TW385257B - Separation processes utilizing solid adsorbents - 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.

Description

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vL§Kr's Subsidiary of the Ministry of Economic Affairs, Central Bureau of Standards and Quarantine, Shellfish Consumer Cooperatives_B7_V. Description of Invention (8) Separation of sorbent in chromatography type, solution M contains more than sorbent on acid The acid concentration of the adsorption capacity is better. After the solution containing the acid / impurities is introduced, a second liquid, such as water, an aqueous solution containing an acid but substantially free of impurities, or an organic solvent, at a first temperature M and the The forward of one or more impurities passes through the contact zone under conditions that achieve effective separation in the contact zone. The acid front is then washed out of the contact zone via the liquid medium at a temperature higher than the first temperature, such as 10 TC above the first temperature and at least 20 t above the first temperature: better, the second temperature. In this way, a “thermally controlled” chromatography procedure can be achieved, in which the affinity cone of the adsorbent for the acid is maintained at a relatively high level in the heterogeneous phase—the rib is separated from the acid from a variety of impurities In the elution phase, after the impurities have been separated from the acid front * the affinity of the adsorbent for the acid is maintained at a relatively low level-it helps the removal or elution of the acid from the contact zone and causes elution in a period of time Increase in acidity. Therefore, the preferred method of the present invention is superior to the traditional adsorption / thermal desorption phenomenon in the chromatographic separation facet, which can achieve effective purification of the acid product from one or more impurities, and recover the washing containing the highly reduced product. Out part. Generally speaking, a liquid-solid separation method for recovering valuable chemical products is known, and various adsorbent resins and appropriate liquid eluents have been confirmed. Therefore, those skilled in the art should easily select and use an appropriate adsorbent resin and eluent medium according to the present invention. Generally speaking, the adsorbent used must have the ability to adsorb the desired product, and must be stable (ie, it will not decompose significantly) under the processing conditions that will be described further below. Although this adsorbent can be any substance that can adsorb the desired product (including activated carbon, zeolite, etc.), it is better to use in the present invention (Jing first read the precautions on the back before filling this page) Order C. This paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 11-correction page Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative A7 ____B7_____ 5. Description of the invention (i) Background of the invention Technology of valuable chemical products. In particular, the present invention is directed to an efficient and economical method for entangled recovery of a desired product from a liquid medium in which the desired product coexists with impurities, including a novel thermally-assisted rib decantation technique (ther π a 1 1 y-assistedchr 〇. bat graphic techniques) 〇 In a further background, M has been studying the recovery and purification of acidic compounds such as carboxylic acids and other valuable chemical products from the medium for a long time, hoping to develop efficient and cost-effective manufacturing paths. For example, carboxylic acids such as mongolic acid and lactic acid are produced worldwide by fermentation. This fermentation produces fermentation broths from which the desired acid is recovered for passivation. When it comes to making large-scale chess, it is even more important to minimize recycling costs. Recent recycling efforts have focused on the recovery of carboxylic acids from fermentative media using solid polymer sorbent materials. In this treatment method, the fermentation broth is passed through an adsorbent that adsorbs carboxylic acid, and the carboxylic acid is desorbed in some manner to obtain a product. Generally speaking, various adsorbents and adsorption / desorption methods have been proposed. For example, 1 (3 \ ^ 5813 et al., In U.S. Patent No. 4,323,702, describes a method for recovering carboxylic acid from a material whose main component M is a polymer adsorbent having a pyridine skeleton structure and a complexing framework. The carboxylic acid is adsorbed on The adsorbent is then desorbed with an alkaline organic substance such as an aliphatic enzyme, a ketone, or a zeolite. "1. Gate 0 丨 0" 3 et al., US Patent Nos. 4,72〇, 579, 4, 8 5 1,57 3 and 4, 85 1,57 No. 4 teaches solid polymer adsorbents, including neutral, non-hatching, giant net, water-insoluble complexed styrene-$ (vinyl ) Benzene and benzene have a fixed tertiary amine functional group to form a pyridine functional group. The paper size is suitable for home care ^ T (CNS) A4 specification (210X297 mm) 7 (Please read the Note $ Item on the back side # Fill this page) 'i *. I--7-- We have determined C / A, B7, D7, B7, B7, B7, B7, B7, B7, A5, B7, A5, B5, A5, B3, A5, B3, A5, B3, A7, B7, etc. Masterbatches, or acrylic or stupid vinyl resin masterbatches with fixed cell-group quaternary amine functionalities. In their study, kulprathipanja et al. The "pulse tests" performed under the conditions of annual isothermal conditions are described, in which he and water are desorbing agents. The South African Application No. 855 155, filed on July 9, 985, describes the product Procedure for recovering acid from its aqueous solution. In the adsorption step, the acid-containing solution is passed through the polymer containing vinylimidazole / methylenebispropeneamine polymer, vinylpyridine / trimethylolpropane trimethylpropanoate / Vinyl trimethyl silane polymer, vinyl oxazole / N-vinyl-N-methyl ethyl amine / methylene 5? Propionamine polymer, Amberlite IRA 35 (Roh & H. aas-dimethylamine-containing acrylate / divinylbenzyl polymer), or Amberlite IRA 93 SP (Rohm & Haas) or Dowex HWA-1 or WGR-2 (Dow Chemical) (the latter three are A column of adsorption pin resin consisting of dimethylamino styrene / divinylphenyl polymer). To desorb the acid, water is usually passed through the column at a temperature of 90 * C. However, The described single-pass elution procedure has poor thermal energy utilization efficiency and does not substantially increase the potential effectiveness of the resin to obtain a highly full-scale desorption solution In addition, the resin used in this South African application is quite unstable to heat, so the desorption step using hot water will cause degradation. Declared on March 12, 1992 B-Application PCT / US92 / 02107 (Announcement of October 1, 1992, V092 / 16534) and PCT / US92 / 0 1 986 U, which was filed on March 12, 1992, Announcement of October 1, 992, W092 / 16490), both proposed by Reilly Industries Inc., published _ Use steam or thermal paper size to apply Chinese National Standards (CNS) Λ4 specifications (2 丨 〇X25 > 7 mm) 5 (Please read the back note first (Save this page)

A7 B7 V. Description of the invention (3) ¥ and TL capacity 18 with Ϊ and Ϊ 脱 〇W ΪΪ Ha / points attached to the liposuction arsenic, the more he has a higher or higher pyridylpyridine base The lower ene is attached with "E-Best". The enoic acid of benzene heat group in the decomplexation method is the most effective one. Compared with the liquid solvent, the degree of desorption attached to the zeolite CZD is highly repellent and more useful, so that the fattening ground can be improved and changed in the easy order process. Table 41 shows 5, many of the countries that have already taken advantage of the law. The steps of recovering the acid of the French side are based on the fact that the fatty acid is added to the acid-absorbing birch rubber No. 0 and the amine is removed.水 脱 68 料 2, t. 3 materials ο will be 5, then the first profit. French Fangmei ’s C acid peeling method is used to recover the acid from the amine. The resin is used to describe the number 11 8 6 2 8 3 5 Acid 0 撺 will be treated as 0. After the first solution of acid-like matter, and pure sodium acid is not acidic, it will be described as volatility 0. Then the material will be pure and separated. (Please read the notes on the back before filling out this page) Method β Phase L is here and other backgrounds in this field 'There is still a need for improved and effective methods for passivation and recovery of carboxylic acids and other valuable products. The present invention is Focus on this need. SUMMARY OF THE INVENTION Accordingly, a preferred embodiment of the present invention provides a method for separating an acid from a mass of impurities, which encompasses thermo-fflanaged chromatographic separation and eluent. Therefore, 嘀 provides a better method for recovering acid from a mixture of acid and impurities. It includes decanting the acid and impurities on the adsorbent resin at the first Myanmar temperature, and then The temperature is high, for example, at least higher than 10t :, at the second temperature, the acid product is washed out of the adsorbent resin and the paper size is in accordance with Chinese National Standard (CNS) A4 (2 丨 0X 297) (Centi) -6-9 • Post 1 MU Yin Ju Α7 Β7, Consumer Work Cooperative of Central Ministry of Economic Affairs of the Ministry of Economic Affairs V. Description of Invention (4)

