CN1203535A - Thermally-managed separation and dewatering processes for recovering acid products - Google Patents

Abstract

Described are preferred processes separating desired chemical products from impurities in solution utilizing thermally-managed chromatography over solid adsorbents. The preferred processes involve chromatographic principles which are assisted by varying the temperature of operation in separation and elution phases. Also described are processes for treating aqueous acids to dewater and recover the acids in an organic solvent such as an alcohol.

Description

The thermal control separation and the dewatering of recovered acid product

Background of invention

The present invention relates generally to reclaim the technology of valuable chemical products.More particularly, the present invention relates to be used for optionally reclaiming the efficient and economic method of purpose product, relate to new heat and help the chromatography technology from the liquid medium that contains other compound simultaneously.

As further background be, for a long time, for reclaim and the purification medium in acid compound such as carboxylic acid and other valuable chemicals carried out research, try hard to find the production method that it is effective and economic.For example, to carboxylic acid such as citric acid and lactic acid, be exactly to produce by fermentation process on a large scale in the world.This class fermentation process production be must therefrom reclaim and the zymotic fluid of the required acid of purifying.Allly relate to large-scale production, all can not overemphasize the importance that keeps minimum cost recovery.

The research of recovery aspect recently, is on the carboxylic acid of focal attention in applying solid polymer absorbant material recovery fermentation media.In this way, make zymotic fluid pass the adsorbent that can absorb carboxylic acid, desorption carboxylic acid in some way again, output product.The suggestion of many relevant adsorbents and absorption/desorption scheme has been proposed in general.

For example, Kawabata etc. are at United States Patent (USP), and USP 4,323, described a kind of method that the polymeric adsorbant material recovery carboxylic acid of pyridine skeleton structure and cross-linked structure is arranged with the main component cording in 702.Earlier carboxylic acid is adsorbed on the adsorbent, after use a kind of polar organic matter such as fatty alcohol, ketone or ester with its desorption again.

Kulprathipanja etc. are at U.S. Pat P 4; 720; 579,4; 851,573 and 4,851; point out in 574; that the solid polymer adsorbent comprises is neutral, noniogenic, huge netted, water-insoluble cross-linked styrene-poly-(vinyl-) benzene, is connected with the crosslink propylene acyl group or the styrene base resin parent of tertiary amine functional group or pyridine functional groups, or is connected with the crosslink propylene acyl group or the styrene resin parent of fatty quaternary amine functional group.In its work, Kulrathipanja etc. have described at them and have confirmed " pulse testing " of being carried out under acetone, sulfuric acid and the water warm condition as desorbing agent.

In the south african patent application 855155 that on July 9th, 1985 submitted to, the method that reclaims product acid from its aqueous solution has been described.In adsorption step, acid-containing solution is passed dress resin sorbent post in, and this absorbent resin comprises: vinyl imidazole/methylene-two-acrylamide polymer, vinylpyridine/trimethylol-propane trimethacrylate/vinyl front three silane polymer, vinyl imidazole/N-vinyl-N-methylacetamide/methylene-two-acrylamide polymer, Amberlite IRA 35 (Rohm ﹠amp; Haas-is to contain the acrylate/divinyl benzene polymers of dimethylamino group) or Amberlite IRA 93 SP (Rohm ﹠amp; Haas) or DowexMWA-1 or WGR-2 (Dow Chemical) (back three kinds be contain the dimethylamino group be polymer based) with styrene/divinylbenzene.Usually allowing to feed water to adsorption column under 90 ℃ of temperature comes the desorption should acid.But described one way elution process is insufficient to heat energy utilization, also can not utilize this resin highly enriched solution to be carried out the potentiality of desorption basically fullest.In addition, applied resin is unstable to heat in the application of this piece south african patent, therefore all will degrade basically in the hot water desorption process.

International Patent Application PCT/the US92/02107 that submits on March 12nd, 1992, (issue on October 1st, 1992, WO 92/16534) and in the PCT/US92/01986 of submission on March 12nd, 1992 (issue on October 1st, 1992, WO 92/16490), the two all belongs to Reilly Industries, Inc. company has disclosed on divinyl benzene crosslinked vinylpyridine or other resin with steam or hot water difference desorption lactic acid or methods of citric acid.Used resin adsorption/desorption ability is stronger, in described hot water desorption process to Heat stability is good.Yet the method for having improved is used for desorption can be higher to the utilization ratio of resin and heat, also is easy to obtain production concentration even higher desorption solution.

Also report has the method for some recovered acid products.For example, U.S. Pat P 5,412, and 126 have disclosed on basic resin the absorption citric acid carries out wash-out again with alkylamine method.Then, reclaim free acid again to this material thermal dehydration with drive out amine.U.S. Pat P 5,032,686 have disclosed a kind of method with acidic resins separation of citric acid from sugar, while USP 5,382,681 have disclosed a kind of method, wherein contain the citric acid solution of another compound earlier with alkali treatment, make citric acid be converted into natrium citricum, again this alkaline media is passed basic resin and separate other compound.

Given this such or such background in the field still needs through improving and can effectively purify and reclaim the process of carboxylic acid and other valuable product.The present invention is just at such demand.

Summary of the invention

Therefore, one group of preferred embodiment of the present invention provides a kind of method that is used to separate acid and a kind of or several compounds of carrying out thermal control chromatography and wash-out mutually to several that relates to.For example, provide a kind of method for optimizing that from its mixture, separates acid and another compound, comprising under first temperature, on absorbent resin, chromatography being carried out in this acid and another compound, then again under second temperature higher than first temperature, as high at least 10 ℃, this acid product of wash-out from the absorbent resin.Preferred method used a kind of in the dress adsorbent sour affinity is compared another or several compounds affinity is higher and reduce the contact zone that sour affinity is more strengthened with temperature.First solution that will contain acid and another compound is incorporated in this contact zone.Big for making it operation capacity, this solution acid content can substantially exceed the level of this adsorbent to sour adsorption capacity.This contact zone is passed in second solution (eluent) introducing.This second solution is under first temperature and can make in the contact zone under the condition that effectively separate in another or several compounds forward position with this of sour forward position and pass.Then use again a kind of liquid in second temperature at least than first temperature under the condition of high 10 ℃ or 20 ℃, sour forward position in this contact zone of wash-out.According to such method, separating phase time, just can make this adsorbent that acid absorption affinity is remained on relative higher level, thereby be detained acid, help acid and the separating of other compound, and at the wash-out phase time, this adsorbent but maintains relatively low level to the affinity of acid, and has increased the acid amount of wash-out in during certain.Therefore, preferable methods of the present invention can be utilized tradition absorption/thermal desorption phenomenon in other compound of chromatography, finishes to effective purification of acid product with to the fraction of highly enriched product and reclaims.

Particularly preferred the inventive method has been used a kind of Continuous Contact device comprising many resin fills contact zone (as resin column).The Disengagement zone of being set up comprise many contact zones with in be equipped be enough to reach acid originally separate the adsorbent of requirement with other compound-base.This chromatography district operates under the first relatively low temperature.In case then being acid product and other compound, the elution zone of being set up separates on substantially, just from elution zone wash-out acid product.This elution zone operates in than under the second higher temperature of first temperature.After elution zone, resin fill contact zone (present essentially no product) will preferably stand cooling step, so that this Continuous Contact device reaches optimum temperature in the Disengagement zone that goes on foot in the circulation down.Preferred cooling step comprises makes the temperature liquid medium lower than resin temperature pass this contact zone.Mounted valve on the Continuous Contact device rightly is so that sequentially make step such as contact zone experience separation, heating, wash-out and cooling and finish the process of thermal control chromatography of the present invention.

According to another aspect of the present invention, a kind of thermal control chromatography method comprises setting up a kind ofly can make wherein many contact zones that adsorbent is housed be subjected to the method for sequential processes, this processing comprises that its product content is surpassed this adsorbent passes this adsorbent to the liquid medium of product adsorption capacity, under first temperature, carry out acid product and other compound chromatography, then under second temperature higher at least 10 ℃, carry out wash-out again than first temperature.In this point of the present invention or others, in the mutually used eluent of chromatography, can comprise containing the product medium in a part of pre-treatment contact zone.

