CN104910031B - The combine production method and device of glycine and hydantoins - Google Patents
The combine production method and device of glycine and hydantoins Download PDFInfo
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- CN104910031B CN104910031B CN201510199303.5A CN201510199303A CN104910031B CN 104910031 B CN104910031 B CN 104910031B CN 201510199303 A CN201510199303 A CN 201510199303A CN 104910031 B CN104910031 B CN 104910031B
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Abstract
The invention discloses the combine production method and device of a kind of glycine and hydantoins, it is with hydroxyacetonitrile, ammonia, carbon dioxide and water, or with hydroxyacetonitrile, ammonia, ammonium hydrogen carbonate and water, or with hydroxyacetonitrile, ammonium carbonate, carbon dioxide and water as raw material, by hydroxyacetonitrile in reaction system：Ammonia：Carbon dioxide：The mol ratio of water is 1:3~5:2~4:46～50, temperature be 60 DEG C～120 DEG C, pressure be 1.5MPa～3.0MPa under the conditions of carry out ammonia oxonation, ammonia oxonation liquid is obtained；Again by ammonia oxonation liquid acidified prepared hydantoins product, or ammonia oxonation liquid Jing ammonifications hydrolysis is obtained into glycine product；The inventive method and device not only can save the investment of production equipment of glycine and hydantoins, reduce production cost, it is easy to adjust the yield of glycine and hydantoins, it is particularly possible to which hydrolyzing for glycine presence is thorough, have the shortcomings that iminodiacetic acid generation, many accessory substances, glycine purification difficult, yield are low to overcome current glycolylurea method to prepare.
Description
Technical field
The invention belongs to chemical field, is related to a kind of method and device of two kinds of compounds of Joint Production.
Background technology
Hydroxyacetonitrile method production glycine is the new method reported in recent years.The method is divided into two kinds again：The first is as in
Described in state's patent CN1962611B, it is the ammonia spirit that hydroxyacetonitrile and ammoniacal liquor reaction are obtained aminoacetonitriles, in the solution
Add inorganic base to obtain the alkali solution liquid containing glycinate, neutralize, decolourize, concentrate fractional crystallization by alkali solution liquid deamination, with inorganic acid
And recrystallization, then respectively obtain glycine and inorganic salts；The shortcoming of the method is：Reaction scheme is longer, and process condition is severe
Carve, reacted de-salting operation is more numerous and diverse, and product is difficult to refine, glycine separates tired with iminodiacetic acid, nitrilotriacetic acid
Difficulty, and glycine crystallization mother liquid is difficult to recycled, glycine loss is larger, produces the inorganic salts and a large amount of hardly possiblies of a large amount of low values
With the waste water and dregs for processing, production cost is higher；For second glycolylurea method, the method be by hydroxyacetonitrile under high temperature, high pressure
Be synthesized hydantoins with carbon dioxide and ammoniacal liquor or with ammonium hydrogen carbonate and ammoniacal liquor, hydantoins again in certain temperature and
Hydrolysis under pressure obtains glycine, while discharging carbon dioxide and ammonia；The shortcoming of the method be hydrolyze not thoroughly, have imido
Base oxalic acid is produced, accessory substance is more, and glycine purification difficult, yield are low, in actual production the yield of glycine there was only 80%～
85%, the single extraction efficiency of glycine only has 72% or so.
The current main production process of hydantoins is glycine method and hydroxyacetonitrile method.Glycine method be with glycine,
NaOH and urea are raw material, in sulfuric acid absorption ammonia and sulfuric acid and obtain hydantoins, producing ammonium sulfate byproduct and sulfuric acid
Sodium, the method production cost are higher, and produce the inorganic salts of a large amount of low values.Hydroxyacetonitrile method is by hydroxyacetonitrile and bicarbonate
Ammonium is reacted with carbon dioxide and ammonia, then is concentrated, is acidified, decolourizing to obtain hydantoins product, the method low cost, yield
Height, is a good approach of industrialized production, but the scale using hydroxyacetonitrile method production hydantoins domestic at present is less.
