CN112876374A - Method and device for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor - Google Patents
Method and device for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor Download PDFInfo
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- CN112876374A CN112876374A CN201911209396.XA CN201911209396A CN112876374A CN 112876374 A CN112876374 A CN 112876374A CN 201911209396 A CN201911209396 A CN 201911209396A CN 112876374 A CN112876374 A CN 112876374A
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 130
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 70
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 55
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- -1 acetoacetyl arylamine Chemical class 0.000 claims abstract description 26
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012429 reaction media Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 238000009833 condensation Methods 0.000 claims description 23
- 230000005494 condensation Effects 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- 238000000926 separation method Methods 0.000 description 15
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SKSDEMJMLMCQRL-UHFFFAOYSA-N 3-oxobutanehydrazide Chemical compound CC(=O)CC(=O)NN SKSDEMJMLMCQRL-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- VCWRWMWHBSZKPM-UHFFFAOYSA-N n-hydroxy-3-oxobutanamide Chemical compound CC(=O)CC(=O)NO VCWRWMWHBSZKPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/04—Preparation of carboxylic acid amides from ketenes by reaction with ammonia or amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0004—Crystallisation cooling by heat exchange
- B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor. A method for recovering residual materials of mother liquor of acetoacetyl arylamine alcohol method comprises the steps of taking alcohol as a reaction medium, taking diketene and arylamine as reactants for continuous reaction, cooling, centrifuging and drying the reaction mother liquor after the reaction is finished, recovering acetoacetyl arylamine in the mother liquor, wherein the cooling is deep cooling, and the deep cooling is to cool the mother liquor to-30 to-20 ℃. By deeply cooling the mother liquor of the reaction acetoacetyl arylamine alcohol method, the recovery rate of products in the mother liquor can be improved, the yield of products is improved, the waste is reduced, and the production cost is reduced.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method and a device for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor.
Background
The acetoacetylamide is an important raw material for preparing industrial pigments, is a white crystalline solid in appearance, is slightly soluble in water, is soluble in organic solvents such as ethanol, ether, chloroform, hot benzene and the like, can also be soluble in a dilute aqueous solution of caustic soda, is insoluble in aqueous solution of ammonia and sodium carbonate, is purple when meeting ferric chloride, and has the following solubility: 5g/L (20 ℃ C.). The synthesis method comprises the following steps: taking water and alcohol as main reaction media, and taking diketene and arylamine as reactants to continuously react to prepare the acetoacetyl arylamine compound, wherein the alcohol can adopt methanol, ethanol, normal propyl alcohol, isopropyl alcohol and butanol, the methanol, the ethanol and the propanol are completely mutually soluble with the water, the ethanol is preferred for industrial hygiene reasons, and the reaction temperature is at least 60 ℃ so as to be fast enough to carry out the reaction; the temperature regulation and limitation of the strongly exothermic reaction is carried out later on its own (but if desired with the addition of heat), followed by external refrigeration, cooling of the resulting mixture, by precooling the feed stream or by increasing the amount of alcohol/water mixture to a heat capacity which allows the heat of reaction liberated to be absorbed to the desired temperature. During the synthesis process, alcohol can dissolve acetoacetyl arylamine, so that after the acetoacetyl arylamine is separated, a part of the product is still remained in the mother liquor.
The method comprises the steps of dissolving acetoacetylamide in alcohol, carrying out pyrolysis on the acetoacetylamide to generate arylamine and diketene, reacting the diketene with ethanol under the heating condition by using aniline as a catalyst to generate ethyl acetoacetate, reacting the arylamine with the ethyl acetoacetate to generate 3- (aryl) -2-butenoic acid ethyl ester, wherein the byproduct is an oily substance, is easy to evaporate out along with ethanol and water vapor, enters acetoacetylamide reaction liquid along with the reuse of the alcohol, is continuously accumulated in alcohol distillate, is difficult to remove from acetoacetylamide products, has poor crystal form of the obtained products, has small crystal particles and uneven distribution, and is easy to agglomerate after being placed.
