CN109553575A - A kind of adsorption-edulcoration method of high-purity ethoxyquinoline - Google Patents
A kind of adsorption-edulcoration method of high-purity ethoxyquinoline Download PDFInfo
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- CN109553575A CN109553575A CN201710891404.8A CN201710891404A CN109553575A CN 109553575 A CN109553575 A CN 109553575A CN 201710891404 A CN201710891404 A CN 201710891404A CN 109553575 A CN109553575 A CN 109553575A
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- ethoxyquinoline
- adsorption
- purity
- temperature
- edulcoration
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- C—CHEMISTRY; METALLURGY
- 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
- C07D215/20—Oxygen atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention belongs to feed separation in chemical field and purifications, more particularly to a kind of adsorption-edulcoration method of high-purity ethoxyquinoline, it is designed to ensure that the adsorbent equipment that product ethoxyquinoline and impurity para aminophenyl ethyl ether efficiently separate, obtains high-purity, high value added product ethoxyquinoline.Impurity para aminophenyl ethyl ether is separated using fixed bed first, after adsorbent adsorption saturation, adsorbent of living again is desorbed by eluent washing, vacuum high-temperature, completes entire absorption-desorption period.The present invention can efficiently separate ethoxyquinoline and para aminophenyl ethyl ether, greatly improve product ethoxyquinoline purity, it is ensured that para aminophenyl ethyl ether concentration is less than 2.5ppm in product.This method is produced in ethoxyquinoline and separating-purifying field has broad application prospects.
Description
Technical field
The invention belongs to chemical field feed separation and purifications, are related to a kind of adsorption-edulcoration work of high-purity ethoxyquinoline
Skill.
Background technique
Ethoxyquinoline is widely used in feed addictive due to its excellent inoxidizability, but in ethoxyquinoline third
The separation problem of high bio-toxicity para aminophenyl ethyl ether in product is faced in ketone method production process.The ethoxy of domestic production at present
Contained para aminophenyl ethyl ether concentration is not able to satisfy International New Standard in base quinoline product, limits the production enterprise and moves towards state
Border market.Therefore, the isolation technics for studying micro para aminophenyl ethyl ether in ethoxyquinoline, which exports antioxidant product, to be created
It converges most important.
The separation of para aminophenyl ethyl ether mainly uses the way of distillation in ethoxyquinoline at present.Para aminophenyl ethyl ether and acetone exist
Under the conditions of catalyst is existing, carries out condensation reaction and generate ethoxyquinoline.The water generated in reaction due to needing toluene to take out of,
So ethoxyquinoline obtains crude product firstly the need of vacuum distillation removal toluene, subsequent crude product is refining to obtain production by vacuum fractionation
Product.But the content of para aminophenyl ethyl ether is about 4% in the obtained product of the way of distillation at present, with the appearance of International New Standard,
How using advanced isolation technics high-purity ethoxyquinoline is obtained most important for domestic production producer.
Summary of the invention
It, can will be in ethoxyquinoline it is an object of the present invention to provide a kind of adsorption-edulcoration method of high-purity ethoxyquinoline
The content of para aminophenyl ethyl ether is reduced to 2.5ppm hereinafter, ethoxyquinoline yield is more than 90%.
The invention adopts the following technical scheme:
A kind of adsorption-edulcoration method of high-purity ethoxyquinoline, it is characterised in that: be filtered ethoxyquinoline crude product
Particulate matter is removed, gained filtrate is sent into head tank and is preheated；Filtrate coutroi velocity after preheating passes through thermostatic absorption from bottom to top
Column, qualified products enter products pot through top gravity flow；The adsorption column of saturation is washed by constant temperature eluent, subsequent negative pressure high temperature
Desorption and regeneration, desorption liquid are condensed by cold-trap, and storage tank is collected.
The content of para aminophenyl ethyl ether is lower than 100ppm in the ethoxyquinoline crude product.
Further, the ethoxyquinoline filtrate preheating temperature is 30 DEG C~35 DEG C.
Further, it is 1-10BV/h, temperature inside adsorption column that ethoxyquinoline filtrate, which enters the feed flow rate of thermostatic absorption column,
Degree is constant at 40-90 DEG C.
The adsorption-edulcoration method of high-purity ethoxyquinoline according to the present invention, the eluent feed flow rate are 1-
5BV/h, temperature are 20-30 DEG C, wash time 2h~3h.
The adsorption-edulcoration method of high-purity ethoxyquinoline according to the present invention, the negative pressure desorption under high temperature regenerative process
Vacuum degree is 0.1-50mbar, and temperature is 100-300 DEG C, desorbs 4h~6h.
