阅读说明：本技术 蛋氨酸的制造方法和制造设备 (The manufacturing method and manufacturing equipment of methionine ) 是由 大本宣仁 佐藤庆孝 森川正幸 古泉善行 山城直也 片上良辅 于 2018-04-27 设计创作，主要内容包括：本申请发明提供蛋氨酸的制造方法,其包括：(1)反应工序：在碱性化合物的存在下,将5-[2-(甲硫基)乙基]咪唑烷-2,4-二酮进行水解,得到包含蛋氨酸的碱盐的反应液的工序；(2)第一结晶工序：向前述反应液中导入二氧化碳,使蛋氨酸从前述反应液中析出,得到蛋氨酸初晶和初晶母液的工序；以及(3)第二结晶工序：向前述初晶母液中添加醇并导入二氧化碳,得到包含析出的析出物的浆料、且所述析出物包含蛋氨酸次晶,将所得浆料供于离心分离,固液分离成蛋氨酸次晶和次晶母液,使用过滤器将残留在所得次晶母液中的前述析出物进行分离的工序。(The manufacturing method of the present application offer methionine, comprising: (1) reaction process: in the presence of alkali compounds, 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is hydrolyzed, the process for obtaining the reaction solution of the alkali salt comprising methionine；(2) first Crystallization Procedures: methionine is precipitated from aforementioned reaction solution in introducing carbon dioxide in Xiang Qianshu reaction solution, the process for obtaining methionine primary crystal and primary crystal mother liquor；And (3) second Crystallization Procedure: alcohol and introducing carbon dioxide are added in Xiang Qianshu primary crystal mother liquor, it obtains the slurry comprising the precipitate being precipitated and the precipitate includes methionine para-crystal, by gained slurry for centrifuge separation, solid-liquid separation into methionine para-crystal and para-crystal mother liquor, the process for being separated the aforementioned precipitate remained in gained para-crystal mother liquor using filter.)

1. the manufacturing method of methionine, which is characterized in that including following processes (1) ~ (3):

(1) reaction process: in the presence of alkali compounds, 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is carried out Hydrolysis, the process for obtaining the reaction solution of the alkali salt comprising methionine；

(2) first Crystallization Procedures: introducing carbon dioxide in Xiang Suoshu reaction solution is precipitated methionine from the reaction solution, obtains To the process of methionine primary crystal and primary crystal mother liquor；

(3) second Crystallization Procedures: adding alcohol and introducing carbon dioxide in Xiang Suoshu primary crystal mother liquor, obtains the precipitate comprising being precipitated Slurry and the precipitate include methionine para-crystal after,

By the slurry for centrifuge separation, solid-liquid separation into methionine para-crystal and para-crystal mother liquor, will be remained in using filter The process that the precipitate in gained para-crystal mother liquor is separated.

2. the manufacturing method of methionine according to claim 1, wherein so that the precipitate is dissolved in the primary crystal female Liquid, and be added in the reaction solution.

3. the manufacturing method of methionine according to claim 1 or 2, wherein follow a part of the para-crystal mother liquor again Ring is to second Crystallization Procedure.

4. the manufacturing method of methionine described according to claim 1 ~ any one of 3, wherein the centrifugation in the separation of solid and liquid Power is 100 times or more and 4000 times or less relative to gravity.

5. the manufacturing method of methionine described according to claim 1 ~ any one of 4, wherein the material of the filter is poly- Diphenyl sulfide or polypropylene.

6. the manufacturing equipment of methionine, which is characterized in that it is provided with

Consersion unit, wherein carrying out 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione in the presence of alkali compounds Hydrolysis obtains the reaction solution of the alkali salt comprising methionine；

First crystallizer, wherein the introducing carbon dioxide into the reaction solution, is precipitated methionine from the reaction solution；

Second crystallizer, wherein to separation primary crystal mother liquor as obtained from after the methionine that first crystallizer obtains Thus middle addition alcohol and introducing carbon dioxide obtain the slurry of the precipitate comprising being precipitated；

Centrifugal separator is used to be separated by solid-liquid separation the slurry comprising the precipitate；And

Filter, wherein separating remaining described in the para-crystal mother liquor obtained from being separated by solid-liquid separation using the centrifugal separator Precipitate.

