CN109516623A - A kind of method of comprehensive utilization of tri butylethyl phosphate waste water - Google Patents
A kind of method of comprehensive utilization of tri butylethyl phosphate waste water Download PDFInfo
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- CN109516623A CN109516623A CN201811367616.7A CN201811367616A CN109516623A CN 109516623 A CN109516623 A CN 109516623A CN 201811367616 A CN201811367616 A CN 201811367616A CN 109516623 A CN109516623 A CN 109516623A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/046—Treatment of water, waste water, or sewage by heating by distillation or evaporation under vacuum produced by a barometric column
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a kind of processing methods of tri butylethyl phosphate waste water, it is the following steps are included: saponification occurs for TBEP alkali-wash waste water and alkaline solution, remaining phosphate in waste water is set thoroughly to react generation phosphoric acid ester sodium, obtain saponification waste-water, stratification after acid solution reacts is filled into saponification waste-water, isolates lower layer's acidity water phase and upper oil phase；Lower layer's acidity water phase is distilled after neutralizing, and obtains Nacl and distilled water；Upper oil phase continues distillation and obtains ethylene glycol monobutyl ether crude product and distillation bottom liquid, ethylene glycol monobutyl ether crude product is collected after molecular sieve filling tower dehydration cycle after distillation dehydration；Bottom liquid is neutralized for distillation, obtains TBEP sodium salt after distillation dehydration.The present invention solves in the wastewater treatment method of the prior art, and dangerous solid waste leading to the problem of and handling, and thoroughly solves the problems, such as that the fouling blockage of efficient Distallation systm MVR pipeline phosphoric acid ester sodium can not normal use.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of tri butylethyl phosphate waste water.
Background technique
Tri butylethyl phosphate fire retardant, English name Tris (2-butoxyethyl) pHospHate, abbreviation TBEP, separately
Claim ethylene glycol monobutyl ether phosphotriester, molecular formula is C18H42O10P, molecular weight 449.4955.It is a kind of flame-retardant plasticizer,
It is mainly used for the fire-retardant of polyurethane rubber, cellulose, polyvinyl alcohol etc. and plasticising, has the characteristics that good low temperature.The product is used
Extensively, the market demand continues to increase on way, and has many characteristics, such as low cigarette, Halogen, nontoxic, meets the development side of fire retardant halogen-free environmental
To, therefore there is good development prospect.1 ton of TBEP finished product of every production can produce 0.5 ton of left side in fire retardant TBEP generating process
Right alkaline waste water, the waste water enormous amount of generation.TBEP, TBEP sodium salt, sodium chloride, hydrogen are mainly contained in the production waste water of TBEP
Several substances of sodium oxide molybdena, ethylene glycol monobutyl ether.COD is more than 10000mg/l in general TBEP production waste water, and total phosphorus is more than
30000ppm, limiting emission object content severely exceed, and need to realize discharged wastewater met the national standard by complicated waste water treatment process.
The domestic research in terms of phosphate flame retardant wastewater processing technology at present is less, for the place of TBEP alkaline waste water
Reason technology is even more not have.And country's TBEP alkali-wash waste water is generally used general treatment of Phosphorus Containing Waste Water technology at present: aoxidize,
Flocculation sedimentation dephosphorization, efficient distillation dehydration desalination steam water into biochemical treatment qualified discharge, isolate Nacl, vinasse
As dangerous waste processing.Above method can guarantee that water outlet is qualified, and but there are the following problems:
Pretreatment measure can not remove the P elements in water removal before 1.TBEP wastewater oxidation, flocculation sedimentation dephosphorization etc. are distilled,
P elements are still dissolved in waste water in the form of TBEP sodium salt, and pretreatment causes danger because increasing the medicaments such as flocculant instead
Strategically secure useless increase.
2.TBEP waste water continuous still dehydration come when separating chlorine element and P elements in water, TBEP sodium salt in waste water with
Water is reduced and is precipitated, and similar to high viscosity mud, sodium chloride mode can not be crystallized by is centrifugated form, easily causes to set
Standby encrustation turns material return line blocking, very poor so as to cause steam heating effect, distillation efficiency is low, equipment fault stops
The problems such as vehicle rate is high.
Sodium chloride content is extremely low in 3.TBEP waste water, and when TBEP waste water is useless with other phosphates after environmental protection station pre-processes
When being hydrated and carrying out MVR dehydration, the Nacl isolated by salt is largely present such that appearance and chlorine due to TBEP sodium salt
Change sodium content and does not meet Nacl quality standard.