At present, 2g of product is precipitated after the temperature of mother liquor to be steamed is reduced to-20 ℃ per 100ml in the acetoacetyl arylamine alcohol production method, and the existing production process is to reduce the temperature of the mother liquor to-5 to-2 ℃, and then the mother liquor after material separation enters a rectification system to rectify ethanol. Sequentially adding raw materials of ethanol and arylamine into a condensation kettle, dropwise adding diketene, controlling the reaction temperature through a refrigerant, and preserving heat for a specified time after the dropwise adding of the diketene is finished; after condensation is finished, pouring the mixture into a cooling kettle to be cooled to 5 ℃ to crystallize and separate out materials; after the temperature reduction is finished, the materials enter a centrifugal machine and a flash evaporation drying unit in batches for dealcoholization and drying; and finally, the products are packaged and stacked in a packaging machine and a stacking machine. The temperature of the mother liquor needs to be reduced to-5 to-2 ℃ before rectification, and products contained in the mother liquor to be steamed can not be completely recovered, so that the yield of the products is reduced, and the material waste is caused.
In conclusion, the prior acetoacetyl arylamine alcohol production method mainly has the following problems:
1. acetyl arylamine in the mother liquor can not be efficiently recovered;
2. the acetoacetyl arylamine product is easy to agglomerate;
3. the process of recovering the acetoacetyl arylamine in the mother liquor takes a long time.
Chinese patent application No. 94117293.7 discloses a process for the preparation of acetoacetarylamides in which the acetoacetarylamides still remaining in the mother liquor are further recovered by recycling the mother liquor several times. At the same time, the mother liquor is replenished with a fresh alcohol/water mixture in an amount corresponding to the amount of mother liquor which remains as product moisture in the separated crude product and is subsequently removed by washing. However, the method has low mother liquor recovery efficiency and long time consumption, further reduces the production efficiency of the acetoacetyl aromatic amide, and does not effectively solve the problem of easy caking of the product.
The present invention has been made in view of this situation.
Disclosure of Invention
The first purpose of the invention is to overcome the defects of the prior art and provide a method for recovering the residual materials of the acetoacetyl arylamine alcohol process mother liquor.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for recovering residual materials of mother liquor of acetoacetyl arylamine alcohol method comprises the steps of taking alcohol as a reaction medium, taking diketene and arylamine as reactants for continuous reaction, cooling, centrifuging and drying the reaction mother liquor after the reaction is finished, recovering acetoacetyl arylamine in the mother liquor, wherein the cooling is deep cooling, and the deep cooling is to cool the mother liquor to-30 to-20 ℃.
Further, the mother liquor is cooled to-25 to-20 ℃.
Further, the mother liquor is cooled to-20 ℃ according to the actual energy consumption and the product recovery condition.
Further, the deep cooling is to place the reaction mother liquor in a cooling kettle, cool the condensation medium in the outer coil pipe of the cooling kettle to-40 to-30 ℃, and then cool the reaction mother liquor to-20 ℃ by utilizing the cooled condensation medium.
Further, the condensing medium is ethylene glycol.
The second purpose of the invention is to provide a residual material recovery device of acetoacetyl arylamine alcohol process mother liquor, which comprises the following components: buffer tank, cooling cauldron, cooling module and circulating line, the outer coil pipe has on the perisporium of cooling cauldron, the buffer tank passes through the circulating line intercommunication with the outer coil pipe, the buffer tank is used for holding the condensation medium, the condensation medium flows out through the circulating line by the buffer tank and gets into the outer coil pipe to flow back to the buffer tank through the circulating line by the outer coil pipe outflow, the circulation is reciprocal, the cooling module sets up the temperature that is used for reducing the condensation medium in the circulating line on the circulating line.
Further, the cooling module includes a freezing unit at least, freezing unit has first inlet and first liquid outlet, the circulating line has first pipeline and second pipeline, first inlet is through first pipeline intercommunication buffer tank, first liquid outlet is through second pipeline intercommunication outer coil pipe.
Further, the buffer tank has a second inlet and a second liquid outlet, the second inlet is located the upper portion of the buffer tank, the second liquid outlet is located the lower portion of the buffer tank, the second liquid outlet is communicated with the first inlet through a first pipeline, the circulating pipeline has a third pipeline, and the second inlet is communicated with the outer coil pipe through a third pipeline.
