CN104910031A - Method for co-producing glycine and hydantoin, and apparatus thereof - Google Patents
Method for co-producing glycine and hydantoin, and apparatus thereof Download PDFInfo
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Abstract
The invention discloses a method for co-producing glycine and hydantoin, and an apparatus thereof. The method adopting hydroxyacetonitrile, ammonia, carbon dioxide and water, or hydroxyacetonitrile, ammonia, ammonium bicarbonate and water, or hydroxyacetonitrile, ammonium carbonate, carbon dioxide and water as raw materials comprises the following steps: carrying out an amidocarbonylation reaction on the raw materials at a temperature of 60-120DEG C under a pressure of 1.5-3.0MPa according to a molar ratio of hydroxyacetonitrile: ammonia: carbon dioxide: water of 1:3-5:2-4:46-50 in a reaction system to prepare an amidocarbonylation reaction solution; acidifying the amidocarbonylation reaction solution to obtain a hydantoin product, or carrying out ammonification hydrolysis on the amidocarbonylation reaction solution to prepare a glycine product The method and the apparatus can save the investment of apparatuses for prodcuign glycine and hydantoin, reduce the production cost, are convenient for adjusting the outputs of glycine and hydantoin, and especially overcome the disadvantages of incomplete hydrolysis, generation of iminodiacetic acid, many byproducts, difficult purification of glycine, and low yield of present hydantoin methods for preparing glycine.
Description
Technical field
The invention belongs to chemical field, relate to method and the device of a kind of combination producing two kinds of compounds.
Background technology
It is the novel method reported in recent years that hydroxyacetonitrile method produces glycine.The method is divided into again two kinds: the first is as described in Chinese patent CN1962611B, it is ammonia soln hydroxyacetonitrile and ammoniacal liquor being obtained by reacting aminoacetonitriles, the alkali solution liquid that mineral alkali obtains containing glycinate is added in this solution, by alkali solution liquid deamination, with mineral acid neutralization, decolouring, concentrated fractional crystallization and recrystallization, then obtain glycine and inorganic salt respectively; The shortcoming of the method is: reaction scheme is longer, process conditions is harsh, reacted de-salting operation is more numerous and diverse, product is not easily refined, the separation difficulty of glycine and iminodiethanoic acid, nitrilotriacetic acid(NTA), and glycine crystallization mother liquid is difficult to recycled, glycine loss is larger, produce the inorganic salt of a large amount of low value and a large amount of reluctant waste water and dregs, production cost is higher; The second is glycolylurea method, the method be by hydroxyacetonitrile under high temperature, high pressure with carbonic acid gas and ammoniacal liquor or with bicarbonate of ammonia and ammoniacal liquor Reactive Synthesis glycolylurea, glycolylurea is hydrolyzed under certain temperature and pressure and obtains glycine, discharges carbonic acid gas and ammonia simultaneously; The shortcoming of the method is hydrolyzed thoroughly, has that iminodiethanoic acid produces, by product is many, and glycine purification difficult, yield is low, and in actual production, the yield of glycine only has 80% ~ 85%, and the single extraction efficiency of glycine only has about 72%.
The current main production process of glycolylurea is glycine method and hydroxyacetonitrile method.Glycine method is with glycine, sodium hydroxide and urea for raw material, and obtain glycolylurea, producing ammonium sulfate byproduct and sodium sulfate through sulfuric acid absorption ammonia and sulfuric acid neutralization, the method production cost is higher, and produces the inorganic salt of a large amount of low value.Hydroxyacetonitrile method be by hydroxyacetonitrile and bicarbonate of ammonia or with carbonic acid gas and ammonia gas react, reconcentration, acidifying, decolouring obtain glycolylurea product, the method cost is low, yield is high, be a good approach of suitability for industrialized production, but the scale of current domestic employing hydroxyacetonitrile method production glycolylurea is less.
