WO2017000867A1 - 一种蛋氨酸纯化的工艺 - Google Patents

一种蛋氨酸纯化的工艺 Download PDF

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WO2017000867A1
WO2017000867A1 PCT/CN2016/087428 CN2016087428W WO2017000867A1 WO 2017000867 A1 WO2017000867 A1 WO 2017000867A1 CN 2016087428 W CN2016087428 W CN 2016087428W WO 2017000867 A1 WO2017000867 A1 WO 2017000867A1
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methionine
resin
adsorption
desorbent
solution
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PCT/CN2016/087428
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English (en)
French (fr)
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寇晓康
王日升
王刚
刘琼
任婉萍
布泰·朱利安
杨元斌
吉达尔·瓦伦汀
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西安蓝晓科技新材料股份有限公司
蓝星安迪苏南京有限公司
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Application filed by 西安蓝晓科技新材料股份有限公司, 蓝星安迪苏南京有限公司 filed Critical 西安蓝晓科技新材料股份有限公司
Priority to KR1020177037896A priority Critical patent/KR102045531B1/ko
Priority to EP16817231.0A priority patent/EP3318552A4/en
Priority to JP2017567237A priority patent/JP6691557B2/ja
Priority to SG11201710689TA priority patent/SG11201710689TA/en
Priority to US15/740,792 priority patent/US10287244B2/en
Publication of WO2017000867A1 publication Critical patent/WO2017000867A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C07C319/28—Separation; Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/12—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the preparation of the feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/265—Adsorption chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/42—Selective adsorption, e.g. chromatography characterised by the development mode, e.g. by displacement or by elution
    • B01D15/424—Elution mode
    • B01D15/426—Specific type of solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton

Definitions

  • the invention belongs to the field of chemical industry, and particularly relates to a process for purifying methionine.
  • Methionine also known as methionine or methylthiobutyrate, is closely related to the metabolism of various sulfur compounds in living organisms. In the absence of methionine, it can cause loss of appetite, slow growth or no increase in body weight, kidney enlargement and iron accumulation in the liver, and finally lead to liver necrosis or fibrosis.
  • methionine hydroxy derivative ie, liquid methionine
  • methionine nutritional supplement when used as a feed additive to promote animal growth and development.
  • Both methionine and liquid methionine belong to one of the amino acids, except that in the alpha position, methionine is attached to -NH2, and liquid methionine is linked to -OH.
  • solution pH ⁇ pI isoelectric point
  • solution pH> pI it exists as an anion
  • non-polar macroporous adsorption resin can be selected to make full use of the difference in binding ability between methionine and salt substance and resin, and selectively adsorb methionine on resin, thereby making methionine and vice The salt-producing substances are sufficiently separated.
  • the method for industrially producing methionine is mainly the Haiin method
  • the method for producing liquid methionine is mainly the acrolein method.
  • the yield increases the production cost of methionine.
  • Patent 201310317849.2 "Method and apparatus for removing impurities in secondary methionine mother liquor” discloses a method and a device for removing impurities in a secondary methionine mother liquor by using diatomaceous earth, activated carbon or activated clay, and the adsorption efficiency of these adsorbents It is low and cannot be recycled through effective channels after adsorption, resulting in secondary pollution of the environment and is not suitable for industrial applications.
  • a methionine production process discloses a method for separating methionine crystallization mother liquor, and separating the methionine crystallization mother liquor through a continuous chromatographic separation system filled with a sodium or potassium type chromatography resin to obtain a methionine solution and an inorganic salt solution; This method is only applicable to the crystallization mother liquor with lower methionine content, and the separation of high content of methionine solution and by-product salt in industrial production has not been verified and an effective solution has been proposed.
  • the macroporous adsorption resin is used to separate methionine and by-product salts.
  • the methionine is adsorbed on the macroporous adsorption resin and then the methionine is recovered by the desorbent desorbing resin.
  • the by-product salt is not adsorbed by the macroporous resin into the adsorption and effluent during the adsorption process.
  • liquid it mainly includes the following steps:
  • Resin adsorption adjust the pH of the methionine solution, and pass the macroporous adsorption resin layer from top to bottom at a certain flow rate. When the content of methionine in the resin column effluent is greater than or equal to 10% (w/w) of the inlet content, stop. Resin adsorption; resin adsorption effluent as a by-product salt.
