CN108892222A - A kind for the treatment of method and apparatus of the waste water generated when producing epoxy chloropropane through glycerine method - Google Patents
A kind for the treatment of method and apparatus of the waste water generated when producing epoxy chloropropane through glycerine method Download PDFInfo
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- CN108892222A CN108892222A CN201810860062.8A CN201810860062A CN108892222A CN 108892222 A CN108892222 A CN 108892222A CN 201810860062 A CN201810860062 A CN 201810860062A CN 108892222 A CN108892222 A CN 108892222A
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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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
- 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
- C02F1/66—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
- 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
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Abstract
The present invention provides a kind for the treatment of method and apparatus of the waste water generated when producing epoxy chloropropane through glycerine method, the processing method of the waste water includes pretreatment, catalysis oxidation, recycles catalyst.Wastewater treatment method provided by the present invention is suitable for the high organic wastewater of salt content, process flow is easy, easy to operate, high degree of automation, environmental-friendly, without secondary pollution, TOC removal rate reaches 99% or more in high salt organic waste water, and the direct emission of wastewater treatment may be implemented.
Description
Technical field
The present invention relates to technical field of waste water processing, produce when in particular to a kind of producing epoxy chloropropane through glycerine method
The treating method and apparatus of raw waste water.
Background technique
Epoxychloropropane (i.e. ECH) is a kind of important Organic Chemicals and fine chemical product, and purposes is very extensive.
A large amount of waste water is discharged in epoxychloropropane production process, this waste water is mainly derived from cyclisation tower reactor discharge
Raffinate.This waste water mainly contain the stronger organic chloride of the toxicity such as epoxychloropropane, dichlorohydrin, glycerol, glycidol,
The generality inorganic matters such as organic matter and sodium hydroxide (calcium), sodium chloride (calcium) such as polyglycereol, therefore be a kind of typical with high salt
Organic wastewater.
For wastewater biochemical processing for, high salt organic waste water refer to containing at least 3.5% total dissolved solidss object (TDS) with
And the waste water of high-enriched organics.Not only contain a large amount of organic matter in these waste water, also contains such as Cl-、SO4 2+、Na+、Ca2 +、Mg2+Etc. a large amount of inorganic salts zwitterions, these inorganic ions are able to suppress the growth metabolism of microorganism, so that standard biologic
The treatment effeciency of processing method is substantially reduced.
Epoxychloropropane technique waste water has the characteristics that water is big, salinity is high, and independent processing difficulty is very big, and Shandong seaization is public
Department undergoes technological transformation to original producing epoxy chloropropane by propylene high temperature chlorination technique, chlorohydrin action and saponification it
Between increase complexometric extraction, improve the salt content in reaction solution, reduce additional issue energy consumption, still, the technology is not in saponification liquor
Organic matter carry out harmless treatment, organic matter only in a disguised form be transferred in Nacl, will lead under Nacl quality in this way
Drop.
The patent document of 105271597 A of Publication No. CN discloses a kind of epoxychloropropane producing wastewater treatment,
By light electrolysis, deep oxidation, flocculation sedimentation, absorption retardance, the kinds of processes technology such as UF membrane, to epoxychloropropane waste water into
Capable targetedly online processing, obtains certain effect, but the processing method process flow is long, cumbersome, and there are adsorbents
And the frequent regenerations such as active carbon, heavy workload are uneconomical.
The patent document of 105621764 A of Publication No. CN discloses a kind of processing work of epoxychloropropane production waste water
Skill passes through wet oxidation, ultraviolet-H2O2Mineralization of organic material in waste water is achieved certain effect by oxidation, but the processing side
In method, the solid slag of wet oxidation separation cannot be utilized effectively, as fixed-end forces, secondary pollution be caused, in combination with purple
- H outside2O2Oxidation, processing cost is high, increases enterprise operation pressure.
The patent document of 106745927 A of Publication No. CN is related to a kind of integrated treatment of epoxychloropropane production waste water
Then method, the processing method utilize sanitary sewage or salt-free industrial wastewater using the calcium ion in sulfuric acid precipitation waste water
It is diluted, then carries out biochemical treatment.The processing method generates a large amount of calcium precipitation, causes solid slag, and salt water is still after precipitating
Fresh water dilution is needed just to can be carried out biochemical treatment, epoxychloropropane waste water higher for salinity is not applicable.
The patent document of 103342434 B of Publication No. CN, a kind of cyclization in glycerol method epoxy chloropropane production method
Hydrolysis, advanced oxidation or wet type oxygen including organic high-salinity wastewater are described in the wastewater produced processing method of step
Change, be concentrated and dried and etc. method, preferably solve the quality problem of by-product industrial calcium chloride, but this method uses
Advanced oxidation or Wet Oxidation Process are actually to utilize Fenton catalyst, and there are a large amount of solid waste Fenton iron mud, processing
It is at high cost.
To sum up, there is many defects for the prior art.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of processing side of the waste water generated when producing epoxy chloropropane through glycerine method
Method, the method are suitble to high salt organic waste water, have that process flow is easy, easy to operate, high degree of automation, environmental-friendly
The advantages that, it can be achieved that the direct emission of high salt organic waste water generated in the production of glycerol method epoxychloropropane.