The co-production raw material of glycine and glycolylurea is all hydroxyacetonitrile, carbonic acid gas and ammonia, and the maximum difference that both produce is feed ratio and temperature of reaction, pressure and the difference of time of material.Consider to utilize same set of equipment to produce the two simultaneously, regulate all highly beneficial to making full use of equipment, reduction production cost and production, therefore, the technique developing a combination producing glycine and glycolylurea is necessary very much, especially overcomes current glycolylurea method and is hydrolyzed thoroughly, has the shortcoming that iminodiethanoic acid produces, by product is many, glycine purification difficult, yield are low.
Summary of the invention
In view of this, the object of the present invention is to provide combine production method and the device of a kind of glycine and glycolylurea, same set of equipment not only can be utilized to produce the two simultaneously, make full use of equipment, reduce production cost, be convenient to produce and regulate, especially can overcome hydrolysis that current glycolylurea legal system exists for glycine not thoroughly, have iminodiethanoic acid generation, by product is many, glycine purification difficult, yield are low shortcoming.
For achieving the above object, the invention provides following technical scheme:
1.the combine production method of glycine and glycolylurea, comprises the following steps:
1) with hydroxyacetonitrile, ammonia, carbonic acid gas and water for raw material, or with hydroxyacetonitrile, ammonia, bicarbonate of ammonia and water for raw material, or with hydroxyacetonitrile, volatile salt, carbonic acid gas and water for raw material, by hydroxyacetonitrile in reaction system: ammonia: carbonic acid gas: the mol ratio of water is 1:3 ~ 5:2 ~ 4:46 ~ 50, temperature be 60 DEG C ~ 120 DEG C, pressure carries out ammonia oxonation under being 1.5MPa ~ 3.0MPa condition, obtained ammonia oxonation liquid;
2) with the obtained ammonia oxonation liquid of step 1) for raw material, obtain glycolylurea product through acidifying;
3) with the obtained ammonia oxonation liquid of step 1) for raw material, through the obtained glycine product of ammonification hydrolysis.
The reaction principle of aforesaid method is as follows:
In step 1), when with hydroxyacetonitrile, ammonia, bicarbonate of ammonia and water, or during with hydroxyacetonitrile, volatile salt, carbonic acid gas and water for raw material, the molar ratio system of each raw material is according to hydroxyacetonitrile in reaction system: ammonia: carbonic acid gas: the mol ratio of water is convert in 1:3 ~ 5:2 ~ 4:46 ~ 50.
Further, step 1) is with hydroxyacetonitrile, ammonia, carbonic acid gas and water for raw material, temperature be 90 DEG C ~ 100 DEG C, pressure carries out ammonia oxonation under being 1.5MPa ~ 3.0MPa condition, reaction terminates the unreacted ammonia of rear removing and carbonic acid gas.
Further, step 2) be with the obtained ammonia oxonation liquid of step 1) for raw material, through concentrated, acidifying, decolouring, crystallization, obtained glycolylurea product.
Further, step 2) be that ammonia oxonation liquid is evaporated to 20wt% ~ 80wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 10wt% ~ 20wt%, acidification reaction is carried out under temperature 40 DEG C ~ 100 DEG C conditions, gained acidizing fluid adds gac, under temperature 40 DEG C ~ 100 DEG C conditions, carry out desolventing technology, finally crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtains glycolylurea product.
Further, step 2) be that ammonia oxonation liquid is evaporated to 40wt% ~ 80wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 12wt% ~ 17wt%, acidification reaction is carried out under temperature 80 DEG C ~ 90 DEG C conditions, gained acidizing fluid adds gac, under temperature 80 DEG C ~ 90 DEG C conditions, carry out desolventing technology, finally crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtains glycolylurea product.
Further, step 2) in the crystalline mother solution recycled of glycolylurea to the acidification reaction of lower batch.
Further, step 3) for raw material, through ammonification hydrolysis, reclaims ammonia, decolouring, concentrated, crystallization, obtained glycine product with the obtained ammonia oxonation liquid of step 1).