  • step 2 Resin desorption: in step 1, the adsorbed resin is completed, and a certain volume, a certain concentration of desorbent is used to desorb the resin from top to bottom at a certain flow rate, and the desorbed liquid is collected;
  • the process for purifying methionine wherein the by-product salt substance is one or a mixture of sodium carbonate, sodium sulfate, ammonium sulfate, potassium carbonate, potassium sulfate;
  • the process for purifying methionine adjusting the pH of the methionine solution to be adsorbed to 1.00-10.0; preferably pH 1.0-5.0, more preferably pH 2.0-3.0.
  • the flow rate of the methionine solution through the macroporous adsorption resin layer is 1-10 BV/h; preferably 1-5 BV/h, more preferably 1-3 BV/h.
  • the invention relates to a process for purifying methionine: the desorbent is one of sodium hydroxide, hydrochloric acid, sodium chloride, ammonia water, methanol, ethanol, isopropanol and acetone;
  • the concentration of the desorbent is from 1% to 10% (w/w) (mass percent); preferably from 2% to 8% (w/w), more preferably from 4 to 8% (w/w)
  • the volume of the resin desorbent is 1-3 BV;
  • the flow rate of the resin desorbent is 1-5 BV/h.
  • the methionine comprises a hydroxy derivative of methionine and methionine
  • the by-product salt substance is one or a mixture of sodium carbonate, sodium sulfate, ammonium sulfate, potassium carbonate and potassium sulfate;
  • Step 1) In the adsorption of the resin, first adjust the pH of the methionine solution to be adsorbed to 2.0-3.0;
  • the flow rate of the methionine solution through the macroporous adsorption resin layer is 1-3 BV / h;
  • the desorbent is selected from the group consisting of sodium hydroxide, potassium hydroxide, hydrochloric acid, sodium chloride, ammonia, methanol, ethanol, isopropanol, acetone;
  • the concentration of the desorbent is 4-8% by mass percentage
  • the volume of the resin desorbent is 1-3 BV;
  • the flow rate of the resin desorbent is 1-5 BV/h.
  • BV refers to the bed volume of the resin loaded in the resin column, that is, the bed volume, referred to as BV, 1BV means the volume of 1 bed, and 2BV is the volume of 2 beds.
  • the invention relates to a process for purifying methionine, in particular to separating methionine and by-product salt by macroporous adsorption resin, and obtaining methionine product with purity ⁇ 99% (w/w) by adsorption and desorption process,
  • the content of methionine in the salt-producing substance is ⁇ 0.03% (w/w).
  • the resin extraction methionine yield was ⁇ 98% (w/w).
  • the method of the invention can simplify the existing production process, improve the quality of the methionine product, and reduce the production cost of methionine.
  • FIG. 1 is a process flow diagram of the present invention
  • Resin adsorption a solution of methionine (pH: 10.72, methionine content 17.24% (w/w), sodium carbonate content 10.35% (w/w)), passing 100 ml from top to bottom at a flow rate of 1 BV/h.
  • the XDA-1 resin bed (manufactured by Xi'an Lanxiao Technology New Material Co., Ltd.) separately collects the resin effluent.
  • the methionine content at the bottom of the resin column is 1.7% (w/w)
  • the feeding into the resin column is stopped.
  • Resin desorption 2 BV of 3% (w/w) sodium hydroxide solution was used to desorb the resin from top to bottom at a flow rate of 1 BV/h, and the desorbed solution was collected.
  • Resin adsorption The liquid methionine solution was adjusted to pH 2.2 with a 2% (w/w) sulfuric acid solution (methionine content 2.8% (w/w), potassium sulfate content 17.4% (w/w)), at 1 BV/h. The flow rate was uniformly passed from top to bottom through a 100 ml XDA-8 resin bed (manufactured by Xi'an Lanxiao Technology New Materials Co., Ltd.), and the resin effluent was separately collected. When the methionine content of the bottom of the resin column was 0.3% (w/w) , stop feeding into the resin column.
