CN111362819A - Process and device for producing glycine by alcohol phase method - Google Patents
Process and device for producing glycine by alcohol phase method Download PDFInfo
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- CN111362819A CN111362819A CN202010255550.3A CN202010255550A CN111362819A CN 111362819 A CN111362819 A CN 111362819A CN 202010255550 A CN202010255550 A CN 202010255550A CN 111362819 A CN111362819 A CN 111362819A
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000004471 Glycine Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 321
- 239000013078 crystal Substances 0.000 claims abstract description 88
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 42
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 40
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 38
- 238000000605 extraction Methods 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 3
- 229960002449 glycine Drugs 0.000 description 50
- 239000012071 phase Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- MHMUIIBVMBOAON-UHFFFAOYSA-N azane;2,2,2-trichloroacetic acid Chemical compound [NH4+].[O-]C(=O)C(Cl)(Cl)Cl MHMUIIBVMBOAON-UHFFFAOYSA-N 0.000 description 1
- TYZDRHAKWOGSHU-UHFFFAOYSA-N azanium;2,2-dichloroacetate Chemical compound [NH4+].[O-]C(=O)C(Cl)Cl TYZDRHAKWOGSHU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- 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
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process and a device for producing glycine by an alcohol phase method, wherein the main process comprises the steps of taking methanol as a solvent, urotropine as a catalyst and liquid or solid chloroacetic acid as an initial raw material, introducing ammonia to produce mixed crystals of glycine and ammonium chloride, repeatedly applying filtrate obtained after mixed crystals are centrifuged for synthesis of the mixed crystals, dissolving the mixed crystals by pure water, and extracting a glycine product by using methanol; and (3) feeding the filtrate after the glycine is centrifuged into a rectifying tower to recover methanol, feeding the rectified residual liquid into a film evaporator to be concentrated until the water is evaporated to dryness, directly producing an ammonium chloride product as a byproduct, and repeatedly applying water evaporated by the film evaporator for dissolving mixed crystals. The process is implemented by devices such as a glycine synthesis kettle, a glycine extraction kettle, a mixed crystal filtrate head tank, a centrifuge, a mixed crystal filtrate receiving tank, a chloroacetic acid dissolving kettle, a methanol rectifying tower, a film evaporator and the like. The method can greatly reduce the unit consumption levels of urotropine, liquid ammonia, steam and the like, further reduce the production cost and avoid the generation of waste water.
Description
Technical Field
The invention discloses a device and a process for producing glycine by an alcohol phase method, belongs to the technical field of chemical production, and particularly relates to a new method for synthesizing glycine by the alcohol phase method and reducing wastewater.
Background
Glycine, aminoacetic acid, is an important fine chemical intermediate and chemical raw material, and is widely applied to the fields of pesticide glyphosate, medicines, foods, feed additives and the like. At present, the traditional chloroacetic acid ammonolysis method using water as solvent is still adopted in the domestic industrial production process of glycine, and the method has the following problems: (1) the production cost is high. The catalyst urotropin cannot be recovered; 1 ton glycine requires about 6-7 tons of steam to be consumed; the method has the advantages of high requirements on equipment and pipelines, high maintenance frequency and high equipment operation and maintenance cost when the ammonium chloride with low added value is recycled. (2) The yield is low and is difficult to break through 85 percent. The alkalinity of a water phase system is strong, the conversion rate of chloroacetic acid into glycine is low, and about 15 percent of chloroacetic acid is hydrolyzed to generate glycolic acid; iminodiacetic acid (NH (CH) is easily generated when high-temperature ammonia is insufficient2COOH)2]And nitrilotriacetic acid [ N (CH)2COOH)3]And the like. (3) The environmental risk cannot be completely eliminated. The problems of decomposition of ammonium chloride and a catalyst urotropine at high temperature, complex chemical reaction caused by high temperature and the like can generate evaporation condensate water with high ammonia nitrogen and high COD and red filtrate. In addition, hazardous waste (ammonium dichloroacetate, ammonium trichloroacetate, urotropine and the like) exists in the low-purity ammonium chloride product, the related national regulations are not met, and the current disposal mode has legal risks.