Technical field

Patent application claims are based on the Paris of Japanese patent application 2017-087750 (application on April 27th, 2017) The priority and right of pact is so far entered the full content group recorded in above-mentioned application in this specification by reference.

Methionine is manufactured the present invention relates to the hydrolysis by 5- [2- (methyl mercapto) ethyl] imidazolidine -2,4- diketone Method.

Background technique

Methionine is a kind of necessary amino acid that can not be synthesized in animal body, is widely used as animal feed addition Agent is industrially manufactured using chemical plant's equipment.

Method as manufacture methionine, it is known to which 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is subjected to water The method of solution (referring for example to patent document 1).The first Crystallization Procedure is carried out in this method and carries out the second brilliant process, described first In Crystallization Procedure, after 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is hydrolyzed, introducing carbon dioxide and make Methionine is precipitated, and is separated into methionine and mother liquor, in the described second brilliant process, makes the mother liquor obtained by first Crystallization Procedure The effective components such as the methionine of middle dissolution are precipitated, and are separated into the effective component and mother liquor.

Summary of the invention

Subject to be solved by the invention

When by above-mentioned second Crystallization Procedure by being separated as the precipitate of effective component and mother liquor, the one of the precipitate Part will not perhaps settle and swim in mother liquor or swim on the liquid level of mother liquor, thus there is effective component residue and exist Situation in mother liquor.Since the loss of this effective component will affect manufacturing cost, it is therefore important that reducing the loss.

It is an object of the present invention to which effectively recycling is dissolved in through the first crystallization work in the manufacturing method of methionine The effective components such as the methionine in mother liquor after the separation methionine of sequence, reduce manufacture loss.

Means for solving the problems

The inventors of the present invention have made intensive studies, as a result, it has been found that: make after being dissolved in the separation methionine by the first Crystallization Procedure Mother liquor in effective components such as methionine when being precipitated and being recycled using separation of solid and liquid, by using centrifugal separator and mistake Filter carries out the separation of solid and liquid and can effectively recycle the effective component, and reduces manufacture loss.

Present invention includes technical solution below.

1. the manufacturing method of methionine (is denoted as " manufacturer of methionine of the invention sometimes in the present specification below Method "), which is characterized in that including following processes (1) ~ (3):

(1) reaction process: in the presence of alkali compounds, 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is carried out Hydrolysis, the process for obtaining the reaction solution of the alkali salt comprising methionine；

(2) first Crystallization Procedures: introducing carbon dioxide in Xiang Qianshu reaction solution is precipitated methionine from aforementioned reaction solution, obtains To the process of methionine primary crystal and primary crystal mother liquor；And

(3) second Crystallization Procedures: adding alcohol and introducing carbon dioxide in Xiang Qianshu primary crystal mother liquor, obtains the precipitate comprising being precipitated Slurry and after the precipitate includes methionine para-crystal, by afore-mentioned slurry for centrifuge separation, solid-liquid separation into methionine time Brilliant and para-crystal mother liquor, the process for being separated the aforementioned precipitate remained in gained para-crystal mother liquor using filter.

2. according to the manufacturing method of methionine described in preceding paragraph 1, wherein so that aforementioned precipitate is dissolved in aforementioned primary crystal female Liquid, and be added in previous reaction liquid.

3. the manufacturing method of the methionine according to preceding paragraph 1 or 2, wherein follow a part of aforementioned para-crystal mother liquor again Ring is to aforementioned second Crystallization Procedure.

4. the manufacturing method of the methionine according to any one of preceding paragraph 1 ~ 3, wherein in aforementioned separation of solid and liquid from Mental and physical efforts are 100 times or more and 4000 times or less relative to gravity.

