CN102432478B - Preparation process of glycine - Google Patents
Preparation process of glycine Download PDFInfo
- Publication number
- CN102432478B CN102432478B CN2011103518930A CN201110351893A CN102432478B CN 102432478 B CN102432478 B CN 102432478B CN 2011103518930 A CN2011103518930 A CN 2011103518930A CN 201110351893 A CN201110351893 A CN 201110351893A CN 102432478 B CN102432478 B CN 102432478B
- Authority
- CN
- China
- Prior art keywords
- glycine
- mother liquor
- ammonia
- solid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation process of glycine, which comprises amination, alkaline hydrolysis, ammonia discharge acidification, decolorizing, concentration, desalting, crystallization and recrystallization steps, wherein in the amination step, hydroxyacetonitrile and ammonia water are mixed in a tubular reactor, and a reaction is undergone at the temperature of 50-100 DEG C under the pressure of 0.5-2.0 MPa for 4-10 minutes; and in the alkaline hydrolysis step, 30-50 percent of sodium hydroxide solution is added into an alkaline hydrolysis reactor in advance, an amination liquid is collected from an amination liquid outlet, a reaction is undergone at the temperature of 60-90 DEG C under the pressure of between -0.01 MPa and -0.09 MPa, and ammonia in a system is recovered simultaneously. In the process, the tubular reactor is taken as an amination reactor, so that the reaction temperature and pressure are raised, the reaction time is shortened, and raw material decomposition, pyrolytic polymerization of aminoacetonitrile and the generation of byproducts are reduced; alkaline hydrolysis is performed during the collection of the amination liquid, the concentration of an alkaline liquor and the alkaline hydrolysis temperature are raised simultaneously, and ammonia in the system is recovered under reduced pressure, so that the alkaline hydrolysis reaction is more complete, the speed is higher, and the generation of colored impurities is reduced; and a mother liquor circular utilizing mode is established, so that the treatment amount of waste mother liquor is reduced, the product yield is increased, and the production cost is reduced.
Description
Technical field
The present invention relates to chemical field, particularly take hydroxyacetonitrile and ammoniacal liquor, prepare the technique of glycine as raw material.
Background technology
Glycine is a kind of important fine chemical product, is widely used in the fields such as medicine, food, chemical industry, agricultural chemicals.The preparation technology of glycine has multiple, Chinese patent CN1962611B discloses a kind of technique of preparing glycine by hydroxy acetonitrile method, comprise the steps: 1) hydroxyacetonitrile, ammoniacal liquor are mixed, the mol ratio of reaction feed liquid is hydroxyacetonitrile: ammonia=1:2 ~ 10, control temperature of reaction between 20 ~ 60 ℃, reaction times is 0.5 ~ 8 hour, obtains the ammonia soln of aminoacetonitriles; 2) directly add mineral alkali in the ammonification liquid that obtains to step 1), the mol ratio of reaction mass is aminoacetonitriles: mineral alkali=1:0.7 ~ 3.0, and temperature of reaction is controlled and is no more than 100 ℃, reacts 1 ~ 8 hour, obtains containing the alkali solution liquid of glycinate; 3) with step 2) after the alkali solution liquid deamination that obtains with the mineral acid neutralization, the consumption of mineral acid be in and the consumption of mineral alkali, the mol ratio that adopts during reaction is glycinate: mineral acid=1:0.7 ~ 3.0, obtains neutralizer; 4) neutralizer that step 3) is obtained adds activated carbon decolorizing, and destainer obtains glycine and inorganic salt through concentrated fractional crystallization and recrystallization.Above-mentioned preparation technology's reaction conditions is gentle, easily control, and aftertreatment is simple, but its there are the following problems: in step 1), the reaction times grow (〉=0.5 hour), causes easily that raw material decomposes, aminoacetonitriles pyrolysis polymerization and by product generation; Step 2) concentration lower (32%) of mineral alkali sodium hydroxide solution in, alkaline hydrolysis temperature lower (40 ~ 60 ℃), alkaline hydrolysis speed is slower, easily cause foreign pigment to generate, thereby increase decolouring difficulty and discoloring agent consumption, in addition, the alkali solution liquid volume is large, and follow-up concentration time prolongation, energy consumption are increased; Do not disclose the recycle mode of mother liquor in step 4), the waste mother liquor treatment capacity is larger, and product yield is lower, and production cost is higher.
Summary of the invention
In view of this, the object of the invention is to the technique of preparing glycine by hydroxy acetonitrile method is improved,, to shorten the aminating reaction time, reduce raw material decomposition, aminoacetonitriles pyrolysis polymerization and by product and generate; Accelerate the alkaline hydrolysis speed of reaction, reduce foreign pigment and generate; Set up the mother liquid recycling mode, reduce the waste mother liquor treatment capacity, improve product yield, reduce production costs.
