ppm 8 ppm Magneslum 120 ppm 0 ppm 60 ppm Density 1.27 g/ml 1.07 g/ml1.00 g/ml The productivity of the plant amounts to 2.87 tons (metr~c) of citric acld anhydrate per day, the yield of 99.9 percent is substantially better than those of the known purificat~on processes for citric ac1d. It is evident that virtually all impurities, whether cationic, I anionlc or uncharged, are separated.
' EXAMPLE 10:
!: Example 9 was repeated with crude phosphoric acid. A prefiltered ~ wet phosphoric acid (green acid) of a concentration of 37 percent¦ of P205 was introduced. The columns were switched in flow direction ':
d ''~
.
2007~26 every 1500 seconds. An analysis of the samples of product and raffinate in the equilibrated state showed the following values:
Product Raff~nate t1trable ac1d as P205 15.60 1.90 X
color (405 nm, 1 cm) 0.047 1.486 The y1eld of phosphor1c ac1d amounted to 89.9 percent, a comparison of cat1On charge before and after chromatographic separat1On shows the h1gh pur~f1cat1On performance of the system (all concentrat~ons based on 100 percent P205).
beforeafter Magnes1um 20800 42 mg/kg Calc1um 358 9 mg/kg Alum1num 3390 410 mg/kg Iron 4620 1200 mg/kg ;.
Z1nc 855 15 mg/kg . :
Chrom1um 614 102 mg/kg .
Copper 29 0 mg/kg N1ckel 56 0 mg/kg Manganese 21 0 mg/kg Cadm1um 23 0 mg/kg ~ .,, ~ - 19 -,~ I ...
.'~ ~, .
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process of separating acids from substrates containing salts and carbohydrates, in which the substrates are made to pass over resins absorptively removing the acids from the substrate, and the acids are subsequently separated from the resins by elution, in which the resins used are basic ion exchange resins.
2. The process according to claim 1, wherein the basic ion exchange resin are used for the isolation and/or purification of inorganic acids.
3. The process according to claim 1, wherein the basic ion exchange resins are used for the isolation and/or purification of organic acids.
4. The process according to claim 3, wherein the basic ion exchange resins are used for the isolation and/or purification of fruit acids.
5. The process according to any one of claim 2 to 4, wherein the basic ion exchange resins are used for the isolation and/or purification of acids of a pKs value within the range of from 1.2 to 4.8.
6. The process according to any one of claim 2 to 4, wherein the basic ion exchange resins are used for the isolation and/or purification of acids of a pKs value within the range of from 2.1 to 3.9.
7. The process according to any of claims 1 to 4, wherein basic ion exchange resins charged with acids are used.
8. The process according to any of claims 1 to 4, wherein the ion exchange resins used are charged with an acid to which they have a higher affinity than to the acid to be isolated or purified.
9. The process according to any of claims 1 to 4, wherein basic ion exchange resins charged with hydrochloric acid, nitric acid, phosphoric acid, citric acid or sulfuric acid, preferably with sulfuric acid, are used.
10. The process according to any of claims 1 to 4, wherein diluted hydrochloric acid is used as the eluant.
11. The process according to any one of claim 2 to 4, wherein the basic ion exchange resins are used for the isolation and/or purification of acids of a pKs value within the range of from 1.2 to 4.8 and in which said basic ion exchange resins charged with acids are used.
12. The process according to any one of claim 2 to 4, wherein the basic ion exchange resins are used for the isolation and/or purification of acids of a pKs value within the range of from 1.2 to 4.8 and in which the ion exchange resins used are charged with an acid to which they have a higher affinity than to the acid to be isolated or purified.
13. The process according to any one of claim 2 to 4, wherein the basic ion exchange resins are used for the isolation and/or purification of acids of a pKs value within the range of from 1.2 to 4.8 and in which said basic ion exchange resins charged with hydrochloric acid, nitric acid, phosphoric acid, citric acid or sulfuric acid, preferably with sulfuric acid, are used.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA23/89 | 1989-01-05 | ||
| AT2389 | 1989-01-05 | ||
| AT277389 | 1989-12-06 | ||
| ATA2773/89 | 1989-12-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2007126A1 true CA2007126A1 (en) | 1990-07-05 |
Family
ID=25591146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2007126 Abandoned CA2007126A1 (en) | 1989-01-05 | 1990-01-04 | Process of separating acids from substrates containing salts and carbohydrates |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0377430A1 (en) |
| CA (1) | CA2007126A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744241A (en) * | 2013-12-30 | 2015-07-01 | 中粮营养健康研究院有限公司 | Method for purification of citric acid from citric acid fermentation liquid |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0483831B1 (en) * | 1990-11-02 | 1995-09-06 | Mitsubishi Chemical Corporation | Process for separating an organic acid or acids from an organic acid-containing solution |
| US5786185A (en) * | 1991-09-13 | 1998-07-28 | Reilly Industries, Inc. | Process for producing and recovering lactic acid |
| US6114577A (en) * | 1995-02-15 | 2000-09-05 | Reilly Industries, Inc. | Desorption process and apparatus |
| US5965771A (en) * | 1997-10-03 | 1999-10-12 | The Regents Of The University Of California | Regeneration of carboxylic acid-laden basic sorbents by leaching with a volatile base in an organic solvent |
| NL1010090C2 (en) * | 1998-09-15 | 2000-03-17 | Gerard Kessels Sociedad Anonim | Process for the preparation of 2- and 4-hydroxymandelic acid. |
| FR2900654B1 (en) * | 2006-05-05 | 2008-08-01 | Applexion | PROCESS FOR PURIFYING ORGANIC ACID BY CHROMATOGRAPHY |
| DE102016001070A1 (en) | 2015-02-06 | 2016-08-11 | Rwth Aachen | Process for the separation of organic dicarboxylic acids by adsorption of hydrophobic porous materials |
| WO2017095686A1 (en) * | 2015-12-01 | 2017-06-08 | Dow Global Technologies Llc | Chromatographic separation of organic acids using resin having strong and weak base anion exchange capacity |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1194165A (en) * | 1959-11-06 | |||
| US2697725A (en) * | 1950-03-18 | 1954-12-21 | Sharples Corp | Recovery of organic acids from aqueous solutions |
| US2664441A (en) * | 1951-07-19 | 1953-12-29 | Harry S Owens | Separation of organic acids |
| CH523861A (en) * | 1967-05-22 | 1972-06-15 | Sun Oil Co | Carboxylic acid prepn by microbiological oxidn in |
| JPS52156814A (en) * | 1976-06-21 | 1977-12-27 | Tokuyama Soda Co Ltd | Purification of tartaric acid |
-
1989
- 1989-12-18 EP EP89890323A patent/EP0377430A1/en not_active Withdrawn
-
1990
- 1990-01-04 CA CA 2007126 patent/CA2007126A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744241A (en) * | 2013-12-30 | 2015-07-01 | 中粮营养健康研究院有限公司 | Method for purification of citric acid from citric acid fermentation liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0377430A1 (en) | 1990-07-11 |
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