阅读说明：本技术 一种高胱氨酸反应液的后处理方法 (Post-treatment method of homocystine reaction solution ) 是由 骆建轻 周以鸿 何文秀 程龙进 周建雄 赖立冬 于 2020-06-08 设计创作，主要内容包括：本发明提供了一种高胱氨酸反应液的后处理方法,涉及高胱氨酸制备技术领域。本发明提供的高胱氨酸反应液的后处理方法,包括以下步骤：将高胱氨酸反应液吸附于酸性离子交换树脂中,利用水对吸附离子交换树脂进行一次洗脱,得到水洗脱液和脱酸离子交换树脂,所述水洗脱液中包括回收硫酸和氢溴酸；利用酸洗脱剂或碱洗脱剂对所述脱酸离子交换树脂进行二次洗脱,得到酸洗脱液或碱洗脱液,所述酸洗脱液或碱洗脱液中含有高胱氨酸。本发明提供的后处理方法中,硫酸及氢溴酸在酸性离子树脂吸附能力弱,很容易用水洗脱而从反应液中分离开,避免了利用碱液中和反应液而产生大量的废盐,绿色环保；也无需采用复杂装置,成本低。(The invention provides a post-treatment method of homocystine reaction liquid, and relates to the technical field of homocystine preparation. The post-treatment method of homocystine reaction solution provided by the invention comprises the following steps: adsorbing the homocystine reaction solution in acidic ion exchange resin, and eluting the adsorbed ion exchange resin by using water for one time to obtain water eluent and deacidification ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid; and carrying out secondary elution on the deacidified ion exchange resin by using an acid-washing eluent or an alkali-washing eluent to obtain an acid-washing eluent or an alkali-washing eluent, wherein the acid-washing eluent or the alkali-washing eluent contains homocystine. In the post-treatment method provided by the invention, the sulfuric acid and the hydrobromic acid have weak adsorption capacity in the acidic ion resin, and are easy to elute by water and separate from the reaction liquid, so that a large amount of waste salt generated by neutralizing the reaction liquid by using alkali liquor is avoided, and the post-treatment method is green and environment-friendly; and a complex device is not needed, and the cost is low.)

1. A post-treatment method of homocystine reaction solution is characterized by comprising the following steps:

adsorbing the homocystine reaction solution in acidic ion exchange resin, and eluting the adsorbed ion exchange resin by using water for one time to obtain water eluent and deacidification ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid;

carrying out secondary elution on the deacidified ion exchange resin by using an acid washing eluent or an alkali washing eluent to obtain an acid washing eluent or an alkali washing eluent, wherein the acid washing eluent or the alkali washing eluent contains homocystine;

the homocystine reaction solution is obtained by mixing methionine, sulfuric acid, hydrobromic acid and water and then carrying out a hydrothermal reaction.

2. The post-treatment method according to claim 1, characterized in that the acidic ion exchange resin is a strongly acidic cation exchange resin.

3. The post-treatment method according to claim 1, characterized in that the acid stripper comprises a hydrochloric acid solution and/or an acetic acid solution;

the alkaline eluent comprises at least one of ammonia water, sodium hydroxide solution and potassium hydroxide solution.

4. The post-treatment method according to claim 3, wherein the mass percentage concentration of the hydrochloric acid solution is 10-36%;

the mass percentage concentration of the acetic acid solution is 10-80%;

the mass percentage concentration of the ammonia water is 5-25%;

the mass percentage concentration of the sodium hydroxide solution is 5-20%;

the mass percentage concentration of the potassium hydroxide solution is 5-20%.

5. The post-treatment method according to claim 1, further comprising, after the one elution: and concentrating the water eluent to be used as a raw material for preparing homocystine.

6. The post-treatment method according to claim 1, further comprising diluting the homocystine reaction solution with a diluent before the adsorption.

7. The post-treatment method according to claim 6, wherein the diluent comprises water, methanol, ethanol or acetone.

8. The post-treatment method according to claim 6 or 7, wherein the mass ratio of the homocystine reaction solution to the diluent is 1: (2-20).

9. The post-treatment method according to claim 1, wherein the temperature of the hydrothermal co-heating reaction is 100 to 140 ℃ and the time is 4 to 30 hours.

Technical Field

The invention relates to the technical field of homocystine preparation, in particular to a post-treatment method of homocystine reaction liquid.

