Patent ID: 12195422

1.) Carbonation unit for neutralization of process solution;2.) n Crystallization units for controlled crystallization.

a-feed to neutralizationb-CO2supplyc-cooling circulationd-feed carbonized solution to crystallizer loope-suspension with fine crystalsf-supersaturated mixtureg-feed of mix to the crystallizerh-product suspension

In the following, the invention is illustrated by non-limiting examples and exemplifying embodiments.

EXAMPLES

Example 1 (Comparative): Carbonation Process at 30° C.

An autoclave with agitator, fumigation, pH measurement and temperature control is equipped with potassium containing process solution with 13.5 wt. % methionine and 8.3 wt. % potassium (1200 g). Further, a silicon oil based defoamer formulation (described in EP 2641898 B) comprising ionic and non-ionic surfactants as emulsifier is added. The process solution is neutralized with carbon dioxide to pH 8 at a pressure of 3.0 bar and a temperature of 32° C. The mixture is continuously stirred with a speed of 500 rpm for evenly distributing the carbon dioxide. The resulting suspension is depressurized, filtered using vacuum (900 mbar for 10 min.+500 mbar 10 min), washed with 0° C. cold water, and finally dried. The time, necessary to collect 500 ml of filtrate is used to evaluate filtration performance. The results are summarized in Table 1.

TABLE 1Carbonation of methionine process solution at 30° C.c(Met)c(K+)FiltrationK-ResidualBulkstartstartDefoamerTime(500 ml)YieldPuritycontentmoisturedensity[%][%][ppm][min][s][g][%][%][%][g/L]13.58.35022322133767.25541113.58.325021118120825.156271

In above-described carbonation at 30° C. raw methionine is precipitated, which contains impurities from incorporated mother liquor and high residual moisture (crystals are shown inFIG.1). The solid-liquid separation shows low performance. Increasing concentration of defoamer is improving the filtration performance. The formed particles are agglomerated and can be easily destroyed by ultrasound (PSD, Horiba LA-950 V Fa. Retsch,FIG.2). Due to the low purity of the obtained product, the bulk density is a non-relevant parameter.

Example 2 (Comparative): Carbonation at Elevated Temperature and Subsequent Crystallization without Seed Material

An autoclave with agitator, fumigation, pH measurement and temperature control is equipped with potassium containing process solution with 13.5 wt. % methionine and 8.7 wt. % potassium (1200 g).

Further, 500 ppm of a silicon oil based defoamer formulation (described in EP 2641898 B) comprising ionic and non-ionic surfactants as emulsifier is added. The process solution is neutralized to pH 8 with carbon dioxide at a pressure of 1.0-3.0 bar. Temperature is kept above 80° C.

A controlled cooling program from 80 to 32° C. is applied for controlled crystallization during continuous stirring at a speed of 250 rpm. The typical shape of the cubic cooling profile for 180 min and 300 min is shown inFIG.3.

The thus-obtained suspension is depressurized, filtered using vacuum (900 mbar for 10 min. & 500 mbar 10 min), washed with 0° C. cold water, and finally dried. The time, necessary to collect 500 ml of filtrate is used to evaluate filtration performance. The results are summarized in Table 2.

TABLE 2Carbonation and crystallization of methionine raw solution without seedingc(Met)c(K+)TimeFiltrationResidualBulkstartstartDefoamer(cooling)(500 ml)YieldPuritymoisturedensity[%][%][ppm][min][s][g][%][%][g/L]13.58.75001804099699.631248

The filtration of the obtained methionine suspension is difficult. The particles are comparable to those flat leaflet type crystals gained by carbonation at 30° C. (Example 1). But the obtained product has a higher purity, as there is less mother liquor is incorporated. The filter cake retains only 31% residual moisture. After drying, the bulk density is very low. This can be explained by the morphology (flat, fine particles with rough surfaces; SEM pictures (FIG.4) and many fine crystals below 100 μm. Particles sizes (compare PSD,FIG.6) are similar to material gained by carbonation at 30° C. (Example 1).

Example 3: Carbonation at Elevated Temperature and Subsequent Crystallization with Seed Material

General Procedure

An autoclave with agitator, fumigation, pH measurement and temperature control is equipped with 1200 g potassium containing process solution with a defined concentration of methionine in the range of 12.0-17.0 wt. % and potassium in the range of 7.0-12.0 wt. %.

