CN102659650A - Device and method for preparing DL-methionine salt - Google Patents
Device and method for preparing DL-methionine salt Download PDFInfo
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- CN102659650A CN102659650A CN2012101302885A CN201210130288A CN102659650A CN 102659650 A CN102659650 A CN 102659650A CN 2012101302885 A CN2012101302885 A CN 2012101302885A CN 201210130288 A CN201210130288 A CN 201210130288A CN 102659650 A CN102659650 A CN 102659650A
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- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical class CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 21
- 235000011089 carbon dioxide Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 2
- 150000002742 methionines Chemical class 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000000630 rising effect Effects 0.000 abstract 4
- 229940091173 hydantoin Drugs 0.000 abstract 2
- 238000004064 recycling Methods 0.000 abstract 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 235000006109 methionine Nutrition 0.000 description 27
- 229930182817 methionine Natural products 0.000 description 27
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 27
- 239000004470 DL Methionine Substances 0.000 description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- -1 metals ion Chemical class 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 1
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 206010020852 Hypertonia Diseases 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960005139 epinephrine Drugs 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a device for preparing DL-methionine salt. The device comprises a three-stage series kettle type reactor and a gas stripping tower, wherein a material inlet of the gas stripping tower is communicated with a material outlet of the third-stage kettle type reactor. The invention also discloses a method for preparing the DL-methionine salt by using the device. The method comprises the following steps of charging an aqueous solution of hydantoin and an aqueous solution of inorganic alkali in the three-stage series kettle type reactor, performing continuous three-stage reaction, and controlling the pressure in the three-stage series reactor to be between 1.4 and 2.6MPa; performing gradient temperature rising of the first-stage reactor from 50 DEG C to 100 DEG C, performing gradient temperature rising of the second-stage reactor from 100 DEG C to 140 DEG C, and performing gradient temperature rising of the third-stage reactor from 140 DEG C to 180 DEG C; and feeding the liquid flowing out of the material outlet of the third-stage reactor to the atmospheric pressure vapor stripping tower, and separating and recycling carbon dioxide and ammonia, wherein the liquid flowing out of the bottom of the tower is an aqueous solution of DL-methionine salt, and the mixed gas discharged from the top of the tower is used for recycling and preparing an aqueous solution of carbon dioxide and ammonia and can be circularly used for preparing the hydantoin. By the device and the method, gradient temperature rising is easy to realize, high-efficiency mixing is realized, reaction is complete, reaction speed is high, a small quantity of by-products are generated, and yield is high; and moreover, the device and the method can be used for realizing the refinement of the DL-methionine salt conveniently and efficiently, and the DL-methionine salt has high quality.
Description
Technical field
The invention belongs to chemical field, relate to a kind of improved preparation facilities and method of Chemicals.
Background technology
Methionine(Met) has another name called methionine(Met); Be to constitute one of proteinic fundamental unit; Be unique amino acid that contains sulphur in the indispensable amino acid, in participating in animal body the metabolism of the transfer of methyl, phosphorus and suprarenin, choline, creatine synthetic, or the raw material of synthetic protein and Gelucystine.Methionine(Met) is widely used in fields such as medicine, food, feed and makeup, and is wherein maximum as the consumption of fodder additives, but the methionine(Met) of China almost all relies on import at present, and domestic self output is very low, can not satisfy the demands far away.
DL-methionine(Met) salt is that glycolylurea (chemical name is 5-(2-methylmercaptoethyl)-NSC 9226) legal system is equipped with the midbody of DL-methionine(Met); The reactant aqueous solution of 3-methylthiopropionaldehyde, prussiate and carbonic acid gas and ammonia is made glycolylurea; Glycolylurea is made DL-methionine(Met) salt with basic hydrolysis, DL-methionine(Met) salt is promptly made the DL-methionine(Met) with the acid neutralization.In the existing technology; It is under high temperature, condition of high voltage, to react that the glycolylurea basic hydrolysis prepares DL-methionine(Met) salt; Reaction conditions is wayward, causes the side reactions such as degraded, polymerization of organic raw material easily, thus cause DL-methionine(Met) salt yield to descend or technology unstable.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation facilities and method of DL-methionine(Met) salt, easily control reaction temperature is controlled the generation of by product well, improves the quality and the yield of DL-methionine(Met) salt.
