CN109160893A - A kind of preparation method of first seleno propionic aldehyde - Google Patents
A kind of preparation method of first seleno propionic aldehyde Download PDFInfo
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- CN109160893A CN109160893A CN201811196648.5A CN201811196648A CN109160893A CN 109160893 A CN109160893 A CN 109160893A CN 201811196648 A CN201811196648 A CN 201811196648A CN 109160893 A CN109160893 A CN 109160893A
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- propionic aldehyde
- hydroselenide
- methyl
- seleno
- seleno propionic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
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Abstract
The invention discloses a kind of methods by methyl-hydroselenide and methacrylaldehyde reactive liquid solution preparation first seleno propionic aldehyde, this method is the part reaction product that will flow out from reactor as the Absorption of Medium methyl-hydroselenide gas of circular response, it is uniformly mixed again with the methacrylaldehyde liquid containing catalyst, reactor is passed through to be reacted, the reactant liquid flowed out from reactor is divided into two parts, a part isolates and purifies process into subsequent as crude product, and another part is recycled to methyl-hydroselenide absorbing medium as circulation fluid and continues next round reaction.The present invention contributes to form the reaction mixture of relatively stable, the equal perseverance of temperature, concentration and reaction speed, it can be avoided because of methyl-hydroselenide or by-product generate caused by methacrylaldehyde local concentration is excessively high and/or hot-spot, improve the purity and yield of first seleno propionic aldehyde product.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation method of first seleno propionic aldehyde.
Background technique
Patent CN1219760C disclose it is a kind of selenomethionine is prepared using glycolylurea method principle, through addition, cyclization, water
Solution neutralizes four-step reaction, obtains selenomethionine: reacting after addition reaction occurs with methyl-hydroselenide as raw material using methacrylaldehyde with NaCN
Cyclization, then open loop at high temperature under high pressure, finally hydrolysis obtains selenomethionine in hydrochloric acid solution, and yield is 95% or more.Though
The preparation method of first seleno propionic aldehyde is disclosed in right patent CN1219760C, but there is no detailed open first selenos for the patent
The preparation process condition of propionic aldehyde only roughly selects copper acetate as catalyst, this necessarily brings copper ion to subsequent product
Pollution, causes the color of first seleno propionic aldehyde product often to show blue, to influence the appearance and subsequent use of product.For
It completely removes its copper ion completely to need to carry out largely to wash and rectification process repeatedly, this necessarily causes to generate big
The washing waste water and a large amount of energy of waste of amount, and in distillation process, when long at high operating temperatures due to first seleno propionic aldehyde
Between stop, decomposition, polymerization can be generated, it is relatively low so as to cause rectifying single yield, generate a large amount of stenches, reluctant tail
Gas.And make catalyst using copper acetate, in the preparation process of first seleno propionic aldehyde, it is easy the residual objects such as hemiacetal and full reduced aldehyde
Matter, these substances are often exactly the reason of leading to high-boiling components, these high-boiling components generate another it is direct the reason is that because
During rectifying isolates and purifies first seleno propionic aldehyde, material is in the condition of high temperature for a long time.For handling these high-boiling components
The only resource is exactly to carry out burning disposal, this not only waste of resource, but also pollution environment.
Summary of the invention
The purpose of the present invention is being the immature in view of the prior art or existing above problem, a kind of first is provided
The preparation method of seleno propionic aldehyde.
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out from reactor as circular response, the medium are first used for
Methyl-hydroselenide gas is absorbed, is cooled to lower than the temperature in reactor, then be uniformly mixed with the methacrylaldehyde liquid containing catalyst, is led to
Enter in reactor, reaction generates first seleno propionic aldehyde, the liquid containing first seleno propionic aldehyde flowed out from reactor at the reaction temperatures
Precursor reactant object is divided into two parts, and a part isolates and purifies process into subsequent as crude product to be processed, and another part is made
The methyl-hydroselenide gas absorption for continuing next round for the medium of cyclic absorption methyl-hydroselenide, continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:0.95~2.0:
0.00095~0.002, preferably 1:1.05~1.20:0.00105~0.0012.