4. the ethylene glycol monobutyl ether that can be recycled in waste water does not have effective recovery process, cause to waste.
Due to not being directed to the patent and document of the alkali-wash waste water of tri butylethyl phosphate fire retardant, now citing is common to
The representative patent and document of phosphotriester waste water: the patent of Patent No. CN104692571A provides a kind of processing weak base
Property waste water method: first rectifying and dewatering isolates Nacl, and raffinate continues the cooling Nacl for refiltering precipitation, filters out
Raffinate is added 250-850 DEG C of pyrophosphorylation of the rear high temperature such as phosphoric acid, liquid alkaline and obtains pyrophosphate for selling.Its innovation of the patent
Point is phosphoric acid ester sodium and residual phosphoric acid ester vendible product is made by high temperature pyrophosphorylation, but does not account for waste water
In using raw material, such as phenol can be back to use the recycling and reusing of the raw material in phosphate production.Patent No.
The patent of CN101979347A provides a kind of method for handling phosphotriester flame retardant wastewater: first acid adding is by phosphate waste water
It is adjusted to pH=4-6, hydrogen peroxide is then added, oxidation reaction is carried out in the presence of surface catalyst, secondly carries out biochemical, flocculation
Settle the operation such as dephosphorization, last qualified discharge.Such method be use typical rudimentary method for oxidation attempt to decompose phosphate for
Phos, but be essentially all to be unable to reach the purpose for thoroughly decomposing phosphate and its sodium salt.Patent No. CN101704606A
Patent disclose a kind of processing method of organism P wastewater: first by organism P wastewater acid adding adjust pH=3-4, add hydrogen peroxide into
Row catalysis oxidation is further aoxidized subsequently into micro-electrolysis device, is removed water again through multistage hydrogen peroxide oxidation, last flocculating setting removes
Phosphorus.This method use electrolysis unit decompose it is organic phosphorus for Phos, if it is for phosphoric acid ester high concentration organism P wastewater,
Electrolytic oxidation needs are first diluted water sample, can generate more waste water, and power consumption is huge.
" chemical industry environmental protection " proposes for 2012 the 01st in interim " organophosphorus ester generates wastewater preprocessing process research " text
" liquid film extraction-acid out sedimentation-complexometric extraction " group technology handles organophosphorous fire retardant waste water, waste water COD, tp removal rate point
Do not reach 93% and 97%, however the technical matters process is complicated, needs using a large amount of solvents and acid, it is additional to generate more give up
Water and solid waste, in general processing cost is high, and improper enterprise's large scale processing phosphate waste water.
With both at home and abroad to phosphoric acid ester substance studies have shown that sufficiently stable, the common oxidation side of the structure of phosphate
Method can not thoroughly destroy its structure, be broken down into Phos, therefore the production waste water of fire retardant TBEP also can not be using conventional
The modes such as oxidation, flocculation, precipitating remove the phosphorus containg substances in waste water and decomposing organic matter.And use high temperature and pressure oxidation, electrolysis
The high-end method for oxidation such as method, catalytic electrolysis method, although can achieve the effect for decomposing that phosphate is Phos, presence can not be fitted
It answers high phosphate ester content waste water, the problems such as treatment effeciency is low, power consumption is at high cost, all limits it in the practical application of factory.
Silkete penetrating agent and ethylene glycol monobutyl ether phosphoric acid ester sodium (TBEP sodium salt) purposes introduction:
For textile when carrying out mercerising link, the viscosity of soda bath is larger, and the permeability of lye is poor, and mercerising is added and seeps
After saturating agent, high alkali liquid surface tension is reduced, the infiltration of lye is conducive to, improve the uniformity of mercerising, reduces surface mercerising.Cotton
When the direct mercerising of yarn embryo, since containing hydrophobicitys natural impuritys such as wax, pectin, in concentrated alkali solution, cotton yarn surface fiber is acute
Strong swelling, length sharply shorten, and make lye that can not penetrate into fibrous inside.Must be added to the strong silkete penetrating agent of penetration can just make
Mercerization is rapid and uniform, and can greatly shorten the mercerising time.Apply in general to the fatty alcohol carbon atom of silkete penetrating agent
Number is less than 8, preferably 4-6, and fatty alcohol carbochain is short, and alkali resistance is relatively high, and in neutral aqueous solution, surface-active is very low,
Permeability is very poor, but under the conditions of 180-280g/l lye, and since electrolyte acts on, silkete penetrating agent is enriched in fiber surface,
Fatty alcohol carbochain is again shorter, and regular mono layer adsorption film easy to form, reduction in surface tension makes lye penetrate into fibre rapidly
Dimension is internal.
