CN109553575B - Adsorption impurity removal method for high-purity ethoxyquinoline - Google Patents
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- CN109553575B CN109553575B CN201710891404.8A CN201710891404A CN109553575B CN 109553575 B CN109553575 B CN 109553575B CN 201710891404 A CN201710891404 A CN 201710891404A CN 109553575 B CN109553575 B CN 109553575B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention belongs to material separation and purification in the field of chemical industry, and particularly relates to an adsorption impurity removal method for high-purity ethoxyquinoline, which is used for designing an adsorption device for ensuring effective separation of the product ethoxyquinoline and impurity p-phenetidine to obtain the high-purity ethoxyquinoline with high added value. Firstly, a fixed bed is adopted to separate impurity p-phenetidine, and after the adsorbent is adsorbed and saturated, the adsorbent is regenerated through eluent washing and vacuum high-temperature desorption, so that the whole adsorption-desorption period is completed. The method can effectively separate the ethoxyquinoline and the p-phenetidine, greatly improve the purity of the ethoxyquinoline product and ensure that the concentration of the p-phenetidine in the product is less than 2.5 ppm. The method has wide application prospect in the fields of ethoxyquinoline production, separation and purification.
Description
Technical Field
The invention belongs to material separation and purification in the field of chemical industry, and relates to an adsorption impurity removal process of high-purity ethoxyquinoline.
Background
Ethoxyquin is widely used as a feed additive due to its excellent oxidation resistance, but the ethoxyquin acetone method has a problem of separating highly biotoxic p-phenetidine from the product. The concentration of the p-phenetidine contained in the ethyoxyl quinoline product produced at home at present cannot meet the new international standard, and the product production enterprises are limited to move to the international market. Therefore, the research on the separation technology of trace p-phenetidine in ethoxyquinoline is important for creating foreign exchange for the product outlet of the antioxidant.
Currently, the p-phenetidine in ethoxyquinoline is mainly separated by a distillation method. The condensation reaction of phenetidine and acetone in the presence of catalyst to produce ethoxy quinoline. As toluene is needed to carry out water generated in the reaction, ethoxyquinoline firstly needs to be distilled under reduced pressure to remove toluene to obtain a crude product, and then the crude product is refined by reduced pressure fractional distillation to obtain the product. However, the content of the p-phenetidine in the product obtained by the distillation method is about 4 percent at present, and with the coming of the international new standard, how to obtain the high-purity ethoxyquinoline by utilizing the advanced separation technology is very important for domestic manufacturers.
Disclosure of Invention
The invention aims to provide an adsorption impurity removal method of high-purity ethoxyquinoline, which can reduce the content of p-phenetidine in the ethoxyquinoline to be below 2.5ppm and ensure that the yield of the ethoxyquinoline exceeds 90 percent.
The invention adopts the following technical scheme:
an adsorption impurity removal method of high-purity ethoxyquinoline is characterized by comprising the following steps: filtering the crude ethoxyquinoline to remove particles, and sending the obtained filtrate into a raw material tank for preheating; the preheated filtrate passes through the constant-temperature adsorption column from bottom to top at a controlled flow rate, and the qualified product automatically flows into the product tank from the top; washing the saturated adsorption column with constant temperature eluent, desorbing and regenerating at negative pressure and high temperature, condensing the desorption liquid with cold trap, and collecting in storage tank.
The content of the p-phenetidine in the crude product of the ethoxyquin is lower than 100 ppm.
Further, the preheating temperature of the ethoxyquinoline filtrate is 30-35 ℃.
Further, the feeding flow rate of the ethyoxyl quinoline filtrate into the constant-temperature adsorption column is 1-10 BV/h, and the internal temperature of the adsorption column is constant at 40-90 ℃.
According to the method for adsorbing and removing impurities of high-purity ethoxyquinoline, the feeding flow rate of eluent is 1-5 BV/h, the temperature is 20-30 ℃, and the washing time is 2-3 h.
According to the method for adsorbing and removing impurities of high-purity ethoxyquinoline, the vacuum degree in the negative pressure high-temperature desorption regeneration process is 0.1-50 mbar, the temperature is 100-300 ℃, and the desorption is carried out for 4-6 h.
Further, the adsorbent filled in the constant-temperature adsorption column is activated carbon, macroporous adsorption resin, ion exchange resin, diatomite, zeolite molecular sieve, polyacrylamide or alumina.
Further, the eluent of the adsorption column is one or more of pentane, acetone, toluene, ammonia water, xylene or cyclohexane.
According to the adsorption impurity removal method of the high-purity ethoxyquinoline, the obtained filtrate is sent into a raw material tank through a gear pump for preheating; and conveying the filtrate to a constant-temperature adsorption column through a gear pump in a variable-frequency manner.
