阅读说明：本技术 甲硫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：本申请发明提供甲硫氨酸的制造方法,其特征在于,包括：在碱化合物的存在下将5-[2-(甲硫基)乙基]咪唑烷-2,4-二酮水解,得到包含甲硫氨酸的碱盐的反应液的步骤；通过向前述反应液导入二氧化碳,使甲硫氨酸析出,得到包含该甲硫氨酸的第1浆料的步骤；使前述第1浆料流入加压过滤机,由前述第1浆料得到固体甲硫氨酸和母液的步骤；和,从前述母液中回收二氧化碳的步骤。通过该制造方法,抑制了在析晶步骤中导入的二氧化碳从母液中释放,能够回收该二氧化碳。(The manufacturing method of the present application offer methionine characterized by comprising 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is hydrolyzed in the presence of alkali cpd, obtains the step of including the reaction solution of the alkali salt of methionine；By methionine being precipitated to aforementioned reaction solution introducing carbon dioxide, the step of including 1 slurry of the methionine is obtained；The step of making aforementioned 1st slurry flow into pressing filter, solid methionine and mother liquor are obtained by aforementioned 1st slurry；With, from aforementioned mother liquor recycle carbon dioxide the step of.Pass through the manufacturing method, it is suppressed that the carbon dioxide imported in Devitrification step is discharged from mother liquor, can recycle the carbon dioxide.)

1. the manufacturing method of methionine comprising following step (1) ~ (4):

(1) reaction step: 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is hydrolyzed in the presence of alkali cpd, is obtained To the alkali salt for including methionine reaction solution the step of；

(2) Devitrification step: by the introducing carbon dioxide into aforementioned reaction solution, being precipitated methionine, obtains comprising the first sulphur The step of 1 slurry of propylhomoserin；

(3) it solid-liquid separation step: flows into aforementioned 1st slurry in pressing filter, solid first sulphur ammonia is obtained by aforementioned 1st slurry The step of acid and mother liquor；With

(4) carbon dioxide recovery step: the step of by aforementioned disposing mother liquor carbon dioxide.

2. the manufacturing method of methionine according to claim 1, wherein aforementioned solid-liquid separation step includes the 1st solid-liquid Separating step and the 2nd solid-liquid separation step；

Aforementioned 1st solid-liquid separation step is that aforementioned 1st slurry is made to flow into pressing filter, is obtained by aforementioned 1st slurry aforementioned solid The step of body methionine and aforementioned mother liquor；

Aforementioned 2nd solid-liquid separation step is to be further decreased obtained in the 1st solid-liquid separation step by dry or filter press admittedly The step of liquid holdup of body methionine.

3. the manufacturing method of methionine according to claim 2 comprising: it will be obtained in aforementioned 1st solid-liquid separation step To solid methionine and the mixing of repulped liquid and the repulped step of the 2nd slurry is made；

Aforementioned 2nd solid-liquid separation step carries out the separation of solid and liquid of aforementioned 2nd slurry, obtain in aforementioned 1st solid-liquid separation step Obtained solid methionine compares the lower solid methionine of liquid holdup.

4. the manufacturing method of methionine according to any one of claim 1 to 3, wherein aforementioned pressing filter is Continuous pressing filter.

5. the manufacturing equipment of methionine comprising:

5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is hydrolyzed in the presence of alkali cpd, is obtained by consersion unit The reaction solution of alkali salt comprising methionine；

Methionine is precipitated by the introducing carbon dioxide into aforementioned reaction solution in crystallization equipment, obtains comprising the first sulphur ammonia 1st slurry of acid；

Pressure filtration facility obtains aforesaid solid methionine and mother liquor by aforementioned 1st slurry；With

Carbon dioxide recovery plant, by aforementioned disposing mother liquor carbon dioxide.

6. the manufacturing equipment of methionine according to claim 5 has in the downstream side of aforementioned pressure filtration facility Solid-liquid separating equipment.

7. the manufacturing equipment of methionine according to claim 5 or 6, wherein aforementioned pressure filtration facility is continous way Pressure filtration facility.

Technical field

Patent application claims are based on Japanese patent application 2017-087751 (on April 27th, 2017 files an application) Priority and interests as defined in Paris Convention, by being hereby incorporated, the full content recorded in above-mentioned application is incorporated into this explanation In book.

First sulphur ammonia is manufactured the present invention relates to the hydrolysis by 5- [2- (methyl mercapto) ethyl] imidazolidine -2,4- diketone The method of acid.

Background technique

Methionine is can not to be widely used as animal feed in the one kind for the essential amino acid of animal synthesized in vivo Additive industrially manufactures in chemical plant.

