CN109626683A - The processing method of waste water in a kind of plasticizer DINCH esterification process technique - Google Patents
The processing method of waste water in a kind of plasticizer DINCH esterification process technique Download PDFInfo
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- CN109626683A CN109626683A CN201710929779.9A CN201710929779A CN109626683A CN 109626683 A CN109626683 A CN 109626683A CN 201710929779 A CN201710929779 A CN 201710929779A CN 109626683 A CN109626683 A CN 109626683A
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- water
- waste water
- filter residue
- washing
- organic solvent
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
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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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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention proposes the processing methods that waste water is generated in a kind of plasticizer DINCH esterification process technique, comprising the following steps: (1) filters after merging the washing water generated in the neutralization water and washing step that generate in neutralization step, obtain water phase and filter residue 1；(2) organic solvent is added in filtering out water phase and carries out air-distillation, the water phase set steamed is for washing step next time；(3) distillation kettle liquid is filtered, the liquid phase filtered out is applied as the organic solvent distilled next time, and the filter residue 2 and filter residue 1 filtered out is handled after merging as solid waste high temperature incineration.The invention enables entire DINCH esterification techniques not to generate waste water, only generates a small amount of solid waste, can high temperature incineration processing；Organic solvent can reduce reagent cost with recovery, reduce processing difficulty, operation difficulty is low.
Description
Technical field
The present invention relates to the wastewater treatment methods of plasticizer DINCH a kind of, belong to chemical industry processing, chemical technology field.
Background technique
Hexamethylene -1,2- dioctyl phthalate dinonyl, abbreviation DINCH, structural formula are as follows:
DINCH has the structure and property similar with dioctyl phthalate (DOP) and diisononyl phthalate (DINP)
Can, it is that one kind aims at PVC sensibility using (such as medical facilities, food fresh keeping membrane, food packaging, toy for children and human body are close
Cut relevant plastic products) and the non-phthalic ester plasticizer of exploitation, have efficient, nontoxic, safe, biodegradable
The features such as, it is the favorable substitutes of benzene carboxylic acid ester plasticizer.
Currently, the method for synthesizing cyclohexane 1 alkane -1,2- dioctyl phthalate dinonyl (DINCH) includes hydrogenation method and esterification process.Its
Middle hydrogenation method process route is simple, cleaning, but technical difficulty is big, and reaction needs high temperature and pressure, high to equipment and catalyst requirement,
Investment is big, high production cost, and only BASF Aktiengesellschaft has grasped the key problem in technology in the world at present, domestic to go back in a short time
It is difficult to realize industrialize.Therefore, esterification process is the main method of industrial production DINCH at present, and this method is with hexahydro neighbour's benzene
Dicarboxylic acid anhydride and isononyl alcohol are raw material, and high temperature is esterified under the action of catalyst, molten with sodium hydroxide after esterification
Liquid is neutralized, is washed, then dealcoholysis, and DINCH finished product is obtained by filtration in decoloration.
In the esterification process synthesis technology of DINCH, the waste water of generation mostlys come from neutralization and washing step: thick ester with
NaOH solution is neutralized, and for the monoesters acid in thick ester by alkali neutralization at monoesters acid sodium, catalyst is hydrolyzed into TiO2Hydrate, produce
It is raw to neutralize waste water；Oil is mutually washed, and washing waste water is generated.Neutralization step and this two parts waste water of washing step are organic waste
Water, complicated component mainly contain hexahydro-phthalic acid, hexahydro-phthalic acid monoesters, hexahydro-phthalic acid two
Ester, hexahydro-phthalic acid sodium salt, isononyl alcohol and TiO2Hydrate.The waste water of differential responses batch is detected,
As a result as follows:
1 wastewater recycle tables of data of table
As can be seen from Table 1, the BOD of waste water is neutralized5/ COD ratio is less than 0.3, it is difficult to biochemical；The BOD of washing waste water5/ COD ratio
Value is greater than 0.3, is suitable for biochemical treatment；After two strands of waste water are mixed, COD value is 40000~60000 mg/L, BOD5Value
For 10000~12000 mg/L, BOD5/ COD ratio is still less than 0.3, it is difficult to biochemical treatment.
Currently, the patent and paper for DINCH esterification process technique are seldom.CN1962736A is disclosed with single step height
Warm esterification process synthesizing cyclohexane 1 alkane 1, the method for 2- dioctyl phthalate dinonyl, at 250 DEG C of reaction temperature, 5 h reaction pressure of reaction time
5 ~ 760mbar of power synthesizes DINCH.CN101613282A is disclosed to be esterified in the presence of the metal solvents such as titanium system or tin system
Reaction, esterification are reacted in two stages, rear to improve temperature extremely first with (120 ~ 160 DEG C) progress single-esterifications of lower temperature
250 DEG C and add catalyst carry out double esterification reaction, after the reaction was completed with the hydroxide aqueous solution of alkali or alkaline earth metal into
Row neutralization reaction, the rear removing for carrying out excessive response alcohol, dry, filtering are prepared into the carboxylate of plasticizer, but reaction time
It is longer.The above patent is expected that by the improvement of process aspect to reduce wastewater flow rate, reduces the pollution to environment, not fundamentally
The wastewater through organic matter content solved in DINCH esterification process technique is high, handles difficult problem.