Another preferred embodiment of the inventive method, provide a kind of dewater and recycle-water solution in the method for organic acid product, be included on the adsorbent with the mixable solvent of water such as alcohol and under the condition of wash-out acid product, the acid product aqueous solution carried out chromatography handle as mobile phase with in substantially anhydrous alcoholic solution.Owing to provide a kind of being equipped with in it to introduce in the contact zone, made such method be able to smooth realization to the contact zone of the strong adsorbent of sour affinity comparison water with aqueous acid.Under making organic acid forward position in the contact zone and the condition that effectively separates in the water forward position, liquid alcohol is passed through this contact zone, organic acid forward position in this contact zone of wash-out, to obtain the containing organic acid eluate in the alcoholic solution, wherein this eluate is anhydrous (promptly containing the water that is no more than about 15% (weight)) basically.

Also have another group to be used for the preferred chromatograph separation method that the organic acid product is dewatered, comprise that step is as follows:

(a), provide the contact zone of many interior dresses to the strong adsorbent of organic acid product affinity comparison water;

(b), order handles the contact zone by the chromatography district, wherein with pure elute soln with contain aqueous acid and pass this contact zone together, with finish acid and moisture from the process of chromatography; With

(c), after (b) step, order is handled the contact zone by elution zone, so as in substantially anhydrous alcoholic solution the acid product in the one or more contact zones of wash-out.

On the other hand, the invention still further relates to,, can distinguish the discovery of wash-out and this weak acid of recovery and alkali in the enterprising circumstances in which people get things ready for a trip layer of weak base resin separating treatment as ammonium lactate about salting liquid to weak acid and alkali.Therefore the present invention also provides a kind of method of chromatography, can reclaim weak bronsted lowry acids and bases bronsted lowry respectively from the salting liquid of weak acid and alkali.The inventive method comprise provide a kind of in harness the contact zone of the polymer of tertiary amine functional group is arranged, this salting liquid is introduced so far in the contact zone, and under effectively setting up organic acid forward position in the contact zone and the condition that separates in the water forward position, eluent is passed this contact zone.The path of eluent is continuous, so that wash-out goes out weak acid forward position and alkali forward position in the contact zone respectively.This method be particularly conducive to recovery with fermentation method continuously ferment produce and actual be neutral weak acid.For example, when reclaiming lactic acid, at low pH and have in the presence of the free lactic acid, used thalline was suppressed during it was produced, and therefore when fermenting generation lactic acid, generally will neutralize it with for example ammonia.This has just formed the medium that contains ammonium lactate, just can be handled according to this method of the present invention, reclaims free lactic acid.

Thermal control method of the present invention can be used for reclaiming the product in the concentrated liquid medium, also can effectively utilize heat energy simultaneously, promotes to reclaim, and also can make it structure operation under the condition that the high and required reserve of adsorbent capacity reduces.Dewatering of the present invention provides and reclaimed the acids product in substantially anhydrous eluent, helps acid recovery and/or help in subsequent operation the acid reaction that is carried out.The present invention also provides some easy operatings and can be used for reclaiming the method for the various purpose products of many concentrated solutions.Other preferred embodiments of the present invention, feature and advantage will become more clear by following description.

The accompanying drawing summary

Figure 1A and Figure 1B are illustrated in REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers under cold feed/elution requirement under (Fig.1A) and the hot feed/elution requirement (Fig.1B) chromatography handle the elution profile shape of aqueous citric acid/glucose mixture.

Fig. 2 is for being illustrated in REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers under cold feed and hot elution requirement chromatography handle the chromatography elution profile shape of aqueous citric acid/glucose mixture.

Fig. 3 A and Fig. 3 B are the elution profile shape that is illustrated on the IRA-93 resin when cold feed/wash-out (3A) condition and aqueous citric acid/glucose mixture is handled in chromatography during hot feed/wash-out (3B) condition.

Fig. 4 A and Fig. 4 B are for being illustrated in REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers when cold feed/wash-out (4A) condition and during hot feed/wash-out (4B) condition chromatography handle the elution profile shape of aqueous acetic acid/glucose mixture.

Fig. 5 A and Fig. 5 B are for being illustrated in REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers when cold feed/wash-out (5A) condition and during hot feed/wash-out (5B) condition chromatography handle the elution profile shape of moisture ascorbic acid/glucose mixture.

Fig. 6 A and Fig. 6 B are for illustrating at REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers when cold feed/wash-out (6A) condition and during hot feed/wash-out (6B) condition chromatography handle the elution profile shape of lactic acid/glucose mixture.

Fig. 7 A and Fig. 7 B are for illustrating at REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers with butanols as eluent when cold feed/wash-out (7A) condition and during hot feed/wash-out (7B) condition chromatography handle the elution profile shape of dextrose hydrate/citric acid mixture.

Fig. 8 is for being illustrated in REILLEX ^TMHandle the elution profile shape of dextrose hydrate/citric acid mixture on the HP cross-linking polyethylene pyridine polymers as the eluent chromatography with ethanol.

Fig. 9 is for illustrating at REILLEX ^TMOn the HP cross-linking polyethylene pyridine polymers when cold feed and hot elution requirement chromatography handle the elution profile shape of dextrose hydrate/phenol mixture.

Figure 10 is the profile part side elevation view that can be used in exemplary Continuous Contact device of the present invention.

Figure 11 is the schematic diagram of explanation following examples 12 used Continuous Contact device nozzle structures.

Figure 12 is the schematic diagram of explanation following examples 13 used Continuous Contact device nozzle structures.

Figure 13 is the schematic diagram of explanation following examples 14 used Continuous Contact device nozzle structures.

Figure 14 is for illustrating at REILLEX ^TMHandle the elution profile shape of lactic acid aqueous solution on the HP cross-linking polyethylene pyridine polymers with the methyl alcohol chromatography that is eluent when the isothermy.

The preferred embodiment explanation

For helping the understanding to the principle of the invention, now enumerate its some embodiment as a reference, And with special-purpose language it is described. Yet, it will be appreciated that, more like this according at this Consider and the principle addressed to variation of the present invention, improvement and application, be not to model of the present invention The restriction of enclosing, these all belong to the thing of normal scope for the personnel that are familiar with field of the present invention.

As mentioned above, one group of preferred embodiment of the present invention provides a kind of thermal control chromatography side Method is utilized absorbent resin that product is separated with another compound and is reclaimed. The inventive method Characteristics have been to use traditionally with absorption/hot desorption manipulation in the chromatography relevant adsorbent tree Fat and phenomenon. Therefore for the product in the separation solution and other compound, adopted a kind of connecing Contact area is equipped with in it and a kind of acid absorption affinity is compared other chemical combination object height and with drop in temperature pair The adsorbent that acid affinity strengthens. First solution that will contain acid and other compound is introduced so far contact In the district. More effective for reach operation capacity height and adsorbent utilization in the separation of chromatograph type, this is molten Liquid preferably contains the acid of high concentration, and for example optional reaching substantially adsorbed capacity above this adsorbent to acid Level. After introducing contains the solution of acid/other compound, again in first temperature with can make In the contact zone under the condition of sour forward position and other compound forward position effective separation, make second liquid as Water, contain acid but the aqueous solution or the organic solvent that substantially do not have other compound passes this contact zone. Again in Under high second temperature, preferably higher 10 ℃ than first temperature than first temperature, be more preferably up to few 20 ℃, with the sour forward position of this contact zone of a kind of liquid medium wash-out. Set up by this way so-called " heat Control " the chromatography method, wherein when separating phase, adsorbent remains on than Gao Shui sour affinity Put down-namely be conducive to the level of acid and a kind of or several other compound separation-, and in the wash-out phase The time, after had separated in other compound and sour forward position, adsorbent was but protected the affinity of acid Be held in relatively low level ,-be conducive to take off from the contact zone except or wash-out acid, and over a period to come Wash-out acid amount is increased. Therefore, this kind of the present invention method for optimizing can be sharp in the chromatography process Take off phenomenon with traditional absorption/heat, finish effective purified acid product from a kind of or several compounds The product fraction that thing and recovery highly concentrate.

Usually, the method that valuable product is reclaimed in liquid-solid separation is known, approved adsorbent Resin and suitable liquid wash-out liquid are of a great variety. Therefore generally being familiar with these those skilled in the art all is easy to According to choice and operation of the present invention suitable absorbent resin and wash-out liquid medium.