Under the environment-friendly high-pressure situation in recent years, although domestic glycine enterprises strive to optimize the water phase method process, the process defects can not be fundamentally solved. The chloroacetic acid method for producing the glycine must start from the process source. Currently, the gravity center of glycine production enterprises is put through a new process technology for producing crude glycine, and most of glycine production enterprises stay in a laboratory stage, for example, in an alcohol phase, a technology for separating glycine from ammonium chloride by using a mixed solvent or organic amine, or a technology for separating glycine from ammonium chloride by using a halogen-type novel formula reagent, and the like. Moreover, under the environment of low profit of the existing glycine enterprises, the glycine enterprises cannot completely abandon the water phase method device, invest large capital to construct a new process device, and only can be modified on the existing device.
The invention with publication number CN109836344A provides a method for producing glycine by mixing organic solvents, which comprises the steps of preparing a mixed solvent from ethylene glycol, propylene glycol, dimethylacetamide, methanol and ethanol, adding a catalyst urotropine, adding chloroacetic acid ammonia to synthesize a glycine product, adding chloroacetic acid or ammonium chloroacetate to a glycine filtrate to obtain an ammonium chloride byproduct, and recycling the organic solvent. This method has drawbacks: (1) the yield of the byproduct ammonium chloride obtained every time is limited, the yield of single-kettle production of glycine is influenced, in order to obtain more ammonium chloride in a single kettle, the organic solvent needs to be frozen and cooled, and the energy consumption is high. (2) After the organic solvent is circulated for a plurality of times, the recovery difficulty is high, and the organic solvent needs to be recovered by adopting a mode of combining membrane separation, reduced pressure distillation and rectification; the residual liquid with color can be processed into chemical fertilizer raw materials through catalytic oxidation treatment.
Disclosure of Invention
The invention aims to provide a device and a process for producing glycine by an alcohol phase method, wherein methanol is used as a solvent, urotropine is used as a catalyst, liquid or solid chloroacetic acid is used as an initial raw material, ammonia is introduced to produce mixed crystals (hereinafter, the mixed crystals are both called as mixed crystals) of glycine and ammonium chloride, the mixed crystals are intermediate products (glycine is a hexagonal crystal system, and ammonium chloride is an octahedral crystal system), filtrate obtained after the mixed crystals are centrifuged is repeatedly applied to synthesis of the mixed crystals, and pure water is used for dissolving the mixed crystals and then methanol is used for extracting glycine products; and (3) feeding the filtrate after the glycine is centrifuged into a rectifying tower to recover methanol, feeding the rectified residual liquid into a film evaporator to be concentrated until the water is evaporated to dryness, directly producing an ammonium chloride product as a byproduct, and repeatedly applying water evaporated by the film evaporator for dissolving mixed crystals. The process is implemented by devices such as a glycine synthesis kettle, a glycine extraction kettle, a mixed crystal filtrate head tank, a centrifuge, a mixed crystal filtrate receiving tank, a chloroacetic acid dissolving kettle, a methanol rectifying tower, a film evaporator and the like. The method can greatly reduce the unit consumption levels of urotropine, liquid ammonia, steam and the like, further reduce the production cost and avoid the generation of waste water.
In order to achieve the purpose of the invention, the invention adopts the above device, which comprises the following devices and pipelines (see the attached figure 1):
a device for producing glycine by an alcohol phase method is characterized in that the bottom of a chloroacetic acid dissolving kettle is connected to a mixed crystal synthesis kettle through a pipeline, an inlet on the chloroacetic acid dissolving kettle is connected with a methanol pipeline, and an ammonia gas inlet pipe is arranged on the mixed crystal synthesis kettle; the mixed crystal synthesis kettle is connected with a centrifuge; the centrifugal machine is respectively connected with the mother liquor receiving tank and the diluted methanol tank; the mother liquor receiving tank is connected with the mother liquor jacket elevated tank through a mother liquor pump, and the mother liquor jacket elevated tank is connected with the mixed crystal synthesis kettle.