Further 0-800 ppm of a silicon oil based defoamer formulation containing mixtures of ionic and non-ionic surfactants as emulsifier (described in EP 2641898 B) is added. The solution is neutralized to pH 8 with carbon dioxide at a pressure of 1.0-3.0 bar and a temperature in the range of 65 to 95° C. depending on the concentration to prevent precipitation.

About 5° C. above nucleation temperature, seed crystals (0 g-100 g) are added in one batch. The seed crystals used, consist of two fractions in mass ratio from 1.6:1 to 1.2:1 (250 μm to 1000 μm:125 to 250 μm). The seed crystals are prepared from a matrix in which crystallization additives according to EP 2641898 B are present and separated by sieving to fractions. The particle size distribution (PSD) of the seeds (all fractions) is shown inFIG.7. The maximum is located at approx. 250 μm.

During continuous stirring at a speed of 100 and 500 rpm a cubic temperature controlled cooling program to 32° C. controls crystallization (compareFIG.3). The obtained suspension is depressurized, filtered using vacuum (900 mbar for 10 min & 500 mbar 10 min), washed with 0° C. cold water, and finally dried. The time, necessary to collect 500 ml of filtrate is used to evaluate filtration performance. For all PSD, ultrasound (120 s) is applied before starting the measurement (PSD, Horiba LA-950 V Fa. Retsch).

Example 3a

An autoclave with agitator, fumigation, pH measurement and temperature control is equipped with potassium containing process solution with 13.1 wt. % methionine and 8.0 wt. % potassium (1200 g).

Further, 600 ppm of a silicon oil based defoamer formulation (EP 2641898 B) is added. The process solution is neutralized to pH 8 with carbon dioxide at a pressure of 2.0-3.0 bar and at a temperature of 85° C.

At 83° C. seed crystals (60 g) are added. During continuous stirring at a speed of 250 rpm a temperature controlled cooling program to 32° C. is applied (cubic profile within 180 min, avg. 0.28 K/min, compareFIG.3). The thus-obtained suspension is depressurized, filtered using vacuum (900 mbar for 10 min & 500 mbar 10 min), washed with 0° C. cold water, and finally dried. The time, necessary to collect 500 ml of filtrate is used to evaluate filtration performance. The results are summarized in Table 3.

TABLE 3Crystallization with seeds, 600 ppm defoamer and 80 g/kg potassiumSeedc(Met)c(K+)crystals/TimeFiltrationResidualBulkstartstartratioDefoamer(cooling)(500 ml)YieldPuritymoisturedensity[%][%][g][ppm][min][s][g][%][%][g/L]13.18.0160 g/1.4:16001908713910013601

The quality of the obtained D,L-methionine is excellent with respect to purity and bulk density. The filtration properties of the thus-obtained particles are improved versus those gained by reference carbonation at 30° C. (Example 1). The filter cake retains 12.5% residual moisture after a fast filtration time. The particle size distribution (bimodal profile) shows formation of new crystals gained by nucleation and growth of the seeds to bigger particles, compared to the seed material (FIG.7)

Example 4: Carbonation at Elevated Temperature and Subsequent Crystallization with Seed Material (Repeatability)

In order to evaluate the repeatability of the results with the chosen setup, the experiment is repeated three times in accordance with the general procedure indicated in Example 3.

An autoclave with agitator, fumigation, pH measurement and temperature control is equipped with 1200 g potassium containing process solution with a defined concentration of methionine of 13.5 wt. %. Further, 250 ppm of a silicon oil based defoamer formulation (described in EP 2641898 B) is added. The process solution is neutralized to pH 8 with carbon dioxide at a pressure of <3.0 bar and the temperature is kept above 80° C.

At 85° C., seed crystals (60 g, 1.4:1; see general procedure Example 3) are added and under continuous stirring a temperature controlled cooling program is applied (from 80 to 32° C. in cubic profile within 210 min, avg. 0.25 K/min). The thus-obtained suspension is depressurized, filtered using vacuum (900 mbar for 10 min & 500 mbar 10 min), washed with 0° C. cold water, and finally dried.

