CN1196392A - Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase - Google Patents
Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase Download PDFInfo
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- CN1196392A CN1196392A CN98113523A CN98113523A CN1196392A CN 1196392 A CN1196392 A CN 1196392A CN 98113523 A CN98113523 A CN 98113523A CN 98113523 A CN98113523 A CN 98113523A CN 1196392 A CN1196392 A CN 1196392A
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Abstract
A process for preparing levo-methionine includes such technological steps as acetylating heterogeneous methionine to obtain acetylated one, extracting high-activity amino-acylase from animal viscera used as enzyme source, decomposing the acetylated heterogeneous methionine at 10-41 deg.C for 40-110 hr, decolouring with activated carbon, concentration, cooling, addition of CH3OH, stirring crystallizing at 0-6 deg.C, separation and drying, and features high output rate up to 99.0% or more (theoretical value), easily available enzyme source and low cost.
Description
(D, L-Met) the butyro-method of preparation L-Methioine (L-Met) 1-2-amino-4-(methylthio group) reaches obtaining of amino acidylate lytic enzyme to the present invention relates to amino acidylate lytic enzyme method fractionation DL METHIONINE FEED GRADE.
Amino acid is to constitute the proteinic major ingredient of organism, is the base substance that earns a bare living, and the L-methionine(Met) is a kind of in eight kinds of essential hydrogen base acid of human body, and the health of human body is played an important role.Be widely used in the Biochemical Research of medical and health, and the amino acid infusion solutions, foodstuff additive, order field such as apply some make up.
In the DL METHIONINE FEED GRADE mapping foreign body object, right type and levorotation the two except the difference on making plane polarized light generation different directions equal angular deflection this point, other physics, there is not difference under the chemical property general condition, therefore isolate right type body and the levorotation body is very difficult, traditional chemical resolution method, utilize the salt of the method formation diastereomer of D bromocamphor ammonium sulphonate and DL METHIONINE FEED GRADE salt derivative, utilize the difference of its solubleness, thereby reach the purpose that DL METHIONINE FEED GRADE splits, this method will consume a large amount of natural camphors, use a large amount of Br, the sulphur acid iodide, the industrial chemicals that corrodibility such as chloroform are strong, production cycle is long, toxic side effect is big, and the natural camphor shortage, the production cost height, so industry law production L-Methioine is greatly limited.
The special permission communique, clear 41-22380, clear 42-1534 disclose the technology that amino acidylate lytic enzyme method is produced L-Methioine, adopt aspergillus oryzae, and the water liquid after bent dissolving of kind that obtains with Wheat bran-husk adds [Co (H
2O)
6]
3119mg/l; with the acetyl DL METHIONINE FEED GRADE substrate of 0.17M concentration in PH7.0,37 ℃ of effects down; make carrier with the diethylamine ethyl; on the chromatography column that is filled with the DEAE fiber; allowing crude enzyme liquid flow out passes through; the effluent liquid concentrating under reduced pressure filters and obtains crystal product; filtrate is used ethyl alcohol recrystallization again, and this method advantage efficient is higher, productive rate 67%; yeast culture condition and cost are low; enzyme can use repeatedly, and reaction needs more than 150 hours slowly at the bottom of the shortcoming enzyme; enzyme deactivation is higher in the solidification process, reclaims D-Thiomedon complex procedures.
The clear 48-23915 of special permission communique discloses a kind of amino acidylate lytic enzyme method and has split DL-Met production L-Met technology; utilization contain produce corynebacterium glutamicum nutrient solution directly and concentration be 0.006M acetyl DL METHIONINE FEED GRADE substrate reactions; at PH6.8; temperature was reacted 24 hours down for 37 ℃; the reaction terminating liquid heating; cooling bactofugation body foreign protein; supernatant liquor is through the highly acidic cation post, and effluent liquid is the D-Thiomedon, after pillar water indenes is clean; the ammoniacal liquor wash-out; concentrated crystallisation by cooling gets product; the advantage of this method is the efficient height, productive rate 64%, and yield in unit time is higher relatively; operate easier; directly use thalline can economize operation and carrier, shortcoming purity is not high, yeast culture cost height; to use gravy; albumen freezes; dextrose culture-medium is cultivated, and reclaims D-Thiomedon complex procedures.
The purpose of this invention is to provide a kind of amino acidylate lytic enzyme and split DL METHIONINE FEED GRADE system L-Methioine novel method, the used amino acid acylase (E, C, 3,5,1,14) of this method has high reactivity, is easy to get, and production cost is low.
