CN103497118B - Treatment method for lysine-containing solution - Google Patents
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Abstract
The invention provides a treatment method for lysine-containing solution. The treatment method comprises the steps of enabling the lysine-containing solution to contact with a plurality of cation exchange resin column groups, wherein each cation exchange resin column group passes through an adsorption zone, an alkali guidance zone and a regeneration zone sequentially and circularly, and one or more cation exchange resin column groups which are sequentially connected in series are simultaneously located in the adsorption zone; introducing the lysine-containing solution from the upper end of the cation exchange resin column group on the first place of the adsorption zone under a condition that pH value is 3.0-3.5, enabling the lysine-containing solution to sequentially flow through other cation exchange resin column groups in the adsorption zone under a condition that pH value is 2.2-2.6 or lysine concentration is no less than 1.0g/dL, and making the lysine-containing solution flow out from the lower end of the cation exchange resin column group on the last place of the adsorption zone to obtain waste fluid. The treatment method can improve purity and yield of lysine, and reduce calcium and magnesium ion residue in the cation exchange resin column groups; the obtained waste fluid can be directly used for preparing ammonium sulfate.
Description
Technical field
The present invention relates to a kind for the treatment of process containing lysine solution.
Background technology
Methionin is one of eight kinds of primary amino acids (also known as indispensable amino acid, they are Methionin, Threonine, leucine, Isoleucine, methionine(Met), α-amino-isovaleric acid, phenylalanine and tryptophane) of needed by human.The solubleness of Methionin in water is very large, and easily absorbs the carbonic acid gas in air, is difficult to obtain its crystallization.Therefore as commodity, it often occurs with the form of mono-hydrochloric salts.Methionin is of many uses, is mainly used in following industry: foodstuffs industry, prepares nutrition-fortifying agent, tasty agents, sweeting agent; Fodder industry, prepares nutrition-fortifying agent; Medicine industry, Preparation of amino acid transfusion, amino acid derivative, amino acid salts; Chemical industry, making detergent, skin care product, leatheroid; Agricultural, prepares public nuisance-free agricultural chemicals etc.At present, the lysine product of more than 90% is used for fodder industry, as added appropriate Methionin in feed, can increase the synthesis of animal body internal protein, promotes animal growth.
Lysine hydrochloride is generally adopted and is prepared with the following method: strain fermentation obtains fermented liquid, add a large amount of vitriol oils in fermented liquid and carry out acidifying, through metallic membrane or ceramic membrane filter removing thalline after acidifying, obtain Methionin membrane filtration liquid namely containing lysine solution, adopt strongly acidic cation-exchange to carry out absorption containing lysine solution to exchange, the saturated rear weak ammonia of resin absorption carries out wash-out, the Methionin eluted, through concentrated, salt acid for adjusting pH value, crystallization, solid-liquid separation, oven dry, obtains lysine hydrochloride finished product.
Along with the raising of modernization level, large chemical equipment ISEP system is generally adopted to carry out containing the ion exchange purification Methionin of lysine solution at present, principle is: make to contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize the cation exchange resin column that cation exchange resin column group comprises one or more parallel connection, often organize cation exchange resin column group successively and cyclically through adsorption zone, back filled region, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, purify and again adsorb, desorb and regeneration, elutriant is obtained after desorb.Methionin mainly exists with monovalent cation form, and the ion exchange reaction formula of adsorption and desorption is as follows:
R-H＋HLysH
+→R-HLysH＋H
+
R-HLysH＋NH
4 +＋OH-→R-NH
4＋HLys＋H
2O
As shown in Figure 1, the technique of current use generally comprises: in adsorption zone, cation exchange resin column group is sequentially connected in series, introduce containing the upper end of lysine solution from the cation exchange resin column group being in first place, adsorption zone, flow through each group of cation exchange resin column group in this adsorption zone successively, and obtain waste liquid from the lower end outflow of the cation exchange resin column group being in position, end, adsorption zone, make the described at least part of Methionin contained in lysine solution be adsorbed onto on Zeo-karb; In back filled region, with obtain elution fractions backfill cation exchange resin column, make cation exchange resin column purify and and be tending towards absorption saturated; In Jian Dao district, make basic solution flow through cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain elutriant; In breeding blanket, first use hot wash cation exchange resin column, with air compression leg, the water in cation exchange resin column is discharged again, then sulfuric acid adjust pH is added to 1.0-1.4 in the waste liquid obtained to adsorption zone, with the waste liquid backfill cation exchange resin column after adjust pH, cation exchange resin column is made the transition, and then cation exchange resin column returns to adsorption zone again and adsorbs, and completes and once circulates.