, through research repeatedly, the invention provides following technical scheme:
The preparation technology of glycine, comprise the steps:
A. ammonification: being that 1:3 ~ 6 are mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, is that 50 ~ 100 ℃, pressure are to react 4 ~ 10 minutes under the condition of 0.5 ~ 2.0MPa in temperature, obtains the aminoacetonitriles reaction solution;
B. alkaline hydrolysis: be that to add in advance mass percentage concentration be 30 ~ 50% sodium hydroxide solution to 1.05 ~ 1.3:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, the aminoacetonitriles reaction solution that flows out from the tubular reactor outlet directly enters the alkaline hydrolysis reactor, temperature be 60 ~ 90 ℃, pressure be-0.01 ~-reacted 2 ~ 4 hours under the condition of 0.09MPa, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution;
C. ammonia excretion, acidifying: the Sodium glycocollate reaction solution is carried out ammonia excretion process, the reaction solution after ammonia excretion is neutralized to pH5 ~ 6 with sulfuric acid, obtains glycine reactant liquid;
D. decolouring:, with glycine reactant liquid activated carbon decolorizing, obtain the glycine destainer;
E. concentrated desalination, crystallization: it is 25 ~ 35% that the glycine destainer is concentrated into the glycine mass percentage concentration, and sodium sulfate is separated out, and solid-liquid separation obtains respectively sodium sulfate solid and glycine solution; Again the gained glycine solution is stirred and is cooled to 20 ~ 35 ℃, glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor Ia;
F. recrystallization:, with glycine crude product recrystallization, obtain glycine product.
Preferably, in step e, gained sodium sulfate solid is washed with water, washings and mother liquor Ia merge into mother liquor Ib, and mother liquor Ib is mixed with the glycine destainer when next batch is produced, and concentrate desalination, crystallization; Like this recycled, stop applying mechanically when the mass percentage concentration accumulation of iminodiethanoic acid in mother liquor Ib surpasses 8%, mother liquor Ib is carried out double concentrated desalination, crystallization treatment:
I. mother liquor Ib being concentrated into the glycine mass percentage concentration is 25 ~ 26%, and sodium sulfate is separated out, solid-liquid separation, and the gained solid sodium sulfate washes with water, and washings is standby; The gained liquid agitation is cooled to 20 ~ 35 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIa; Washings and mother liquor IIa are merged into mother liquor IIb;
II. mother liquor IIb being concentrated into the glycine mass percentage concentration is 25 ~ 26%, and sodium sulfate is separated out, solid-liquid separation, and the gained solid sodium sulfate washes with water, and washings is standby; The gained liquid agitation is cooled to 20 ~ 35 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIIa; Washings and mother liquor IIIa are merged into mother liquor IIIb.The processing mode of mother liquor IIIb can be considered following two kinds: a kind of is as waste liquid, directly burning disposal; Another kind is to extract iminodiethanoic acid from mother liquor IIIb, and surplus solution returns to concentrated desalination again, crystallisation step removes to continue to extract glycine.Definite needs of above-mentioned two kinds of processing modes consider technically with on the industrial production cost.
Preferred, step e stirs the gained glycine solution to be cooled to 25 ~ 28 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor Ia.Step I and II are cooled to 25 ~ 28 ℃ with the gained liquid agitation, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIa or IIIa.
Preferably, in step f, with glycine crude product water recrystallization, solid-liquid separation, obtain respectively glycine product and recrystallization mother liquor, the gained recrystallization mother liquor is as the recrystallization solvent recycled of next batch glycine crude product, to glycine product purity, stops applying mechanically during lower than criterion of acceptability, recrystallization mother liquor is mixed with the glycine destainer when next batch is produced, concentrate desalination, crystallization.
Preferably, step a is to be that 1:3 ~ 5 are mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, in temperature, is that 60 ~ 95 ℃, pressure are to react 4 ~ 8 minutes under the condition of 0.7 ~ 1.3MPa, obtains the aminoacetonitriles reaction solution.Preferred, step a is to be that 1:4 is mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, in temperature, is that 83 ℃, pressure are reaction 6 minutes under the condition of 1.3MPa, obtains the aminoacetonitriles reaction solution.
Preferably, step b is to be that to add in advance mass percentage concentration be 40 ~ 50% sodium hydroxide solution to 1.1 ~ 1.2:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, temperature be 70 ~ 90 ℃, pressure be-0.02 ~-reacted 2 ~ 3 hours under the condition of 0.5MPa, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution.Preferred, step b is to be that to add in advance mass percentage concentration be 50% sodium hydroxide solution to 1.1:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, temperature be 80 ℃, pressure for the condition of-0.02MPa under reaction 3 hours, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution.
