CN104987303B - A kind of complexometric extraction technique extracts 5-sodium sulfo isophthalate method from three monomer waste water - Google Patents
A kind of complexometric extraction technique extracts 5-sodium sulfo isophthalate method from three monomer waste water Download PDFInfo
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Abstract
The invention discloses a kind of three monomers and produce M-phthalic acid 5 sodium sulfonate method of extracting in waste water, comprise the following steps successively: prepare extractant, adjust pH value, extraction, back extraction, anti-stripping agent concentration, acidifying, condensing crystallizing, drying steps.Selecting trioctylamine, di-tertiary amine 2,4 two (N, N dihexyl) aminododecane base benzene double-component in described extractant is complexing agent, and selecting 2 heptyl undecyl alcohols is cosolvent, and selecting sulfonated kerosene, n-octyl alcohol double-component is diluent.The invention provides a kind of employing complexometric extraction technique, the method extracting M-phthalic acid 5 sodium sulfonate waste liquid at the bottom of tower after three MONOMER RECOVERY methyl alcohol, have chosen optimal extraction system and rational extraction conditions, the extraction yield making M-phthalic acid 5 sodium sulfonate reaches more than 99%, substantially increase the economic benefit of three monomer products, it is achieved that comprehensive utilization of resources.
Description
The present invention is application number 201410356437.9, the applying date: on July 25th, 2014, denomination of invention: " a kind of three is single
Body produces 5-sodium sulfo isophthalate method of extracting in waste water " divisional application.
Technical field
The invention belongs to containing organic wastewater utilization field, exactly belong to three monomers and produce wastewater utilization neck
Territory.
Background technology
Three monomers (chemical name Sodium Dimethyl Isophthalate-5-sulfonate, SIPM write a Chinese character in simplified form in English) are poly-as producing modification
A kind of important modifying agent of ester product (CDP/ECDP etc.), after introducing SIPM in polyester slice, the cation-modified of production is washed
Synthetic fibre long filament, although its outward appearance does not has the biggest difference with ordinary polyester long filament, but cation-modified owing to have employed, the most greatly
Improve greatly the suction look performance of fiber, and reduce degree of crystallinity, thus adapt to the Silk of polyester fiber further, improve
The class of product.The production technology of the most domestic and international three monomers mainly has: (1) S03Sulfonation method, is initial with M-phthalic acid
Raw material, with gaseous state or hot S03After preparing M-phthalic acid-5-sulfonic acid for sulfonating agent, through over-churning, neutralize, post-process, be dried
Prepare etc. operation；(2) concentrated acid sulfonation method, when the concentrated sulfuric acid is as sulfonating agent, often generates 1 mole of sulfonated products, will generate 1 and rub
Your water, this will make sulfuric acid concentration be gradually reduced, and reaction speed slows down.After concentration drops to a certain degree, sulfonating reaction is the most not
Can carry out, thus often use the concentrated sulfuric acid of excess.The sulfuric acid of these excess neutralizes with alkali after completing sulfonating reaction, and this will
Consume substantial amounts of alkali, make again product contain substantial amounts of sulfate impurities simultaneously.It is huge, in eliminating that this technique produces wastewater flow rate
Gesture；(3) oleum method of sulfonation, with M-phthalic acid as initiation material, oleum (SO3Content is from 20% to 80%) be
Sulfonating agent, then obtains product by operations such as being esterified, neutralize, refine.
The most domestic three monomer industries use oleum method of sulfonation to produce mostly, the waste liquid amount that technical process produces
Generally 4 tons of waste liquid/ton three monomers, in waste liquid containing sodium sulphate, Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid-
5-sodium sulfonate, M-phthalic acid mono-methyl-5-sodium sulfonate, containing phenyl ring sulfone compound, containing phenyl ring carbonizing matter, containing phenyl ring be polymerized
The multiple inorganic and organic compounds such as thing, methyl alcohol, dimethyl suflfate, wherein minority material is poisonous and harmful substance, belongs to extremely difficult
Biodegradable waste water, if without processing directly discharge, by serious environment pollution, the health of the harm mankind.Although domestic certain
A little enterprises use distillation technology to be extracted methyl alcohol from three monomer waste water, but Sodium Dimethyl Isophthalate-5-sulfonate in waste liquid,
5-sodium sulfo isophthalate, M-phthalic acid mono-methyl-5-sodium sulfonate etc. have essential industry to be worth and the material of using value
The most not reclaiming, waste liquid at the bottom of the tower after recovery methyl alcohol has highly-water-soluble due to organic matter contained therein, it is difficult to uses and passes
The flucculation process of system is removed, simultaneously its high Salinity Characteristics cause such waste water to have to pass through after the dilution of a large amount of clear water just have can
Can carry out biochemical treatment, this makes this waste water become one of the most intractable current wastewater from chemical industry.Water rush dilute after carry out at biochemistry
Reason, wastes a large amount of precious resources, directly increases three monomer production costs.The most both at home and abroad such waste water is processed main employing
Adsorb, decolour, physics and the biochemical combination treatment technology such as oxidation, processing cost is the highest.