For achieving the above object, the present invention provides following technical scheme:
1.DL-the preparation facilities of methionine(Met) salt; Comprise three grades of series connection tank reactors and gas stripping column; Wherein the discharge port of first step tank reactor is communicated with the opening for feed of second stage tank reactor; The discharge port of second stage tank reactor is communicated with the opening for feed of third stage tank reactor, and the discharge port of third stage tank reactor is communicated with the opening for feed of gas stripping column.
Preferably, the cat head of said gas stripping column also is provided with gas-liquid separator, like cyclonic separator etc.This device can be removed well and reclaim the liquid that is had in the gas.
Preferably, said third stage tank reactor discharge port also is provided with pressure release valve to the path of gas stripping column opening for feed.Adopt this device, can be easily with behind the effusive highly pressurised liquid removal of third stage tank reactor discharge port certain pressure, sending into gas stripping column again.
2. utilize said apparatus to prepare the method for DL-methionine(Met) salt; May further comprise the steps: with carrying out continuous third order reaction in the glycolylurea aqueous solution and three grades of series connection of the inorganic base aqueous solution feeding tank reactors; The pressure-controlling of three grades of series connection in the tank reactor is at 1.4-2.6MPa; Wherein the temperature in the first step tank reactor is from 50 ℃ of gradient increased temperatures to 100 ℃; Temperature in the tank reactor of the second stage is from 100 ℃ of gradient increased temperatures to 140 ℃; Temperature in the third stage tank reactor is from 140 ℃ of gradient increased temperatures to 180 ℃; Send into carbonic acid gas and the ammonia that generates the reaction of atmospheric steam gas stripping column Separation and Recovery from the effusive liquid of third stage tank reactor discharge port, the liquid that goes out from tower bottom flow is DL-methionine(Met) salt brine solution, and the gas mixture of discharging from cat head is used to reclaim the aqueous solution of preparation carbonic acid gas and ammonia and the preparation that circulation is used for glycolylurea.
Hydrolysis reaction is favourable having alkali to exist at the very start certainly, so the adding sequencing of reaction raw materials is to add inorganic base aqueous solution earlier in the aforesaid method, adds the glycolylurea aqueous solution again.
Preferably, said mineral alkali is a sodium hydroxide.The present invention preferably adopts following path of preparing DL-methionine(Met): 1) reactant aqueous solution with 3-methylthiopropionaldehyde, sodium cyanide and carbonic acid gas and ammonia makes the aqueous solution that contains glycolylurea and yellow soda ash; 2) step 1) gained solution is added sodium hydroxide hydrolysis and reclaims carbonic acid gas and the ammonia that reaction generates, make the aqueous solution that contains DL-methionine(Met) sodium and yellow soda ash; 3) with step 2) gained solution adds vitriol oil neutralization and reclaims the carbonic acid gas that reaction generates, and makes the aqueous solution that contains DL-methionine(Met) and sodium sulfate, the crystallization of DL-methionine(Met) separated out and sodium sulfate is retained in the solution, promptly obtains the DL-methionine(Met).The reaction equation that each step relates to is following:
Because prussic acid torpescence and severe toxicity is arranged, so preferred sodium cyanide is as the raw material of preparation glycolylurea, because the metals ion of mineral alkali introducing separates with the consistent product that helps of metals ion that sodium cyanide contains; So the preferred sodium hydroxide of the present invention is as hydrolyst; Because sodium ion is the strong basicity metals ion, so subsequent technique preferably has the highly acid vitriol oil as neutralizing agent, thereby reduces by product as much as possible; Make the final product kind of entire reaction few; And the component separate easily in each step gained reaction mixture, carbonic acid gas can separate and recycle through the mode that reclaims gas with ammonia, thereby guarantees that product gets into subsequent processing with the form of not having carbonic acid gas and ammonia basically; The dissolubility difference of end product methionine(Met) and sodium sulfate is very big; Can utilize dissolubility difference that the crystallization of DL-methionine(Met) is separated out, the mother liquor after the crystallization can evaporate reclaim(ed) sulfuric acid sodium, and the sodium sulfate of recovery can be used as product and sells.