In general, sorbent used should have the absorption ability to the purpose product, and in following institute use Should be stable (being the unlikely obvious degradation that suffers) under the reason condition. Although adsorbent can be any energy The material (comprising active carbon, zeolite etc.) of absorption purpose product, but be used for more reason of the present invention Think that adsorbent is that those possess cross-linked polymeric thing suction heat and mechanically stable and favourable profile Attached dose of resin. The granulated sorbent resin is preferred, and particularly those granularities are about 20 to about 200 The purpose particle, especially about 40 to about 120 orders.

Be used for reclaiming the various suitable polymer of required absorption matter product such as carboxylic acid or other sour class Adsorbent is existing report all, also can be used for fixing in the thermal control chromatography recovery method of the present invention Phase. These polymer absorbants be by a kind of or several generally include a kind of monomer of cross-linking monomer Polymerization consists of. Carry out polymerization to obtain round resin particle gel or huge net-shaped. In addition, To the also in addition chemical modification of these round resin particles, in to resin, add such as quaternary amine or acidity The ion group of salt groups. The resin that obtains then can be anion, cation or non-ionic, And have various physics and a chemical characteristic.

For example, the suitable resin of reporting comprises nonionic and ion polymer, comprise neutral, Noniogenic, huge netted, the insoluble cross-linked styrene of water-poly-(vinyl) benzene, alkalescence is poly-Laminate material is such as the crosslinked pyridine polymers that contains, such as vinylpyridine polymer, tertiary amine functional group is arranged Or the crosslink propylene acyl group or the styrene resin parent that connect of pyridine functional groups, fatty season amine official energy is arranged The crosslink propylene acidic group that group connects or styrene resin parent etc. (are seen such as Kawabata and are reached People's patents such as Kulprathipanpa are quoted as proof among background of invention). These and known being used as are inhaled Many other polymer of attached dose, for example alkalescence or acid ion exchange resin comprise styryl , acryloyl group, epoxy amine, the styrene polyamines, and phenolic aldehyde or non-ionic suction Attached resin all is to be applicable to according to temperature inversion of the present invention to adsorb/take off attached method; Yet preferably Be, this polymer absorbant should be a kind of crosslinked alkaline polymer, such as the crosslinked N-fat that contains Or N-heterocycle tertiary amine functional group, as contain the polymer of dialkylamino or pyridine functional groups.

The particularly preferred pyridine polymers that contains is polyethylene yl pyridines polymer, such as poly-2-and poly-4-second Alkene yl pyridines gel or be the huge mesh resin of spherolite shape. These resins be preferably at least about 2% with Suitable crosslinking agent is crossed such as divinyl benzene crosslinked. Preferred resin is 2～50% crosslinked spherolite shapes Vinylpyridine polymer, such as poly-2-and poly 4 vinyl pyridine polymer.

For example, preferred resin comprises poly-2-and poly 4 vinyl pyridine resin, is REILLEX^TMSeries of polymers is by Reilly Industries Inc., (Indianapolis, Indiana) Company provides. These REILLEX^TMPolymer is generally 2% or above crosslinked mistake, and shows Have good heat endurance and absorption now and take off attached capacity and other preferred spy as mentioned above Levy. For example, to take off attached capacity be at least about 200 milligrams of lemons of every gram polymer to the preferred resin of this kind Acid. Another preferred resin is the REILLEX that is provided by identical source^TMThe HP series of polymers. This A little REILLEX^TMThe HP polymer also has suitable capacity, also can fully regenerate. Relevant REILLEX^TMBut many data lists of references of polymer comprise Reilly Industries, and Inc. company is with REILLEX^TMProvide in the report 1,2 and 3.

Other resin is for example by Rohm and Haag company (Philadelphia, Pennsylvania) The AMBERLYST A-21 that provides, AMBERLITE IRA 68 or AMBERLITE IRA 93 resins, or by the DOWEX MWA-1 resin that Dow Chemical company provides, also can Be applied in the present invention. The A-21 resin is by diethylbenzene (more than 2%) in these resins Crosslinked, and contain fat tertiary amine functional group (particularly, connection dialkylamino (dimethylamino) base Group); The acryloyl group mother of the fatty tertiary amine group of IRA 68 resins, a kind of divinyl benzene crosslinked Body, and be the form of gel; With IRA 93 and MWA-1 resin contain the fat tertiary amine group and Take the styrene parent of divinyl benzene crosslinked as the basis, be huge net-shaped. Relevant these and other The similar other information that can be used for resin of the present invention can be with reference to the money that is provided by manufacturer is provided The material document.

For the balance concentration between the product of paying close attention to and the adsorbent obviously with what temperature changed be System, as adsorbent temperature is relatively low under to the absorption of purpose acid product or delay Capacity Ratio Temperature much higher than relative superiority or inferiority in (by the dried adsorbent of every gram the milligram equivalent, at least 5% with On), thermal control method of the present invention is with advantageous particularly. According to the present invention, sour class belongs to preferred recovery Product, the particularly pKa value sour class in about 2.0～4.5 scope. More in general, suitable Sour class pKa value should be in about 2.0～6.0 scope, have a kind of pKa value about 3.0～5.0 The preferred group of scope. Being used for the exemplary sour class of the present invention for example comprises: aromatic acid class such as phenol, Salicylic acid, M-phthalic acid, phthalic acid, benzoic acid, 3-chlorobenzene formic acid; The 'alpha '-hydroxy acids class As citric acid, lactic acid, lactyl-lactic acid, malic acid, mandelic acid, diphenylglycollic acid, diglycolic acid, Glycolic, tartaric acid, formic acid, glutaric acid, fumaric acid, acetyl acetic acid, acetic acid, butanedioic acid, The acid of clothing health; Pyridine carboxylic acid class such as nicotinic acid or isonicotinic acid; Piperidine carboxylic acid such as different nipecotic acid (isonipecotic acid); Inorganic acids such as phosphoric acid, sulfonic acid, zincic acid, molybdic acid, gallium (III) ion, Mercury (II) ion etc. Other is applicable to sour class of the present invention, can be with reference at U.S. Pat P Those acid of approving in 4,552,905,4,323,702 and 5,412,126. According to the present invention When reclaiming them, all these sour classes and other weak acid compound separation can be come, comprise as carbohydrate, Amino acids, acid amides class (as from corresponding acid amides, isolating carboxylic acid), or other natural or worker The similar acid compounds that industry processing produces.

The present invention especially meaningfully reclaims organic acid, especially from fermentation, promptly adopts microorganism that suitable carbon source is fermented and reclaims carboxylic acids such as aliphatic acid in the medium that generates.

For example, major part is all undertaken by fermentation process such as the organic carboxyl acid production of aliphatic acid and lactic acid in the world.For citric acid, zymotic fluid can be taken from the suitable bacterium that produces citric acid or other as the microorganism of aspergillus niger (Aspergillus Niger) through to the product such as corn sugar or molasses carbon source through fermentation.The bacterium or the microorganism that can generate lactic acid when carbon source is carried out biological metabolism then adopted in the production of lactic acid.Although other microorganism such as fungi also can be adopted, generally all adopt newborn bar to belong to family (Family Lactobacillaceae).For example, Rhizopus family (Rhizopus) belongs to (Rhizopus oryzae) NRRL 395 (United State Department ofAgriculture, Peoria such as rhizopus oryzae, Illinois) fungi, can be used to produce pure substantially L+ lactic acid, as International Patent Application PCT/US92/07738, in September 14 in 1992 by Reilly Industries, Inc. Companies Registry, (WO 993/06226, in 1993, and issue on April 1).Select and use suitable fermentative microorganism to produce to contain as the organic acid of carboxylic acid and it can be handled the zymotic fluid of recovered acid, the thing in those of skill in the art's the extent of competence just according to the present invention.

When relating to the fermentation media that contains carboxylic acid, it is moisture usually, product is sour, salt, amino acid, sugar and the few various components of other amount.Before the beginning adsorption step, can filter such fermentation media, remove suspended solid particle.In addition, the fermentation media that contains carboxylic acid according to the present invention just can be taken from the process at the fermenting and producing carboxylic acid, therefore depickling can combine with its fermentation production process and carry out, the described relevant lactic acid embodiment of WO 93/06226 (International Patent Application PCT/US92/07738, registration on September 14th, 1992) as issue on April 1st, 1993.This in conjunction with the process of producing in, the charging of separation process can be the part of fermentation media, is ideally filtering or other is suitable for preparing fermentation media by after the processing of separating feed path of the present invention.This carboxylic acid is to reclaim by separation method described here, and the carboxylic acid of discharging from the separation process liquid logistics of " giving up " then can be back to the fermentor, becomes the nutrient of fermentation again.Like this certain methods can effectively reduce since acid product to producing the feedback inhibition of sour cell, as the known effect that occurs when the lactic fermentation.