The extraction treatment technology of organic wastewater has wide application prospects.The present invention uses solvent extraction to process organic sulfonic acid
Class waste water, uses the dissolving of serotonin kind of extractants and carries secretly the least in extraction process, extraction process generation complex reaction, extraction
Agent distribution coefficient is high, and the organic matter of band sulfonic acid group occurs strong anionic associative to make with amine extractant in acid condition
With.Using alkali to carry out back extraction, extractant recycles, and obtains valuable 5-sodium sulfo isophthalate.Isophthalic diformazan
Acid-5-sodium sulfonate is commonly used to preparation and is applicable to various environment protecting water-based paint waterborne polyurethane resin it can also be used to ink, magnetic
Band, and polyester and nylon fiber, make PET bottle charge of oil ink have more preferable printability, outstanding tape interlayer adhesion, improve polyester
With colourability and the light resistance of nylon fiber, three monomers can be substituted and participate in the esterification of polyester, product can be improved
Quick-drying.It is also used as catalyst for fields such as medicine, agricultural chemicals, polyester.In view of domestic three monomer industry waste water process
Severe situation and the domestic pay attention to day by day to efforts at environmental protection and the increase of management intensity, for three monomer waste water compositions and material
Physicochemical characteristic, it is proposed that reclaim the new technology of waste liquid comprehensive utilization at the bottom of the tower after methyl alcohol.Above-mentioned waste liquid after treatment, can obtain
To products such as 5-sodium sulfo isophthalate, industry sal glauberis.So, both fully utilized three monomer waste water, reclaimed
Value product, improves the economic benefit of three monomers the most indirectly, it is achieved that the zero-emission of production process waste water, its society's effect
Benefit and economic benefit are especially prominent.
Summary of the invention
The present invention is to overcome prior art not enough, it is provided that a kind of employing complexometric extraction technique, after three MONOMER RECOVERY methyl alcohol
Tower at the bottom of waste liquid extracts the method for 5-sodium sulfo isophthalate, selected optimal extraction system and reasonably extraction conditions,
Reclaim 5-sodium sulfo isophthalate to greatest extent, improve the economic benefit of three monomer products, it is achieved comprehensive utilization of resources.
For achieving the above object, the present invention is by the following technical solutions:
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, including preparing extractant step, institute
State the extractant prepared in extractant step to be made up of complexing agent, cosolvent and diluent.
The following is and the further of technique scheme is improved:
Described complexing agent is trioctylamine and di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene.
Described cosolvent is 2-heptyl undecyl alcohol.
Described diluent is sulfonated kerosene and n-octyl alcohol.
In described extractant, the weight ratio of each material is: trioctylamine: di-tertiary amine 2,4-bis-(N, N-dihexyl) amino ten
Dialkyl benzene: 2-heptyl undecyl alcohol: sulfonated kerosene: n-octyl alcohol=100:30-70:10-30:60-90:40-90.
The extraction yield of 5-sodium sulfo isophthalate is more than 99%.
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, also include adjusting pH value step, described
Adjusting in pH value step, in pH value regulation still, adding concentration in three monomer waste water after dealcoholysis is 93% or 98% sulfuric acid, by water
Phase pH value is adjusted to 2-3.5.
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, also include extraction step, described extraction
Taking in step, extraction temperature is 30-50 DEG C.
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, also include strip stage, described
In strip stage, strippant is the NaOH solution of 12-16%, and back extraction temperature is 30-40 DEG C.
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, also include that anti-stripping agent concentrates step
Suddenly, described anti-stripping agent concentration step, control vacuum is 0.08-0.09MPa, temperature 60-70 DEG C；When observing gas phase temperature
On a declining curve and when having solids to occur less than 60 DEG C, in anti-stripping agent concentration kettle, stop jacket steam heating.Continue on
Vavuum pump, is passed through cooling water to chuck, when temperature of charge reaches 33-35 DEG C in still, opens bottom baiting valve, is added by material in still
Enter centrifuge to be centrifuged.
Beneficial effect:
1, selecting double-component macromolecule, Long carbon chain tertiary amine as complexing agent, the tertiary amine of two kinds of different structures is collaborative to be extracted
Taking, loading capacity is big, and the extraction yield of 5-sodium sulfo isophthalate is brought up to use double-component by the 95% of one-component tertiary amine
After tertiary amine more than 99%.
2, selecting 2-heptyl undecyl alcohol to add in extraction system as during cosolvent, it can combine with amine molecule, breaks
The self-polymerization of amine, reduces its effective molecular weight, increases alkyl tertiary amine solubility in diluent, promotes complexing agent and is extracted
Take the reaction of thing, improve the relative stability of complex compound and in the solubility of organic phase, extraction process can accelerate divide mutually
From, reduce emulsification, improve extraction efficiency.
3, selecting double-component diluent, one is alcohols, and one is sulfonated kerosene, the diluent of two kinds of different physicochemical properties
Can work in coordination with and promote the formation of tertiary amine and M-phthalic acid-5-sulfonic acid complex compound and be easily achieved phase transfer, increase complex compound and exist
Solubility in organic phase, reduces the extraction water yield of extractant, not only can change extracting operation performance, also can produce the strongest dilution
Agent effect, improves the extraction ability of extractant, makes extracting power be improved.
4, extraction and back extraction all use low-temperature operation, and the operation cycle is short, and energy consumption is low, and organic phase is difficult to emulsification, decreases
Third phase generates.Especially in back extraction operation, it is complete that the strong basicity of NaOH can ensure that back extraction process is carried out, and selects to close
The NaOH solution of suitable concentration, it is to avoid the solubility of sodium salt is relatively small and makes the concentration of NaOH solution restricted, it is to avoid
When during low concentration, strip liquor volume is unfavorable for more greatly subsequent treatment and high concentration, strip liquor can cause crystallization, and back extraction effect is not
Good, separate the adverse consequences such as difficulty.
5, finished product 5-sodium sulfo isophthalate is used dehydration under double-cone type drier, condition of negative pressure, it is therefore prevented that use
Easily caking that vibratory sieve drier brings, particle diameter gap is big, dry uneven etc. deficiency, and finished particle is uniform, the operating time
There is not oxidation etc., constant product quality in short, material, between different batches, quality index gap is little.