Further, step 3) ammonia oxonation liquid is added the ammonia or ammoniacal liquor that are equivalent to hydroxyacetonitrile 2 ~ 8 times of molar weights, temperature 120 DEG C ~ 170 DEG C Water Under solution reactions 3 ~ 5 hours, after hydrolysis reaction terminates, reclaim ammonia by stripping regime, then add gac, desolventing technology is carried out under temperature 40 DEG C ~ 70 DEG C conditions, gained destainer is evaporated to glycine concentration not higher than 40wt%, and finally crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtains glycine product.
Further, step 3) ammonia oxonation liquid is added the ammonia or ammoniacal liquor that are equivalent to hydroxyacetonitrile 3 ~ 5 times of molar weights, temperature 140 DEG C ~ 165 DEG C Water Under solution reactions 3 ~ 4 hours, after hydrolysis reaction terminates, reclaim ammonia by stripping regime, then add gac, desolventing technology is carried out under temperature 40 DEG C ~ 70 DEG C conditions, gained destainer is evaporated to glycine concentration not higher than 40wt%, and finally crystallization under temperature 0 DEG C ~ 10 DEG C conditions, obtains glycine product.
Further, the ammonia recycled reclaimed in step 3) is in the ammonification hydrolysis reaction of lower batch; In the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the ammonification hydrolysis reaction of lower batch.
For realizing the device of the combine production method of glycine and glycolylurea, comprise ammonia oxonation liquid productive unit, glycolylurea productive unit and glycine productive unit, described ammonia oxonation liquid productive unit comprises the static mixer I be communicated with successively, tubular reactor I, gas stripping column I and storage tank, described glycolylurea productive unit comprises acidizing device, described glycine productive unit comprises the static mixer II and tubular reactor II that are communicated with successively, in described ammonia oxonation liquid productive unit, the outlet of storage tank is respectively by valve I, the opening for feed of acidizing device in valve II and glycolylurea productive unit, in glycine productive unit, the opening for feed of static mixer II is communicated with.
Further, described glycolylurea productive unit comprises the MVR vapo(u)rization system I be communicated with successively, acidizing device, decoloration device I, crystallization apparatus I, centrifugal device I and drying installation I, described glycine productive unit comprises the static mixer II be communicated with successively, tubular reactor II, gas stripping column II, decoloration device II, MVR vapo(u)rization system II, crystallization apparatus II, centrifugal device II and drying installation II, in described ammonia oxonation liquid productive unit, the outlet of storage tank is respectively by valve I, the opening for feed of MVR vapo(u)rization system I in valve II and glycolylurea productive unit, in glycine productive unit, the opening for feed of static mixer II is communicated with.
Beneficial effect of the present invention is: compared with prior art, the present invention first with hydroxyacetonitrile, ammonia, carbonic acid gas and water for ammonia oxonation liquid prepared by raw material, again respectively with ammonia oxonation liquid for raw material prepares glycolylurea and glycine, not only can save the investment of production equipment of glycine and glycolylurea, reduce production cost, be convenient to the output regulating glycine and glycolylurea, especially can overcome the hydrolysis that current glycolylurea legal system exists for glycine thorough, have iminodiethanoic acid generation, by product is many, glycine purification difficult, yield are low shortcoming.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is combine production method of the present invention and device schematic diagram.
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 reactor having pressurization sampling unit and whipping appts, add water 2364g, then ammonia 216.5g and carbon dioxide 420.4g is passed into, be warming up to 100 DEG C, at the uniform velocity drip the hydroxyl acetonitrile aqueous solution 453.8g of 40wt% with the speed of 5.05g/min, finish reaction 1.5 hours, the pressure of reaction system is 1.6MPa, then the decompression unreacted ammonia of removing and carbonic acid gas, obtain ammonia oxonation liquid.Gained ammonia oxonation liquid is equally divided into two parts, carries out the production of glycolylurea and the production of glycine respectively.
The production of glycolylurea: ammonia oxonation liquid is evaporated to 40wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 15wt%, 90 DEG C of acidification reactions 1 hour, gained acidizing fluid uses activated carbon decolorizing under the condition of insulation 90 DEG C, liquid cooling to 20 DEG C crystallization after decolouring, suction filtration, dries and obtains glycolylurea product 151.2g, yield 94%, purity 99%.The crystalline mother solution recycled of glycolylurea is sour as acidifying to the acidification reaction of lower batch.