According to the adsorption impurity removal method of the high-purity ethoxyquin, the filtering precision is 5 microns, and a hollow polypropylene fiber filter element is adopted for filtering.
The crude ethoxyquin is prepared by an acetone method by the company, and is synthesized by taking phenetidine and acetone as raw materials and carrying out condensation reaction in the presence of a catalyst; and then, preparing the crude product of ethoxyquinoline by adopting a multistage molecular distillation technology. Removing high-boiling-point impurities (the high-boiling-point impurities are impurities with the boiling point higher than 300 ℃) in the crude product of the ethoxyquin through primary molecular distillation, taking the collected light components as raw materials for secondary separation, and controlling the process conditions in the following range: the heating temperature of the main distiller is 130-160 ℃, the temperature of the condenser is 3-10 ℃, the pressure of the system is 0.1-5 mbar, the feeding rate is 10-50 mL/min, and the rotating speed of the film scraper is 400-500 rpm. The content of the phenetidine is reduced to 200ppm by secondary molecular distillation, and the collected heavy components are used as raw materials for tertiary separation. The process conditions are controlled in the following ranges: the heating temperature of the main distiller is 100-160 ℃, the temperature of the condenser is 3-10 ℃, the pressure of the system is 0.1-10 mbar, the feeding rate is 10-100 mL/min, and the rotating speed of the film scraper is 300-400 rpm. The content of the aminophenylethyl ether is reduced to 20ppm by three-stage molecular distillation, and the collected heavy components are qualified products. The process conditions are controlled in the following ranges: the heating temperature of the main distiller is 100-160 ℃, the temperature of the condenser is 3-10 ℃, the pressure of the system is 0.1-10 mbar, the feeding rate is 10-100 mL/min, and the rotating speed of the film scraper is 300-400 rpm.
The method comprises the steps of filtering ethoxyquinoline with the p-phenetidine content of 100ppm (the filtering precision is 5 microns, and the hollow polypropylene fiber filter core is adopted for filtering) to remove particles, and conveying the filtrate into a raw material tank of an adsorption device through a gear pump.
Preheating ethoxyquinoline in a raw material tank (a jacket heat exchanger is used for preheating, and hot water at a temperature of 30 ℃ is used for circulating preheating) to 30 ℃, conveying the ethoxyquinoline through a gear pump in a variable frequency manner, passing through an adsorption column from bottom to top at a flow rate of 1-10 BV/h, controlling the temperature in the adsorption process to be constant at 40-90 ℃, and allowing qualified products to flow out of the top of the adsorption column and automatically flow into a product tank.
The saturated adsorption column is washed for 2 hours by eluent at the controlled flow rate of 1-5 BV/h and the temperature of 20-30 ℃. After the washing is finished, the desorption temperature is 300 ℃ and the desorption degree is 0.1-50 mbar, and the desorption is carried out for 4h by the adsorption column. And finally, condensing the desorption liquid through a cold trap (the temperature set by the cold trap is minus 5 ℃), and collecting the desorption liquid through a storage tank.
The adsorbent filled in the adsorption column is active carbon, macroporous adsorption resin, ion exchange resin, diatomite, zeolite molecular sieve, polyacrylamide and alumina.
The activated carbon is as follows: iodine value is more than or equal to 1100mg/g, strength is more than or equal to 97%, specific gravity is 450-500 g/l, and water content is less than or equal to 5%.
The macroporous adsorption resin: the specific surface area is more than or equal to 1100m2In g, average pore diameter of
Dry state, water content less than or equal to 5 percent.
The ion exchange resin: ion form is H+The exchange equivalent is more than or equal to 10mmol/g, and the lower limit of the particle size is less than or equal to 300 mu m.
The diatomite: the specific surface area is more than or equal to 100m2Per g, the permeability is more than or equal to 1Darcy, and the water content is less than or equal to 5 percent.
The zeolite molecular sieve: the absorption capacity of normal hexane is 9.5-10.5%, the ratio of silicon to aluminum is more than or equal to 25, and the average pore diameter is
The alumina: the specific surface area is more than or equal to 310m2The pore volume is more than or equal to 0.5 cc/g.
The eluent of the adsorption column is pentane, acetone, toluene, ammonia water, xylene or cyclohexane or a composition thereof.
The invention has the beneficial technical effects that:
the invention provides an adsorption impurity removal method of high-purity ethoxyquin, which can reduce the content of p-phenetidine in ethoxyquin to be below 2.5ppm and ensure that the yield of ethoxyquin exceeds 90%.