The co-production raw material of glycine and hydantoins is all hydroxyacetonitrile, carbon dioxide and ammonia, and both productions are most
Big difference is the difference of rate of charge and reaction temperature, pressure and the time of material.Consider to be produced using same complete equipment simultaneously
The two, adjusts all highly beneficial to making full use of equipment, reducing production cost and produce, therefore, one Joint Production of exploitation is sweet
The technique of propylhomoserin and hydantoins is highly desirable to, especially overcome the hydrolysis of current glycolylurea method not thoroughly, have iminodiacetic acid
The low shortcoming of generation, many accessory substances, glycine purification difficult, yield.
The content of the invention
In view of this, it is an object of the invention to provide the combine production method and dress of a kind of glycine and hydantoins
Put, the two not only can be produced simultaneously using same complete equipment, make full use of equipment, reduce production cost, be easy to production to adjust,
Can especially overcome current glycolylurea method prepare the hydrolysis of glycine presence not thoroughly, have iminodiacetic acid to produce, accessory substance is more,
The low shortcoming of glycine purification difficult, yield.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1. glycine and the combine production method of hydantoins, comprise the following steps：
1）With hydroxyacetonitrile, ammonia, carbon dioxide and water as raw material, or with hydroxyacetonitrile, ammonia, ammonium hydrogen carbonate and water as original
Material, or with hydroxyacetonitrile, ammonium carbonate, carbon dioxide and water as raw material, by hydroxyacetonitrile in reaction system：Ammonia：Carbon dioxide：
The mol ratio of water is 1:3~5:2~4:46～50, temperature be 60 DEG C～120 DEG C, pressure be 1.5MPa～3.0MPa under the conditions of enter
Row ammonia oxonation, is obtained ammonia oxonation liquid；
2）With step 1）Obtained ammonia oxonation liquid be raw material, acidified prepared hydantoins product；
3）With step 1）Obtained ammonia oxonation liquid be raw material, Jing ammonifications hydrolysis be obtained glycine product.
The reaction principle of said method is as follows：
Step 1）In, when with hydroxyacetonitrile, ammonia, ammonium hydrogen carbonate and water, or with hydroxyacetonitrile, ammonium carbonate, carbon dioxide
With water be raw material when, the molar ratio system of each raw material is according to hydroxyacetonitrile in reaction system：Ammonia：Carbon dioxide：Water mole
Than for 1:3~5:2~4:46～50 are converted.
Further, step 1）Be with hydroxyacetonitrile, ammonia, carbon dioxide and water as raw material, temperature be 90 DEG C～100 DEG C,
For ammonia oxonation is carried out under the conditions of 1.5MPa～3.0MPa, reaction removes unreacted ammonia and carbon dioxide after terminating to pressure.
Further, step 2）It is with step 1）Obtained ammonia oxonation liquid is raw material, through concentration, acidifying, decolourizes, ties
Crystalline substance, is obtained hydantoins product.
Further, step 2）It is that ammonia oxonation liquid is evaporated to into 20wt%～80wt%, adds equivalent to concentrate
The concentrated sulfuric acid of the 98wt% of 10wt%～20wt%, carries out acidification reaction under the conditions of 40 DEG C～100 DEG C of temperature, and gained acidifying solution adds
Enter activated carbon, desolventing technology is carried out under the conditions of 40 DEG C～100 DEG C of temperature, finally crystallize under the conditions of 0 DEG C～20 DEG C of temperature, obtain
To hydantoins product.
Further, step 2）It is that ammonia oxonation liquid is evaporated to into 40wt%～80wt%, adds equivalent to concentrate
The concentrated sulfuric acid of the 98wt% of 12wt%～17wt%, carries out acidification reaction under the conditions of 80 DEG C～90 DEG C of temperature, and gained acidifying solution is added
Activated carbon, carries out desolventing technology under the conditions of 80 DEG C～90 DEG C of temperature, finally crystallizes under the conditions of 0 DEG C～20 DEG C of temperature, obtains
Hydantoins product.
Further, step 2）In the acidification reaction of the crystalline mother solution recycled of middle hydantoins to lower batch.
Further, step 3）With step 1）Obtained ammonia oxonation liquid is raw material, through ammonification hydrolysis, reclaims ammonia, takes off
Color, concentration, crystallization, are obtained glycine product.