Background

Homocystine and a reduction cyclization product (homocysteine thiolactone hydrochloride) thereof are important medicine and pesticide intermediates, and the structural formula of homocystine is as follows:

chem,1999, biol.biol; 135-142 the first proposed synthetic approaches for homocystine: methionine and excessive sulfuric acid are heated to prepare homocystine, the method is used up to now, but the reaction yield is low, and in the post-treatment process, alkaline solution is adopted to neutralize excessive sulfuric acid, so that a large amount of inorganic salt is generated, and great pressure is generated for environmental protection. The above process is improved in european patent EP 0844239: the method for preparing homocystine by heating mixed acid of methionine and sulfuric acid/hydrobromic acid can greatly improve the yield of homocystine, but the subsequent treatment process still adopts alkaline solution to neutralize excessive mixed acid, so that a large amount of waste salt (sulfate and bromide) is generated, the treatment difficulty of the waste salt is increased, and the process still has great environmental protection pressure. Chinese patent CN101348452A discloses a method for preparing homocystine from methionine and sulfuric acid/hydrohalogen acid, wherein the post-treatment method of the reaction solution is to dialyze the reaction solution to recover the excessive sulfuric acid, so as to reduce the generation of waste salt to a great extent, but because the dialysis has balanced ion concentration, the excessive acid in the reaction solution cannot be completely recovered in production, and the dialysis recovery device is complex and has high cost.

Disclosure of Invention

In view of this, the invention aims to provide a post-treatment method of homocystine reaction liquid, which basically does not generate waste salt, is green and environment-friendly, does not need a complex device and has low cost.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a post-treatment method of homocystine reaction solution, which comprises the following steps:

adsorbing the homocystine reaction solution in acidic ion exchange resin, and eluting the adsorbed ion exchange resin by using water for one time to obtain water eluent and deacidification ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid;

carrying out secondary elution on the deacidified ion exchange resin by using an acid washing eluent or an alkali washing eluent to obtain an acid washing eluent or an alkali washing eluent, wherein the acid washing eluent or the alkali washing eluent contains homocystine;

the homocystine reaction solution is obtained by mixing methionine, sulfuric acid, hydrobromic acid and water and then carrying out a hydrothermal reaction.

Preferably, the acidic ion exchange resin is a strongly acidic cation exchange resin.

Preferably, the acid-washing remover comprises hydrochloric acid solution and/or acetic acid solution;

the alkaline eluent comprises at least one of ammonia water, sodium hydroxide solution and potassium hydroxide solution.

Preferably, the mass percentage concentration of the hydrochloric acid solution is 10-36%;

the mass percentage concentration of the acetic acid solution is 10-80%;

the mass percentage concentration of the ammonia water is 5-25%;

the mass percentage concentration of the sodium hydroxide solution is 5-20%;

the mass percentage concentration of the potassium hydroxide solution is 5-20%.

Preferably, the method further comprises the following steps after the primary elution: and concentrating the water eluent to be used as a raw material for preparing homocystine.

Preferably, the method further comprises diluting the homocystine reaction solution with a diluent before the adsorption.

Preferably, the diluent comprises water, methanol, ethanol or acetone.

Preferably, the mass ratio of the homocystine reaction solution to the diluent is 1: (2-20).

Preferably, the temperature of the water co-heating reaction is 100-140 ℃, and the time is 4-30 h.

The invention provides a post-treatment method of homocystine reaction solution, which comprises the following steps: adsorbing the homocystine reaction solution in acidic ion exchange resin, and eluting the adsorbed ion exchange resin by using water for one time to obtain water eluent and deacidification ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid; carrying out secondary elution on the deacidified ion exchange resin by using an acid washing eluent or an alkali washing eluent to obtain an acid washing eluent or an alkali washing eluent, wherein the acid washing eluent or the alkali washing eluent contains homocystine; the homocystine reaction solution is obtained by mixing methionine, sulfuric acid, hydrobromic acid and water and then carrying out a hydrothermal reaction. In the post-treatment method provided by the invention, the sulfuric acid and the hydrobromic acid have weak adsorption capacity in the acidic ion resin, and are easy to elute by water and separate from the reaction liquid, so that a large amount of waste salt generated by neutralizing the reaction liquid by using alkali liquor is avoided, and the post-treatment method is green and environment-friendly; a complex device is not needed, and the cost is low; and the recovery rate of the sulfuric acid and the hydrobromic acid in the obtained water eluent reaches over 90 percent, and the recovered sulfuric acid and the recovered hydrobromic acid can be used as a raw material for preparing homocystine, so that the production cost of the homocystine is reduced.

Drawings

Fig. 1 is a schematic diagram of the post-treatment method of homocystine reaction solution in the example, wherein → represents that secondary elution is continued after completion of primary elution, and ← represents that the ion exchange resin after secondary elution is activated and then recycled for primary elution.