Ethylene glycol monobutyl ether phosphate, that is, TBEP has excellent permeability, can be made in 180g/l or more lye
Silkete penetrating agent, generally based on TBEP dibasic acid esters sodium salt, dibasic acid esters permeability is better than monoesters, and steeps face very little, does not influence light alkali
Recovery process.What certain pairs of silkete penetrating agent alkali resistances required can then select based on TBEP monoester sodium salt.Open market is normal
The silkete penetrating agent seen compounds other auxiliary agents and improves its permeability or alkali resistance performance often using phosphoric acid ester sodium as major ingredient.
Generally as follows with the common production technology of TBEP sodium salt: butyl glycol ether is reacted with P2O5 or polyphosphoric acids, then
With NaOH aqueous solution liquid tune pH value (1% aqueous solution) 7.0~9.0.Finally plus on a small quantity hydrogen peroxide for decoloration, filters to obtain finished product.It is logical
Cross the content ratio of the feed ratio adjustable monoesters and dibasic acid esters of adjustment ethylene glycol monobutyl ether and P2O5.
Application publication number is a kind of patent " silkete penetrating agent of resistance to highly basic ethylene glycol monobutyl ether phosphate of CN102503973A
Preparation method " be exactly that polyphosphoric acids conduct is used using similar above method synthesizing glycol monobutyl ether phosphoric acid ester sodium
Bonderite replaces P2O5, can prepare the phosphate monoester mass content silkete penetrating agent high in 90% or more content, alkali resistance
Performance is splendid.Know to be typically all to require according to the compounding of silkete penetrating agent producer, designs different production technologies to obtain not
With dibasic acid esters and monoester content.
There is a large amount of ethylene glycol monobutyl ether phosphoric acid ester sodium in the waste water that TBEP production process generates, and passes through patent document
Retrieval be not found the pertinent literature about the purification of ethylene glycol monobutyl ether phosphoric acid ester sodium in waste water.TBEP produces waste water
In ethylene glycol monobutyl ether phosphate diester sodium salt mass content 75% or more, due in the original technique of company than not to by nothing
The link that machine salt and organic salt are separated causes to contain nearly 1/ in the phosphoric acid ester sodium solid of last waste water distillation dehydration acquisition
The sodium chloride of 3 mass, the mass content of effective component ethylene glycol monobutyl ether phosphate diester sodium salt are difficult less than 50% as silk
The main compounding ingredient of light bleeding agent is sold, instead can only be as dangerous fixed-end forces.Fire retardant TBEP belongs to environmentally friendly resistance
Fire agent one kind, since it is widely used, the market demand is vigorous, and domestic production amount also increases year by year, how efficiently, low cost
The production waste water of processing TBEP be that limitation enterprise increases production-scale main bottleneck, and the main developing way of this new technology
Raw material is exactly recycled, byproduct is prepared, reduces processing links, component in integrated treatment waste water, finally playing reduces TBEP waste water
Processing cost guarantees that sewage treatment equipment keeps higher running rate.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of three fourth oxygen ethyl phosphonic acids
The method of comprehensive utilization of ester waste water produces various products for waste water as a kind of available resources by means of the present invention,
And ensure the qualified discharge of waste water, the processing for solving the alkali-wash waste water of tri butylethyl phosphate fire retardant from the root is difficult
Topic.