In order to improve the yield of Methionin, at present research and development are sent as an envoy to containing lysine solution be under the condition of 1.0-2.0 in pH value or be not less than the condition of 1.0g/dL at lysine concentration under by the method for cation exchange resin column group.But the pH value of the method gained waste liquid is 3.0-3.5.The technique gained waste liquid of current use has two kinds of purposes usually, sub-fraction adds sulfuric acid adjust pH as mentioned above to 1.0-1.4, and backfill cation exchange resin column, makes cation exchange resin column make the transition, the overwhelming majority enters ammonium sulfate factory, for the preparation of ammonium sulfate after adjust pH 4.0-5.0.The method gained waste liquid is prepared ammonium sulfate and is needed to consume a large amount of alkali adjust ph.
And in the elutriant adopting aforesaid method to obtain, calcium ions and magnesium ions content is high, and Methionin purity is low, and in cation exchange resin column During Process of Long-term Operation, calcium ions and magnesium ions salt easily deposits and occurs white precipitate and dirt, blocking chromatographic column, therefore, long-time running also can cause Methionin yield to decline.
Summary of the invention
The object of the invention is to overcome in existing technique that Methionin purity is low, yield is low, in cation exchange resin column, calcium ions and magnesium ions residual quantity is high, gained waste liquid is prepared ammonium sulfate and is needed to consume a large amount of alkali, the defect that cost is higher, provides a kind for the treatment of process containing lysine solution newly.
The present inventor surprisingly finds under study for action, making containing lysine solution is introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value, be be not less than all the other each group cation exchange resin column groups flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.2-2.6 or at lysine concentration in pH value, the purity of Methionin can be improved, yield, reduce calcium ions and magnesium ions residual quantity in cation exchange resin column, and the pH value of gained waste liquid is 4.0-5.0, can be directly used in and prepare ammonium sulfate, greatly reduce production cost.
Therefore, to achieve these goals, the invention provides a kind for the treatment of process containing lysine solution, it is characterized in that, described method comprises: make described contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, desorb and regeneration, elutriant is obtained after desorb, the described cation exchange resin column often organized cation exchange resin column group and comprise one or more parallel connection, wherein,
One or more groups cation exchange resin column group of connecting successively is in adsorption zone simultaneously, described is introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value containing lysine solution, be be not less than all the other each group cation exchange resin column groups flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.2-2.6 or at lysine concentration in pH value, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, the described at least part of Methionin contained in lysine solution is made to be adsorbed onto on Zeo-karb, and make lysine concentration in described waste liquid not higher than 0.1g/dL, in Jian Dao district, make basic solution flow through described cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain described elutriant, in breeding blanket, after making water, air and adjust pH pH value be the described waste liquid of 1.0-1.4 successively by cation exchange resin column, cation exchange resin column is regenerated.
Preferably, under the condition of pH value for 2.4-2.6 or lysine concentration be not less than to flow through successively in this adsorption zone under the condition of 1.0g/dL described in all the other each group cation exchange resin column groups.
Treatment process containing lysine solution provided by the invention, can improve purity and the yield of Methionin, as shown in embodiment 1 and comparative example 1, the purity of embodiment 1 Methionin is 99.89%, yield is 98.46%, and the purity of comparative example 1 Methionin is 97.85%, and yield is 96.62%; Calcium ions and magnesium ions residual quantity in cation exchange resin column can be reduced, as shown in embodiment 1 and comparative example 1, in the cation exchange resin column of embodiment 1, calcium, magnesium ion residual quantity are respectively 1.2g, 0.5g, and in the cation exchange resin column of comparative example 1, calcium, magnesium ion residual quantity are respectively 8.0g, 6.0g; The pH value of the inventive method gained waste liquid is 4.0-5.0, can be directly used in and prepare ammonium sulfate, greatly reduce production cost.Treatment process containing lysine solution provided by the invention, can be widely used in industrial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that in the technique used at present, the process of ISEP system contains lysine solution;
Fig. 2 is the process flow sheet containing lysine solution according to the ISEP system process of the inventive method.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind for the treatment of process containing lysine solution, the method comprises: make described contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, desorb and regeneration, elutriant is obtained after desorb, the described cation exchange resin column often organized cation exchange resin column group and comprise one or more parallel connection, wherein
One or more groups cation exchange resin column group of connecting successively is in adsorption zone simultaneously, described is introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value containing lysine solution, be be not less than all the other each group cation exchange resin column groups flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.2-2.6 or at lysine concentration in pH value, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, the described at least part of Methionin contained in lysine solution is made to be adsorbed onto on Zeo-karb, and make lysine concentration in described waste liquid not higher than 0.1g/dL, in Jian Dao district, make basic solution flow through described cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain described elutriant, in breeding blanket, after making water, air and adjust pH pH value be the described waste liquid of 1.0-1.4 successively by cation exchange resin column, cation exchange resin column is regenerated.