Detailed description of the invention
Embodiment 1
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, the selection analysis of extractant:
Complexometric extraction is theoretical:
Extraction as important separation means, have that disposal ability is big, separative efficiency is high, the rate of recovery is high, applied range,
Strong adaptability, good economy performance, it is easy to accomplish operate continuously and automatically control.For the separation method such as rectifying, crystallization should not be used
Occasion, extraction process has certain technical advantage: the fusing point of (1) each component or boiling point closely or form azeotropic mixture, use
Rectification method cannot or hardly separate；(2) a small amount of high boiling component of involatile matter, the inorganic matter of complexing, the returning of metallics
Receive；(3) heat-sensitive component, causes decomposition with rectification method swimming suit, is polymerized or occurs other chemical reaction, and has following excellent
Point: higher than chemical precipitation method separation degree；Than ion-exchange selectively the best, mass transfer is fast；Lower than way of distillation energy consumption；
Extraction is to utilize the difference of solute distribution coefficient between immiscible two-phase to make solute be purified or dense
The technology of contracting.Extraction separating method based on reversible complex reaction is called for short complexing abstraction, divides for polarity organic water solution
From having high efficiency and high selectivity.Complexing abstraction is to be contacted with the organic solvent containing complexing agent by material to be separated,
Both reacting forming complex, make material to be separated be transferred to organic phase, thus the method realizing separating.It is transferred to organic treat each other
Separate substance recycling temperature, diluent, pH value, the hunt effect of salinity carry out back extraction, it is achieved it divides with extraction organic phase
From.Complexing abstraction Key of Implementation is to select complexing agent, cosolvent and diluent for different systems.
Extractant and extraction system:
Extraction system organic phase includes the components such as complexing agent, cosolvent and diluent.
Selection to complexing agent:
(1) for extracting three monomers and producing waste water, complexing agent typically should contain and band sulfonic group chemical combination to be separated
The lewis alkali functional group that thing is corresponding, participates in both binding reactions with it.The bond energy of bonding is generally at 10-60KJ/mol, key
The too low degree that can affect reaction of energy and the efficiency of phase transfer, bond energy is too high, can affect next step backward reaction and complexing agent
Regeneration.A complexing agent molecule at least extraction functional group, forms complex compound by it with extract.Must there is long carbochain
Or aromatic hydrocarbons, make extractant and extracted species be soluble in organic solvent.But carbochain is long, molecular weight is big, and viscosity increase is probably solid,
Using inconvenience, loading capacity reduces.So extractant molecules amount is advisable between 350-500.
(2) complexing agent molecule must be containing bigger lipophilic group, the damage caused to reduce complexing agent to dissolve in aqueous phase
Lose, increase extracted species dissolving in organic phase, it is achieved the transfer that material to be separated is alternate simultaneously.Without secondary in complexation extraction
Reaction occurs, and complexing agent Heat stability is good is not easily decomposed, little to equipment corrosion；Complex compound can be formed, it is achieved phase transfer,
Complex compound regenerating easily when back extraction can be made again；There is certain density contrast with the liquid phase being extracted, and viscosity is low, interfacial tension
Moderate, the beneficially dispersion of phase and two-phase laminated flow.
(3) not reacting with water, the extraction water yield is little, molten moderate boiling point, is difficult to emulsification；Security is good, to human non-toxic's property or poison
Property is low；Good economy performance, environmental friendliness.
(4) reaction speed is fast, all should have sufficiently fast on extraction the Direction of Reaction positive and negative with back extraction at different conditions
Kinetic mechanism, in order in actual production process, the time of staying is shorter and equipment volume is suitable.
(5) extracting power is strong, and capacity is big, the highest, stable performance, and solution loss is little, easy back extraction, and recycling design is convenient
Deng.
The selection of cosolvent:
For promoting the reaction of complexing agent and extract, improve the relative stability of complex compound and in the dissolving of organic phase
Degree, adds cosolvent meaning obvious.Produce in waste water containing for three monomer homologues for extracting three monomers, the hydrotropy of selection
Agent is with big side chain, the low-density alcohol of macromolecule, has that chain length is suitable, freezing point is low, is difficult to emulsification, layering is fast, do not have
Lower aliphatic alcohols pungent taste, in water, solubility is little, and oil-soluble is good, is a kind of colourless nontoxic thick liquid, in extraction process
Can accelerate to be separated, reduce emulsification, improve extraction efficiency.
The selection of diluent:
In complexation extraction, the effect of diluent is highly important.Diluent should be the formation promoting complex compound
Be easily achieved phase transfer, should be not only the good solvent of complexing agent, it can regulate the viscosity of mixed extractant, density
With surface tension etc., increase complex compound solubility in organic phase, reduce the extraction water yield of extractant, thus play extracting
The facilitation of journey.Not only can change extracting operation performance, also can produce the strongest diluent effect, improve the extraction of extractant
Performance, makes extracting power be improved, and makes the process being originally difficult to separate be achieved.Diluent should meet following requirement:
(1) good thermal stability, is not easily decomposed, in order to avoid causing the improper of operating condition during extraction and back extraction
Fluctuation；
(2) to extractant favorable solubility, in order to aqueous phase separates with organic phase；
(3) to complex compound favorable solubility, in order to increase the stability of complex compound and improve SSIPA in two-phase
Distribution coefficient；
(4) solubility in water is the least or insoluble, simultaneously should be nontoxic, non-volatile；
According to theory analysis and through test of many times, the proportioning of the selection of extractant of the present invention and each material of extractant is such as
Under:
Complexing agent: select trioctylamine, di-tertiary amine di-tertiary amine 2, the double group of 4-bis-(N, N-dihexyl) aminododecane base benzene
Part is complexing agent.
Cosolvent: selecting 2-heptyl undecyl alcohol is cosolvent.
Diluent: selecting sulfonated kerosene, n-octyl alcohol double-component is diluent.