Further, the outer coil pipe is provided with at least one third liquid inlet and a third liquid outlet, the third liquid inlet is communicated with the first liquid outlet through a second pipeline, and the third liquid outlet is communicated with the second liquid inlet through a third pipeline.
Further, the third liquid inlet is arranged in the middle of the cooling kettle or at the lower part of the cooling kettle, and the third liquid outlet is arranged at the upper part of the cooling kettle.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. by deeply cooling the mother liquor of the reaction acetoacetyl arylamine alcohol method, the recovery rate of the product in the mother liquor can be improved, the yield of the product is improved, the waste is reduced, the operation is simple and convenient, the production cost is reduced, and the method can be widely applied to industrial production.
2. Through the deep cooling of the mother liquor, the generation of a byproduct, namely 3- (aryl) -2-ethyl crotonate, can be reduced, and the occurrence of the product caking condition is further reduced.
3. By reducing the temperature of the condensing medium, the molecular motion of the acetoacetyl arylamine product and the mother liquor can be effectively reduced, the time for recovering the acetoacetyl arylamine in the mother liquor is further shortened, and the production efficiency is further improved.
4. The refrigerating units can be installed at optional positions and in optional number, the requirements of different production requirements can be met, and the purpose of improving the recovery rate of the residual materials in the mother liquor to the maximum extent is realized while resources are reasonably utilized.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic diagram of a residue recovery device of acetoacetyl aromatic amine alcohol process mother liquor of the invention;
1. cooling the kettle; 11. an outer coil pipe; 111. a third liquid inlet; 112. a third liquid outlet; 2. a refrigerating unit; 21. a first liquid inlet; 22. a first liquid outlet; 3. a buffer tank; 31. a second liquid inlet; 32. a second liquid outlet; 4. a first conduit; 5. a second conduit; 6. a second pipe branch; 7. a third pipeline; 8. and a liquid inlet pipeline of the buffer tank.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
The first embodiment is as follows:
the invention provides a method for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor, which specifically comprises the following steps:
step 1: alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred.
Step 2: after the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: acetoacetyl arylamine, ethanol, diketene and arylamine.
And step 3: the mother liquor in the cooling kettle is cooled through a cooling module, namely a refrigerating unit, the mother liquor is placed in the cooling kettle, a condensing medium in an outer coil pipe of the cooling kettle is cooled to-40 to-30 ℃ through the refrigerating unit, the cooled condensing medium is used for cooling the reaction mother liquor to-30 to-20 ℃, and the acetoacetyl arylamine in the mother liquor is separated.
And 4, step 4: and (4) carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol process mother liquor.
And 5: drying the product obtained by centrifugal separation, and further recovering the acetoacetylamide separated from the mother liquor.
Example two:
step 1: alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred.
Step 2: after the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: acetoacetyl arylamine, ethanol, diketene and arylamine.
And step 3: the mother liquor in the cooling kettle is cooled through a cooling module, namely a refrigerating unit, the mother liquor is placed in the cooling kettle, a condensing medium in an outer coil pipe of the cooling kettle is cooled to-40 to-30 ℃ through the refrigerating unit, the cooled condensing medium is used for cooling the reaction mother liquor to-25 to-20 ℃, and the acetoacetyl arylamine in the mother liquor is separated.
And 4, step 4: and (4) carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol process mother liquor.
And 5: drying the product obtained by centrifugal separation, and further recovering the acetoacetylamide separated from the mother liquor.
Example three:
step 1: alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred.
Step 2: after the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: acetoacetyl arylamine, ethanol, diketene and arylamine.
And step 3: the mother liquor in the cooling kettle is cooled through a cooling module, namely a refrigerating unit, the mother liquor is placed in the cooling kettle, a condensing medium in an outer coil of the cooling kettle is cooled to-40 to-30 ℃ through the refrigerating unit, the cooled condensing medium is used for cooling the reaction mother liquor to-20 ℃, and the acetoacetyl arylamine in the mother liquor is separated.
And 4, step 4: and (4) carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol process mother liquor.
And 5: drying the product obtained by centrifugal separation, and further recovering the acetoacetylamide separated from the mother liquor.