Drawings
FIG. 1 is a schematic diagram of an experimental device in the adsorption impurity removal method for high-purity ethoxyquinoline provided by the invention: a V-01 raw material tank, a V-02 condensate desorption liquid storage tank, a V-03 product tank, a P-01 feed pump, a P-02 vacuum pump, an X-01 adsorption column, an X-02 cold trap, a PG01 vacuum meter, a PG02 vacuum meter, a PG03 vacuum meter, a TI01 thermometer and a TI02 thermometer; 1-1# valve, 2-2# ball valve, 3-3# ball valve, 4-4# ball valve, 5-5# valve, 6-6# valve, 7-7# ball valve, 8-8# ball valve, 9-9# ball valve, 10-10# ball valve and 11-11# ball valve.
FIG. 2 is a gas chromatogram of a product obtained by the adsorption impurity removal method of high-purity ethoxyquinoline.
Detailed Description
The present invention is described in more detail by the following examples. These examples are merely illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
As shown in FIG. 1, the whole impurity removing system of the adsorption device comprises: a raw material tank V-01, a condensate storage tank V-02, a product tank V-03, a feed pump P-01, a vacuum pump P-02, an adsorption column X-01, a cold trap X-02, a heating system and a monitoring instrument.
The adsorption column is filled with active carbon, macroporous adsorption resin, ion exchange resin, diatomite, zeolite molecular sieve, polyacrylamide and alumina.
The eluent of the adsorption column is pentane, acetone, toluene, ammonia water, xylene or cyclohexane or a composition thereof.
The vacuum system controls the internal pressure of the adsorption column to be stabilized at 0.1-50 mbar.
The heating system controls the temperature in the adsorption column to be stabilized at 40-90 ℃ during adsorption and the temperature to be stabilized at 100-300 ℃ during desorption.
Example 1
(1) Pretreating the ethoxyquin with the p-phenetidine content of 100ppm to ensure that no solid matter exists in the crude oil and then performing adsorption operation;
(2) preheating 5kg of ethoxyquin in a raw material tank to 30 ℃ through a jacket heat exchanger, passing through a filled alumina adsorption column from bottom to top at a flow rate of 5BV/h through a gear pump, controlling the temperature in the adsorption process to be constant at 90 ℃, and allowing qualified products to flow out of the top of the adsorption column and enter a product tank;
(3) after the adsorption filler is saturated, washing for 2 hours by controlling the flow rate of ammonia water to be 5BV/h and the temperature to be 30 ℃. After washing, the vacuum degree is controlled to be 2mbar, the desorption temperature is controlled to be 100 ℃, and desorption is carried out for 4 hours. The adsorption tower can carry out adsorption again, and the product is 4.75 kg.
The product was analyzed by gas chromatography to find that the concentration of phenetidine was 2.4ppm and the yield was 95%.
Example 2
(1) Pretreating the ethoxyquin with the p-phenetidine content of 100ppm to ensure that no solid matter exists in the crude oil and then performing adsorption operation;
(2) preheating 5kg of ethoxyquin in a raw material tank to 30 ℃ through a jacket heat exchanger, passing through a macroporous adsorption resin adsorption column from bottom to top at a flow rate of 3BV/h through a gear pump, controlling the temperature in the adsorption process to be constant at 80 ℃, and allowing qualified products to flow out of the top of the adsorption column and enter a product tank;
(3) after the adsorption filler is saturated, washing for 2 hours by controlling the flow rate of toluene to be 5BV/h and the temperature to be 30 ℃. After washing, the vacuum degree is controlled to be 1mbar, the desorption temperature is controlled to be 95 ℃, and desorption is carried out for 4 hours. The adsorption tower can carry out adsorption again, and the product is 4.50 kg.
The product was analyzed by gas chromatography to find that the concentration of phenetidine was 2.0ppm and the yield was 90%. .
Example 3
(1) Pretreating the ethoxyquin with the p-phenetidine content of 100ppm to ensure that no solid matter exists in the crude oil and then performing adsorption operation;
(2) preheating 5kg of ethoxyquin in a raw material tank to 30 ℃ through a jacket heat exchanger, passing through a zeolite molecular sieve-filled adsorption column from bottom to top at a flow rate of 5BV/h through a gear pump, controlling the temperature in the adsorption process to be constant at 90 ℃, and allowing qualified products to flow out of the top of the adsorption column and enter a product tank;
(3) after the adsorption filler is saturated, washing for 2 hours by controlling the flow rate of acetone to be 5BV/h and the temperature to be 30 ℃. After washing, the vacuum degree is controlled to be 1mbar, the desorption temperature is controlled to be 95 ℃, and desorption is carried out for 4 hours. The adsorption tower can carry out adsorption again, and the product is 4.60 kg.
The product was analyzed by gas chromatography to find that the concentration of phenetidine was 1.6ppm and the yield was 92%.