ne, no. Here, the formula 20, the degree of brightness, the degree of force Z, and the degree of degree M will be equal to the equation. Cheng Chenggao S and the acid-concentrated concentrated solution are separated from the original U by 1 η. As the acid soluble 10W high score low , I'm back to ct's. to. | §'s # 此 _ 和 taii will make the Mnuiiif out of phase and phase, _, on the first, high-capacity} 少于 于 肫. / «« 化 (C Yes. Attach this nt down to washing and holding without attaching the pure area with up to suction. Γ0 pieces, the area-dimensional species increase the absorption effect of the material into the area (f article, such as multi-touch There are pure and pure acid. Examples of acid strikes and or not in the amount are not low and middle butt before the separation, the self-acidic acid _ _ _ plant drop zone agent over the high and pure The attached polyacid becomes a liquid acid, and the acid does not absorb or absorb η, so that the degree M is too warm for the layer species. The front temperature is too high. ^ The previous one is attached with an internal transmission or with a more powerful solution. Some are sucked once and the suction is used to make the acid and the solute solution available. The acid and solute solution are used to dissolve and blunt the parent species. In the middle of the stagnation formula, the content of the formula is not included in the two-phase phase-blocking phase, and the method of producing the second-filled scent of the saccharine, which can be extracted before the middle of the squaric acid, and the better. Change the material solution to one or more, and make it better. And it is purely soluble and then the first acid P,-and, W --- Mi JI ¥ --C Pack-(Please read the back first (Notes for refilling this page)-Order the employee spending agreement of the Central Bureau of Standards of the Ministry of Economic Affairs The concentrated product produced by the company is the most concentrated. A particularly preferred method of the invention uses a coupling device including a resin-filled fine zone (for example, a resin column). A chroiiatographic separation zone ) Includes a large number of contact zones containing a sufficient amount of adsorbent, K achieves a substantial separation between the acid and the impurities. The chromatographic separation zone operates at the first • fairly low temperature. The establishment of the elution zone makes the product acid Once it is substantially separated from the impurities, it is eluted. The elution zone is operated at a second temperature higher than the first temperature. After the elution zone, M will fill the contact area of the tree cells (now roughly The size of the paper without product is applicable to the Chinese National Standard (CNS) Λ4 specification (2) 0X297 mm 7 A 7 B7 _ V. Description of the invention (5) In) Stacking cooling steps to obtain a winding device The most entrapped irrigation level in the next cycle is better. The preferred cooling step includes flowing a liquid medium with a temperature lower than the resin through the contact area. The contact-type contact device can be appropriately adjusted by a valve to make contact. Sub-area mining Sickle, washing, cooling step «M and performing the thermally controlled ephemeral separation method of the present invention. According to another aspect of the present invention, the thermally controlled chromatography method includes establishing a contact plaque in which a plurality of adsorbents are contained. A method for treating ores. This treatment includes passing a liquid medium containing the product's adsorption capacity of the product to the product through adsorption, so that the acid and impurities are separated by dialysis at the first temperature, and then The product is eluted at a second temperature that is at least 10 υ above the first temperature. In this and other aspects of the invention, the medium containing the product from the pre-treated contact plaque may be included in the Chromatographic separation phase in the eluent. Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, India. The method of the present invention provides the recovery of the product in the tritium liquid medium, and effectively uses the heat energy to help the recovery. Configuration with high capacity M and reduced adsorbent inventory requirements. The present invention also provides a procedure that is easy to handle and can be applied to recover various desired products produced in a suspect solution. Other preferred embodiments, characteristics and advantages of the present invention will be made clearer by the following description. Brief description of the drawing_ U and 1B are shown in the following table: Polyacrylic acid complexed with aqueous acid solution / glucose mixture M REILLEk'THP, pyridine polymer in cold feed / eluent (i picture 1A) and hot feed The elution side is chromatographically treated in the case of material / elution (circle 1B). 8 (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standards (CNS) Λ4 specifications (2 丨 OX297) 消费 Printed by A7 B7_5, Consumer Cooperation Cooperation between the Central and Provincial Bureau of the Ministry of Economic Affairs Invention description (6)

Circle 2 shows the chromatographic elution of the betulinic acid aqueous solution / grapevine mixture MREILLEXWHP complexed polyethylene-sulfonyl " itidine polymer under cold feed and hot agglutination conditions; side view. Circles 3A and 3B show the JS analysis in the case of betulinic acid water-soluble / grape vineyard port + M + -IRA-93 tree spore% cold feed / leaf extraction (3A) and hot feed / leaf extraction (3B) Washing foot noodles. _4A and 4B show the acetic acid aqueous solution / grapefruit mixture WREILLEX ™ HP entangled polyethylene pops, beer polymers pass under the conditions of soil material / elution (4A) and hot feed / elution (4B). Elution side view of the elution process. 5A and 5B show ascorbic acid aqueous solution 7, and the glucose mixture is REILLEX τ " 丨 丨 t version. It is known that polyvinylpyridine polymer is in cold feed / elution (5 Λ) and hot feed / In the case of elution (5 B), the elution side garden is subjected to abrasion treatment. Circles 6 Α and 6 Β show the lactic acid / glucose mixture with R E I L L Ε × ΤΜ ΡΡ-linked polyethylpyridine polymer in cold feed / extraction (6A) and hot infusion / eluent

V (6B) side view of the elution process in the lower layer. Figures 7A and 7B show an aqueous glucose / acid-like acid mixture that enables us to use MREILLEX'HP complexed polyethylene glycol-based batches of polymers (cold feed / pick-up) and hot feed / wash (7B) The extraction side view of the employment analysis boundary. Circle 8 shows the chromatogram of the eluted foot using the glucosamine aqueous solution / silicic acid mixture using acetic acid as the eluent W REILLEXTM HP-linked polyethylene polymer. Circle. 9 shows that the glucose aqueous solution / phenol mixture is articulated with ILLEX TM HP. This paper is suitable for national standards (CNS) A4 specifications (210X297 mm). 9-Factory ----- ^- ------ Order (please read the note on the back before filling this page) • an— Hi In V. Description of the invention (7) A7 B7 Polyvinylpyridine polymer in cold feed and hot elution In the case of chromatography, he dragged his ring gear. 'Sun Ϊ0 is a side view of the cross section of the exemplary quick-speed contact device that can be used in the present invention. I 11 is a diagram illustrating a port group. 1 2 is a diagram illustrating a valve configuration. .3 is a schematic diagram illustrating the state of the il 镝 -type contact device of Example 10, which is used in Example 10, and illustrates a preferable specific example of the valve configuration. The meaning of the buried ore contact device of Example 11 used under M. The intended use of the submerged contact device of Cell Example 12 below. Note Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to help with this and will use specific, not limited, modifications and applications. As mentioned earlier, the method of separation of impurities with suction chromatography and the separation of dialysis acids with hydrazones and solutions with a higher affinity than solutions that are lowered and improved are introduced into the terminology of the invention. Some specific examples will be explained. However, it is necessary to understand the scope of the present invention and the changes often used in the principles of the present invention. The skilled person should understand that it still belongs to the scope of the present invention. A preferred embodiment of the present invention provides a Thermal control of separation to recover the product on the resin. The typical method of the present invention uses sorbent resin and phenomena related to the adsorption / thermal desorption operation in 1 ion. In order to separate the i- or polypyrene impurities, a contact zone containing an adsorbent for acid to one or more impurities and an affinity for acid with temperature is used. The first contact area containing acid and impurities is placed. In order to achieve high operating capacity and more effective use of this paper size, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable. 10 n--! I— -I-W--if— Is--rA- ^-!-—Ιί--I —I—-—I!-, 1T1-. -------- I-(Please read the note on the back before filling this page) Ί:

vL§Kr's Subsidiary of the Ministry of Economic Affairs, Central Bureau of Standards and Quarantine, Shellfish Consumer Cooperatives_B7_V. Description of Invention (8) Separation of sorbent in chromatography type, solution M contains more than sorbent on acid The acid concentration of the adsorption capacity is better. After the solution containing the acid / impurities is introduced, a second liquid, such as water, an aqueous solution containing an acid but substantially free of impurities, or an organic solvent, at a first temperature M and the The forward of one or more impurities passes through the contact zone under conditions that achieve effective separation in the contact zone. The acid front is then washed out of the contact zone via the liquid medium at a temperature higher than the first temperature, such as 10 TC above the first temperature and at least 20 t above the first temperature: better, the second temperature. In this way, a “thermally controlled” chromatography procedure can be achieved, in which the affinity cone of the adsorbent for the acid is maintained at a relatively high level in the heterogeneous phase—the rib is separated from the acid from a variety of impurities In the elution phase, after the impurities have been separated from the acid front * the affinity of the adsorbent for the acid is maintained at a relatively low level-it helps the removal or elution of the acid from the contact zone and causes elution in a period of time Increase in acidity. Therefore, the preferred method of the present invention is superior to the traditional adsorption / thermal desorption phenomenon in the chromatographic separation facet, which can achieve effective purification of the acid product from one or more impurities, and recover the washing containing the highly reduced product. Out part. Generally speaking, a liquid-solid separation method for recovering valuable chemical products is known, and various adsorbent resins and appropriate liquid eluents have been confirmed. Therefore, those skilled in the art should easily select and use an appropriate adsorbent resin and eluent medium according to the present invention. Generally speaking, the adsorbent used must have the ability to adsorb the desired product, and must be stable (ie, it will not decompose significantly) under the processing conditions that will be described further below. Although this adsorbent can be any substance that can adsorb the desired product (including activated carbon, zeolite, etc.), it is better to use in the present invention (Jing first read the precautions on the back before filling this page) Order C. This paper The scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 11-correction page i A7 B7 V. Description of invention (9) (Please read the note on the back before filling this page) The adsorption surface is for meridian connection Polymer adsorption resin with thermal and mechanical stability and favorable physical form. Adsorbent resins in the form of beads are preferred. Especially those with a particle size of about 20 to about 200 meshes, and more preferably about 40 to about 120 meshes. Various polymer adsorbents for recovering desired adsorbate products such as post-acids or other acids have been published, and they can be used as a stationary phase for the method of thermal control chromatography recovery of the present invention. These polymeric sorbents are made by polymerizing one or more monomers, which typically include complexed monomers. Polymerization was carried out to obtain resin beads of the macroscopic type or macroreticular type. In addition, these lipid beads can be modified, for example, by adding ions based on the resin such as a quaternary salt or acid salt group. The resulting resin is therefore de-ionized, ion-limited or non-ionic and has a variety of physical and chemical properties. Printed by the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs. For example, the published dendrites include non-ionic and ionic polymers > including neutral, non-ionized, giant, and insoluble in water. Complexed styrene-poly (vinyl) benzene, sexual polymer materials such as complexed pyridine-containing polymers such as vinylpyridine polymers, complexed with fixed tertiary amine or pyridine functional groups Acrylic or stupid vinyl resin masterbatches, acrylic or stupid vinyl resin masterbatches with fixed aliphatic tetraamine functional groups i complexed, and the like (see, for example, Kawabata and kuprathipanja cited in the background) Et al.) These and a variety of other polymers known to be used as adsorbents in this technology, such as test or acid ion exchange cells, including styrene, acrylic, epoxyamine, styrene Polyamines, formaldehyde, and non-ionic adsorption resins are suitable for use in the Zhandu broadcast adsorption / desorption process of the present invention; Contains aliphatic or Ν- 雑 cyclamidine Functional groups 12 This paper uses Chinese National Standards (CNS) A4 specifications (2 丨 〇297297 mm) A7 ___ B7__ 5. Description of the invention (to) Polymers, for example, containing diamidoamino groups to form pyridine functions Based polymer. Particularly preferred polymers containing «pyridine> are polyvinylpyridine polymers such as beads (please read the note f on the back before filling this page) in the form of poly 2- and poly 4-vinylpyridine or macro Suspicious resin. These dendritic cells are better complexed with a suitable complexing agent, such as divinylbenzyl, but at least about 2X. More preferred resins are vinyl-pyridine polymers in the form of beads in the range of 2 to 50 «!, such as poly2- and poly4-vinylpyridine polymers. For example, better resins include poly 2- and poly 4-vinylpyridine dendrimers from REILLEX ™ polymer bars from Reilly Industries, Inc., Indianapolis, Indiana. These REILLEX ™ polymers are generally complexed on 2XM, and have good thermal stability and adsorption and desorption capabilities M and other preferred characteristics as described herein. For example, a preferred resin of this type has a desorption capacity of at least about 20 Omg perylene polymer per gram of polymer. Other preferred resins were purchased from the REILLEX ™ HP polymer line from the same source. These REILLEX ™ HP polymers also have superior capacity and are highly recyclable. Additional resources for these REILLEX ™ polymers can be found in the literature, including REILLEX ™ reports 1, 2 and 3 from Reilly Industries. Inc. The Central Ministry of Economic Affairs, the Shellfish Consumer Cooperatives, and other resins, such as AMBERLYST A-21, AMBERLITE IRA 68, or AMBERLITE IRA 93, or Do * Chemical's DOWEX MWA-1 tree Jfe from Rohm and Haas, Philadelphia, Pennsylvania , Can also be used in the present invention. Among these resins, the 'A ** 21 resin is complexed with divinylbenzene (greater than 2X) and contains aliphatic triamine functional groups (especially fixed dialkylamino (dimethylamino)): IR A 68 resin contains cell tertiary amine groups, divinylbenzene complexed with acrylic fluorene, and has a hip morphology; and IRA 93 and MVA-1 resins contain aliphatic tertiary amine groups *, and this paper size Applicable to Chinese national standard icNS) Λ4 specification (210X297 mm) 13 Printed by the Central Government of the Ministry of Economic Affairs of the People's Republic of China Consumers Cooperative A7 B7 V. Description of the invention Ul) Based on styrene masterbatch complexed with diethylbenzene, with Giant net form. Additional information on these and other similar resins that can be used in the present invention can be found in the literature, including those available from manufacturers. The method of the present invention has special advantages, in which the equilibrium concentration between the important product and the adsorbent changes significantly due to temperature changes. The tarnished acid product has substantially greater tolerances (ie, at least greater than 5X in terms of milliequivalents per gram of dry adsorbent). According to the present invention, acids are preferred recovery products, especially acids having a pKa value between about 2.0 and about 4.5 milliliters. It includes, for example, aromatic acids such as phenol, aquatic acid, phthalic acid, isophthalic acid, benzoic acid, 3-nitrobenzoic acid; ot-hydroxy acids such as gallic acid, lactic acid, bislactic acid, malic acid, mandelic acid (Mandelic acid), diphenylacetic acid, glyoxylic acid, acetic acid, tartaric acid, formic acid, glutaric acid, fumaric acid, acetic acid, acetic acid, and itaconic acid (itaconic ac 丨 d) Eucalyptus acids such as sulfonic acid, acid, molybdic acid, gallium (B) ion, mercury (H) ion, and the like. Of particular interest in the present invention is the recovery of organic acids, especially carboxylic acids such as aliphatic carboxylic acids, from a medium produced from organic acids via fermentation, ie, carbon removal by carbon sources. For example, the production of fluorene carboxylic acids such as acetic acid and lactic acid around the world is largely derived from fermentation. In the case of mentholic acid • The soup can come from a carbon source such as corn sugar or glutinous honey and tangled citric-acid-producing bacteria or other aquatic organisms such as Aspergillus Niger Fermentation. Lactic acid is produced using bacteria or other organisms that can produce lactic acid through the metabolism of carbon sources. The bacteria of the Lactobacillus family are typically used, although other paper sizes apply the Chinese national standard? M CNS > Λ4 specification (2 丨 0X297 male f) 14 (Please read the precautions on the back before filling this page) —J Lin ·-If---- I n -Order --- I--= ·-· 1—rt ^ l ^^ i ------ 1, one. Bu — ^^ 1. Ministry of Economic Affairs Central Oak Printed by the Zhuhai Bureau Shellfish Consumer Cooperative A7 --------- B7 V. Description of the invention (12) The withdrawn organisms such as pinworms can also be used. For example, the genus Pycnidium of the fadly Rhizopus family, such as Weigen || (Rhizopus oryzae) NRRL 395 〇r ί a 'Illinois), which can be used to produce substantially pure L + lactic acid, as in Beta Interpretation H0.PCT / US92, filed on September 14, 1992, by Re 1 1 1 y hdustries, Inc. / 07738 (Announcement dated April 1, 1993, WQ93 / Q6226). Yi Ding and the fermented microorganisms I K D ϋ The fermentation broth containing gallic acid such as carboxylic acid is in the ability of heat-scientists II. This broth can be processed according to the method of the present invention to recover the acid. . When a carboxylic acid-containing fermentation medium is involved, it usually contains water, product acids' M, amino acids, amidines, and various other ingredients with less suspension. This fermentation medium can be filtered to remove suspended solids before adsorption. In addition, according to the present invention, a carboxylic acid-containing fermentation medium can be taken from an ongoing acetic acid-producing fermentation, and the removal of the acid can therefore be incorporated into its fermentation manufacturing, such as WO published on April 1, 1993 93/06226 (Published International Application No. PCT / US92 / 07738, filed on September 14, 1992) The description of Nine Acids in this combination procedure, the feed into the separation procedure may be As part of the fermentation medium, it is preferably filtered through. Carboxylic acid is recovered by the thermally controlled separation described in the text. The “waste” effluent stream from the separation process to remove carboxylic acid is sent to the fermenter M to return nutrients for fermentation. Such a procedure is effective for feedback inhibition of acid products across acid-producing cel Is, such as those known to be present in lb acid fermentation. This paper size is applicable to China National Fengfeng (CNS) A4 specification (210X297) ^ _ 1 c _ ---- Γ ΓΚ_ I | _ ^ ----- Order ---- (Please read the back Note: Please fill in this page again.) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7, B7. 5. Description of the invention (13 > Stomach & Eluent can be used in the present invention. These eluents include, « »! 'Stomach« | Soluble_, such as aromatic cocoon or polar soluble_ such as yeast (ethanol, propionate and butyrate >, eyebrows and stuffing, and water-soluble stomach) ο # (Essentially water), acid or water argon acid, acid or sodium hydroxide solution, or water / water such as water / fermentation mixture. Certain preferred methods of the present invention make fflTKWiS available without An unnecessary solubilized or co-soluble BI desorbent medium (< iesorbate ie (MuB)) that restores the recovery of the desired product. Other preferred methods use cocoon-soluble cocoons, such as yeasts, to dissolve cocoon. The acid is produced into the acid product. When yeast is used in the method of the present invention, the product can be contained in the yeast with a minimum content (for example, less than 20 reunion percentages and less than 10 weights). Water is recovered), and for example, in the case of carboxylic acid (such as clavulanic acid), the recovered product can be reacted in a chemical process to obtain the phase of "carboxylic acid or part of (partiai ester) The elution phase of the present invention generally involves relative to the present temperature of the furnace phase, and these temperatures are sufficient to effectively strip the product from the self-adsorption resin. In a preferred method, the degree of desorption is generally higher than about 50. * C, more typically higher than about 70 Ό and usually higher than about 90 Ό. When recovering a carboxylic acid such as citric acid or lactic acid, the desorption temperature M is higher than 90 t: better. The preferred heat in the present invention In the control calendar analysis method, a concentrated product containing the product content of the super beta adsorption product with the highest β content is used, and it is better to exceed this capacity at 20 × K, and more preferably to 100 μL. At this point, the adsorption The capacity of adsorbing the product of interest in this article is a well-known notation. It can be calculated by, for example, calculating the product adsorbed by the adsorbent in contact with the product and a certain concentration of product in the solution. Mm) [β (Please read the note on the back first Fill in this page again) ------------ ί —, .----- / 1¾ ------: Order ------- Mlu ------ Printed by A7 _B7_ ___ of the shellfish consumer cooperation of the Central Bureau of Standards, Ministry of Economic Affairs 5. The difference between the description of the invention (14), as shown in the brewing such as balance, is determined. It is possible to make better use of the tree for separation, and the operating capacity can reach a value higher than the adsorption capacity of the product load equal to or lower than the adsorption capacity. For example, the specific cell in M For example, in the method described and described in · 12, a 50 × fluorene acid feed was used (over 200 × M of resin volume), and the result was that the procedure could be regarded as per gram of adsorbent (dry) of Zhao Bian 3 Milli-equivalent mortise. This kind of adsorption utilization reduces the desirability of the adsorbent stock and lifts off the production managers. This is a significant advantage that can be used in large-scale seeding separation procedures. Therefore, in a better method of separating mentholic acid from non-stewed products, such as osmium, the shrinking solution of osmium betulinic acid, for example, the degree of super «about 25X , More than 30 ×, it is better to use as product feed. Qi Huajun's concentrated inlay can be obtained by, for example, ′ concentrating the aqueous solution containing osmic acid from fermentation and the initial acidity of betulinic acid is less than about 2 0 <. This concentration step can be performed in any acceptable manner, including, for example, evaporation of water from the medium. Then, the medium having an increased concentration of methanoic acid after such decoration is used as a feed for the method of the present invention. A more preferred method of the invention involves the inclusion of the product-containing eluent in the difficult phase. Such a product-containing eluent, such as from a previous elution operation of the recovered product, can effectively help the dehydration between the blunt substance and the acid product, and similarly, the presence of the product in the eluent will increase and The degree of product in the final product stream. Therefore, in a preferred operation, the product eluent stream from a part of the ore-type recovery operation is diverted to a scrubbing step to increase the product's sharpness in the product stream. This paper size applies to Chinese National Standards (CNS) Λ4 specifications (210X 297 mm) 17 (Please read the back note of $ before filling this page)