A kind of processing method of tri butylethyl phosphate waste water, it is characterised in that include the following steps:
1) saponification: TBEP alkali-wash waste water is warming up to 60-85 DEG C, alkaline solution is added with stirring, controls waste water
PH value is maintained at 8-9, stirs insulation reaction, so that remaining TBEP reaction in waste water is generated phosphoric acid ester sodium, obtains saponification waste-water；Soap
It is as follows to change reaction process:
2) acidizing extraction: step 1) saponification waste-water temperature is kept for 60-85 DEG C, is slowly added dropwise under stirring into acid solution, control
The pH stable of saponification waste-water processed stirs insulation reaction in 1-2, keeps sodium phosphate reactant salt generation in saponification waste-water not soluble in water
Ethylene glycol monobutyl ether phosphate, then stratification, separates lower layer's acidity water phase and upper oil phase；Acidizing extraction reaction process
It is as follows:
3) recycle ethylene glycol monobutyl ether: upper oil phase obtained by step 2) is evaporated under reduced pressure, to remove recycling upper oil phase
In water and ethylene glycol monobutyl ether, distillation obtain acid distilled water, thick ethylene glycol monobutyl ether and kettle base solution, the thick ethylene glycol list
The water content of butyl ether is in 0.15%-0.2%；
4) in sour water and distill: acid distilled water obtained by lower layer's acidity water phase obtained by step 2) and step 3) merges,
After merging obtained mixed liquor by alkaline solution adjusting pH to neutrality, it is evaporated under reduced pressure, steams recycling moisture, obtain industry
Salt and distilled water, gained distilled water meet TBEP production soda-wash water scouring water standard；
5) molecular sieve dehydration: at normal temperature, thick ethylene glycol monobutyl ether obtained by step 3) is followed by molecular sieve filling tower
Ring dehydration obtains the ethylene glycol monobutyl ether finished product that water content is lower than 0.1%, and it is anti-that gained ethylene glycol monobutyl ether finished product meets TBEP esterification
Standard should be used；
6) it prepares TBEP sodium salt: after alkaline solution adjusting PH to neutrality is added in kettle base solution obtained by step 3), putting into steaming
It evaporates progress vacuum distillation dehydration in kettle to release the material in distillation still while hot after there is no moisture to steam, the hot object of releasing
Material is cooled to 40 DEG C of thoroughly solidifications in drying box, obtains cured TBEP sodium salt；Step 6) prepares TBEP sodium salt reaction process
It is as follows:
A kind of processing method of the tri butylethyl phosphate waste water, it is characterised in that in step 2), acid solution
For aqueous hydrochloric acid solution, the mass fraction of the aqueous hydrochloric acid solution is 15-30%；The time for stirring insulation reaction is 0.5~1.5h,
Preferably 1h.
The processing method of a kind of tri butylethyl phosphate waste water, it is characterised in that in step 4), depressurized
The temperature of distillation dehydration is 70~80 DEG C, and vacuum degree is within 10KPa.
A kind of processing method of the tri butylethyl phosphate waste water, it is characterised in that in step 3), upper oil phase
It carries out vacuum distillation and is divided into two stages, first stage is distillation dehydration, and vapo(u)rizing temperature is 70~75 DEG C, and vacuum degree is
Within 200Pa；Second stage is to distill de- ethylene glycol monobutyl ether, and vapo(u)rizing temperature is 145~150 DEG C, vacuum degree be 200Pa with
It is interior.
The processing method of a kind of tri butylethyl phosphate waste water, it is characterised in that in step 5), molecular sieve is filled out
Expect that molecular sieve model used in tower is 3A molecular sieve.
A kind of processing method of the tri butylethyl phosphate waste water, it is characterised in that in step 6), vacuum distillation
The temperature of dehydration is 145~150 DEG C, and vacuum degree is within 6KPa.
A kind of processing method of the tri butylethyl phosphate waste water, it is characterised in that in step 6), gained TBEP
Sodium salt carries out the spectrum PMNR detection of nuclear-magnetism phosphorus, and testing result is TBEP dibasic acid esters sodium salt content 75~85%, TBEP monoesters double sodium salt contains
Amount 10~25%, water content 2~5%, sodium chloride mass content≤0.1%, organic phosphorus active constituent content >=94.9%.
The processing method of a kind of tri butylethyl phosphate waste water, it is characterised in that step 1), step 4) and step
It is rapid 6) in, alkaline solution is sodium hydrate aqueous solution, and the mass fraction of the sodium hydrate aqueous solution is 20~30%.
A kind of processing method of the tri butylethyl phosphate waste water, it is characterised in that in step 2), acid solution
Rate of addition be added dropwise.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
(1) it by saponification, reacts the tri butylethyl phosphate in tri butylethyl phosphate waste water and generates phosphorus
Sodium salt, and generate more recyclable ethylene glycol monobutyl ether；Prepare the alkaline cleaning procedure temperature one of tri butylethyl phosphate
As do not exceed 70 DEG C, and the time is shorter, is difficult the tri butylethyl phosphate that will be dissolved in water layer and passes through saponification to generate
Phosphoric acid ester sodium, saponification of the invention are exactly to use to increase temperature, and extend the time to realize phosphate reaction at phosphoric acid
Ester sodium salt, to improve phosphoric acid ester sodium effective content in final product.
(2) for the separation and recovery of ethylene glycol monobutyl ether in saponification waste-water, if separated back using conventional rectificating method
It receives, first has to all steam water, then steam ethylene glycol monobutyl ether again.This conventional recovery methods have two,
One, rectificating method dehydration cannot using vacuum distillation, otherwise will cause ethylene glycol monobutyl ether and be carried over, and normal pressure steam water consume when compared with
Long and energy consumption is very big；Second, after dehydration to a certain extent, although phosphoric acid ester sodium is liquid at high temperature to second two in bottom material
The evaporating temperature requirement of alcohol monobutyl ether is higher, and ethylene glycol monobutyl ether is less with respect to bottom material total amount, even more increases vapo(u)rizing temperature,
Improve distillation difficulty and energy consumption.The invention is characterized in that acidizing extraction reacts, keep sodium phosphate reactant salt in saponification waste-water raw
At ethylene glycol monobutyl ether phosphate hydroxy compounds not soluble in water, ethylene glycol monobutyl ether phosphate hydroxy compounds is to ethylene glycol
Monobutyl ether has extremely strong effect of extracting, can extract the ethylene glycol monobutyl ether in water layer, after layering, obtains contain second respectively
Upper oil phase and sodium chloride-containing based on glycol monobutyl ether phosphate hydroxy compounds and ethylene glycol monobutyl ether, hydrogen chloride, water are
Main lower layer's acidity water phase.
(3) in acidic aqueous phase and distill: by neutralizing lower layer's acidity water phase to after neutrality, waste water can pass through distillation behaviour
Make desalination, steams and meet the desired distilled water of TBEP production washing.The Nacl that this stage obtains is extracted in acidification
The stage is taken to be generated by hydrochloric acid and TBEP the sodium salt reaction being added, small part comes from alkali-wash waste water stoste and sour water neutralization reaction.This
In invention acidic aqueous phase and obtained distilled water is distilled, TBEP production technology is required with water: appearance colorless transparency liquid, PH=6-
8, COD COD≤1000mg/L, An Dan≤5mg/L, Zong Lin≤10mg/L, Tie≤0.3mg/L, COD therein are main
From residual ethylene glycol monobutyl ether.
(4) recycle ethylene glycol monobutyl ether, although by acidizing extraction control temperature reduce upper oil phase water content, continuously
Most water but still it not can avoid the moisture of micro amount in distillation dehydration removing upper oil phase and be brought into the ethylene glycol steamed
In monobutyl ether, and ethylene glycol monobutyl ether of the moisture content greater than 0.1% cannot be used directly for preparing the ester of tri butylethyl phosphate
The problems such as changing reaction, will cause catalyst inactivation, it is therefore desirable to the ethylene glycol monobutyl ether of recycling is further dehydrated, and it is of the invention
Acidizing extraction, the water content of the ethylene glycol monobutyl ether of recycling is reduced to extremely low degree and (contained by continuous still dehydration
0.2%) water is lower than, therefore molecular sieve filling tower can be used and further remove moisture, and molecular sieve has good adsorption moisture
The effect of son, and can be reused by drying and dewatering, cost is relatively low for relative motion, by molecular sieve adsorbing and dewatering, so that
The ethylene glycol monobutyl ether of recycling meets the quality standard of recycling and reusing.
(5) TBEP sodium salt is prepared: since viscosity is very big at low temperatures and is easy solidification for pure TBEP sodium salt, and
140 DEG C the above are the flowable states compared with low viscosity, therefore reaction control temperature is kept for 140 DEG C or more not will cause inside consersion unit
Fouling and bottom valve blocking, while dehydration can make it easier to solidify and instant packed storage.
(6) the method for the invention realizes phosphorus-containing matter in waste water is prepared into the higher ethylene glycol only son of effective component
Ethylene glycol monobutyl ether recycling in waste water is returned again to the use of tri butylethyl phosphate esterification, incited somebody to action by ether phosphate sodium salt
Sodium ion and chloride ion in waste water are solidified into available Nacl, the distilled water isolated are applied to Hui Sanding oxygen ethyl phosphonic acid
Each process of ester re-uses, and finally realizes the mesh for maximumlly utility in waste water being made to generate new economic value
's.It is solved in the wastewater treatment method of the prior art by this technique simultaneously, dangerous solid waste leading to the problem of and handling, thoroughly
Solve the problems, such as efficient Distallation systm MVR pipeline phosphoric acid ester sodium fouling blockage can not normal use, to push three fourth oxygen ethyls
The renewable generation that is recycled of phosphate flame retardant is of great significance.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
The unit % of following embodiment content, refers both to the unit of mass percent content.
Embodiment 1:
Waste water: TBEP produces alkali-wash waste water, through analyzing: total phosphorus=14058.7ppm, COD=112965.3mg/L, pH=
9, sodium chloride 0.0347%, ethylene glycol monobutyl ether 4.85%, TBEP6.04%, TBEP dibasic acid esters sodium salt 9.2%, after precipitating filtering outside
Seeing is colourless transparent liquid.
A kind of processing method of tri butylethyl phosphate waste water, steps are as follows:
1) saponification: TBEP alkali-wash waste water 330kg is stirred in a kettle and is warming up to 85 DEG C, is added with stirring 30%
Sodium hydrate aqueous solution, controlling the pH value of waste water in reaction kettle, to be maintained at 8-9 (total that sodium hydrate aqueous solution is added
10.47kg), insulation reaction terminated saponification after 3 hours, obtained saponification waste-water；
2) acidizing extraction: step 1) saponification waste-water temperature is kept for 85 DEG C, instills 30% aqueous hydrochloric acid solution under stirring dropwise,
The pH stable of saponification waste-water is controlled 1-2 (total that aqueous hydrochloric acid solution 31.46kg is added), insulation reaction 1h is stirred, makes to be saponified
The reaction of Phosphorus From Wastewater sodium salt generates ethylene glycol monobutyl ether phosphate not soluble in water, then stratification, separates lower layer's acid
Property water phase 304.6kg and upper oil phase 65.2kg；Measurement gained lower layer acidity water phase COD=351.7mg/L, COD examination criteria
For GB11914-89；
3) recycle ethylene glycol monobutyl ether: upper oil phase 65.2kg obtained by step 2) is evaporated under reduced pressure, first control distillation temperature
Within 70~72 DEG C of degree, vacuum degree 200Pa, distillation dehydration is carried out, until after being steamed without moisture, then control vapo(u)rizing temperature 145
~147 DEG C, within vacuum degree 200Pa, carry out distilling de- ethylene glycol monobutyl ether；Final total recycling acidity distilled water 0.91kg with
Thick ethylene glycol monobutyl ether 24.59kg, remaining kettle base solution adds up to about 38.75kg in kettle；Water is carried out to the thick ethylene glycol monobutyl ether of gained
Sorting is surveyed, water content 0.15%；
4) in sour water and distill: acid distilled water obtained by lower layer's acidity water phase obtained by step 2) and step 3) merges
The mixed liquor 305.51kg arrived, merge gained mixed liquor by 30% sodium hydrate aqueous solution adjust pH to it is neutral (it is total plus
Enter sodium hydrate aqueous solution 10.67kg), vacuum distillation dehydration is then carried out, vapo(u)rizing temperature is 80 DEG C, and distillation vacuum degree is
10KPa, distillation obtain the Nacl 15.7kg and colourless distillation condensed water 298.4kg that appearance is white crystal free from admixture；It is right
The Nacl of acquisition is detected, and examination criteria is GB/T 5462-2003, testing result are as follows: sodium chloride 96%, moisture 4%,
There is no substance not soluble in water, calcium ions and magnesium ions are not detected, and sulfate ion is not detected, and meet solarization Nacl first quality mark
It is quasi-；
5) molecular sieve dehydration: at normal temperature, thick ethylene glycol monobutyl ether obtained by step 3) is followed by molecular sieve filling tower
Ring dehydration, is filled with model 3A molecular sieve in molecular sieve filling tower, the dehydration cycle time be for 24 hours, it is colorless and transparently final
Ethylene glycol monobutyl ether product 24.09kg, detecting its water content is 0.05%, uses gas chromatographic detection ethylene glycol monobutyl ether product
Purity be 99.6%；
6) prepare TBEP sodium salt: kettle base solution obtained by step 3), be added with stirring 30% sodium hydrate aqueous solution adjust it is molten
Liquid pH to 7 (total that sodium hydrate aqueous solution 23.64kg is added) then heats to 145~147 DEG C of insulated and stirred reaction 1h, then
It puts into together and carries out vacuum distillation dehydration in distillation still, 145~147 DEG C of vapo(u)rizing temperature, distill within vacuum degree 6KPa, until
There is no moisture to steam, total distillation recovery obtains distilled water 17.6kg, detects material liquid pH value in distillation still and keeps kettle still 7
Interior material temperature releases material in kettle at 145~147 DEG C while hot, and the material of releasing is cooled to 40 DEG C of thoroughly solidifications in drying box, obtains
43.77kg TBEP sodium salt solid is obtained, the spectrum PMNR detection of nuclear-magnetism phosphorus is carried out to the TBEP sodium salt solid of acquisition, phosphorous group after conversion
Mass content in point are as follows: TBEP 1.71%, TBEP dibasic acid esters sodium salt 83.50%, TBEP monoesters double sodium salt 14.79%, in component
The silkete penetrating agent compounding that TBEP diester sodium salt content meets high osmosis requirement requires.Detection gained TBEP sodium salt solid contains
Water is 3%, measures the chloride ion content 0.096% in TBEP sodium salt solid by 13025.3 method of GB/T.
