CN107868042A - Polycondensation reaction liquid continuously neutralizes, continuously divides the method for water in age resistor TMQ production processes - Google Patents
Polycondensation reaction liquid continuously neutralizes, continuously divides the method for water in age resistor TMQ production processes Download PDFInfo
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- CN107868042A CN107868042A CN201610855684.2A CN201610855684A CN107868042A CN 107868042 A CN107868042 A CN 107868042A CN 201610855684 A CN201610855684 A CN 201610855684A CN 107868042 A CN107868042 A CN 107868042A
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- age resistor
- polycondensation reaction
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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
- C07D215/04—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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Abstract
The invention belongs to technical field of fine, is a kind of raising stability, improves the continuous treatment method that polycondensation reaction liquid in the age resistor TMQ production processes for neutralizing, dividing water efficiency and effect was neutralized, divided water.The mode that the present invention is combined using static mixer and water knockout drum realizes that TMQ is continuously neutralized, continuously divided water, serialization obtains TMQ crude products and TMQ waste water, substitute intermittent still reaction operation, realize that TMQ productions neutralize, divided the automation mechanized operation of water process, labor intensity can be greatly reduced, save human cost；Improve the stability of age resistor TMQ production processes.
Description
Technical field
The invention belongs to technical field of fine, is related to TMQ polycondensation reactions liquid in a kind of age resistor TMQ production processes and connects
The continuous processing method for neutralizing, continuously dividing water, is a kind of green preparation technology.
Background technology
Age resistor TMQ is two, three, four condensates of 2,2,4- trimethyl -1,2- dihyaroquinolines, also known as anti-aging agent RD,
It is a kind of ketone amines antioxidants, moors coloured particles or thin slice to ruins to be faint yellow, be mainly used as rubber antioxidant, be domestic and international market
On one of the rubber antioxidant product that has the call.
Age resistor TMQ synthesis is by aniline and acetone（Or derivatives thereof）, it is anti-by being condensed under acid catalyst effect
2,2,4- trimethyl -1,2- dihyaroquinoline monomers should be generated, then the monomer of gained polymerisation under acid catalyst effect
Into dimer or three, four condensates and polymer etc., alkali is neutralized, divides water, and oil phase is distilled to obtain age resistor TMQ.
Age resistor TMQ synthesis can be divided into " one-step method " and " two-step method "." two-step method " is to be condensed that 2,2,4- is made first
Trimethyl -1,2- dihyaroquinoline monomer, after removing reaction water, unreacted reactant and other low-boiling-point substances, then enter in acid condition
The polymerization of row monomer, neutralize, oil phase distills to obtain TMQ finished products；And " one-step method " is to make 2,2,4- trimethyl -1,2- dihydro quinolines
Complete to obtain TMQ polycondensation reaction liquid simultaneously in the preparation of quinoline monomer and the same reactor of polymerisation, then polycondensation reaction liquid
After being neutralized with liquid caustic soda, then unnecessary reactant and other low-boiling-point substances are separated, obtain TMQ finished products.Two-step process process is grown, consumption
Greatly, the substance content but in products obtained therefrom is high；And one-step method process is simple, consumption is small, but substance content is low.
In traditional age resistor TMQ industrial preparative method, either one-step method or two-step method, all using the kettle of interval
Formula method operates, i.e.,：By raw material and catalyst（And solvent etc.）Quantitatively throw into reactor, reaction obtains TMQ contractings after terminating
Poly- reaction solution, then TMQ polycondensation reaction liquid is transferred to neutralize in kettle and added in quantitative liquid caustic soda and acid catalyst, reach the pH of requirement
After value, water is divided after stratification, the aqueous phase separated is TMQ waste water, is carried out after stripping the organic matters such as aniline recovery, biochemical treatment；
Oil phase is TMQ crude products（Main component is the monomer and two, three, four condensates, benzene of 2,2,4- trimethyl -1,2- dihyaroquinolines
Amine, acetone etc.）, go distillation system removing acetone, water, aniline and front-end volatiles to obtain age resistor TMQ.
Difference the time required to being neutralized due to the time of polycondensation reaction and polycondensation reaction liquid, generally（Polycondensation reaction time is
3 ~ 5 times the time required to neutralizing）One neutralization kettle need to handle the material of 2-4 reactor（TMQ polycondensation reaction liquid）, by multiple
Reactor and the handover operation for neutralizing kettle, are neutralized, water-separating time about 2-3 hours per kettle, although having reached semi-continuous operative employee
Skill, but there is also defect for this technique：
（1）Process is semicontinuous, even if technical process enters DCS system, is needed remain for manually between reactor, neutralization kettle
Ceaselessly handover operation, wherein step include for progress：Neutralize the charging of kettle polycondensation reaction liquid, the preparation of liquid caustic soda and dropwise addition, stirring
Neutralize, neutralize after standing and divide water（Including the discharging of TMQ crude products and the discharging of TMQ waste water）Deng having a strong impact on production efficiency.
（2）During the control of pH value be to use manual site's sampling analysis, brought to production management it is certain cumbersome,
Also increase human cost.
（3）Need to add liquid caustic soda repeatedly during the adjustment of pH value, pH value is measured by sampling repeatedly.
3 points of the above is cumbersome, constrains the continuity of process, adds the labour costs of production, has had a strong impact on production
The stability of product, occasionally there are the phenomenon of nigrescence for TMQ products.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind raising stability, change
TMQ polycondensation reaction liquid is neutralized, divided the serialization of water in the kind age resistor TMQ production processes for neutralizing, dividing water efficiency and effect
Processing method.
The purpose of the present invention can be achieved through the following technical solutions：TMQ polycondensation reactions in age resistor TMQ production processes
Liquid neutralizes the continuous treatment method with dividing water, it is characterised in that this method comprises the following steps：
（1）In age resistor TMQ production process, aniline and acetone (or derivatives thereof such as isopropylidene acetone) are in acid condition
Obtained TMQ polycondensation reaction liquid is condensed and is polymerize, the polycondensation reaction liquid of the TMQ is concentrated together, is placed in storage tank, is buffered
Storage；
（2）Above-mentioned TMQ polycondensation reactions liquid and liquid caustic soda are imported into one or more groups of static mixers from respective storage tank through pump conveying
In, mixed, obtain mixed solution（TMQ neutralizers）；
（3）The online pH meter interlocked with the flow of liquid caustic soda, on-line control control solution are provided with the outlet of static mixer group
PH value be 7-11, that is, obtain the qualified TMQ neutralizers of pH value；
（4）TMQ neutralizers continuously enter in one or more levels water knockout drum, are layered in water knockout drum, water knockout drum upper strata is continuous
Produce oil phase, as age resistor TMQ crude products；Water knockout drum lower floor continuously produces aqueous phase, as TMQ waste water.
Described step（2）In TMQ polycondensation reactions liquid and the addition of liquid caustic soda controlled by flowmeter and regulating valve
System.
Described step（2）In liquid caustic soda include sodium hydroxide, sodium carbonate, sodium acid carbonate, potassium hydroxide, potassium carbonate,
Saleratus, sodium phosphate, one or more of mixed solutions of dibastic sodium phosphate and its solution.
Described step（4）In mixed solution upper strata or lower floor by potential difference or other means from first order water knockout drum
Collect or flow into the water knockout drum of the second level,.
Described step（4）In one or more levels water knockout drum include heating and stabilizing control system etc..
The signal of described flowmeter, regulating valve and pH meter is automatically controlled by dcs.
The present invention is the processing method that TMQ polycondensation reaction liquid continuously neutralized, divided water in age resistor TMQ production processes, is utilized
The mode that static mixer and water knockout drum combine realizes that TMQ is continuously neutralized, continuously divided water, and serialization obtains TMQ crude products and TMQ
Waste water, intermittent still reaction operation is substituted, realize that TMQ productions neutralize, divided the automation of water process, it is strong that work can be reduced
Degree reduces production cost, keeps the stability of production and product quality.
Compared with prior art, invention fully achieves continuous operation and DCS to control, and realizes on-line continuous pH value
Measure, while gone with the pH value signal of measure to control the proportioning of TMQ polycondensation reactions liquid, liquid caustic soda, there is advantages below：
（1）The present invention is continuous process, compared with batch technology, solves the TMQ polycondensation reactions for perplexing plant produced always
Liquid neutralizes and divides the serialization problem of water, and labor intensity can be greatly reduced, saved human cost；
（2）The stability of age resistor TMQ production processes is improved, avoids product appearance caused by neutralizing not exclusively from blacking；
（3）Realize DCS to automatically control, charging employs burden control；
（4）Static mixer is employed, substantially improves mixed effect, is advantageous to the stability of pH value, greatly improved simultaneously
Production efficiency, investment reduction and construction land；
（5）The measure of on-line pH value is realized, and control charging proportioning is gone with this signal.
Brief description of the drawings
Fig. 1 is that the TMQ polycondensation reaction liquid of the embodiment of the present invention continuously neutralizes, continuously divides the general flow chart of water.
Wherein：1-liquid caustic soda storage tank, 2-TMQ polycondensation reaction liquid storage tank, 3-static mixer（Group）, 4-one fraction water
Device, 5-secondary water segregator, 6-for flowmeter and regulating valve, 7-flowmeter and regulating valve（Interlock pH meter）, 8-online pH meter.
Embodiment
The method of the present invention is described in further detail with reference to specific embodiments and the drawings:
The flow of following examples method is referring to accompanying drawing 1.
Embodiment 1
（1）By in age resistor TMQ production process, aniline and acetone are condensed and polymerize to obtain TMQ's in acid condition
Polycondensation reaction liquid, it is placed in TMQ polycondensation reaction liquid storage tank, buffering storage；
（2）Using dcs (DCS system) according to pH=7, flowmeter and regulating valve are controlled by TMQ polycondensation reaction liquid
With liquid caustic soda（Sodium hydroxide solution）One group of static mixer mixing is imported after tentatively being matched, obtains mixed solution；
（3）Out rear online pH meter shows pH=8 to mixed solution from static mixer, is continuously divided by one-level water knockout drum
Water, once oil phase continuous overflow is collected to obtain TMQ crude products on water knockout drum, and bottom aqueous phase is continuously collected and obtains TMQ waste water.Prevent after testing
Old agent TMQ crude product pH=7.5, reach pH Con trolling index of the TMQ productions to TMQ crude products, wherein water content 3.34%；TMQ wastewater pHs
=8, wherein age resistor TMQ contents 1.36%.
Ton TMQ devices, neutralize, Fen Shui posies, after being intermittently changed to the continuous processing of this device, operating personnel are from 7
People is reduced to 3 people, neutralizes, water-separating time, was reduced to from 2.5 hours 0.3 ~ 0.4 hour, TMQ product year nigrescence numbers are from 5 ~ 7 times
It is reduced to 0 time.
Embodiment 2
（1）By in the age resistor such as " two-step method " or " one-step method " TMQ production process, aniline and isopropylidene acetone are in acid condition
It is lower to be condensed and polymerize the polycondensation reaction liquid for obtaining TMQ, it is placed in storage tank, buffering storage；
（2）Using dcs (DCS system) according to pH=8, flowmeter and regulating valve are controlled by TMQ polycondensation reaction liquid
With liquid caustic soda（10% dibastic sodium phosphate and 25% sodium hydroxide mixed solution）Four groups of static mixer groups are imported after tentatively being matched to mix
Close, obtain mixed solution；
（3）Cause concentration of hydrochloric acid in polycondensation reaction liquid too high due to TMQ previous production process polycondensation steps, mixed solution
Out rear online pH meter shows that pH=6, DCS increase liquid caustic soda automatically by the proportioning adjusting parameter of setting from static mixer
Flow, out rear online pH meter shows pH=8 to mixed solution from static mixer, is continuously divided by one-level water knockout drum
Water, oil phase overflow to secondary water segregator continue a point water, and secondary water segregator upper strata continuously produces TMQ crude products, under I and II water knockout drum
The continuous extraction TMQ waste water of layer.Age resistor TMQ crude products pH=8 after testing, reach TMQ production pH Con trolling index, wherein water content
0.20%；TMQ wastewater pH=8, wherein age resistor TMQ contents 0.12%.Neutralize, water-separating time, it is small to be reduced to 0.3 from 2.5 hours
When.
Embodiment 3
（1）By in the age resistor such as " two-step method " or " one-step method " TMQ production process, aniline and acetone are carried out in acid condition
Condensation and polymerization obtain TMQ polycondensation reaction liquid, are placed in storage tank, buffering storage；
（2）Using dcs (DCS system) according to pH=8, flowmeter and regulating valve are controlled by TMQ polycondensation reaction liquid
With liquid caustic soda（Sodium bicarbonate solution）Four groups of static mixer groups mixing are imported after tentatively being matched, obtain mixed solution；
（3）Cause concentration of hydrochloric acid in polycondensation reaction liquid too low due to TMQ previous production process polycondensation steps, mixed solution
Out rear online pH meter shows that pH=12, DCS reduce liquid caustic soda automatically by the proportioning adjusting parameter of setting from static mixer
Flow, mixed solution from static mixer out after online pH meter show pH=9, continuously divided by one-level water knockout drum
Water, oil phase overflow to secondary water segregator continue a point water, and secondary water segregator upper strata continuously produces TMQ crude products, under I and II water knockout drum
The continuous extraction TMQ waste water of layer.Age resistor TMQ crude products pH=10 after testing, reach TMQ production pH Con trolling index, wherein water content
0.16%；TMQ wastewater pH=9, wherein age resistor TMQ contents 0.23%.
Embodiment 4
（1）By in the age resistor such as " two-step method " or " one-step method " TMQ production process, aniline and acetone are carried out in acid condition
Condensation and polymerization obtain TMQ polycondensation reaction liquid, are placed in storage tank, buffering storage；
（2）Using dcs (DCS system) according to pH=9, flowmeter and regulating valve are controlled by TMQ polycondensation reaction liquid
With liquid caustic soda（Potassium hydroxide solution）Four groups of static mixer groups mixing are imported after tentatively being matched, obtain mixed solution；
（3）Cause concentration of hydrochloric acid in polycondensation reaction liquid too low due to TMQ previous production process polycondensation steps, mixed solution
Out rear online pH meter shows that pH=12, DCS reduce liquid caustic soda automatically by the proportioning adjusting parameter of setting from static mixer
Flow, mixed solution from static mixer out after online pH meter show pH=9, continuously divided by one-level water knockout drum
Water, oil phase overflow to secondary water segregator continue a point water, and secondary water segregator upper oil phase overflow to three-level water knockout drum continues a point water, and three
Level water knockout drum upper strata continuously produces TMQ crude products, and one, two, three water knockout drum lower floor continuously produces TMQ waste water.Age resistor after testing
TMQ crude product pH=10, reach TMQ production pH Con trolling index, wherein water content 0.06%；TMQ wastewater pH=9, wherein age resistor
TMQ contents 0.11%.
Although the present invention is illustrated with embodiment referring to the drawings, it will be clear that for those skilled in the art
For, on the premise of without departing substantially from the spirit and scope of the present invention, various modifications and variations can be made to the present invention.Therefore,
Various changes, the change of the present invention is covered by the content of appended claims and its equivalent.
Claims (6)
1. polycondensation reaction liquid continuously neutralizes, continuously divides the method for water in a kind of age resistor TMQ production processes, it is characterised in that should
Method comprises the following steps：（1）In age resistor TMQ production process, acetone or derivatives thereof and aniline enter in acid condition
Row condensation and polymerization obtain TMQ polycondensation reaction liquid, and the polycondensation reaction liquid of the TMQ is concentrated together, is placed in storage tank, buffering is deposited
Put；（2）Above-mentioned TMQ polycondensation reactions liquid and liquid caustic soda are imported into one or more groups of static mixers from respective storage tank through pump conveying
In, mixed, obtain TMQ neutralizers；（3）The online pH interlocked with the flow of liquid caustic soda is set in the outlet of static mixer group
Meter, it is 7-11 that on-line control, which controls the pH value of solution, that is, obtains the qualified TMQ neutralizers of pH value；（4）TMQ neutralizers are continuous
Into in one or more levels water knockout drum, it is layered in water knockout drum, water knockout drum upper strata continuously produces oil phase, as age resistor TMQ
Crude product；Water knockout drum lower floor continuously produces aqueous phase, as TMQ waste water.
2. according to the method for claim 1, it is characterized in that described step（2）In TMQ polycondensation reactions liquid and liquid caustic soda
Addition is controlled by flowmeter and regulating valve.
3. according to the method for claim 1, it is characterized in that described step（2）In liquid caustic soda include sodium hydroxide, carbonic acid
Sodium, sodium acid carbonate, potassium hydroxide, potassium carbonate, saleratus, sodium phosphate, the one or more of dibastic sodium phosphate.
4. according to the method for claim 1, it is characterized in that described step（4）In the upper strata of mixed solution pass through potential difference
Collect or flow into the water knockout drum of the second level from first order water knockout drum.
5. according to the method for claim 1, it is characterized in that the step described in described step（4）In one or more levels point
Hydrophone includes heating and stabilizing control system.
6. according to the either method described in one of claim 1-6, it is characterized in that the letter of described flowmeter, regulating valve and pH meter
Number automatically controlled by dcs.
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| CN201610855684.2A CN107868042A (en) | 2016-09-28 | 2016-09-28 | Polycondensation reaction liquid continuously neutralizes, continuously divides the method for water in age resistor TMQ production processes |
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| CN201610855684.2A CN107868042A (en) | 2016-09-28 | 2016-09-28 | Polycondensation reaction liquid continuously neutralizes, continuously divides the method for water in age resistor TMQ production processes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610230A (en) * | 2018-03-09 | 2018-10-02 | 惠州大亚湾伊科思新材料科技发展有限公司 | A kind of method and apparatus controlling styrene pH value after styrene extraction device decolourizes |
| CN112661331A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Method for recycling materials in anti-aging agent TMQ production wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875669A (en) * | 2009-04-28 | 2010-11-03 | 苏州佳辉化工有限公司 | Continuous treatment method for neutralizing solvent in process of producing glyphosate by using glycine method |
| CN103539962A (en) * | 2013-10-21 | 2014-01-29 | 科迈化工股份有限公司 | Method for preparing low-amine rubber anti-aging agent TMQ |
| CN103694169A (en) * | 2012-09-28 | 2014-04-02 | 中国石油化工股份有限公司 | Method for synthesis of 2,2,4-trimethyl-1,2-dihydroquinoline and polymer thereof by utilizing microchannel reactors |
| CN104592108A (en) * | 2013-10-31 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | One-step synthetic process of rubber antioxidant RD |
-
2016
- 2016-09-28 CN CN201610855684.2A patent/CN107868042A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875669A (en) * | 2009-04-28 | 2010-11-03 | 苏州佳辉化工有限公司 | Continuous treatment method for neutralizing solvent in process of producing glyphosate by using glycine method |
| CN103694169A (en) * | 2012-09-28 | 2014-04-02 | 中国石油化工股份有限公司 | Method for synthesis of 2,2,4-trimethyl-1,2-dihydroquinoline and polymer thereof by utilizing microchannel reactors |
| CN103539962A (en) * | 2013-10-21 | 2014-01-29 | 科迈化工股份有限公司 | Method for preparing low-amine rubber anti-aging agent TMQ |
| CN104592108A (en) * | 2013-10-31 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | One-step synthetic process of rubber antioxidant RD |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610230A (en) * | 2018-03-09 | 2018-10-02 | 惠州大亚湾伊科思新材料科技发展有限公司 | A kind of method and apparatus controlling styrene pH value after styrene extraction device decolourizes |
| CN112661331A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Method for recycling materials in anti-aging agent TMQ production wastewater |
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