The mixed crystal synthesis kettle is also provided with a primary condenser, a secondary condenser and a vacuum unit. The inlet of the mixed crystal synthesis kettle is connected with an ammonia pipeline, a vacuum pipeline and a mother liquid application pipeline, the jacket of the mixed crystal synthesis kettle is connected with a circulating water pipeline, and the bottom valve of the mixed crystal synthesis kettle is connected with a centrifuge. The inlet of the centrifuge is connected with a mixed crystal pipeline, a methanol pipeline, a nitrogen pipeline and an extract liquid pipeline.
The first-stage condenser and the second-stage condenser are respectively connected with a methanol collecting tank through pipelines, the methanol receiving tank is respectively connected with a centrifuge, a chloroacetic acid dissolving kettle and an extraction kettle through a methanol pump, and the extraction kettle is connected with the centrifuge. The inlet of the extraction kettle is connected with a pure water pipeline, a methanol pipeline and a mixed crystal feeding pipeline. The inlet of the methanol receiving tank is connected with the liquid phase outlets of the first-stage condenser and the second-stage condenser, the inlet of the methanol receiving tank is also connected with an emptying pipeline, a nitrogen pipeline and a vacuum pipeline, and the vacuum pipeline on the methanol receiving tank is connected with a vacuum unit.
The dilute methanol tank is connected with a methanol rectifying tower through a dilute methanol pump, and the methanol rectifying tower is connected with a film evaporator.
In order to realize another purpose of the invention, the invention provides a process for generating glycine by an alcohol phase method, which mainly comprises the following steps (shown in the attached figure 1):
(1) adding chloroacetic acid into a chloroacetic acid dissolving kettle, adding a solvent methanol, and stirring until the solvent methanol is dissolved;
(2) adding methanol and urotropine into a mixed crystal synthesis kettle, stirring until the methanol and the urotropine are dissolved, heating (40-64.5 ℃) and introducing ammonia gas (pH = 7.0-9.5) into the mixed crystal synthesis kettle, dropwise adding a methanol solution of chloroacetic acid, and reacting under the condition of heat preservation for 1-6 hours.
(3) After the reaction is finished, centrifuging the synthetic liquid in the mixed crystal synthetic kettle to obtain mixed crystals by a centrifugal machine, and feeding the mixed crystals into an extraction kettle; the centrifugal filtrate is transferred to a mother liquor jacket elevated tank through a mother liquor receiving tank and a mother liquor pump for the next batch of mixed crystal synthesis, and urotropine is effectively recycled.
(4) Adding water (1500L water dissolves about 1000-1300 kg mixed crystal of the step (3)) into the mixed crystal in the extraction kettle, heating to 30-50 ℃, fully stirring until the mixed crystal is completely dissolved, then sequentially adding methanol into the extraction kettle, wherein the total amount of the methanol is about 7500L-8000L, and extracting, wherein the final discharge temperature is 28-35 ℃.
(5) After extraction, the extract liquid is centrifuged by a centrifuge to obtain the glycine, and then the production of the glycine is finished.
In the step (2), the concentration of the urotropine is 0.05-0.5 kg/L, the flow rate of the introduced ammonia gas is 200-250 kg/h, the total amount of the introduced ammonia is about 300-380kg, and the flow rate of the methanol solution of the chloroacetic acid is 500-650L/h, wherein the concentration of the methanol of the chloroacetic acid is 0.5-2 kg/L.
And (3) keeping the pH value of the reaction solution in the step (2) to be 7.0-9.5, measuring the pH value once every 15min, controlling the temperature in the reaction kettle to be 40-64.5 ℃, starting the heat preservation timing when the methanol solution of chloroacetic acid is added, and keeping the temperature for 1-6 h.