The second object of the present invention is the waste water generated when providing producing epoxy chloropropane through glycerine method described in one kind
Apparatus system.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of processing method of the waste water generated when producing epoxy chloropropane through glycerine method, includes the following steps：
Wastewater pH=1-4 is adjusted, then under the conditions of catalyst and oxygen-containing gas, carries out catalytic oxidation treatment, recycling is urged
After agent, the water for capableing of direct emission is obtained；
Preferably, the TOC of the water for capableing of direct emission is less than 30mg/L.
Preferably, the temperature of the catalysis oxidation is 190~280 DEG C, and pressure is 3~7MPa；It is furthermore preferred that the catalysis
The temperature of oxidation is 200~270 DEG C, and pressure is 4~6MPa；Still more preferably, the temperature of the catalysis oxidation be 220~
260 DEG C, pressure is 4.5~5.5MPa.
Preferably, the time of the catalysis oxidation is 2~6h；More preferably 2.5~5.5h is still more preferably
3.0~5.0h.
Preferably, it is 20%~30% and/or Ca (OH) that the waste water, which is the mass concentration of calcium chloride or sodium chloride,2Matter
Measure the waste water that concentration is 0.2%~0.5% and/or the mass concentration of NaOH is 0.05%~0.1%.
Preferably, the catalyst is soluble zinc salt, it is furthermore preferred that the catalyst is selected from zinc chloride, zinc sulfate, phosphorus
One of sour zinc, zinc dihydrogen phosphate, zinc tartrate, zinc pyrophosphate or several combinations；It is furthermore preferred that the catalyst
Dosage is the 0.2%~1.0% of waste water weight.
Preferably, the oxygen-containing gas is selected from one of air or industrial pure oxygen or two kinds.
Preferably, the TOC of the waste water is 2000~6000mg/L.
Preferably, pH=8~10 of the waste water.
Preferably, the process of the recycling catalyst, specifically includes following steps：
The pH of waste water after adjusting catalytic oxidation treatment is adjusted to neutrality, and is then separated by solid-liquid separation, and it is solid to obtain catalyst
Mutually obtained with the water phase containing catalyst-solvent, the water phase containing catalyst-solvent by cation exchange resin and chelating resin
To the water for capableing of direct emission.
A kind of device of the waste water generated when producing epoxy chloropropane through glycerine method, including sequentially connected pretreatment system,
Catalytic oxidation system and catalyst recovery system；
The pretreatment system, including sequentially connected pretreatment adjuster, discharge pump, millipore filter and the first storage
Tank；
Preferably, the pretreatment adjuster is also connected with waste pipe and hydrochloric acid pipeline；
Preferably, the pretreatment adjuster is connected with the discharge pump by adjuster drainage line；
Preferably, the discharge pump is connected with the millipore filter by filter feed pipe；
Preferably, the millipore filter is connected with first storage tank by filter discharge pipeline；
Preferably, first storage tank includes the first storage tank drainage line and catalyst channels；
Preferably, the first storage tank drainage line is connected with the catalytic oxidation system by storage tank drainage line；
The catalytic oxidation system, including it is sequentially connected high-pressure pump, heat exchanger, heater, oxidizing tower, heat exchanger, cold
But device and the second storage tank；
Preferably, the oxidizing tower further includes：Oxidizing tower feed pipe, oxidizing tower admission line, oxidizing tower drainage line
With exhaust gas drainage line；
Preferably, the heater is connected with the oxidizing tower by oxidizing tower feed pipe；
Preferably, the oxidizing tower is logical is connected with the heat exchanger by oxidizing tower drainage line；
Preferably, second storage tank further includes the second storage tank drainage line of the second storage tank feed pipe and bottom,
Described in the second storage tank feed pipe be connected with the heat exchanger, the second storage tank drainage line and the catalyst recycling be
System is connected；
The catalyst recovery system includes that sequentially connected pH adjusts tank, sludge dewatering equipment, water conveying pump, the first tree
Rouge tower and the second resin tower；
It includes adjusting tank feed pipe and lye feed pipe that the pH, which adjusts tank, the adjusting tank feed pipe with it is described
Second storage tank drainage line is connected；
The sludge dewatering equipment includes solid phase discharge line and water phase discharge line, and the solid phase discharge line is urged with described
Agent pipeline is connected；
The water phase discharge line is connected with concatenated first resin tower and the second resin tower.
Compared with prior art, beneficial effects of the present invention are：Method provided by the present invention have process flow it is easy,
Easy to operate, high degree of automation, advantages of environment protection are, it can be achieved that is generated in the production of glycerol method epoxychloropropane with high salt has
The direct emission of machine waste water.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the schematic device of pretreatment system in the embodiment of the present invention；
Fig. 2 is the schematic device of catalytic oxidation system in the embodiment of the present invention；
Fig. 3 is the schematic device of catalyst recovery system in the embodiment of the present invention.