According to the actual energy consumption and the product recovery condition, the temperature of the reaction mother liquor is reduced to-20 ℃, and the acetoacetyl arylamine in the mother liquor can be efficiently separated at the temperature. The condensing medium can be alcohols, glycol is preferred in the invention, the glycol is widely used in production, meanwhile, the condensing effect is better, correspondingly, the concentration of the glycol used as the condensing medium must ensure that the freezing point is lower than-20 ℃, so that the freezing and the frost cracking of pipelines are prevented.
The method can effectively improve the recovery rate of the excess materials in the acetoacetyl arylamine alcohol method mother liquor, simultaneously improve the yield of the synthesis reaction, reduce the resource waste, and in addition, can further reduce the incidence rate of the reaction of arylamine and ethyl acetoacetate to generate 3- (aryl) -2-ethyl crotonate and reduce the occurrence of the phenomenon of product agglomeration by reducing the temperature of the mother liquor.
The temperature of the condensing medium can be adjusted according to the temperature of the mother liquor and the amount of the mother liquor, when the amount of the mother liquor is large and the temperature is high, the temperature of the condensing medium can be reduced to be below minus 40 ℃ to minus 30 ℃, so that the mother liquor can be cooled to be minus 30 ℃ to minus 20 ℃ by the condensing medium, and the temperature of the mother liquor is further reduced to be minus 20 ℃. According to the method, the temperature of the condensing medium ethylene glycol is adjusted through the refrigerating unit, but the temperature cannot be lower than the freezing point of the condensing medium, so that the circulating condensing medium is prevented from becoming solid, and the effect of circulating condensation cannot be guaranteed.
Example four:
alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred. After the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: cooling a condensation medium ethylene glycol to-40 ℃ through a refrigerating unit, further cooling a mother liquor to-30 ℃, carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol method mother liquor, drying a product obtained by the centrifugal separation, and further recovering the acetoacetyl arylamine separated from the mother liquor. The acetoacetyl arylamine can be efficiently recovered at the temperature, and the yield of the acetoacetyl arylamine is improved.
Example five:
alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred. After the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: cooling a condensation medium ethylene glycol to-30 ℃ through a refrigerating unit, further cooling a mother liquor to-20 ℃, carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol method mother liquor, drying a product obtained by the centrifugal separation, and further recovering the acetoacetyl arylamine separated from the mother liquor. The method has the advantages of higher efficiency of recovering the acetoacetyl arylamine at the temperature, low production cost, less energy consumption increase, improvement of the acetoacetyl arylamine yield on the premise of less energy consumption increase, and suitability for industrial production.
Example six:
alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred. After the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: cooling a condensation medium ethylene glycol to-35 ℃ through a refrigerating unit, further cooling a mother liquor to-25 ℃, carrying out centrifugal separation on the condensed acetoacetyl arylamine alcohol method mother liquor, drying a product obtained by the centrifugal separation, and further recovering the acetoacetyl arylamine separated from the mother liquor.
Example seven:
alcohol is taken as a reaction medium, and diketene and arylamine are taken as reactants for continuous reaction, wherein the alcohol can be methanol, ethanol, n-propanol, isopropanol and butanol, and ethanol is preferred. After the reaction is finished, placing reaction mother liquor in a cooling kettle, wherein the mother liquor contains: cooling a condensation medium ethylene glycol to-35 ℃ through a refrigerating unit, further cooling the mother liquor to-23 ℃, carrying out centrifugal separation on the condensed acetoacetylaminoalcohol mother liquor, drying a product obtained by the centrifugal separation, and realizing the recovery of acetoacetylaminoamine.
Comparative example:
the method of the present invention is compared to prior art methods, wherein the prior art methods refer to: the comparison table of the effect of the recovery method that the mother liquor of the acetoacetyl arylamine alcohol method is cooled to-5 to-2 ℃ for excess material recovery:
by adopting the method and the device for recovering the excess material of the acetoacetyl arylamine alcohol process mother liquor, the production efficiency of the product is improved, and the product yield is improved from 92.08 percent to 97.73 percent. Meanwhile, the method effectively shortens the recovery time of the excess material of the acetoacetyl arylamine alcohol process mother liquor, and is suitable for industrial production.