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 0.5~2.0, preferably 0.5~1.0.
It may further be preferable that the reaction temperature be 20 DEG C~75 DEG C, preferably 30 DEG C~50 DEG C, particularly preferred 30 DEG C~
40℃。
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor 50%~75% as crude product to be processed into
Enter it is subsequent isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 25%~50% be used as cyclic absorption first selenium
The methyl-hydroselenide gas that the medium of alcohol continues next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 35 DEG C~60 DEG C, and preferably 40 DEG C~50 DEG C, particularly preferred 40 DEG C~45 DEG C, the light component stripped is by being condensed back to
Receive the preparation for being recycled to the first seleno propionic aldehyde of lower batch.
The purity of the first seleno propionic aldehyde product is 99.0% or more, 98% or more yield.
The beneficial effects of the present invention are: the present invention is detailed for the first time to elaborate the preparation method of first seleno propionic aldehyde, provides
It is a kind of it is practicable, can be with the preparation process of the first seleno propionic aldehyde of large-scale production.The present invention uses liquid liquid hybrid reaction,
Make the mixing of its reaction system sufficiently, it can be to avoid because of methyl-hydroselenide or caused by methacrylaldehyde local concentration be excessively high and/or hot-spot
Side reaction reduces the generation of by-product；Reaction mass, which is partly recycled to, absorbs methyl-hydroselenide gas, reduces methyl-hydroselenide and individually condenses
Energy consumption, so that its methyl-hydroselenide is fully absorbed and is reacted, obtained first seleno propionic aldehyde reactant is only stripped, removal
Light component avoids the high-boiling components of conventional high-temperature rectifying formation, greatly reduces by-product generation, improves the production of first seleno propionic aldehyde
The purity and yield of object, the product of available main 99% or more content, yield have reached 98% or more (in terms of methacrylaldehyde).
Specific embodiment
Embodiment 1
1287.0000 grams of the sodium methyl-hydroselenide aqueous solution (2.2 moles) that mass percentage is 20% is added in the reactor, then
120.0000 grams of the sulfuric acid (1.2 moles) that mass percentage is 98% is added, reaction temperature is controlled at 50 DEG C, first selenium out
Alcohol gas, using 120.0000 grams of reaction solution of first seleno propionic aldehyde, is absorbed under the conditions of -20 DEG C, is obtained after washing
327.0000 gram mixed liquor, for reacting in next step.
To configuration by the supply port for methacrylaldehyde and catalyst, the reactor for the supply port of methyl-hydroselenide,
The methacrylaldehyde (purity 99.0%) of (2.0 moles) is packed into reactor by the supply port of methacrylaldehyde and catalyst and is urged
113.3638 grams of mixture of agent (0.1738 gram of pyridine, 0.06 gram of acetic acid), by the supply port of methyl-hydroselenide to reactor
It is middle that 327.0000 grams of methyl-hydroselenide mixed liquors obtained above are added, and reacted in 30 DEG C to 50 DEG C of reaction temperature, it goes through
When 30 minutes reaction time, obtain 440.3638 grams of reaction mixture.Obtained reaction mixture is divided into two parts, one
Divide 264.2183 grams for stripping, which is such that the reaction mixture of the part being heated to 60 DEG C, then
The nitrogen (50 DEG C) for being passed through preheating carries out purging and removes light component, and cooling under the conditions of -30 DEG C of the gas process of purging is led through analysis
If the complete methyl-hydroselenide of unreacted and 14.366 grams of methacrylaldehyde, are recycled to the synthesis of first seleno propionic aldehyde next time, after purging
251.1078 grams of first seleno propionic aldehyde is obtained, yield 99%, purity 99.5%, wherein high-boiling components mass percentage is lower than 0.3%.