Detailed description of the invention：
1- pre-processes adjuster；11- waste pipe；12- hydrochloric acid pipeline；13- adjuster drainage line；2- adjuster discharge
Pump；3- millipore filter；31- filter feed pipe；32- filter discharge pipeline；The first storage tank of 4-；41- process fluid；
42- the first storage tank drainage line；5- high-pressure pump, 6- heat exchanger；7- heater；8- oxidizing tower；81- oxidizing tower feed pipe；82-
Oxidizing tower admission line；83- oxidizing tower drainage line；84- exhaust gas drainage line；9- cooler；The second storage tank of 10-；101-
Two storage tank feed pipes；102- the second storage tank drainage line；11-pH adjusts tank；111- adjusts tank feed pipe；112- lye into
Pipe material；12- sludge dewatering equipment；121- solid phase discharge line；122- water phase discharge line；13- water conveying pump；14- first
Resin tower；The second resin tower of 15-.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of processing method of the waste water generated when producing epoxy chloropropane through glycerine method, includes the following steps：
Wastewater pH=1-4 is adjusted, then under the conditions of catalyst and oxygen-containing gas, carries out catalytic oxidation treatment, recycling is urged
After agent, the water for capableing of direct emission is obtained；
Preferably, the TOC of the water for capableing of direct emission is less than 30mg/L.
Preferably, the temperature of the catalysis oxidation is 190~280 DEG C, and pressure is 3.0~7.0MPa；It is furthermore preferred that described
The temperature of catalysis oxidation is 200~270 DEG C, and pressure is 4.0~6.0MPa；Still more preferably, the temperature of the catalysis oxidation
Degree is 220~260 DEG C, and pressure is 4.5~5.5MPa.
Preferably, the time of the catalysis oxidation is 2~6h；More preferably 2.5~5.5h is still more preferably
3.0~5.0h.
Preferably, it is 20%~30% or Ca (OH) that the waste water, which is the mass concentration of calcium chloride or sodium chloride,2Matter
Measure the waste water that concentration is 0.2%~0.5% or the mass concentration of NaOH is 0.05%~0.1%.
Preferably, the catalyst is soluble zinc salt, it is furthermore preferred that the catalyst is selected from zinc chloride, zinc sulfate, phosphorus
One of sour zinc, zinc dihydrogen phosphate, zinc tartrate, zinc pyrophosphate or several combinations；It is furthermore preferred that the catalyst
Dosage is the 0.2%~1.0% of waste water weight.
Preferably, the oxygen-containing gas is selected from one of air or industrial pure oxygen or two kinds.
Preferably, the TOC of the waste water is 2000~6000mg/L.
Preferably, pH=8~10 of the waste water.
Preferably, the process of the recycling catalyst, specifically includes following steps：
The pH of waste water after adjusting catalytic oxidation treatment is adjusted to neutrality, and is then separated by solid-liquid separation, and it is solid to obtain catalyst
Mutually obtained with the water phase containing catalyst-solvent, the water phase containing catalyst-solvent by cation exchange resin and chelating resin
To the water for capableing of direct emission.
A kind of device of the waste water generated when producing epoxy chloropropane through glycerine method, including sequentially connected pretreatment system,
Catalytic oxidation system and catalyst recovery system；
The pretreatment system, including sequentially connected pretreatment adjuster, discharge pump, millipore filter and the first storage
Tank；
Preferably, the pretreatment adjuster is also connected with waste pipe and hydrochloric acid pipeline；
Preferably, the pretreatment adjuster is connected with the discharge pump by adjuster drainage line；
Preferably, the discharge pump is connected with the millipore filter by filter feed pipe；
Preferably, the millipore filter is connected with first storage tank by filter discharge pipeline；
Preferably, first storage tank includes the first storage tank drainage line and catalyst channels；
Preferably, the first storage tank drainage line is connected with the catalytic oxidation system by storage tank drainage line；
The catalytic oxidation system, including it is sequentially connected high-pressure pump, heat exchanger, heater, oxidizing tower, heat exchanger, cold
But device and the second storage tank；
Preferably, the oxidizing tower further includes：Oxidizing tower feed pipe, oxidizing tower admission line, oxidizing tower drainage line
With exhaust gas drainage line；
Preferably, the heater is connected with the oxidizing tower by oxidizing tower feed pipe；
Preferably, the oxidizing tower is logical is connected with the heat exchanger by oxidizing tower drainage line；
Preferably, second storage tank further includes the second storage tank drainage line of the second storage tank feed pipe and bottom,
Described in the second storage tank feed pipe be connected with the heat exchanger, the second storage tank drainage line and the catalyst recycling be
System is connected；
The catalyst recovery system includes that sequentially connected pH adjusts tank, sludge dewatering equipment, water conveying pump, the first tree
Rouge tower and the second resin tower；
It includes adjusting tank feed pipe and lye feed pipe that the pH, which adjusts tank, the adjusting tank feed pipe with it is described
Second storage tank drainage line is connected；
The sludge dewatering equipment includes solid phase discharge line and water phase discharge line, and the solid phase discharge line is urged with described
Agent pipeline is connected；
The water phase discharge line is connected with concatenated first resin tower and the second resin tower.