The production of glycine: ammonia oxonation liquid is added in autoclave, the molar ratio of the ammoniacal liquor 288.7g(ammonia and hydroxyacetonitrile that add 25wt% is 4:1), be warming up to 160 DEG C immediately, self-formed from reaction pressure is 4.5MPa, stir hydrolysis reaction 4 hours, organic compound in hydrolyzed solution is analyzed, the generation of iminodiethanoic acid, nitrilotriacetic acid(NTA) do not detected, the residual of glycolylurea, hydantoic acid, hydantoic acid acid amides also do not detected.By hydrolyzed solution pressure release to normal pressure, be cooled to 70 DEG C, reclaim the ammonia existed in reaction system, the ammonia recycled of recovery is in the hydrolysis reaction of lower batch, and surplus solution uses activated carbon decolorizing under the condition of insulation 70 DEG C.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, suction filtration, dries and obtains glycine product.In the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the hydrolysis reaction of lower batch, through repeatedly circulating, on average obtain glycine product 113.4g, yield 94%, purity 99%.
embodiment 2
The production of ammonia oxonation liquid: in the 5000ml voltage-resistant reactor having pressurization sampling unit and whipping appts, add water 2364g, then ammonia 216.5g and carbon dioxide 420.4g is passed into, be warming up to 100 DEG C, at the uniform velocity drip the hydroxyl acetonitrile aqueous solution 453.8g of 40wt% with the speed of 5.05g/min, finish reaction 1.5 hours, the pressure of reaction system is 1.6MPa, then the decompression unreacted ammonia of removing and carbonic acid gas, obtain ammonia oxonation liquid.Gained ammonia oxonation liquid is equally divided into two parts, carries out the production of glycolylurea and the production of glycine respectively.
The production of glycolylurea: ammonia oxonation liquid is evaporated to 80wt%, add the glycolylurea crystalline mother solution of embodiment 1,90 DEG C of acidification reactions 1 hour, gained acidizing fluid uses activated carbon decolorizing under the condition of insulation 90 DEG C, liquid cooling to 20 DEG C crystallization after decolouring, suction filtration, dries and obtains glycolylurea product 154.4g, yield 96%, purity 99%.The crystalline mother solution recycled of glycolylurea is sour as acidifying to the acidification reaction of lower batch.
The production of glycine: ammonia oxonation liquid is added in autoclave, the molar ratio of the ammoniacal liquor 225.6g(ammonia and hydroxyacetonitrile that add 40wt% is again 5:1), be warming up to 160 DEG C immediately, self-formed from reaction pressure is 4.3MPa, stir hydrolysis reaction 4 hours, organic compound in hydrolyzed solution is analyzed, the generation of iminodiethanoic acid, nitrilotriacetic acid(NTA) do not detected, the residual of glycolylurea, hydantoic acid, hydantoic acid acid amides also do not detected.By hydrolyzed solution pressure release to normal pressure, be cooled to 70 DEG C, reclaim the ammonia existed in reaction system, the ammonia recycled of recovery is in the hydrolysis reaction of lower batch, and surplus solution uses activated carbon decolorizing under the condition of insulation 70 DEG C.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, suction filtration, dries and obtains glycine product.In the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the hydrolysis reaction of lower batch, through repeatedly circulating, on average obtain glycine product 113.4g, yield 94%, purity 99%.
embodiment 3
The production of ammonia oxonation liquid: in the 5000ml voltage-resistant reactor having pressurization sampling unit and whipping appts, add water 2364g, then ammonia 216.5g and carbon dioxide 420.4g is passed into, be warming up to 100 DEG C, at the uniform velocity drip the hydroxyl acetonitrile aqueous solution 453.8g of 40wt% with the speed of 5.05g/min, finish reaction 1.5 hours, the pressure of reaction system is 1.6MPa, then the decompression unreacted ammonia of removing and carbonic acid gas, obtain ammonia oxonation liquid.Gained ammonia oxonation liquid is equally divided into two parts, carries out the production of glycolylurea and the production of glycine respectively.