Beneficial effect of the present invention is:
1. the present invention is used tubular reactor as the ammoniation reactor of hydroxyacetonitrile and ammoniacal liquor, and on this basis the ammonification processing parameter is optimized: temperature of reaction is that 50 ~ 100 ℃, reaction pressure are that 0.5 ~ 2.0MPa, reaction times are 4 ~ 10 minutes; With the disclosed ammonification processing parameter of Chinese patent CN1962611B: temperature of reaction is that 20 ~ 60 ℃, normal pressure, reaction times are to compare in 0.5 ~ 8 hour, ammonification technique of the present invention has improved temperature of reaction and reaction pressure, make the reaction times shorten at least 3 times, this means that the ammonification throughput under same time has improved 3 times at least, simultaneously, owing to having shortened the reaction times, also, with regard to the corresponding generation that reduces raw material decomposition, aminoacetonitriles pyrolysis polymerization and by product, improved the yield of aminoacetonitriles.
2. the present invention selects sodium hydroxide cheap and easy to get as alkaline hydrolysis reagent, and on this basis alkaline hydrolysis technique and parameter are optimized: it is that 50% solution adds in the alkaline hydrolysis reactor in advance that sodium hydroxide is made into mass percentage concentration, directly in the outlet of ammonification liquid, collect ammonification liquid with the alkaline hydrolysis reactor again, make enter the alkaline hydrolysis reactor ammonification liquid immediately temperature be 60 ~ 90 ℃, pressure be-0.02 ~-reaction that is hydrolyzed under the condition of 0.09MPa, 2 ~ 4 hours time; With the disclosed alkaline hydrolysis technique of Chinese patent CN1962611B and parameter: to the sodium hydroxide solution that adds 32% in ammonification liquid, 40 ~ 60 ℃ of reactions of temperature were compared in 4 ~ 5 hours, alkaline hydrolysis technique of the present invention is that ammonification liquid limit alkaline hydrolysis is collected on limit, reduce the retention time of ammonification liquid as far as possible, make unsettled aminoacetonitriles be converted into as early as possible stable Sodium glycocollate; Simultaneously, the present invention has improved concentration of lye and alkaline hydrolysis temperature, and the ammonia that exists in the reclaim under reduced pressure reaction system in hydrolysis reaction (comprising the ammonia that generates in the excess ammonia that adds in step a and alkaline hydrolysis process), the alkaline hydrolysis molecular balance is moved to right, alkaline hydrolysis is more complete, alkaline hydrolysis speed is accelerated, thereby improve the yield of Sodium glycocollate, reducing foreign pigment generates, reduce decolouring difficulty and discoloring agent consumption (in the glycine theoretical yield, the activated carbon dosage of the inventive method can be contracted to 5% by 20% before improving), reduce production costs, environmental contamination reduction; In addition, the present invention brings up to 50% with concentration of lye from 32%, and the volume of gained alkali solution liquid technique compared with before-improvement dwindles greatly, can significantly shorten the concentration time of follow-up enrichment process, reduces concentrated energy consumption.
3. openly the mother liquid recycle method after concentrated desalination, crystallization and the using method of glycine recrystallization mother liquor in Chinese patent CN1962611B, the present invention has set up the using method of above-mentioned mother liquor through research repeatedly.wherein, concentrated desalination, mother liquid recycle method after crystallization is that the mother liquor Ia that last consignment of production obtains is mixed with the glycine destainer when next batch is produced, concentrate desalination, crystallization, when surpassing 8%, the amount accumulation of by product iminodiethanoic acid in mother liquor Ia stops applying mechanically that (iminodiethanoic acid surpasses 8%, the glycine crude product purity that crystallization obtains is sharply descended, and then affect the recrystallization of glycine, cause the glycine product purity defective), carry out double concentrated desalination, crystallization treatment, the sodium sulfate solid that collection is separated out and glycine crude product, to reduce the loss of glycine as far as possible, improve the glycine product yield, reduce the waste mother liquor treatment capacity, reduce environmental pollution.The contriver is at the beginning of research, also once attempted the continuous circulation with mother liquor Ia, and with the using method of the circulating mother liquor continuous lateral line extraction of imido-oxalic acid 8% left and right, but found that, this processing mode easily causes the content of glycine in destainer to be in all the time the criticality of with iminodiethanoic acid, separating and to be difficult to obtain qualified glycine crude product, and production can't be carried out continuously.Finally, the contriver has set up the mother liquid recycle method after concentrated desalination of the present invention, crystallization, has successfully solved the problems referred to above.The using method of glycine recrystallization mother liquor is that the mother liquor after last consignment of glycine crude product recrystallization is carried out recycled as the recrystallization solvent of next batch glycine crude product, stop during lower than criterion of acceptability (as 98%) to gained glycine product purity applying mechanically, recrystallization mother liquor when producing, is mixed with the glycine destainer next batch, concentrate desalination, crystallization, the method can reduce the loss of glycine equally, improve the yield of glycine product, reduce the waste mother liquor treatment capacity, reduce environmental pollution.