In the extraction process in the step (4), methanol is added in a manner of gradually increasing the speed by 200-300L/h, 500-600L/h and 7500-8000L/h (the duration time is about 15-20min, 15-20min and 60-90min respectively), and the concentration of the methanol in the extraction kettle is controlled to be 75-82%; and simultaneously controlling the temperature in the extraction process to be 30-50 ℃. The alcohol phase method of the invention is that the mixed crystal production process is in a high-purity environment, and does not involve water. Because methanol is alcohol with lower price, the ammonium chloride and the glycine in the mixed crystal are separated and generally industrially adopt methanol, the glycine crystallization process is related to the dropping speed of the methanol in the extraction process, and the glycine with smaller particles is easily generated when the dropping speed of the methanol is too high.
The filtrate centrifuged in the step (5) enters a rectifying tower through a dilute methanol tank and a dilute methanol pump to recover methanol, and the feeding amount of the rectifying tower is 20-60 m3And h, controlling the temperature at the bottom of the tower to be 95-110 ℃, controlling the temperature at the top of the tower to be 60-70 ℃ and obtaining the concentrated methanol.
And (3) concentrating the residual liquid in the rectifying tower by using a vacuum film evaporator to obtain a byproduct ammonium chloride product, and applying the concentrated white water to the step (4) of mixed crystal dissolution, wherein the temperature of the materials in the film evaporator is 50-100 ℃, the vacuum degree is 0.07-0.09 Mpa, and the feeding amount is 300-500 kg/h.
The process and the device for producing the glycine by the alcohol phase method have the following beneficial effects:
(1) compared with water as a solvent, the mixed crystal is synthesized by taking high-alcohol methanol (more than or equal to 99%) as the solvent, the chloroacetic acid has higher conversion rate (more than or equal to 98% and the conversion rate of the traditional aqueous phase method process in the current industry is less than 90%) in the ammonolysis process, and the mother liquor can be repeatedly used.
(2) The unit consumption of each raw material can be greatly reduced, and the catalyst urotropine can be completely recovered and then recycled for the next batch of mixed crystal synthesis.
(3) The rectification mother liquor does not contain urotropine, no complex reaction occurs in the processes of rectifying and recovering methanol, recovering ammonium chloride with double effects and recovering ammonium chloride with a film evaporator in the mother liquor, and finally, almost no waste liquor (commonly called as 'red water') is generated, so that the environmental protection benefit is obvious.
(4) Compared with the traditional water phase method, the industrial production cost can be reduced by 500 plus 800 yuan/ton glycine, and the economic benefit is obvious.
The invention has the main innovation points that: the idea of synthesizing mixed crystals by using the mixed crystal filtrate (containing urotropine) repeatedly in a low-temperature and anhydrous environment (high-purity methanol and anhydrous chloroacetic acid) is that the average yield of the mixed crystals exceeds 98 percent, and the average yield of glycine produced by methanol extraction exceeds 92 percent.
Drawings
FIG. 1 is a process flow diagram of a device for synthesizing glycine by an alcohol phase method. The system comprises a mixed crystal synthesis kettle 1, an extraction kettle 2, a mother liquor jacket overhead tank 3, a chloroacetic acid dissolution kettle 4, a centrifuge 5, a mother liquor receiving tank 6, a mother liquor pump 7, a dilute methanol tank 8, a dilute methanol pump 9, a first-stage condenser 10, a second-stage condenser 11, a methanol receiving tank 12, a methanol pump 13, a vacuum unit 14, a methanol rectifying tower 15 and a thin film evaporator 16.