5. the manufacturing method of the methionine according to any one of preceding paragraph 1 ~ 4, wherein the material of aforementioned filter is Polyphenylene sulfide or polypropylene.

6. the manufacturing equipment of methionine (is denoted as that " manufacture of methionine of the invention is set sometimes in the present specification below It is standby "), which is characterized in that it is provided with

Consersion unit, wherein carrying out 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione in the presence of alkali compounds Hydrolysis obtains the reaction solution of the alkali salt comprising methionine；

First crystallizer, wherein the introducing carbon dioxide into aforementioned reaction solution, is precipitated methionine from aforementioned reaction solution；

Second crystallizer, wherein to separation primary crystal mother liquor as obtained from after the methionine that aforementioned first crystallizer obtains Thus middle addition alcohol and introducing carbon dioxide obtain the slurry of the precipitate comprising being precipitated；

Centrifugal separator is used to be separated by solid-liquid separation the slurry comprising aforementioned precipitate；And

Filter, wherein separating remaining aforementioned in the para-crystal mother liquor obtained from being separated by solid-liquid separation using the centrifugal separator Precipitate.

According to the manufacturing method of the methionine of the present application, by using centrifugal separator pair in the second Crystallization Procedure After slurry comprising precipitate is separated by solid-liquid separation, and it is female in the para-crystal separated by the separation of solid and liquid using filter separation Remaining precipitate in liquid, thus, it is possible to recycle can not being separated with centrifugal separator or swim on liquid or swim Precipitate in liquid can reduce loss when manufacture methionine.

Detailed description of the invention

Fig. 1 is centrifugation used in the manufacturing method for the methionine that the embodiment of manufacturing method described herein is related to Explanatory diagram around seperator.

Before and after Fig. 2 is the second Crystallization Procedure in the manufacturing method for the methionine that embodiment described herein is related to Flow chart.

Fig. 3 is the schematic configuration diagram of filter performance test device used in the filtration test of para-crystal mother liquor.

Fig. 4 is the figure for indicating the relationship of filtration time and filtration yield of each filter.

Specific embodiment

Illustrate the manufacturing method of methionine.Wherein, embodiments described below exemplifies the methionine for explanation The manufacturing method of manufacturing method, methionine is not limited to the following contents.

In the manufacturing method of the methionine of the application, by the way that 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is used It is hydrolyzed in the presence of alkali compounds in raw material, and by it, to obtain the reaction of the methionine containing base salt forms Liquid ((1) reaction process).

5- [2- (methyl mercapto) ethyl] imidazolidine -2,4- diketone as raw material can be for example, by making 2- hydroxyl -4- first sulphur Base butyronitrile reacts with ammonia and carbon dioxide or reacts with ammonium carbonate to prepare.

As alkali compounds, can enumerate such as potassium hydroxide, sodium hydroxide, potassium carbonate, saleratus, it can also be with Use two or more in them as needed.For the dosage of alkali compounds, relative to 1 mole of 5- [2- (methyl mercapto) second Base] imidazolidine-2,4-dione is usually 2 ~ 10 moles, preferably 3 ~ 6 moles in terms of potassium or sodium.In addition, the dosage of water relative to 1 parts by weight 5- [2- (methyl mercapto) ethyl] imidazolidine -2,4- diketone is usually 2 ~ 20 parts by weight.

The hydrolysis carried out in reaction process utilizes stirring-type or non-stirred formula and continous way or interval (in batches) formula Reactive tank carry out.

The hydrolysis can the heated under pressure that 0.5 ~ 1MPa or so is calculated as with gauge pressure to 150 ~ 200 DEG C or so come into Row.Reaction time is usually 10 minutes ~ 24 hours.

In order to take out methionine from the hydrolysis liquid obtained in this way, and the introducing carbon dioxide into the reaction solution Crystallized, and using filtering, decantation etc. by gained pulp separation at precipitate and mother liquor, to be analysed in the form of primary crystal Methionine ((2) first Crystallization Procedure) out.In this specification, " primary crystal mother liquor " refers to the separation egg ammonia in the first Crystallization Procedure Mother liquor obtained from acid.