Description of drawings
Fig. 1 is the schematic flow sheet of process for preparing glycine of the present invention.
Embodiment
, in order to make the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.Should be appreciated that preferred embodiment only for the present invention is described, rather than in order to limit the scope of the invention.
The preferred flow schematic diagram of technique of the present invention as shown in Figure 1.
Embodiment 1
First production specifically comprises the following steps:
A. ammonification: the ammoniacal liquor 1175g that is 23% with hydroxyacetonitrile 228.06g and mass percentage concentration mixes (mol ratio of hydroxyacetonitrile and ammonia is 1:4), pump in tubular reactor, it is 83 ℃ in temperature, pressure is to carry out aminating reaction under the condition of 1.3MPa, be 6 minutes by the coutroi velocity adjusting reaction time, obtain the aminoacetonitriles reaction solution;
b. alkaline hydrolysis: adding in advance mass percentage concentration in the alkaline hydrolysis reactor is that 50% sodium hydroxide solution 351.82g(sodium hydroxide and the mol ratio of hydroxyacetonitrile are 1.1:1), collect the aminoacetonitriles reaction solution with the alkaline hydrolysis reactor in the outlet of tubular reactor, the aminoacetonitriles reaction solution that enters in the alkaline hydrolysis reactor is 80 ℃ in temperature immediately, carry out the alkaline hydrolysis reaction under the condition of pressure for-0.02MPa, in alkaline hydrolysis reaction time, reclaimed the ammonia that exists in reaction system (comprising the ammonia that generates in the excess ammonia that adds in step a and alkaline hydrolysis process), after the whole collections of aminoacetonitriles reaction solution are complete, continuation was reacted 3 hours under above-mentioned reaction conditions, obtain the Sodium glycocollate reaction solution,
C. ammonia excretion, acidifying: the Sodium glycocollate reaction solution is carried out ammonia excretion process under the condition that temperature is 75 ℃, pressure for-0.09MPa, when the free ammonia content in reaction solution lower than 0.5% the time, slowly drip sulfuric acid in reaction solution, conditioned reaction liquid pH to 5.5, control during this time reacting liquid temperature and be no more than 100 ℃, obtain glycine reactant liquid;
D. decolouring: add gac 40g in glycine reactant liquid, 90 ℃ decoloured 30 minutes, and suction filtration obtains the glycine destainer;
E. concentrated desalination, crystallization: the mass percentage concentration that the heating of glycine destainer is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively sodium sulfate solid and glycine solution; The gained glycine solution stirs and is cooled to 26 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor Ia; Gained sodium sulfate solid adds the water washing that is equivalent to sodium sulfate weight 45%, and 50 ℃ of heated and stirred 30 minutes are centrifugal, obtain respectively sodium sulfate solid and washings; Washings and mother liquor Ia are merged into mother liquor Ib, standby;
F. recrystallization: the glycine crude product such as is added at the water gaging, be heated to 98 ℃ and make abundant dissolving, then be cooled to 26 ℃, stirred crystallization was separated out glycine in 1 hour, and is centrifugal, obtains respectively glycine product and recrystallization mother liquor; The gained glycine product is in 102 ℃ of dryings; The gained recrystallization mother liquor is standby.
After second batch reaches, batch production: step e mixes the mother liquor Ib that glycine destainer and last consignment of production obtain, and concentrates desalination, crystallization; Like this recycled, to the
nBatch (
nFor positive integer) the mass percentage concentration accumulation of producing by product iminodiethanoic acid in the mother liquor Ib obtain stops above-mentioned applying mechanically while surpassing 8%, and mother liquor Ib is carried out double concentrated desalination, crystallization treatment according to following step:
I. the mass percentage concentration that mother liquor Ib heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 26 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIa; Washings and mother liquor IIa are merged into mother liquor IIb;
II. the mass percentage concentration that mother liquor IIb heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 26 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIIa; Washings and mother liquor IIIa are merged into mother liquor IIIb, as waste liquid, carry out burning disposal.
Step f is the recrystallization mother liquor that adds last consignment of production to obtain in the glycine crude product, carries out recrystallization after heating is fully dissolved glycine; Like this recycled, to the
mBatch (
mFor positive integer) stop above-mentioned applying mechanically while producing the glycine product purity obtain lower than criterion of acceptability (98%), recrystallization mother liquor when producing, is mixed with the glycine destainer next batch, concentrate desalination, crystallization.
Adopt the present embodiment technological cycle to produce six times, obtain altogether glycine product 1771.67g, take average folding hundred yields of hydroxyacetonitrile as 97.0%.