Seal of the Central Samples Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives A7 _B7__ V. Description of the Invention (1δ) The preferred method of the present invention is to use a continuous contacting apparatus (CCA) !! For example, 'continuous contact devices that can be effectively used in the present invention include, for example, ISEP or CSEP Continuous Contactors purchased from Advanced Separations Technology. Inc. (AST, Inc.) · Lakeland. Florida, It is also generally described in US Patent No. 4,764,276, published on August 16, 1988; No. 4,808,317, published on February 28, 1989; and No. 4,522,726, published on June 11, 1985. A brief description of this CCA device described in these benefits is described below. For further details on the design and operation of CC A used in the present invention, please refer to the literature from AST, Inc., including "The ISEP ™ Principle of Continuous Adsorption", the beauty quoted on M and M. B patent. A preferred CCA for use in the present invention is a liquid-solid contact device comprising a plurality of compartments which are used to receive solid adsorption materials and which can collectively or separately provide a contact zone for the method of the present invention. This chamber has a feed inlet and a discharge opening, respectively, and is arranged so that its center «(Rotary_M advances the chamber through the supply and discharge in synergy with the inlet and outlet. In particular, the liquid pan is supplied to the inlets of the tops of these compartments through conduits connected to the valve assembly located above the compartment. This valve assembly has a large number of The supply port that acts in conjunction with the feed port. Similarly, the duct connects the discharge port located in the lower part of each compartment with the valve assembly below the compartment, and it has a flow that cooperates with the discharge port when the compartment advances. The outlet. The valve assembly includes a movable plate with a grooved eaves, which can hold and open the feeding port when the plate «turns 18 and rotates. By changing the paper size of the grooved plate in the plate, the China National Mission (CNS) Α4 specification is applied (210X297 public address) 18 (Please read the notes on the back before filling in this page)