Absorbing medium of 176.1455 grams of the another part reaction mixture circulations for methyl-hydroselenide gas next time is used.
Embodiment 2
1199.2500 grams of the sodium methyl-hydroselenide aqueous solution (2.05 moles) that mass percentage is 20% is added in the reactor, then
120.0000 grams of the sulfuric acid (1.2 moles) that mass percentage is 98% is added, reaction temperature is controlled at 50 DEG C, first selenium out
Alcohol gas, using 176.1455 grams of reaction solution of the first seleno propionic aldehyde of embodiment 1, absorbs after washing under the conditions of -20 DEG C,
370.8955 grams of mixed liquors are obtained, for reacting in next step.
To configuration by the supply port for methacrylaldehyde and catalyst, the reactor for the supply port of methyl-hydroselenide,
The methacrylaldehyde (purity 99.0%) of (2.0 moles) is packed into reactor by the supply port of methacrylaldehyde and catalyst and is urged
The nitrogen purging that 113.3638 grams of the mixture and embodiment 1 of agent (0.1738 gram of pyridine, 0.0600 gram of acetic acid) obtain
14.3660 grams of condensate, 370.8955 grams of methyl-hydroselenides obtained above are added into reactor by the supply port of methyl-hydroselenide
Mixed liquor, and reacted in 40 DEG C to 50 DEG C of reaction temperature, 30 minutes reaction time is lasted, reaction mixture is obtained
498.6253 gram.Obtained reaction mixture is divided into two parts, 322.4798 grams of a part are used to strip, the steam stripped operation
It is such that the reaction mixture of the part being heated to 60 DEG C, the nitrogen (50 DEG C) for then passing to preheating carries out purging removing
Light component, it is cooling under the conditions of -30 DEG C of the gas process of purging, it is mainly the complete methyl-hydroselenide and methacrylaldehyde of unreacted through analysis
14.366 grams, it is recycled to the synthesis of first seleno propionic aldehyde next time, obtains 308.1138 grams of first seleno propionic aldehyde, yield after purging
99%, purity 99.5%, wherein high-boiling components mass percentage is lower than 0.2%.
Absorbing medium of 176.1455 grams of the another part reaction mixture circulations for methyl-hydroselenide gas next time is used.
Comparison implements 1
1287.0000 grams of the sodium methyl-hydroselenide aqueous solution (2.2 moles) that mass percentage is 20% is added in the reactor, then
120.0000 grams of the sulfuric acid (1.2 moles) that mass percentage is 98% is added, reaction temperature is controlled at 50 DEG C, first selenium out
Alcohol gas is after washing for reacting in next step.
To configuration by the supply port for methacrylaldehyde and catalyst, the reactor for the supply port of methyl-hydroselenide,
The methacrylaldehyde (purity 99.0%) of (2.0 moles) is packed into reactor by the supply port of methacrylaldehyde and catalyst and is urged
113.3638 grams of mixture of agent (0.1738 gram of pyridine, 0.0600 gram of acetic acid), by the supply port of methyl-hydroselenide to reaction
Be passed through in device it is above-mentioned obtain methyl-hydroselenide gas, and reacted in 40 DEG C to 50 DEG C of reaction temperature, last 30 minutes anti-
Between seasonable, 322.3638 grams of reaction mixture are obtained.Obtained reaction mixture is directly used in stripping, which is
It is such: the reaction mixture of the part to be heated to 60 DEG C, the nitrogen (50 DEG C) for then passing to preheating carries out purging and removes gently
Component, it is cooling under the conditions of -30 DEG C of the gas process of purging, it is mainly the complete methyl-hydroselenide and methacrylaldehyde of unreacted through analysis
45.1426 grams, it is recycled to the synthesis of first seleno propionic aldehyde next time, obtains 277.2212 grams of first seleno propionic aldehyde after purging, is received
Rate 89%, purity 97.0%, wherein high-boiling components mass percentage is 2.8%.