Embodiment 2
First production specifically comprises the following steps:
A. ammonification: the ammoniacal liquor 881.3g that is 23% with hydroxyacetonitrile 228.06g and mass percentage concentration mixes (mol ratio of hydroxyacetonitrile and ammonia is 1:3), pump in tubular reactor, it is 50 ℃ in temperature, pressure is to carry out aminating reaction under the condition of 2.0MPa, be 4 minutes by the coutroi velocity adjusting reaction time, obtain the aminoacetonitriles reaction solution;
b. alkaline hydrolysis: adding in advance mass percentage concentration in the alkaline hydrolysis reactor is that 50% sodium hydroxide solution 416g(sodium hydroxide and the mol ratio of hydroxyacetonitrile are 1.3:1), collect the aminoacetonitriles reaction solution with the alkaline hydrolysis reactor in the outlet of tubular reactor, the aminoacetonitriles reaction solution that enters in the alkaline hydrolysis reactor is 60 ℃ in temperature immediately, carry out the alkaline hydrolysis reaction under the condition of pressure for-0.09MPa, in alkaline hydrolysis reaction time, reclaimed the ammonia that exists in reaction system (comprising the ammonia that generates in the excess ammonia that adds in step a and alkaline hydrolysis process), after the whole collections of aminoacetonitriles reaction solution are complete, continuation was reacted 4 hours under above-mentioned reaction conditions, obtain the Sodium glycocollate reaction solution,
C. ammonia excretion, acidifying: the Sodium glycocollate reaction solution is carried out ammonia excretion process under the condition that temperature is 80 ℃, pressure for-0.09MPa, when the free ammonia content in reaction solution lower than 0.5% the time, slowly drip sulfuric acid in reaction solution, conditioned reaction liquid pH to 6.0, control during this time reacting liquid temperature and be no more than 100 ℃, obtain glycine reactant liquid;
D. decolouring: add gac 40g in glycine reactant liquid, 90 ℃ decoloured 30 minutes, and suction filtration obtains the glycine destainer;
E. concentrated desalination, crystallization: the mass percentage concentration that the heating of glycine destainer is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively sodium sulfate solid and glycine solution; The gained glycine solution stirs and is cooled to 20 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor Ia; Gained sodium sulfate solid adds the water washing that is equivalent to sodium sulfate weight 45%, and 50 ℃ of heated and stirred 30 minutes are centrifugal, obtain respectively sodium sulfate solid and washings; Washings and mother liquor Ia are merged into mother liquor Ib, standby;
F. recrystallization: the glycine crude product such as is added at the water gaging, be heated to 98 ℃ and make abundant dissolving, then be cooled to 20 ℃, stirred crystallization was separated out glycine in 2 hours, and is centrifugal, obtains respectively glycine product and recrystallization mother liquor; The gained glycine product is in 102 ℃ of dryings; The gained recrystallization mother liquor is standby.
After second batch reaches, batch production: step e mixes the mother liquor Ib that glycine destainer and last consignment of production obtain, and concentrates desalination, crystallization; Like this recycled, to the
nBatch (
nFor positive integer) the mass percentage concentration accumulation of producing by product iminodiethanoic acid in the mother liquor Ib obtain stops above-mentioned applying mechanically while surpassing 8%, and mother liquor Ib is carried out double concentrated desalination, crystallization treatment according to following step:
I. the mass percentage concentration that mother liquor Ib heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 20 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIa; Washings and mother liquor IIa are merged into mother liquor IIb;
II. the mass percentage concentration that mother liquor IIb heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 20 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIIa; Washings and mother liquor IIIa are merged into mother liquor IIIb, as waste liquid, carry out burning disposal.
Step f is the recrystallization mother liquor that adds last consignment of production to obtain in the glycine crude product, carries out recrystallization after heating is fully dissolved glycine; Like this recycled, to the
mBatch (
mFor positive integer) stop above-mentioned applying mechanically while producing the glycine product purity obtain lower than criterion of acceptability (98%), recrystallization mother liquor when producing, is mixed with the glycine destainer next batch, concentrate desalination, crystallization.
Adopt the present embodiment technological cycle to produce six times, obtain altogether glycine product 1723.93g, take average folding hundred yields of hydroxyacetonitrile as 94.3%.