The present invention can be with various liquid eluents.These eluents for example comprise that organic solvent based such as aromatic hydrocarbon solvent or polar organic solvent such as alcohols are (as C ₁～C ₅Alcohols such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols and methyl isobutyl carbinol), ketone and ester class, and water-bearing media such as water (promptly not adding the pure water of solute basically), aqueous solution example hydrochloric acid, sulfuric acid or the sodium hydroxide solution of acid and alkali, or water/organic cosolvent medium such as water/alcohol mixture etc.Some preferred inventive method adopts water, makes it to become the medium of desorption matter, and does not have the unnecessary solute or the cosolvent that can make purpose product removal process complicated.Other preferred inventive method adopts as pure organic solvent, then is for acid being dewatered and recovered acid product in organic solvent.When in such process, adopting alcohol, product can the band minimal amount of water (as 20% heavy below, even 10% is heavy following) alcohol in reclaim, for example, for carboxylic acid (as citric acid), the product medium of recovery can be reacted by esterification process, obtains corresponding carboxylic acid ester or partial ester.

Usually, the wash-out of thermal control method of the present invention relates to mutually and adopts score from the higher temperature of phase temperature, and its temperature will be enough to the product on the wash-out absorbent resin effectively.Used concrete eluting temperature depends on some kinds of factors, such as the acid product of being paid close attention to, used eluent or the like.High to boiling point or all applicable above the temperature (as under) of eluent boiling point at superatmospheric pressure.In a preferred method, eluting temperature is generally about more than 50 ℃, and is more typical about more than 70 ℃, and usually about more than 90 ℃.When the carboxylic acid that reclaims such as citric acid or lactic acid, desorption temperature about be preferred more than 90 ℃.

In preferred thermal control chromatography method of the present invention, to add enriched product be to contain the high charging of production concentration.For some method, content substantially exceeds the product of adsorbent capacity and also can use, as surpassing its adsorption capacity 20% or above, or even 100% or above, in the time of like this in, will form product than this adsorbent institute more Disengagement zone of adsorbable product in the Disengagement zone with this charging displacement pile.In this, adsorbent has a method for expressing common to all to the adsorption capacity of concern product, for example, can be determined by calculating by the product of constant density in the solution shown in the isothermal equilibrium phasor being adsorbed the poor of the production concentration that caused the back with contacting of adsorbent.Should be known in that used concrete product input concentration is selected according to the various factors of being grasped, comprise and for example wish when making product stream reach required purity, will maximally utilise resin.

When adopting so concentrated charging, people can utilize resin more effectively to separate, and make production capacity than adopting in that to be equal to or less than the ability that is reached under the product load of adsorbents adsorb capacity high a lot.For example, in following specific embodiment, in the method for carrying out in conjunction with Figure 12 narration, adopted a kind of charging (surpassing the resin adsorption capacity more than 200%) of 50% citric acid, constitute a kind of production capacity and surpassed every gram adsorbent (doing agent) 3 milliequivalent methods of citric acid.The high-caliber like this adsorbent that utilizes has reduced requirement to the adsorbent reserve, has improved output.These all are very important advantages, can be applicable to extensive separation process.

Therefore, in the preferred method of separation of citric acid and impurity such as sugar, can use a kind of concentrated citric acid solution as the product charging, for example concentration surpasses approximately 25%, more preferably surpasses 30%.For example adopt to make citric acid content, can obtain the charging of this concentrated citric acid solution about the method that the primary fermentation medium solution below 20% concentrates.This concentration step can carry out with any acceptable manner, as comprises the medium dehydration by evaporation.The medium of Nong Suoing like this, citric acid concentration increases, again as the charging of the inventive method.

In another feature of the present invention, have now found that, relatively weaker acid, for example the pKa value is more than 3.5 as 3.5 to 6.0 carboxylic acid, such as lactic acid or acetic acid, when isothermal chromatography and aforesaid thermal control condition are issued to favourable wash-out and distribute, can also effectively dewater.Therefore, as described in following examples 13, weakly acidic aqueous solution can be added to the polar organic solvent such as the alcohol that have as eluent and send in the chromatography district that passes through.Adsorbent in the Disengagement zone is preferably the uncle's amino group that contains such as pyridine radicals, presents the also high affinity of acid comparison water, thereby has realized a kind of separation process that obtains to contain in the substantially anhydrous alcoholic solution sour eluent.In this regard, used as this section, " not having substantially ... " refer to the water that contains about 20% (weight) in the alcoholic solution that contains the recovered acid product at most.More preferably be, contain no more than about 10% (weight) in the recovery alcoholic solution, be most preferably not exceeding 5% (weight).In addition, in a preferred method, contain acid product concentration in the alcoholic solution of recovery with respect to the concentration height that enters.For example in a preferred method, acid concentration is at least about 50% of acid solution charging in the alcohol eluen of recovery, more preferably at least about 75%.

Preferred thermal control of the present invention and dewatering relate to the eluent medium that contains product and separate the charging of phase as this process.This eluent that contains product for example obtained before wash-out reclaims the product operation, can be used for effectively promoting separating of other compound and acid product, and the existence of product can increase production concentration in the end product stream simultaneously in this eluent.Therefore, in preferred operations, production concentration increases in the product stream in order to make, and a part of eluted product in the continuous reclaimer operation is flow to rinsing step.

The present invention also has another feature, relates to a kind of salting liquid that forms by weak acid and alkali interaction is handled to reclaim the process of weak acid and alkali respectively.Adopt suitable eluent such as water, contain tertiary amine functional group being equipped with, be preferably in the contact zone of polymer of pyridine functional groups solution is handled, so that the weak acid forward position of eluent in the contact zone is separated with the alkali forward position of eluent by the chromatography method.Continue (generally under isothermal or thermal control condition as mentioned above) and feed eluent, with weak acid forward position and the alkali forward position in the wash-out contact zone respectively.When fermenting or after the fermentation, this method can be used for reclaiming weak acid such as the lactic acid that ferments generation and neutralize with alkali.For example, producing under the situation of lactic acid, it is low and be subjected to inhibition when having free lactic acid to exist in pH value to produce used thalline, therefore with as the lactic acid that neutralizes owing to the generation of fermenting of ammonia, calcium hydroxide (lime) or NaOH be favourable.This just causes medium to contain lactate (as ammonium lactate, calcium or sodium), can be handled it according to this method of the present invention, reclaims free lactic acid.

What the present invention received an acclaim is the certain methods that adopts Continuous Contact device (" CCA ") to carry out.For example, effectively the Continuous Contact device comprises such as by AdvancedSeparation Technology Inc. in the present invention, (the AST Inc. of company, Lakeland, Florida) those ISEP that provide or the continuous contactor of CSEP also have those at U.S. Pat P 4,764,276 (promulgations) in August 16,1988; 4,808,317 (promulgations) in February 28,1989; 4,522,726 (promulgation) institute's general description in June 11,1985.Now the brief introduction of the described this CCA device of relevant these patents is recited in down.Relevant CCA device of the present invention further design and the details of operation of being applicable to can comprise " TheISEP with reference to the reference that is provided by AST company ^TMPrinciple of Continuous Adsorption " and above-mentioned United States Patent (USP).

Being used for preferred CCA of the present invention is a kind of liquid-solid contact device, comprises many cylindrical chamber that contain solid adsorbent materials and can concentrate or respectively the inventive method be provided the contact zone that are applicable to.These cylindrical chamber have respectively that it is gone into, outlet spout, and are installed on the rotatable central shaft so that advance that cylindrical chamber is gone into, outlet spout cooperates and connects feed, the discharging mouth of pipe.Particularly, the mouth of pipe is gone at the top that liquid is delivered to respectively these cylindrical chamber that are connected with its top valve system by the road, and this valve system can provide many and go into the feed mouth of pipe that the mouth of pipe cooperates connection with it when cylindrical chamber advances.Equally, pipeline also connects each cylindrical chamber lower end outlet spout and the following valve system of cylindrical chamber, and this valve system also provides the discharging mouth of pipe to match with the cylindrical chamber outlet spout when cylindrical chamber advances.These valve systems comprise the removable valve plate that has slit, and valve plate is closed and opened these during with dial rotation and goes into the mouth of pipe.Change the size and the position of valve plate slit, can add the flow of cylindrical chamber feed pipeline and the flow of outflow cylindrical chamber discharging pipeline by predetermined way control.Valve plate then moving of a valve plate just can constitute continuous or mobile by scale.Liquid flows into and the time of outflow cylindrical chamber is exactly the functions of these cylindrical chamber along the central shaft rotary speed.