Detailed Description
The invention will be further described by way of the following examples, which are not intended to limit the scope of the invention:
example 1
A device for producing glycine by an alcohol phase method comprises a chloroacetic acid dissolving kettle 4 inlet connected with a methanol pipeline, a chloroacetic acid dissolving kettle 4 bottom valve connected to a mixed crystal synthesis kettle 1; an inlet of the mixed crystal synthesis kettle 1 is connected with an ammonia pipeline, a vacuum pipeline and a mother liquid application pipeline, a jacket of the mixed crystal synthesis kettle 1 is connected with a circulating water pipeline, and a bottom valve of the mixed crystal synthesis kettle is connected with a centrifuge; the inlet of the centrifuge 5 is connected with a mixed crystal pipeline, a methanol pipeline, a nitrogen pipeline and an extract liquor pipeline, and the mother liquor discharge port of the centrifuge is connected with a mother liquor receiving tank 6 and a diluted methanol tank 8; a bottom valve pipeline of the mother liquor receiving tank 6 is connected with the mother liquor jacket elevated tank 3 through a mother liquor pump; the dilute methanol tank 8 is connected with a methanol rectifying tower 15 through a dilute methanol pump 9, and the bottom of the methanol rectifying tower 15 is connected with a film evaporator 16; the inlet of the extraction kettle 2 is connected with a pure water pipeline, a methanol pipeline and a mixed crystal feeding pipeline. The vacuum pipeline on the mixed crystal synthesis kettle 1 is sequentially connected with a primary condenser 10, a secondary condenser 11 and a vacuum unit 14; the inlet of the methanol receiving tank 12 is connected with the first-stage condenser 10 and the liquid 11 phase outlet of the second-stage condenser, the inlet of the methanol receiving tank 12 is also connected with an emptying pipeline, a nitrogen pipeline and a vacuum pipeline, and the vacuum pipeline on the methanol receiving tank is connected with a vacuum unit.
Example 2
1000kg of solid chloroacetic acid (95.7%) was dissolved in 1000L of methanol in a K2000L chloroacetic acid dissolution tank, and the mixture was stirred well. 400kg of urotropine was dissolved in 2000L of methanol in a K8000L mixed crystal synthesis kettle, stirred well and warmed to 45 ℃. Introducing ammonia gas into the mixed crystal synthesis kettle at 200kg/h, simultaneously dropwise adding a methanol solution of chloroacetic acid into the mixed crystal synthesis kettle at 600L/h, measuring the pH once every 15min, maintaining the pH =7.5 in the whole reaction process, controlling the temperature in the kettle to be 50 ℃ through a coil pipe and a jacket in the mixed crystal synthesis kettle, and introducing the total amount of ammonia to be about 340 kg. When the methanol solution of chloroacetic acid is added dropwise, the heat preservation timing is started, and the heat preservation time is 4 h. And the synthetic liquid in the mixed crystal synthesis kettle is centrifuged by a centrifuge to obtain mixed crystals, and the centrifuged filtrate is transferred to a mother liquid jacket elevated tank through a mother liquid receiving tank and a mother liquid pump for the next batch of mixed crystal synthesis, so that urotropine is effectively recycled. Dissolving the mixed crystal in 1500L of water in an extraction kettle, heating to 50 ℃, and fully stirring until the mixed crystal is completely dissolved. Then, methanol is added into the extraction kettle in a manner of gradually increasing and dropping at 300L/h, 600L/h and 7500L/h (respectively lasting for about 15min, 15min and 60 min), the total amount of methanol dropped into the extraction kettle is about 7500L, the concentration of the methanol in the extraction kettle is ensured to be about 80%, and the final discharging temperature is 30 ℃. The extract in the extraction kettle is centrifuged by a centrifuge to obtain crude glycine, and 721kg of glycine with the main content of 98.6 percent and the chloride ion content of 0.32 percent is obtained after methanol washing, filtration and drying, and the yield of the glycine is 94.9 percent.
The mixed crystal filtrate is circularly used for 10 times according to the operation, the average main content of the glycine is 98.4 percent, the average content of the chloride ions is 0.28 percent, and the average yield of the glycine is 95.4 percent.