Principle of the present invention is
Only L type acylated amino hydrolysis
The method steps that amino acidylate lytic enzyme of the present invention splits DL METHIONINE FEED GRADE system L-Methioine is:
(1) the acetyl DL METHIONINE FEED GRADE is added the substrate that deionized water dissolves into 0.4-1.0mol/L, transfer PH to 2-9 with NaOH solution, preferred PH3.8-8 filters, and adds 100-150ml CoCl by the 3000ml substrate solution
225 * 10
-4The solution of mol/L;
(2) get amino acidylate lytic enzyme, join in the above-mentioned filtration gained substrate in the ratio of 17000-20000m/lM acetyl DL METHIONINE FEED GRADE, at 10-41 ℃, preferred 20-38 ℃, kept 40-110 hour, carry out the DL METHIONINE FEED GRADE fractionation,
(3) the folding separatory is warmed up to 80-90 °, adds activated carbon decolorizing, filters;
(4) decolorization filtering liquid is at 70-80 ℃ of 1/20-1/30 postcooling that is concentrated to the stoste volume;
(5) add CH in the cooling fluid
3OH, its amount stirs for 6-8 times of substrate protein propylhomoserin weight, in 0-6 ℃ of following crystallization 3-6 hour, centrifugation, the dry product L-Methioine that gets.
The preparation of above-mentioned used acetyl DL METHIONINE FEED GRADE is carried out as follows:
(1) gets the DL METHIONINE FEED GRADE of 1 part of weight, join in the reactor of 2 parts of weight percent acetic acids, stir while adding;
(2) drip the aceticanhydride of 0.9 part of weight again in the reactor, stir simultaneously, treat that thermopositive reaction finishes, this moment retortable recovery acetic acid;
(3) cool off, add the water of 2 parts of weight simultaneously, place cooling and carried out crystallization in 〉=20 hours;
(4) Crystallization Separation, washing, dry m, p114-115 ℃ of acetyl DL METHIONINE FEED GRADE raw material.
Above-mentioned used amino acidylate lytic enzyme, promptly amino acid acylase (E, C, 3,5,1,14) makes as follows:
(1) the fresh animal internal organ of getting 1 part of weight place the high speed stamp mill to wear into screened stock under 0-6 ℃, place container;
(2) add the sodium phosphate salt damping fluid of 2-3 part weight 0.05-0.1M concentration in the screened stock, at 0-5 ℃ of following stirring and leaching 30-40mln,
(3) the vat liquor mixing places refrigerated centrifuge in rotating speed 3000rpm, and temperature 0-5 ℃ of following centrifugal settling 〉=20mln receives to such an extent that protein concentration is 40-45mg/ml, and enzyme activity is the 1860-3890u/ml supernatant liquor;
(4) transfer PH to 3-8 with 0.05-0.1M phosphorus concentration acid sodium-salt damping fluid the gained supernatant liquor, and then place refrigerated centrifuge at rotating speed 3000rpm, temperature 0-5 ℃ of following centrifugal settling 〉=20mln collects its supernatant liquor;
(5) transfer PH to 3-8 with the sodium phosphate salt damping fluid of 0.05-0.1M concentration (4) gained supernatant liquor, receive to such an extent that protein concentration is 11-28mg/ml, the supernatant liquor of enzyme activity 1950-3380u/ml;
(6) the 1/4-1/2 weight by every part of internal organ weight adds (NH in (5) gained supernatant liquor
4)
2SO
4Powder was stored in the refrigerator-freezer salt folding 8-20 hour;
(7) salt folding liquid places refrigerated centrifuge in rotating speed 4000rpm, and temperature 0-5 ℃ of following centrifugal settling 〉=20mln gets salt folding sediment;
(8) salt folding sediment dissolves it with deionized water fully, and in the bag made of the commercially available dialysis membrane of packing in 0-5 ℃ of dialysis 〉=12 hours down, often change deionized water, do not have SO to checking in the dialyzate
4 2-End during ion;
(9) saltout gained dialysis enzyme liquid concentration be the sodium phosphate salt damping fluid of 0.05-0.1M to be made into protein concentration be 8-10mg/ml, enzyme activity is the enzyme liquid of 23000-25000u/ml, places refrigerator-freezer standby.