Specifically, the method for glycerol two-step method synthesizing epoxy chloropropane is in the presence of excess base by glycerol chloro-product
Dichlorohydrin dehydrochlorination and obtain epoxychloropropane, epoxychloropropane is stripped off out-of-bounds using water vapour.The alkali
Property condition is by Ca (OH)2Lotion or NaOH solution provide.The alkali that is participated in during dehydrochlorination and hydrogen chloride be neutralized into salt with
And the organic by-products that other side reactions generate, the epoxychloropropane not being stripped and the dichlorohydrin for also having neither part nor lot in reaction exist
Hydrolyzed under basic conditions is discharged from tower reactor together, obtains at glycerol, the salt, glycerol, other organic by-products, water and excess base
To the high salt organic waste water.For prior art situation, present invention mainly solves produce when producing epoxy chloropropane through glycerine method
Existing TOC problem when raw treatment of Organic Wastewater with high salt.
In the present invention, the high salt organic waste water be containing with the high salt organic waste water total weight 20%~
30%CaCl2Or NaCl, 0.2%~0.5%Ca (OH)2Or 0.05%~0.1%NaOH, TOC (total organic carbon) be 2000~
6000mg/L, pH 8~10.
Specific step is as follows for the processing method：
A, it pre-processes
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 1~4, is then led to by adjusting high salt organic waste water and hydrochloric acid flow
The adjuster drainage line 13 crossed positioned at pretreatment 1 bottom of adjuster is defeated through adjuster discharge pump 2 and filter feed pipe 31
It is sent to 3 top of millipore filter, is wherein being filtered to remove suspended particulate present in waste water, filtrate is by being located at millipore filter
The filter discharge pipeline 32 of 3 bottoms is sent to 4 top of the first storage tank, while catalyst is also sent to the first storage by process fluid 41
4 top of tank, filtrate carry out catalytic pretreatment in the first storage tank 4, and obtained pretreated waste water is by being located at 4 lower part of the first storage tank
First storage tank drainage line 42 is sent to subsequent processing steps processing.
In some preferred embodiments of the present invention, pretreatment adjuster 1 is a kind of adjusting appearance with electric mixer
Device, such as the product sold by Kodak chemical machinery Co., Ltd of Laizhou City with trade name reaction kettle.This electric mixer
Main function is so that hydrochloric acid pH adjusting agent is uniformly dispersed during adjusting wastewater pH, and make the water-insoluble in waste water in acidity
Under the conditions of be completely dissolved.
In the present invention, the pH of high salt organic waste water is adjusted to 1~4.If the pH adjusting of high salt organic waste water is higher than
4, then the water-insoluble in waste water is more, increases fixed-end forces cost；Therefore, it is proper that the pH of high salt organic waste water, which is adjusted to 1~4,
When.
In some preferred embodiments of the present invention, millipore filter 3 is a kind of filtering with miillpore filter or filter column
Container, such as the product that Shanghai Xi Yao environmental protection equipment Co., Ltd is sold with trade name millipore filter, the honest filtering of Haining City
The product that equipment Co., Ltd is sold with trade name microporous element filter.Its basic role is to separate adjusting the with high salt of pH
Suspended particulate present in waste water prevents from entering in subsequent oxidative system, leads to the foulings such as oxidizing tower, heat exchanger and blocking.
In some preferred embodiments of the present invention, filtrate basic object of catalytic pretreatment in the first storage tank 4 is to make
High salt organic waste water is dispersed with catalyst.
According to the present invention, the catalyst is soluble zinc salt, such as zinc chloride or zinc sulfate, they are all current cities
The product sold on field, for example, sold by Zouping County prosperous chemical plant of long mountain gold with trade name technical grade zinc chloride product, by south
The product that happy county Rui Xiangxin Trade Co., Ltd. is sold with trade name zinc sulfate.
In some preferred embodiments of the present invention, the dosage of the catalyst is 0.2~1.0% in terms of waste water weight.
If the dosage of the catalyst is lower than 0.2%, catalytic effect is bad, and water outlet is not achieved and requires；If the catalyst
Dosage is higher than 1.0%, then less, catalyst excess increases processing cost for catalytic effect variation；Therefore, the use of the catalyst
Amount is suitable for 0.2~1.0%.
In some preferred embodiments of the present invention, the high salt organic waste water be calcium chloride or sodium chloride concentration be with
Poidometer 20~30%, Ca (OH)2It is for by weight 0.05~0.1%, TOC for by weight 0.2~0.5% or NaOH
8~10 waste water of pH of 2000~6000mg/L.
B, catalysis oxidation
By the pretreated waste water from the first storage tank drainage line 42, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while oxygen-containing gas also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 190~280 DEG C of temperature is with 3.0~7.0MPa of pressure, pretreated waste water and oxygen-containing gas into
2~6h of row oxidation processes；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water
Steam is discharged by the exhaust gas drainage line 84 for being located at 8 top of oxidizing tower；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
Pretreated waste water and oxygen-containing gas from the second storage tank drainage line 42 are in 190~280 DEG C of temperature and pressure 3.0
2~6h of oxidation processes under conditions of~7.0MPa.When oxidation processes pressure and time are in the range, if at oxidation
It manages temperature and is lower than 190 DEG C, then the effect that pretreated waste water is oxidized is bad；If oxidation temperature is higher than 280 DEG C, aoxidize
Effect does not significantly improve, but energy consumption is excessive, uneconomical；Therefore, oxidation temperature be 190~280 DEG C be it is reasonable,
Preferably 200~270 DEG C, more preferably 220~260 DEG C.