Comparison implements 2
1287.0000 grams of the sodium methyl-hydroselenide aqueous solution (2.2 moles) that mass percentage is 20% is added in the reactor, then
120.0000 grams of the sulfuric acid (1.2 moles) that mass percentage is 98% is added, reaction temperature is controlled at 50 DEG C, first selenium out
Alcohol gas is cooled to -30 DEG C after washing and obtains 209.0000 grams of methyl-hydroselenide liquid, for reacting in next step.
To configuration by the supply port for methacrylaldehyde and catalyst, the reactor for the supply port of methyl-hydroselenide,
The methacrylaldehyde (purity 99.0%) of (2.0 moles) is packed into reactor by the supply port of methacrylaldehyde and catalyst and is urged
113.3638 grams of mixture of agent (0.1738 gram of pyridine, 0.0600 gram of acetic acid), by the supply port of methyl-hydroselenide to reaction
Be added in device it is above-mentioned obtain 209.0000 grams of methyl-hydroselenide liquid, and reacted, lasted in 40 DEG C to 50 DEG C of reaction temperature
30 minutes reaction time obtained 322.3638 grams of reaction mixture.Obtained reaction mixture is directly used in stripping, the vapour
The operation mentioned is such that the reaction mixture of the part being heated to 60 DEG C, then passes to (50 DEG C) of nitrogen progress of preheating
Purging removes light component, and cooling under the conditions of -30 DEG C of the gas process of purging is mainly the complete methyl-hydroselenide and third of unreacted through analysis
32.4315 grams of olefine aldehydr, it is recycled to the synthesis of first seleno propionic aldehyde next time, obtains first seleno propionic aldehyde 289.9323 after purging
Gram, yield 95%, purity 99.0%, wherein high-boiling components mass percentage is 0.5%.
Comparison implements 3
1287.0000 grams of the sodium methyl-hydroselenide aqueous solution (2.2 moles) that mass percentage is 20% is added in the reactor, then
120.0000 grams of the sulfuric acid (1.2 moles) that mass percentage is 98% is added, reaction temperature is controlled at 50 DEG C, first selenium out
Alcohol gas is cooled to -30 DEG C after washing and obtains 209.0000 grams of methyl-hydroselenide liquid, for reacting in next step.
To configuration by the supply port for methacrylaldehyde and catalyst, the reactor for the supply port of methyl-hydroselenide,
The methacrylaldehyde (purity 99.0%) of (2.0 moles) is packed into reactor by the supply port of methacrylaldehyde and catalyst and is urged
113.3638 grams of mixture of agent (0.1738 gram of pyridine, 0.0600 gram of acetic acid), by the supply port of methyl-hydroselenide to reaction
Be added in device it is above-mentioned obtain 209.0000 grams of methyl-hydroselenide liquid, and reacted, lasted in 40 DEG C to 50 DEG C of reaction temperature
30 minutes reaction time obtained 322.3638 grams of reaction mixture.By obtained reaction mixture directly under reduced pressure in 70
DEG C to 120 DEG C distill, to distill out first seleno propionic aldehyde, and respectively by light component and the residue of distillation (i.e. higher boiling oligomer)
Weighing.258.1095 grams of first seleno propionic aldehyde is obtained, yield 85%, purity 99.5%, wherein high-boiling components mass percentage is lower than
0.2%；Light component quality is 40.1426 grams, and residue (the i.e. higher boiling oligomer) quality of distillation is 24.1117 grams, is accounted for anti-
Answer liquid total weight 7.5%.