Further, step 3）It is that ammonia oxonation liquid is added the ammonia or ammonia equivalent to 2 ~ 8 times of moles of hydroxyacetonitrile
Water, the hydrolysis 3～5 hours under the conditions of 120 DEG C～170 DEG C of temperature, after hydrolysis terminates, are reclaimed by stripping regime
Ammonia, is subsequently adding activated carbon, under the conditions of 40 DEG C～70 DEG C of temperature carries out desolventing technology, and gained destainer is evaporated to sweet ammonia
Acid concentration is not higher than 40wt%, finally crystallizes under the conditions of 0 DEG C～20 DEG C of temperature, obtains glycine product.
Further, step 3）It is that ammonia oxonation liquid is added the ammonia or ammonia equivalent to 3 ~ 5 times of moles of hydroxyacetonitrile
Water, the hydrolysis 3～4 hours under the conditions of 140 DEG C～165 DEG C of temperature, after hydrolysis terminates, are reclaimed by stripping regime
Ammonia, is subsequently adding activated carbon, under the conditions of 40 DEG C～70 DEG C of temperature carries out desolventing technology, and gained destainer is evaporated to sweet ammonia
Acid concentration is not higher than 40wt%, finally crystallizes under the conditions of 0 DEG C～10 DEG C of temperature, obtains glycine product.
Further, step 3）In the ammonification hydrolysis of the ammonia recycled of middle recovery to lower batch；The crystallization of glycine
During Recycling Mother Solution is applied to the crystallization operation of lower batch or in the ammonification hydrolysis of recycled to lower batch.
For realizing the device of glycine and the combine production method of hydantoins, including ammonia oxonation liquid production list
Unit, hydantoins production unit and glycine production unit, it is quiet that the ammonia oxonation liquid production unit includes being sequentially communicated
State blender I, tubular reactor I, stripping tower I and storage tank, the hydantoins production unit include acidizing device, described sweet
Propylhomoserin production unit includes the static mixer II and tubular reactor II being sequentially communicated, the ammonia oxonation liquid production unit
The outlet of middle storage tank is respectively by the charging aperture of acidizing device, glycine in valve I, valve II and hydantoins production unit
The charging aperture connection of static mixer II in production unit.
Further, the hydantoins production unit includes MVR vapo(u)rization systems I being sequentially communicated, acidizing device, decolourize dress
I, crystallization apparatus I, centrifugal device I and drying device I are put, the glycine production unit includes the static mixer being sequentially communicated
II, tubular reactor II, stripping tower II, decoloration device II, MVR vapo(u)rization system II, crystallization apparatus II, centrifugal device II and drying
Device II, in the ammonia oxonation liquid production unit, the outlet of storage tank passes through valve I, valve II respectively and hydantoins is given birth to
In product unit, in the charging aperture of MVR vapo(u)rization systems I, glycine production unit, the charging aperture of static mixer II is connected.
The beneficial effects of the present invention is：Compared with prior art, the present invention first with hydroxyacetonitrile, ammonia, carbon dioxide and
Water prepares ammonia oxonation liquid for raw material, then prepares hydantoins and glycine by raw material of ammonia oxonation liquid respectively, not only
The investment of production equipment of glycine and hydantoins can be saved, production cost is reduced, is easy to adjust glycine and hydantoins
Yield, it is particularly possible to overcome current glycolylurea method prepare the hydrolysis of glycine presence not thoroughly, have iminodiacetic acid to produce, it is secondary
Product is more, the shortcoming that glycine purification difficult, yield are low.
Description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, below in conjunction with accompanying drawing to the present invention
It is described further：
Fig. 1 is combine production method of the present invention and schematic device.
Specific embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment 1
The production of ammonia oxonation liquid：In the 5000ml voltage-resistant reactors of pressurization sampler and agitating device are possessed,
Water 2364g is added, ammonia 216.5g and carbon dioxide 420.4g is then passed to, is warming up to 100 DEG C, with 5.05g/min's
Speed is at the uniform velocity added dropwise the hydroxyl acetonitrile aqueous solution 453.8g of 40wt%, finishes reaction 1.5 hours, and the pressure of reaction system is
1.6MPa, is then removed under reduced pressure unreacted ammonia and carbon dioxide, obtains ammonia oxonation liquid.Gained ammonia oxonation liquid is put down
Two parts are divided into, the production of hydantoins and the production of glycine is carried out respectively.