Embodiment 3
First production specifically comprises the following steps:
A. ammonification: the ammoniacal liquor 1762.5g that is 23% with hydroxyacetonitrile 228.06g and mass percentage concentration mixes (mol ratio of hydroxyacetonitrile and ammonia is 1:6), pump in tubular reactor, it is 100 ℃ in temperature, pressure is to carry out aminating reaction under the condition of 0.5MPa, be 10 minutes by the coutroi velocity adjusting reaction time, obtain the aminoacetonitriles reaction solution;
b. alkaline hydrolysis: adding in advance mass percentage concentration in the alkaline hydrolysis reactor is that 50% sodium hydroxide solution 384g(sodium hydroxide and the mol ratio of hydroxyacetonitrile are 1.2:1), collect the aminoacetonitriles reaction solution with the alkaline hydrolysis reactor in the outlet of tubular reactor, the aminoacetonitriles reaction solution that enters in the alkaline hydrolysis reactor is 90 ℃ in temperature immediately, carry out the alkaline hydrolysis reaction under the condition of pressure for-0.06MPa, in alkaline hydrolysis reaction time, reclaimed the ammonia that exists in reaction system (comprising the ammonia that generates in the excess ammonia that adds in step a and alkaline hydrolysis process), after the whole collections of aminoacetonitriles reaction solution are complete, continuation was reacted 2 hours under above-mentioned reaction conditions, obtain the Sodium glycocollate reaction solution,
C. ammonia excretion, acidifying: the Sodium glycocollate reaction solution is carried out ammonia excretion process under the condition that temperature is 70 ℃, pressure for-0.08MPa, when the free ammonia content in reaction solution lower than 0.5% the time, slowly drip sulfuric acid in reaction solution, conditioned reaction liquid pH to 5.0, control during this time reacting liquid temperature and be no more than 100 ℃, obtain glycine reactant liquid;
D. decolouring: add gac 20g in glycine reactant liquid, 90 ℃ decoloured 30 minutes, and suction filtration obtains the glycine destainer;
E. concentrated desalination, crystallization: the mass percentage concentration that the heating of glycine destainer is concentrated into glycine is that 25%(sodium sulfate is separated out), centrifugal while hot, obtain respectively sodium sulfate solid and glycine solution; The gained glycine solution stirs and is cooled to 35 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor Ia; Gained sodium sulfate solid adds the water washing that is equivalent to sodium sulfate weight 45%, and 50 ℃ of heated and stirred 30 minutes are centrifugal, obtain respectively sodium sulfate solid and washings; Washings and mother liquor Ia are merged into mother liquor Ib, standby;
F. recrystallization: the glycine crude product such as is added at the water gaging, be heated to 98 ℃ and make abundant dissolving, then be cooled to 35 ℃, stirred crystallization was separated out glycine in 1.5 hours, and is centrifugal, obtains respectively glycine product and recrystallization mother liquor; The gained glycine product is in 102 ℃ of dryings; The gained recrystallization mother liquor is standby.
After second batch reaches, batch production: step e mixes the mother liquor Ib that glycine destainer and last consignment of production obtain, and concentrates desalination, crystallization; Like this recycled, to the
nBatch (
nFor positive integer) the mass percentage concentration accumulation of producing by product iminodiethanoic acid in the mother liquor Ib obtain stops above-mentioned applying mechanically while surpassing 8%, and mother liquor Ib is carried out double concentrated desalination, crystallization treatment according to following step:
I. the mass percentage concentration that mother liquor Ib heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 35 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIa; Washings and mother liquor IIa are merged into mother liquor IIb;
II. the mass percentage concentration that mother liquor IIb heating is concentrated into glycine is that 25 ~ 26%(sodium sulfate is separated out), centrifugal while hot, obtain respectively solid sodium sulfate and liquid, the gained solid sodium sulfate adds the water washing that is equivalent to sodium sulfate weight 45%, 50 ℃ of heated and stirred 30 minutes, centrifugal, obtain respectively solid sodium sulfate and washings; The gained liquid agitation is cooled to 35 ℃ (glycine is separated out), and is centrifugal, obtains respectively glycine crude product and mother liquor IIIa; Washings and mother liquor IIIa are merged into mother liquor IIIb, as waste liquid, carry out burning disposal.
Step f is the recrystallization mother liquor that adds last consignment of production to obtain in the glycine crude product, carries out recrystallization after heating is fully dissolved glycine; Like this recycled, to the
mBatch (
mFor positive integer) stop above-mentioned applying mechanically while producing the glycine product purity obtain lower than criterion of acceptability (98%), recrystallization mother liquor when producing, is mixed with the glycine destainer next batch, concentrate desalination, crystallization.
Adopt the present embodiment technological cycle to produce six times, obtain altogether glycine product 1753.44g, take average folding hundred yields of hydroxyacetonitrile as 95.7%.