Example eight:
as shown in fig. 1, the invention provides a residue recovery device for acetoacetyl arylamine alcohol process mother liquor, which comprises: buffer tank 3, cooling cauldron 1, cooling module and circulating line, cooling cauldron 1's the perisporium on have outer coil 11, outer coil 11 can twine on cooling cauldron 1's internal perisporium or periphery wall, preferred winding is on the periphery wall, buffer tank 3 passes through the circulating line intercommunication with outer coil, buffer tank 3 is used for holding the condensation medium, the condensation medium flows out through circulating line and gets into outer coil 11 by buffer tank 3 to flow out through circulating line by outer coil 11 and flow back to buffer tank 3, the circulation is reciprocal, the temperature that cooling module set up the condensation medium that is used for reducing in the circulating line on the circulating line. After having set up the cooling module, cooling efficiency is high, promotes the rate of recovery of result in the mother liquor, has both improved the yield of product, has reduced the waste again, and is easy and simple to handle, has reduced manufacturing cost simultaneously, can extensively apply to industrial production.
The cooling module includes a refrigerating unit 2 at least, refrigerating unit 2 has first inlet 21 and first liquid outlet 22, the circulating line has first pipeline 4 and second pipeline 5, first inlet 21 is through first pipeline 4 intercommunication buffer tank 3, first liquid outlet 22 passes through second pipeline 5 intercommunication outer coil pipe 11, constitutes a circulation system through above connected mode with refrigerating unit 2 and buffer tank 3 and outer side 11, and the condensing medium is reciprocal at this circulation system inner loop, reaches the effect of cooling.
Buffer tank 3 has second inlet 31 and second liquid outlet 32 in this embodiment, second inlet 31 is located buffer tank 3's upper portion, second play liquid 32 mouth is located buffer tank 3's lower part, second liquid outlet 32 is through first pipeline 4 intercommunication first inlet 21, the circulating line has third pipeline 7, second inlet 31 is through third pipeline 7 intercommunication outer coil pipe 11, and the operation of condensing medium in circulation system can effectively be realized to this kind of connected mode, reaches the effect of lasting cooling.
In this embodiment, the outer coil 11 at least has a third liquid inlet 111 and a third liquid outlet 112, the third liquid inlet 111 is communicated with the first liquid outlet 22 through the second pipeline 5, the third liquid outlet 112 is communicated with the second liquid inlet 31 through the third pipeline 7, wherein the third liquid outlets 111 may also be provided in plurality, so as to accelerate the condensing medium to enter the outer coil, thereby improving the condensing efficiency.
Third inlet 111 sets up in the middle part of cooling cauldron 1 or the lower part of cooling cauldron 1, third liquid outlet 112 sets up on cooling cauldron 1's upper portion, set up third inlet 111 in the middle part of cooling cauldron 1 or the lower part of cooling cauldron 1, perhaps set up in middle part and lower part, can effectively promote the cooling effect of condensing medium in outer coil pipe 11, make the condensing medium at the in-process that the lower part by cooling cauldron 1 flows to the upper portion of cooling cauldron, the effect of the cold and hot exchange of full play further cools down the mother liquor in the cooling cauldron 1 high-efficiently, promote clout recovery effect.
Through above connected mode, buffer tank 3, refrigerating unit 2, cooling cauldron 1 and its outer coil pipe 11 have passed through the tube coupling and have constituted a circulation system, and concrete circulation step is:
step 1: the condensing medium enters the interior of the buffer tank 3 through a buffer tank liquid inlet pipeline 8;
step 2: the condensed medium flows out of the buffer tank 3 and enters a first pipeline 4;
and step 3: the condensing medium ethylene glycol in the first pipeline 4 flows through the refrigerating unit 2 to be subjected to cooling treatment;
and 4, step 4: the condensing medium flowing out of the refrigerating unit 2 flows into the outer coil 11 through the second pipeline 5 and the second pipeline branch 6;
and 5: the condensing medium flows to a third liquid outlet 112 from a third liquid inlet 111 of the outer coil 11, and the mother liquor in the cooling kettle 1 is cooled;
step 6: the condensed medium flows out of the third liquid outlet 112, and the condensed medium flows through the third pipeline 7 and enters the buffer tank 3 again;
and 7: and (5) circulating the steps from 2 to 6.