By introducing carbon dioxide, carbon dioxide is absorbed by reaction solution, the alkali salt of methionine form free methionine and It is precipitated.

The importing of carbon dioxide can in terms of gauge pressure be usually 0.1 ~ 1MPa, preferably 0.2 ~ 0.5MPa pressurization under into Row.

Crystallization temperature is usually 0 ~ 50 DEG C, preferably 10 ~ 30 DEG C.In addition, for crystallization time, near hydrolysis liquid because Carbon dioxide and be saturated, the time until methionine is sufficiently precipitated is as benchmark, usually 10 minutes ~ 24 hours.

Separated methionine as needed cleaned, pH adjust etc. after, product is made i.e. and being dried It can.The drying can be by the way that under the pressure that shades, atmospheric pressure or heated under pressure is carried out to 50 ~ 160 DEG C or so, drying time be logical It is often 10 minutes ~ 24 hours.

Fig. 2 indicates the stream before and after the second Crystallization Procedure in the manufacturing method for the methionine that embodiments of the present invention are related to Cheng Tu.Remain the considerable amount of methionine of solubility in primary crystal mother liquor, further comprises as aforementioned base compounds and recyclable Compound.In this specification, effective component refers to methionine and the compound recyclable as aforementioned base compounds. For the compound recyclable as aforementioned base compounds, such as saleratus, potassium carbonate, hydroxide can be enumerated Potassium and the potassium (methionine potassium, potassium formate, potassium acetate etc.) in conjunction with organic matter.Due to including that these are effective in primary crystal mother liquor Ingredient, therefore, it is desirable to by the hydrolysis of primary crystal mother liquor recycle to process (1), on the other hand, also comprising miscellaneous in raw material Matter, as hydrolyzing when side reaction caused by impurity, such as glycine, alanine etc the amino acid in addition to methionine, Therefore color ingredient etc. causes these impurity to be swept along into hydrolysis because of recycling.Thus, the recycling of primary crystal mother liquor Not total amount, but need to carry out in the range of impurity is not accumulated, ratio relative to the total amount of primary crystal mother liquor be usually 50 ~ 90 weight %, preferably 60 ~ 85 weight %.

Although not being documented in Fig. 2, expectation primary crystal mother liquor recirculated through by the primary crystal mother liquor be concentrated and incite somebody to action The concentrate is carried out as recirculated liquid.By the concentration, carbon dioxide can be evaporated from primary crystal mother liquor, alkali can be obtained Property is improved and is conducive to the recirculated liquid of hydrolysis.In addition, by carrying out the concentration with 100 ~ 140 DEG C of high temperature, just Saleratus in brilliant mother liquor is converted to the reaction (2KHCO of potassium carbonate₃→K₂CO₃+ H₂O+CO₂) promoted, it can obtain Obtain the alkaline recirculated liquid further increased and be conducive to hydrolysis.The concentration can under atmospheric pressure, decompression is lower or pressurization Lower progress, but as described above in order to carry out at high temperature, effectively use pressurized conditions.Enrichment factor is usually 1.2 ~ 4 times, excellent 1.5 ~ 3.5 times are selected as, herein, enrichment factor refers to that the liquid weight before concentration is (dense relative to the ratio of the liquid weight after concentration The liquid weight after liquid weight/concentration before contracting), it is also identical below.

In order to make the effective component being dissolved in the primary crystal mother liquor be precipitated and recycled in the form of precipitate, will not by Part or all of the primary crystal mother liquor (concentrated mother liquor) of the part of recycling is for crystallizing.In present embodiment, the knot Crystalline substance is carried out by adding alcohol and introducing carbon dioxide into primary crystal mother liquor, as the pulp separation by obtained by precipitate and para-crystal Mother liquor, so that the effective component being dissolved in primary crystal mother liquor is recycled ((3) second Crystallization Procedure).