In preparing lysine through fermentation process, strain fermentation obtains fermented liquid, adding a large amount of vitriol oils in fermented liquid adjusts pH to 3.0-3.5 to carry out acidifying, Methionin membrane filtration liquid is obtained through metallic membrane or ceramic membrane filter removing thalline after acidifying, in the present invention, comprise this Methionin membrane filtration liquid containing lysine solution, in Methionin membrane filtration liquid, the concentration of Methionin is generally 14.0-18.0g/dL.
In the present invention, pH value regulates preferably by adding sulfuric acid.
According to the present invention, although be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value containing lysine solution, be be not less than all the other each group cation exchange resin column groups flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.2-2.6 or at lysine concentration in pH value, object of the present invention can be realized, namely the purity of Methionin is improved, yield, reduce the residual quantity of calcium ions and magnesium ions in cation exchange resin column, and the pH value of gained waste liquid is 4.0-5.0, can be directly used in and prepare ammonium sulfate, greatly reduce production cost.But under preferable case, be be not less than all the other each group cation exchange resin column groups flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.4-2.6 or at lysine concentration in pH value, can further improve the purity of Methionin, reduce the residual quantity of calcium ions and magnesium ions in cation exchange resin column.
In the present invention, during the cation exchange resin column group adopting many groups to connect successively, in order to alleviate the pressure in the cylinder of cation exchange resin column, increase the work-ing life of cylinder and resin, under preferable case, between the two adjacent groups cation exchange resin column group of adsorption zone, be provided with transfer tank, two adjacent groups cation exchange resin column group is connected in series through transfer tank.And transfer tank is set, also facilitate adjust ph, when needs adjust ph, can in transfer tank adjust ph.
In the present invention, the cation exchange resin column group being simultaneously in adsorption zone is preferably three groups, and often group comprises the cation exchange resin column of 3-6 parallel connection.In order to not only reach good adsorption effect but also save the consumption of sulfuric acid further, under preferable case, containing lysine solution be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 1.0-2.0g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, be by being in the cation exchange resin column group of position, end, adsorption zone in pH value under the condition of 2.4-2.6.
Be by being in the implementation method of the cation exchange resin column group of position, end, adsorption zone in pH value under the condition of 2.4-2.6, can in the process of the cation exchange resin column group absorption of position, end, adsorption zone, sulfuric acid adjust ph is added in the cation exchange resin column group of position, end, adsorption zone, also sulfuric acid adjust ph can be added in the transfer tank before the cation exchange resin column group being in position, end, adsorption zone, in order to make pH value condition more stable, being preferably adjust pH in the transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.4-2.6.
What those skilled in the art should understand that is, generally, cation exchange resin column all can not adsorb saturated behind adsorption zone, and when flowing through cation exchange resin column group containing lysine solution, also can remain in cation exchange resin column containing a small amount of impurity in lysine solution, therefore, in order to reduce the impurity remained in cation exchange resin column, also be tending towards saturated to make cation exchange resin column adsorb, the inventive method preferably also comprises cation exchange resin column after adsorption zone, before Jian Dao district, also through back filled region, in back filled region, cation exchange resin column is backfilled with elution fractions, cation exchange resin column is made to carry out purification and again adsorb.
Owing to containing Methionin after backfill from the liquid that described cation exchange resin column flows out, therefore, under preferable case, the liquid flowed out from cation exchange resin column after backfill returns to adsorption zone, mix with Methionin membrane filtration liquid as described containing lysine solution, therefore, describedly also to comprise after backfill from the liquid that cation exchange resin column flows out containing lysine solution, be generally 10.0-15.0g/dL containing the concentration of Methionin in lysine solution.