  • the resin effluent was collected 700 ml, and the methionine content was 0.01% (w/w), and the potassium sulfate content was 17.38% (w/w). 302 ml of the desorption solution was collected, and the methionine content was 6.45% (w/w), and the methionine yield was 98.76% (w/w).
  • the specific embodiment is the same as the first embodiment, and the influence of the methionine solution of different pH on the adsorption capacity of the resin is mainly investigated. (Not stated in the experiment are mass percent concentration)
  • Methionine content 2.80% (w/w), ammonium sulfate content 43.5% (w/w), potassium carbonate content 2.1% (w/w).
  • the feed volume was 7 BV
  • the feed flow rate was 1 BV/h
  • 5 parts of XDA-1 resin was prepared, each of which was 100 ml of resin.
  • the methionine solution was adjusted to pH 1.0, 3.0, 7.0, 9.0, and 10.0 with 4% (w/w) sodium hydroxide or 4% (w/w) sulfuric acid solution, respectively, and subjected to an adsorption control test.
  • Resin adsorption capacity (feed methionine content * feed volume - effluent methionine content * effluent volume) / resin volume
  • the specific embodiment is the same as the first embodiment, and the influence of different adsorption speeds on the adsorption capacity of the resin is mainly investigated. (No explanation in the experiment is the mass percent concentration)
  • the methionine content was 3.28% (w/w), the sodium sulfate content was 40.19% (w/w), and the pH was 2.40.
  • the feed volume was 7 BV, and 5 parts of XDA-200 resin was prepared, and each 100 ml of resin was used. , adsorption of resin at different flow rates.
  • Example Flow rate (BV/h) Resin adsorption capacity (g/L) Example 10 1 229.6
  • the specific embodiment is the same as the first embodiment, and the desorption efficiency and the desorption liquid quality of different desorbents are mainly investigated. (No explanation in the experiment is the mass percent concentration)
  • the methionine content was 2.95% (w/w), the ammonium sulfate content was 42.04% (w/w), and the pH was 2.20.
  • the feed volume is 7BV each, and 7 parts of 100ml XDA-300 resin is passed at 1BV/h (Xi'an). Production of Lanxiao Technology New Materials Co., Ltd.).
  • the specific embodiment is the same as the examples 16-24, mainly to investigate the effects of different concentration desorbents on the desorption quality and yield.
  • the content of methionine was 2.64% (w/w), the content of ammonium sulfate was 42.04% (w/w), and the pH was 2.20.
  • the feed volume was 8 BV each, and passed through 4 ml of 100 ml XDA-8G resin at a flow rate of 1 BV/h (manufactured by Xi'an Lanxiao Technology New Materials Co., Ltd.).
  • the methionine content was 3.07%, the ammonium sulfate content was 44.55%, and the pH was 2.41.
  • the feed volume was 7 BV each, and passed through 4 ml of 100 ml XDA-200 resin at a flow rate of 1 BV/h (manufactured by Xi'an Lanxiao Technology New Materials Co., Ltd.). After the end of the adsorption, 1 BV of 4% (w/w) methanol, 2 BV of 4% (w/w) methanol, 3 BV of 4% (w/w) methanol, 5 BV of 4% (w/w) methanol were used. A flow rate of 1 BV/h desorbs the resin.
  • Example 30 1BV 12.47 58.03
  • Example 31 2BV 8.75 81.47
  • Example 32 3BV 6.99 97.79
  • Example 33 5BV 4.21 98.02
  • the methionine content was 2.58% (w/w), the ammonium sulfate content was 44.55% (w/w), and the pH was 2.41.
  • the feed volume was 8 BV each, and the flow rate of 1 BV/h was passed through 4 parts of 100 ml XDA-300 resin (manufactured by Xi'an Lanxiao Technology New Materials Co., Ltd.). After the end of the adsorption, the resin was desorbed with a 3 BV 4% (w/w) acetone solution at a flow rate of 1 BV/h, 3 BV/h, 7 BV/h, and 10 BV/h.
  • Resin adsorption methionine solution (pH: 2.75, methionine content 2.98% (w / w), ammonium sulfate content 41.59% (w / w), at a flow rate of 1BV / h from top to bottom through the 100ml XDA-1 Resin bed (manufactured by Xi'an Lanxiao Technology New Material Co., Ltd.), the resin effluent was collected separately, and when the methionine content of the bottom of the resin column was 0.3% (w/w), the feeding into the resin column was stopped.