The distilled water that 1 step 4) of embodiment and step 6) obtain merges, and technique is total to obtain distilled water 315.99kg,
Combined distilled water is detected, ammonia nitrogen examination criteria is GB7479-87, and total phosphorus examination criteria is GB11893-89, iron inspection
Mark standard is GB11911-89, final detection result are as follows: appearance colorless transparency liquid, PH=7, COD=338.89mg/L, ammonia nitrogen
Without detection, total phosphorus without detection, iron without detection；Gained distillation aquatic products conform to quality requirements, and can apply back in TBEP production.
Embodiment 2: a kind of processing method of tri butylethyl phosphate waste water, method condition with embodiment 1, but with reality
It applies unlike example 1, acidizing PH value control finds that saponification waste-water is in the emulsified state that can not be layered, examine in 3-4 in step 2)
Worry is that TBEP sodium salt does not react into TBEP hydroxy compounds.
Embodiment 3: a kind of processing method of tri butylethyl phosphate waste water, method condition with embodiment 1, but with reality
It applies unlike example 1, acidizing PH value control is 1 hereinafter, sampling survey lower layer's acidity water phase COD=359.1mg/L, is examined in step 2)
Considering detection, there are errors, it is believed that identical as 1 result of embodiment.
Embodiment 4: a kind of processing method of tri butylethyl phosphate waste water, method condition with embodiment 1, but with reality
It applies unlike example 1, the temperature that step 6) changes vacuum distillation dehydration is 155-158 DEG C, until steaming without water, acquisition is most
The moisture content in TBEP sodium salt solid is 1.1% afterwards, releases cooling TBEP sodium salt and smoothly solidifies.
Embodiment 5: a kind of processing method of tri butylethyl phosphate waste water, method condition with embodiment 1, but with reality
It applies unlike example 1, the temperature that step 6) changes vacuum distillation dehydration is 135-138 DEG C, until steaming without water, acquisition is most
The moisture content in TBEP sodium salt solid is 5.5% afterwards, releases cooling TBEP sodium salt and smoothly solidifies.