In the present invention, Zeo-karb in cation exchange resin column can be used for the cationic various Zeo-karb that can adsorb Methionin or Methionin for this area, but be preferably sulfonic group strong-acid type cation exchange resin, the total exchange capacity of Zeo-karb is preferably greater than 5mmol/g, more preferably 6-15mmol/g, is further preferably 6-10mmol/g.
In the present invention, from easy cation exchange resin column after absorption Methionin, Methionin is eluted and the aspect facilitating cation exchange resin column to regenerate consideration, basic solution is preferably ammoniacal liquor, and pH value is preferably 10.0-14.0, is more preferably 11.0-12.5.
Because the present invention is relative to the improvement of prior art, in adsorption zone, limited by the lysine concentration of cation exchange resin column group and pH value condition containing lysine solution, therefore, otherwise parameter and numerical value thereof, without particular requirement, all can refer to prior art.Such as, the time that adsorption zone is contacted with Zeo-karb containing lysine solution and temperature, the flow velocity of back filled region elution fractions and temperature, the flow velocity of Jian Dao district basic solution and temperature, the flow velocity of breeding blanket water and temperature, the air pressure of air and temperature, after adjust pH, pH value is that the flow velocity of the waste liquid of 1.0-1.4 and temperature are without particular requirement, the condition that this area is conventional can be adopted, such as, the condition of absorption comprises, temperature is 40-60 DEG C, be the time contacted with Zeo-karb under the condition of 2.2-2.6 at adjust pH containing lysine solution be 8-10min, the time contacted with Zeo-karb under all the other conditions is 17-20min, purification and the again condition of adsorbing comprise, the flow velocity of elution fractions be 2.0-4.0 times of column volume/hour, temperature is 40-60 DEG C, the condition of desorb comprises, the flow velocity of basic solution be 4.0-8.0 times of column volume/hour, temperature is 40-60 DEG C, the condition of regeneration comprises, the flow velocity of water be 4.5-8.5 times of column volume/hour, temperature is 40-60 DEG C, the air pressure of air is 0.07-0.15MPa, temperature is 15-30 DEG C, pH value to be the flow velocity of the waste liquid of 1.0-1.4 be 2.5-6.5 times of column volume after adjust pH/hour, temperature is 20-45 DEG C.
In the present invention, the consumption backfilling the elution fractions of every root cation exchange resin column is preferably the 0.4-0.6 of column volume doubly; The consumption of basic solution without particular requirement, as long as the Methionin of absorption is eluted; In breeding blanket, the consumption of the water that every root cation exchange resin column uses is preferably the 0.35-0.65 of column volume doubly, the consumption of the air of 0.07-0.15MPa is without particular requirement, as long as discharged by the water in cation exchange resin column, after adjust pH, pH value is that the consumption of the waste liquid of 1.0-1.4 is preferably the 0.25-0.5 of column volume doubly.
In the present invention, waste liquid refers to and flows out from the lower end of the cation exchange resin column group of position, end, adsorption zone the liquid obtained.
Therefore, as shown in Figure 2, a kind of preferred implementation according to the inventive method is: make to contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, back filled region, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, purification and Adsorption and desorption and regeneration again, elutriant is obtained, wherein after desorb
Three groups of cation exchange resin column groups of connecting successively are in adsorption zone simultaneously, often organize the cation exchange resin column that cation exchange resin column group preferably includes 3-6 parallel connection, Zeo-karb in cation exchange resin column is sulfonic group strong-acid type cation exchange resin, the total exchange capacity of Zeo-karb is greater than 5mmol/g, transfer tank is provided with between two adjacent groups cation exchange resin column group, two adjacent groups cation exchange resin column group is connected in series through transfer tank, concentration containing lysine solution is 10.0-15.0g/dL, temperature is 40-60 DEG C, be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value, flow through each group of cation exchange resin column group in this adsorption zone successively, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 1.0-2.0g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, adding sulfuric acid adjust pH in transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.4-2.6, be the time contacted with Zeo-karb under the condition of 2.4-2.6 at adjust pH be 8-10min, the time contacted with Zeo-karb under all the other conditions is 17-20min, namely the time contacted with the cation exchange resin column group of position, end, adsorption zone is 8-10min, the time contacted with deputy cation exchange resin column group with first place, adsorption zone is 17-20min altogether, finally make from adsorption zone end position cation exchange resin column group lower end flow out waste liquid lysine concentration not higher than 0.1g/dL,