Embodiment 3
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will be from anti-
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out in device as circular response is answered, which is first used to absorb
Methyl-hydroselenide gas is cooled to lower than the temperature in reactor, then is uniformly mixed with the methacrylaldehyde liquid containing catalyst, is passed through anti-
It answers in device, reaction generates first seleno propionic aldehyde at the reaction temperatures, and the liquid containing first seleno propionic aldehyde flowed out from reactor is anti-
Object is answered to be divided into two parts, a part isolates and purifies process into subsequent as crude product to be processed, and another part is used as and follows
The methyl-hydroselenide gas that the medium that ring absorbs methyl-hydroselenide continues next round absorbs, and continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:0.95:
0.00095。
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 0.5.
It may further be preferable that the reaction temperature is 20 DEG C.
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The 75% of the liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor enters subsequent as crude product to be processed
Isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 25% as cyclic absorption methyl-hydroselenide medium after
The methyl-hydroselenide gas of continuous next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 35 DEG C, and the light component stripped is recycled to the preparation of the first seleno propionic aldehyde of lower batch by condensing recovery.
Embodiment 4
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will be from anti-
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out in device as circular response is answered, which is first used to absorb
Methyl-hydroselenide gas is cooled to lower than the temperature in reactor, then is uniformly mixed with the methacrylaldehyde liquid containing catalyst, is passed through anti-
It answers in device, reaction generates first seleno propionic aldehyde at the reaction temperatures, and the liquid containing first seleno propionic aldehyde flowed out from reactor is anti-
Object is answered to be divided into two parts, a part isolates and purifies process into subsequent as crude product to be processed, and another part is used as and follows
The methyl-hydroselenide gas that the medium that ring absorbs methyl-hydroselenide continues next round absorbs, and continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:1.05:
0.00105。
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 1.0.
It may further be preferable that the reaction temperature is 30 DEG C.
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The 50% of the liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor enters subsequent as crude product to be processed
Isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 50% as cyclic absorption methyl-hydroselenide medium after
The methyl-hydroselenide gas of continuous next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 40 DEG C, and the light component stripped is recycled to the preparation of the first seleno propionic aldehyde of lower batch by condensing recovery.
Embodiment 5
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will be from anti-
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out in device as circular response is answered, which is first used to absorb
Methyl-hydroselenide gas is cooled to lower than the temperature in reactor, then is uniformly mixed with the methacrylaldehyde liquid containing catalyst, is passed through anti-
It answers in device, reaction generates first seleno propionic aldehyde at the reaction temperatures, and the liquid containing first seleno propionic aldehyde flowed out from reactor is anti-
Object is answered to be divided into two parts, a part isolates and purifies process into subsequent as crude product to be processed, and another part is used as and follows
The methyl-hydroselenide gas that the medium that ring absorbs methyl-hydroselenide continues next round absorbs, and continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:1.20:
0.0012。
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 1.0.
It may further be preferable that the reaction temperature is 40 DEG C.
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The 50% of the liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor enters subsequent as crude product to be processed
Isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 50% as cyclic absorption methyl-hydroselenide medium after
The methyl-hydroselenide gas of continuous next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 45 DEG C, and the light component stripped is recycled to the preparation of the first seleno propionic aldehyde of lower batch by condensing recovery.
Embodiment 6
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will be from anti-
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out in device as circular response is answered, which is first used to absorb
Methyl-hydroselenide gas is cooled to lower than the temperature in reactor, then is uniformly mixed with the methacrylaldehyde liquid containing catalyst, is passed through anti-
It answers in device, reaction generates first seleno propionic aldehyde at the reaction temperatures, and the liquid containing first seleno propionic aldehyde flowed out from reactor is anti-
Object is answered to be divided into two parts, a part isolates and purifies process into subsequent as crude product to be processed, and another part is used as and follows
The methyl-hydroselenide gas that the medium that ring absorbs methyl-hydroselenide continues next round absorbs, and continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:1.20:
0.0012。
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 1.0.
It may further be preferable that the reaction temperature is 50 DEG C.