Further, the adsorbent loaded in the thermostatic absorption column is active carbon, macroporous absorbent resin, amberlite
Rouge, diatomite, zeolite molecular sieve, polyacrylamide or aluminium oxide.
Further, the adsorption column eluent is one of pentane, acetone, toluene, ammonium hydroxide, dimethylbenzene or hexamethylene
Or more than one.
The adsorption-edulcoration method of high-purity ethoxyquinoline, gained filtrate are pumped into raw material by gear according to the present invention
It is preheated in tank；Filtrate is conveyed to thermostatic absorption column by gear pump frequency conversion.
The adsorption-edulcoration method of high-purity ethoxyquinoline according to the present invention, filtering accuracy are 5 microns, using hollow poly-
Tacryl filter element filtering.
Above-mentioned ethoxyquinoline crude product is that our company is prepared by acetone method, using para aminophenyl ethyl ether and acetone as raw material,
Under the conditions of existing for the catalyst, condensation reaction, the ethoxyquinoline of synthesis are carried out；It is produced again using multiple-grade molecular distillation technology
Ethoxyquinoline crude product.Distill in removing ethoxyquinoline crude product that (high-boiling-point impurity is high-boiling-point impurity by first order molecular
Boiling point is higher than 300 degree of impurity), raw material of the light component of collection as the second-order separation, process regulation is in following range: main
130~160 DEG C of distiller heating temperature, 3~10 DEG C of condenser temperature, 0.1~5mbar of system pressure, feed rate 10~
400~500rpm of 50mL/min and blade applicator revolving speed.It is distilled by secondary molecules and is reduced to para aminophenyl ethyl ether content
200ppm, the raw material that the heavy constituent of collection is separated as three-level.Process regulation is in following range: main distiller heating temperature
100~160 DEG C, 3~10 DEG C of condenser temperature, 0.1~10mbar of system pressure, 10~100mL/min of feed rate and knifing
300~400rpm of device revolving speed.Phenetidine content is reduced to 20ppm by three-level molecular distillation, the heavy constituent of collection is
For qualified product.Process regulation is in following range: 100~160 DEG C of main distiller heating temperature, condenser temperature 3~
10 DEG C, 300~400rpm of 0.1~10mbar of system pressure, 10~100mL/min of feed rate and blade applicator revolving speed.
The method of the present invention is that the ethoxyquinoline for being 100ppm by para aminophenyl ethyl ether content is filtered that (filtering accuracy is
5 microns, using hollow polypropylene fibres filter element filtering) particulate matter is removed, filtrate is pumped into the raw material of adsorbent equipment by gear
In tank.
By the ethoxyquinoline preheating (jacket heat-exchanger preheating, preheated with 30 degree of hot water circuits) in head tank to 30
DEG C, it is conveyed by gear pump frequency conversion, adsorption column is passed through from bottom to top with the flow velocity of 1-10BV/h, while controlling adsorption process temperature
40-90 DEG C are constant at, for qualified products through flowing out at the top of adsorption column, gravity flow enters products pot.
It is 1-5BV/h that the adsorption column of saturation, which is passed through coutroi velocity, and temperature is 20-30 DEG C, and eluent washs 2h.Washing knot
Shu Hou is 0.1-50mbar by control vacuum degree, and desorption temperature is 100-300 DEG C, and adsorption column desorbs 4h.Finally by desorption liquid
By cold-trap (temperature that cold-trap is set is -5 degree) condensation, storage tank is collected.
The adsorbent loaded in the adsorption column be active carbon, macroporous absorbent resin, ion exchange resin, diatomite,
Zeolite molecular sieve, polyacrylamide, aluminium oxide.
The active carbon: iodine number >=1100mg/g, intensity >=97%, 450-500g/l of specific gravity, water content≤5%.
The macroporous absorbent resin: specific surface area >=1100m2/ g, average pore size areDry state, water content≤5%.
The ion exchange resin: ionic forms H+, exchanging equivalent >=10mmol/g, particle diameter limit≤300 μm.
The diatomite: specific surface area >=100m2/ g, permeability >=1Darcy, water content≤5%.
The zeolite molecular sieve: n-hexane adsorbance 9.5-10.5%, silica alumina ratio >=25, average pore size are
The aluminium oxide: specific surface area >=310m2/ g, Kong Rong >=0.5cc/g.
The eluent of the adsorption column is pentane, acetone, toluene, ammonium hydroxide, dimethylbenzene or hexamethylene, or combinations thereof object.
Advantageous effects of the present invention:
The present invention provides a kind of adsorption-edulcoration method of high-purity ethoxyquinoline, can be by p-aminophenyl in ethoxyquinoline
The content of ether is reduced to 2.5ppm hereinafter, ethoxyquinoline yield is more than 90%.
Detailed description of the invention
Fig. 1 provides experimental provision schematic diagram in the adsorption-edulcoration method of high-purity ethoxyquinoline: V -01 raw material for the present invention
Tank, V -02 condensation desorption liquid storage tank, V -03 products pot, P -01 feed pump, P -02 vacuum pump, X -01 adsorption column, X -02 cold-trap,
PG01 vacuum meter, PG02 vacuum meter, PG03 vacuum meter, TI01 temperature instrumentation and TI02 temperature instrumentation；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,
11-11# ball valve.
Fig. 2 is a kind of gas chromatogram of the adsorption-edulcoration method products obtained therefrom of high-purity ethoxyquinoline of the present invention.
Specific embodiment
It is for a more detailed description to the present invention with embodiment below.These embodiments are only to the best embodiment party of the present invention
The description of formula, does not have any restrictions to the scope of the present invention.
As shown in Figure 1, including: head tank V -01, condensate tank V -02, products pot in entire adsorbent equipment impurity removed system
V -03, feed pump P -01, vacuum pump P -02, adsorption column X -01, cold-trap X -02, heating system and measuring instrument.
What is loaded in the adsorption column is active carbon, macroporous absorbent resin, ion exchange resin, diatomite, zeolite point
Sub- sieve, polyacrylamide, aluminium oxide.
The eluent of the adsorption column is pentane, acetone, toluene, ammonium hydroxide, dimethylbenzene or hexamethylene, or combinations thereof object.
The vacuum system control adsorption column internal pressure is stable at 0.1-50mbar.
Adsorption column internal temperature is stable at 40-90 DEG C when the heating system controls absorption, and temperature is stable at when desorption
100–300℃。
Embodiment 1
(1) ethoxyquinoline that para aminophenyl ethyl ether content is 100ppm is pre-processed, is guaranteed in crude oil without solid matter
Adsorption operation is carried out again；
(2) ethoxyquinoline of 5kg in head tank is preheated to 30 DEG C by jacket heat-exchanger, by gear pump with 5BV/
The flow velocity of h controls adsorption process temperature and is constant at 90 DEG C from bottom to top by filling alumina adsorption column, qualified products warp
Outflow enters products pot at the top of adsorption column；
It (3) is 5BV/h by control ammonia flow rate after filler saturation to be adsorbed, temperature is 30 DEG C, washs 2h.Washing knot
Shu Hou is 2mbar by control vacuum degree, and desorption temperature is 100 DEG C, desorbs 4h.Adsorption tower can re-start absorption work,
Product is 4.75kg.
By gas chromatographic analysis, the concentration of para aminophenyl ethyl ether is 2.4ppm, yield 95% in product.
Embodiment 2
(1) ethoxyquinoline that para aminophenyl ethyl ether content is 100ppm is pre-processed, is guaranteed in crude oil without solid matter
Adsorption operation is carried out again；
(2) ethoxyquinoline of 5kg in head tank is preheated to 30 DEG C by jacket heat-exchanger, by gear pump with 3BV/
The flow velocity of h controls adsorption process temperature and is constant at 80 DEG C from bottom to top by filling macroporous absorbent resin adsorption column, qualification
Product enters products pot through outflow at the top of adsorption column；
It (3) is 5BV/h by control toluene flow velocity after filler saturation to be adsorbed, temperature is 30 DEG C, washs 2h.Washing knot
Shu Hou is 1mbar by control vacuum degree, and desorption temperature is 95 DEG C, desorbs 4h.Adsorption tower can re-start absorption work,
Product is 4.50kg.
By gas chromatographic analysis, the concentration of para aminophenyl ethyl ether is 2.0ppm, yield 90% in product.
Embodiment 3
(1) ethoxyquinoline that para aminophenyl ethyl ether content is 100ppm is pre-processed, is guaranteed in crude oil without solid matter
Adsorption operation is carried out again；
(2) ethoxyquinoline of 5kg in head tank is preheated to 30 DEG C by jacket heat-exchanger, by gear pump with 5BV/
The flow velocity of h controls adsorption process temperature and is constant at 90 DEG C from bottom to top by filling zeolite molecular sieve adsorption column, and qualification produces
Product enter products pot through outflow at the top of adsorption column；
It (3) is 5BV/h by control acetone flow velocity after filler saturation to be adsorbed, temperature is 30 DEG C, washs 2h.Washing knot
Shu Hou is 1mbar by control vacuum degree, and desorption temperature is 95 DEG C, desorbs 4h.Adsorption tower can re-start absorption work,
Product is 4.60kg.