  • Resin Desorption A 6% (w/w) aqueous ammonia solution of 3 BV was used to desorb the resin from top to bottom at a flow rate of 1 BV/h, and the desorbed solution was collected.

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  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
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Abstract

本发明提供了一种用于蛋氨酸纯化的工艺，采用大孔吸附树脂分离蛋氨酸和副产盐类物质，经过吸附、解吸工艺，可得到纯度≥99％的蛋氨酸产品，副产盐类产品中蛋氨酸含量≤0.03％。树脂提取蛋氨酸收率≥98％。使用本发明方法可以简化现有的生产工艺流程，提高蛋氨酸产品质量，降低蛋氨酸生产成本。

Description

一种蛋氨酸纯化的工艺 技术领域：
本发明属于化工领域，具体涉及一种蛋氨酸纯化的工艺。
背景技术：
蛋氨酸，又称甲硫氨酸或甲硫基丁氨酸，与生物体内各种含硫化合物的代谢密切相关。当缺乏蛋氨酸时，会引起食欲减退、生长减缓或不增加体重、肾脏肿大和肝脏铁堆积等现象，最后导致肝坏死或纤维化。另外一种蛋氨酸，称为蛋氨酸羟基衍生物(即液体蛋氨酸)，广泛用作饲料添加剂时可作为蛋氨酸营养补充剂，促进动物生长发育。
蛋氨酸和液体蛋氨酸都属于氨基酸的一种，其差异仅在于在α位上，蛋氨酸连接的为-NH2，而液体蛋氨酸连接的为-OH。当溶液pH<pI(等电点)时，以阳离子形式存在；当溶液pH>pI时，以阴离子形式存在；pH＝pI时，溶解度最小。蛋氨酸可以溶于水，但难溶于非极性物质，有相当高的熔点，其水溶液性质与具有高偶极矩的水溶液相似。根据蛋氨酸分子结构中的C-S-C的分子结构，可以选择非极性大孔吸附树脂，充分利用蛋氨酸与盐类物质与树脂结合力的差异，选择性的将蛋氨酸吸附在树脂上，从而使蛋氨酸与副产盐类物质得到充分分离。
目前工业化生产蛋氨酸的方法主要为海因法，生产液体蛋氨酸的方法主要为丙烯醛法。两种方法在生产过程中都会存在蛋氨酸溶液和含盐副产物需要分离的工艺需求，现有生产方法中无有效的脱盐手段，致使产品结晶时导致大量的盐类物质伴随析出，影响产品的品质和收率，增加了蛋氨酸的生产成本。
专利201310317849.2《去除二级蛋氨酸母液中杂质的方法及装置》中公开了一种去除二级蛋氨酸母液中杂质的方法及装置，该方法是用硅藻土，活性炭或者活性白土，这些吸附剂吸附效率较低，且吸附后无法通过有效的途径进行回收利用，造成了环境的二次污染，不适合于工业化应用。专 利201310194709.5《一种蛋氨酸生产工艺》中公开了一种蛋氨酸结晶母液的分离方法，将蛋氨酸结晶母液通过填充有钠型或者钾型色谱树脂的连续色谱分离系统分离，得蛋氨酸溶液和无机盐溶液；该方法只适用于蛋氨酸含量较低的结晶母液，而对于工业化生产中的高含量的蛋氨酸溶液和副产盐类物质的分离并没有进行验证和提出有效的解决方案。
发明内容：
本发明的目的在于提供一种用于蛋氨酸纯化的工艺。
采用大孔吸附树脂分离蛋氨酸和副产盐类物质，蛋氨酸被吸附在大孔吸附树脂上然后用解吸剂解吸树脂回收蛋氨酸，副产盐类物质在吸附过程中不被大孔树脂吸附进入吸附流出液中，主要包括以下步骤：
1)树脂吸附：调节蛋氨酸溶液的pH，以一定的流速自上而下通过大孔吸附树脂层，当树脂柱流出液中含蛋氨酸含量大于等于进口含量的10％(w/w)时，停止树脂吸附；树脂吸附流出液作为副产盐类物质。
2)树脂解吸：步骤1中完成了吸附的树脂，用一定体积，一定浓度的解吸剂，以一定的流速自上而下解吸树脂，并收集解吸液；
3)后续工艺过程：解吸液按照现有工艺流程进行后续处理；
所述的一种用于蛋氨酸纯化的工艺：其中的蛋氨酸包括蛋氨酸及蛋氨酸的羟基衍生物(即液体蛋氨酸)；