More particularly, be used for a kind of preferred contact device summary of the present invention and be shown in Figure 10.This device comprises that supports upright drives the rectangular framework 11 of rotating shaft 12.Rotating disk 13 is loaded on and drives in the rotating shaft so that rotation.This rotating disk is fixed in the rotating shaft, drives rotating shaft by the motor 14 that is contained on the framework 11.Many cylinder barrel shaped chamber 15 (as 30) erectly be contained on the rotating disk 13.Cylindrical chamber is preferably arranged alternately along the rotating disk contour.Each cylindrical chamber is interior according to used concrete grammar casting resin or other solid absorbent that is suitable for.Sectional view shown in Figure 10 left side, solid adsorbent materials 16 preferably approximately be fills up to cylindrical chamber 15 height half or higher.The arrangement of each cylindrical chamber 15 all helps introducing and draw off solid material by this container top.The entrance and exit place of each cylindrical chamber 15 top and bottom is equipped with pipe joint 17 and 18 respectively.Upper valve body 19 reaches down, and valve body 20 all is loaded on the rotating shaft 12.Valve body 19 and 20 all has the feed and the discharging mouth of pipe (as each 20) respectively.Each pipeline 21 and 22 connects respectively goes up pipe joint 17 and lower pipe connection 18 and valve body 19 and 20 separately, thereby the going into of cylindrical chamber 15, outlet spout are combined with feed, the discharging mouth of pipe of valve body 19 and 20.Feed pipeline 23 (discharging also is possible) is loaded on the top of framework 11, and extends upward from valve body 19.Equally, discharging pipeline 24 (also may feed) extends downward framework 11 by following valve body 19.According to the method, when rotating disk rotation advanced cylindrical chamber 15, the going into of cylindrical chamber 15, outlet spout just can cooperate with confession, the discharging mouth of pipe of valve body 19 and 20, and the advantageous methods that circulates by cylindrical chamber 15 is provided.

According to one aspect of the present invention, should be to comprise Disengagement zone and elution zone with Figure 10 equipment preferable configuration.Lock out operation can be carried out by the absorbent resin that loads in the cylindrical chamber 15 routinely in its Disengagement zone, purpose product such as citric acid and other compound in the separating feed solution.Usually, the feedstock solution that contains citric acid or other product all is that adverse current is passed cylindrical chamber and the resin of flowing through.Should be known in that the mouth of pipe number that belongs to separation and elution zone on the CCA is changeable, and can be determined according to overall process economy performance maximum.In addition, also to know, shunt method that a part of product goes to the Disengagement zone from elution zone and can realize effectively utilizing product stream the Disengagement zone by aforesaid.Specifying of these structures now 11 and 12 is discussed at down in conjunction with the embodiments:

Embodiment 1～11

General formality

Carried out the series of pulses test in these embodiments, illustrated that the thermal control chromatography is applicable to various acids and adopts the various tertiary amine polymer that contain.The adsorption column of a long 60cm internal diameter 2.54cm is assemblied on the feeding line of using for eluent (as water or alcohol) and acid product charging separately.Adsorption column is temperature automatically controlled non-jacket type or jacket type, all annotates to some extent in following each specific embodiment.The eluent feeding line comprises a heat exchanger, is used to control the temperature that eluent is fed to adsorption column, and the mixture of aqueous acids product/glucose then adds in room temperature or after heating, shown in concrete.Except as otherwise noted, the acid product addition is by there being 50% (weight), and glucose adds the charging of this product/glucose of 100 gram pulsed quantities by having 2% (weight) at least in post, load to this post is the acid amount of every gram resin 3meq (milliequivalent), except as otherwise noted.For the preparation of post, the resin slurries that will suit are packed in the post, and the water backwash removes air bubble.Set the control temperature again,, set up system balancing by bed recycling elution liquid.Incoming mixture is pumped into bed, then feed eluent immediately.By volume increment collects elution samples in the clustered column, generally for first three bed volume (BV), is that 1/10BV collects the collection of then pressing 1/2BV for the sample in later period by increment.Sample adopts HPLC (high pressure liquid chromatography (HPLC)) and suitable standard to be analyzed.Each time test resin volume is 350ml.

Embodiment 1A and embodiment 1B

A kind of aqueous citric acid/glucose products charging is at the REILLEX in non-chuck post under the flow rate 20.3mL/min ^TMIt is that eluent is handled that HP resin (30～60 order) is gone up with water.For embodiment 1A, charging and eluent temperature are 25 ℃.For embodiment 1B, charging and eluent temperature are respectively 75 ℃ and 86 ℃.Its result is shown in respectively among Figure 1A and Figure 1B.Shown in Figure 1A, glucose is good with separating of citric acid under relatively lower temp; It is only about 3% that but point concentration in the peak of citric acid reaches, and obvious conditions of streaking is arranged.On the other hand, shown in Figure 1B, the peak point concentration of citric acid is high a lot of under relative higher temperature, but relative with separating of glucose relatively poor.Therefore, the present invention can be applicable to such separation and advantageous particularly, and the forward position of when separating, adopting lower temperature and adopting higher temperature to pass citric acid at basic after separating, can access and separate and all good result of citric acid elution profile shape.

Embodiment 2

A kind of citric acid/glucose products charging is at the REILLEX in non-chuck post under the flow rate 20.8mL/min ^TMIt is that eluent is handled that HP resin (30～60 order) is gone up with water.The acid product feeding temperature is 25 ℃, then adds of short duration water charging down in 25 ℃.Under 86 ℃ of temperature, add eluent (water) again.By this way, be to maintain relatively low temperature in that post is passed in product/glucose forward position passing to separating phase time, and when wash-out, make zone, citric acid forward position be in higher relatively temperature.Fig. 2 has listed concrete outcome, shows with Figure 1A to compare its citric acid elution profile shape and its separating resulting of comparing with Figure 1B, and both all make moderate progress.Therefore, can reach favourable separation and product recovery in the thermal control that separates and wash-out is carried out coupled columns in mutually.

Embodiment 3A and 3B

A kind of citric acid/glucose products charging is to go up water at the IRA-93 resin in the chuck post (30～60 order) under the flow rate 21mL/min to handle as eluent.The acid product feeding temperature is 25 ℃.Then add of short duration water charging down in 25 ℃.For embodiment 3A, charging and eluent temperature are 25 ℃.For embodiment 3B, charging and eluent temperature are respectively 85 ℃ and 86 ℃.Its result is shown in respectively among Fig. 3 A and Fig. 3 B separately.Generally shown in Figure 1A and Figure 1B, under the charging/eluent condition of low temperature, separate and carry out better, and the elution profile shape of citric acid is even more ideal under the charging/eluent condition of higher temperature.But also show that thermal control chromatography of the present invention can be applied to promotion separates.

Embodiment 4A and 4B

A kind of 15% acetic acid/1% glucose products charging is the REILLEX in the chuck post ^TMHP resin (30～60 order) is gone up water and is handled as eluent.60.5 gram chargings are packed in the post, and the load on resin reaches the level of every gram resin 2meq acetic acid.For embodiment 4A, flow rate is 20.6mL/min, and the eluent temperature is 25 ℃.For embodiment 4B, flow rate is 22.0mL/min, and charging and eluent temperature are respectively 85 ℃ and 86 ℃.The result lists in respectively among Fig. 4 A and Fig. 4 B, shown in the eluent explanation the present invention that distributes be applicable to separation.

Embodiment 5A and 5B

A kind of 10% ascorbic acid/1% glucose products charging is the REILLEX in the chuck post ^TMWater is handled as eluent in the HP resin (30～60 order).Add combined feed 205.5 grams in the post, the load on resin reaches the level of every gram resin 0.72meq ascorbic acid.For embodiment 5A, flow rate is 20.6mL/min, and charging and eluent temperature are 25 ℃.For embodiment 5B, flow rate is 22.0mL/min, and charging and eluent temperature are respectively 85 ℃ and 86 ℃.The result lists in respectively among Fig. 5 A and Fig. 5 B, illustrates that equally the present invention is applicable to separating and the recovery ascorbic acid.