Similarly, when oxidation temperature and time are in the range, if oxidation processes pressure is lower than
3.0MPa, then high-salt wastewater vaporizes at said temperatures；If oxidation processes pressure is higher than 7.0MPa, to the oxygen of high pressure waste water
It is little to change influential effect；Therefore, it is reasonable, preferably 4.0~6.0MPa that oxidation processes pressure, which is 3.0~7.0MPa, more
Preferably 4.5~5.5MPa.
When oxidation temperature and pressure are in the range, if oxidation treatment time is less than 2h, oxidation is anti-
It should be incomplete；If oxidation treatment time is longer than 6h, TOC removal rate is held essentially constant；Therefore, oxidation treatment time 2
~6h is suitable, preferably 2.5~5.5h, more preferably 3.0~5.0h.
Preferably, under conditions of 200~270 DEG C of temperature with 4.0~6.0MPa of pressure, pretreated waste water and oxygen-containing gas
Carry out 3~4h of oxidation processes.
The oxygen-containing gas that the present invention uses is air or industrial pure oxygen.
In some preferred embodiments of the present invention, heat exchanger 6, heater 7 and the cooler 9 used is all heat exchange
Device, such as the product sold by Wuxi big Yu Yunshenghua machine equipment Co., Ltd with trade name tubular heat exchanger, it is cold by Nanjing
The product that moral energy conservation Science and Technology Ltd. is sold with trade name tube side detachable heat exchanger.The effect of heat exchanger 6 is recycling oxidation
Heat in salt water afterwards needs the waste water into oxidative system using oxidation salt water as heat source heating, saves resource；Heater
7 effect is supplemental heat source, and high-salt wastewater temperature is made to reach required oxidizing reaction temperature, and the heating of heater 7 is by steam reality
Existing；The effect of cooler 9 is further to cool down the oxidation high-salt wastewater of heat exchange, lead it will not because of high temperature after pressure reduction
Cause flash distillation.
In some preferred embodiments of the present invention, the oxidizing tower 8 is a kind of oxidation reaction with empty tower structure
Tower, it is a kind of off-gauge pressure vessel, is easy for that the manufacturer of this kind of equipment can be found at home, as Shanghai East Asia is pressed
Force container Manufacturing Co., Ltd, Jiangsu Jin Nuo chemical equipment Co., Ltd, Shenyang Orient Titanium Industry Co., Ltd. etc..
Gas by being located at exhaust gas drainage line (84) discharge at 8 top of oxidizing tower is containing CO296%, moisture 0.8%,
Oxygen 1.0% and other 2.2% mixed gas.
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to progress two-stage absorption in the first resin tower 14 and the second resin tower 15 connected in a series arrangement, are discharged direct emission
Or for producing Nacl.
In some preferred embodiments of the present invention, the purpose that the pH of sewage oxidation treatment is adjusted to neutrality is to make catalyst
A kind of sediment is formed, is conducive to recycle.If sewage oxidation treatment is dissolved in solution in acidity, catalyst, recycling is difficult；If
Sewage oxidation treatment is in alkalinity, then the calcium ion in waste water can also precipitate together, increases dosage sour in pretreatment, uneconomical,
Therefore it is reasonable for adjusting sewage oxidation treatment to neutrality.
In some preferred embodiments of the present invention, sludge dewatering equipment 12 is set known to the engineers and technicians of this field
It is standby, it is current market sales of product, such as spiral shell formula sludge is folded with trade name by Dezhou Xin Dinghao Environmental Protection Technology Co., Ltd
The product of dewaterer sale folds the sale of spiral shell sludge thickening dehydrator by Yixing City Hai Cheng environmental protection equipment Co., Ltd with trade name
Product.
In some preferred embodiments of the present invention, the resin tower 14 and resin tower 15 used is a kind of filling ionic adsorption
The nonstandard non-pressure vessel of resin or chelating resin, be it is usually used in the art, for those skilled in the art of the present technique
For design and manufacture this container there is no hell and high water.
The resin that the present invention uses is current market sales of product, such as the resin loaded in the first resin tower 14
It is by the cation exchange resin of Shanghai Kai Ping resin Co., Ltd sale, the resin that is loaded in the second resin tower 15 is by day
The product that Jin Yunkai resin Science and Technology Ltd. is sold with trade name chelating resin.
According to the present invention, after the first resin tower 14 and the absorption of 15 two-stage of the second resin tower the TOC that is discharged be 30mg/L with
Under.