4 4 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7 -_B7_ V. The size and position of the invention description (ιβ) can be controlled in a predetermined way from the supply pipeline into the compartment and from the compartment flow Flow to exhaust conduits. The time of the person and the outflow of the chamber is a function of the rotation angle of the center of the chamber. In particular, those used in the present invention. This device includes a rectangular frame 11 that supports a vertical fu (d "iye shaft) 12. The turntable 13 is arranged to rotate on the Fu moving shaft. The turntable is fixed to the shaft and the shaft is driven by a motor 14 mounted on the frame 11. Most of the simple chambers 15 (for example, 30 chambers) are vertically mounted on the turntable 13 ° The chambers are preferably staggered around the turntable's weekly garden. Each chamber is filled with κ according to the β-type program performed Resin or other solid solid adsorption materials. As shown in the tip section on the left side of face 10, it is better to fill solid adsorbent material 16M to about half the height of compartments 15. Each compartment 15 is provided with a plug on the top of the container. The configuration of the person and the removed solid material. The pipe fittings 17 and 18 are provided at the inlet and outlet of the top and bottom of each compartment 15, respectively. The upper «ying 19 and the lower MU body 20 is installed in the drive sleeve 12 Upper. The valve bodies 19 and 20 are respectively provided with a supply and an outlet (for example, 20 sessions each). Individual conduits 21 and 22 connect the valve bodies 19 and 20M and the respective upper and lower pipe fittings 17 and 18 ′ M to make the valve 》 The supply and outflow ports of 19 and 20 can cooperate with the inlet and outlet of compartment 15. Supply The tube 23 is installed on the top of the frame 11 and extends upward from the valve body 9. Similarly, the outflow conduit 24 extends downward from the lower body 19 to the frame 11. In this way, when the turntable is rotated to advance the compartment 15 The inlet and outlet of the chamber 15 can cooperate with the supply and discharge ports of the valve bodies 19 and 20 to provide a convenient way for the liquid to cycle through the chamber 15. This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 19 ---- 1.1 · ----- f Pack -------- Order ------ / ^ · ί--11 (Please read the note $ on the back first Fill in this again I) A7 B7 V. Description of the invention (17) According to one aspect of the present invention, the device M of the garden 10 is preferably configured to include a separation and a plaque. The separation area can be obtained in a conventional manner. The material of interest in the feed solution, such as the acid, is separated from the impurities on the adsorbent resin contained in the chamber 15. The feed solution usually containing gallic acid or other products passes through the chamber 15 countercurrently. And resin. It must be understood that the number of CCA valves used in the separation and stripping zone can vary, and that it maximizes the economic benefits of the overall process It is decided. In addition, it should be understood that the beneficial use of product streams in the divided areas as discussed above can be achieved by diverting some of the products from the washing plaque to the separation area. A clear description of this structure is discussed below and The relevant figures are 11 and 12. Examples 1-9 General steps Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) A series of these examples * The pulsation test M confirms that the thermal control chromatography is used for various acids and uses different tertiary amine-containing polymers. A 60cb inner diameter 2.54cm column is provided to an individual feed line as an eluent (water or Fermentation) and acid products. The tubing is not jacketed or jacketed, respectively, for automatic temperature control, as shown in the specific embodiments described below. The eluent feed line includes a heat exchanger M to control the temperature of the eluent fed to the column, while the acid product aqueous solution / glucose mixture is fed at room temperature or under heating as indicated. Unless specifically noted, the content of apricot acid product is 50 mM by weight) and grape vinegar is 2! «(By weight), and the 100s product / glucose feed pulse is fed to the column, unless specifically noted, Otherwise the page load of the column is 3i »eq (milli-equivalent) of acid per gram of dendrite.阚 For the preparation of the tubing string, fill the tubing column with M. This paper is in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 〇297297) 2〇A7 B7 Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation (18) 1 I When the resin is slurried and backwashed with water to remove the air bubbles. Set the temperature control and 1 1 | After the eluent is recirculated in the bed, the system will reach equilibrium. The mixed 1 1 compound is pumped into the bed and then the eluent is pumped to 0 Km. Incremental collection. Please wash the extracted sample in a 1 1 white column first. The typical situation is the first three bed volumes (BV , Read back 1 tbed V 0 1 uwe) is 1/10 Β V and the rest of the collection cycle is 1 Α 2 BV sample Λ Note 1 4 ο counterfeit products are analyzed by HPLC and a common narrower product 0 in each experiment 9 1 item 1 \ I resin 99 product is 3 5 0 ° Then fill in k Cell examples 1A and 1B Pack this page 1 Feed the silver silver acid solution / grapevine product to the REILUX TH HP tree On 1 I (30- 60 mesh one hundred) [mu] flow 20. 3π L / min in the non-jacketed column line 11 into the water treatment using as eluent. For cell 1A, the temperature of the feed and eluent 11 was set to 25V. For Example 1B, the degrees of the feed and the eluent were 1 75 and 86 VC, respectively. The results are presented on the surfaces 1A and 1B. As shown in Figure 1Λ> At a relatively low temperature of 1 1 a good fraction m of glucose and osmanthulin can be achieved, but the concentration of betulinic acid at the peak value of 1 1 is only about 3 ί, with a careful tailing pattern ( tai 1 i ng) 1 occurs 0 On the other hand, as shown by 臞 1B »狞 m at a peak value T | ·· at a relatively high irrigation degree, the degree of acid eaves is higher but the separation m from glucose is relatively poor ο therefore & gt 1. The present invention m is used for this sub-carving and has special advantages. It uses a lower degree of j at 1: 1 sub-division operation and uses a higher temperature for moving 撺 1 | m acid after substantive separation. The striker can get a good separation at the same time, and pick the pickling side 1 1 side_ 0 1 1 1 賨 Example 2 1 1 撺The acid / glucose product was fed to REILLEX ™ HP dendrites (30-60 mesh 1 1 g) at a flow rate of M 20.8 m L / mi η and processed in a final jacketed column, 1 1 paper The standard is applicable to China National Building Standard (CNS) Λ4 specification (210X297 mm) -2 1-A7 B7 V. Description of the invention (19) Use water as eluent. The acid product was fed at a temperature of 2 5 TC, and then fed with 25t of water. Then the eluent (water) was fed at a temperature of 86t :. In this way * as the product / grapevine front moves through the string in the split phase, its temperature is maintained at a fairly low level; however, in the eluted phase, the area of the mirabilis front has a fairly high temperature . The unambiguous results are shown in circle 2, which shows the modified elliptic acid eluate side circle M with respect to FIG. 1A and the improved separation with respect to FIG. 1B. Therefore, thermal control of the column in the separation and elution phases can provide superior separation and product recovery. Examples 3A and 3B The osmic acid / glucose product was fed onto an IRA-9 3 resin at a flow rate of about 2 1 m L / m η and treated in a jacketed column using water as the eluent. For blister example 3A, the temperature of the feed and eluent was 25C. For real cells Example 3B * The feed and eluent temperatures were 8 5 1C and 8 6 t, respectively. The results are presented in gardens 3A and 3B, respectively. It is probably as shown in Figures 1A and 1B. The better separation occurs in the case of low temperature feed / eluent. However, the side view of the better acid pickling takes place in the feed / eluent solution at higher temperature. In addition, the thermal control chromatography of the present invention is advantageous for the separation. Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

Examples 4A and 4B 15! U acetic acid / 1 »! Grape vinegar product was fed to a REILLEXTMHP resin (30-60 mesh) and treated in a tubular column using water as an eluent. A 60.5 g feed was placed on the column | column while the resin load was 毎 g resin 2me ^ acetic acid. For Example 4A, the flow rate was 20.6 mL / min and the temperature of the feed and eluent was 25 ° C. For Example 48, the flow rate was 22.0 mL / m i η and the temperatures of the feed and eluent were 8 5 1C and 8 6 1C, respectively. The results are 22 (please read the note on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Description of the invention (20) Presented in 圔 4A and 4B. The flank of the flank illustrates the usefulness of the present invention for separation.