Embodiment 6A and 6B

A kind of 18% lactic acid/1% glucose products charging is the REILLEX in the chuck post ^TMHP resin (30～60 order) is gone up water and is handled as eluent.Load on resin reaches the level of every gram resin 3mcq lactic acid.For embodiment 6A, flow rate is 20.0mL/min, and charging and eluent temperature are 25 ℃ and reach.For embodiment 6B, flow rate is 21.6mL/min, and charging and eluent temperature are respectively 85 ℃ and 86 ℃.The result has shown the distribution pattern of eluent shown in Fig. 6 A and Fig. 6 B, illustrates that the present invention separates applicable to lactic acid.

Embodiment 7A and 7B

A kind of aqueous citric acid/glucose products charging is the REILLEX in the chuck post ^TMIt is that 20mL/min handles as eluent with butanols that HP resin (30～60 order) is gone up in flow rate.For embodiment 7A, charging and eluent temperature are 25 ℃ and reach.For embodiment 7B, charging and eluent temperature are respectively 85 ℃.The gained result is shown in respectively among Fig. 7 A and Fig. 7 B, and shown in Fig. 7 A, it is that a side presents good separating with citric acid between the opposing party that relatively lower temp can make glucose and water.Shown in Fig. 7 B, higher temperature can be used for increasing citric acid peak point concentration relatively.Therefore, the present invention is separating phase time employing relatively lower temp and is reclaiming phase time at product and adopt relative higher temperature to can be applicable to promote this separation, simultaneously, also can make product charging dehydration and the basic pure recovery product that is is provided.After this such a product for example can make it reaction, so that the esterification citric acid.

Embodiment 8

Repeat the test of embodiment 7A, but adopt ethanol as eluent, gained the results are shown in Fig. 8.These results show between citric acid and water and the glucose separate good.Repeat the test of embodiment 7B, but adopt ethanol, show that equally the recovery distribution of citric acid is improved, descend but separate as eluent.Therefore, proved that helping chromatography and ethanol with heat is the acid product that can be applied to produce dehydration and purification.

Embodiment 9

A kind of moisture 6.5% phenol/1% glucose products charging is the REILLEX in the chuck post ^TMHP resin (30～60 order) is gone up water and is handled under cold feed and the hot eluent condition as eluent with described as embodiment 2.The results are shown among Fig. 9, prove that heat helps chromatography to can be applicable to separate and reclaim phenol.

Embodiment 10

The pH value to 6.45 of regulating a kind of 16.1% lactic acid aqueous solution with ammoniacal liquor, and the REILLEX in the chuck post ^TMHP resin (30～60 order) is gone up water and is handled under cold feed and the hot eluent condition as eluent with described as embodiment 2.The result shows that it is to can be applicable to the salt that this is sour to be separated into free acid (lactic acid) and free alkali (ammonia) that heat helps chromatography.Ammonium lactate also separates under cold eluent condition.

Embodiment 11

A kind of moisture 1% nicotinic acid/30% niacin hydroxyacyl amine product charging is the REILLEX in the chuck post ^TMHP resin (30～60 order) is gone up water and is handled under cold feed and the hot eluent condition as eluent with described as embodiment 2.The result proves that it is the separation that can be applicable to picolinic acid such as the nicotinic acid acid amides (as niacin hydroxyacyl amine) corresponding with it that heat helps chromatography.

Embodiment 12

This example is to enumerate example in contrast.Figure 11 illustrates a kind of utilization structure of CCA as mentioned above.Utilize the structure of Figure 11 in the CCA device of the ISEP L100 pilot-scale that AST company provides, to carry out battery of tests.This device operation is basic according to the method described in the CCA, and this device has fixed set pipe and rotating disk that has 30 resin columns that cooperate with these mouths of pipe of 20 mouths of pipe.The valve running makes these resin columns cut off with different logistics, keeps the logistics continuous flow in these mouths of pipe again simultaneously.What the pilot-plant of this 100ml was installed is glass column (1 inch of internal diameter), band polypropylene cap, in adorn the resin that 70 mesh sieves divide.The system of the upper and lower valve that is connected with these posts is built into by polypropylene and 316 stainless steels.All connecting tubes by device are all by polypropylene, polyethylene or polytetrafluoroethylene (PTFE) (Teflon) tube manufacture of 1/4 inch internal diameter of standard.Heat exchanger shown in Figure 11 is shell-and-tube or plate and frame heat exchanger.The heating of employing low-pressure steam, and adopt chilled water (about 15 ℃) and running water (environment temperature) to cool off.Peristaltic pump with band various sizes (14～18) neoprene pipe fitting transmits all solution.This kind pipe fitting is heat insulation, to limit the heat transfer between itself and the surrounding environment.

Be used in and connect on the dial plate 1/4 inch stainless steel J type thermocouple and axially measure and the record temperature at yokogawaHR 1300 type table record instrument.Be used in the stainless steel pressure table that connects on the dial plate and axially measure pressure.The logistics flow rate then by manual metering respectively go into, the logistics weight of outlet spout place (general per 30 minutes) measured over time.

Anhydrous USP/FCC level citric acid, maltose monohydrate and anhydrous-D (+)-glucose, mixing anomer and deionized water are used to prepare citric acid solution.These solution were all just prepared before using, in order to avoid vegetative possibility.

REILLEX ^TMThe HP polymer is the water wet type, is that company provides by Reilly Industries Inc..This resin is got its 30～60 purpose particle through screening.Again this resin is soaked in 15% the citric acid solution and spends the night, and be delivered in the glass column of L100.Each post is all used the water backwash in addition times over the bed volume, removes fine powder, is connected on the L100 again.The resin of the citric acid swelling of 10.5 liters of total amounts is loaded in 30 posts, is equivalent to about 7.55 liters water-soluble bloated resin or 2.10 kilograms dried resin.

Figure 11 represents to be used for the exemplary flow of the preferred nozzle structure of L100 of IMViC test.The rotation of the post of this L100 counter to flow of solution to, promptly be dextrosinistral in Figure 11.The position of temperature, flow rate and the pans of measuring also all is shown among Figure 11.Concisely describing this structure is, by the general subordinate's streaming of flow pattern of this post, carries out the absorption of cold citric acid at mouth of pipe P5-P9, and P1-P4 washes at the mouth of pipe, and P14-P17 carries out the hot water desorption at the mouth of pipe.Carry out the cooling of resin after the desorption stage with mouth of pipe P10-P13, carry out at the desorption resin that preheating is loaded before the stage with mouth of pipe P18-P19 simultaneously.The mouth of pipe 20 is used for driveing the remaining cleaning solution of resin.

More particularly, the citric acid feedstock solution is to be added to mouth of pipe P5 through heat exchanger 32 (cooling) from jar 30 with pump 31.Charging pans 33 are introduced in mouth of pipe P5 outlet logistics.Introduce mouth of pipe P6 and P7 with pump 34 by heat exchanger 35 (cooling is provided) and stream from the solution that charging pans 33 come out.Introduce mouth of pipe P8 and P9 from the logistics that mouth of pipe P6 and P7 come out through heat exchanger 36 (cooling is provided) and stream.Introduce precooling/waste liquid pans 37 again from the logistics that P8 and P9 come out.The solution that comes out from pans 37 is introduced mouth of pipe P10 and P11 with pump 38 through heat exchanger 39 (cooling is provided), and the logistics of coming out from mouth of pipe P11 and P12 directly returns jars 37.Like this " pump circulation " makes it carry out precooling to resin bed before entering the citric acid adsorption section.The waste liquid overflow is also carried out at jar 37.

In the desorption stage, desorption medium is water for example, from head tank 40 usefulness pumps 41 with and the stream mode be delivered to mouth of pipe P12 and P13.Mouth of pipe P12 and P13 outlet stream flow into and separate pans 42.With pump 43 solution is returned jar 42 from jar 42 pumpings again through heat exchanger 44 (heating).This kind pump circulation through heat exchanger heats in jars 42 solution be used for desorption manipulation.Should be noted that separating other used jar in pans 42 and this structure all is preferably opening and leads to air suspended type.Allow solution to discharge gas like this, especially in heating, go out so that made it before entering resin column loss.Resin bed can cause the cause of channel and countermeasure set valid function because gas is flowed through, and it is favourable doing like this.