所述的一种用于蛋氨酸纯化的工艺：其中的副产盐类物质为碳酸钠、硫酸钠、硫酸铵、碳酸钾、硫酸钾中的一种或者几种混合物；
所述的一种用于蛋氨酸纯化的工艺：调节待吸附的蛋氨酸溶液pH1.0-10.0；优选为pH1.0-5.0，更优选为pH2.0-3.0。
所述的一种用于蛋氨酸纯化的工艺：蛋氨酸溶液通过大孔吸附树脂层的流速为1-10BV/h；优选为1-5BV/h，更优选为1-3BV/h。
所述的一种用于蛋氨酸纯化的工艺：解吸剂为氢氧化钠、盐酸、氯化钠、氨水、甲醇、乙醇、异丙醇、丙酮中的一种；
所述的解吸剂的浓度为1％-10％(w/w)(质量百分比)；优选为2％-8％(w/w)，更优选为4-8％(w/w)
所述的树脂解吸剂的体积为1-3BV；
所述的树脂解吸剂的流速为1-5BV/h。
本发明更优选的方案中，蛋氨酸包括蛋氨酸及蛋氨酸的羟基衍生物；
其中的副产盐类物质为碳酸钠、硫酸钠、硫酸铵、碳酸钾、硫酸钾中的一种或者几种混合物；
步骤1)树脂吸附中，先调节待吸附的蛋氨酸溶液pH为2.0-3.0；
蛋氨酸溶液通过大孔吸附树脂层的流速为1-3BV/h；
所述解吸剂选自氢氧化钠、氢氧化钾、盐酸、氯化钠、氨水、甲醇、乙醇、异丙醇、丙酮；
所述解吸剂的浓度以质量百分比计为4-8％；
所述树脂解吸剂的体积为1-3BV；
所述树脂解吸剂的流速为1-5BV/h。
本发明中，BV指的是树脂柱内装载树脂的床体积，即床容积(bed volume)，简称BV，1BV即指1倍床的体积，2BV就是2倍床的体积。
本发明涉及一种用于蛋氨酸纯化的工艺，具体涉及通过大孔吸附树脂分离蛋氨酸和副产盐类物质，经过吸附、解吸工艺，可得到纯度≥99％(w/w)的蛋氨酸产品，副产盐类物质中蛋氨酸含量≤0.03％(w/w)。树脂提取蛋氨酸收率≥98％(w/w)。使用本发明方法可以简化现有的生产工艺流程，提高蛋氨酸产品质量，降低蛋氨酸生产成本。
由于目前尚未有针对蛋氨酸及液体蛋氨酸纯化的工艺方法，因此本方法具有独创性，在产生经济效益方面有着巨大的意义。
附图说明：
附图1为本发明的工艺流程图
具体实施方式：
实施例用于进一步说明本发明，所用蛋氨酸溶液分别来自重庆和南京某两家企业。
实施例1：
1.树脂吸附：将蛋氨酸溶液(pH：10.72，蛋氨酸含量17.24％(w/w)，碳酸钠含量10.35％(w/w))，以1BV/h的流速自上而下匀速通过100ml XDA-1树脂床(西安蓝晓科技新材料股份有限公司生产)，单独收集树脂流出液，当树脂柱底部流出液蛋氨酸含量为1.7％(w/w)时，停止向树脂柱内进料。
2.树脂解吸：2BV的3％(w/w)的氢氧化钠溶液以1BV/h的流速自上而下解吸树脂，收集解吸液。
3.收集树脂流出液300ml，检测蛋氨酸含量为0.02％(w/w)，碳酸钠含量10.35％(w/w)。收集解吸液200ml，检测蛋氨酸含量24.60％(w/w)，蛋氨酸收率95.15％(w/w)。
实施例2：
1.树脂吸附：将液体蛋氨酸溶液用2％(w/w)硫酸溶液调pH至2.2(蛋氨酸含量2.8％(w/w)，硫酸钾含量17.4％(w/w))，以1BV/h的流速自上而下匀速通过100ml XDA-8树脂床(西安蓝晓科技新材料股份有限公司生产)，单独收集树脂流出液，当树脂柱底部流出液蛋氨酸含量为0.3％(w/w)时，停止向树脂柱内进料。
2.树脂解吸：3BV的4％(w/w)的甲醇溶液以1BV/h的流速自上而下解吸树脂，收集解吸液。
3.收集树脂流出液700ml，检测蛋氨酸含量为0.01％(w/w)，硫酸钾含量17.38％(w/w)。收集解吸液302ml，检测蛋氨酸含量6.45％(w/w)，蛋氨酸收率98.76％(w/w)。
实施例3-实施例9：
具体实施方案同实施例1，主要考察不同pH的蛋氨酸溶液对树脂的吸附容量影响。(实验中未做说明均为质量百分比浓度)
蛋氨酸含量:2.80％(w/w)，硫酸铵含量43.5％(w/w)，碳酸钾含量2.1％(w/w)。进料体积7BV，进料流速1BV/h，准备XDA-1树脂5份，每份各100ml树脂。蛋氨酸溶液分别用4％(w/w)氢氧化钠或者4％(w/w)硫酸溶液调pH为1.0、3.0、7.0、9.0、10.0，进行吸附对照试验。