Material ratio (weight ratio) trioctylamine during configuration extractant: di-tertiary amine 2,4-bis-(N, N-dihexyl) amino 12
Alkylbenzene: 2-heptyl undecyl alcohol: sulfonated kerosene: n-octyl alcohol=100:30-70:10-30:60-90:40-90.
Compared with phosphorus-contained extractant, amine extractant is the best, stability is strong, range is wide, but amine extractant
Itself can not dissolve the complex compound that it is formed with material to be separated, need to add Polar diluents during use and strengthen dissolving.
In actual extract and separate operation, organic phase and aqueous phase sometimes can produce emulsification or generate third phase, emulsification
Or generation third phase all can affect being normally carried out of operation, so add extraction when using 2-heptyl undecyl alcohol as cosolvent
In system, it can combine with amine molecule, breaks the self-polymerization of amine, reduces its effective molecular weight, increases alkyl tertiary amine dilute
Release the solubility in agent, to eliminate third phase, reduce emulsion, improve extraction efficiency.
Test result analysis:
(1) selecting double-component macromolecule, Long carbon chain tertiary amine as complexing agent, the tertiary amine of two kinds of different structures is collaborative to be extracted
Taking, loading capacity is big；
Testing respectively according to embodiment 2-5, the single component of trioctylamine is tested as complexing agent, di-tertiary amine 2,
4-bis-(N, N-dihexyl) aminododecane base benzene, as single component complexing agent, is drawn one-component tertiary amine by result of the test
It is 95% as the extraction yield of phthalic acid-5-sodium sulfonate during complexing agent；
And select double-component tertiary amine all to reach to more than 99% as the extraction yield of phthalic acid-5-sodium sulfonate during complexing agent.
(2) not proposing to use cosolvent in the most domestic and international same industry, the present invention selects 2-heptyl undecyl alcohol conduct
Cosolvent adds in extraction system, and it can combine with amine molecule, breaks the self-polymerization of amine, reduces its effective molecular weight, increases
Add alkyl tertiary amine solubility in diluent, promote the reaction of complexing agent and extract, improve the most stable of complex compound
Property and in the solubility of organic phase, extraction process can accelerate be separated, reduce emulsification, improve extraction efficiency.
(3) selecting double-component diluent, one is alcohols, and one is sulfonated kerosene, the dilution of two kinds of different physicochemical properties
Agent can be worked in coordination with and promoted the formation of tertiary amine and M-phthalic acid-5-sulfonic acid complex compound and be easily achieved phase transfer, increases complex compound
Solubility in organic phase, reduces the extraction water yield of extractant, not only can change extracting operation performance, also can produce the strongest dilute
Release agent effect, improve the extraction ability of extractant, make extracting power be improved；
Although organic sulfonic acid class extract in also use chloroform, carbon tetrachloride compounds as diluent, but due to
Sulfonated kerosene, the difference of n-octyl alcohol polarity, work in coordination with and promote the formation of tertiary amine and M-phthalic acid-5-sulfonic acid complex compound and be prone to real
Existing phase transfer sulfonated kerosene to be significantly lower than, the diluent of n-octyl alcohol double-component composition.Test according to embodiment 2-5, examination
Test and show: being used alone or as a mixture chloroform, carbon tetrachloride as diluent, the extraction yield of 5-sodium sulfo isophthalate is only up to
To about 95%；And selecting sulfonated kerosene, n-octyl alcohol double-component is diluent, the extraction yield of 5-sodium sulfo isophthalate reaches
More than 99%.
Embodiment 2:
A kind of three monomers produce 5-sodium sulfo isophthalate method of extracting in waste water, comprise the following steps successively: prepare
Extractant, adjust pH value, extraction, back extraction, anti-stripping agent concentrations, acidifying, condensing crystallizing, dry.
1, extractant is prepared:
In extractant, the quality proportioning of each material is carried out by following three kinds of schemes:
Scheme one:
Weigh trioctylamine 700Kg, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 210Kg, 2-respectively
Heptyl undecyl alcohol 70Kg, sulfonated kerosene 420Kg, n-octyl alcohol 280Kg, add in extraction kettle, stir 40-60 minute, stand-by.
Scheme two:
Weigh trioctylamine 700Kg, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 300Kg, 2-respectively
Heptyl undecyl alcohol 100Kg, sulfonated kerosene 585Kg, n-octyl alcohol 325Kg, add in extraction kettle, stir 40-60 minute, stand-by.
Scheme three:
Weigh trioctylamine 700Kg, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 490Kg, 2-respectively
Heptyl undecyl alcohol 210Kg, sulfonated kerosene 630Kg, n-octyl alcohol 630Kg, add in extraction kettle, stir 40-60 minute, stand-by.
2, pH value is adjusted
In pH value regulation still, adding concentration in three monomer waste water after dealcoholysis is 93% or 98% sulfuric acid, by aqueous phase pH
Value is adjusted to 2-3.5.
The pH value impact on extracting operation: pH value affects distribution coefficient, affects material and dissociates situation.At certain pH value model
In enclosing, along with the increase of inorganic ion concentration, distribution coefficient reduces rapidly with the increase of salinity；After extraction, ph value of aqueous phase is with salt
The increase of concentration all has rising in various degree；Under same ionic strength, extractant concentration is the highest, and after extraction, ph value of aqueous phase rises
Amplitude is the biggest, and through test, it is best that pH value controls the effect of extracting when 2-3.5.
3, extraction
The waste water that 2000-2100Kg regulates pH value adds extraction kettle, opens stirring, opens jacket steam valve, at 15-
It is further continued for stirring 10-20 minute after temperature of charge in still being heated to 30-50 DEG C in 30 minutes, stands 10-15 minute, carefully will
Aqueous phase is released.Organic phase is stand-by in being placed on extraction kettle.