Used concentration is that the sodium phosphate salt damping fluid of 0.05-0.1M is the damping fluid that Sodium phosphate dibasic and sodium dihydrogen phosphate are mixed with.
Advantage of the present invention is efficient height, yield 78%, and enzyme source is wide, and cost is low; Directly split, need not solidify, product and byproduct Separation and Recovery operation are simple.Insufficient is that enzyme can only use once.
Embodiment 1 acetyl DL METHIONINE FEED GRADE (D, L-N-AC-Met) synthetic
The 150kg DL METHIONINE FEED GRADE is joined in the reactor of 300kg Glacial acetic acid; the limit edged is stirred to dissolving fully; drip the 135kg aceticanhydride again; stir simultaneously; because of exothermic heat of reaction; temperature rises; treat that thermopositive reaction finishes (this moment distill recycle-water acetic acid); cooling adds 300kg water simultaneously, places cooling crystallization more than 20 hours; centrifugation, washing, the dry 190kg product that gets; generally can get 185.6-193.8kg acetyl DL METHIONINE FEED GRADE product, yield is 90-94%, and m, p114-115 ℃ acetyl DL METHIONINE FEED GRADE product is stored standby.
Producing of embodiment 2 amino acidylate lytic enzymes
1 part of (100-200g) fresh animal internal organ put in the high speed stamp mill wear into screened stock, place the 1000ml beaker, the sodium phosphate salt damping fluid that adds the 0.05M concentration of 2-3 times of screened stock weight, stirring and leaching 30-40mln under 0-5 ℃ of temperature, place refrigerated centrifuge in rotating speed 3000rpm its mixed solution then, 0 ℃-5 ℃ of temperature, centrifugal settling 20mln, collect supernatant liquor 320ml, sampling records protein concentration 41.4mg/ml, enzyme activity 1860-3890u/ml, transfer PH to 3-8 with the sodium phosphate salt damping fluid of 0.05M concentration its supernatant liquor again, and then place refrigerated centrifuge at rotating speed 3000rpm, centrifugal settling 20mln in 0 ℃-5 ℃ of the temperature, collect its supernatant liquor, transfer PH to 3-8 with above-mentioned damping fluid again, collect supernatant liquor 195ml, it is 11-28mg/ml that protein concentration is surveyed in sampling, collects and records enzyme activity at 1950-3380u/ml.
In the supernatant liquor of gained 195ml, add chemical pure (NH
4)
2SO
4Powder 48g saltouts, and deposits in the refrigerator-freezer more than 8 hours.The liquid of will saltouing places refrigerated centrifuge at rotating speed 4000rpm, 0-5 ℃ of temperature centrifugal settling 20mln, and sediment 188 obtains saltouing.In the dialysis tubing that the commercially available dialysis membrane of then it being packed into is made, put into deionized water in 0-5 ℃ of dialysis 12-24 hour, often change deionized water, check that dialysis did not finish when dialyzate had the SO2-4 ion, with the sodium phosphate salt damping fluid of 0.06M concentration join enzyme liquid 38ml, protein concentration 9.48mg/ml is surveyed in sampling, and enzyme activity 24400u/ml places refrigerator-freezer standby enzyme liquid.
Embodiment 3
Amino acidylate lytic enzyme splits DL METHIONINE FEED GRADE system L-Methioine production example 1.
Get D, L-N-AC-Met (acetyl DL METHIONINE FEED GRADE) 100kg, add deionized water 1000kg, NaOH2.5kg, filter in splitting still, filtrate PH-5.5 adds 3500ml CoCl
25 * 10
-4Mol/l solution; getting amino acidylate lytic enzyme adds in the substrate; its enzyme concentration is a 20000u/lM acetyl DL METHIONINE FEED GRADE; split 40-110 hour at 26-40 ℃; make temperature be raised to 80-90 ℃ because of splitting heat release; add the 1kg activated carbon decolorizing, its destainer is concentrated to 1/30 volume at 70-80 ℃, adds 700kg CH
3OH stirs, in 0-6 ℃ of crystallization 3-6 hour, centrifugation mother liquor, dehydration, dry L-Methioine product 35.90kg, yield 99.2% (with respect to the theoretical quantities received of the once fractionation of DL METHIONINE FEED GRADE).
Embodiment 4
Amino acidylate lytic enzyme splits DL METHIONINE FEED GRADE system L-Methioine production example 2.