The production of hydantoins：Ammonia oxonation liquid is evaporated to into 40wt%, is added equivalent to concentrate 15wt%'s
The concentrated sulfuric acid of 98wt%, 90 DEG C of acidification reactions 1 hour, gained acidifying solution use activated carbon decolorizing under conditions of 90 DEG C of insulation, decolourize
Liquid cooling afterwards is crystallized to 20 DEG C, suction filtration, and drying obtains hydantoins product 151.2g, yield 94%, purity 99%.Acyl in second
As acidifying acid in the acidification reaction of the crystalline mother solution recycled of urea to lower batch.
The production of glycine：Ammonia oxonation liquid is added the ammoniacal liquor 288.7g that 25wt% is added in autoclave（Ammonia
Molar ratio with hydroxyacetonitrile is 4:1）, 160 DEG C are warming up to immediately, self-formed from reaction pressure is 4.5MPa, and stirring hydrolysis is instead
Answer 4 hours, the organic compound in hydrolyzate be analyzed, be not detected by the generation of iminodiacetic acid, nitrilotriacetic acid,
It is not detected by hydantoins, hydantoic acid, the residual of hydantoic acid acid amides.By hydrolyzate pressure release to normal pressure, 70 DEG C are cooled to, reclaim anti-
Ammonia present in system is answered, in the hydrolysis of the ammonia recycled to lower batch of recovery, surplus solution is in the bar for being incubated 70 DEG C
Activated carbon decolorizing is used under part.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, is taken out
Filter, drying obtain glycine product.In the crystallization operation of the crystalline mother solution recycled of glycine to lower batch or circulating sleeve
With in the hydrolysis to lower batch, through repeatedly circulation, glycine product 113.4g, yield 94%, purity 99% are averagely obtained.
Embodiment 2
The production of ammonia oxonation liquid：In the 5000ml voltage-resistant reactors of pressurization sampler and agitating device are possessed,
Water 2364g is added, ammonia 216.5g and carbon dioxide 420.4g is then passed to, is warming up to 100 DEG C, with 5.05g/min's
Speed is at the uniform velocity added dropwise the hydroxyl acetonitrile aqueous solution 453.8g of 40wt%, finishes reaction 1.5 hours, and the pressure of reaction system is
1.6MPa, is then removed under reduced pressure unreacted ammonia and carbon dioxide, obtains ammonia oxonation liquid.Gained ammonia oxonation liquid is put down
Two parts are divided into, the production of hydantoins and the production of glycine is carried out respectively.
The production of hydantoins：Ammonia oxonation liquid is evaporated to into 80wt%, the hydantoins knot of embodiment 1 is added
Brilliant mother liquor, 90 DEG C of acidification reactions 1 hour, gained acidifying solution use activated carbon decolorizing, the liquid after decolouring under conditions of 90 DEG C of insulation
Body is cooled to 20 DEG C of crystallizations, and suction filtration, drying obtain hydantoins product 154.4g, yield 96%, purity 99%.The knot of hydantoins
Brilliant Recycling Mother Solution is applied to conduct acidifying acid in the acidification reaction of lower batch.
The production of glycine：Ammonia oxonation liquid is added in autoclave, the ammoniacal liquor 225.6g of 40wt% is added
（Ammonia is 5 with the molar ratio of hydroxyacetonitrile:1）, 160 DEG C are warming up to immediately, self-formed from reaction pressure is 4.3MPa, stirs hydrolysis
Reaction 4 hours, is analyzed to the organic compound in hydrolyzate, is not detected by the generation of iminodiacetic acid, nitrilotriacetic acid,
Also hydantoins, hydantoic acid, the residual of hydantoic acid acid amides are not detected by.By hydrolyzate pressure release to normal pressure, 70 DEG C are cooled to, are reclaimed
Ammonia present in reaction system, in the hydrolysis of the ammonia recycled to lower batch of recovery, surplus solution is being incubated 70 DEG C
Under the conditions of use activated carbon decolorizing.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, is taken out
Filter, drying obtain glycine product.In the crystallization operation of the crystalline mother solution recycled of glycine to lower batch or circulating sleeve
With in the hydrolysis to lower batch, through repeatedly circulation, glycine product 113.4g, yield 94%, purity 99% are averagely obtained.