Detailed Description

The invention provides a post-treatment method of homocystine reaction solution, which comprises the following steps:

adsorbing the homocystine reaction solution in acidic ion exchange resin, and eluting the adsorbed ion exchange resin by using water for one time to obtain water eluent and deacidification ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid;

carrying out secondary elution on the deacidified ion exchange resin by using an acid washing eluent or an alkali washing eluent to obtain an acid washing eluent or an alkali washing eluent, wherein the acid washing eluent or the alkali washing eluent contains homocystine;

the homocystine reaction solution is obtained by mixing methionine, sulfuric acid, hydrobromic acid and water and then carrying out a hydrothermal reaction.

In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

The method comprises the steps of adsorbing homocystine reaction liquid in acidic ion exchange resin, and eluting the adsorbed ion exchange resin for one time by using water to obtain water eluent and deacidified ion exchange resin, wherein the water eluent comprises recovered sulfuric acid and hydrobromic acid.

In the present invention, the homocystine reaction solution is preferably obtained by mixing methionine, sulfuric acid, hydrobromic acid and water and then performing a hydrothermal reaction. In the invention, the mass percentage of the sulfuric acid is preferably 70-98%, and more preferably 85-98%. In the invention, the hydrobromic acid is preferably 20-47% by mass, and more preferably 35-47% by mass. In the present invention, the molar ratio of methionine, sulfuric acid and hydrobromic acid is preferably 1: (1-5): (1 to 8), more preferably 1: (2-4): (2-7), most preferably 1: (3-4): (3-5). In the present invention, the molar ratio of methionine to water is preferably 1: (1-10), more preferably 1: (3-8), most preferably 1: (4-6).

In the present invention, the methionine, sulfuric acid, hydrobromic acid and water are preferably mixed in this order by mixing methionine, hydrobromic acid and water, and adding sulfuric acid dropwise to the resulting mixture. In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed. The speed of the sulfuric acid is not particularly limited, and the sulfuric acid is added dropwise. In the present invention, the temperature of the mixing is preferably room temperature.

In the invention, the temperature of the water co-heating reaction is preferably 100-140 ℃, more preferably 110-130 ℃, and most preferably 120-130 ℃; the time of the water co-heating reaction is preferably 4-30 h, more preferably 5-25 h, and most preferably 10-20 h. In the present invention, methionine is generated into homocystine under the action of sulfuric acid and hydrobromic acid during the hydrothermal co-reaction.

In the present invention, it is preferable that the adsorption further comprises diluting the homocystine reaction solution with a diluent. In the present invention, the diluent preferably comprises water, methanol, ethanol or acetone, more preferably comprises water, methanol or ethanol, and most preferably water. In the present invention, the mass ratio of the homocystine reaction solution to the diluent is preferably 1: (2-20), more preferably 1: (5-18), most preferably 1: (10-15). In the present invention, the dilution serves to completely adsorb the homocystine reaction solution to the acidic ionic resin.

In the present invention, the adsorption mode is preferably electrostatic adsorption.

In the present invention, the acidic ion exchange resin is preferably a strongly acidic cation exchange resin. The source of the strong acid cation exchange resin is not particularly limited in the present invention, and a commercially available strong acid cation exchange resin well known to those skilled in the art may be used; in the examples of the present invention, the strongly acidic cation exchange resin is preferably an ion exchange resin of the Dowex-50H type (available from the manufacturer in the Dow chemical Co., Ltd.), an ion exchange resin of the Amberlite IR-120H type (available from the manufacturer in the Dow chemical Co., Ltd.), or an ion exchange resin of the Dowex-650C H type (available from the manufacturer in the Dow chemical Co., Ltd.). In the present invention, the acidic ion exchange resin is preferably used after being packed in an ion exchange column. In the examples of the present invention, when the mass of methionine in the homocystine reaction solution preparation raw material is 50g, the mass of the acidic ion exchange resin in the ion exchange column is preferably 500 g.

The invention has no special limit to the dosage and flow rate of water used for one-time elution, and the water eluent which is eluted till the effluent does not contain sulfate ions and bromide ions. In the present invention, the water is preferably pure water. In the present invention, the temperature of the one elution is preferably room temperature.

The first elution is performed to obtain a water eluent and deacidification ion exchange resin, and the obtained water eluent preferably further comprises: and concentrating the water eluent to be used as a raw material for preparing homocystine. In the present invention, the concentration is preferably performed by distillation under reduced pressure. In the present invention, the temperature and time of the reduced pressure distillation are not particularly limited, and water in the recovered sulfuric acid and hydrobromic acid solution can be removed.