The production of glycolylurea: ammonia oxonation liquid is evaporated to 80wt%, add the glycolylurea crystalline mother solution of embodiment 2,90 DEG C of acidification reactions 1 hour, gained acidizing fluid uses activated carbon decolorizing under the condition of insulation 90 DEG C, liquid cooling to 20 DEG C crystallization after decolouring, suction filtration, dries and obtains glycolylurea product 154.4g, yield 96%, purity 99%.The crystalline mother solution recycled of glycolylurea is sour as acidifying to the acidification reaction of lower batch.
The production of glycine: ammonia oxonation liquid is added in autoclave, the molar ratio passing into ammonia 108.3g(ammonia and hydroxyacetonitrile is 4:1), be warming up to 160 DEG C immediately, self-formed from reaction pressure is 4.5MPa, stir hydrolysis reaction 4 hours, organic compound in hydrolyzed solution is analyzed, the generation of iminodiethanoic acid, nitrilotriacetic acid(NTA) do not detected, the residual of glycolylurea, hydantoic acid, hydantoic acid acid amides also do not detected.By hydrolyzed solution pressure release to normal pressure, be cooled to 70 DEG C, reclaim the ammonia existed in reaction system, the ammonia recycled of recovery is in the hydrolysis reaction of lower batch, and surplus solution uses activated carbon decolorizing under the condition of insulation 70 DEG C.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, suction filtration, dries and obtains glycine product.In the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the hydrolysis reaction of lower batch, through repeatedly circulating, on average obtain glycine product 113.4g, yield 94%, purity 99%.
embodiment 4
The production of ammonia oxonation liquid: in the 5000ml voltage-resistant reactor having pressurization sampling unit and whipping appts, add water 2364g, then ammonia 216.5g and carbon dioxide 420.4g is passed into, be warming up to 100 DEG C, at the uniform velocity drip the hydroxyl acetonitrile aqueous solution 453.8g of 40wt% with the speed of 5.05g/min, the pressure of reaction system is 1.7MPa, finishes reaction 1.5 hours, then the decompression unreacted ammonia of removing and carbonic acid gas, obtain ammonia oxonation liquid.Gained ammonia oxonation liquid 1/4th for the production of glycolylurea, 3/4ths for the production of glycine.
The production of glycolylurea: ammonia oxonation liquid is evaporated to 80wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 15wt%, 90 DEG C of acidification reactions 1 hour, gained acidizing fluid uses activated carbon decolorizing under the condition of insulation 90 DEG C, liquid cooling to 20 DEG C crystallization after decolouring, suction filtration, dries and obtains glycolylurea product 75.6g, yield 94%, purity 99%.The crystalline mother solution recycled of glycolylurea is sour as acidifying to the acidification reaction of lower batch.
The production of glycine: ammonia oxonation liquid is added in autoclave, the molar ratio passing into ammonia 108.3g(ammonia and hydroxyacetonitrile is 4:1), be warming up to 160 DEG C immediately, self-formed from reaction pressure is 4.5MPa, stir hydrolysis reaction 4 hours, organic compound in hydrolyzed solution is analyzed, the generation of iminodiethanoic acid, nitrilotriacetic acid(NTA) do not detected, the residual of glycolylurea, hydantoic acid, hydantoic acid acid amides also do not detected.By hydrolyzed solution pressure release to normal pressure, be cooled to 70 DEG C, reclaim the ammonia existed in reaction system, the ammonia recycled of recovery is in the hydrolysis reaction of lower batch, and surplus solution uses activated carbon decolorizing under the condition of insulation 70 DEG C.It is 37wt% that liquid pressure-reducing after decolouring is concentrated into Glycine Levels, then is cooled to 0 DEG C of crystallization, suction filtration, dries and obtains glycine product.In the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the hydrolysis reaction of lower batch, through repeatedly circulating, on average obtain glycine product 170.1g, yield 94%, purity 99%.