Preferably, the molar ratio of said sodium hydroxide and glycolylurea is 1.8-2.2:1.On the one hand, owing to can generate yellow soda ash in the reaction process, and yellow soda ash is strong base-weak acid salt, in follow-up hydrolytic process, also can play the effect of basic catalyst, therefore, can suitably reduce the charging capacity of sodium hydroxide; On the other hand; Excessive sodium hydroxide can increase follow-up with in the acid with the growing amount of DL-methionine(Met) sodium by product inorganic acid salt when preparing the DL-methionine(Met); Thereby make troubles for the Crystallization Separation of DL-methionine(Met), therefore, the charging capacity of sodium hydroxide is unsuitable excessive too many.
Preferably, the pressure-controlling in said three grades of series connection tank reactors is at 1.6-1.8MPa, and total reaction time is 16-20 minute.Under this optimum condition, speed of reaction is fast, and the cycle is short, and productive rate is high.
Preferably, the inwall and the web member material of said three grades of series connection tank reactors are zirconium or Zirconium alloy material.Result of study shows, hydrolysis prepares DL-methionine(Met) salt similar catalyzer appearance effect is arranged zirconium to glycolylurea, and on the other hand, zirconium or Zirconium alloy material have the erosion resistance of height.
Preferably, be connected with the water vapour that pressure is 0.2-0.8MPa in the said gas stripping column tower.The gas band liquid phenomenon of the too high then recovered overhead of water vapour pressure is serious, causes DL-methionine(Met) salt partial loss, reduces yield, and the carbonic acid gas that makes with recovery gas and the aqueous solution bad of ammonia, influences the preparation of glycolylurea; Dissolved ammonia reclaims insufficient in the too low then solution of water vapor pressure.Under this optimum condition, the recovery of carbonic acid gas and ammonia is more abundant, the basic free of losses of DL-methionine(Met) salt.
Preferably, saidly to 0.8-1.0MPa, send into gas stripping column through the pressure release valve pressure release again from the effusive liquid of third stage tank reactor discharge port.Reaction mixture is directly sent into the atmospheric gas stripper with high temperature, high voltage style, easily tower body is caused corrosion.Suitably send into the atmospheric gas stripper again after the pressure release, not only can well carry out water vapour gas and propose operation, can also reduce the tower body corrosion, prolong the equipment usage period.
Beneficial effect of the present invention is: the present invention adopts three grades of alternative single reaction vessels of the prior art of series connection tank reactors to carry out the basic hydrolysis of glycolylurea; Can easily realize gradient increased temperature, high efficient mixed, fully reaction; Speed of reaction is fast, and by product is few, and yield is high; Adopt the carbonic acid gas and the ammonia that generate in the reaction of atmospheric steam gas stripping column Separation and Recovery; Do not bring new impurity into; Not only can make things convenient for, realize efficiently the refining of DL-methionine(Met) salt, and the gas mixture of water vapour, dioxide gas and the ammonia of discharging from cat head can be used for reclaiming the aqueous solution of preparation carbonic acid gas and ammonia and the preparation that circulation is used for glycolylurea; Preparation facilities of the present invention and method have a good application prospect.
Description of drawings
In order to make the object of the invention, technical scheme and advantage clearer, will combine accompanying drawing that the present invention is made further detailed description below, wherein:
Fig. 1 is an apparatus and method schematic flow sheet of the present invention.
Embodiment
Below will carry out detailed description to the preferred embodiments of the present invention with reference to accompanying drawing.
Device synoptic diagram of the present invention is as shown in Figure 1.The preparation facilities of DL-methionine(Met) salt comprises three grades of series connection tank reactors and gas stripping column; Wherein the discharge port of first step tank reactor is communicated with the opening for feed of second stage tank reactor; The discharge port of second stage tank reactor is communicated with the opening for feed of third stage tank reactor, and the discharge port of third stage tank reactor is communicated with the opening for feed of gas stripping column.
As a preferred embodiment of apparatus of the present invention, the cat head of said gas stripping column also is provided with gas-liquid separator; Said third stage tank reactor discharge port also is provided with pressure release valve to the path of gas stripping column opening for feed.