As the method for manufacture methionine, disclose including by by 5- [2- (methyl mercapto) ethyl] imidazolidine -2, Introducing carbon dioxide (such as is joined to the method that the Devitrification step of methionine is precipitated in reaction solution obtained from the hydrolysis of 4- diketone According to patent document 1).

Summary of the invention

Subject to be solved by the invention

In above-mentioned method, after methionine is precipitated, it is filtered, be decanted etc. and be separated by solid-liquid separation, separation methionine and mother liquor. Dissolved with the carbon dioxide imported in Devitrification step in the mother liquor, which forms gas when being separated by solid-liquid separation and releases It puts.It is considered that, if it is possible to it recycles the carbon dioxide and recycles, then can cut down cost when methionine manufacture, together When can reduce discharge because of carbon dioxide into atmosphere caused by environmental pressure.

The present invention by the separation of solid and liquid after Devitrification step in view of the foregoing, and it is an object of the present invention to provide can be by being separated The manufacturing method of the disposing mother liquor carbon dioxide arrived and the methionine recycled.

The means used to solve the problem

The inventors of the present invention have made intensive studies, as a result, it has been found that, the solid-liquid after Devitrification step point is carried out by pressing filter From thus, it is possible to by separated disposing mother liquor carbon dioxide.

Present invention includes mode below.

1. the manufacturing method of methionine (hereinafter, be denoted as the " manufacturer of methionine of the invention sometimes in this specification Method ") comprising following step (1) ~ (4): (1) reaction step: by 5- [2- (methyl mercapto) ethyl] in the presence of alkali cpd Imidazolidine-2,4-dione hydrolysis, obtains the step of including the reaction solution of the alkali salt of methionine；(2) Devitrification step: by forward Introducing carbon dioxide in reaction solution is stated, methionine is precipitated, obtains the step of including 1 slurry of the methionine；(3) solid Liquid separating step: flowing into aforementioned 1st slurry in pressing filter, by aforementioned 1st slurry obtain aforesaid solid methionine and The step of mother liquor；(4) carbon dioxide recovery step: the step of by aforementioned disposing mother liquor carbon dioxide.

2. the manufacturing method of methionine described in aforementioned 1st mode, wherein aforementioned solid-liquid separation step includes the 1st solid Liquid separating step and the 2nd solid-liquid separation step；Aforementioned 1st solid-liquid separation step is that aforementioned 1st slurry is made to flow into pressing filter, The step of aforesaid solid methionine and aforementioned mother liquor are obtained by aforementioned 1st slurry；Aforementioned 2nd solid-liquid separation step is by dry Dry or filter press further decrease solid methionine obtained in the 1st solid-liquid separation step (for example, its cake, powder) containing liquid The step of rate.

3. according to the manufacturing method of methionine described in aforementioned 2nd mode comprising: the aforementioned 1st is separated by solid-liquid separation and is walked Solid methionine (for example, its cake, powder) obtained in rapid and repulped liquid (that is, being used for repulped liquid) are mixed and are made At the repulped step of the 2nd slurry；Aforementioned 2nd solid-liquid separation step carries out the separation of solid and liquid of aforementioned 2nd slurry, obtain with it is aforementioned Solid methionine obtained in 1st solid-liquid separation step compares the lower solid methionine of liquid holdup.

4. the manufacturing method of the methionine according to any one of the 1st to the 3rd mode, wherein aforementioned pressure filtration Machine is continuous pressing filter.

5. the manufacturing equipment of methionine (hereinafter, be denoted as that " manufacture of methionine of the invention is set sometimes in this specification It is standby "), consersion unit is included, by 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione in the presence of alkali cpd Hydrolysis obtains the reaction solution of the alkali salt comprising methionine；Crystallization equipment, by importing titanium dioxide into aforementioned reaction solution Methionine is precipitated in carbon, obtains the 1st slurry comprising the methionine；Pressure filtration facility is obtained by aforementioned 1st slurry To aforesaid solid methionine and mother liquor；With carbon dioxide recovery plant, by aforementioned disposing mother liquor carbon dioxide.

6. being had according to the manufacturing equipment of methionine described in the 5th mode in the downstream side of aforementioned pressure filtration facility There is solid-liquid separating equipment.

7. according to the manufacturing equipment of methionine described in the 5th or the 6th mode, wherein aforementioned pressure filtration facility is to connect The pressure filtration facility of continuous formula.

8. according to the manufacturing method of methionine described in aforementioned 1st mode, further include: (5) by solid-liquid separation step Obtained in the dry step of methionine.