embodiment 5
As shown in Figure 1, the joint production of glycine and glycolylurea comprises ammonia oxonation liquid productive unit, glycolylurea productive unit and glycine productive unit, described ammonia oxonation liquid productive unit comprises the static mixer I be communicated with successively, tubular reactor I, gas stripping column I and storage tank, described glycolylurea productive unit comprises the MVR vapo(u)rization system I be communicated with successively, acidizing device, decoloration device I, crystallization apparatus I, centrifugal device I and drying installation I, described glycine productive unit comprises the static mixer II be communicated with successively, tubular reactor II, gas stripping column II, decoloration device II, MVR vapo(u)rization system II, crystallization apparatus II, centrifugal device II and drying installation II, in described ammonia oxonation liquid productive unit, the outlet of storage tank is respectively by valve I, the opening for feed of MVR vapo(u)rization system I in valve II and glycolylurea productive unit, in glycine productive unit, the opening for feed of static mixer II is communicated with.
The combine production method of glycine and glycolylurea is as follows:
The production of ammonia oxonation liquid: water 2364Kg, ammonia 216.5Kg and carbon dioxide 420.4Kg are mixed to get carbon ammonium aqueous solution in static mixer I, this solution is preheated to 100 DEG C, with in the speed of 2000.6Kg/h input tubular reactor I; Another fresh feed pump also inputs in tubular reactor I after being mixed with above-mentioned carbon ammonium aqueous solution by the hydroxyl acetonitrile aqueous solution 453.8Kg of 40wt% with the speed of 302.54Kg/h, hydroxyacetonitrile in reaction system: ammonia: carbonic acid gas: the mol ratio of water is 1:4:3:46, material in the duct retention time is 1.5 ~ 3 hours, temperature of reaction is 100 DEG C, and the pressure in pipeline and the pressure of reaction system are 1.7MPa.Gas stripping column I is directly entered from tubular reactor I feed liquid out, the tower top of gas stripping column I is provided with gas-liquid separator, tower top pressure is normal pressure, temperature is 100 DEG C, the water vapour that pressure is 0.5MPa is connected with in tower, the complete carbonic acid gas of unreacted of discharging from tower top and the gas mixture of ammonia are for reclaiming the aqueous solution of preparing carbonic acid gas and ammonia and being cycled to used in as reaction raw materials ammonia oxonation, and the liquid gone out from tower bottom flow is ammonia oxonation liquid, enters storage tank and stores.Gained ammonia oxonation liquid distributes the amount of carrying out the production of follow-up glycolylurea and glycine production by valve I and valve II.Be, by valve I and valve II, gained ammonia oxonation liquid is equally divided into two parts in the present embodiment, carry out glycolylurea respectively and produce and glycine production.
The production of glycolylurea: utilize MVR vapo(u)rization system I to be evaporated to 40wt% ammonia oxonation liquid, proceed in acidizing device, add the vitriol oil of the 98wt% being equivalent to concentrated solution 15wt%, 90 DEG C of acidification reactions 1 hour, gained acidizing fluid enters in decoloration device I, with activated carbon decolorizing under the condition of insulation 90 DEG C, liquid after decolouring proceeds in crystallization apparatus I, stirring is cooled to 20 DEG C of crystallizations, feed liquid after crystallization isolates glycolylurea by centrifugal device I, adopt drying installation I drying to obtain glycolylurea product 154.4Kg, yield 96%, purity is 99%.As acidifying acid in centrifugal device I isolated glycolylurea crystalline mother solution recycled to the acidification reaction of lower batch.