Method flow synoptic diagram of the present invention is as shown in Figure 1.Successively the aqueous sodium hydroxide solution and the glycolylurea aqueous solution are joined in the first step tank reactor continuously; The aqueous sodium hydroxide solution and the glycolylurea aqueous solution adopt the high-precision measuring pump delivery, accurately control the ingredient proportion of sodium hydroxide and glycolylurea through mass flowmeter.Material high efficient mixed and under the certain pressure condition, carry out continuous three grades of gradient increased temperatures reaction in three grades of series connection tank reactors; The inwall and the web member material of three grades of series connection tank reactors are Zirconium alloy material; Wherein the temperature in the first step tank reactor is from 50 ℃ of gradient increased temperatures to 100 ℃; Temperature in the tank reactor of the second stage is from 100 ℃ of gradient increased temperatures to 140 ℃, and the temperature in the third stage tank reactor is from 140 ℃ of gradient increased temperatures to 180 ℃.To 0.8-1.0MPa, send into carbonic acid gas and the ammonia that generates the reaction of gas stripping column Separation and Recovery through the pressure release valve pressure release from the effusive liquid of third stage tank reactor discharge port; The gas stripping column cat head is provided with gas-liquid separator; Tower top pressure is that normal pressure, temperature are 101 ℃; Be connected with the water vapour that pressure is 0.5MPa in the tower, the gas mixture of discharging from cat head is used to reclaim the aqueous solution of preparation feedback feed carbon dioxide and ammonia and the preparation that circulation is used for glycolylurea, and the liquid that goes out from tower bottom flow is DL-methionine(Met) sodium water solution; Also comprise by product yellow soda ash in this solution, can be directly with acid neutralization preparation DL-methionine(Met).The condition and the result of specific embodiment see table 1.
The preparation condition and the result of table 1 DL-methionine(Met) sodium
Can find out from the foregoing description 1-7; Though the reaction mol ratio of glycolylurea and sodium hydroxide is 1:2; But owing to will generate by product yellow soda ash in the reaction process; And the yellow soda ash that generates also can play the effect of basic catalyst in follow-up hydrolysis reaction, so the molar ratio of sodium hydroxide and glycolylurea is preferably 1.8-2.2, and the consumption of sodium hydroxide is unsuitable too much; Otherwise can increase greatly follow-up with in the acid with the growing amount of DL-methionine(Met) sodium by product inorganic acid salt when preparing the DL-methionine(Met), and make troubles for the Crystallization Separation of DL-methionine(Met).Can find out that from embodiment 8-14 if reaction time is too short, the temperature of material from Reactor inlet to outlet rises too fast; Can cause glycolylurea to be decomposed into methylthiopropionaldehyde, and produce polymerization, thereby reduce the yield of DL-methionine(Met) sodium; Therefore, reaction time was advisable with 16-20 minute.In the glycolylurea hydrolyzing process, control reaction pressure, purpose is that the assurance entire reaction is carried out under liquid phase, to improve speed of reaction.Can find out that from embodiment 15-22 during hypotony, speed of reaction is low, incomplete at the reaction time internal reaction, influence the yield of DL-methionine(Met) sodium; Hypertonia is then had relatively high expectations to materials such as variable valve in the industrial production, and therefore, reaction pressure is preferably 1.4-2.6MPa, more preferably 1.6-1.8MPa.Can find out from embodiment 23-35, adopt mass flowmeter, under the optimal conditions of feed ratio, reaction time, reaction pressure, carry out 8 times and 4 times continuously and produce; Speed of reaction is fast, and by product is few, and yield is high; Technology stability is good, and the serialization production level is high.
The present invention to three grades of series connection tank reactors and one-level tank reactors under the same conditions reaction effect carried out comparison (embodiment 35).The result shows; Use single tank reactor to carry out 50-180 ℃ of gradient increased temperature reaction, because the intensification span is bigger, temperature is wayward; Cause the side reaction such as degraded, polymerization of glycolylurea easily; And use single tank reactor can't guarantee competent reaction time, can not fully react, the yield of DL-methionine(Met) sodium lower (82.51%).
The present invention has also carried out relatively (embodiment 36) to the reaction effect of the tank reactor of the tank reactor of zirconium alloy material and ordinary steel material.The result shows, compares with the tank reactor of zirconium alloy material, uses the tank reactor of ordinary steel material, the DL-methionine(Met) sodium yield lower (92.28%) under same reaction conditions.
To 0.8-1.0MPa, send into gas stripping column through the pressure release valve pressure release from the effusive highly pressurised liquid of third stage tank reactor discharge port; Carbonic acid gas and the ammonia that generates in the reaction is reclaimed in low-pressure water steam flash distillation with different pressures; Realize the refining of DL-methionine(Met) sodium, effect is seen table 2-4.