The extraction filtrate which circulates for 10 times enters a rectifying tower together through a dilute methanol tank and a dilute methanol pump to recover methanol, and the feeding amount of the rectifying tower is 20m3And h, controlling the temperature of the bottom of the tower at 110 ℃ and the temperature of the top of the tower at 65 ℃ to obtain concentrated methanol. And (3) concentrating the residual liquid in the rectifying tower by using a vacuum film evaporator, wherein the temperature of the material in the film evaporator is 80 ℃, the vacuum degree is 0.08Mpa, the feeding amount is 300-500 kg/h, and finally 5651kg of by-product ammonium chloride with the nitrogen content of 25.5% is produced.
Example 3
1000kg of solid chloroacetic acid (95.1%) was dissolved in 1000L of methanol in a K2000L chloroacetic acid dissolution tank, and the mixture was stirred well. 300kg of urotropine was dissolved in 2000L of methanol in a K8000L mixed crystal synthesis kettle, stirred well and warmed to 45 ℃. Introducing ammonia gas into the mixed crystal synthesis kettle at 200kg/h, simultaneously dropwise adding a methanol solution of chloroacetic acid into the mixed crystal synthesis kettle at 600L/h, measuring the pH once every 15min, maintaining the pH =7.5 in the whole reaction process, controlling the temperature in the mixed crystal synthesis kettle to be 60 ℃ through a coil and a jacket in the mixed crystal synthesis kettle, and introducing the total amount of ammonia to be about 340 kg. When the methanol solution of chloroacetic acid is added dropwise, the heat preservation timing is started, and the heat preservation time is 3 h. And the synthetic liquid in the mixed crystal synthesis kettle is centrifuged by a centrifuge to obtain mixed crystals, and the centrifuged filtrate is transferred to a mother liquid jacket elevated tank through a mother liquid receiving tank and a mother liquid pump for the next batch of mixed crystal synthesis, so that urotropine is effectively recycled. Dissolving the mixed crystal in 1500L of water in an extraction kettle, heating to 60 ℃, and fully stirring until the mixed crystal is completely dissolved. Then, methanol is added into the extraction kettle in a manner of gradually increasing and dropping at 300L/h, 600L/h and 7500L/h (respectively lasting for about 15min, 15min and 60 min), wherein the total amount of the methanol is about 8000L, the concentration of the methanol in the extraction kettle is ensured to be about 85%, and the final discharging temperature is 30 ℃. Centrifuging the extract liquor in the extraction kettle to obtain a glycine crude product through a centrifugal machine, washing with methanol, filtering and drying to obtain 702kg of glycine with the main content of 98.1 percent and the chloride ion content of 0.57 percent, wherein the yield of the glycine is 94.9 percent.
The mixed crystal filtrate is circularly used for 10 times according to the operation, the average main content of glycine is 98.3 percent, the average content of chloride ions is 0.50 percent, and the average yield of glycine is 93.4 percent.
The extraction filtrate which circulates for 10 times enters a rectifying tower together through a dilute methanol tank and a dilute methanol pump to recover methanol, and the feeding amount of the rectifying tower is 20m3And h, controlling the temperature of the bottom of the tower at 110 ℃ and the temperature of the top of the tower at 65 ℃ to obtain concentrated methanol. And (3) concentrating the residual liquid in the rectifying tower by using a vacuum film evaporator, wherein the temperature of the material in the film evaporator is 80 ℃, the vacuum degree is 0.08Mpa, the feeding amount is 300-500 kg/h, and finally, 5260kg of by-product ammonium chloride with the nitrogen content of 24.9% is produced.
Claims (10)
1. The device for producing the glycine by the alcohol phase method is characterized in that the bottom of a chloroacetic acid dissolving kettle (4) is connected to a mixed crystal synthesis kettle (1) through a pipeline, and an ammonia gas inlet pipe (17) is arranged on the mixed crystal synthesis kettle (1); the mixed crystal synthesis kettle (1) is connected with a centrifuge (5); the centrifuge (5) is respectively connected with a mother liquor receiving tank (6) and a diluted methanol tank (8); the mother liquor receiving tank (6) is connected with the mother liquor jacket elevated tank (3) through a mother liquor pump (7), and the mother liquor jacket elevated tank (3) is connected with the mixed crystal synthesis kettle (1).