Have in more document reports and mention, Fenton oxidation method is a kind of common higher waste water of processing content of organics
Method.This method uses hydrogen peroxide for oxidant, using ferrous salt as catalyst, in acid condition, the HO- generated in reaction
Free radical is a kind of very strong free radical of oxidability, and oxidation-reduction potential with higher, energy is rapidly in oxidized waste water
Pollutant and non-selectivity can make the organic structure in waste water that demolase occur, and make to be difficult to biodegradable macromolecular organic
Object is cracked into CO2And H2O.This method is applied relatively broad at present, and traction is higher.But Fenton oxidation method is lacked there are following
Point: (1) hydrogen peroxide operation difficulty is big, and it must be solid that ferrous sulfate, which adds, and ferrous sulfate iron content 20% or so, relative to poly-
11% iron content of iron, considerably increases Treatment of Sludge intensity；(2) Fenton processing is at high cost, and sludge is more, especially hydrogen peroxide
Reagent cost is high；(3) Fenton processing is easy to return color.As the dosage of hydrogen peroxide and ferrous sulfate with add ratio control it is bad,
It is easy to cause waste water to show yellowish or yellowish-brown；(4) process conditions are difficult to control.Because hydrogen peroxide and ferrous sulfate are most
Good ratio need to carry out orthogonal experiment just it can be concluded that, and by pH value in reaction, reaction time length, be stirred degree
It influences, so ratio is difficult to control；(5) most of waste water are unable to direct emission after Fenton oxidation is handled, it is necessary to be given birth to again
Change processing, it means that Fenton oxidation method is only a kind of preprocessing means for most of waste water.
Summary of the invention
The invention proposes the processing methods that waste water is generated in a kind of plasticizer DINCH esterification process technique.For DINCH ester
The problem of wastewater through organic matter content is high in change method technique, difficult biochemical treatment, the present invention are not necessarily to wastewater preprocessing process, can directly by
The waste water neutralize, generated in washing step is recycled after merging and is covered for washing step next time, and does not influence product quality.
The present invention handles the method for generating waste water in DINCH esterification process technique and carries out as follows:
(1) will the washing water that generated in the neutralization water and washing step that are generated in neutralization step merge after filter, obtain water phase and
Filter residue 1；
(2) organic solvent is added in filtering out water phase and carries out air-distillation, the water phase set steamed is for washing step next time；
(3) distillation kettle liquid is filtered, obtains liquid phase and filter residue 2, the liquid phase filtered out is as the organic solvent distilled next time
It is applied, the filter residue 2 and filter residue 1 filtered out is handled after merging as solid waste high temperature incineration.
In the step (1), the COD value of waste water is 40000~60000 mg/ after neutralization waste water and washing waste water merging
L, BOD5Value is 10000~12000 mg/L.
In the step (2), organic solvent, organic solvent N, N '-dimethyl formamide, second need to be added in when distillation
Alcohol, isononyl alcohol, acetone, Benzene Chloride it is therein any one, or be made of wherein any two kinds of mixing, the body of two kinds of solvents
Product is than being 1:3~8.
In the step (2), when distillation the additive amount of organic solvent be washing water, neutralize water gross mass 20%~
50%。。
In the step (3), the control of kettle liquid temperature is filtered after being cooled to room temperature between 88~220 DEG C when distillation.
Compared with Fenton oxidation method, the invention has the following advantages that (1) present invention is not necessarily to Wastewater Pretreatment process, it can be straight
The waste water generated in processing reaction process is connect, including neutralizes water and washing water；(2) water phase that the present invention distills out can all cover
For washing step, so that entire DINCH esterification technique does not generate waste water, a small amount of solid waste is only generated, it can high temperature incineration processing；
(3) present invention is without being added Fenton reagent hydrogen peroxide, catalyst ferrous salt etc., it is only necessary to be added in distillation process organic molten
Agent, and organic solvent to reduce reagent cost, and can will not be generated iron cement, be reduced processing difficulty with recovery；
(4) process procedures such as filtering, distillation are relatively simple, carry out condition optimizings without carrying out a large amount of orthogonal tests, operation difficulty is low.
Detailed description of the invention
Fig. 1 is the process flow chart that waste water is generated in embodiment processing plasticizer DINCH esterification process technique.
Specific embodiment
Following embodiment, which is handled, generates the technique of waste water referring to attached drawing 1 in plasticizer DINCH esterification process technique.
Embodiment 1
The neutralization water generated during esterification process synthesis DINCH and washing water are merged and are added in beaker, totally 196.5 g, through examining
It surveys, COD value of waste water is 47200 mg/L, BOD5Value is 11328 mg/ L.Filtered wastewater obtains 8.9 g of filter residue, filters out water
182.1 g.Water will be filtered out to pour into four-hole boiling flask, be added the N that volume ratio is 1:3, N '-dimethyl formamide and isononyl alcohol it is mixed
60 g of solution, air-distillation are closed, until kettle temperature stops when being 180 DEG C.Kettle liquid is cooled to room temperature filtering, obtains 13.8 g of filter residue, filtrate
150.2 g.Make high temperature incineration processing after filtering the filter residue mixing of generation twice.The water phase set distilled out is used for washing step,
The content of gained DINCH product is 99.1%.
Embodiment 2
The neutralization water generated during esterification process synthesis DINCH and washing water are merged and are added in beaker, totally 200.3 g, through examining
It surveys, COD value of waste water is 42481 mg/L, BOD5Value is 10622 mg/ L.Filtered wastewater obtains 10.2 g of filter residue, filters out water
184.5 g.Water will be filtered out to pour into four-hole boiling flask, 70 g of mixed solution of ethyl alcohol and isononyl alcohol that volume ratio is 1:5 is added, often
Pressure distillation, until kettle temperature stops when being 140 DEG C.Kettle liquid is cooled to room temperature filtering, obtains 12.9 g of filter residue, 149.6 g of filtrate.It crosses twice
Make high temperature incineration processing after the filter residue mixing that filter generates.The water phase set distilled out is used for washing step, gained DINCH product
Content is 99.2%.
Embodiment 3
The neutralization water generated during esterification process synthesis DINCH and washing water are merged and are added in beaker, totally 198.7 g, through examining
It surveys, COD value of waste water is 51922 mg/L, BOD5Value is 11423 mg/ L.Filtered wastewater obtains 9.4 g of filter residue, filters out water
185.1 g.Water will be filtered out to pour into four-hole boiling flask, 65 g of mixed solution of acetone and isononyl alcohol that volume ratio is 1:4 is added, often
Pressure distillation, until kettle temperature stops when being 120 DEG C.Kettle liquid is cooled to room temperature filtering, obtains 13.2 g of filter residue, 151.4 g of filtrate.It crosses twice
Make high temperature incineration processing after the filter residue mixing that filter generates.The water phase set distilled out is used for washing step, gained DINCH product
Content is 99.4%.
Protection scope of the present invention is not limited only to above embodiments, mention on all claims and this field
The deformation that technical staff can be extrapolated to is in protection scope.
Claims (5)
1. the processing method of waste water in a kind of plasticizer DINCH esterification process technique, it is characterised in that it is not necessarily to Wastewater Pretreatment process,
It recycles and covers after directly the waste water for neutralizing, generating in washing step is merged and be used for washing step next time, processing method packet
It includes following steps: (1) filtering, obtain after merging the washing water generated in the neutralization water and washing step that generate in neutralization step
Water phase and filter residue 1；(2) organic solvent is added in filtering out water phase and carries out air-distillation, the water phase set steamed is for water next time
Wash process；(3) distillation kettle liquid is filtered, obtains liquid phase and filter residue 2, the liquid phase filtered out is organic molten as what is distilled next time
Agent is applied, and the filter residue 2 and filter residue 1 filtered out is handled after merging as solid waste high temperature incineration.
2. according to the method described in claim 1, it is characterized in that the COD value for neutralizing waste water after waste water and washing waste water merging is
40000~60000 mg/L, BOD5Value is 10000~12000 mg/L.
3. according to the method described in claim 1, the organic solvent being added when it is characterized in that distilling is N, N '-dimethyl formyl
Amine, ethyl alcohol, isononyl alcohol, acetone, Benzene Chloride it is therein any one, or be made of wherein any two kinds of mixing, two kinds are molten
The volume ratio of agent is 1:3~8.
4. according to the method described in claim 1, it is characterized in that the additive amount of organic solvent is washing water, neutralizes water gross mass
20%~50%.
5. according to the method described in claim 1, it is characterized in that distillation when kettle liquid temperature control between 88~220 DEG C, it is cold
But to filtering after room temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5834003A (en) * | 1981-08-21 | 1983-02-28 | Asahi Chem Ind Co Ltd | Recovery of oil and fat |
| CN103086547A (en) * | 2013-02-28 | 2013-05-08 | 常州大学 | Dioctyl phthalate wastewater treatment method |
| CN106256785A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | One-step synthesis N-phenylmaleimide technique middle and high concentration, the processing method of highly acidity waste water |
-
2017
- 2017-10-09 CN CN201710929779.9A patent/CN109626683A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5834003A (en) * | 1981-08-21 | 1983-02-28 | Asahi Chem Ind Co Ltd | Recovery of oil and fat |
| CN103086547A (en) * | 2013-02-28 | 2013-05-08 | 常州大学 | Dioctyl phthalate wastewater treatment method |
| CN106256785A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | One-step synthesis N-phenylmaleimide technique middle and high concentration, the processing method of highly acidity waste water |
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