树脂吸附容量＝(进料蛋氨酸含量*进料体积-流出液蛋氨酸含量*流出液体积)/树脂体积
Figure PCTCN2016087428-appb-000001
Figure PCTCN2016087428-appb-000002
实施例10-实施例15
具体实施方案同实施例1，主要考察不同吸附速度对树脂的吸附容量影响。(实验中未做说明均为质量百分浓度)
蛋氨酸含量3.28％(w/w)，硫酸钠含量为40.19％(w/w)，pH2.40。进料体积7BV，准备XDA-200树脂5份，每份各100ml树脂。，以不同的流速树脂吸附。
实施例 流速(BV/h) 树脂吸附容量(g/L)
实施例10 1 229.6
实施例11 2 225.1
实施例12 3 211.9
实施例13 5 139.2
实施例14 7 91.4
实施例15 10 55.8
实施例16-实施例24
具体实施方案同实施例1，主要考察不同解吸剂的解吸效率及解吸液质量。(实验中未做说明均为质量百分浓度)
蛋氨酸含量2.95％(w/w)，硫酸铵含量为42.04％(w/w)，pH2.20。进料体积各7BV，以1BV/h流速分别通过100ml XDA-300树脂7份(西安 蓝晓科技新材料股份有限公司生产)。吸附结束后，分别用3BV的4％(w/w)氢氧化钠、4％(w/w)氢氧化钾、4％(w/w)盐酸，4％(w/w)氯化钠，4％(w/w)氨水，4％(v/v)甲醇，4％(v/v)乙醇，4％(v/v)异丙醇，4％(v/v)丙酮以1BV/h的流速解吸树脂。
Figure PCTCN2016087428-appb-000003
实施例25-实施例29
具体实施方案同实施例16-24，主要考察不同浓度解吸剂对解吸质量及收率的影响。
蛋氨酸含量2.64％(w/w)，硫酸铵含量为42.04％(w/w)，pH2.20。进料体积各8BV，以1BV/h流速分别通过100ml XDA-8G树脂4份(西安蓝晓科技新材料股份有限公司生产)。吸附结束后，分别用3BV的1％(w/w)氨水、2％(w/w)氨水、4％(w/w)氨水、氨水8％(w/w)氨水、10％(w/w)氨水以1BV/h的流速解吸树脂。
Figure PCTCN2016087428-appb-000004
Figure PCTCN2016087428-appb-000005
实施例30-实施例33
具体实施方案同实施例16-24，主要考察不同解吸剂体积对解吸收率的影响。
蛋氨酸含量3.07％，硫酸铵含量为44.55％，pH2.41。进料体积各7BV，以1BV/h流速分别通过100ml XDA-200树脂4份(西安蓝晓科技新材料股份有限公司生产)。吸附结束后，分别用1BV的4％(w/w)甲醇、2BV的4％(w/w)甲醇、3BV的4％(w/w)甲醇、5BV的4％(w/w)甲醇以1BV/h的流速解吸树脂。
实施例 解吸体积 解吸液蛋氨酸浓度(％) 解吸收率(％)
实施例30 1BV 12.47 58.03
实施例31 2BV 8.75 81.47
实施例32 3BV 6.99 97.79
实施例33 5BV 4.21 98.02
实施例34-实施例37
具体实施方案同实施例16-24，主要考察不同解吸剂体积对解吸收率的影响。
蛋氨酸含量2.58％(w/w)，硫酸铵含量为44.55％(w/w)，pH2.41。进料体积各8BV，以1BV/h流速分别通过100ml XDA-300树脂4份(西安蓝晓科技新材料股份有限公司生产)。吸附结束后，分别用3BV的4％(w/w)的丙酮溶液以1BV/h、3BV/h、7BV/h、10BV/h流速解吸树脂。
Figure PCTCN2016087428-appb-000006
Figure PCTCN2016087428-appb-000007
实施例38：