By gas chromatographic analysis, the concentration of para aminophenyl ethyl ether is 1.6ppm, yield 92% in product.
Embodiment 4
(1) ethoxyquinoline that para aminophenyl ethyl ether content is 100ppm is pre-processed, is guaranteed in crude oil without solid matter
Adsorption operation is carried out again；
(2) ethoxyquinoline of 5kg in head tank is preheated to 30 DEG C by jacket heat-exchanger, by gear pump with 5BV/
The flow velocity of h passes through filling ion-exchange resin adsorption column from bottom to top, while controlling adsorption process temperature and being constant at 90 DEG C, qualification
Product enters products pot through outflow at the top of adsorption column；
It (3) is 5BV/h by control pentane flow velocity after filler saturation to be adsorbed, temperature is 30 DEG C, washs 2h.Washing knot
Shu Hou is 1mbar by control vacuum degree, and desorption temperature is 95 DEG C, desorbs 4h.Adsorption tower can re-start absorption work,
Product is 4.55kg.
By gas chromatographic analysis, the concentration of para aminophenyl ethyl ether is 0.8ppm, yield 91% in product.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (10)
1. a kind of adsorption-edulcoration method of high-purity ethoxyquinoline, it is characterised in that: be filtered ethoxyquinoline crude product and remove
Degranulation object, gained filtrate are sent into head tank and are preheated；Filtrate coutroi velocity after preheating passes through thermostatic absorption column from bottom to top,
Qualified products enter products pot through top gravity flow；The adsorption column of saturation is washed by constant temperature eluent, subsequent negative pressure high temperature solution
Regeneration is inhaled, desorption liquid is condensed by cold-trap, and storage tank is collected.
2. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: ethoxyquinoline crude product
The content of middle para aminophenyl ethyl ether is lower than 100ppm.
3. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: the ethoxyquinoline
Filtrate preheating temperature is 30 DEG C~35 DEG C.
4. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: ethoxyquinoline filtrate
Feed flow rate into thermostatic absorption column is 1-10BV/h, and adsorption column internal temperature is constant at 40-90 DEG C.
5. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: the eluent into
Stream speed is 1-5BV/h, and temperature is 20-30 DEG C, wash time 2h~3h.
6. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: the negative pressure high temperature
Desorption and regeneration process vacuum degree is 0.1-50mbar, and temperature is 100-300 DEG C, desorbs 4h~6h.
7. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: the thermostatic absorption column
The adsorbent of middle filling is active carbon, macroporous absorbent resin, ion exchange resin, diatomite, zeolite molecular sieve, polyacrylamide
Or aluminium oxide.
8. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: the adsorption column is washed
De- liquid be one of pentane, acetone, toluene, ammonium hydroxide, dimethylbenzene or hexamethylene or more than one.
9. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: gained filtrate passes through tooth
Wheel, which is pumped into head tank, to be preheated；Filtrate is conveyed to thermostatic absorption column by gear pump frequency conversion.
10. the adsorption-edulcoration method of high-purity ethoxyquinoline according to claim 1, it is characterised in that: filtering accuracy is 5 micro-
Rice, using hollow polypropylene fibres filter element filtering.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710891404.8A CN109553575B (en) | 2017-09-27 | 2017-09-27 | Adsorption impurity removal method for high-purity ethoxyquinoline |
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| Publication Number | Publication Date |
|---|---|
| CN109553575A true CN109553575A (en) | 2019-04-02 |
| CN109553575B CN109553575B (en) | 2022-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710891404.8A Active CN109553575B (en) | 2017-09-27 | 2017-09-27 | Adsorption impurity removal method for high-purity ethoxyquinoline |
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| WO (1) | WO2019061594A1 (en) |
Citations (1)
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-09-27 CN CN201710891404.8A patent/CN109553575B/en active Active
- 2017-10-20 WO PCT/CN2017/107027 patent/WO2019061594A1/en active Application Filing
Patent Citations (1)
| 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 | Publication date |
|---|---|
| CN109553575B (en) | 2022-06-03 |
| WO2019061594A1 (en) | 2019-04-04 |
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