According to the present processes and device, the separation of solid and liquid after Devitrification step is carried out by pressing filter, thus It inhibits the carbon dioxide imported in Devitrification step to discharge from mother liquor, carbon dioxide can be recycled.By will recycle two Carbonoxide recycling can cut down cost when methionine manufacture, while can reduce environmental pressure.

Detailed description of the invention

Fig. 1 is an example of the manufacturing method of methionine involved in the embodiment for the manufacturing method for indicating the application Flow chart.

Specific embodiment

Hereinafter, the embodiment based on the present processes and device is illustrated.But embodiment as shown below The manufacturing method of the methionine for embodying technical idea of the invention and the manufacturing equipment of methionine are exemplified, The present invention is not limited to as described below.

In this specification, 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione is used for raw material, by it in alkali cpd In the presence of hydrolyze, thus obtain the reaction solution (hereinafter sometimes referred to as " this reaction solution ") for containing methionine in the form of alkali salt [(1) reaction step].The preparation method of 5- [2- (methyl mercapto) ethyl] imidazolidine-2,4-dione as raw material, can enumerate Such as the method prepared and reacting 2- 2-hydroxy-4-methylthio butyronitrile with ammonia and carbon dioxide or ammonium carbonate.

As alkali cpd, it can be cited for example that potassium hydroxide, sodium hydroxide, potassium carbonate, saleratus etc., as needed Two or more in these can also be used.The usage amount of alkali cpd is relative to 5- [2- (methyl mercapto) ethyl] imidazolidine -2,4- 1 mole of diketone, in terms of potassium or sodium, usually 2 ~ 10 moles, preferably 3 ~ 6 moles.In addition, the usage amount of water is relative to 5- [2- (methyl mercapto) ethyl] 1 parts by weight of imidazolidine-2,4-dione, usually 2 ~ 20 parts by weight.

The hydrolysis carried out in reaction step is stirring-type or non-stirred formula, in the anti-of continous way or interval (in batches) formula It answers in slot and carries out.

The hydrolysis can be heated to 150 ~ 200 DEG C or so progress under the pressurization of 0.5 ~ 1MPa or so in terms of gauge pressure. Reaction time is usually 10 minutes ~ 24 hours.

Devitrification step is carried out to obtain methionine from this reaction solution.In Devitrification step, by being flowed into crystallization equipment This reaction solution, so that methionine be made to be precipitated, obtains the 1st comprising the methionine to introducing carbon dioxide in this reaction solution Slurry [(2) Devitrification step].

By the importing of carbon dioxide, absorbing carbon dioxide, the alkali salt of methionine form free in this reaction solution Methionine and be precipitated.The importing of carbon dioxide in Devitrification step can 0.1 ~ 1.0MPa in terms of gauge pressure, preferably 0.2 ~ It is carried out under the pressurization of 0.5MPa.Crystallization temperature is usually 0 ~ 50 DEG C, preferably 10 ~ 30 DEG C.In addition, as long as the crystallization time is substantially It is set as the time until this reaction solution is sufficiently precipitated by carbon dioxide saturation, methionine, usually 10 minutes ~ 24 is small When.

The 1st slurry comprising methionine be precipitated is set to be subjected to solid-liquid separation step.In solid-liquid separation step, made 1st slurry obtained in Devitrification step flow into pressing filter, by the 1st slurry obtain solid methionine (for example, its cake, Powder) and mother liquor operation [(3) solid-liquid separation step].In the mother liquor, dissolved with being led under elevated pressure in above-mentioned Devitrification step The carbon dioxide entered.It in solid-liquid separation step, is separated by solid-liquid separation using pressing filter, so that the carbon dioxide will not shape It is discharged at gas.As pressing filter, using can air-tight state carry out slurry filtering filter, as described Pressing filter, it can be cited for example that rotary drum pressing filter, blade (leaf) formula pressing filter, candle formula pressure filtration Machine, belt pressing type filter press, screw pressurizing formula filter press and rotary presser formula filter press.In addition, pressing filter can be continuous Any one in formula and interval (in batches) formula, but in order to improve productivity ratio, preferably continuous pressing filter.

Pressure in pressing filter with gauge pressure be calculated as 0.1 ~ 1.0MPa, it is preferably identical as the pressure in Devitrification step or More than it.Filtration temperature is usually 0 ~ 50 DEG C, preferably 10 ~ 30 DEG C.