Embodiment 3
The production of ammonia oxonation liquid：In the 5000ml voltage-resistant reactors of pressurization sampler and agitating device are possessed,
Water 2364g is added, ammonia 216.5g and carbon dioxide 420.4g is then passed to, is warming up to 100 DEG C, with 5.05g/min's
Speed is at the uniform velocity added dropwise the hydroxyl acetonitrile aqueous solution 453.8g of 40wt%, finishes reaction 1.5 hours, and the pressure of reaction system is
1.6MPa, is then removed under reduced pressure unreacted ammonia and carbon dioxide, obtains ammonia oxonation liquid.Gained ammonia oxonation liquid is put down
Two parts are divided into, the production of hydantoins and the production of glycine is carried out respectively.
The production of hydantoins：Ammonia oxonation liquid is evaporated to into 80wt%, the hydantoins knot of embodiment 2 is added
Brilliant mother liquor, 90 DEG C of acidification reactions 1 hour, gained acidifying solution use activated carbon decolorizing, the liquid after decolouring under conditions of 90 DEG C of insulation
Body is cooled to 20 DEG C of crystallizations, and suction filtration, drying obtain hydantoins product 154.4g, yield 96%, purity 99%.The knot of hydantoins
Brilliant Recycling Mother Solution is applied to conduct acidifying acid in the acidification reaction of lower batch.
The production of glycine：Ammonia oxonation liquid is added in autoclave, ammonia 108.3g is passed through（Ammonia and hydroxyl second
The molar ratio of nitrile is 4:1）, 160 DEG C are warming up to immediately, self-formed from reaction pressure is 4.5MPa, stirs hydrolysis 4 hours,
Organic compound in hydrolyzate is analyzed, the generation of iminodiacetic acid, nitrilotriacetic acid is not detected by, is also not detected by
Hydantoins, hydantoic acid, the residual of hydantoic acid acid amides.By hydrolyzate pressure release to normal pressure, 70 DEG C are cooled to, are reclaimed in reaction system
The ammonia of presence, in the hydrolysis of the ammonia recycled to lower batch of recovery, surplus solution is under conditions of being incubated 70 DEG C with work
Property carbon decoloring.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, and suction filtration is dried
To glycine product.In the crystallization operation of the crystalline mother solution recycled of glycine to lower batch or recycled is to lower batch
Hydrolysis in, through repeatedly circulation, averagely obtain glycine product 113.4g, yield 94%, purity 99%.
Embodiment 4
The production of ammonia oxonation liquid：In the 5000ml voltage-resistant reactors of pressurization sampler and agitating device are possessed,
Water 2364g is added, ammonia 216.5g and carbon dioxide 420.4g is then passed to, is warming up to 100 DEG C, with 5.05g/min's
Speed is at the uniform velocity added dropwise the hydroxyl acetonitrile aqueous solution 453.8g of 40wt%, and the pressure of reaction system is 1.7MPa, finishes reaction 1.5 little
When, unreacted ammonia and carbon dioxide are then removed under reduced pressure, ammonia oxonation liquid is obtained.The four of gained ammonia oxonation liquid/
One production for being used for hydantoins, 3/4ths are used for the production of glycine.
The production of hydantoins：Ammonia oxonation liquid is evaporated to into 80wt%, is added equivalent to concentrate 15wt%'s
The concentrated sulfuric acid of 98wt%, 90 DEG C of acidification reactions 1 hour, gained acidifying solution use activated carbon decolorizing under conditions of 90 DEG C of insulation, decolourize
Liquid cooling afterwards is crystallized to 20 DEG C, suction filtration, and drying obtains hydantoins product 75.6g, yield 94%, purity 99%.Acyl in second
As acidifying acid in the acidification reaction of the crystalline mother solution recycled of urea to lower batch.