1.树脂吸附：将蛋氨酸溶液(pH：2.75，蛋氨酸含量2.98％(w/w)，硫酸铵含量41.59％(w/w)，以1BV/h的流速自上而下匀速通过100ml XDA-1树脂床(西安蓝晓科技新材料股份有限公司生产)，单独收集树脂流出液，当树脂柱底部流出液蛋氨酸含量为0.3％(w/w)时，停止向树脂柱内进料。
2.树脂解吸：3BV的6％(w/w)的氨水溶液以1BV/h的流速自上而下解吸树脂，收集解吸液。
3.收集树脂流出液750ml，检测蛋氨酸含量为0.01％(w/w),硫酸铵含量41.55％(w/w)。收集解吸液300ml，检测蛋氨酸含量6.75％(w/w)，蛋氨酸收率98.18％(w/w)。

Claims (17)

  1. 一种用于蛋氨酸纯化的工艺，其特征在于：
    采用大孔吸附树脂分离蛋氨酸和副产盐类物质，蛋氨酸被吸附在大孔吸附树脂上然后用解吸剂解吸树脂回收蛋氨酸，副产盐类物质在吸附过程中不被大孔吸附树脂吸附进入吸附流出液中，主要包括以下步骤：
    1)树脂吸附：蛋氨酸溶液自上而下通过大孔吸附树脂层，当树脂柱流出液中含蛋氨酸含量大于等于进口含量的10％(w/w)时，停止树脂吸附；树脂吸附流出液作为副产盐类物质；
    2)树脂解吸：步骤1)中完成了吸附的树脂，用解吸剂自上而下通过，解吸树脂，并收集解吸液；
    3)后续工艺过程：解吸液按照现有工艺流程后续处理。
  2. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，其中的蛋氨酸包括蛋氨酸及蛋氨酸的羟基衍生物。
  3. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，其中的副产盐类物质为碳酸钠、硫酸钠、硫酸铵、碳酸钾、硫酸钾中的一种或者几种混合物。
  4. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，步骤1)树脂吸附中，先调节待吸附的蛋氨酸溶液pH为1.0-10.0。
  5. 根据权利要求4所述的一种用于蛋氨酸纯化的工艺，步骤1)树脂吸附中，先调节待吸附的蛋氨酸溶液pH为1.0-5.0。
  6. 根据权利要求5所述的一种用于蛋氨酸纯化的工艺，步骤1)树脂吸附中，先调节待吸附的蛋氨酸溶液pH为2.0-3.0。
  7. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，蛋氨酸溶液通过大孔吸附树脂层的流速为1-10BV/h。
  8. 根据权利要求7所述的一种用于蛋氨酸纯化的工艺，蛋氨酸溶液通过大孔吸附树脂层的流速为1-5BV/h。
  9. 根据权利要求8所述的一种用于蛋氨酸纯化的工艺，蛋氨酸溶液通过大孔吸附树脂层的流速为1-3BV/h。
  10. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，所述解吸剂选自 氢氧化钠、氢氧化钾、盐酸、氯化钠、氨水、甲醇、乙醇、异丙醇、丙酮。
  11. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，所述解吸剂的浓度以质量百分比计为1-10％。
  12. 根据权利要求11所述的一种用于蛋氨酸纯化的工艺，所述解吸剂的浓度以质量百分比计为2-8％。
  13. 根据权利要求12所述的一种用于蛋氨酸纯化的工艺，所述解吸剂的浓度以质量百分比计为4-8％。
  14. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，所述树脂解吸剂的体积为1-3BV。
  15. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，所述树脂解吸剂的流速为1-5BV/h。
  16. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，其特征在于：其中的蛋氨酸包括蛋氨酸及蛋氨酸的羟基衍生物；
    其中的副产盐类物质为碳酸钠、硫酸钠、硫酸铵、碳酸钾、硫酸钾中的一种或者几种混合物；
    步骤1)树脂吸附中，先调节待吸附的蛋氨酸溶液pH为2.0-3.0；