In some preferred embodiments of the present invention, TOC (total organic carbon english abbreviation) is to make catalyst with platinum in temperature
Make water sample oxidizing fire to be determined at 900 DEG C, measures CO in gas2Increment, so that it is determined that total phosphorus content in water sample, to indicate
Total amount of organic in water sample to be determined.It, can be by the organic matter in water sample to be determined since the measurement of TOC uses high-temp combustion
All oxidations, it more can directly indicate the total amount of organic matter than BOD or COD.
In the present invention, direct emission is according to GB31571-2015《Petro chemical industry pollutant emission standard》Middle table 1
Defined Sewage Water Emissions limit value executes, and direct emission is defined in the standard, i.e., pollutant discharging unit is directly to ring
The behavior of border discharge into water water pollutant, and the direct emission limit value of clear stipulaties epoxychloropropane waste water TOC is in table 1
30mg/L。
In the present invention, if the oxidation-treated waste water production Nacl up to direct emission standard be by multiple-effect evaporation,
What concentration and drying and other steps were realized.
Embodiment 1
The method handled provided by the present embodiment, specifically includes following steps：
A, it pre-processes
The high salt organic waste water of embodiment processing is that calcium chloride concentration is 20%, Ca (OH) by weight2For with weight
Meter 0.3%, 8.0 waste water of pH that TOC is 2000mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 4, then passes through position by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 in pretreatment 1 bottom of adjuster is transported to through adjuster discharge pump 2 and filter feed pipe 31
3 top of millipore filter is wherein being filtered to remove suspended particulate present in waste water, and filtrate is by being located at 3 bottom of millipore filter
The filter discharge pipeline 32 in portion is sent to the top of the first storage tank 4, while zinc chloride catalyst is also sent to the by process fluid 41
One storage tank, 4 top, the catalyst amount are 0.2% in terms of waste water weight, and filtrate carries out catalytic pretreatment in storage tank (4),
Obtained pretreated waste water is sent to subsequent processing steps processing by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while compressed air also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 200 DEG C of temperature with pressure 4.0MPa, pretreated waste water and compressed air carry out oxidation processes
6.0h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by being located at
The exhaust gas drainage line 84 at 8 top of oxidizing tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 is straight with progress two-stage absorption, water outlet in the second resin tower of chelating resin 15 by the sale of Tianjin Yun Kai resin Science and Technology Ltd.
Run in and puts or for producing Nacl.
The present embodiment also uses copper chloride and ferric chloride catalyst to carry out wastewater treatment test in parallel.
3100 instrument of the multi N/C item described in the instrument operation instructions sold using Jena, Germany company
Under part, detection the present embodiment is listed in table 1 using the TOC content being discharged after waste water raw water and the present embodiment processing, testing result
In.
Table 1：TOC testing result in waste water
| Sample | TOC(mg/L) |
| Waste water raw water | 2000 |
| After oxidation | 10.74 |
Embodiment 2
The method handled provided by the present embodiment, specifically includes following steps：
A, it pre-processes
The high salt organic waste water of embodiment processing is that calcium chloride concentration is 25%, Ca (OH) by weight2For with weight
Meter 0.2%, the pH10.0 waste water that TOC is 3560mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 3, then passes through position by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 in pretreatment 1 bottom of adjuster is transported to through adjuster discharge pump 2 and filter feed pipe 31
3 top of millipore filter is wherein being filtered to remove suspended particulate present in waste water, and filtrate is by being located at 3 bottom of millipore filter
The filter discharge pipeline 32 in portion is sent to the top of the first storage tank 4, while zinc chloride catalyst is also sent to the by process fluid 41
One storage tank, 4 top, the catalyst amount is 0.5% in terms of waste water weight, and filtrate carries out being catalyzed pre- place in the first storage tank 4
Reason, obtained pretreated waste water are sent to subsequent processing steps by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank
Reason；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while compressed air also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 220 DEG C of temperature with pressure 4.0MPa, pretreated waste water and compressed air carry out oxidation processes
5.5h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by being located at
The exhaust gas drainage line 84 at 8 top of oxidizing tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 with carry out two-stage absorption in the second resin tower of chelating resin 15 for being sold by Lang Sheng Chemical Co., Ltd., be discharged direct emission or
For producing Nacl.
It detects after the present embodiment is handled using waste water raw water and the present embodiment and is discharged according to the detection method that embodiment 1 describes
TOC content, testing result is listed in Table 2 below.
Table 2：TOC testing result in waste water
| Sample | TOC(mg/L) |
| Waste water raw water | 3560 |
| The present embodiment processed waste water | 17.28 |
Embodiment 3：
Processing method provided by the present embodiment specifically includes following steps：
A, it pre-processes
The high salt organic waste water of embodiment processing is that sodium chloride concentration is by weight 28%, NaOH for by weight
0.08%, TOC is 8.6 waste water of pH of 3810mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 3, then passes through position by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 in pretreatment 1 bottom of adjuster is transported to through adjuster discharge pump 2 and filter feed pipe 31
3 top of millipore filter is wherein being filtered to remove suspended particulate present in waste water, and filtrate is by being located at 3 bottom of millipore filter
The filter discharge pipeline 32 in portion is sent to the top of the first storage tank 4, while ferric chloride catalyst is also sent to the by process fluid 41
One storage tank, 4 top, the catalyst amount is 1.0% in terms of waste water weight, and filtrate carries out being catalyzed pre- place in the first storage tank 4
Reason, obtained pretreated waste water are sent to subsequent processing steps by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank
Reason；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while compressed air also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 240 DEG C of temperature with pressure 5.0MPa, pretreated waste water and compressed air carry out oxidation processes
5h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by be located at oxygen
The exhaust gas drainage line 84 for changing 8 top of tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 with carry out two-stage absorption in the second resin tower of chelating resin 15 for being sold by Lang Sheng Chemical Co., Ltd., be discharged direct emission or
For producing Nacl.