Claims (8)
1. the preparation technology of glycine, is characterized in that, comprises the steps:
A. ammonification: being that 1:3 ~ 6 are mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, is that 50 ~ 100 ℃, pressure are to react 4 ~ 10 minutes under the condition of 0.5 ~ 2.0MPa in temperature, obtains the aminoacetonitriles reaction solution;
B. alkaline hydrolysis: be that to add in advance mass percentage concentration be 30 ~ 50% sodium hydroxide solution to 1.05 ~ 1.3:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, the aminoacetonitriles reaction solution that flows out from the tubular reactor outlet directly enters the alkaline hydrolysis reactor, temperature be 60 ~ 90 ℃, pressure be-0.01 ~-reacted 2 ~ 4 hours under the condition of 0.09MPa, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution;
C. ammonia excretion, acidifying: the Sodium glycocollate reaction solution is carried out ammonia excretion process, the reaction solution after ammonia excretion is neutralized to pH5 ~ 6 with sulfuric acid, obtains glycine reactant liquid;
D. decolouring:, with glycine reactant liquid activated carbon decolorizing, obtain the glycine destainer;
E. concentrated desalination, crystallization: it is 25 ~ 26% that the glycine destainer is concentrated into the glycine mass percentage concentration, and sodium sulfate is separated out, and solid-liquid separation obtains respectively sodium sulfate solid and glycine solution; Again the gained glycine solution is stirred and is cooled to 20 ~ 35 ℃, glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor Ia;
Gained sodium sulfate solid is washed with water, and washings and mother liquor Ia merge into mother liquor Ib, and mother liquor Ib is mixed with the glycine destainer when next batch is produced, and concentrate desalination, crystallization; Like this recycled, stop applying mechanically when the mass percentage concentration accumulation of iminodiethanoic acid in mother liquor Ib surpasses 8%, mother liquor Ib is carried out double concentrated desalination, crystallization treatment:
I. mother liquor Ib being concentrated into the glycine mass percentage concentration is 25 ~ 26%, and sodium sulfate is separated out, solid-liquid separation, and the gained solid sodium sulfate washes with water, and washings is standby; The gained liquid agitation is cooled to 20 ~ 35 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIa; Washings and mother liquor IIa are merged into mother liquor IIb;
II. mother liquor IIb being concentrated into the glycine mass percentage concentration is 25 ~ 26%, and sodium sulfate is separated out, solid-liquid separation, and the gained solid sodium sulfate washes with water, and washings is standby; The gained liquid agitation is cooled to 20 ~ 35 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIIa; Washings and mother liquor IIIa are merged into mother liquor IIIb;
F. recrystallization:, with glycine crude product recrystallization, obtain glycine product.
2. the preparation technology of glycine according to claim 1, it is characterized in that, in step f, with glycine crude product water recrystallization, solid-liquid separation, obtain respectively glycine product and recrystallization mother liquor, the gained recrystallization mother liquor is as the recrystallization solvent recycled of next batch glycine crude product, stop during lower than criterion of acceptability to glycine product purity applying mechanically, recrystallization mother liquor is mixed with the glycine destainer when next batch is produced, concentrate desalination, crystallization.
3. the preparation technology of glycine according to claim 1 and 2, it is characterized in that, step a is to be that 1:3 ~ 5 are mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, be that 60 ~ 95 ℃, pressure are to react 4 ~ 8 minutes under the condition of 0.7 ~ 1.3MPa in temperature, obtain the aminoacetonitriles reaction solution.
4. the preparation technology of glycine according to claim 3, it is characterized in that, step a is to be that 1:4 is mixed in tubular reactor with hydroxyacetonitrile and ammoniacal liquor according to the mol ratio of hydroxyacetonitrile and ammonia, be that 83 ℃, pressure are reaction 6 minutes under the condition of 1.3MPa in temperature, obtain the aminoacetonitriles reaction solution.
5. the preparation technology of glycine according to claim 1 and 2, it is characterized in that, step b is to be that to add in advance mass percentage concentration be 40 ~ 50% sodium hydroxide solution to 1.1 ~ 1.2:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, temperature be 70 ~ 90 ℃, pressure be-0.02 ~-reacted 2 ~ 3 hours under the condition of 0.06MPa, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution.
6. the preparation technology of glycine according to claim 5, it is characterized in that, step b is to be that to add in advance mass percentage concentration be 50% sodium hydroxide solution to 1.1:1 according to the mol ratio of sodium hydroxide and hydroxyacetonitrile in the alkaline hydrolysis reactor, temperature be 80 ℃, pressure for the condition of-0.02MPa under reaction 3 hours, reclaim simultaneously the ammonia that exists in reaction system, obtain the Sodium glycocollate reaction solution.
7. the preparation technology of glycine according to claim 1 and 2, is characterized in that, step e stirs the gained glycine solution to be cooled to 25 ~ 28 ℃, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor Ia.