The temperature impact on extracting operation: temperature raises, intersolubility increases；Temperature reduces, and product stability improves, viscosity
Increasing, diffusion reduces；It is said that in general, the generation of extracted species is an exothermic reaction in complexometric extraction, Extraction equilibrium constants
Declining with the rising of temperature, in time testing slective extraction temperature and be 30-50 DEG C, effect of extracting is best.
The salinity (sodium sulphate is main component) in the aqueous phase impact on extracting operation: the existence of sodium sulphate can change non-
Electrolyte activity coefficient in aqueous, consequently, it is possible to cause system split-phase, affects the liquid-liquid equilibrium of system the most further.
The ion hydration of sodium sulphate, has attracted a part of free water molecule, makes the amount of free water molecule in the aqueous solution reduce, i.e. subtracts
Lack free water molecule concentration, it is suppressed that the hydration of 5-sodium sulfo isophthalate, made SSIPA be easier to entrance organic
Phase；Sodium sulphate can reduce aqueous phase dielectric constant, charging point active force can be made to increase, beneficially the carrying out of extraction process.
4, back extraction
NaOH solution 280-340Kg that concentration is 12-16% is added extraction kettle (extract and operate all same with back extraction
Platform equipment is carried out), open stirring, open jacket steam valve, in 10-15 minute, temperature of charge in still is heated to 30-40
It is further continued for stirring 10-15 minute after DEG C, stands 10-15 minute.Carefully aqueous phase being put into strip liquor basin, organic phase is placed on extraction
Next group extraction is continued on in still.
The selection of strippant: can not introduce the needs of other impurity in view of system, selection NaOH solution is back extraction
Agent, uses the advantage of NaOH to be that its strong basicity can ensure that back extraction process is carried out complete.
The selection of NaOH concentration: owing to the solubility of sodium salt is relatively small, limit the concentration of NaOH solution；Low dense
When spending, strip liquor volume is relatively big, is unfavorable for subsequent treatment；During high concentration, strip liquor has crystallization, back extraction poor effect, separates tired
Difficult.
The selection of back extraction temperature: stripping process is actually an acid-base neutralization reaction, i.e. stripping process is a heat release
Process, therefore favors low temperature is in the carrying out of stripping process.But under low temperature, the concentration of extractant and liquid caustic soda is relatively big, increases extractant
With the resistance to mass tranfer of liquid caustic soda, and the salt generated can separate out, and causes back extraction effect to decline and separates difficulty.Therefore, select properly
The concentration of NaOH solution particularly important with temperature.
Through test of many times, selecting the back extraction temperature of 30-40 DEG C, effect is best.
5, anti-stripping agent concentrates
Anti-stripping agent pump is squeezed into anti-stripping agent concentration kettle from strip liquor basin, opens stirring, open jacket steam valve,
Begin to warm up material in still.When material rises to 90-98 DEG C in still, opening vacuum jet pump, in control still, vacuum is 0.08-
0.09MPa, controls temperature in the kettle and is 60-70 DEG C.When observe gas phase temperature on a declining curve and less than 60 DEG C, anti-stripping agent dense
When contracting still has solids to occur, stop jacket steam heating.Continue on vavuum pump, be passed through cooling water to chuck, in treating still
When temperature of charge reaches 33-35 DEG C, open bottom baiting valve, material in still is added centrifuge and is centrifuged.Centrifuge mother liquor is sent into
Continuing reuse after pH regulation tank regulation pH value, solid material is acidified for next step.
6, acidifying
Add 1000-1100Kg deionized water to acidifying still, open stirring, open jacket steam valve, begin to warm up in still
Material, by still temperature rise to 35-40 DEG C in 20-30 minute, then addition 800-850Kg centrifugal solids material in still, 30-40 minute
Inside add.Stirring 20-30 minute is continued after adding solid material.Then in 15-30 minute, add the sulfuric acid 250-that concentration is 93%
295Kg, sulfuric acid finishes, and by still temperature rise to 85-90 DEG C in 20-30 minute, continues stirring 25-30 minute.By material pump in still
Condensing crystallizing still is squeezed into after accurate filter.
7, condensing crystallizing
Opening stirring, be passed through cooling water to crystallization kettle chuck, cooling water valve aperture is less than half.Open airless injection
Pump, in control still, vacuum is 0.08-0.09MPa, starts to crystallize under vacuum condition.When temperature in the kettle reaches below 35 DEG C,
Cooling water valve is fully open, strengthen cooling water flow.When temperature in the kettle reaches below 30 DEG C, open bottom baiting valve,
Material in still is added centrifuge be centrifuged.Solid material is dry for next step with softening after water rinses three times, all centrifugal
Mother liquor is sent into anti-stripping agent concentration kettle and is continuing with.
8, it is dried
Centrifugal solids material after rinsing is sent into double-cone type drying machine, fastens lid, start motor and make double-cone type drying machine
Rotary drum starts to rotate.Opening vacuum jet pump, in control drier, vacuum is 0.07-0.092MPa；Open steam valve, open
Begin to heat.Control temperature and be 120-130 DEG C, be dried 2.5-3 hour.Steam off valve, continuing to be evacuated to temperature is 50-60
DEG C, close vacuum jet pump, open lid.Packaging after sample analysis is qualified.
Through the extraction yield of test of many times 5-sodium sulfo isophthalate all more than 99%.
Embodiment 3
1, extractant is prepared
Weighing trioctylamine 700Kg respectively, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 300Kg, just
Octanol 325Kg, 2-heptyl undecyl alcohol 100Kg, sulfonated kerosene 585Kg, add in extraction kettle, stir 40-60 minute, stand-by.
2, pH value is adjusted
At 12.5m3 In pH regulation still, three monomer waste water after metering adds dealcoholysis add 10.5m3, adding concentration is 93%
Sulfuric acid 200Kg, aqueous pH values is adjusted to 2.3.