Embodiment 6: a kind of processing method of tri butylethyl phosphate waste water, method condition with embodiment 1, but with reality
It applies unlike example 1, the temperature that step 6) changes vacuum distillation dehydration is 118-120 DEG C, until steaming without water, acquisition is most
The moisture content in TBEP sodium salt solid is 13.3% afterwards, is released after cooling TBEP sodium salt is cooled to 40 DEG C still more than 12 hours
It can not so solidify in ooze state.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (9)
1. a kind of processing method of tri butylethyl phosphate waste water, it is characterised in that include the following steps:
1) saponification: TBEP alkali-wash waste water is warming up to 60-85 DEG C, is added with stirring alkaline solution, controls the pH value of waste water
It is maintained at 8-9, stirs insulation reaction, so that remaining TBEP reaction in waste water is generated phosphoric acid ester sodium, obtains saponification waste-water；
2) acidizing extraction: step 1) saponification waste-water temperature is kept for 60-85 DEG C, is slowly added dropwise under stirring into acid solution, is controlled soap
Change the pH stable of waste water in 1-2, stirs insulation reaction, sodium phosphate reactant salt in saponification waste-water is made to generate second not soluble in water
Glycol monobutyl ether phosphate, then stratification, separates lower layer's acidity water phase and upper oil phase；
3) recycle ethylene glycol monobutyl ether: upper oil phase obtained by step 2 is evaporated under reduced pressure, in removing recycling upper oil phase
Water and ethylene glycol monobutyl ether, distillation obtain acid distilled water, thick ethylene glycol monobutyl ether and kettle base solution, the thick ethylene glycol monobutyl ether
Water content in 0.15%-0.2%；
4) in sour water and distill: acid distilled water obtained by lower layer's acidity water phase obtained by step 2 and step 3) merges, and merges
Obtained mixed liquor by alkaline solution adjust pH to neutrality after, be evaporated under reduced pressure, steam recycling moisture, obtain Nacl and
Distilled water, gained distilled water meet TBEP production soda-wash water scouring water standard；
5) molecular sieve dehydration: at normal temperature, thick ethylene glycol monobutyl ether obtained by step 3) carries out circulation by molecular sieve filling tower and takes off
Water, obtains the ethylene glycol monobutyl ether finished product that water content is lower than 0.1%, and gained ethylene glycol monobutyl ether finished product meets TBEP esterification and makes
Use standard；
6) it prepares TBEP sodium salt: after alkaline solution adjusting PH to neutrality is added in kettle base solution obtained by step 3), putting into distillation still
Interior carry out vacuum distillation dehydration releases the material in distillation still after not having moisture to steam while hot, and the thermal material of releasing exists
It is cooled to 40 DEG C of thoroughly solidifications in drying box, obtains cured TBEP sodium salt.
2. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 2
In, acid solution is aqueous hydrochloric acid solution, and the mass fraction of the aqueous hydrochloric acid solution is 15-30%；Stirring insulation reaction time be
0.5 ~ 1.5h, preferably 1h.
3. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 4)
In, the temperature for carrying out vacuum distillation dehydration is 70 ~ 80 DEG C, and vacuum degree is within 10KPa.
4. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 3)
In, upper oil phase carries out vacuum distillation and is divided into two stages, and first stage is distillation dehydration, and vapo(u)rizing temperature is 70 ~ 75 DEG C, very
Reciprocal of duty cycle is within 200Pa；Second stage is to distill de- ethylene glycol monobutyl ether, and vapo(u)rizing temperature is 145 ~ 150 DEG C, and vacuum degree is
Within 200Pa.
5. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 5)
In, molecular sieve model used in molecular sieve filling tower is 3A molecular sieve.
6. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 6)
In, the temperature of vacuum distillation dehydration is 145 ~ 150 DEG C, and vacuum degree is within 6KPa.
7. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 6)
In, gained TBEP sodium salt carries out the spectrum PMNR detection of nuclear-magnetism phosphorus, and testing result is TBEP dibasic acid esters sodium salt content 75 ~ 85%, TBEP is mono-
Ester double sodium salt content 10 ~ 25%, water content 2 ~ 5%, sodium chloride mass content≤0.1%, organic phosphorus active constituent content >=94.9%.
8. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 1),
In step 4) and step 6), alkaline solution is sodium hydrate aqueous solution, the mass fraction of the sodium hydrate aqueous solution is 20 ~
30%。
9. a kind of processing method of tri butylethyl phosphate waste water according to claim 1, it is characterised in that step 2
In, the rate of addition of acid solution is to be added dropwise.
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| CN112607946A (en) * | 2020-12-17 | 2021-04-06 | 浙江万盛股份有限公司 | Method for recycling organic waste in BDP wastewater |
| CN114853580A (en) * | 2022-06-09 | 2022-08-05 | 浙江万盛股份有限公司 | Process for separating and purifying by-product 2-butoxychloroethane in production process of tri (butoxyethyl) phosphate |
| CN114853580B (en) * | 2022-06-09 | 2023-10-31 | 浙江万盛股份有限公司 | Process for separating and purifying 2-butoxychloroethane as byproduct in production process of tri (butoxyethyl) phosphate |
| WO2023236938A1 (en) * | 2022-06-09 | 2023-12-14 | 浙江万盛股份有限公司 | Process for separating and purifying by-product 2-chloroethyl n-butyl ether in production process of tris(2-butoxyethyl)phosphate |
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