    蛋氨酸溶液通过大孔吸附树脂层的流速为1-3BV/h；
    所述解吸剂选自氢氧化钠、氢氧化钾、盐酸、氯化钠、氨水、甲醇、乙醇、异丙醇、丙酮；
    所述解吸剂的浓度以质量百分比计为4-8％；
    所述树脂解吸剂的体积为1-3BV；
    所述树脂解吸剂的流速为1-5BV/h。
  17. 根据权利要求1所述的一种用于蛋氨酸纯化的工艺，其特征在于包括以下步骤：
    1)树脂吸附：将蛋氨酸溶液pH：2.75，蛋氨酸含量2.98％(w/w)，硫酸铵含量41.59％(w/w))，以1BV/h的流速自上而下匀速通过100ml西安蓝晓科技新材料股份有限公司生产的XDA-1树脂床，单独收集树脂流出液，当树脂柱底部流出的蛋氨酸含量为0.3％时，停止向树脂柱内进料；
    2)树脂解吸：3BV的6％的氨水溶液以1BV/h的流速自上而下解吸树 脂，收集解吸液。
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See also references of EP3318552A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018520146A (ja) * 2015-06-30 2018-07-26 西安藍暁科技新材料股▲ふん▼有限公司Ｓｕｎｒｅｓｉｎ Ｎｅｗ Ｍｅｔｅｒｉａｌｓ Ｃｏ．Ｌｔｄ，．Ｘｉ’Ａｎ メチオニンの精製プロセス
WO2019017415A1 (ja) * 2017-07-19 2019-01-24 住友化学株式会社 精製メチオニンの製造方法及びメチオニンの固結防止方法
CN110740990A (zh) * 2017-07-19 2020-01-31 住友化学株式会社 纯化甲硫氨酸的制造方法及甲硫氨酸的固结防止方法
JPWO2019017415A1 (ja) * 2017-07-19 2020-05-28 住友化学株式会社 精製メチオニンの製造方法及びメチオニンの固結防止方法
EP3656761A4 (en) * 2017-07-19 2021-04-07 Sumitomo Chemical Company, Limited PROCESS FOR THE PRODUCTION OF PURIFIED METHIONINE AND METHOD FOR PREVENTING THE AGGLUTINATION OF METHIONINE
US10995065B2 (en) 2017-07-19 2021-05-04 Sumitomo Chemical Company, Limited Method for producing purified methionine and method for preventing caking of methionine
JP7181199B2 (ja) 2017-07-19 2022-11-30 住友化学株式会社 精製メチオニンの製造方法及びメチオニンの固結防止方法

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US20180194723A1 (en) 2018-07-12
KR20180038421A (ko) 2018-04-16
US10287244B2 (en) 2019-05-14
CN104926701A (zh) 2015-09-23
CN104926701B (zh) 2017-05-03
EP3318552A1 (en) 2018-05-09
KR102045531B1 (ko) 2019-12-02
EP3318552A4 (en) 2019-02-20
JP6691557B2 (ja) 2020-04-28
JP2018520146A (ja) 2018-07-26
SG11201710689TA (en) 2018-01-30

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