In back filled region, with elution fractions, temperature is 40-60 DEG C, with 2.0-4.0 times of column volume/hour flow velocity backfill cation exchange resin column, the consumption backfilling the elution fractions of every root cation exchange resin column is 0.4-0.6 times of column volume, the liquid flowed out from cation exchange resin column after backfill returns to adsorption zone, mixes containing lysine solution with described;
In Jian Dao district, make pH value be 11.0-12.5, temperature be 40-60 DEG C ammoniacal liquor with 4.0-8.0 times of column volume/hour flow velocity flow through cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain elutriant;
In breeding blanket, with temperature be 40-60 DEG C of water with 4.5-8.5 times of column volume/hour flow velocity flow through cation exchange resin column, the 0.35-0.65 that the consumption of the water that every root cation exchange resin column uses is column volume doubly, then temperature is made to be that the air of 15-30 DEG C passes through cation exchange resin column with the air pressure of 0.07-0.15MPa, then temperature is made to be 20-45 DEG C, pH value be 1.0-1.4 waste liquid with 2.5-6.5 times of column volume/hour flow velocity flow through cation exchange resin column, the 0.25-0.5 that the consumption of the waste liquid that every root cation exchange resin column uses is column volume doubly, cation exchange resin column is regenerated.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In following embodiment and comparative example:
The special strongly acidic cation-exchange of WD-2 type Methionin is sulfonic group strong-acid type cation exchange resin, is purchased from Chuzhou City Guan Dong Chemical Co., Ltd. of Anhui Province.
PH value detects and adopts SevenEasy pH meter (being purchased from plum Teller-Tuo benefit Shanghai International Trading Company Ltd).
Atomic absorption instrument (being purchased from U.S.'s thermoelectricity, Thermo Atomic Absorption Spectroscopy AAS) is adopted to measure respectively containing calcium, the magnesium ion content in lysine solution and waste liquid.
Calcium ion residual quantity in cation exchange resin column=containing the calcium ion content in the calcium ion content-waste liquid in lysine solution
Magnesium ion residual quantity in cation exchange resin column=containing the magnesium ion content in the magnesium ion content-waste liquid in lysine solution
Lysine content (in lysine hydrochloride) is detected according to ninhydrin colorimetry.
Lysine content/elutriant dry matter × 100% in Methionin purity=elutriant
Elutriant dry matter adopts oven method measuring: elutriant being placed in temperature is that the baking oven of 105 DEG C is dried to constant weight, the weight of gained material.
Lysine content in Methionin yield=elutriant/containing lysine content × 100% in lysine solution
Embodiment 1
Adopt the technique shown in Fig. 2, make to contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, back filled region, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, purification and Adsorption and desorption and regeneration again, elutriant is obtained after desorb, wherein
Three groups of cation exchange resin column groups of connecting successively are in adsorption zone simultaneously, often organize cation exchange resin column group to be made up of 4 cation exchange resin columns in parallel, Zeo-karb in cation exchange resin column is the special strongly acidic cation-exchange of WD-2 type Methionin, the total exchange capacity of Zeo-karb is 8mmol/g, transfer tank is provided with between two adjacent groups cation exchange resin column group, two adjacent groups cation exchange resin column group is connected in series through transfer tank, concentration containing lysine solution is 13.0g/dL, temperature is 50 DEG C, be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.2 in pH value, flow through each group of cation exchange resin column group in this adsorption zone successively, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 1.5g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, adding sulfuric acid adjust pH in transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.4, the time contacted with the cation exchange resin column group of position, end, adsorption zone is 8.5min, the time contacted with deputy cation exchange resin column group with first place, adsorption zone is 17min altogether.
In back filled region, every root cation exchange resin column elution fractions (0.525 times for column volume), temperature is 50 DEG C, with 3.5 times of column volumes/hour flow velocity backfill cation exchange resin column, the liquid flowed out from cation exchange resin column after backfill returns to adsorption zone, mixes containing lysine solution with described;
In Jian Dao district, make pH value be 11.5, temperature be 50 DEG C ammoniacal liquor with 6.0 times of column volumes/hour flow velocity flow through cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain elutriant;
In breeding blanket, every root cation exchange resin column temperature be 50 DEG C of water (0.45 times for column volume) with 6.0 times of column volumes/hour flow velocity flow through cation exchange resin column, then temperature is made to be that the air of 20 DEG C passes through cation exchange resin column with the air pressure of 0.12MPa, then make that temperature is 20 DEG C, adjust pH be 1.2 waste liquid (0.25 times for column volume) with 2.5 times of column volumes/hour flow velocity flow through cation exchange resin column, cation exchange resin column is regenerated.