The heated solution and the stream of self-separation pans 42 are delivered to mouth of pipe P14 and P15 in the future with pump 45.The outlet stream of mouth of pipe P14 and P15 is collected in the middle knockout drum 46.Solution in the jar 46 also is to carry out the pump circulation with pump 47 and heat exchanger 48 (heating).Again solution in the jar 46 and stream are delivered to mouth of pipe P16 and P17, each outlet stream all is collected in preheating/product pans 49.Solution in the jar 49 also carries out the pump circulation by pump 50 and heat exchanger 51 (heating).A part of solution in jars 49 as product overflow reclaimed.Another part is then sent among mouth of pipe P18 and the P19 with pump 52, exports stream accordingly and send and return in jars 49.Pump circulation by P18 and P19 play they enter add the operation of thermal desorption section before the effect of preheating resin bed.Another part solution in the jar 49 then is conveyed into mouth of pipe P20 with pump 53, also is at the P20 place resin bed to be preheating to a certain degree.

The important part of the present invention is, the outlet stream of mouth of pipe P20 is carried through heat exchanger 54 (heating), operates to washing section again.Particularly, with the outlet of mouth of pipe P20 stream with and streamed mouth of pipe P1 and the P2 of sending into respectively.In this explanation and preferred construction, from the unique washing agent effect of playing in the washing operation of product stream of mouth of pipe P20.But know, such product stream can with other washing agent that is added to washing section use that combines, for example with water.The outlet stream of collecting from mouth of pipe P1 and P2 with and the stream mode be added to mouth of pipe P3 and P4.Therefore, in mouth of pipe P1-P4, the resin bed of load product such as citric acid is to deviate from such as carbohydrate not to be adsorbed or the difficult material that is adsorbed through flushing.The outlet stream of mouth of pipe P3 and P4 is collected in the charging pans 33, makes it to flow out the citric acid charging with mouth of pipe P5 and mix in pans 33, and the method for discussing by the above-mentioned initial stage is handled again.

In the demonstration test that structure is carried out in utilizing Figure 11, the L100 device is operation three hours continuously before collecting sample, and system reaches or near equilibrium condition before being beneficial to take a sample.The output sample was collected in more than 30 minutes, with the representativeness of guaranteeing that it is suitable, and took a sample more than one, and carry out segmentation by the speed of rotation sample time, in order to avoid sample flow repeats from same post.In such test, the duration added 14.7% the citric acid charging that contains 0.43% glucose and 2.03% maltose to system more than 28 hours.The flow rate and the temperature of the fluent solution at each vital point place of system are listed among Figure 11 in this test.Product stream contains average 9.73% citric acid (by the rate of recovery 96%), wherein deviates from 94% glucose and 97% maltose.In another group identical test, except that deletion heat exchanger 32 and thus to the cooling of post 5 chargings, product stream contains average 9.76% citric acid (by the rate of recovery 98%), and glucose of wherein deviating from and maltose are respectively 94% and 98%.

Embodiment 13

Figure 12 provides a kind of L100 structure schematic flow sheet that can be used for several method of the present invention.Identical among this structure and Figure 11, so GU Generic Unit need not to add narration again.But the structure of Figure 12 is by the carrying out that helps using thermal control chromatography and elution process and adopts the product load that substantially exceeds this adsorbent effective adsorption capacity and arrange.Contrast Figure 11 and Figure 12 as can be seen, belong to the portion of product stream step of the adsorption column of product (mouth of pipe P19-20 and P1-6) of having passed first load, and its mouth of pipe number is existing to be increased.The increase of mouth of pipe number provides additional separating power like this, and even under higher product load, the impurity that can make feed stream in the post is deviate from before adding thermal desorption stage (mouth of pipe P13-18).As shown in figure 11, temperature of being measured and flow rate also all are shown among Figure 12.Also shown out the concentration of the impurity in each charging/eluent in product (citric acid) concentration and the process among Figure 12.Obviously, as can be seen, adopt and wherein to be easy to carbonization material (RCS) content when being 0.486 50% citric acid charging, reclaim that citric acid concentration reaches 20.9% in the product stream, and RCS content only is 0.073.Therefore, the product of gained stream citric acid content height, RCS content is low.In addition, method described in conjunction with Figure 12, its operational capacity is more high than shown in Figure 11, and the latter operates under every gram dried resin 1.3 millinormal citric acids (meq/g), and the former operates under about 3 (meq/g dried resins).The operational capacity increase so more to be helped reducing resin reserve and equipment size greatly, and production capacity and process economy are significantly improved.

Embodiment 14

Figure 13 provides a kind of explanation to can be used in nozzle structure exemplary flow in the CSEP device (also by AdvancedSeparations Technologies, Ins. company provides).This kind CSEP device is more suitable for chromatography operation than aforementioned ISEP device, and it has 20 adsorption columns and 20 mouths of pipe, and order with the adsorption column label after the mouth of pipe.As from shown in Figure 13, demonstration CSEP device comprises the arrangement of a common adverse current to downflow system, has wherein avoided parallel mouth of pipe charging (ISEP structure as described above), so just can utilize the separating power of resin reserve most effectively.The charging that enters mouth of pipe P1 is the charging that contain acid product stream of a part from mouth of pipe P20 (being discussed at down).After leaving the adsorption column relevant with mouth of pipe P1, this charging is passed heat exchanger 60 and is cooled off, and another mistake stream is by mouth of pipe P2-P5.This logistics converges mutually with the feedstock solution of coming out from 61 pumpings of feedstock solution storage tank with pump 62 (as containing 50% citric acid and sugared impurity) then, enters mouth of pipe P6 after cooling off by heat exchanger 63 again.This solution adverse current is passed mouth of pipe P7-P9, then cools off by heat exchanger 64, enters mouth of pipe P10 again.Product acid is relatively rarer light in the logistics of outflow mouth of pipe P10, and impurity (as carbohydrate) is to have concentrated, and then sends to waste residue.

The water and other liquid that pump from storage tank 65 through pump 66 cool off through heat exchanger 67, enter mouth of pipe P11.To flow out mouth of pipe P11 logistics and feed pre-cold tundish 68.A part of solution cools off through pump 69 warp let-off heat exchangers 70 in jars 68, feeds mouth of pipe P12 again, after return in jars 68.Resin has been cooled off in this pump circulation by mouth of pipe P12.With the solution in the jar 68 again with adverse current through mouth of pipe P13-P14 and heat exchanger 71, continue again to feed and pass mouth of pipe P15-P17 with reflux type.Outlet stream warp let-off heat exchanger 72 with P17 heats again, passes P18 with reflux type again.Again preheating pans 73 are sent in the outlet logistics of mouth of pipe P18.Solution warp let-off heat exchanger 74 in the part jar 73 is heated, upwards flow and passes mouth of pipe P19, return jar 73 again.This pump circulation at mouth of pipe P19 makes the resin heating.Solution in the part jar 73 is passed through mouth of pipe P20 through down flowing.The logistics of coming out from mouth of pipe P20 is a kind of purpose acid (as citric acid) does not have original impurity (as carbohydrate) the charging substantially through concentrating a solution.This outlet logistics of a part is collected as product, and another part is as the charging of mouth of pipe P1, as mentioned above.

The CSEP structure of Figure 13 can effectively be handled acid product (as the citric acid) solution that contains other compound and concentrated, even in that to add its content also passable when substantially exceeding solid absorbent in the post (REILLEX HP resin as described above) to the charging of sour adsorption capacity.Like this, several method of the present invention can utilize chromatograph and two kinds of traditional absorption/thermal desorption phenomenons, thereby significantly reduces the demand of commercial run to adsorbent, and can obtain highly concentrated product fraction.

What need know is, it is exemplary that the mouth of pipe that Figure 13 provides and other are handled structure, and other structure also can be applicable to enforcement of the present invention.For example, the post number that belongs to segregation section or rectifying section and wash-out section be can according to method/or the demand of product changed.Comprise between mouth of pipe P10 in Figure 13 and the P11 that it also is possible utilizing the buffering area of or several.In addition, understandablely be, implementing when of the present invention, heat exchanger (heating or cooling are provided) but the position be change in operation.