The condensation medium ethylene glycol is cooled to-40 to-30 ℃ by the refrigerating unit 2, further, the condensation medium ethylene glycol in the outer coil 11 of the cooling kettle 1 cools the mother liquor in the cooling kettle 1, the cooled mother liquor is centrifuged and dried to obtain a product, and the recovery of the residual materials in the mother liquor of the acetoacetyl arylamine alcohol method is further realized.
The number of the refrigerating units 2 related to the invention can be one, two or more in the whole cooling system, and the number of the refrigerating units depends on the temperature of the total reaction system, the quantity of reaction products, the flow rate of a condensing medium in a pipeline or the refrigerating effect of a condenser. The above conditions can also be comprehensively considered, and the number of the refrigerating units is selected according to different conditions to achieve the expected cooling effect.
The temperature in the synthesis reaction of acetoacetyl arylamine alcohol method is mainly concentrated between 60 ℃ and 80 ℃, and when more reactants are used and more mother liquor is generated, two or three refrigerating units can be selected according to actual conditions. When the refrigerating efficiency of the refrigerating unit is low and the cooling requirement cannot be met, the refrigerating unit can be additionally arranged, and deep cooling is realized. When the velocity of flow of condensing medium was very fast in the circulating line, the mother liquor that produces simultaneously was when more, and at this moment, a refrigerating unit can't satisfy the demand, suitably increases refrigerating unit's number, can effectively improve the cooling effect. In the method, the number of the refrigerating units 2 can be selected, and the requirement of cooling the mother liquor in cooling kettles under different production conditions is flexibly met.
As shown in fig. 1, the installation position of the refrigerating unit 2 in the invention can be selected, the refrigerating unit 2 cools the condensing medium in the circulating pipeline through refrigeration, and further cools the reaction mother liquor, however, according to different production design requirements, in the process flow installation process, the installation position of the refrigerating unit can be specifically selected according to specific situations.
Specifically, there is at least one refrigerating unit 2 to install on the circulating line of outer coil liquid inlet end, and the condensing medium is after the refrigerating unit 2 cooling, is divided into two tributaries by second pipeline branch 6 branch, gets into outer coil 11 from third liquid inlet 111, flows out by third liquid outlet 112 again, flows into circulating line through third liquid outlet 112, and this process of circulation is reciprocal, realizes the degree of depth cooling to the condensing medium, further realizes the cooling to reaction mother liquor, retrieves the clout.
Or, there are a plurality of refrigerating unit 2 among the device, refrigerating unit 2 evenly distributed is on circulating line 3, cools down the condensing medium through a plurality of refrigerating unit 2, can shorten the cooling time effectively, simultaneously, because refrigerating unit 2 evenly distributed is on circulating line 3, so, condensing medium in the circulating line can evenly cool down, and the cooling effect is better.
Furthermore, the refrigerating unit 2 can be arranged according to different industrial requirements. The flexibility of the installation position of the refrigerating unit 2 determines the practicability of the refrigerating unit, and the refrigerating unit can be designed according to different industrial site requirements, thereby greatly providing convenience for industrial production.
The refrigeration mode of the refrigerating unit comprises an intermittent type mode and a continuous type mode, and the refrigeration mode of the refrigerating unit can be set according to the specific actual cooling effect.
When the temperature of the mother liquor is low and the amount of the generated mother liquor is small, an intermittent cooling mode can be adopted, namely, the refrigerating unit 2 is started when the product is synthesized, the refrigerating unit 2 is closed after a period of time, and the starting is continued after the set interval time is reached, so that the operation is repeated in a circulating mode, and the mode can be set in the refrigerating unit 2 without manual operation;
or when the amount of the reactant is small, the refrigerating unit 2 is started after the reaction is carried out for a period of time, namely, the deep temperature reduction can be realized, and the resources can be saved.