The production of glycine：Ammonia oxonation liquid is added in autoclave, ammonia 108.3g is passed through（Ammonia and hydroxyl second
The molar ratio of nitrile is 4:1）, 160 DEG C are warming up to immediately, self-formed from reaction pressure is 4.5MPa, stirs hydrolysis 4 hours,
Organic compound in hydrolyzate is analyzed, the generation of iminodiacetic acid, nitrilotriacetic acid is not detected by, is also not detected by
Hydantoins, hydantoic acid, the residual of hydantoic acid acid amides.By hydrolyzate pressure release to normal pressure, 70 DEG C are cooled to, are reclaimed in reaction system
The ammonia of presence, in the hydrolysis of the ammonia recycled to lower batch of recovery, surplus solution is under conditions of being incubated 70 DEG C with work
Property carbon decoloring.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, and suction filtration is dried
To glycine product.In the crystallization operation of the crystalline mother solution recycled of glycine to lower batch or recycled is to lower batch
Hydrolysis in, through repeatedly circulation, averagely obtain glycine product 170.1g, yield 94%, purity 99%.
Embodiment 5
As shown in figure 1, glycine is included in ammonia oxonation liquid production unit, second with the joint production of hydantoins
Uride production unit and glycine production unit, the ammonia oxonation liquid production unit include the static mixer being sequentially communicated
I, tubular reactor I, stripping tower I and storage tank, MVR vapo(u)rization systems I that the hydantoins production unit includes being sequentially communicated,
Acidizing device, decoloration device I, crystallization apparatus I, centrifugal device I and drying device I, the glycine production unit are included successively
The static mixer II of connection, tubular reactor II, stripping tower II, decoloration device II, MVR vapo(u)rization system II, crystallization apparatus II,
Centrifugal device II and drying device II, the outlet of storage tank in the ammonia oxonation liquid production unit pass through valve I, valve respectively
Door II is entered with static mixer II in the charging aperture of MVR vapo(u)rization systems I, glycine production unit in hydantoins production unit
Material mouth is connected.
Glycine is as follows with the combine production method of hydantoins：
The production of ammonia oxonation liquid：By water 2364Kg, ammonia 216.5Kg and carbon dioxide 420.4Kg in static state
Carbon ammonium aqueous solution is mixed to get in blender I, the solution is preheated to into 100 DEG C, it is anti-with the speed input tubular type of 2000.6Kg/h
In answering device I；Separately with feed pump with the speed of 302.54Kg/h by the hydroxyl acetonitrile aqueous solution 453.8Kg of 40wt% and above-mentioned carbon ammonium
Also it is input in tubular reactor I after aqueous solution mixing, hydroxyacetonitrile in reaction system：Ammonia：Carbon dioxide：The mol ratio of water is 1:
4:3:46, retention time is 1.5～3 hours to material in the duct, and reaction temperature is 100 DEG C, and the pressure in pipeline is reactant
The pressure of system is 1.7MPa.Stripping tower I is directly entered from tubular reactor I feed liquids out, the tower top of stripping tower I is provided with gas
Liquid/gas separator, tower top pressure are normal pressure, and temperature is 100 DEG C, be connected with the vapor that pressure is 0.5MPa, discharge from tower top in tower
The gaseous mixture of the complete carbon dioxide of unreacted and ammonia prepares the aqueous solution of carbon dioxide and ammonia for recovery and circulates for ammonia carbonyl
Ammonia oxonation liquid is, is stored into storage tank as reaction raw materials, the liquid flowed out from bottom of towe in changing reaction.Gained ammonia carbonyl
Change reactant liquor carries out the amount of follow-up hydantoins production and glycine production by valve I and valve II distribution.In the present embodiment
It is that the ammonia oxonation liquid by obtained by is equally divided into two parts as valve I and valve II, carries out hydantoins production and sweet ammonia respectively
Acid production.
The production of hydantoins：Ammonia oxonation liquid is evaporated to into 40wt% using MVR vapo(u)rization systems I, acidifying is proceeded to
The concentrated sulfuric acid of the 98wt% equivalent to concentrate 15wt%, 90 DEG C of acidification reactions 1 hour, gained acidifying solution in device, is added to enter
In decoloration device I, under conditions of being incubated 90 DEG C use activated carbon decolorizing, the liquid after decolouring to proceed in crystallization apparatus I, stir cold
But crystallize to 20 DEG C, the feed liquid after crystallization is isolated hydantoins by centrifugal device I, is dried to obtain second using drying device I
Interior uride product 154.4Kg, yield 96%, purity are 99%.The hydantoins crystalline mother solution recycled that centrifugal device I is isolated
Into the acidification reaction of lower batch as acidifying acid.
