CN106698783B - A kind for the treatment of process of epoxy grease plasticizer production waste water - Google Patents

A kind for the treatment of process of epoxy grease plasticizer production waste water Download PDF

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Publication number
CN106698783B
CN106698783B CN201610995977.0A CN201610995977A CN106698783B CN 106698783 B CN106698783 B CN 106698783B CN 201610995977 A CN201610995977 A CN 201610995977A CN 106698783 B CN106698783 B CN 106698783B
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waste water
treatment
epoxy
production waste
plasticizer production
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CN106698783A (en
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聂勇
吴振宇
吴利航
卢美贞
解庆龙
夏凡
计建炳
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Zhejiang University of Technology ZJUT
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41Preparation of salts of carboxylic acids
    • C07C51/412Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00Solid fuels
    • C10L5/40Solid fuels essentially based on materials of non-mineral origin
    • C10L5/46Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/043Details
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/16Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/16Regeneration of sorbents, filters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The present invention relates to a kind for the treatment of process of epoxy grease plasticizer production waste water, it mainly includes neutralization, heat pump distillation, evaporative crystallization and activated carbon adsorption and four parts of regeneration.Waste water is in neutrality after neutralizing with hydroxide, and for neutral waste water by concentrate after heat pump distillation, concentrated liquid obtains high boiling organic matter and formates through evaporative crystallization after centrifugation;Waste water qualified discharge after activated carbon adsorption is handled is steamed, the active carbon of adsorption saturation passes through heating, vacuum desorption and regeneration.The beneficial effects of the present invention are: 1) produce formates using the formic acid in the technique recoverable wastewater, the waste of resource is reduced;2) method associated with heat pump distillation and activated carbon adsorption can be used for handling the waste water that the very wide grease epoxidation process of COD range generates, adaptable;3) a small amount of low boiling organic matter is contained only in waste water after distilling, so that regenerating active carbon is simple, not easy in inactivation.