Embodiment 15

In glass column (5.8cm (internal diameter) X75cm), air is driven in water flowing, uses the methyl alcohol replacing water again with the resin fill of the REILLEX HP of 1500ml.The moisture lactic acid solution that a kind of 13% (weight) contained 1.29% glucose pumps in the post, and uses methyl alcohol with speed 100ml/min wash-out in addition immediately.This tests under 25 ℃ and carries out.Collect and analyze and flow out sample, eluent bed feed volume is mapped according to each concentration of component.The results are shown among Figure 14, the result shows that lactic acid is separated with glucose, separates fully with water base, has obtained being mainly the lactic acid methyl alcohol fraction that relative altitude concentrates.Therefore, the chromatography dewatering that adopts alcohol eluen is described, has obtained even all very good lactic acid elution profile shape when under isothermy, testing.Therefore, the aqueous solution of lactic acid or other similar weak acid such as acetate can be under isothermy be handled the acid of dewatering and reclaiming high concentration in alcoholic solvent in as Figure 12 and CCA fluidal texture shown in Figure 13.

Elaborating and describing what the present invention had done by accompanying drawing and above specification; these all should regard exemplary as; be not to be restriction on the feature; it is also to be understood that; existing illustrated and what describe only is embodiment preferred, and according to all changes of doing in the present invention's spirit scope with improve all to belong to and be required to be protected.

Here the disclosure of all references all is declarative to those skilled in the art, and what quote as proof for reference here also is individually to quote and list as a reference entirely.

Claims (41)

1, a kind of being used for from the thermal control method of acid with the mixture recovered acid of another compound, being included on the absorbent resin under first temperature chromatography should acid and another compound, then under second temperature conditions higher at least 10 ℃ than first temperature from the absorbent resin this acid product of wash-out.

2, according to the process of claim 1 wherein that described acid is selected from phenol, salicylic acid, phthalic acid, M-phthalic acid, benzoic acid, 3-chlorobenzoic acid, citric acid, lactic acid, lactyl-lactic acid, malic acid, mandelic acid, diphenylglycollic acid, diglycolic acid, glycolic acid, butanedioic acid, tartaric acid, formic acid, glutaric acid, fumaric acid, acetoacetate, acetic acid, furoate clothing, sulfonic acid, wolframic acid, molybdic acid, picolinic acid, piperidine carboxylic acid, gallium ion (III) and mercury ion (II).

3, according to the method for claim 2, wherein said acid is carboxylic acid.

4, according to the method for claim 3, wherein said acid is citric acid or lactic acid.

5, according to the method for claim 4, wherein said product is a citric acid.

6, according to the process of claim 1 wherein that described adsorbent is a kind of cross-linked polymeric resin that contains tertiary amine group.

7, according to the method for claim 4, wherein said adsorbent is a kind of cross-linked polymeric resin that contains tertiary amine group.

8, according to the method for claim 7, wherein said adsorbent is a kind of cross-linked polymeric resin that contains pyridine.

9, according to the method for claim 7, wherein said fluoropolymer resin divinyl benzene crosslinked.

10, according to the method for claim 8, wherein said fluoropolymer resin divinyl benzene crosslinked.

11, according to the method for claim 8, wherein said fluoropolymer resin is a kind of poly--2-or poly--4-vinylpridine of divinyl benzene crosslinked.

12, according to the method for claim 11, wherein said resin is a kind of huge netted spherolite shape.

13, according to the method for claim 12, wherein said resin is the usefulness divinyl benzene crosslinked of about 2%～50% (weight).

14, according to the method for claim 13, wherein said product is a citric acid.

15, according to the process of claim 1 wherein that described eluent is to use when described chromatography is carried out in the acid that wherein contains a certain quantity.

16, according to the process of claim 1 wherein that described acid offers described chromatography with the aqueous solution, wherein alcohol eluen is used for described acid is dewatered when described chromatography.

17, according to the process of claim 1 wherein that described other compound is sugar, amino acid or acid amides.

18, according to the method for claim 17, wherein said acid is the acid amides that a kind of picolinic acid and described another compound are a kind of correspondences of picolinic acid.

19, according to the method for claim 17, wherein said acid is that nicotinic acid and described another compound are niacin hydroxyacyl amines.

20, according to the method for claim 17, wherein said acid is that a kind of acid and described another compound that produces by sweat is a seed amino acid or sugar.

21, according to the method for claim 20, acid wherein is citric acid.

22, according to the method for claim 20, acid wherein is lactic acid.

23, the method for the acid in a kind of separation solution and a kind of or several other compounds comprises: provide a kind of being equipped with in it sour affinity to be compared this is a kind of or several other compound affinity are high and with the descend contact zone of adsorbent that sour affinity is increased of temperature;

In the contact zone, introduce this and contain acid and this first solution a kind of or several other compounds;

First temperature with can in the contact zone, make the condition that this acid forward position is a kind of with this or effectively separate in several other compound forward positions under, second solution is fed and passes this contact zone;

Second temperature than the high at least 10 ℃ condition of first temperature under sour forward position in the wash-out contact zone.

24, a kind of heat that is used to separate a kind of acid product and another compound helps the chromatography method, comprising:

(a), provide many contact zones to be equipped with in it and a kind of the adsorbent that another compound affinity is high and its affinity descends and raises with temperature is compared in acid;

(b), process chromatography district handles described contact zone in proper order, wherein a kind of eluent and a kind of product solution that contains acid and another compound is passed through this contact zone together, to finish the chromatography process of separating acid and another compound under first temperature; With

(c), afterwards in step (b), by elution zone sequential processes contact zone so that second temperature than the high at least 10 ℃ condition of first temperature under acid product in the one or more contact zones of wash-out.

25, according to the method for claim 24, elute soln wherein contains the acid of a certain quantity.

26, the method for organic acid product in a kind of dehydration and the recycle-water solution, be included on the absorbent resin with alcohol as mobile phase and therein acid product be under the condition of wash-out from substantially anhydrous alcoholic solution aqueous acids product solution to be carried out the chromatography processing.

27, a kind of organic acid is carried out dehydration method, comprising:

The contact zone of a kind of interior dress to the high adsorbent of sour affinity comparison water is provided;

Aqueous acid is introduced into the contact zone;

Under making organic acid forward position in the contact zone and the condition that effectively separates in the water forward position, liquid alcohol is fed and passes this contact zone;

Organic acid forward position in the wash-out contact zone obtains containing the alcoholic solution that thing is taken off in organic pickling, and described eluate is substantially anhydrous.

28, a kind of the organic acid product is carried out dehydration method, comprising:

(a), provide the contact zone of many interior dresses to the high adsorbent of acid product comparison water affinity;

(b), order handles described contact zone by the chromatography district, wherein a kind of alcohol eluen and a kind of this aqueous acid that contains fed and pass this contact zone together, to finish wherein the chromatography process of acid and water;

(c), afterwards in step (b), by this contact zone of elution zone sequential processes so that in these one or more contact zones the acid product in this substantially anhydrous alcoholic solution of wash-out.

29, according to the method in the claim 26,27 or 28, acid wherein is a kind of carboxylic acid.

30, according to the method in the claim 29, carboxylic acid wherein is a lactic acid.

31, according to the method in the claim 29, alcohol wherein is to be selected from methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols and methyl isobutyl carbinol.

32, according to the method in the claim 29, alcoholic solution wherein is to contain the water that is no more than 5% (weight).

33, a kind of method that reclaims the chromatography of weak acid and alkali from the salt of weak acid and alkali respectively comprises:

A kind of contact zone that contains the polymer of tertiary amine group is provided;

A kind of solution of salt is introduced so far in the contact zone;

Under making weak acid forward position in the contact zone and the condition that effectively separates in the alkali forward position, a kind of eluent is fed and passes this contact zone;

From then on distinguish wash-out weak acid forward position and alkali forward position in the contact zone.

34, according to the method for claim 33, wherein said polymer comprises the pyridine group.

35, according to the method for claim 33, wherein said weak acid pKa value is about 3～5.

36, according to the method for claim 35, wherein said weak acid is a kind of acid by fermenting and producing.

37, according to the method for claim 36, wherein said weak acid is lactic acid.

38, according to the method for claim 37, wherein said salt is sodium lactate, calcium lactate or ammonium lactate.

39, according to the method for claim 38, wherein said salt is ammonium lactate.

40, according to each the method in the claim 33～39, wherein said acid is to be higher than under the condition of the used temperature of described feeding eluent step wash-out in addition in temperature.

41, according to each the method in the claim 33～39, wherein acid is to be same as substantially in temperature to feed under the used temperature conditions of eluent step wash-out in addition.

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