The flow velocity introduced from the upper end of the cation exchange resin column group being in first place, adsorption zone containing lysine solution is 45m
3/ h, the flow velocity that waste liquid flows out from the lower end of the cation exchange resin column group being in position, end, adsorption zone is 35m
3/ h, after stable circulation 20h, the lysine concentration measured the waste liquid flowed out from the lower end of the cation exchange resin column group of position, end, adsorption zone is 0.01g/dL, and waste liquid pH value is 4.3; Measure and calculate calcium, the magnesium ion residual quantity in cation exchange resin column, measuring the lysine content in elutriant, calculating Methionin purity and yield, the results are shown in Table 1.
Embodiment 2
Adopt the technique shown in Fig. 2, make to contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, back filled region, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, purification and Adsorption and desorption and regeneration again, elutriant is obtained after desorb, wherein
Three groups of cation exchange resin column groups of connecting successively are in adsorption zone simultaneously, often organize cation exchange resin column group to be made up of 3 cation exchange resin columns in parallel, Zeo-karb in cation exchange resin column is the special strongly acidic cation-exchange of WD-2 type Methionin, the total exchange capacity of Zeo-karb is 8mmol/g, transfer tank is provided with between two adjacent groups cation exchange resin column group, two adjacent groups cation exchange resin column group is connected in series through transfer tank, concentration containing lysine solution is 10.0g/dL, temperature is 40 DEG C, be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0 in pH value, flow through each group of cation exchange resin column group in this adsorption zone successively, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 1.0g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, adding sulfuric acid adjust pH in transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.5, the time contacted with the cation exchange resin column group of position, end, adsorption zone is 9.5min, the time contacted with deputy cation exchange resin column group with first place, adsorption zone is 19min altogether.
In back filled region, every root cation exchange resin column elution fractions (0.5 times for column volume), temperature is 40 DEG C, with 3.0 times of column volumes/hour flow velocity backfill cation exchange resin column, the liquid flowed out from cation exchange resin column after backfill returns to adsorption zone, mixes containing lysine solution with described;
In Jian Dao district, make pH value be 11.0, temperature be 40 DEG C ammoniacal liquor with 4.8 times of column volumes/hour flow velocity flow through cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain elutriant;
In breeding blanket, every root cation exchange resin column temperature be 40 DEG C of water (0.375 times for column volume) with 4.5 times of column volumes/hour flow velocity flow through cation exchange resin column, then temperature is made to be that the air of 15 DEG C passes through cation exchange resin column with the air pressure of 0.15MPa, then make that temperature is 45 DEG C, adjust pH be 1.0 waste liquid (0.5 times for column volume) with 6.5 times of column volumes/hour flow velocity flow through cation exchange resin column, cation exchange resin column is regenerated.
The flow velocity introduced from the upper end of the cation exchange resin column group being in first place, adsorption zone containing lysine solution is 45m
3/ h, the flow velocity that waste liquid flows out from the lower end of the cation exchange resin column group being in position, end, adsorption zone is 35m
3/ h, after stable circulation 20h, the lysine concentration measured the waste liquid flowed out from the lower end of the cation exchange resin column group of position, end, adsorption zone is 0.02g/dL, and waste liquid pH value is 4.6; Measure and calculate calcium, the magnesium ion residual quantity in cation exchange resin column, measuring the lysine content in elutriant, calculating Methionin purity and yield, the results are shown in Table 1.
Embodiment 3
Adopt the technique shown in Fig. 2, make to contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, back filled region, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, purification and Adsorption and desorption and regeneration again, elutriant is obtained after desorb, wherein
Three groups of cation exchange resin column groups of connecting successively are in adsorption zone simultaneously, often organize cation exchange resin column group to be made up of 6 cation exchange resin columns in parallel, Zeo-karb in cation exchange resin column is the special strongly acidic cation-exchange of WD-2 type Methionin, the total exchange capacity of Zeo-karb is 8mmol/g, transfer tank is provided with between two adjacent groups cation exchange resin column group, two adjacent groups cation exchange resin column group is connected in series through transfer tank, concentration containing lysine solution is 15.0g/dL, temperature is 60 DEG C, be introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.5 in pH value, flow through each group of cation exchange resin column group in this adsorption zone successively, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 2.0g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, adding sulfuric acid adjust pH in transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.6, the time contacted with the cation exchange resin column group of position, end, adsorption zone is 8.5min, the time contacted with deputy cation exchange resin column group with first place, adsorption zone is 17min altogether.