It detects after the present embodiment is handled using waste water raw water and the present embodiment and is discharged according to the detection method that embodiment 1 describes
TOC content, testing result is listed in Table 3 below.
Table 3：TOC testing result in waste water
| Sample | TOC(mg/L) |
| Waste water raw water | 3810 |
| The present embodiment processed waste water | 14.33 |
Embodiment 4：
The method handled provided by the present embodiment, specifically includes following steps：
A, it pre-processes
The high salt organic waste water of embodiment processing is that sodium chloride concentration is by weight 30%, NaOH for by weight
0.06%, TOC is 8.4 waste water of pH of 4430mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 3, then passes through position by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 in pretreatment 1 bottom of adjuster is transported to through adjuster discharge pump 2 and filter feed pipe 31
3 top of millipore filter is wherein being filtered to remove suspended particulate present in waste water, and filtrate is by being located at 3 bottom of millipore filter
The filter discharge pipeline 32 in portion is sent to the top of the first storage tank 4, while zinc chloride catalyst is also sent to the by process fluid 41
One storage tank, 4 top, the catalyst amount is 0.8% in terms of waste water weight, and filtrate carries out being catalyzed pre- place in the first storage tank 4
Reason, obtained pretreated waste water are sent to subsequent processing steps by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank
Reason；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while compressed air also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 250 DEG C of temperature with pressure 5.5MPa, pretreated waste water and compressed air carry out oxidation processes
3h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by be located at oxygen
The exhaust gas drainage line 84 for changing 8 top of tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 with carry out two-stage absorption in the second resin tower of chelating resin 15 for being sold by Lang Sheng Chemical Co., Ltd., be discharged direct emission or
For producing Nacl.
It detects after the present embodiment is handled using waste water raw water and the present embodiment and is discharged according to the detection method that embodiment 1 describes
TOC content, testing result is listed in Table 4 below.
Table 4：TOC testing result in waste water
Embodiment 5：
The method handled provided by the present embodiment, specifically includes following steps：
A, it pre-processes
The high salt organic waste water of embodiment processing is that calcium chloride concentration is 25%, Ca (OH) by weight2For with weight
Meter 0.4%, 9.0 waste water of pH that TOC is 5890mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 3.5, is then passed through by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 positioned at pretreatment 1 bottom of adjuster is conveyed through adjuster discharge pump 2 and filter feed pipe 31
To 3 top of millipore filter, it is wherein being filtered to remove suspended particulate present in waste water, filtrate is by being located at millipore filter 3
The filter discharge pipeline 32 of bottom is sent to 4 top of the first storage tank, while zinc chloride catalyst is also sent to by process fluid 41
First storage tank, 4 top, the catalyst amount is 0.6% in terms of waste water weight, and filtrate carries out being catalyzed pre- place in the first storage tank 4
Reason, obtained pretreated waste water are sent to subsequent processing steps by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank
Reason；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while industrial pure oxygen also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 255 DEG C of temperature with pressure 5.5MPa, pretreated waste water and industrial pure oxygen carry out oxidation processes
2.5h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by being located at
The exhaust gas drainage line 84 at 8 top of oxidizing tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 with carry out two-stage absorption in the second resin tower of chelating resin 15 for being sold by Lang Sheng Chemical Co., Ltd., be discharged direct emission or
For producing Nacl.
It detects after the present embodiment is handled using waste water raw water and the present embodiment and is discharged according to the detection method that embodiment 1 describes
TOC content, testing result is listed in Table 5 below.
Table 5：TOC testing result in waste water
| Sample | TOC(mg/L) |
| Waste water raw water | 5890 |
| The present embodiment processed waste water | 18.85 |
Embodiment 6：
The method handled provided by the present embodiment, specifically includes following steps：
The high salt organic waste water of embodiment processing is that sodium chloride concentration is by weight 22%, NaOH for by weight
0.06%, TOC is 9.5 waste water of pH of 6000mg/L.