Example 5A and 5B-, 10 S! Ascorbic acid / 1 ϋ glucose product was fed to REILLEX ™ Η P resin (30-60 mesh) in a # sleeve column for treatment, using water as washing Lift liquid. A total of 20.5 g of Wiil feed was fed to the human column, and the resin loading was 0.72 neg of ascorbic acid per gram of resin. For Example 5A, the flow rate was 20.6 mL / Bin and the temperature of the feed and eluent was 25C. For Example 5B, the flow rate was 22.0i «L / inin and the temperatures of the feed and eluent were 85v and 86v, respectively. The results appear in _ 5 Α and 5 Β, respectively, which also illustrates the applicability of the present invention against the separation and recovery of osmic acid.

Examples 6A and 6B The 18¾lactic acid / 1¾glucose product was fed onto a REILLEXTMHP resin (30-60 mesh) and treated in a jacketed column using water as a tritium extract. The resin loading was lactic acid per gram of resin. For Example 6 /, the flow rate was 20.0 mL / min and the temperature of the feed and eluent was 251C. For Example 6B, the flow rate was 21.6 nL / min and the superficiality of the feed and eluent were 85 ° C and 861C, respectively. The side effects of the eluent shown in the results presented in the gardens 6A and 6B illustrate the applicability of the present invention to the separation of ricin. Examples 7A and 7B A sample acid solution / glucose product was fed to a REILLEX ™ HP resin (30-60 mesh) at a flow rate of M20nL / nin and treated with dilute yeast as eluent. For Example 7A, the temperature of the feed and eluent was 25 υ. For cell 7B, the temperature of the feed and eluent was 85C. The results are respectively 71 in this paper. The Chinese national standard (CNS) Λ4 size (210X297 mm) is applicable to this paper size. _ 23-(Please read the note f on the back before filling this page)

A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) 1 Figures 7A and 7B ° as shown in Figure 7A at a relatively low temperature *-Aspects of the regulations 1 1 1 Good separation, on the other hand, shows and good silver acid separation 1 1 Separation 0 As shown in Figure 7B, you can use a relatively high temperature to increase the peak value — / *-S. Please 1 1 m acid eaves first. Therefore, the present invention uses a relatively low temperature in the separation phase and a relatively high temperature in the product recovery phase to facilitate the separation. At the same time, the injection of the product is dehydrated to provide substantial fermentation Of recycled products. The product of item I 1 and item 1 can be used, for example, it can be reacted afterwards to kryptonate. Fill in 1 again (write 1) Example 8 This page covers Example 7 but uses acetic acid as the eluent * The results are in circles.-^ 1 1 8 > These results show that the sample-like acid and water and Good separation of glucose. Repeated 1 I Example 7B but using acetic acid as eluent also showed improved koji 1 acid recovery side view but reduced separation. Therefore, heat assisted 1 I using acetic acid was confirmed Applicability of Assisted Chromatography to Provide Dehydrated, Purified Acid Product 01 1 Example 9 1 1 6.5 * phenol aqueous solution / 1 inferior glucose product was fed to REILLEX ™ HP resin (30- 60 mesh) on the column of the funnel, using water as the eluent, 1: cold feed and hot eluent, as described in Example 2 above, 1 1 1; the next processing. Result The results shown in Figure 9 demonstrate the applicability of the heat-assisted separation and recovery of phenol. 1 1 Example 10 1 I This The test line is used for comparison. The state of M using CCA 1 | as described above is described. The experiment using the configuration of garden 11 is in IS EP 1 1 L purchased from AST, I n C.). In large-scale CC A, the operation of this device is basically the same as that of M 1 1 to CCA. This device is equipped with a fixed manifold M with 20 steam valves and 1 1 ) A4 size (210X297mm) -24-Printed by the Ministry of Economic Affairs + Central Standards Bureau Shellfish Consumer Cooperative A7 ______B7 _ V. Description of the invention (22) A turntable of 30 resin pipe strings with the effect of the valve association. The operation of the resulting valve separates the string from the different fluid streams while maintaining a buried flow through the valve. The test unit contained resin from a glass column (with an inner diameter of 1 and a volume of 350 ml) with an acrylic cap and a 70 mesh screen. The valve assembly system connected above and below the tubing string is made of polypropylene and 316 stainless steel mesh. All connections in the entire unit are made of polypropylene, polyethylene or Teflon tubing with an internal diameter of about 1/4 hour. The heat exchanger described in 圔 11 is a tube-and-shell or plate-and-frane heat exchanger. Use low pressure steam for heating and cool water (about 15t!) Or tap water (room temperature) for cooling. All pumps were pumped using a pump with various sizes (14-18) of neoprene tubing. The pipes are all limited by the heat margin K and the heat transfer between Zhou Puyu. The temperature was measured online at the connection panel using a 1 / 4-hour stainless steel D-type hot-roller and recorded on a Yokogawa HR 1300 meter recorder. Use a stainless steel net to measure the on-line force at the connection panel. The flow rate is obtained by manually regaining the time (usually 30 minutes) of each input or output port. Anhydrous USP / FCC grade osmic acid, maltose monohydrate and anhydrous D-(+)-glucose, mixed reverse isomers (anomer), and deionized water were used to prepare the osmium nickel acid feed solution. These solutions are prepared immediately before use to avoid possible bacterial growth. REIL.LEX HP ™ polymer was purchased from Reilly Industries, Inc. and is a water wet form. Tree wax was hoofed to obtain beads with a size range of 30-60 mesh. Then apply the resin on the 15S: acid-soluble gravel paper scale to the Chinese National Standard (CNS) A4 specification (2 丨 〇 parent 297 male t)-25-(Please read the note on the back before filling in this page ) Order A7 ____ B7_______ V. Description of the invention (23) Soak in liquid overnight and transfer to L100 glass tube column. The accumulated water in several beds of each column was subjected to reverse removal, and then reached L100. Fill 30 tubes with 10.5L of citric acid swelling resin, and wait for 7.55L of water-swelled tree spores or 2.10 kg of dried tree spores. _11 shows the schematic diagram of the better auto M configuration used in L100 for citric acid experiment. The column rotation system of L100 is opposite to the solution flow, that is, from right to left in _11. The irrigation density, flow velocity, and position of the inter-stage trough are also shown in circle 11. This group is briefly described. The flow pattern flowing through the pipe column is generally downward flow, in which cold volatilization is adsorbed on the steam valve P5-P9, and washed on the steam valve P1-P4, K and hot water desorption. Performed in the buckets P14-P17. Valves P10-P13 are used to cool the resin after the desorption phase, while valves P18-P19 are used to preheat the load tree before the desorption phase. The steam valve 20 is used to scoop out the remaining washing liquid from the dendritic column. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In particular, the feed solution of the mentholic acid is introduced by the eaves 30 using a pump through the "heat exchanger 32 (provides cooling)" feed man valve P5. The stream flowing out of the valve P5 feeds the feed interlevel eaves 33. The solution from the feed stage interseeder 33 is fed to the valves P6 and P7 in a co-current state using a pump 34 through a heat exchanger 35 (providing cooling). The streams from the valves P6 and P7 »are fed into the valves P8 and P9 via the« heat exchanger 36 (providing cooling) M parallel current group. The streams flowing from the valves P8 and P9 are fed into the pre-> gold / waste stage inter-seeding 37 °. The solution from the eaves 37 is pumped via the «heat exchanger 39 (providing cooling) _ into the valves P10 and P11, and The exit streams from the valves P10 and P11 are then returned to 37. This "ring-type pump (punp-aroun (〇 " provides pre-cooling of the resin bed before it enters the hydration-like acid adsorption stage. The spillage of the waste section also occurs at right 37. 阚 in the desorption phase • desorption medium For example, water, the pump 26 is used by the feed eaves 40 (please read the note on the back before filling this page) This paper size is applicable to China National Standards (CNS) Λ4 specification (21〇X297 mm) A7 ______B7___ 5 Description of the invention (2 4) 41 Feed the valves P12 and P13 in a co-current configuration. The outlet stream from the valves P12 and P13 flows to the strip. 42 »The pump 43 passes the solution of the eaves 42 through «The heat exchanger 44 (providing heating) returns to the eaves 42. This ring pump of the side heat exchanger heats the solution in the eaves 42 to perform desorption operation. It should be noted that it is a matter of elution. 42 and other weights used in this configuration are preferably open to the atmosphere. This allows air thoron to be released from the solution, especially when heated, it can be released before entering the resin column. This is an advantage because When the gas flows through the resin bed, it will cause channeling and interfere with the effective operation of the device. Consumption cooperation Du printed the heating solution from the stripping stage 42 to feed the valves P14 and P15 with a 45K pump and roll. The exit streams from P14 and P15 were collected in the nidstrip 鈒 46. The material in the tank 46 is also pumped with a pump 47 and a heat exchanger 48 (providing heating). The material from the eaves 46 should also be fed into the valves P16 and P17, while the corresponding outlet logistics is The materials collected in the preheating / product inter-level rights 49 »right 49 are also pumped using a pump 50 and a heat exchanger 51 (providing heating). Part of the materials in the right 49 are recovered as product overflow. Another part is The pumps 52 are fed to the steam valves P18 and P19, and the corresponding outlet streams are fed back to "149. The ring pump between P18 and P19 provides preheating of the resin bed before entering the desorption stage of the operation. Eaves 49 The other one of the materials is fed to the valve P20 by the pump 53, which also uses the resin bed of P20 for more or less preheating. In an important aspect of the present invention * comes from the valve P20 Of the exit stream is fed into the washing stage of the operation via a heat exchanger 54 (providing cooling). Explicitly 2 7 (Please read the “Notes on ^ K” before filling out this page) The paper size is applicable to the Chinese national standard (CNS > Λ4 specification (210X297) > ψ ψ Shellfish consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs The printed paper size is applicable to China National Standard (CNS) A4 specification (2IOX297 mm > Α7 __Β7__ V. Description of the invention (25) said that the outlet of the valve P20 should be fed to the valve ^ and P2 \ The better group described here is that the product stream from the steam P20 is used exclusively for the purpose of purlin operations. However, it should be understood that this product stream can be used in combination with other predators such as water *. The collected outlet streams M from the steam valves P1 and P2 are fed into the steam 卩 51 > 3 and P4 °. Therefore, at the valves P1-P4, the products of M are loaded, such as the resin bed of susceptible acid. Detergent washing to remove materials that are not adsorbed to a lesser extent, such as sugar ° The exit streams from the valves P3 and P4 are collected in the feed inter-stage tank 33 'where they enter with the paramenic acid leaving the valve P5 The materials are mixed, and then the processing at the beginning of the above discussion is performed. In the exemplary experiment using the configuration of Fig. 11, the "L100 unit is run for 3 hours before the sample is collected" so that the system is brought to a balanced or near-balanced state before mining. _The sample is collected for 30 minutes, and Μ ensures that it is representative. When the number of samples is 1 mile, the collection time should be wrong for the rotation speed, so that the material will not come from the same. Columns ° In one of these experiments, the reading was super-treated for 28 hours, and a 14.7XWSI acid feed containing 0.43S! ® grapes and 2,03 malt was fed to the system. The flow velocity and irrigation of the flowing solution at each bond point in the system are shown in Figure 1. The product contains an average of 9.73X ergotulinic acid (96X recovery), 94X glucose and 97¾ maltose removal rate. In another set of similar tests, the heat exchanger 32 and therefore the cooling of the feed to column 5 were omitted, and the product stream contained 9.76X mentholic acid (98X recovery), and grapes and The removal rates of maltose were 96X and 98X, respectively. Example 11 28-(Please read the note on the back before filling this page)