The production of glycine: be 4:1 with the molar ratio of hydroxyacetonitrile by ammonia oxonation liquid and ammonia 108.3g(ammonia) mix in static mixer II, after mixture is preheated to 100 DEG C, enter in tubular reactor II with the speed of 863.7Kg/h, be warming up to 160 DEG C immediately, self-formed from reaction pressure is 4.5MPa, stir hydrolysis reaction 4 hours, organic compound in hydrolyzed solution is analyzed, the generation of iminodiethanoic acid, nitrilotriacetic acid(NTA) do not detected, the residual of glycolylurea, hydantoic acid, hydantoic acid acid amides do not detected yet.From tubular reactor II hydrolyzed solution pressure release out to normal pressure, be cooled to 100 DEG C and directly enter gas stripping column II, the tower top of gas stripping column II is provided with gas-liquid separator, tower top pressure is normal pressure, temperature is 100 DEG C, the water vapor that pressure is 0.5MPa is connected with in tower, the ammonia of discharging from tower top can the hydrolysis reaction of recycled to lower batch, the liquid gone out from tower bottom flow is glycine solution, proceed in decoloration device II, with activated carbon decolorizing under the condition of insulation 70 DEG C, liquid after decolouring utilizes MVR vapo(u)rization system II to be evaporated to Glycine Levels for 37wt%, concentrated solution proceeds in crystallization apparatus II, stirring is cooled to 0 DEG C of crystallization, feed liquid after crystallization isolates glycine by centrifugal device II, drying installation II drying is adopted to obtain glycine product.In centrifugal device II isolated glycine crystallization mother liquid recycled to the crystallization operation of lower batch or recycled in the hydrolysis reaction of lower batch, through repeatedly circulating, on average obtain glycine product 113.4Kg, yield 94%, purity 99%.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (10)
1. the combine production method of glycine and glycolylurea, is characterized in that: comprise the following steps:
1) with hydroxyacetonitrile, ammonia, carbonic acid gas and water for raw material, or with hydroxyacetonitrile, ammonia, bicarbonate of ammonia and water for raw material, or with hydroxyacetonitrile, volatile salt, carbonic acid gas and water for raw material, by hydroxyacetonitrile in reaction system: ammonia: carbonic acid gas: the mol ratio of water is 1:3 ~ 5:2 ~ 4:46 ~ 50, temperature be 60 DEG C ~ 120 DEG C, pressure carries out ammonia oxonation under being 1.5MPa ~ 3.0MPa condition, obtained ammonia oxonation liquid;
2) with the obtained ammonia oxonation liquid of step 1) for raw material, obtain glycolylurea product through acidifying;
3) with the obtained ammonia oxonation liquid of step 1) for raw material, through the obtained glycine product of ammonification hydrolysis.
2. the combine production method of glycine according to claim 1 and glycolylurea, it is characterized in that: step 1) is for raw material with hydroxyacetonitrile, ammonia, carbonic acid gas and water, temperature be 90 DEG C ~ 100 DEG C, pressure carries out ammonia oxonation under being 1.5MPa ~ 3.0MPa condition, reaction terminates the unreacted ammonia of rear removing and carbonic acid gas.
3. the combine production method of glycine according to claim 1 and glycolylurea, is characterized in that: step 2) be with the obtained ammonia oxonation liquid of step 1) for raw material, through concentrated, acidifying, decolouring, crystallization, obtained glycolylurea product; Step 3) for raw material, through ammonification hydrolysis, reclaims ammonia, decolouring, concentrated, crystallization, obtained glycine product with the obtained ammonia oxonation liquid of step 1).
4. the combine production method of glycine according to claim 3 and glycolylurea, it is characterized in that: step 2) be that ammonia oxonation liquid is evaporated to 20wt% ~ 80wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 10wt% ~ 20wt%, acidification reaction is carried out under temperature 40 DEG C ~ 100 DEG C conditions, gained acidizing fluid adds gac, under temperature 40 DEG C ~ 100 DEG C conditions, carry out desolventing technology, finally crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtains glycolylurea product.
5. the combine production method of glycine according to claim 4 and glycolylurea, it is characterized in that: step 2) be that ammonia oxonation liquid is evaporated to 40wt% ~ 80wt%, add the vitriol oil of the 98wt% being equivalent to concentrated solution 12wt% ~ 17wt%, acidification reaction is carried out under temperature 80 DEG C ~ 90 DEG C conditions, gained acidizing fluid adds gac, under temperature 80 DEG C ~ 90 DEG C conditions, carry out desolventing technology, finally crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtains glycolylurea product.