Description

A kind for the treatment of process of epoxy grease plasticizer production waste water
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of efficient, low energy consumption epoxy grease plasticizer is raw Produce the treatment process of waste water.
Background technique
Epoxy grease plasticizer has nontoxic, thermal stability as a kind of novel, environmental-friendly green plasticization agent Well, the advantages that intermiscibility is good, volatility is low, migration is small, substitution phthalic ester plasticizer are widely used as polyvinyl chloride (PVC) nontoxic plasticizer.The epoxy grease plasticizer industrially produced, such as epoxidized soybean oil, epoxy aliphatic acid methyl ester, Chang Cai Epoxy grease plasticizer is produced with formic acid technique: grease, hydrogen peroxide and formic acid reaction;Obtained crude product is reacted through alkali cleaning, water It washes and is dehydrated and obtain plasticizer product.Entire production process can generate the waste water containing formic acid, hydrogen peroxide and other organic matters, COD concentration is high, and processing difficulty is big.
Epoxy grease plasticizer produces waste water in acidity, and main acidic materials are formic acid, and quality percentage contains formic acid in water Amount is that 0.5%-6% is differed, and as the extension of waste water standing time, formic acid content can further decrease, main cause is useless There are hydrogen peroxide in water, and hydrogen peroxide can generate peroxyformic acid with formic acid reaction, and unstable peroxyformic acid can be decomposed into dioxy Change the substances such as carbon, water, oxygen.
Chinese patent CN 1793103A proposes to recycle the method that formic acid produces calcium formate from epoxy soybean oil waste water: ring Oxygen waste water reacts after inclined plate grease slot removes oil droplet and sediment with powdered whiting, adjusts PH using calcium hydroxide, uses Na2S removes removing heavy metals, with precipitating and filtering removal solid impurity is centrifuged and obtains product first after drying filtrate evaporative crystallization Sour calcium.
Chinese patent CN 101200423A proposes epoxy ester wastewater recycling treatment method: will be in epoxy ester production process Waste water obtains calcium formate solution after oil removal is handled, with calcium carbonate reaction.After being precipitated and further repeatedly being neutralized with calcium carbonate, By the dosing coagulant into solution and precipitating reagent, heavy metal and solid impurity are further removed, using filter, decoloration, steaming Hair and drying, obtain formic acid calcium powder.
Chinese patent CN 103772184A proposes a kind of to utilize the method containing formic acid wastewater: will contain formic acid wastewater and subtract Pressure distillation obtains steam containing formic acid and vapor gaseous mixture, and the gaseous mixture of formic acid vapor and vapor is passed directly into containing carbonic acid The slurry liquid contacts of calcium produce calcium formate.
Above-mentioned patent realizes the recycling to formic acid in epoxy wastewater, but neutralized reaction and evaporation are obtained Waste water how to handle and not refer to, this kind of waste water is handled using traditional biological method, foul gas can be generated simultaneously and sludge is solid It is useless, bring secondary pollution problems.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of efficient, low energy consumption rings The treatment process of oxygen grease plasticizer production waste water.
A kind for the treatment of process of epoxy grease plasticizer production waste water, including neutralization, heat pump distillation, evaporation knot Brilliant, activated carbon adsorption and regeneration, it is characterised in that including following treatment process:
1) waste water is neutralized with hydroxide;
2) waste water after neutralization is subjected to heat pump distillation, system absolute pressure contains low boiling point in 0.8-0.9 bar, removing The moisture of organic matter, obtains formates concentrate, the low-boiling-point organic compound in epoxy aliphatic acid methyl ester production waste water include methanol, Ethyl alcohol, propylene oxide etc., low-boiling-point organic compound are sold through further separation as product;
3) the formates concentrate that step 2 obtains is evaporated crystallization, system pressure is normal pressure, evaporates kettle liquid temperature Control steams moisture between 100-110 DEG C, and residue is crystallized, byproduct formic acid salt is obtained after centrifugation and oiliness is high boiling has Machine object, the high boiling organic matter of oiliness carry out burning processing as fuel;
4) moisture that evaporation and crystal process steams in moisture obtained in step 2 and step 3) is squeezed into activated carbon adsorption Bed is adsorbed, and is discharged again after reaching discharge standard;
5) after the activated carbon adsorption saturation in step 4), the heated vacuum desorption regeneration of active carbon bed, regenerating active carbon After reuse.
The treatment process of a kind of epoxy grease plasticizer production waste water, it is characterised in that hydroxide is hydroxide Sodium or calcium hydroxide, formates are sodium formate or calcium formate.
The treatment process of a kind of epoxy grease plasticizer production waste water, it is characterised in that in the waste water warp of step 1) It is in neutrality with after processing.
The treatment process of a kind of epoxy grease plasticizer production waste water, it is characterised in that the waste water of step 1) is ring Oxygen soybean oil or epoxy aliphatic acid methyl ester produce generated waste water.
The treatment process of a kind of epoxy grease plasticizer production waste water, it is characterised in that crystallize in step 3) with molten Agent is methanol.