Hereinafter, the precipitate being precipitated and adding alcohol and introducing carbon dioxide into primary crystal mother liquor is denoted as " this precipitation Object ".In addition, " para-crystal mother liquor " refers to separates mother liquor obtained from this precipitate in the second Crystallization Procedure in this specification, meaning Refer to it is aftermentioned be separated by solid-liquid separation using centrifugal separator obtained from mother liquor and separated obtained from this precipitate using filter Both mother liquors.It should be noted that can not also be recycled to the primary crystal mother liquor after concentration, but its total amount is used for The crystallization.

Although not being documented in Fig. 2, for the second Crystallization Procedure primary crystal mother liquor preferably with want recycled primary crystal Mother liquor is equally concentrated.By the concentration, the rate of recovery of this precipitate can be improved.The concentration can with want recycled The concentration of primary crystal mother liquor carry out under the same conditions, after the total amount of primary crystal mother liquor can also being concentrated, be divided into recycling purposes With the second Crystallization Procedure purposes.

In the concentration of primary crystal mother liquor, the alkalinity in mother liquor rises, the free egg converted by the first Crystallization Procedure Propylhomoserin restores to the alkali salt of methionine.Thus, in the second Crystallization Procedure, also by after concentration primary crystal mother liquor and alcohol it is mixed It closes introducing carbon dioxide in liquid and the alkali salt of methionine is again converted into free methionine.

Furthermore it is preferred that being heated after the concentration of above-mentioned primary crystal mother liquor, pass through methionylmethionine wherein included The hydrolysis of (dehydration condensations of two molecule methionine) and the regeneration for promoting methionine.The heat treatment can be calculated as with gauge pressure It is carried out under the pressurization of 0.5 ~ 2.0MPa or so with 140 ~ 180 DEG C or so of temperature, heat treatment time is usually 10 minutes ~ 24 small When.

As the aforementioned alcohol being added in primary crystal mother liquor, the alkylol that the carbon atom number usually using alkyl is 1 ~ 5, In, 1 preferably in the alcohol that can be mixed with water with arbitrary proportion of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, tert-butyl alcohol etc Kind or two or more, particularly preferably isopropanol.The dosage of alcohol is usually 0.05 ~ 5 weight relative to the primary crystal mother liquor for crystallization Again, preferably 0.1 ~ 2 times of weight.It should be noted that the operation for adding alcohol into primary crystal mother liquor can be in introducing carbon dioxide It carries out, can also be carried out simultaneously with the importing of carbon dioxide before.

The importing of carbon dioxide in second Crystallization Procedure can be in the same manner as the first Crystallization Procedure usual in terms of gauge pressure For 0.1 ~ 1.0MPa, preferably 0.2 ~ 0.5MPa pressurization under carry out.

Crystallization temperature is usually 0 ~ 50 DEG C, preferably 5 ~ 20 DEG C.In addition, for crystallization time, it is near first added with alcohol Time until brilliant mother liquor is saturated because of carbon dioxide, this precipitate is sufficiently precipitated as benchmark, usually 10 minutes ~ 24 Hour.

Fig. 1 shows in the second Crystallization Procedure that the continuous separation costs precipitate of the slurry comprising this precipitate and para-crystal is female The explanatory diagram on the centrifugal separator periphery of liquid.The outline that Fig. 1 describes the decanter 10 as one of horizontal centrifugal seperator is cut Face figure etc..The presentation of decanter 10 is had the rotary barrel 11 rotated centered on the center line drawn with Fig. 1 and can Have the composition of the screw rod 13 of rotation speed difference, in present embodiment, continuously flow into slurry to center with the rotary barrel 11 It near line, flows out this precipitate from the first outflux 11a of the paper upper left side of Fig. 1, and makes para-crystal mother liquor from Fig. 1 The second outflux 11b outflow on the right side of rotary barrel on paper, thus separation costs precipitate and para-crystal mother liquor.It needs to illustrate , for the model of centrifugal separator, it is not particularly limited, in the case where expanding the scale of production, preferably continous way.It can To use vertical centrifugal separator, horizontal or cylinder type centrifugal separator can also be used.