6. the combine production method of glycine according to claim 3 and glycolylurea, it is characterized in that: step 3) ammonia oxonation liquid is added the ammonia or ammoniacal liquor that are equivalent to hydroxyacetonitrile 2 ~ 8 times of molar weights, temperature 120 DEG C ~ 170 DEG C Water Under solution reactions 3 ~ 5 hours, after hydrolysis reaction terminates, ammonia is reclaimed by stripping regime, then gac is added, desolventing technology is carried out under temperature 40 DEG C ~ 70 DEG C conditions, gained destainer is evaporated to glycine concentration not higher than 40wt%, last crystallization under temperature 0 DEG C ~ 20 DEG C conditions, obtain glycine product.
7. the combine production method of glycine according to claim 6 and glycolylurea, it is characterized in that: step 3) ammonia oxonation liquid is added the ammonia or ammoniacal liquor that are equivalent to hydroxyacetonitrile 3 ~ 5 times of molar weights, temperature 140 DEG C ~ 165 DEG C Water Under solution reactions 3 ~ 4 hours, after hydrolysis reaction terminates, ammonia is reclaimed by stripping regime, then gac is added, desolventing technology is carried out under temperature 40 DEG C ~ 70 DEG C conditions, gained destainer is evaporated to glycine concentration not higher than 40wt%, last crystallization under temperature 0 DEG C ~ 10 DEG C conditions, obtain glycine product.
8. the combine production method of glycine according to claim 3 and glycolylurea, is characterized in that: step 2) in the crystalline mother solution recycled of glycolylurea to the acidification reaction of lower batch; In the ammonia recycled reclaimed in step 3) to the ammonification hydrolysis reaction of lower batch, the crystalline mother solution recycled of glycine to the crystallization operation of lower batch or recycled in the ammonification hydrolysis reaction of lower batch.
9. for realizing the device of the combine production method of glycine described in claim 1 and glycolylurea, it is characterized in that: comprise ammonia oxonation liquid productive unit, glycolylurea productive unit and glycine productive unit, described ammonia oxonation liquid productive unit comprises the static mixer I be communicated with successively, tubular reactor I, gas stripping column I and storage tank, described glycolylurea productive unit comprises acidizing device, described glycine productive unit comprises the static mixer II and tubular reactor II that are communicated with successively, in described ammonia oxonation liquid productive unit, the outlet of storage tank is respectively by valve I, the opening for feed of acidizing device in valve II and glycolylurea productive unit, in glycine productive unit, the opening for feed of static mixer II is communicated with.
10. the device of the combine production method for realizing glycine and glycolylurea according to claim 10, it is characterized in that: described glycolylurea productive unit comprises the MVR vapo(u)rization system I be communicated with successively, acidizing device, decoloration device I, crystallization apparatus I, centrifugal device I and drying installation I, described glycine productive unit comprises the static mixer II be communicated with successively, tubular reactor II, gas stripping column II, decoloration device II, MVR vapo(u)rization system II, crystallization apparatus II, centrifugal device II and drying installation II, in described ammonia oxonation liquid productive unit, the outlet of storage tank is respectively by valve I, the opening for feed of MVR vapo(u)rization system I in valve II and glycolylurea productive unit, in glycine productive unit, the opening for feed of static mixer II is communicated with.
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| CN201510199303.5A CN104910031B (en) | 2015-04-24 | 2015-04-24 | The combine production method and device of glycine and hydantoins |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109678744A (en) * | 2017-10-18 | 2019-04-26 | 阳泉煤业（集团）有限责任公司 | A kind of method that serialization prepares glycine |
| 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 |
| 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 |
| 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678744A (en) * | 2017-10-18 | 2019-04-26 | 阳泉煤业（集团）有限责任公司 | A kind of method that serialization prepares glycine |
| CN109678744B (en) * | 2017-10-18 | 2021-11-26 | 阳泉煤业（集团）有限责任公司 | Method for continuously preparing glycine |
| 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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| CN104910031B (en) | 2017-03-29 |
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