The production of glycine：By ammonia oxonation liquid and ammonia 108.3g（Ammonia is 4 with the molar ratio of hydroxyacetonitrile:
1）Mix in static mixer II, after mixed material is preheated to 100 DEG C, tubular reactor is entered with the speed of 863.7Kg/h
In II, 160 DEG C are warming up to immediately, self-formed from reaction pressure is 4.5MPa, stirs hydrolysis 4 hours, to organising in hydrolyzate
Compound is analyzed, and is not detected by the generation of iminodiacetic acid, nitrilotriacetic acid, is also not detected by hydantoins, hydantoic acid, sea
Because of the residual of sour acid amides.From tubular reactor II hydrolyzate pressure releases out to normal pressure, it is cooled to 100 DEG C and is directly entered stripping tower
The tower top of II, stripping tower II is provided with gas-liquid separator, and tower top pressure is normal pressure, and temperature is 100 DEG C, and pressure is connected with tower is
The water vapour of 0.5MPa, during the ammonia discharged from tower top can be with the hydrolysis of recycled to lower batch, flows out from bottom of towe
Liquid is glycine solution, proceeds in decoloration device II, uses activated carbon decolorizing, after decolouring under conditions of being incubated 70 DEG C
Liquid is evaporated to Glycine Levels for 37wt% using MVR vapo(u)rization systems II, and concentrate is proceeded in crystallization apparatus II, stirs
0 DEG C of crystallization is cooled to, the feed liquid after crystallization isolates glycine by centrifugal device II, is dried to obtain using drying device II sweet
Propylhomoserin product.In the crystallization operation of the glycine crystallization mother liquid recycled that centrifugal device II is isolated to lower batch or circulate
It is applied in the hydrolysis of lower batch, through repeatedly circulation, averagely obtains glycine product 113.4Kg, yield 94%, purity
99%。
Finally illustrate, preferred embodiment above is only unrestricted to illustrate technical scheme, although logical
Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be
Various changes are made to which in form and in details, without departing from claims of the present invention limited range.
Claims (8)
1. the combine production method of glycine and hydantoins, it is characterised in that：Comprise the following steps：
1）With hydroxyacetonitrile, ammonia, carbon dioxide and water as raw material, or with hydroxyacetonitrile, ammonia, ammonium hydrogen carbonate and water as raw material,
Or with hydroxyacetonitrile, ammonium carbonate, carbon dioxide and water as raw material, by hydroxyacetonitrile in reaction system：Ammonia：Carbon dioxide：Water
Mol ratio be 1:3~5:2~4:46～50, temperature be 60 DEG C～120 DEG C, pressure be 1.5MPa～3.0MPa under the conditions of carry out
Ammonia oxonation, is obtained ammonia oxonation liquid；
2）With step 1）Obtained ammonia oxonation liquid is raw material, through concentration, acidifying, decolourizes, crystallizes, hydantoins being obtained and produces
Product；
3）With step 1）Obtained ammonia oxonation liquid is raw material, through ammonification hydrolysis, reclaims ammonia, decolouring, concentration, crystallization, system
Obtain glycine product.
2. the combine production method of glycine according to claim 1 and hydantoins, it is characterised in that：Step 1）Be with
Hydroxyacetonitrile, ammonia, carbon dioxide and water be raw material, temperature be 90 DEG C～100 DEG C, pressure be 1.5MPa～3.0MPa under the conditions of
Ammonia oxonation is carried out, reaction removes unreacted ammonia and carbon dioxide after terminating.
3. the combine production method of glycine according to claim 1 and hydantoins, it is characterised in that：Step 2）Being will
Ammonia oxonation liquid is evaporated to 20wt%～80wt%, adds the dense sulphur of the 98wt% equivalent to concentrate 10wt%～20wt%
Acid, carries out acidification reaction under the conditions of 40 DEG C～100 DEG C of temperature, and gained acidifying solution adds activated carbon, in 40 DEG C～100 DEG C of temperature
Under the conditions of carry out desolventing technology, finally crystallize under the conditions of 0 DEG C～20 DEG C of temperature, obtain hydantoins product.