.1T Printed by DuPont of the Central Bureau of Standards, Ministry of Economic Affairs, A7 B7 V. Description of the Invention (2β) Circle 12 is a schematic representation of the LIOO sister state that can be used in the method of the present invention. This configuration is similar to that shown in Figure 11, so its common components need not be described again. However, it is an advantageous procedure for formulating M for separation and elution using thermally controlled chromatography *. Comparing _ 1 2 and Figure 11, it can be noticed that some of the products used in it (P19-20 and P1-6) have been increased. This * «addition provides additional points ** & Under higher product load, the impurities in the feed stream can also be removed from the pipe column before the heating and desorption stage (valve P13_P18) ° Similar to surface 11, the measured Zhan degree and flow rate are shown in Sun 12 . Also shown in Figure 12 are the products (Betulinic acid) and impurities in each feed / eluent in the program. It can be clearly seen that the product stream with a concentration of 20.9¾ and a RES level of only 0.073 can be recovered by using the Αί acid feedstock containing a degree of easy carbide carbide (RCS, readHy carbonizable substance) of 0.486. . It is therefore possible to obtain a product stream containing ammonium acid and Rcs with a low content. In particular, the procedure described in circle 12 has a higher working capacity than the one described in circle 0, where the latter is operated at 3 milliequivalent arsenic acid (me + / g dry resin) per gram of dry resin, The former is operated at about 15 g / g of dry resin. This increase in operating capacity can be used to significantly reduce the amount of resin stock and equipment size, resulting in considerable improvements in production and process economics. Example 12 H1 3 shows the intention of illustrating a valve configuration that can be used in a CSEP device (also purchased from Advanced Separations Technologies, Inc.). This CSEP device is more suitable for chromatographic separation than the ISEP device described in K '. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -29-(Please read the note on the back before filling in This page) Order .0. A7 __—__ B7__ 5. The description of the invention (27) and contains 20 tilting pipe strings and 20 steam valves, among which the pipe string is continuously dirty code through the steam bucket. As can be seen in _1 3, the CSEP device of this example includes a configuration that is mostly countercurrent and rolling down, in which the parallel feed to the steam P3 (as it exists in the ISEP sister state described on K) ) Was cancelled, K 馒 effectively used the separation ability of the tree stock suspension. The feed to valve P1 is part of an acid-containing product stream from valve P2 0 (discussed below). After leaving the pipe column opposite to steam P3 P1 *, this feed passes through a heat exchanger 60 providing cooling and then passes through the steam P5 P2-P5 in a countercurrent manner. This stream is then combined with a feed solution (e.g., containing 50! K of betulinic acid and sugar blunts) from a feed solution storage tank 61 via a pump 62 and entered through a heat exchanger 63 that provides cooling Steam valve P6. This solution M passes through the hoppers P7-P9, and then passes through the heat exchanger 64, which provides cooling, and enters the valve P10. The product in this stream leaving the valve 10 is quite thin, but the impurities (such as sugar) are quite meager, which is sent to the waste. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Water or another liquid is pumped from the storage tank 65 by a pump 66 through a heat exchanger 67 providing cooling into the valve P11. The stream leaving the car P3P11 enters the pre-cooled inter-air station 68. A part of the solution K pump 69 in the tank 68 is pumped into the valve P12 through the heat exchanger 70 which provides cooling. The export logistics from P12 was sent back to broadcast 68. The solution flows from the eaves 68M countercurrently through the valves P13-P14, and then feeds through the heat exchanger 71 which provides heating, and passes the valves P15-IM7 countercurrently. The flow from P17 provides another heating bismuth soak χ · 72, and still passes through the bucket pis in an injection flow mode. The exit stream from the steam pgpis is fed into the preheated rafters 73. Part of the solution in the eaves 73 flows through the heat exchanger 74 providing heating and upwards through the valve P19. The material opened from P19 »is then fed back to tank 73. The divided material in 懵 73 also flows downward through the bucket P20. Exit 30 from P20 (please read the note f on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) M is present (2 丨 0X297 mm) A7 B7 V. Description of the invention (28) Logistics is A shrinking solution of the desired acid (such as tsukazuka acid) that is essentially free of impurities (such as sugar) present in the original department. Part of this exit stream is collected as a product, while another is fed as discussed above. Hopper P 1. The CSEP configuration of 臞 13 can effectively process a concentrated, non-blunt product acid (such as betulinic acid) solution, which makes its M substantially exceed the solid adsorbent (such as M on the column) The R ILL ILL X P resin) is fed to the concentration of the adsorption capacity of the acid. In this way, the program of the present invention utilizes both the chromatography and the traditional adsorption / thermal desorption phenomenon, so it can be reduced carefully. It is necessary to understand the commercial procedure for the adsorption of the adsorbent and obtain highly suspected product components. It is necessary to understand that the steam valve and the chemical configuration given in Figure 13 are exemplary, and other configurations can be used. For practicing the invention herein. For example, for separation The number of columns in the purified W fraction and the extraction part can be different according to the program and / or the product box. It can also include the use of one or more valves in the slow balance area. The valves P10 and P11 in Figure 13 In addition, it can also be understood that the position of the heat exchanger (providing heating or cooling) in operation can be changed when the present invention is implemented. The detailed description and description in the foregoing description * should also be considered as examples rather than limitations. It should be understood that only the best specific examples are shown and described, and all changes and modifications made within the spirit of the present invention and Modifications should be protected. All the publications cited in the article indicate the degree of know-how, and are incorporated into this article as reference and test materials as if they have been individually incorporated as reference materials and fully explained. 31 (Please Read the note f on the back before filling in this page) This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297 mm)