2. The device for producing glycine by the alcohol phase method according to claim 1, wherein the mixed crystal synthesis kettle (1) is further provided with a primary condenser (10), a secondary condenser (11) and a vacuum unit (14).
3. The device for producing glycine by the alcohol phase method according to claim 2, wherein the primary condenser (10) and the secondary condenser (11) are respectively connected with the methanol collection tank (12) through pipelines, the methanol receiving tank (12) is respectively connected with the centrifuge (5), the chloroacetic acid dissolution kettle (4) and the extraction kettle (2) through the methanol pump (13), and the extraction kettle (2) is connected with the centrifuge (5).
4. An apparatus for producing glycine by the alcohol phase method according to claim 2 wherein the dilute methanol tank (8) is connected to the methanol rectifying tower (15) via the dilute methanol pump (9), the methanol rectifying tower (15) being connected to the thin film evaporator (16).
5. The process for producing glycine by using the apparatus for producing glycine by the alcohol phase method according to any one of claims 1 to 4, comprising the steps of:
(1) adding chloroacetic acid into a chloroacetic acid dissolving kettle, adding a solvent methanol, and stirring until the solvent methanol is dissolved;
(2) adding methanol and urotropine into a mixed crystal synthesis kettle, stirring until the methanol and the urotropine are dissolved, heating, introducing ammonia gas into the mixed crystal synthesis kettle, dropwise adding a methanol solution of chloroacetic acid, and preserving heat for reaction;
(3) after the reaction is finished, centrifuging the synthetic liquid in the mixed crystal synthetic kettle to obtain mixed crystals by a centrifugal machine, and feeding the mixed crystals into an extraction kettle;
(4) adding water into the mixed crystals in the extraction kettle, stirring until the mixed crystals are completely dissolved, and then sequentially adding methanol into the extraction kettle for extraction;
(5) after extraction, the extract liquid is centrifuged by a centrifuge to obtain the glycine, and then the production of the glycine is finished.
6. The process for producing glycine as claimed in claim 5, wherein the concentration of urotropine in step (2) is 0.05-0.5 kg/L, the flow rate of ammonia gas is 200-250 kg/h, and the flow rate of methanol solution of chloroacetic acid is 500-650L/h, wherein the concentration of methanol of chloroacetic acid is 0.5-2 kg/L.
7. The process for producing glycine as claimed in claim 6, wherein the reaction solution in the step (2) is maintained at a pH of 7.0 to 9.5, the temperature in the reaction vessel is controlled to be 40 to 64.5 ℃, and the reaction time is kept at 1 to 6 hours.
8. The process for producing glycine as claimed in claim 7, wherein in the step (4), methanol is added in a stepwise increasing manner of 200-; and simultaneously controlling the temperature in the extraction process to be 30-50 ℃.
9. The production process of glycine as claimed in claim 8, wherein the filtrate centrifuged in step (5) enters a rectifying tower through a dilute methanol tank and a dilute methanol pump to recover methanol, and the feeding amount of the rectifying tower is 20-60 m3And h, controlling the temperature at the bottom of the tower to be 95-110 ℃, controlling the temperature at the top of the tower to be 60-70 ℃ and obtaining the concentrated methanol.
10. The process for producing glycine as claimed in claim 9, wherein the raffinate from the rectification column is concentrated in a vacuum film evaporator to obtain a byproduct ammonium chloride product, and the white water obtained by the concentration is used in the step (4) of dissolving the mixed crystals, wherein the temperature of the materials in the film evaporator is 50-100 ℃, the vacuum degree is 0.07-0.09 Mpa, and the feeding amount is 300-500 kg/h.
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