3, extraction
The waste water that 2000Kg regulates pH value adds extraction kettle, opens stirring, opens jacket steam valve, in 20 minutes
It is further continued for after temperature of charge in still is heated to 35 DEG C stirring 15 minutes, stands 10 minutes, carefully aqueous phase is released.Organic phase is put
In extraction kettle stand-by.
4, back extraction
NaOH solution 310Kg that concentration is 14% is added extraction kettle, and (extraction operates all in same equipment with back extraction
Carry out), open stirring, open jacket steam valve, in 15 minutes by still in temperature of charge be heated to 40 DEG C after be further continued for stirring
10 minutes, stand 10 minutes.Aqueous phase is carefully put into strip liquor basin, and organic phase continues on for next group extraction in being placed on extraction kettle
Take.
5, anti-stripping agent concentrates
Anti-stripping agent pump is squeezed into anti-stripping agent concentration kettle from strip liquor basin, opens stirring, open jacket steam valve,
Begin to warm up material in still.When material rises to 95-98 DEG C in still, opening vacuum jet pump, in controlling still, vacuum is
0.085-0.09MPa, controls temperature in the kettle and is 65-70 DEG C.When observing that gas phase temperature is on a declining curve and is less than 60 DEG C, back extraction
Take time liquid concentration kettle has solids to occur, stop jacket steam heating.Continue on vavuum pump, be passed through cooling water to chuck,
When temperature of charge reaches 33-35 DEG C in still, open bottom baiting valve, material in still is added centrifuge and is centrifuged.Centrifugal mother
Liquid continues reuse after sending into pH regulation tank regulation pH value, and solid material is acidified for next step.
6, acidifying
Add 1050Kg deionized water to acidifying still, open stirring, open jacket steam valve, begin to warm up material in still,
By still temperature rise to 35 DEG C in 20 minutes, in still, then add 820Kg centrifugal solids material, add in 30 minutes.Add solid material
Rear continuation stirs 20 minutes.Then adding the sulfuric acid 265Kg that concentration is 93% in 20 minutes, sulfuric acid finishes, will in 30 minutes
Still temperature rise, to 90 DEG C, continues stirring 25 minutes.Material pump in still is squeezed into condensing crystallizing still after accurate filter.
7, condensing crystallizing
Opening stirring, be passed through cooling water to crystallization kettle chuck, cooling water valve aperture is less than half.Open airless injection
Pump, in control still, vacuum is 0.08-0.088MPa, starts to crystallize under vacuum condition.When temperature in the kettle reaches 32 DEG C, by cold
But penstock is fully open, strengthens cooling water flow.When temperature in the kettle reaches below 27 DEG C, open bottom baiting valve, by still
Interior material adds centrifuge and is centrifuged.Solid material is dry for next step with softening after water rinses three times, all centrifuge mother liquors
Send into anti-stripping agent concentration kettle to be continuing with.
8, it is dried
Centrifugal solids material after rinsing is sent into double-cone type drying machine, fastens lid, start motor and make double-cone type drying machine
Rotary drum starts to rotate.Opening vacuum jet pump, in control drier, vacuum is 0.07-0.08MPa；Open steam valve, open
Begin to heat.Control temperature and be 120-125 DEG C, be dried 3 hours.Steam off valve, continuing to be evacuated to temperature is 50 DEG C, closes
Vacuum jet pump, opens lid.Packaging after sample analysis is qualified.
The extraction yield of this embodiment 5-sodium sulfo isophthalate is 99.2%, the 5-sodium sulfo isophthalate of preparation
Quality index is shown in Table 1
The 5-sodium sulfo isophthalate quality index of table 1 preparation
Embodiment 4
1, extractant is prepared
Weigh trioctylamine 700Kg, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 210Kg, 2-respectively
Heptyl undecyl alcohol 70Kg, sulfonated kerosene 420Kg, n-octyl alcohol 280Kg, add in extraction kettle, stir 40-60 minute, stand-by.
2, pH value is adjusted
At 12.5m3 In pH regulation still, three monomer waste water after metering adds dealcoholysis add 11m3, adding concentration is 98% sulphur
Acid 200Kg, aqueous pH values is adjusted to 2.0.
3, extraction
The waste water that 2100Kg regulates pH value adds extraction kettle, opens stirring, opens jacket steam valve, in 25 minutes
It is further continued for after temperature of charge in still is heated to 40 DEG C stirring 10 minutes, stands 15 minutes, carefully aqueous phase is released.Organic phase is put
In extraction kettle stand-by.
4, back extraction
NaOH solution 370Kg that concentration is 12% is added extraction kettle, and (extraction operates all in same equipment with back extraction
Carry out), open stirring, open jacket steam valve, in 10 minutes by still in temperature of charge be heated to 30 DEG C after be further continued for stirring
15 minutes, stand 15 minutes.Aqueous phase is carefully put into strip liquor basin, and organic phase continues on for next group extraction in being placed on extraction kettle
Take.
5, anti-stripping agent concentrates
Anti-stripping agent pump is squeezed into anti-stripping agent concentration kettle from strip liquor basin, opens stirring, open jacket steam valve,
Begin to warm up material in still.When material rises to 98 DEG C in still, opening vacuum jet pump, in control still, vacuum is 0.08-
0.086MPa, controls temperature in the kettle and is 60-65 DEG C.When observing that gas phase temperature is on a declining curve and is less than 60 DEG C, anti-stripping agent
When concentration kettle having solids occur, stop jacket steam heating.Continue on vavuum pump, be passed through cooling water to chuck, treat still
When interior temperature of charge reaches 34 DEG C, open bottom baiting valve, material in still is added centrifuge and is centrifuged.Centrifuge mother liquor sends into pH
Continuing reuse after regulation tank regulation pH value, solid material is acidified for next step.