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The 50% of the liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor enters subsequent as crude product to be processed
Isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 50% as cyclic absorption methyl-hydroselenide medium after
The methyl-hydroselenide gas of continuous next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 50 DEG C, and the light component stripped is recycled to the preparation of the first seleno propionic aldehyde of lower batch by condensing recovery.
Embodiment 7
A kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, will be from anti-
Medium of the partially liq reactant for containing first seleno propionic aldehyde flowed out in device as circular response is answered, which is first used to absorb
Methyl-hydroselenide gas is cooled to lower than the temperature in reactor, then is uniformly mixed with the methacrylaldehyde liquid containing catalyst, is passed through anti-
It answers in device, reaction generates first seleno propionic aldehyde at the reaction temperatures, and the liquid containing first seleno propionic aldehyde flowed out from reactor is anti-
Object is answered to be divided into two parts, a part isolates and purifies process into subsequent as crude product to be processed, and another part is used as and follows
The methyl-hydroselenide gas that the medium that ring absorbs methyl-hydroselenide continues next round absorbs, and continues next round reaction after absorption.
It may further be preferable that the molar ratio of the methacrylaldehyde, methyl-hydroselenide and catalyst is 1:2.0:
0.002。
It may further be preferable that the catalyst is organic base or transition metal acetate, the organic base is morpholine, pyrrole
One of pyridine, triethylamine and ethanol amine are a variety of, and transition metal acetate is one of copper acetate and zinc acetate or more
Kind.
It may further be preferable that the catalyst participates in reacting after mixing with organic acid；The organic acid is formic acid, vinegar
One or more of acid, propionic acid and butyric acid.
It may further be preferable that the molar ratio of the catalyst and organic acid is 2.0.
It may further be preferable that the reaction temperature is 75 DEG C.
It may further be preferable that the liquid reactants containing first seleno propionic aldehyde flowed out from reactor are divided into two parts,
The 75% of the liquid reactions amount of substance containing first seleno propionic aldehyde flowed out from reactor enters subsequent as crude product to be processed
Isolate and purify process, the liquid reactions amount of substance containing first seleno propionic aldehyde 25 as cyclic absorption methyl-hydroselenide medium continue
The methyl-hydroselenide gas of next round absorbs.
It may further be preferable that it is described isolate and purify process one of be evaporated off using flash distillation, stripping or negative pressure or
It is a variety of.
It may further be preferable that the process that isolates and purifies is using stripping, the steam stripped carrier is nitrogen, nitrogen
Temperature is 60 DEG C, and the light component stripped is recycled to the preparation of the first seleno propionic aldehyde of lower batch by condensing recovery.
Claims (10)
1. a kind of preparation method of first seleno propionic aldehyde prepares first seleno propionic aldehyde using methyl-hydroselenide and methacrylaldehyde reactive liquid solution, special
Sign is, using the partially liq reactant for containing first seleno propionic aldehyde flowed out from reactor as the medium of circular response, is somebody's turn to do
Medium is first used to absorb methyl-hydroselenide gas, is cooled to lower than the temperature in reactor, then with the methacrylaldehyde liquid containing catalyst
It is uniformly mixed, is passed through in reactor, reaction generates first seleno propionic aldehyde at the reaction temperatures, and what is flowed out from reactor contains first selenium
The liquid reactants of base propionic aldehyde are divided into two parts, and a part isolates and purifies process into subsequent as crude product to be processed, separately
Outer a part is absorbed as the methyl-hydroselenide gas that the medium of cyclic absorption methyl-hydroselenide continues next round, is continued after absorption next
Wheel reaction.
2. a kind of preparation method of first seleno propionic aldehyde as described in claim 1, which is characterized in that the methacrylaldehyde, first selenium
The molar ratio of pure and mild catalyst is 1:0.95~2.0:0.00095~0.002.
3. a kind of preparation method of first seleno propionic aldehyde as described in claim 1, which is characterized in that the catalyst is organic base
Or transition metal acetate, the organic base are one of morpholine, pyridine, triethylamine and ethanol amine or a variety of, transition metal
Acetate is one or more of copper acetate and zinc acetate.