100 times or more and 4000 are desired for relative to gravity using the centrifugal force in the separation of solid and liquid of aforementioned centrifugal separator Times or less.That is, centrifugal effect: Z=mr ω²/ mg, m: quality [kg], r: radius of turn [m], ω: angular speed [rad/s], g: weight Power acceleration [m/s²] value be desired for 100 or more and 4000 or less.

In present embodiment, is not separated and remained in para-crystal mother liquor in the separation of solid and liquid using centrifugal separator This precipitate is separated using filter 12.As described above, the slurry comprising this precipitate is separated by centrifuge separation Cost precipitate and para-crystal mother liquor.At this point, a part of this precipitate or swims in a liquid not by sedimentation or swims in liquid On face, thus remain in para-crystal mother liquor.Thus, in present embodiment, it is provided with for analysing remaining in para-crystal mother liquor The filter 12 that object is separated out.

The material of the filter is preferably polypropylene or polyphenylene sulfide, more preferably polyphenylene sulfide.This is because: due to slurry When expecting to be alkaline, therefore the liquid being filtered, it can either ensure that the performance of filter is able to extend the service life of filter again. Thereby, it is possible to mitigate the maintenance operation of replacement filter, and it can be realized the reduction of the cost associated with replacement filter.This Outside, although not shown, but the application as filter, for example, by filter is set side by side, Alternating Liquids institute at regular intervals By filter, so as to which the filter cake use-case such as primary crystal mother liquor collected using filter is returned when liquid does not pass through It receives.In addition it is also possible to be operated by the way that filter is set as 1 and by mother liquor interim storage in tank etc. using 1.

As long as filter can collect the size for the precipitate that para-crystal mother liquor is included, any filtering can be Device.Be set as can collection cut size be 0.1 ~ 1,000 μm, preferably 1 ~ 500 μm precipitate filter.

As shown in Fig. 2, this precipitate recycled is recirculated to the hydrolysis of process (1).At this point, expectation makes this analysis Object is dissolved in the primary crystal mother liquor of recycling purposes out, and is added in reaction solution.

It is still dissolved in para-crystal mother liquor after separating this precipitate by filter and includes effective component.Such as Fig. 2 institute Show, in present embodiment, in order to further recycle effective component from the para-crystal mother liquor, is expected that by para-crystal mother liquor concentrations Afterwards, part of it is heated [heating process], and by the liquid recycle after the heat treatment to (3) second knots Brilliant process (preferably being mixed with the concentrate of primary crystal mother liquor), to recycle effective component.

In addition, para-crystal mother liquor not instead of total amount recycles, simultaneously surplus is discharged in preferred recycling a part.This is because: In the same manner as primary crystal mother liquor, para-crystal mother liquor also includes impurity.By the way that a part of para-crystal mother liquor is recycled to the second crystallization work Sequence, and surplus is excluded, so as to mitigate the adverse effect caused by reaction process, Crystallization Procedure as caused by impurity accumulation. The loss of this precipitate remained in para-crystal mother liquor leads to the increase of manufacturing cost, reduces the loss in recycling para-crystal mother liquor A part and be discharged more and more important in the method for surplus.

By the concentration of para-crystal mother liquor, the rate of recovery of methionine can be improved, and can evaporate and add in the second Crystallization Procedure The alcohol added.

In addition, promoting methionine because of the hydrolysis of methionylmethionine wherein included by the heat treatment after concentration Regeneration.The heat treatment is in the case where being calculated as the pressurization of 0.5 ~ 2MPa or so with gauge pressure at 150 ~ 200 DEG C, preferably with 160 ~ 180 DEG C At a temperature of carry out.Heat treatment time is preferably 0.3 ~ 10 hour, more preferably 0.5 ~ 5 hour.

It is preferably 5 ~ 50 weight % relative to the ratio of methionine that the heat treatment, which can be carried out to methionylmethionine, more excellent Until being selected as 5 ~ 40 weight %.