Get acetyl DL METHIONINE FEED GRADE 200kg, add deionized water 2000kg, NaOH4.5kg, filter in splitting still, filtrate PH-4 adds 7000ml CoCl
25 * 10
-4Mol/l solution; getting amino acidylate lytic enzyme adds in the substrate; wherein the enzyme amount is a 17000u/lM acetyl DL METHIONINE FEED GRADE; split 40-110 hour at 26-40 ℃; because of the resolution reaction heat release, make temperature rise 80-90 ℃, add gac 2kg decolouring; its destainer adds 1500kg CH at 70-80 ℃ of 1/20 volume that is concentrated to original volume
3OH stirs, under 0-6 ℃ of temperature crystallization 3-6 hour, the centrifugation mother liquor, dewater, dry L-Methioine product 71.64kg, yield 99.0%, (with respect to the theoretical quantities received of the once fractionation of DL METHIONINE FEED GRADE).
Claims (6)
1, a kind of amino acidylate lytic enzyme splits the method for DL METHIONINE FEED GRADE system L-Methioine, and its characterization step is:
(1) the acetyl DL METHIONINE FEED GRADE is added the substrate solution that deionized water dissolves into 0.4-1.0mol/L, usefulness NaOH solution transfers PH to 2-9, filters in splitting still to add 100-150ml CoCl by every 3000ml filtration end liquid
25 * 10
-4The solution of mol/L,
(2) get amino acidylate lytic enzyme and add in the above-mentioned filtered liquid substrate, carried out DL METHIONINE FEED GRADE in 40-110 hour 10-41 ℃ of insulation and split in 17000-20000u/M acetyl DL METHIONINE FEED GRADE ratio,
(3) split liquid and be warmed up to 80-90 ° of adding activated carbon decolorizing, filter,
(4) decolorization filtering liquid is at 70-80 ℃ of 1/20-1/30 postcooling that is concentrated to the stoste volume,
(5) add CH
3OH, its amount is substrate weight 6-8 times, stirs, in 0-6 ℃ of following crystallization 3-6 hour, centrifugation, the dry product that gets.
2, the method for producing L-Methioine as claimed in claim 1 is characterized in that substrate solution usefulness NaOH solution accent PH is to 3.8-8.
3, the method for producing L-Methioine as claimed in claim 1, it is characterized in that filtering in the substrate add amino acidylate lytic enzyme after, carried out DL METHIONINE FEED GRADE in 40-110 hour temperature 20-38 ℃ of insulation and split.
4, the preparation steps of the used acetyl DL METHIONINE FEED GRADE of claim 1 is as follows:
(1) get the DL METHIONINE FEED GRADE of 1 part of weight, join in the reactor of 2 parts of weight percent acetic acids, stir while adding,
(2) toward (1) the middle aceticanhydride that drips 0.9 part of weight, stir simultaneously, treat that thermopositive reaction finishes,
(3) cool off, add the water of 2 parts of weight simultaneously, place cooling and carry out crystallization more than 20 hours,
(4) Crystallization Separation, washing, dry m, p114-115 ℃ of acetyl DL METHIONINE FEED GRADE product.
5, the used amino acidylate lytic enzyme of claim 1 is characterized in that making as follows,
(1) the fresh animal internal organ of getting 1 part of weight are worn into screened stock under 0-6 ℃, place container,
(2) the sodium phosphate salt damping fluid of adding 2-3 part weight 0.05-0.1M concentration in screened stock, at 0-5 ℃ of following stirring and leaching 30-40mln,
(3) the vat liquor mixing places refrigerated centrifuge in rotating speed 3000rpm, and temperature 0-5 ℃ of following centrifugal settling 〉=20mln receives to such an extent that protein concentration is 40-45mg/ml, and enzyme activity is the 1860-3890u/ml supernatant liquor,
(4) transfer PH to 3-8 with the sodium phosphate salt damping fluid of 0.05-0.1M concentration (3) gained supernatant liquor, and then place refrigerated centrifuge at rotating speed 3000rpm, temperature 0-5 ℃ of following centrifugal settling 〉=20mln collects its supernatant liquor,
(5) transfer PH to 3-8 with the sodium phosphate salt damping fluid of 0.05-0.1M concentration (4) gained supernatant liquor, receive to such an extent that protein concentration is 11-28mg/ml, the supernatant liquor of enzyme activity 1950-3380u/ml,
(6) the 1/4-1/2 weight by every part of internal organ weight adds (NH in (5) gained supernatant liquor
4)
2SO
4Powder was stored in the refrigerator-freezer salt folding 8-20 hour,
(7) salt folding liquid places refrigerated centrifuge in rotating speed 4000rpm, and temperature 0-5 ℃ of following centrifugal settling 〉=20mln gets salt folding sediment,
(8) in the bag that salt folding sediment is made with the deionized water dissolving and the commercially available dialysis membrane of packing into,, often change deionized water, check in the dialyzate and do not have SO in 0-5 ℃ of dialysis 〉=12 hours down
4 -2End during ion,
(9) saltout that to be made into protein concentration with the sodium phosphate salt damping fluid of 0.05-0.1M concentration be 8-10mg/ml to gained dialysis enzyme liquid, enzyme activity is the enzyme liquid of 23000-25000u/ml, places refrigerator-freezer standby.