When the amount of the mother liquor is large, a continuous cooling mode can be adopted, namely, the refrigerating unit is started when the product is synthesized, and the refrigerating unit is closed when the recovery of the residual materials in the mother liquor is finished.
Or, because the mother liquor is less in products when the reaction is just started, the refrigerating unit 2 can be opened after the reaction is carried out for a period of time, the refrigerating unit 2 is reasonably utilized, and resources are saved.
The input amount of the condensing medium in the buffer tank 3 can influence the circulation speed of the condensing medium, and further can influence the condensation effect, when the condensing medium in the buffer tank 3 is more, the whole pressure in the buffer tank 3 is larger, the flowing speed of the condensing medium in the circulation pipeline is faster, and the cooling effect is better, otherwise, if the input amount of the condensing medium in the buffer tank 3 is less, the whole pressure in the buffer tank 3 is smaller, the flowing speed of the condensing medium in the circulation pipeline is relatively slower, and the cooling effect is relatively poorer.
In addition, after the condensing medium circulation in the circulation system has flowed for a certain time, according to actual production needs, need add or change the condensing medium in buffer tank 3, guarantee production efficiency.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for recovering residual materials of mother liquor of acetoacetyl arylamine alcohol method comprises the steps of taking alcohol as a reaction medium, taking diketene and arylamine as reactants for continuous reaction, cooling, centrifuging and drying the reaction mother liquor after the reaction is finished, and recovering acetoacetyl arylamine in the mother liquor, and is characterized in that: the temperature reduction is deep temperature reduction, and the deep temperature reduction is to reduce the temperature of the mother liquor to-30 to-20 ℃.
2. The method for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 1, wherein the method comprises the following steps: the mother liquor is cooled to-25 to-20 ℃.
3. The method for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 1, wherein the method comprises the following steps: and cooling the mother liquor to-20 ℃.
4. The method for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 1, wherein the method comprises the following steps: the deep cooling is to place the reaction mother liquor in a cooling kettle, cool the condensation medium in the outer coil pipe of the cooling kettle to-40 to-30 ℃, and then cool the reaction mother liquor to-20 ℃ by utilizing the cooled condensation medium.
5. The method for recovering the remainder of the acetoacetyl aromatic amine alcohol process mother liquor as claimed in claim 4, wherein the condensing medium is ethylene glycol.
6. A device for recovering excess materials of acetoacetyl arylamine alcohol process mother liquor is characterized in that: clout recovery unit include: buffer tank, cooling cauldron, cooling module and circulating line, the perisporium of cooling cauldron on have the outer coil, the buffer tank passes through the circulating line intercommunication with the outer coil, the buffer tank is used for holding the condensation medium, the condensation medium flows out through the circulating line by the buffer tank and gets into the outer coil to flow back to the buffer tank through the circulating line by the outer coil outflow, the circulation is reciprocal, the cooling module sets up the temperature that is used for reducing the condensation medium in the circulating line on the circulating line.
7. The device for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 6, wherein: the cooling module at least comprises a refrigerating unit, the refrigerating unit is provided with a first inlet and a first liquid outlet, the circulating pipeline is provided with a first pipeline and a second pipeline, the first inlet is communicated with the buffer tank through the first pipeline, and the first liquid outlet is communicated with the outer coil pipe through the second pipeline.
8. The device for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 7, is characterized in that: the buffer tank has second inlet and second liquid outlet, the second inlet be located the upper portion of buffer tank, the second liquid outlet be located the lower part of buffer tank, the second liquid outlet is through first inlet of first pipeline intercommunication, the circulating line has the third pipeline, the second inlet passes through third pipeline intercommunication outer coil pipe.
9. The device for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 8, wherein: the outer coil pipe is provided with at least one third liquid inlet and a third liquid outlet, the third liquid inlet is communicated with the first liquid outlet through a second pipeline, and the third liquid outlet is communicated with the second liquid inlet through a third pipeline.
10. The device for recovering the residual material of the acetoacetyl arylamine alcohol process mother liquor as claimed in claim 9, is characterized in that: the third liquid inlet is arranged in the middle of the cooling kettle or at the lower part of the cooling kettle, and the third liquid outlet is arranged at the upper part of the cooling kettle.
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