TABLE 4Repeatability of crystallization with seeding, 250 ppm defoamer.c(Met)c(K+)SeedTimeFiltrationResidualBulkstartstartcrystals/Defoamer(cooling)(500 ml)YieldPuritymoisturedensity[%][%]ratio[ppm][min][s][g][%][%][g/L]13.58.360 g/1.4:12502102516799.11553913.58.760 g/1.4:1250210231651001355213.58.360 g/1.4:12502101516510013547

The repeatability of the process setup is proven by repetition of the experiment under the same conditions. It is possible to control the process and to obtain crystalline product in desired quality. The material obtained from three experiments shows very similar PSD, SEM and bulk density (FIGS.8&9). The filter cake retains 13%-15% residual moisture and is easy to wash and handle.

Example 5: Influence of Defoamer and Crystallization Additives

Process solution: 13.5 wt. % methionine and 8.7 wt. % or 8.3 wt. % potassium. Procedure according to general procedure (Example 3).

Different amounts of defoamer are used in order to investigate their influence on the crystallization process. A cubic cooling profile is applied (cooling from 80 to 32° C. in cubic profile within 180 min, avg. 0.28 K/min,FIG.3) and the mass of seed crystals is kept constant (60 g).

TABLE 5Influence of defoamer on the crystallization.Seedc(Met)c(K+)crystals/TimeFiltrationResidualBulkstartstartratioDefoamer(cooling)(500 ml)YieldPuritymoisturedensity[%][%][g][ppm][min][s][g][%][%][g/L]13.58.360 g/1.4:1—18014165.599.91849713.58.760 g/1.4:150180~8159.599.81552013.58.360 g/1.4:125018023165.31001453713.58.760 g/1.4:150018026167.9100.515539

With increasing concentration of the defoamer present in the solution, the bulk density also slightly increases. Above 250 ppm defoamer no significant effect with respect to bulk density is observed. Entries 1-4 in table 5 and the correspondingFIG.10show that the additive amount has significant influence on the particle size distribution (PSD). The additives slow down the crystal growth and the nucleation process is accelerated. The formation of smaller particles increases the bulk density from 497 to 539 g/L. With respect to filtration performance, the optimum is found between 50 ppm and 250 ppm defoamer.

Example 6: Influence of Cooling Profile

Process solution: 13.5 wt. % methionine and 8.7 wt. % potassium. Procedure according to general procedure (Example 3).

In order to determine the influence of the cooling profile, two cubic profiles are tested with duration of 120 min (avg. 0.47 K/min) or 300 min (avg. 0.16 K/min); compareFIG.4.

The amount of seed crystals is kept constant (60 g), but the ratio of seed fractions is varied from 1.2:1 to 1.6:1 (for particular particle size of fractions see general procedure in Example 3).

TABLE 6Influence of cooling profile on the crystallization.Seedc(Met)c(K+)crystals/TimeTFiltrationResidualBulkstartstartratioDefoamer(cooling)(start)(500 ml)YieldPuritymoisturedensity[%][%][g][ppm][min][° C.][s][g][%][%][g/L]13.58.360 g/1.6:125012079.53116799.71652013.58.760 g/1.6:125030079.5201661001256113.58.360 g/1.2:125012079.53016799.91553213.58.760 g/1.2:125030079.51716610013554

An elongated cooling profile improves quality of the obtained methionine crystals. More residence time allows slower crystallization. Supersaturation is reduced by growth on seed crystals and nucleation is suppressed. PSD and SEM prove higher quality of the slow gained material. The bulk density increases from 520 to 560 g/L if the 300 min cooling profile is applied. Reduced time for crystallization increases formation of fine crystals via nucleation. The particle size of the seed crystals have no or only limited effect with respect to the final bulk density or PSD (seeFIGS.12&13).

Example 7: Influence of Seeding Crystal Amount

Process solution: 13.5 wt. % methionine and 8.7 wt. % potassium. Procedure according to general procedure (Example 3). A cubic cooling profile with 180 min (avg. 0.27 K/min; seeFIG.3) is applied.

In order to investigate the influence of the total crystal surface area available for crystal growth, the mass of seed crystals is varied (40 g seed crystals and 80 g seed crystals, ratio of seed fractions 1.4:1).