4. a kind of preparation method of first seleno propionic aldehyde as claimed in claim 3, which is characterized in that the catalyst and organic acid
Reaction is participated in after mixing；The organic acid is one or more of formic acid, acetic acid, propionic acid and butyric acid.
5. a kind of preparation method of first seleno propionic aldehyde as claimed in claim 4, which is characterized in that the catalyst and organic acid
Molar ratio be 0.5~2.0.
6. a kind of preparation method of first seleno propionic aldehyde as described in claim 1, which is characterized in that the reaction temperature is 20 DEG C
~75 DEG C.
7. a kind of preparation method of first seleno propionic aldehyde as described in claim 1, which is characterized in that is flowed out from reactor contains
There are the liquid reactants of first seleno propionic aldehyde to be divided into two parts, i.e., the liquid reactions containing first seleno propionic aldehyde flowed out from reactor
The 50%~75% of amount of substance isolates and purifies process into subsequent as crude product to be processed, and the liquid containing first seleno propionic aldehyde is anti-
Answer the 25%~50% of the amount of substance methyl-hydroselenide gas absorption for continuing next round as the medium of cyclic absorption methyl-hydroselenide.
8. a kind of preparation method of first seleno propionic aldehyde as claimed in claim 1 or 7, which is characterized in that described to isolate and purify work
Sequence one or more of is evaporated off using flash distillation, stripping or negative pressure.
9. a kind of preparation method of first seleno propionic aldehyde as claimed in claim 8, which is characterized in that the process that isolates and purifies is adopted
With stripping, the steam stripped carrier is nitrogen, and the temperature of nitrogen is 35 DEG C~60 DEG C, and the light component stripped is by condensation
Recycling is recycled to the preparation of the first seleno propionic aldehyde of lower batch.
10. a kind of preparation method of first seleno propionic aldehyde as claimed in claim 8, which is characterized in that described to isolate and purify process
Using stripping, the steam stripped carrier is nitrogen, and the temperature of nitrogen is 40 DEG C~45 DEG C, and the light component stripped is through being subcooled
It is solidifying to recycle the preparation for being recycled to the first seleno propionic aldehyde of lower batch.
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| CN1152913A (en) * | 1994-07-11 | 1997-06-25 | 诺沃斯国际公司 | Process for the preparation of 3-(methylthio) propanal |
| CN1369483A (en) * | 2002-02-28 | 2002-09-18 | 董国臣 | Methyleneseleno propanel method for preparing selenoic methionine |
| CN1705641A (en) * | 2002-10-24 | 2005-12-07 | 安迪苏爱尔兰有限公司 | Process for the production of 3-methylthiopropanal |
| CN102796030A (en) * | 2012-08-31 | 2012-11-28 | 重庆紫光天化蛋氨酸有限责任公司 | Method and device for preparing 3-methylmercapto-propionaldehyde through liquid-liquid reaction of methyl mercaptan and acraldehyde |
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2018
- 2018-10-15 CN CN201811196648.5A patent/CN109160893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152913A (en) * | 1994-07-11 | 1997-06-25 | 诺沃斯国际公司 | Process for the preparation of 3-(methylthio) propanal |
| CN1369483A (en) * | 2002-02-28 | 2002-09-18 | 董国臣 | Methyleneseleno propanel method for preparing selenoic methionine |
| CN1705641A (en) * | 2002-10-24 | 2005-12-07 | 安迪苏爱尔兰有限公司 | Process for the production of 3-methylthiopropanal |
| CN102796030A (en) * | 2012-08-31 | 2012-11-28 | 重庆紫光天化蛋氨酸有限责任公司 | Method and device for preparing 3-methylmercapto-propionaldehyde through liquid-liquid reaction of methyl mercaptan and acraldehyde |
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Application publication date: 20190108 |