Claims (1)

7. Scope of patent application 1. A heat control method and method for recovering and recovering acid from a mixture of an acid and an impurity, including absorbing the acid and the impurity at a first temperature of 0 to 501 The chromatographic separation was performed on a gauge 4 & and then the acid product was eluted from the adsorbent resin at a second temperature at least 101 higher than the first temperature but not exceeding the thermal stability temperature of the resin used; The adsorbent resin shows a higher affinity for acid than the impure substance, and the temperature of the acid-affinity sugar decreases and the temperature increases. M and the adsorbent resin are selected from the group consisting of paper triethylpyridine pen containing pendant pyridoyl or Aliphatic triammonium resin. 2. The method according to item 1 of the patent application, wherein the acid is selected from the group consisting of phenol, water. -Acid, phthalic acid, meta-acid, benzoic acid, 3-chlorobenzoic acid; osmic acid, lactic acid, bis Lactic acid, malic acid, mandelic acid (η an de 1 ic.. Acid), diphenylacetic acid, acetaldehyde avoid) glycolic acid, tartaric acid, formic acid, glutaric acid, fumaric acid, acetic acid , Acetic acid, decomposing aconic acid, sulfonic acid, tungstic acid, molybdic acid, gallium (U) ions, and mercury (I) ions. 3. The method according to item 2 of the claim, wherein the acid is a carboxylic acid. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 4. For the method of applying for item 3 of the patent scope, the acid is humic acid or lactic acid. 5. Qiu's method of patent application No. 4 wherein the product is osmic acid. 3. The method according to item 1 of the patent application scope, wherein the polymer resin is di-2-vinyl poly-2- or poly-4-vinylpyridine. 7. The method according to item 6 of the patent application *, wherein the resin has a macroreticular bead morphology. 8. The method according to item 7 of the scope of patent application, in which the resin has a size of 2¾ to this paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -1- 7. Scope of patent application 1. A heat control method and method for recovering and recovering acid from a mixture of an acid and an impurity, including absorbing the acid and the impurity at a first temperature of 0 to 501 The chromatographic separation was performed on a gauge 4 & and then the acid product was eluted from the adsorbent resin at a second temperature at least 101 higher than the first temperature but not exceeding the thermal stability temperature of the resin used; The adsorbent resin shows a higher affinity for acid than the impure substance, and the temperature of the acid-affinity sugar decreases and the temperature increases. M and the adsorbent resin are selected from the group consisting of paper triethylpyridine pen containing pendant pyridoyl or Aliphatic triammonium resin. 2. The method according to item 1 of the patent application, wherein the acid is selected from the group consisting of phenol, water. -Acid, phthalic acid, meta-acid, benzoic acid, 3-chlorobenzoic acid; osmic acid, lactic acid, bis Lactic acid, malic acid, mandelic acid (η an de 1 ic.. Acid), diphenylacetic acid, acetaldehyde avoid) glycolic acid, tartaric acid, formic acid, glutaric acid, fumaric acid, acetic acid , Acetic acid, decomposing aconic acid, sulfonic acid, tungstic acid, molybdic acid, gallium (U) ions, and mercury (I) ions. 3. The method according to item 2 of the claim, wherein the acid is a carboxylic acid. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 4. For the method of applying for item 3 of the patent scope, the acid is humic acid or lactic acid. 5. Qiu's method of patent application No. 4 wherein the product is osmic acid. 3. The method according to item 1 of the patent application scope, wherein the polymer resin is di-2-vinyl poly-2- or poly-4-vinylpyridine. 7. The method according to item 6 of the patent application *, wherein the resin has a macroreticular bead morphology. 8. The method according to item 7 of the scope of patent application, in which the resin has 2¾ to this paper size and is applicable to China National Standard (CNS) A4 specification (210X297 mm) -1 々, patent application scope 50! S (M weight Meter) M divinylbenzene complexing. §. The method of claim 8 in which the product is osmic acid. 10. The method according to the scope of patent application, wherein an eluent containing an acid is used during the chromatographic separation. 11. The method according to the scope of patent application, wherein the acid / soluble in water is separated by chromatography, and wherein an alcohol is used to elute the acid during the chromatographic separation to dehydrate the acid. 12. A method for separating an acid in a solution from one or more impurities, comprising: providing a contact zone containing an adsorbent which exhibits a higher affinity for acid than for one or more impurities, and The affinity for acid increases as the temperature decreases; the first solution containing the acid and one or more impurities is introduced into the contact zone; the second solution is brought to the first temperature of 0 to 50C and the acid is allowed to advance Flow through the contact area under conditions that achieve effective separation with one or more impurities before being released in the contact area; M and the Central Standards Bureau of the Ministry of Economic Affairs® C Industrial Consumer Cooperative Cooperative printed at least 10 ° C higher than the first temperature but At a second temperature that does not exceed the thermal stability of the resin used, the acid front is eluted from the contact zone; »wherein the adsorbent resin is selected from the group consisting of M divinylbenzene complexes containing pendant or aliphatic Tertiary amine based resin. 13. —A thermally-assisted rib chromatography method for separating an acid product from an impurity with a sugar, including: U) providing a plurality of contact areas containing an adsorbent, which exhibits a higher affinity for acid than for impurities; and Affinity to acid with temperature -2- (Please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS > A4 specifications (210 × 297 mm) A8 B8 · C8 D8 々, patent application scope Decrease and increase; (b) Make the contact zone a chromatographic separation zone. The rinse solution and the product solution containing acid and impurities are passed through the junction zone, and the first temperature of the acid and impurities is completed at 0C to 50 ° C. Chromatographic steps of separation; M and (c) After step (b), the contact zone is entangled into an elution zone, K is at least 10t higher than the first temperature: but not more than the thermal stability of the resin used At a second temperature, the acid product is eluted from the one or more contact zones; wherein the adsorbent resin is selected from the group consisting of K-divinylbenzene complexes containing an overhanging pyridyl group or an aliphatic tertiary amine group. Resin 14. If applying for a patent The method of item 13, wherein the elution solution contains an acid product from one or more of the elution steps of the eluting step of B. —I—; ---- η ″ — equipment ------ Order ----- ((^ L—. (Please read the precautions on the back before filling out this page). The paper size of the printed paper is applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) -3-