8. the preparation technology of glycine according to claim 1, is characterized in that, step I and II are cooled to 25 ~ 28 ℃ with the gained liquid agitation, and glycine is separated out, and solid-liquid separation obtains respectively glycine crude product and mother liquor IIa or IIIa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103518930A CN102432478B (en) | 2011-11-09 | 2011-11-09 | Preparation process of glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103518930A CN102432478B (en) | 2011-11-09 | 2011-11-09 | Preparation process of glycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432478A CN102432478A (en) | 2012-05-02 |
| CN102432478B true CN102432478B (en) | 2013-11-13 |
Family
ID=45980874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103518930A Expired - Fee Related CN102432478B (en) | 2011-11-09 | 2011-11-09 | Preparation process of glycine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432478B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744279B (en) * | 2015-04-03 | 2016-09-07 | 重庆紫光化工股份有限公司 | Remove the method for impurity in glycine crystallization mother liquid |
| CN105017047B (en) * | 2015-06-16 | 2017-08-25 | 重庆紫光化工股份有限公司 | The production method and device of a kind of iminodiacetic acid |
| CN106397236A (en) * | 2016-08-31 | 2017-02-15 | 冀州市华阳化工有限责任公司 | Glycine purification method |
| CN106748839B (en) * | 2016-11-17 | 2018-11-16 | 重庆紫光化工股份有限公司 | A kind of clean preparation method of glycine and iminodiacetic acid coproduction |
| CN108623489B (en) * | 2017-03-23 | 2021-02-05 | 重庆紫光川庆化工有限责任公司 | Method for synthesizing glycine by continuously and rapidly alkaline hydrolyzing aminoacetonitrile |
| CN107963975A (en) * | 2017-06-20 | 2018-04-27 | 重庆紫光化工股份有限公司 | The clean preparation method and device of glycine |
| CN107325015B (en) * | 2017-08-15 | 2020-03-17 | 阳泉煤业（集团）有限责任公司 | Method for continuously preparing glycine from hydroxyacetonitrile |
| 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 |
| CN109053596A (en) * | 2018-09-11 | 2018-12-21 | 成都百事兴科技实业有限公司 | A kind of new synthetic method of orotic acid |
| CN113563215B (en) * | 2021-07-30 | 2024-02-02 | 上海蓝科石化环保科技股份有限公司 | Glycine production process |
| CN114057610A (en) * | 2021-11-30 | 2022-02-18 | 湖北省宏源药业科技股份有限公司 | Production method of high-purity guanidine thiocyanate |
| CN115448885A (en) * | 2022-10-24 | 2022-12-09 | 生工生物工程（上海）股份有限公司 | Imidazole purification method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962611A (en) * | 2005-11-11 | 2007-05-16 | 重庆三峡英力化工有限公司 | Process for preparing glycine using hydroxy-acetonitrile method |
| CN101747218A (en) * | 2008-12-16 | 2010-06-23 | 北京紫光英力化工技术有限公司 | Method for removing impurities in glycine synthetic process |
-
2011
- 2011-11-09 CN CN2011103518930A patent/CN102432478B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962611A (en) * | 2005-11-11 | 2007-05-16 | 重庆三峡英力化工有限公司 | Process for preparing glycine using hydroxy-acetonitrile method |
| CN101747218A (en) * | 2008-12-16 | 2010-06-23 | 北京紫光英力化工技术有限公司 | Method for removing impurities in glycine synthetic process |
Non-Patent Citations (2)
| Title |
|---|
| 朱志华等.甘氨酸合成新工艺的研究.《石油化工》.2005,第34卷(第增刊期),279-281. |
| 甘氨酸合成新工艺的研究;朱志华等;《石油化工》;20051231;第34卷(第增刊期);279-281 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432478A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432478B (en) | Preparation process of glycine | |
| JP6931284B2 (en) | How to make taurine | |
| JP2019513688A5 (en) | ||
| CN103880690B (en) | A kind of environment friendly clean producing method of glycine | |
| CN102936214B (en) | Method for clean preparation H acid | |
| CN102442917A (en) | Energy-saving and environment-friendly method for producing glycin based on chloroacetic acid method | |
| CN102241606A (en) | Clean production method of N-cyanoethylaniline | |
| CN101492399B (en) | Method for preparing methylpropene sodium sulfonate | |
| CN111004162B (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| CN104193634B (en) | A kind of separation of ammonia guanidine-acetic acid and the method for ammonium chloride mixed crystal | |
| CN101805371A (en) | Method for recycling glyphosate raw powder from glyphosate mother liquid | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN106220578A (en) | A kind of new benzoguanamine production method | |
| CN103756359B (en) | A kind for the treatment of process of p-β hydroxyethyl sulfone Acetanilide mother liquor waste water | |
| CN102838497A (en) | Cleaning production process of glycine | |
| CN106748839B (en) | A kind of clean preparation method of glycine and iminodiacetic acid coproduction | |
| CN106279052A (en) | The production method that benzoguanamine is new | |
| CN204714732U (en) | The co-generation system of glycine and iminodiethanoic acid | |
| CN204508823U (en) | Its Future about Alkaline Residue Treatment Unit is mixed in indigo production | |
| CN104692422B (en) | Its Future about Alkaline Residue Treatment Unit and treatment process is mixed in indigo production | |
| CN100365071C (en) | Method for producing indigo by recycling unreacted raw materials | |
| CN101591255A (en) | A kind of process for cleanly preparing of iminodiethanoic acid | |
| CN111362819A (en) | Process and device for producing glycine by alcohol phase method | |
| CN106977414B (en) | A kind of preparation method of l-Isoleucine | |
| CN210419811U (en) | Amine alcohol compound reaction system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131113 Termination date: 20201109 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |