CN107311878B - Device for recycling glycine waste liquid and method for recycling glycine waste liquid - Google Patents
Device for recycling glycine waste liquid and method for recycling glycine waste liquid Download PDFInfo
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- CN107311878B CN107311878B CN201710433366.1A CN201710433366A CN107311878B CN 107311878 B CN107311878 B CN 107311878B CN 201710433366 A CN201710433366 A CN 201710433366A CN 107311878 B CN107311878 B CN 107311878B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention provides a device for recycling glycine waste liquid and a method for recycling glycine waste liquid, wherein the device comprises the following steps: the vacuum distillation equipment, the extraction equipment, the extract recovery equipment and the solid glycine crystallization equipment are used for changing the conventional evaporation mode, greatly reducing the operating temperature of the system by utilizing the vacuum characteristic, reducing the generation of side reaction, inhibiting the decomposition of ammonium chloride, enabling a large amount of condensed water to supply glycine production water, improving the water recycling rate and greatly reducing the steam energy consumption. The ammonium chloride, glycine, water, low-boiling-point aging reagent and high-boiling-point amide organic matters in the glycine waste liquid can be respectively recovered, and meanwhile, the whole process is a circulating system, so that the comprehensive recovery rate of the system is greatly improved, the aging reagent is recycled, and the running cost of the process is reduced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a device for recycling glycine waste liquid and a method for recycling glycine waste liquid.
Background
Glycine is also known as glycine, and is mainly applied to the fields of nitrogenous fertilizer industry, medicine, pesticide, organic synthesis, biochemical research and the like, and is an important industrial product. At present, the glycine is prepared by the method of chloroacetic acid ammonolysis, namely, under the condition of normal temperature and normal pressure, using chloroacetic acid and liquid ammonia as raw materials, synthesizing under the catalysis of urotropine, and then performing alcohol precipitation, filtration, refining and drying.
In the extraction crystallization section of glycine production process, a considerable amount of extraction mother liquor is produced, and the main components of the extraction mother liquor are methanol, water, chlorination press, glycine and the like. The liquid obtained after the extraction mother liquor is rectified to recover methanol is called glycine waste liquid. The glycine waste liquid is a mixed aqueous solution, and the main components of the glycine waste liquid are water, inorganic matter chlorination compounds, organic matters such as glycine, urotropine, amides and the like. Since the glycine waste liquid contains various organic pollutants and inorganic pollutants, the concentration of the pollutants is high, and the biodegradability is low; if the waste glycine liquid is directly discharged, huge pollution is caused to the environment, so that the waste glycine liquid is required to be purified.
The existing method for treating the waste liquid mainly comprises a multi-effect evaporation crystallization method and a flue gas evaporation method, and also comprises a natural crystallization method adopted by some factories.
The multiple-effect evaporation crystallization method is to repeatedly use evaporated vapor as heat energy for many times, evaporate glycine waste liquid at 135 ℃, evaporate water and concentrate mother liquor, stir the concentrated mother liquor by using an enamel reaction kettle to cool down, crystallize ammonium chloride in the waste liquid, and finally separate ammonium chloride solid from blackened residual liquid by using a centrifuge. The method has high operation temperature, and ammonium chloride is easy to decompose in the process of concentrating the mother liquor, so that condensate liquid is not pure enough and is difficult to treat; and meanwhile, at high temperature, chloride ions in the mother solution have strong corrosiveness to equipment, and have high requirements on the materials of the equipment, so that the investment cost is increased. In addition, this process produces a large amount of raffinate and is difficult to handle.
The flue gas evaporation method utilizes high-temperature flue gas to provide heat energy, water in glycine waste liquid is evaporated in a drying tower, the solid is discharged through a discharger at the lower part of the drying tower to obtain ammonium chloride solid, and water vapor is separated from the upper part of the drying tower through a gas-solid separator to obtain part of ammonium chloride solid. Although part of ammonium chloride decomposed at high temperature is recovered by the method, the operation temperature is up to 200-350 ℃, the energy consumption is higher, and the equipment corrosion is more serious. In addition, organic components in the waste liquid can be distilled out and even decomposed along with the moisture, so that the moisture and the residual liquid are more difficult to treat.
The natural evaporation method is to pump glycine waste liquid into a waste liquid pool, evaporate water by natural air and obtain crystals. The method is restricted by natural environment, has low efficiency and low purity of crystals, and seriously pollutes the environment.
In the method, the first two recyclable parts of water and ammonium chloride, the third one only recycles ammonium chloride, and glycine and amide organic matters in the system are all treated as hazardous wastes, so that great resource waste is caused.
Disclosure of Invention
The invention provides a device for recycling glycine waste liquid and a method for recycling glycine waste liquid, which are used for improving the recycling effect and reducing the energy waste.
The invention provides a device for recycling glycine waste liquid, which comprises:
a reduced pressure distillation apparatus comprising: the device comprises a flash tower, a first centrifugal machine and a first vacuum crystallization kettle, wherein the first centrifugal machine and the first vacuum crystallization kettle form a circulation loop, and the first centrifugal machine is connected with the flash tower;
extraction apparatus comprising: an extraction kettle for processing the centrifugate generated by the reduced pressure distillation equipment; a second centrifuge connected to the extraction tank;
an extract recovery apparatus comprising: a first vacuum rectifying tower for processing the extracted mother liquor separated by the second centrifugal machine, a third centrifugal machine connected with the first vacuum rectifying tower, and a second vacuum rectifying tower connected with the third centrifugal machine;
a solid glycine crystallization apparatus comprising: a dosing tank for holding the solid glycine separated by the second centrifuge; the device comprises a third vacuum crystallization kettle connected with the material distribution groove, a fourth centrifugal machine connected with the third vacuum crystallization kettle, and a methanol rectifying tower connected with the fourth centrifugal machine.
In the scheme, the conventional evaporation mode is changed, the vacuum characteristic is utilized, the operation temperature of the system is greatly reduced, the generation of side reaction is reduced, the decomposition of ammonium chloride is inhibited, a large amount of condensed water can supply glycine production water, the water recycling rate is improved, and the steam energy consumption is greatly reduced. The ammonium chloride, glycine, water, low-boiling-point aging reagent and high-boiling-point amide organic matters in the glycine waste liquid can be respectively recovered, and meanwhile, the whole process is a circulating system, so that the comprehensive recovery rate of the system is greatly improved, the aging reagent is recycled, and the running cost of the process is reduced.
In a specific embodiment, a condensate recovery system coupled to the flash column is also included.
In a specific embodiment, the first vacuum rectification column is connected to a collection tank.
In a specific embodiment, the device further comprises an activated carbon decoloring system, and the activated carbon decoloring system is respectively connected with the material mixing tank and the third vacuum crystallization kettle.
In a specific embodiment, the formaldehyde crystallization column is connected to the flash column.
The invention also provides a method for recycling glycine waste liquid by using the device for recycling glycine waste liquid, which comprises the following steps:
recycling water in the waste liquid through the flash tower, the first vacuum crystallization kettle and the first centrifugal machine until the water content of the centrifugate in the first centrifugal machine is lower than a set threshold;
stirring and mixing the centrifugate and the extraction reagent in the first centrifuge in an extraction kettle, standing for a set time, and then pumping the mixture into a second centrifuge for solid-liquid separation;
pumping the extraction mother liquor in the second centrifugal machine into a first vacuum rectifying tower, pumping tower bottom liquor in the first vacuum rectifying tower into a third centrifugal machine for solid-liquid separation, and enabling the separated liquor to enter the second vacuum rectifying tower to collect extraction liquor;
placing the solid glycine separated in the second centrifugal machine into a material mixing tank, adding water to dilute the solid glycine into glycine solution, adding the glycine solution and methanol into a third vacuum crystallization kettle, and placing the methanol-glycine solution after precipitation in the third vacuum crystallization kettle into a fourth centrifugal machine for solid-liquid separation, wherein the obtained solid is glycine product;
and (3) pumping the liquid separated by the fourth centrifugal machine into a methanol rectifying tower to recycle methanol.
In the scheme, the conventional evaporation mode is changed, the vacuum characteristic is utilized, the operation temperature of the system is greatly reduced, the generation of side reaction is reduced, the decomposition of ammonium chloride is inhibited, a large amount of condensed water can supply glycine production water, the water recycling rate is improved, and the steam energy consumption is greatly reduced. The ammonium chloride, glycine, water, low-boiling-point aging reagent and high-boiling-point amide organic matters in the glycine waste liquid can be respectively recovered, and meanwhile, the whole process is a circulating system, so that the comprehensive recovery rate of the system is greatly improved, the aging reagent is recycled, and the running cost of the process is reduced.
In a specific embodiment, the set threshold is 30% -80%.
In a specific embodiment, the volume ratio of the centrifugate to the extraction reagent is 1:0.7-5.
In a specific scheme, the diluted glycine solution is a solution with the mass fraction of 20% -30%.
In one embodiment, the method further comprises feeding the glycine solution into an activated carbon decolorization system for decolorization.
In a specific embodiment, the volume ratio of the glycine solution to the methanol is 1:3-6.
In a specific scheme, the method further comprises the step of pumping glycine waste liquid subjected to normal pressure rectification in the methanol rectifying tower into a flash tower for flash evaporation again.
Drawings
FIG. 1 is a flow chart of a device for recycling glycine waste liquid according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, fig. 1 shows a flow chart of the glycine waste liquid recovery provided by the embodiment of the invention, and the flow chart shows the glycine waste liquid recovery device provided by the embodiment of the invention. The device comprises:
the reduced pressure distillation equipment comprises a flash tower 1, a first centrifugal machine 2 and a first vacuum crystallization kettle 3, wherein the first centrifugal machine 2 and the first vacuum crystallization kettle 3 form a circulation loop, and the first centrifugal machine 2 is connected with the flash tower 1; when in use, the water in the glycine waste liquid is recycled through the flash tower 1, the first vacuum crystallization kettle 3 and the first centrifugal machine 2 until the water content of the centrifugate in the first centrifugal machine 2 is lower than a set threshold value of 30-80%; when the method is specifically used, most of water in the waste liquid is recovered in a circulating mode of a flash tower 1-a first vacuum crystallization kettle 3-a first centrifuge 2, firstly, glycine waste liquid with the temperature of 110 ℃ is fed into the flash tower 1 for first-step gas-liquid separation, and the temperature of liquid I after flash evaporation is controlled to be 70 ℃. And the flash tower 1 is also connected with a condensation recovery system. The water vapor I generated by the flash evaporation tower 1 enters a condensation recovery system, the liquid I after flash evaporation enters a first centrifugal machine 2 for solid-liquid separation, the solid is ammonium chloride I, the centrifugate I enters a first vacuum crystallization kettle 3, when the pressure is 5-30 KPa, the heating temperature is controlled at 35-75 ℃ under the vacuum heating condition, the water in the centrifugate I is further evaporated, when crystals are separated out, the crystals are pumped into the first centrifugal machine 2 for solid-liquid separation, the ammonium chloride II and the centrifugate II are obtained, and the water content of the centrifugate II is measured to be 30-80%, such as 30%, 40%, 50%, 60%, 70%, 80% and the like. And pumping the centrifugate II into a subsequent extraction process. The step adopts decompression condition, can greatly reduce the operation temperature, reduce the decomposition of ammonium chloride, and the obtained condensed water can be directly recycled to the batching system of the glycine production process, thereby improving the recycling rate of water. The tower kettle discharge contains a large amount of ammonium chloride solids and a small amount of liquid, and agricultural grade ammonium chloride solids can be directly obtained after solid-liquid separation.
An extraction apparatus for performing an extraction process, the extraction apparatus comprising: an extraction tank 4 for processing a centrifugate (centrifugate II in the above description) generated by the reduced pressure distillation apparatus; and a second centrifuge 5 connected with the extraction kettle 4. When the compound organic solvent is used, the centrifugate II and the extraction reagent I (the compound organic solvent which combines alcohol, glycol and amide reagents according to different proportions) are stirred and mixed uniformly in the extraction kettle 4 according to the volume ratio of 1:0.7-5, and the specific ratio can be different volume ratios of 1:0.7, 1:2, 1:3, 1:4, 1:5 and the like. Standing for 1-5 h, such as 1h, 2h, 3h, 4h, 5h, etc., and feeding the above mixed solution into a second centrifuge 5 for solid-liquid separation, wherein the solid is crude glycine I, the liquid is extraction mother liquor I, the crude glycine I enters solid glycine crystallization equipment, and the extraction mother liquor I enters extraction liquid recovery equipment for recovering extraction reagent.
An extract recovery apparatus for recovering an extraction reagent comprising: a first vacuum rectifying tower 6 for processing the extraction mother liquor separated by the second centrifuge 5 (i.e., the extraction mother liquor I in the above description), a third centrifuge 8 connected to the first vacuum rectifying tower 6, and a second vacuum rectifying tower 9 connected to the third centrifuge 8. When the method is specifically used, the extraction mother liquor I is pumped into a first vacuum rectifying tower 6, the first vacuum rectifying tower 6 is connected with a collecting tank 7, moisture in the extraction mother liquor I is rectified and recovered to the collecting tank 7, solid-liquid separation is carried out on tower bottom liquid through a third centrifugal machine 8, the solid is crude glycine III, the liquid is extraction mother liquor II, the extraction mother liquor II enters the first vacuum rectifying tower 6, extraction reagent I with a low boiling point in the extraction mother liquor I is separated and collected, the extraction mother liquor II is repeatedly used in an extraction process, the tower bottom is finally a mixture I of high-boiling-point amide organic matters I and inorganic salts, the mixture is collected, and after the treatment capacity reaches the treatment capacity of the first vacuum rectifying tower 6, the high-boiling-point amide organic matters are collected in a concentrated mode.
Also included is a solid glycine crystallization apparatus comprising: a dosing tank 10 for holding solid glycine separated by the second centrifuge 5 (i.e. solid glycine I in the above description); a third vacuum crystallization kettle 12 connected with the material mixing tank 10, a fourth centrifuge 13 connected with the third vacuum crystallization kettle 12, and a methanol rectifying tower 14 connected with the fourth centrifuge 13. When in use, the solid glycine I is taken out to be a certain amount, then is placed in the material mixing tank 10, pure water is added to prepare a solution with the mass fraction of 20-30%, the device also comprises an activated carbon decoloring system 11, and the activated carbon decoloring system 11 is respectively connected with the material mixing tank 10 and a third vacuum crystallization kettle 12. Pumping the dissolved glycine solution I into an activated carbon decoloring system 11, allowing the decolored glycine solution II to enter a third vacuum crystallization kettle 12, and adding 3-6 times of methanol I to extract glycine, wherein the following steps are as follows: and after the methanol I is completely precipitated, putting the methanol-glycine mixed solution I into a centrifugal machine for solid-liquid separation, wherein the solid is a refined glycine product I, and the liquid is an extraction mother liquor I. Pumping the extraction mother liquor I into a methanol rectifying tower 14, rectifying under normal pressure to recover methanol I,
in addition, the formaldehyde rectifying tower in the device is also connected with the flash tower 1. The liquid produced by the methanol rectifying tower 14 is glycine waste liquid II. The glycine waste liquid II and the glycine waste liquid I can be mixed and returned to the reduced pressure distillation process for cyclic treatment.
In the scheme, the device changes the conventional evaporation mode, greatly reduces the operation temperature of the system by utilizing the vacuum characteristic, reduces the generation of side reaction, inhibits the decomposition of ammonium chloride, ensures that a large amount of condensed water can supply glycine production water, improves the water recycling rate, and greatly reduces the steam energy consumption. The ammonium chloride, glycine, water, low-boiling-point aging reagent and high-boiling-point amide organic matters in the glycine waste liquid can be respectively recovered, and meanwhile, the whole process is a circulating system, so that the comprehensive recovery rate of the system is greatly improved, the aging reagent is recycled, and the running cost of the process is reduced.
The embodiment of the invention also provides a method for recycling glycine waste liquid by using the device for recycling glycine waste liquid, which comprises the following steps:
recycling water in the waste liquid through the flash tower 1, the first vacuum crystallization kettle 3 and the first centrifugal machine 2 until the water content of the centrifugate in the first centrifugal machine 2 is lower than a set threshold;
stirring and mixing the centrifugate and the extraction reagent in the first centrifuge 2 in the extraction kettle 4, standing for a set time, and then pumping into a second centrifuge for solid-liquid separation;
pumping the extraction mother liquor in the second centrifugal machine into a first vacuum rectifying tower 6, pumping tower bottom liquor in the first vacuum rectifying tower 6 into a third centrifugal machine 8 for solid-liquid separation, and enabling the separated liquor to enter the second vacuum rectifying tower to collect extraction liquor;
placing the solid glycine separated in the second centrifugal machine into a material mixing tank 10, adding water to dilute the solid glycine into glycine solution, adding the glycine solution and methanol into a third vacuum crystallization kettle, and placing the methanol-glycine solution after precipitation in the third vacuum crystallization kettle into a fourth centrifugal machine 13 for solid-liquid separation, wherein the obtained solid is glycine product;
the liquid separated by the fourth centrifuge 13 is fed into a methanol rectifying tower 14, and methanol is recovered.
In the scheme, the conventional evaporation mode is changed, the vacuum characteristic is utilized, the operation temperature of the system is greatly reduced, the generation of side reaction is reduced, the decomposition of ammonium chloride is inhibited, a large amount of condensed water can supply glycine production water, the water recycling rate is improved, and the steam energy consumption is greatly reduced. The ammonium chloride, glycine, water, low-boiling-point aging reagent and high-boiling-point amide organic matters in the glycine waste liquid can be respectively recovered, and meanwhile, the whole process is a circulating system, so that the comprehensive recovery rate of the system is greatly improved, the aging reagent is recycled, and the running cost of the process is reduced.
When glycine waste liquid is recovered specifically, the specific steps are as follows:
step 1: recycling water in the waste liquid through the flash tower, the first vacuum crystallization kettle and the first centrifugal machine until the water content of the centrifugate in the first centrifugal machine is lower than a set threshold;
specifically, when the method is specifically used, most of water in the waste liquid is recovered in a circulation mode of a flash tower, a first vacuum crystallization kettle and a first centrifuge, firstly, glycine waste liquid with the temperature of 110 ℃ is fed into the flash tower for first-step gas-liquid separation, and the temperature of liquid I after flash evaporation is controlled to be 70 ℃. And the flash tower is also connected with a condensation recovery system. And (3) enabling water vapor I generated by the flash evaporation tower to enter a condensation recovery system, enabling a liquid I after flash evaporation to enter a first centrifugal machine for solid-liquid separation, enabling solid to be ammonium chloride I, enabling centrifugal liquid I to enter a first vacuum crystallization kettle, further enabling water in the centrifugal liquid I to evaporate under the vacuum heating condition, and when crystals are separated out, entering the first centrifugal machine for solid-liquid separation to obtain ammonium chloride II and centrifugal liquid II, and determining that the water content of the centrifugal liquid II is 30-80%, such as 30%, 40%, 50%, 60%, 70%, 80% and the like. And pumping the centrifugate II into a subsequent extraction process. The step adopts decompression condition, can greatly reduce the operation temperature, reduce the decomposition of ammonium chloride, and the obtained condensed water can be directly recycled to the batching system of the glycine production process, thereby improving the recycling rate of water. The tower kettle discharge contains a large amount of ammonium chloride solids and a small amount of liquid, and agricultural grade ammonium chloride solids can be directly obtained after solid-liquid separation.
Step 2: stirring and mixing the centrifugate and the extraction reagent in the first centrifuge in an extraction kettle, standing for a set time, and then pumping the mixture into a second centrifuge for solid-liquid separation;
when the centrifugal liquid II and the extraction reagent I (the composite organic solvent which combines alcohol, glycol and amide reagents according to different proportions) are stirred and mixed uniformly in an extraction kettle according to the volume ratio of 1:0.7-5, and the specific ratio can be different volume ratios of 1:0.7, 1:2, 1:3, 1:4, 1:5 and the like. Standing for 1-5 h, such as 1h, 2h, 3h, 4h, 5h, etc., and pumping the mixed solution into a second centrifuge for solid-liquid separation, wherein the solid is crude glycine I, the liquid is extraction mother liquor I, the crude glycine I enters solid glycine crystallization equipment, and the extraction mother liquor I enters extraction liquid recovery equipment for recovering the extraction reagent.
Step 3: pumping the extraction mother liquor in the second centrifugal machine into a first vacuum rectifying tower, pumping tower bottom liquor in the first vacuum rectifying tower into a third centrifugal machine for solid-liquid separation, and enabling the separated liquor to enter the second vacuum rectifying tower to collect extraction liquor;
specifically, when specifically using, throw extraction mother liquor I into first vacuum rectifying column, this first vacuum rectifying column is connected with the collecting vessel, carry out rectification with moisture wherein and retrieve the collecting vessel, tower cauldron liquid carries out solid-liquid separation through the third centrifuge, the solid is crude glycine III, liquid is extraction mother liquor II, extraction mother liquor II gets into first vacuum rectifying column, carry out separation collection with extraction reagent I of low boiling point wherein, reuse extraction process, the final tower cauldron is high boiling point amide organic matter I and inorganic salt's mixture I, collect the mixture, after the throughput reaches the throughput of first vacuum rectifying column, concentrate and collect high boiling point amide organic matter.
Step 4: placing the solid glycine separated in the second centrifugal machine into a material mixing tank, adding water to dilute the solid glycine into glycine solution, adding the glycine solution and methanol into a third vacuum crystallization kettle, and placing the methanol-glycine solution after precipitation in the third vacuum crystallization kettle into a fourth centrifugal machine for solid-liquid separation, wherein the obtained solid is glycine product;
the solid glycine I is taken to be a certain amount and then placed in a material mixing tank, pure water is added to prepare a solution with the mass fraction of 20-30%, the device also comprises an activated carbon decoloring system, and the activated carbon decoloring system is respectively connected with the material mixing tank and a third vacuum crystallization kettle. Pumping the dissolved glycine solution I into an activated carbon decoloring system, allowing the decolored glycine solution II to enter a third vacuum crystallization kettle, and adding 3-6 times of methanol I to extract glycine, wherein the steps are as follows: and after the methanol I is completely precipitated, putting the methanol-glycine mixed solution I into a centrifugal machine for solid-liquid separation, wherein the solid is a refined glycine product I, and the liquid is an extraction mother liquor I.
Step 5: and (3) pumping the liquid separated by the fourth centrifugal machine into a methanol rectifying tower to recycle methanol.
Specifically, the liquid separated by the fourth centrifugal machine is pumped into a methanol rectifying tower to recycle methanol.
Step 6: and (3) pumping glycine waste liquid subjected to normal pressure rectification in the methanol rectifying tower into a flash tower for flash evaporation again.
Specifically, the liquid produced by the methanol rectifying tower is glycine waste liquid II. The glycine waste liquid II and the glycine waste liquid I can be mixed and returned to the reduced pressure distillation process for cyclic treatment.
From the above description, it can be seen that the method provided by the invention has the following advantages:
(1) The method changes the conventional evaporation mode, greatly reduces the operation temperature of the system by utilizing the vacuum characteristic, reduces the generation of side reaction, inhibits the decomposition of ammonium chloride, ensures that a large amount of condensed water can supply glycine production water, improves the water recycling rate and greatly reduces the steam energy consumption.
(2) By selecting a proper solvent for extraction, solid glycine with higher purity can be directly obtained from liquid, the process flow is reduced, the manual operation difficulty is reduced, meanwhile, a new product is obtained from waste liquid, the product can reach industrial grade after purification, and higher product income can be obtained while the productivity is improved for enterprises.
(3) Through multistage vacuum rectification, a small amount of water, an aging reagent, high-boiling-point amide organic matters and ammonium chloride in the raffinate can be separated and refined, the hazardous waste yield of the process is reduced, the high-chlorine waste liquid generated in the traditional evaporation process is converted into a product, waste is changed into valuable, the utilization rate of valuable resources is improved, and the sustainable development of the resources is fully embodied.
(4) Compared with the traditional process, the energy consumption of the whole process flow is reduced by 10%, and two main products can be obtained: glycine and ammonium chloride can improve the economic benefit of the whole process by more than 20 times compared with the original evaporation process due to the high added value of glycine.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A device for recovering glycine waste liquid, comprising:
a reduced pressure distillation apparatus comprising: the device comprises a flash tower, a first centrifugal machine, a first vacuum crystallization kettle and a condensation recovery system, wherein the first centrifugal machine and the first vacuum crystallization kettle form a circulation loop, the first centrifugal machine is connected with the flash tower, and the flash tower is connected with the condensation recovery system;
extraction apparatus comprising: an extraction kettle for processing the centrifugate generated by the reduced pressure distillation equipment; a second centrifuge connected to the extraction tank;
an extract recovery apparatus comprising: the first vacuum rectifying tower is used for processing the extracted mother liquor separated by the second centrifugal machine, a third centrifugal machine connected with the first vacuum rectifying tower, a second vacuum rectifying tower connected with the third centrifugal machine, and a collecting tank is connected with the first vacuum rectifying tower;
a solid glycine crystallization apparatus comprising: a dosing tank for holding the solid glycine separated by the second centrifuge; the device comprises a third vacuum crystallization kettle connected with the material distribution groove, a fourth centrifugal machine connected with the third vacuum crystallization kettle, and a methanol rectifying tower connected with the fourth centrifugal machine.
2. The apparatus for recovering glycine waste liquid of claim 1, further comprising an activated carbon decolorization system, wherein said activated carbon decolorization system is connected to said dosing tank and said third vacuum crystallization kettle, respectively.
3. The apparatus for recovering glycine waste liquid as defined in any one of claims 1 to 2, wherein said methanol rectifying column is connected to said flash column.
4. A method for recovering glycine waste liquid using the apparatus for recovering glycine waste liquid as set forth in claim 1, comprising the steps of:
recycling water in the waste liquid through the flash tower, the first vacuum crystallization kettle and the first centrifugal machine until the water content of the centrifugate in the first centrifugal machine is lower than a set threshold;
stirring and mixing the centrifugate in the first centrifuge and an extraction reagent in an extraction kettle, standing for a set time, and then pumping the mixture into a second centrifuge for solid-liquid separation, wherein the extraction reagent is a compound organic solvent formed by combining alcohol, glycol and amide reagents in different proportions;
pumping the extraction mother liquor in the second centrifugal machine into a first vacuum rectifying tower, pumping tower bottom liquor in the first vacuum rectifying tower into a third centrifugal machine for solid-liquid separation, and enabling the separated liquor to enter the second vacuum rectifying tower to collect extraction liquor;
placing the solid glycine separated in the second centrifugal machine into a material mixing tank, adding water to dilute the solid glycine into glycine solution, adding the glycine solution and methanol into a third vacuum crystallization kettle, and placing the methanol-glycine solution after precipitation in the third vacuum crystallization kettle into a fourth centrifugal machine for solid-liquid separation, wherein the obtained solid is glycine product;
and (3) pumping the liquid separated by the fourth centrifugal machine into a methanol rectifying tower to recycle methanol.
5. The method for recovering glycine waste liquid as defined in claim 4, wherein said set threshold is 30% to 80%.
6. The method for recovering glycine waste liquid as defined in claim 4, wherein the volume ratio of said centrifugate to said extraction reagent is 1:0.7-5.
7. The method for recovering glycine waste liquid as defined in claim 4, wherein said diluted glycine solution is 20% to 30% by mass.
8. The method for recovering glycine waste liquid of claim 4, further comprising feeding glycine solution into an activated carbon decolorization system for decolorization.
9. The method of recovering glycine waste liquid of claim 4, wherein the volume ratio of glycine solution to methanol is 1:3-6.
10. The method for recovering glycine waste liquid as defined in claim 4, further comprising feeding glycine waste liquid after normal pressure rectification of said methanol rectifying tower into a flash tower for flash evaporation again.
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| CN110305028B (en) * | 2019-06-21 | 2022-04-08 | 湖北泰盛化工有限公司 | Device and process for washing glycine crude product by alcohol phase method |
| CN110885295B (en) * | 2019-12-11 | 2022-09-13 | 中国天辰工程有限公司 | Method for separating glycine and ammonium chloride mixed crystals by using high-boiling-point polar solvent |
| CN115215394B (en) * | 2021-04-21 | 2023-05-02 | 湖北泰盛化工有限公司 | Treatment process of ammonium chloride waste liquid in glycine production |
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