Example 4
(1) Pretreating the ethoxyquin with the p-phenetidine content of 100ppm to ensure that no solid matter exists in the crude oil and then performing adsorption operation;
(2) preheating 5kg of ethoxyquin in a raw material tank to 30 ℃ through a jacket heat exchanger, passing through an ion exchange resin adsorption column from bottom to top at a flow rate of 5BV/h through a gear pump, controlling the temperature in the adsorption process to be constant at 90 ℃, and allowing qualified products to flow out of the top of the adsorption column and enter a product tank;
(3) after the adsorption filler is saturated, washing for 2 hours by controlling the flow rate of pentane to be 5BV/h and the temperature to be 30 ℃. After washing, the vacuum degree is controlled to be 1mbar, the desorption temperature is controlled to be 95 ℃, and desorption is carried out for 4 hours. The adsorption tower can carry out adsorption again, and the product is 4.55 kg.
The product was analyzed by gas chromatography to find that the concentration of phenetidine was 0.8ppm and the yield was 91%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (5)
1. An adsorption impurity removal method of high-purity ethoxyquinoline is characterized by comprising the following steps: filtering the crude ethoxyquinoline to remove particles, and sending the obtained filtrate into a raw material tank for preheating; the preheated filtrate passes through the constant-temperature adsorption column from bottom to top at a controlled flow rate, and the qualified product automatically flows into the product tank from the top; washing the saturated adsorption column with constant temperature eluent, desorbing and regenerating at negative pressure and high temperature, condensing the desorption solution with cold trap, and collecting with storage tank;
the content of the p-phenetidine in the crude product of the ethoxyquin is lower than 100 ppm;
the preheating temperature of the ethyoxyl quinoline filtrate is 30-35 ℃;
feeding the ethoxyquinoline filtrate into a constant-temperature adsorption column at a feeding flow rate of 1-10 BV/h, wherein the internal temperature of the adsorption column is constant at 40-90 ℃;
the feeding flow rate of the eluent is 1-5 BV/h, the temperature is 20-30 ℃, and the washing time is 2-3 h;
the vacuum degree in the negative pressure high temperature desorption regeneration process is 0.1-50 mbar, the temperature is 100-300 ℃, and the desorption lasts for 4-6 h.
2. The method for adsorbing and removing impurities of high-purity ethoxyquinoline according to claim 1, which is characterized by comprising the following steps: the adsorbent filled in the constant-temperature adsorption column is activated carbon, macroporous adsorption resin, ion exchange resin, diatomite, zeolite molecular sieve, polyacrylamide or alumina.
3. The method for adsorbing and removing impurities of high-purity ethoxyquinoline according to claim 1, which is characterized by comprising the following steps: the eluent of the adsorption column is one or more of pentane, acetone, toluene, ammonia water, xylene or cyclohexane.
4. The method for adsorbing and removing impurities of high-purity ethoxyquinoline according to claim 1, which is characterized by comprising the following steps: sending the obtained filtrate into a raw material tank through a gear pump for preheating; and conveying the filtrate to a constant-temperature adsorption column through a gear pump in a variable-frequency manner.
5. The method for adsorbing and removing impurities of high-purity ethoxyquinoline according to claim 1, characterized by comprising the following steps: the filtration precision is 5 microns, adopts the filtration of hollow polypropylene fiber filter core.
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| CN201710891404.8A CN109553575B (en) | 2017-09-27 | 2017-09-27 | Adsorption impurity removal method for high-purity ethoxyquinoline |
| PCT/CN2017/107027 WO2019061594A1 (en) | 2017-09-27 | 2017-10-20 | Adsorption-based impurity removal method for high purity ethoxyquinoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823998A (en) * | 2010-05-05 | 2010-09-08 | 江苏利田科技有限公司 | Pollution-free production process for ethoxy quinoline by coupling reactor and simulation moving bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3829292A (en) * | 1971-04-26 | 1974-08-13 | H Monroy | Apparatus for the production of 1,2-dihydroquinolines |
| FR2784988B1 (en) * | 1998-10-23 | 2002-09-20 | Adir | NOVEL DIHYDRO AND TETRAHYDROQUINOLEINIC COMPOUNDS, PROCESS FOR THEIR PREPARATION AND THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM |
| CN102285918A (en) * | 2011-07-29 | 2011-12-21 | 上海福达精细化工有限公司 | Method for producing ethoxy quinoline |
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- 2017-10-20 WO PCT/CN2017/107027 patent/WO2019061594A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823998A (en) * | 2010-05-05 | 2010-09-08 | 江苏利田科技有限公司 | Pollution-free production process for ethoxy quinoline by coupling reactor and simulation moving bed |
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