6, acidifying
Add 1080Kg deionized water to acidifying still, open stirring, open jacket steam valve, begin to warm up material in still,
By still temperature rise to 38 DEG C in 25 minutes, in still, then add 830Kg centrifugal solids material, add in 35 minutes.Add solid material
Rear continuation stirs 25 minutes.Then adding the sulfuric acid 270Kg that concentration is 93% in 15 minutes, sulfuric acid finishes, will in 25 minutes
Still temperature rise, to 88 DEG C, continues stirring 30 minutes.Material pump in still is squeezed into condensing crystallizing still after accurate filter.
7, condensing crystallizing
Opening stirring, be passed through cooling water to crystallization kettle chuck, cooling water valve aperture is less than half.Open airless injection
Pump, in control still, vacuum is 0.086-0.09MPa, starts to crystallize under vacuum condition.When temperature in the kettle reaches 31 DEG C, by cold
But penstock is fully open, strengthens cooling water flow.When temperature in the kettle reaches 28 DEG C, open bottom baiting valve, by thing in still
Material adds centrifuge and is centrifuged.Solid material is dry for next step with softening after water rinses three times, and all centrifuge mother liquors are sent into
Anti-stripping agent concentration kettle is continuing with.
8, it is dried
Centrifugal solids material after rinsing is sent into double-cone type drying machine, fastens lid, start motor and make double-cone type drying machine
Rotary drum starts to rotate.Opening vacuum jet pump, in control drier, vacuum is 0.08-0.086MPa；Open steam valve, open
Begin to heat.Control temperature and be 120-122 DEG C, be dried 3 hours.Steam off valve, continuing to be evacuated to temperature is 55 DEG C, closes
Vacuum jet pump, opens lid.Packaging after sample analysis is qualified.
The extraction yield of this embodiment 5-sodium sulfo isophthalate is 99.4%, the 5-sodium sulfo isophthalate of preparation
Quality index is shown in Table 2.
The 5-sodium sulfo isophthalate quality index of table 2 preparation
Embodiment 5
1, extractant is prepared
Weigh trioctylamine 700Kg, di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene 490Kg, 2-respectively
Heptyl undecyl alcohol 210Kg, sulfonated kerosene 630Kg, n-octyl alcohol 630Kg, add in extraction kettle, stir 40-60 minute, stand-by.
2, pH value is adjusted
At 12.5m3In pH regulation still, three monomer waste water after metering adds dealcoholysis add 10m3, adding concentration is 98% sulphur
Acid 175Kg, aqueous pH values is adjusted to 3.5.
3, extraction
The waste water that 2050Kg regulates pH value adds extraction kettle, opens stirring, opens jacket steam valve, in 30 minutes
It is further continued for after temperature of charge in still is heated to 50 DEG C stirring 10 minutes, stands 12 minutes, carefully aqueous phase is released.Organic phase is put
In extraction kettle stand-by.
4, back extraction
NaOH solution 290Kg that concentration is 15% is added extraction kettle, and (extraction operates all in same equipment with back extraction
Carry out), open stirring, open jacket steam valve, in 15 minutes by still in temperature of charge be heated to 35 DEG C after be further continued for stirring
10 minutes, stand 12 minutes.Aqueous phase is carefully put into strip liquor basin, and organic phase continues on for next group extraction in being placed on extraction kettle
Take.
5, anti-stripping agent concentrates
Anti-stripping agent pump is squeezed into anti-stripping agent concentration kettle from strip liquor basin, opens stirring, open jacket steam valve,
Begin to warm up material in still.When material rises to 96-98 DEG C in still, opening vacuum jet pump, in controlling still, vacuum is
0.084-0.09MPa, controls temperature in the kettle and is 68-70 DEG C.When observing that gas phase temperature is on a declining curve and is less than 60 DEG C, back extraction
Take time liquid concentration kettle has solids to occur, stop jacket steam heating.Continue on vavuum pump, be passed through cooling water to chuck,
When temperature of charge reaches 35 DEG C in still, open bottom baiting valve, material in still is added centrifuge and is centrifuged.Centrifuge mother liquor send
Continuing reuse after entering pH regulation tank regulation pH value, solid material is acidified for next step.
6, acidifying
Add 1065Kg deionized water to acidifying still, open stirring, open jacket steam valve, begin to warm up material in still,
By still temperature rise to 40 DEG C in 30 minutes, in still, then add 825Kg centrifugal solids material, add in 35 minutes.Add solid material
Rear continuation stirs 30 minutes.Then adding the sulfuric acid 267Kg that concentration is 93% in 20 minutes, sulfuric acid finishes, will in 20 minutes
Still temperature rise, to 88 DEG C, continues stirring 25 minutes.Material pump in still is squeezed into condensing crystallizing still after accurate filter.
7, condensing crystallizing
Opening stirring, be passed through cooling water to crystallization kettle chuck, cooling water valve aperture is less than half.Open airless injection
Pump, in control still, vacuum is 0.082-0.088MPa, starts to crystallize under vacuum condition.When temperature in the kettle reaches 34 DEG C, will
Cooling water valve is fully open, strengthens cooling water flow.When temperature in the kettle reaches 29 DEG C, open bottom baiting valve, by still
Material adds centrifuge and is centrifuged.Solid material is dry for next step with softening after water rinses three times, and all centrifuge mother liquors send
Enter anti-stripping agent concentration kettle to be continuing with.
8, it is dried
Centrifugal solids material after rinsing is sent into double-cone type drying machine, fastens lid, start motor and make double-cone type drying machine
Rotary drum starts to rotate.Opening vacuum jet pump, in control drier, vacuum is 0.08-0.082MPa；Open steam valve, open
Begin to heat.Control temperature and be 122-124 DEG C, be dried 3 hours.Steam off valve, continuing to be evacuated to temperature is 50 DEG C, closes
Vacuum jet pump, opens lid.Packaging after sample analysis is qualified.