The treatment process of a kind of epoxy grease plasticizer production waste water, it is characterised in that the oiliness of step 3) is high boiling Organic matter includes C3-C10Alcohol compound, C3-C10Ketone and C3-C10Cyclic compound.
A kind for the treatment of process of the epoxy grease plasticizer production waste water, it is characterised in that in step 5), control volume It is that pressure is less than 50kPa, temperature is between 50-120 DEG C
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
1) present invention produces formates by the formic acid that can be recycled in epoxy grease plasticizer production waste water using the technique, Reduce the waste of resource;
2) present invention by using method associated with heat pump distillation and activated carbon adsorption adapt to processing COD range it is very wide The waste water that grease epoxidation process generates, it is adaptable;
3) a small amount of low boiling organic matter is contained only in waste water after present invention distillation, so that regenerating active carbon is simple, not easy in inactivation, then Active carbon after life can reuse, and reduce costs, improve economic benefit.
Detailed description of the invention
Fig. 1 is technical process schematic diagram of the invention.
Specific embodiment
Below in conjunction with Figure of description and embodiment, the present invention will be described in detail:
As shown in Figure 1, a kind for the treatment of process of epoxy grease plasticizer production waste water of the invention, including neutralize, heat pump Distillation, evaporative crystallization, activated carbon adsorption and regeneration, it is characterised in that including following treatment process:
1) waste water is neutralized with hydroxide;
2) waste water after neutralization is subjected to heat pump distillation, system absolute pressure has in 0.8-0.9 bar, removing containing low boiling The moisture of machine object obtains formates concentrate;
3) the formates concentrate that step 2 obtains is evaporated crystallization, system pressure is normal pressure, evaporates kettle liquid temperature Control steams moisture between 100-110 DEG C, and residue is crystallized, byproduct formic acid salt is obtained after centrifugation and oiliness is high boiling has Machine object, the high boiling organic matter of oiliness carry out burning processing as fuel;
4) moisture that evaporation and crystal process steams in moisture obtained in step 2 and step 3) is squeezed into activated carbon adsorption Bed is adsorbed, and is discharged again after reaching discharge standard;
5) after the activated carbon adsorption saturation in step 4), the heated vacuum desorption regeneration of active carbon bed, control system pressure Less than 50 kPa, temperature reuses after regenerating active carbon power between 50-120 DEG C.
Embodiment 1:
1t epoxy methyl esters waste water (≈ containing formic acid 1.3%, COD=25000) and 0.014t solid NaOH are neutralized, are given up after neutralization Water (PH ≈ 7) enters heat pump distillation system, and system pressure is 0.9 bar, 96 DEG C of temperature, steams waste water (COD=1780) and enters work Property charcoal adsorption bed, flow out active carbon bed waste water (COD=45, COD less than 50) enter general pipeline discharge, heat pump distillation system In concentrate (sodium formate mass fraction is about 40%) enter atmospheric evaporation crystalline portion, crystallization temperature be 102 DEG C, steam A small amount of water steams waste water with heat pump distillation and mixes, and obtains sodium formate solid and the high boiling organic matter of oiliness in bottom, is centrifugated out Sodium formate, the high boiling organic matter of oiliness is mainly C3-C10Alcohols, ketone and cyclic compound, can be used as fuel combustion processing, it is living After property charcoal adsorption saturation, active carbon bed is heated to 100 DEG C, and vacuumize, the low boiling for being adsorbed on activated carbon surface is desorbed out Organic matter and partial moisture, the organic matter main component being desorbed out are methanol, ethyl alcohol, propylene oxide etc., are further separated work For product sale.
Embodiment 2:
By 1t epoxy methyl esters waste water (≈ containing formic acid 1.3%, COD=25000) and 0.011t solid Ca (OH)2It neutralizes, neutralizes Afterwards waste water (PH ≈ 7) enter heat pump distillation system, system pressure be 0.9 bar, 96 DEG C of temperature, steam waste water (COD=1860) into Enter activated carbon adsorption bed, flow out active carbon bed waste water (COD=42, COD less than 50) enter general pipeline discharge.Heat pump distillation Concentrate (calcium formate mass fraction is about 13%) in system enters atmospheric evaporation crystalline portion, and crystallization temperature is 102 DEG C, steams A small amount of water out steams waste water with heat pump distillation and mixes, and obtains calcium formate solid and the high boiling organic matter of oiliness, centrifugation point in bottom Separate out calcium formate.Later separation is the same as embodiment 1.
Embodiment 3:
By 1t epoxidized soybean oil production waste water (≈ containing formic acid 3.5%, COD=56000) and 0.031t solid Ca (OH)2In With, after neutralization waste water (PH ≈ 7) enter heat pump distillation system, system pressure be 0.9 bar, 96 DEG C of temperature, steam waste water (COD= 2350) enter activated carbon adsorption bed, flow out active carbon bed waste water (COD=47, COD less than 50) enter general pipeline discharge.Heat The concentrate (calcium formate mass fraction is about 13%) pumped in Distallation systm enters atmospheric evaporation crystalline portion, crystallization temperature 102 DEG C, a small amount of water steamed steams waste water with heat pump distillation and mixes, calcium formate solid and the high boiling organic matter of oiliness are obtained in bottom, from The heart isolates calcium formate.Later separation is the same as embodiment 1.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape At technical solution, fall within the scope of protection required by the present invention.