4. the combine production method of glycine according to claim 3 and hydantoins, it is characterised in that：Step 2）Being will
Ammonia oxonation liquid is evaporated to 40wt%～80wt%, adds the dense sulphur of the 98wt% equivalent to concentrate 12wt%～17wt%
Acid, carries out acidification reaction under the conditions of 80 DEG C～90 DEG C of temperature, and gained acidifying solution adds activated carbon, in 80 DEG C～90 DEG C bars of temperature
Desolventing technology is carried out under part, is finally crystallized under the conditions of 0 DEG C～20 DEG C of temperature, is obtained hydantoins product.
5. the combine production method of glycine according to claim 1 and hydantoins, it is characterised in that：Step 3）Being will
Ammonia oxonation liquid adds the ammonia or ammoniacal liquor equivalent to 2 ~ 8 times of moles of hydroxyacetonitrile, in 120 DEG C～170 DEG C conditions of temperature
Lower hydrolysis 3～5 hours, after hydrolysis terminates, reclaims ammonia by stripping regime, is subsequently adding activated carbon, in temperature 40
DEG C～70 DEG C under the conditions of carry out desolventing technology, gained destainer is evaporated to glycine concentration and is not higher than 40wt%, finally in temperature
Crystallize under the conditions of 0 DEG C～20 DEG C of degree, obtain glycine product.
6. the combine production method of glycine according to claim 5 and hydantoins, it is characterised in that：Step 3）Being will
Ammonia oxonation liquid adds the ammonia or ammoniacal liquor equivalent to 3 ~ 5 times of moles of hydroxyacetonitrile, in 140 DEG C～165 DEG C conditions of temperature
Lower hydrolysis 3～4 hours, after hydrolysis terminates, reclaims ammonia by stripping regime, is subsequently adding activated carbon, in temperature 40
DEG C～70 DEG C under the conditions of carry out desolventing technology, gained destainer is evaporated to glycine concentration and is not higher than 40wt%, finally in temperature
Crystallize under the conditions of 0 DEG C～10 DEG C of degree, obtain glycine product.
7. the combine production method of glycine according to claim 1 and hydantoins, it is characterised in that：Step 2）Middle second
In the acidification reaction of the crystalline mother solution recycled of interior uride to lower batch；Step 3）The ammonia recycled of middle recovery is to lower batch
Ammonification hydrolysis in, in the crystallization operation of the crystalline mother solution recycled to lower batch of glycine or recycled is under
In the ammonification hydrolysis of batch.
8. it is used for realizing the device of glycine described in claim 1 and the combine production method of hydantoins, it is characterised in that：Bag
Include ammonia oxonation liquid production unit, hydantoins production unit and glycine production unit, the ammonia oxonation liquid production
Unit includes static mixer I, tubular reactor I, stripping tower I and the storage tank being sequentially communicated, and the hydantoins production is single
Unit includes MVR vapo(u)rization systems I, acidizing device, decoloration device I, crystallization apparatus I, centrifugal device I and the drying device being sequentially communicated
I, static mixer II that the glycine production unit includes being sequentially communicated, tubular reactor II, stripping tower II, decoloration device
II, MVR vapo(u)rization system II, crystallization apparatus II, centrifugal device II and drying device II, in the ammonia oxonation liquid production unit
The outlet of storage tank is respectively by the charging aperture of MVR vapo(u)rization systems I, sweet ammonia in valve I, valve II and hydantoins production unit
The charging aperture connection of static mixer II in sour production unit.
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| CN110903209A (en) * | 2018-09-17 | 2020-03-24 | 重庆紫光化工股份有限公司 | Method for efficiently producing glycine and identification of glycine produced by hydantoin method |
| CN109970658A (en) * | 2019-05-06 | 2019-07-05 | 阳泉煤业（集团）有限责任公司 | A kind of method of continuous production glycine coproduction glycolylurea |
| CN110698357A (en) * | 2019-10-08 | 2020-01-17 | 阳泉煤业（集团）有限责任公司 | Method for continuously preparing glycine from hydroxyacetonitrile by using microchannel reactor |
| CN112979556A (en) * | 2021-03-03 | 2021-06-18 | 铂尊投资集团有限公司 | Clean production method of hydantoin and device for implementing method |
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