6, producing of the amino acidylate lytic enzyme described in claim 5 is characterized in that concentration is that the sodium phosphate salt damping fluid of 0.05-0.1M is the damping fluid that Sodium phosphate dibasic and sodium dihydrogen phosphate are mixed with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113523A CN1062604C (en) | 1998-04-27 | 1998-04-27 | Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113523A CN1062604C (en) | 1998-04-27 | 1998-04-27 | Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1196392A true CN1196392A (en) | 1998-10-21 |
| CN1062604C CN1062604C (en) | 2001-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113523A Expired - Fee Related CN1062604C (en) | 1998-04-27 | 1998-04-27 | Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334222C (en) * | 2004-12-03 | 2007-08-29 | 上海化工研究院 | Enzyme method for preparing laevo-rotation and dextro-rotation tryptophane 15N by resolving racemic tryptophase 15N |
| CN102051401A (en) * | 2010-04-01 | 2011-05-11 | 山东阳成生物科技有限公司 | High-efficiency acylation production method of L-methionine nonaqueous solution |
| CN102127583A (en) * | 2010-01-19 | 2011-07-20 | 上海博康精细化工有限公司 | Method for preparing anti-para amino adamantanol |
| CN102827045A (en) * | 2012-08-31 | 2012-12-19 | 重庆紫光天化蛋氨酸有限责任公司 | Method and apparatus for removing impurity in secondary methionine mother liquor |
| CN102925530A (en) * | 2012-11-04 | 2013-02-13 | 宁波市远发生物工程有限公司 | L-methionine preparation method |
| CN104152524A (en) * | 2014-08-08 | 2014-11-19 | 山东阳成生物科技有限公司 | Production technology of L-methionine |
| CN106520899A (en) * | 2017-01-05 | 2017-03-22 | 湖北省八峰药化股份有限公司 | Production method of L-methionine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4981799A (en) * | 1987-08-21 | 1991-01-01 | Takeda Chemical Industries, Ltd. | Acylamino acid racemase, production and use thereof |
-
1998
- 1998-04-27 CN CN98113523A patent/CN1062604C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334222C (en) * | 2004-12-03 | 2007-08-29 | 上海化工研究院 | Enzyme method for preparing laevo-rotation and dextro-rotation tryptophane 15N by resolving racemic tryptophase 15N |
| CN102127583A (en) * | 2010-01-19 | 2011-07-20 | 上海博康精细化工有限公司 | Method for preparing anti-para amino adamantanol |
| CN102051401A (en) * | 2010-04-01 | 2011-05-11 | 山东阳成生物科技有限公司 | High-efficiency acylation production method of L-methionine nonaqueous solution |
| CN102827045A (en) * | 2012-08-31 | 2012-12-19 | 重庆紫光天化蛋氨酸有限责任公司 | Method and apparatus for removing impurity in secondary methionine mother liquor |
| CN102827045B (en) * | 2012-08-31 | 2014-04-23 | 重庆紫光天化蛋氨酸有限责任公司 | Method and apparatus for removing impurity in secondary methionine mother liquor |
| CN102925530A (en) * | 2012-11-04 | 2013-02-13 | 宁波市远发生物工程有限公司 | L-methionine preparation method |
| CN104152524A (en) * | 2014-08-08 | 2014-11-19 | 山东阳成生物科技有限公司 | Production technology of L-methionine |
| CN106520899A (en) * | 2017-01-05 | 2017-03-22 | 湖北省八峰药化股份有限公司 | Production method of L-methionine |
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| Publication number | Publication date |
|---|---|
| CN1062604C (en) | 2001-02-28 |
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