After the primary elution, the deacidification ion exchange resin is subjected to secondary elution by using an acid washing eluent or an alkali washing eluent to obtain an acid washing eluent or an alkali washing eluent, wherein the acid washing eluent or the alkali washing eluent contains homocystine.

In the present invention, the acid eluent is obtained when the secondary elution is performed with the acid eluent, and the alkali eluent is obtained when the secondary elution is performed with the alkali eluent. In the present invention, the acid-washing remover preferably comprises a hydrochloric acid solution and/or an acetic acid solution; the mass percentage concentration of the hydrochloric acid solution is preferably 10-36%, and more preferably 10-20%; the mass percentage concentration of the acetic acid solution is preferably 10-80%, and more preferably 30-50%. In the present invention, the alkali detergent preferably comprises at least one of ammonia water, a sodium hydroxide solution and a potassium hydroxide solution, and more preferably comprises ammonia water, a sodium hydroxide solution or a potassium hydroxide solution; the mass percentage concentration of the ammonia water is preferably 5-25%, and more preferably 5-10%; the mass percentage concentration of the sodium hydroxide solution is preferably 5-25%, and more preferably 5-10%; the mass percentage concentration of the potassium hydroxide solution is preferably 5-25%, and more preferably 5-10%.

The dosage and flow rate of the acid washing and stripping agent or the alkali washing and stripping agent are not specially limited, and homocystine in the ion exchange resin containing the deacidification reaction liquid can be completely eluted; preferably, derivatization is used to detect the presence or absence of homocystine. In the present invention, the temperature of the secondary elution is preferably room temperature.

In the present invention, when a basic eluting agent is used, the second elution preferably further comprises activating the ion exchange resin after the second elution; the eluent generated by the activation is preferably activated by hydrochloric acid; the method of hydrochloric acid activation in the present invention is not particularly limited, and a hydrochloric acid activation method known to those skilled in the art may be used. In the present invention, the method of activation is preferably to elute the ion exchange resin after the secondary elution with the acid-washing eluent. In the invention, when the acid washing and removing agent is adopted, the ion exchange resin is activated in the secondary elution process, and can be directly recycled without being activated. In the invention, the activated ion exchange resin can be recycled, so that the treatment cost of the homocystine reaction solution is reduced.

After the acid washing eluent or the alkali washing eluent is obtained, the acid washing eluent or the alkali washing eluent is sequentially concentrated, neutralized and crystallized to obtain the homocystine pure product.

In the present invention, the concentration is preferably performed by vacuum distillation, and the temperature and time of vacuum distillation are not particularly limited in the present invention, and those skilled in the art can use the temperature and time of vacuum distillation. In the invention, the acid eluent or the alkali eluent recovered in the concentration process can be reused for secondary elution or used as a neutralizing agent for subsequent neutralization, so that the cost is reduced.

After said concentration, the present invention preferably neutralizes the resulting concentrated product. In the present invention, the neutralization is preferably performed using an acidic agent or an alkaline agent; the acidic reagent preferably comprises hydrochloric acid or acetic acid; the alkaline agent preferably comprises ammonia, sodium hydroxide or potassium hydroxide. The dosage of the acidic reagent or the alkaline reagent is not particularly limited, the acidic reagent or the alkaline reagent is neutralized to the isoelectric point of homocystine, and the pH value of the system is preferably 6.5-7. In the invention, in the neutralization process, acid-base neutralization reaction is carried out to generate salt, and homocystine is separated out after the isoelectric point of homocystine is reached.

After the homocystine is separated out, the homocystine is crystallized by the method. In the present invention, the solvent for crystallization is preferably water. The amount of water used for crystallization is not particularly limited, and is preferably adjusted according to the viscosity condition of the neutralized system, so that homocystine can be easily filtered, and the added water can dissolve salts generated in the neutralization process, thereby improving the purity of homocystine.

After the crystallization, the invention preferably further comprises the steps of sequentially carrying out solid-liquid separation, water washing and drying on a crystallization system obtained by the crystallization. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art may be used, and in the embodiment of the present invention, the solid-liquid separation method is preferably filtration. In the present invention, the number of times of the water washing is not particularly limited, and water-soluble impurities (inorganic salts) in the solid-phase product may be removed. In the present invention, the drying is preferably oven drying; the drying temperature is preferably 50-100 ℃, and more preferably 60-80 ℃; the drying time is preferably 2-24 hours, and more preferably 8-12 hours.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.