Each material component and content (kg/h) after table 2 0.5MPa water vapour gas shifts to an earlier date
Each material component and content (kg/h) after table 3 0.2MPa water vapour gas shifts to an earlier date
Each material component and content (kg/h) after table 4 0.8MPa water vapour gas shifts to an earlier date
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although through invention has been described with reference to the preferred embodiments of the present invention; But those of ordinary skill in the art should be appreciated that and can make various changes to it in form with on the details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (10)
1.DL-the preparation facilities of methionine(Met) salt; It is characterized in that; Comprise three grades of series connection tank reactors and gas stripping column; Wherein the discharge port of first step tank reactor is communicated with the opening for feed of second stage tank reactor, and the discharge port of second stage tank reactor is communicated with the opening for feed of third stage tank reactor, and the discharge port of third stage tank reactor is communicated with the opening for feed of gas stripping column.
2. the preparation facilities of DL-methionine(Met) salt according to claim 1 is characterized in that the cat head of said gas stripping column also is provided with gas-liquid separator.
3. the preparation facilities of DL-methionine(Met) salt according to claim 1 and 2 is characterized in that, said third stage tank reactor discharge port also is provided with pressure release valve to the path of gas stripping column opening for feed.
4. utilize each said device of claim 1 to 3 to prepare the method for DL-methionine(Met) salt; It is characterized in that; With carrying out continuous third order reaction in the glycolylurea aqueous solution and three grades of series connection of the inorganic base aqueous solution feeding tank reactors; The pressure-controlling of three grades of series connection in the tank reactor is at 1.4-2.6MPa; Wherein the temperature in the first step tank reactor is from 50 ℃ of gradient increased temperatures to 100 ℃; Temperature in the tank reactor of the second stage is from 100 ℃ of gradient increased temperatures to 140 ℃, and the temperature in the third stage tank reactor is from 140 ℃ of gradient increased temperatures to 180 ℃, sends into carbonic acid gas and the ammonia that generates the reaction of atmospheric steam gas stripping column Separation and Recovery from the effusive liquid of third stage tank reactor discharge port; The liquid that goes out from tower bottom flow is DL-methionine(Met) salt brine solution, and the gas mixture of discharging from cat head is used to reclaim the aqueous solution of preparation carbonic acid gas and ammonia and the preparation that circulation is used for glycolylurea.
5. method according to claim 4 is characterized in that, the pressure-controlling in said three grades of series connection tank reactors is at 1.6-1.8MPa, and total reaction time is 16-20 minute.
6. method according to claim 4 is characterized in that, said mineral alkali is a sodium hydroxide.
7. method according to claim 6 is characterized in that, the molar ratio of said sodium hydroxide and glycolylurea is 1.8-2.2:1.
8. method according to claim 4 is characterized in that, the inwall and the web member material of said three grades of series connection tank reactors are zirconium or Zirconium alloy material.
9. method according to claim 4 is characterized in that, is connected with the water vapour that pressure is 0.2-0.8MPa in the said gas stripping column tower.
10. according to claim 4 or 9 described methods, it is characterized in that, saidly to 0.8-1.0MPa, send into gas stripping column through the pressure release valve pressure release again from the effusive liquid of third stage tank reactor discharge port.
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| CN103864633A (en) * | 2014-04-03 | 2014-06-18 | 重庆紫光国际化工有限责任公司 | Method for preparing alpha-aminoisobutyric acid |
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| CN106748932B (en) * | 2016-12-20 | 2019-03-22 | 山东新和成氨基酸有限公司 | A kind of post-processing approach and device preparing methionine |
| WO2019124370A1 (en) * | 2017-12-19 | 2019-06-27 | 住友化学株式会社 | Method for manufacturing methionine |
| JPWO2019124370A1 (en) * | 2017-12-19 | 2020-12-10 | 住友化学株式会社 | How to make methionine |
| US11192855B2 (en) | 2017-12-19 | 2021-12-07 | Sumitomo Chemical Company, Limited | Method for manufacturing methionine |
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Effective date of registration: 20160526 Address after: 755000 the Ningxia Hui Autonomous Region central defence industrial park Patentee after: NINGXIA ZIGUANG TIANHUA METHIONINE CO., LTD. Address before: 408200, Chongqing County, Zhenjiang Town, Fengdu village Xiangjiaba Patentee before: Chongqing Unisplendour Tianhua Methionine Co., Ltd. |