The extraction yield of this embodiment 5-sodium sulfo isophthalate is 99.5%, the 5-sodium sulfo isophthalate of preparation
Quality index is shown in Table 3
The 5-sodium sulfo isophthalate quality index of table 3 preparation
Claims (2)
1. a complexometric extraction technique extracts 5-sodium sulfo isophthalate method from three monomer waste water, it is characterised in that: bag
Including preparation extractant step, the extractant in described preparation extractant step is made up of complexing agent, cosolvent and diluent；
Described complexing agent is trioctylamine and di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base benzene；
Described cosolvent is 2-heptyl undecyl alcohol；
Described diluent is sulfonated kerosene and n-octyl alcohol；
In described extractant, the weight ratio of each material is: trioctylamine: di-tertiary amine 2,4-bis-(N, N-dihexyl) aminododecane base
Benzene: 2-heptyl undecyl alcohol: sulfonated kerosene: n-octyl alcohol=100:30-70:10-30:60-90:40-90；
Described method, also includes adjusting pH value step, and in described tune pH value step, in pH value regulation still, three after dealcoholysis are single
Adding concentration in body waste water is 93% or 98% sulfuric acid, and aqueous pH values is adjusted to 2-3.5.
2. a kind of complexometric extraction technique as claimed in claim 1 extracts 5-sodium sulfo isophthalate from three monomer waste water
Method, it is characterised in that: also including extraction step, in described extraction step, extraction temperature is 30-50 DEG C.
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| CN201510448476.6A CN104987303B (en) | 2014-07-25 | 2014-07-25 | A kind of complexometric extraction technique extracts 5-sodium sulfo isophthalate method from three monomer waste water |
| CN201410356437.9A CN104086462B (en) | 2014-07-25 | 2014-07-25 | 5-sodium sulfo isophthalate method is extracted in a kind of three monomer factory effluents |
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| CN201510448496.3A Expired - Fee Related CN105061268B (en) | 2014-07-25 | 2014-07-25 | A kind of extraction M-phthalic acid 5 sodium sulfonate method from M-phthalic acid 5 sodium sulfonate waste water |
| CN201410356437.9A Active CN104086462B (en) | 2014-07-25 | 2014-07-25 | 5-sodium sulfo isophthalate method is extracted in a kind of three monomer factory effluents |
| CN201510448460.5A Active CN105017089B (en) | 2014-07-25 | 2014-07-25 | Method for extracting 5-sulfoisophthalic acid monosodium salt by adopting complexation extraction process |
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| CN201410356437.9A Active CN104086462B (en) | 2014-07-25 | 2014-07-25 | 5-sodium sulfo isophthalate method is extracted in a kind of three monomer factory effluents |
| CN201510448460.5A Active CN105017089B (en) | 2014-07-25 | 2014-07-25 | Method for extracting 5-sulfoisophthalic acid monosodium salt by adopting complexation extraction process |
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| CN104310520B (en) * | 2014-11-12 | 2016-01-20 | 中蓝连海设计研究院 | A kind of 4B acid producing waste water comprehensive processing method |
| CN106186149A (en) * | 2016-08-25 | 2016-12-07 | 绵阳市龙鼎环保科技有限公司 | Extractant and use this extractant to process the method for waste water during hydroxyquinoline produces |
| CN114057613A (en) * | 2021-11-03 | 2022-02-18 | 山东德康化工有限公司 | Treatment method of waste liquid from production of m-phthalic acid-5-sodium sulfonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101230025A (en) * | 2008-02-22 | 2008-07-30 | 广东纺织职业技术学院 | Extractive recovery method for aryl sulfonic acid salt in waste water |
| CN102491575A (en) * | 2011-11-24 | 2012-06-13 | 山东金盛新材料科技有限公司 | Method for performing comprehensive treatment by utilizing waste water from production of ternary monomer |
| CN103242205A (en) * | 2013-05-17 | 2013-08-14 | 潍坊沃尔特化学有限公司 | Tri-monomer preparation method capable of reducing waste water production |
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| RU2255083C1 (en) * | 2004-04-20 | 2005-06-27 | Государственное образовательное учреждение профессионального образования "Воронежская государственная технологическая академия" | Method of extraction isolation and concentration of naphtholmonosulfonic acids from aqueous solutions |
| RU2266899C1 (en) * | 2004-04-20 | 2005-12-27 | Государственное образовательное учреждение высшего профессионального образования "Воронежская государственная технологическая академия" | Method for extraction of aminonaphthol disulfoacids from aqueous solutions |
| CN103896438B (en) * | 2014-04-16 | 2015-12-09 | 响水恒利达科技化工有限公司 | The method of the preparation method of J acid and J acid wastewater comprehensive treatment and recycling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230025A (en) * | 2008-02-22 | 2008-07-30 | 广东纺织职业技术学院 | Extractive recovery method for aryl sulfonic acid salt in waste water |
| CN102491575A (en) * | 2011-11-24 | 2012-06-13 | 山东金盛新材料科技有限公司 | Method for performing comprehensive treatment by utilizing waste water from production of ternary monomer |
| CN103242205A (en) * | 2013-05-17 | 2013-08-14 | 潍坊沃尔特化学有限公司 | Tri-monomer preparation method capable of reducing waste water production |
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| CN105061268A (en) | 2015-11-18 |
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| CN104086462B (en) | 2015-12-09 |
| CN105017089B (en) | 2017-01-18 |
| CN105017089A (en) | 2015-11-04 |
| CN104987303A (en) | 2015-10-21 |
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