Mother liquor obtained in solid-liquid separation step is transferred to the accumulator tank of carbon dioxide recovery plant.The accumulator tank and pressurization Pressure in filter is comparably low-pressure, is desired for atmospheric pressure, thus be dissolved in the carbon dioxide in mother liquor formed gas and Release.It is closed in the accumulator tank, therefore the carbon dioxide for having formed gas is recovered [(4) carbon dioxide recovery step].Recycling Carbon dioxide be recirculated to the arbitrary steps in the manufacture of methionine.

The accumulator tank of carbon dioxide recovery plant is so-called flash tank, as long as gas-liquid can be separated, structure is without spy It does not limit.The flash tank of present embodiment flows into mother liquor from the side of slot, separates gas-liquid in the inside of flash tank.Flow to flash tank In the flow of mother liquor do not limit, such as flash tank size and number according to the solid component concentration and mother liquor in slurry Flow and be suitably determined.

In Fig. 1, the manufacturing method of methionine involved in the embodiment of the manufacturing method of the application is illustrated that The flow chart of an example.As shown in Figure 1, the solid-liquid separation step in the present invention may include the 1st solid-liquid separation step and the 2nd Solid-liquid separation step.In this case, the 1st solid-liquid separation step is that the inflow of the 1st slurry obtained in Devitrification step is made to pressurize Filter, the step of obtaining solid methionine and mother liquor by the 1st slurry, the 2nd solid-liquid separation step are to reduce solid first sulphur ammonia The step of liquid holdup of acid.In 1st solid separating step, it is therefore intended that in such a way that carbon dioxide gas will not be discharged from mother liquor The separation of solid and liquid of the 1st slurry is carried out, in the 2nd solid-liquid separation step, it is therefore intended that the liquid holdup for reducing solid methionine, each From the step of in, using solid-liquid separating machine corresponding with purpose, thus, it is possible to respective step is carried out with high efficiency.In addition, being Raising productivity uses continuous pressing filter preferably in the 1st solid-liquid separation step.1st solid-liquid separation step makes It is carried out with continuous pressing filter, it thereafter, can be by disposing mother liquor titanium dioxide by carrying out the 2nd solid-liquid separation step Carbon gas, and can be improved productivity.

Separation of solid and liquid in 2nd solid-liquid separation step is carried out by filtering and decantation etc..In the present invention, the 2nd solid-liquid point It is preferably carried out by centrifuge separation from the separation of solid and liquid in step.In 2nd solid-liquid separation step, with containing for solid methionine The mode that liquid rate reaches 1 ~ 25 weight % is separated by solid-liquid separation.

It should be noted that " downstream side " refers to approaching in the manufacturing method of methionine of the invention in this specification The side of the step of to final products.

The present invention, which may include, to be mixed methionine obtained in the 1st solid-liquid separation step and repulped liquid and is made the The repulped step of 2 slurries." repulped " in general refers to slurry is separated by solid-liquid separation obtained from solid mixed with liquid from And the operation of the state of slurry is made again, as the liquid, the liquid dissolved is difficult to using the solid.In this specification " repulped liquid " refers to for repulped liquid.As repulped liquid, it is difficult to the liquid dissolved using methionine, preferably makes With the saturated aqueous solution of methionine.

In the case where the present invention includes repulped step, in the 2nd solid-liquid separation step, by will be obtained in repulped step To the 2nd slurry be separated by solid-liquid separation, further decrease the liquid holdup of solid methionine.2nd solid-liquid separation step passes through upper The method stated and carry out.It is repulped by carrying out solid methionine obtained in the 1st solid-liquid separation step, reduce first sulphur The amount for the impurity for including in propylhomoserin.By further decreasing liquid holdup, the impurity for including in methionine can be further reduced Amount.

As the 2nd solid-liquid separation step, in the case where not including above-mentioned repulped step, it may be considered that by the 1st solid-liquid The method that solid methionine obtained in separating step directly reduces moisture content.Specifically, passing through dry or filter press Remove the liquid in solid methionine.How is pressure at this time, but energy efficiency is good in the case where implementation under reduced pressure Good situation is more.Material left type, material transfer type, material stirring are had according to the method for carrying of material as drying means Type, hot wind carrying type have heat convection formula, thermally conductive heat exchange type, radiation heat transfer formula, microwave as dry heat exchange mode Heated type etc..In addition, there are also filter presses such as belt pressing type filter press, screw pressurizing formula filter press or rotary presser formula filter press etc. to lead to The method crossed mechanical pressure and reduce moisture content.

Final products are made in methionine obtained in solid-liquid separation step after the drying.Drying is heated in the pressure that shades 50 ~ 120 DEG C or so and carry out.Drying time is usually 10 minutes ~ 24 hours.