Claims (6)

1. a kind for the treatment of process of epoxy grease plasticizer production waste water, including neutralization, heat pump distillation, evaporative crystallization, active carbon Absorption and regeneration, it is characterised in that including following treatment process:
1) waste water is neutralized with hydroxide;
2) waste water after neutralization is subjected to heat pump distillation, system absolute pressure removes organic containing low boiling point in 0.8-0.9 bar The moisture of object obtains formates concentrate;
3) the formates concentrate that step 2 obtains is evaporated crystallization, system pressure is normal pressure, evaporation kettle liquid temperature control Between 100-110 DEG C, moisture is steamed, residue is crystallized, obtains byproduct formic acid salt and the high boiling organic matter of oiliness after centrifugation, The high boiling organic matter of oiliness carries out burning processing as fuel;The high boiling organic matter of oiliness includes C3-C10Alcohol compound, C3-C10Ketone and C3-C10Cyclic compound;
4) by the moisture that evaporation and crystal process steams in moisture obtained in step 2 and step 3) squeeze into activated carbon adsorption bed into Row absorption, is discharged again after reaching discharge standard;
5) after the activated carbon adsorption saturation in step 4), the heated vacuum desorption of active carbon bed regenerates, weight after regenerating active carbon It is multiple to utilize.
2. a kind for the treatment of process of epoxy grease plasticizer production waste water according to claim 1, it is characterised in that hydrogen-oxygen Compound is sodium hydroxide or calcium hydroxide, and formates is sodium formate or calcium formate.
3. a kind for the treatment of process of epoxy grease plasticizer production waste water according to claim 1, it is characterised in that step 1) it is in neutrality after the neutralized processing of waste water.
4. a kind for the treatment of process of epoxy grease plasticizer production waste water according to claim 1, it is characterised in that step 1) waste water is that epoxidized soybean oil or epoxy aliphatic acid methyl ester produce generated waste water.
5. a kind for the treatment of process of epoxy grease plasticizer production waste water according to claim 1, it is characterised in that step 3) crystallization solvent is methanol in.
6. a kind for the treatment of process of epoxy grease plasticizer production waste water according to claim 1, it is characterised in that step 5) in, control system pressure is less than 50kPa, and temperature is between 50-120 DEG C.
CN201610995977.0A 2016-11-12 2016-11-12 A kind for the treatment of process of epoxy grease plasticizer production waste water Active CN106698783B (en)

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CN107572629A (en) * 2017-09-28 2018-01-12 刘秀芬 A kind of sewage-treatment plant
CN111995194A (en) * 2020-09-09 2020-11-27 福建中盟环保科技有限公司 System for recovering heat of biochemical treatment garbage leachate

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JP2949357B2 (en) * 1990-04-10 1999-09-13 コニカ株式会社 Method and apparatus for evaporative concentration of photographic processing waste liquid
CN103360231A (en) * 2012-03-28 2013-10-23 江苏卡特新能源有限公司 Method for extracting formic acid from sewage from production of epoxy biological plasticizer
CN203724981U (en) * 2014-03-17 2014-07-23 苏州物宝天吉节能环保科技有限公司 Activated carbon adsorption system for methanol waste gas
CN103933826B (en) * 2014-04-21 2016-02-24 太仓塑料助剂厂有限公司 A kind of processing method of cumyl peroxide process gas
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