TABLE 7Influence of amount of seed crystals on the crystallization.c(Met)c(K+)SeedTimeTFiltrationResidualBulkstartstartcrystals/Defoamer(cooling)(start)(500 ml)YieldPuritymoisturedensity[%][%]ratio[ppm][min][° C.][s][g][%][%][g/L]13.58.340 g/20018079.43216799.7184761.4:113.58.780 g/20018079.617166100125551.4:1

With increasing mass of seed crystals (surface area), the bulk density and average particle size increases. Entry 2 in Table 7 shows improved crystal quality with less rough surfaces (FIGS.14&15). The chosen parameters allow controlled crystallization, promoting crystal growth and suppressing nucleation. With respect to filtration performance the cake resulting from the second entry has improved filtration properties, less fines and lower residual moisture.

Example 8: Higher Concentrated Process Solution

Process solution: 15.1 wt. % methionine and 9.3 wt. % potassium. Procedure according to general procedure (Example 3). A cubic cooling profile with 180 min is applied and the mass of seed crystals varies from 60 g to 80 g to change the total crystal surface area available for crystal growth (ratio of seed fractions 1.4:1).

TABLE 8Influence of seeding amount on higher concentration crystallizationSeedc(Met)c(K+)crystals/TimeTFiltrationResidualBulkstartstartratioDefoamer(cooling)(start)(500 ml)YieldPuritymoisturedensity[%][%][g][ppm][min][° C.][s][g][%][%][g/L]15.19.360 g/25018079.555196100114901.4:115.19.380 g/25018079.81619810065521.4:1

With higher concentration of methionine and other process parameters maintaining constant, the supersaturation increases. Therefore, the total crystal surface area of the seed crystals is important for controlling the crystal growth. Entry 2 shows higher bulk density and higher average particle size (FIGS.16&17). The chosen parameters still allow controlled crystallization with crystal growth and suppressed nucleation. With respect to filtration performance, the cake resulting from the second entry has improved filtration properties, less fines and very low residual moisture.

Example 9: Continuous Process

FIG.20shows the set up for the continuous process. It requires several process units. In a first process unit, the process solution is neutralized. The second process unit consists of at least one crystallizer. Each crystallizer is operated at constant temperature. Depending on the number (n) of crystallization vessels, the cooling occurs in n-steps, approximating a cooling profile.

Following example describes a set up with one crystallization stage:

A vessel with agitator, fumigation, pH measurement and temperature control is continuously fed with a potassium containing process solution [(a), 12.0-17.0 wt. % methionine 7.0-12.0 wt. % potassium and 250 ppm of a silicon oil based defoamer formulation according EP 2641898 B included)]. The process solution is continuously neutralized to pH 8.0 with carbon dioxide (b) at a pressure of 2.0-3.0 bar and at a temperature of 85° C. (c) under continuous stirring. The neutralized solution is transferred via heat traced piping into the crystallization unit (d) and mixed with the suspension (e).

For the start up, the crystallizer is equipped with a methionine suspension (15 wt. % solids). These solids act as seed crystals during start up. As for the batch process, the solids consist of two fractions in mass ratio from 1.6:1 to 1.2:1 (250 μm to 1000 μm:125 to 250 μm)). During continuous operation, the crystallizer is operated constantly at 32° C. using an external heat exchanger. The crystallizer is kept under the same pressure as the neutralization unit. The mass flow ratio of carbonized feed solution to circulating crystallizer suspension is adjusted to a value in the range between 1:5 and 1:20.

The thus-obtained suspension (h) is collected, depressurized, filtered using vacuum (900 mbar for 10 min & 500 mbar 10 min), washed with 0° C. cold water, and finally dried.

After continuous operation for 24 h (13.5 wt. % methionine 8.3 wt. % potassium and 250 ppm of a silicon oil based defoamer formulation according EP 2641898 B) a sample of 1 L product is collected, depressurized, filtered, washed with 0° C. cold water, and finally dried (Table 9).

TABLE 9Continuous operationc(Met)c(K+)FiltrationResidualBulkstartstartFeedDefoamer(500 ml)YieldPuritymoisturedensity[%][%]ratio[ppm][s][g][%][%][g/L]13.58.51:10250 ppm20120.699.912565

The quality of the obtained D,L-methionine is excellent with respect to purity and bulk density. The filter cake retains 12% residual moisture after a fast filtration time. The particle size distribution shows formation of new crystals gained by nucleation and growth of the seeds to bigger particles, compared to the seed material (FIGS.18&19)