In back filled region, every root cation exchange resin column elution fractions (0.6 times for column volume), temperature is 60 DEG C, with 4.0 times of column volumes/hour flow velocity backfill cation exchange resin column, the liquid flowed out from cation exchange resin column after backfill returns to adsorption zone, mixes containing lysine solution with described;
In Jian Dao district, make pH value be 12.5, temperature be 60 DEG C ammoniacal liquor with 5.5 times of column volumes/hour flow velocity flow through cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain elutriant;
In breeding blanket, every root cation exchange resin column temperature be 60 DEG C of water (0.5 times for column volume) with 6.5 times of column volumes/hour flow velocity flow through cation exchange resin column, then temperature is made to be that the air of 30 DEG C passes through cation exchange resin column with the air pressure of 0.07MPa, then make that temperature is 35 DEG C, adjust pH be 1.4 waste liquid (0.35 times for column volume) with 4.5 times of column volumes/hour flow velocity flow through cation exchange resin column, cation exchange resin column is regenerated.
The flow velocity introduced from the upper end of the cation exchange resin column group being in first place, adsorption zone containing lysine solution is 45m
3/ h, the flow velocity that waste liquid flows out from the lower end of the cation exchange resin column group being in position, end, adsorption zone is 35m
3/ h, after stable circulation 20h, the lysine concentration measured the waste liquid flowed out from the lower end of the cation exchange resin column group of position, end, adsorption zone is 0.03g/dL, and waste liquid pH value is 5.0; Measure and calculate calcium, the magnesium ion residual quantity in cation exchange resin column, measuring the lysine content in elutriant, calculating Methionin purity and yield, the results are shown in Table 1.
Embodiment 4
Lysine solution is contained according to the method process of embodiment 1, unlike, adding sulfuric acid adjust pH in the transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 2.2.The flow velocity introduced from the upper end of the cation exchange resin column group being in first place, adsorption zone containing lysine solution is 45m
3/ h, the flow velocity that waste liquid flows out from the lower end of the cation exchange resin column group being in position, end, adsorption zone is 35m
3/ h, after stable circulation 20h, the lysine concentration measured the waste liquid flowed out from the lower end of the cation exchange resin column group of position, end, adsorption zone is 0.015g/dL, and waste liquid pH value is 4.0.Measure and calculate calcium, the magnesium ion residual quantity in cation exchange resin column, measuring the lysine content in elutriant, calculating Methionin purity and yield, the results are shown in Table 1.
Comparative example 1
Lysine solution is contained according to the method process of embodiment 1, unlike, adding sulfuric acid adjust pH in the transfer tank before the cation exchange resin column group being in position, end, adsorption zone is 1.8.The flow velocity introduced from the upper end of the cation exchange resin column group being in first place, adsorption zone containing lysine solution is 45m
3/ h, the flow velocity that waste liquid flows out from the lower end of the cation exchange resin column group being in position, end, adsorption zone is 35m
3/ h, after stable circulation 20h, the lysine concentration measured the waste liquid flowed out from the lower end of the cation exchange resin column group of position, end, adsorption zone is 0.035g/dL, and waste liquid pH value is 3.2.Measure and calculate calcium, the magnesium ion residual quantity in cation exchange resin column, measuring the lysine content in elutriant, calculating Methionin purity and yield, the results are shown in Table 1.
Table 1
As can be seen from embodiment 1 and comparative example 1, the inventive method Methionin purity is high, and yield is high, and the calcium in cation exchange resin column, magnesium ion residual quantity are low, and gained waste liquid pH value is higher, can be directly used in and prepare ammonium sulfate.
Embodiment 1 and embodiment 4 are compared and can find out, be be not less than the respectively group cation exchange resin column group of all the other except first place flowed through successively under the condition of 1.0g/dL in this adsorption zone under the condition of 2.4-2.6 or at lysine concentration in pH value, can further improve purity and the yield of Methionin, reduce the residual quantity of calcium ions and magnesium ions in cation exchange resin column further.
Treatment process containing lysine solution provided by the invention, can improve purity and the yield of Methionin; Calcium ions and magnesium ions residual quantity in cation exchange resin column can be reduced; The pH value of the inventive method gained waste liquid is 4.0-5.0, can be directly used in and prepare ammonium sulfate, greatly reduce production cost.Treatment process containing lysine solution provided by the invention, can be widely used in industrial production.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. the treatment process containing lysine solution, it is characterized in that, described method comprises: make described contact containing lysine solution carry out ion exchange mechansim with cation exchange resin column group of organizing more, often organize cation exchange resin column group successively and cyclically through adsorption zone, Jian Dao district and breeding blanket, to make cation exchange resin column group successively and cyclically to carry out exchange adsorption, desorb and regeneration, elutriant is obtained after desorb, the described cation exchange resin column often organized cation exchange resin column group and comprise one or more parallel connection, wherein
One or more groups cation exchange resin column group of connecting successively is in adsorption zone simultaneously, described is introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.2 in pH value containing lysine solution, be all the other each group cation exchange resin column groups flowed through successively under the condition of 2.2-2.6 in this adsorption zone in pH value, then flow out from the lower end of the cation exchange resin column group being in position, end, adsorption zone and obtain waste liquid, the described at least part of Methionin contained in lysine solution is made to be adsorbed onto on Zeo-karb, and make lysine concentration in described waste liquid not higher than 0.1g/dL, in Jian Dao district, make basic solution flow through described cation exchange resin column, make the Methionin desorb be adsorbed onto on Zeo-karb obtain described elutriant, in breeding blanket, after making water, air and adjust pH pH value be the described waste liquid of 1.0-1.4 successively by cation exchange resin column, cation exchange resin column is regenerated.
2. method according to claim 1, wherein, flows through all the other each group cation exchange resin column groups described in this adsorption zone successively under the condition of pH value for 2.4-2.6.
3. method according to claim 1 and 2, wherein, is provided with transfer tank, two adjacent groups cation exchange resin column group is connected in series through described transfer tank between the two adjacent groups cation exchange resin column group of adsorption zone.
4. method according to claim 1 and 2, wherein, the cation exchange resin column group being simultaneously in adsorption zone is three groups, and often group comprises the cation exchange resin column of 3-6 parallel connection.
5. method according to claim 4, wherein, described is introduce from the upper end of the cation exchange resin column group being in first place, adsorption zone under the condition of 3.0-3.5 in pH value containing lysine solution, after the cation exchange resin column group of first place, adsorption zone and in the liquid before the deputy cation exchange resin column group in adsorption zone lysine concentration is made to be 1.0-2.0g/dL, by being in the deputy cation exchange resin column group in adsorption zone under the condition of not adjust pH, be by being in the cation exchange resin column group of position, end, adsorption zone in pH value under the condition of 2.4-2.6.
6. method according to claim 1 and 2, wherein, the condition of described absorption comprises, temperature is 40-60 DEG C, be the time contacted with Zeo-karb under the condition of 2.2-2.6 at adjust pH containing lysine solution be 8-10min, the time contacted with Zeo-karb under all the other conditions is 17-20min; The condition of described desorb comprises, the flow velocity of described basic solution be 4.0-8.0 times of column volume/hour, temperature is 40-60 DEG C; The condition of described regeneration comprises, the flow velocity of described water be 4.5-8.5 times of column volume/hour, temperature is 40-60 DEG C, the air pressure of described air is 0.07-0.15MPa, temperature is 15-30 DEG C, pH value to be the flow velocity of the described waste liquid of 1.0-1.4 be 2.5-6.5 times of column volume after adjust pH/hour, temperature is 20-45 DEG C.
7. method according to claim 1 and 2, wherein, described method also comprises described cation exchange resin column after adsorption zone, before Jian Dao district, also through back filled region, in back filled region, backfill described cation exchange resin column with the described elutriant of part, make described cation exchange resin column carry out purification and again adsorb.
8. method according to claim 7, wherein, the liquid flowed out from described cation exchange resin column after backfill returns to adsorption zone, mixes containing lysine solution with described.
9. method according to claim 7, wherein, described purification and the condition of again adsorbing comprise, the flow velocity of the described elutriant of described part be 2.0-4.0 times of column volume/hour, temperature is 40-60 DEG C.
10. method according to claim 1 and 2, wherein, the Zeo-karb in described cation exchange resin column is sulfonic group strong-acid type cation exchange resin, and the total exchange capacity of described Zeo-karb is greater than 5mmol/g.
11. methods according to claim 1 and 2, wherein, pH value regulates by adding sulfuric acid.
12. methods according to claim 1 and 2, wherein, described basic solution is ammoniacal liquor, and pH value is 10.0-14.0.
13. methods according to claim 12, wherein, pH value is 11.0-12.5.
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