High salt organic waste water and hydrochloric acid pH adjusting agent are transported to pretreatment by waste pipe 11 and hydrochloric acid pipeline 12 respectively and adjust
1 top of device is saved the pH of high salt organic waste water is adjusted to 3.0, is then passed through by adjusting high salt organic waste water and hydrochloric acid flow
Adjuster drainage line 13 positioned at pretreatment 1 bottom of adjuster is conveyed through adjuster discharge pump 2 and filter feed pipe 31
To 3 top of millipore filter, it is wherein being filtered to remove suspended particulate present in waste water, filtrate is by being located at millipore filter 3
The filter discharge pipeline 32 of bottom is sent to 4 top of the first storage tank, while copper chloride catalyst is also sent to by process fluid 41
First storage tank, 4 top, the catalyst amount is 0.4% in terms of waste water weight, and filtrate carries out being catalyzed pre- place in the first storage tank 4
Reason, obtained pretreated waste water are sent to subsequent processing steps by the first tank of the storage drainage line 42 for being located at 4 lower part of the first storage tank
Reason；
B, catalysis oxidation
By the pretreated waste water from the first tank drainage line 42 of storage, pass through oxygen through high-pressure pump 5, heat exchanger 6 and heater 7
Change tower feed pipe 81 be sent in oxidizing tower 8 by 8 bottom of oxidizing tower, while industrial pure oxygen also by oxidizing tower admission line 82 into
Enter in oxidizing tower 8, under conditions of 250 DEG C of temperature with pressure 5.0MPa, pretreated waste water and industrial pure oxygen carry out oxidation processes
2h；Sewage oxidation treatment is discharged by the oxidizing tower drainage line 83 for being located at 8 top of oxidizing tower, contains CO2Water vapour by be located at oxygen
The exhaust gas drainage line 84 for changing 8 top of tower is discharged；
Sewage oxidation treatment then exchanges heat with heat exchanger 6 and cooler 9, then is entered by the second storage tank feed pipe 101
Into the second storage tank 10, the second storage tank drainage line 102 by being located at 10 bottom of the second storage tank is discharged, and is sent to subsequent processing steps
Processing；
C, catalyst is recycled
Installation agitating paddle will be transported to by adjusting tank feed pipe 111 from the sewage oxidation treatment of the second storage tank 10
PH is adjusted in tank 11, while lye is transported in pH adjusting tank 11 by adjusting tank feed pipe 112, by sewage oxidation treatment
PH is adjusted to neutrality, and subsequently into being separated by solid-liquid separation in sludge dewatering equipment 12, is obtained a kind of catalytic solid and is contained with one kind
The water phase of catalyst-solvent；Solid phase is discharged by 12 bottom of sludge dewatering equipment by solid phase discharge line 121, through process fluid 41
It is sent to 4 top of the first storage tank；Water phase is discharged by 12 lower part of sludge dewatering equipment, is pumped by water phase discharge line 122 by water conveying
13 are transported to the first resin tower of cation exchange resin sold by Shanghai Kai Ping resin Co., Ltd connected in a series arrangement
14 with carry out two-stage absorption in the second resin tower of chelating resin 15 for being sold by Lang Sheng Chemical Co., Ltd., be discharged direct emission or
For producing Nacl.
It detects after the present embodiment is handled using waste water raw water and the present embodiment and is discharged according to the detection method that embodiment 1 describes
TOC content, testing result is listed in Table 6 below.
Table 6：TOC testing result in waste water
| Sample | TOC(mg/L) |
| Waste water raw water | 6000 |
| The present embodiment processed waste water | 17.76 |
To sum up, it is all absolutely proved by the result of embodiment 1-6, the method in waste water figure provided by the present invention, removes TOC
Removal rate can reach 99% or more, the direct emission of high salt organic waste water may be implemented.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that the above various embodiments is only used
To illustrate technical solution of the present invention, rather than its limitations；Those skilled in the art should understand that：Without departing substantially from this hair
It in the case where bright spirit and scope, is possible to modify the technical solutions described in the foregoing embodiments, or to wherein
Some or all of technical characteristic is equivalently replaced；And these are modified or replaceed, and do not make the essence of corresponding technical solution
It departs from the scope of the technical solutions of the embodiments of the present invention；It is, therefore, intended that in the following claims including belonging to the present invention
All these substitutions and modifications in range.
Claims (10)
1. a kind of processing method of the waste water generated when producing epoxy chloropropane through glycerine method, which is characterized in that include the following steps：
Wastewater pH=1-4 is adjusted, then under the conditions of catalyst and oxygen-containing gas, catalytic oxidation treatment is carried out, recycles catalyst
Afterwards, the water for capableing of direct emission is obtained；
Preferably, the TOC of the water for capableing of direct emission is less than 30mg/L.
2. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the temperature of the catalysis oxidation is 190~280 DEG C, and pressure is 3~7MPa；Preferably, the temperature of the catalysis oxidation is
200~270 DEG C, pressure is 4~6MPa；It is furthermore preferred that the temperature of the catalysis oxidation be 220~260 DEG C, pressure be 4.5~
5.5MPa。
3. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the time of the catalysis oxidation is 2~6h；Preferably 2.5~5.5h, more preferably 3.0~5.0h.
4. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the mass concentration that, the waste water is calcium chloride or sodium chloride be 20%~30% and/or Ca (OH)2Mass concentration be
The waste water that the mass concentration of 0.2%~0.5% and/or NaOH is 0.05%~0.1%.
5. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the catalyst is soluble zinc salt, it is preferred that the catalyst is selected from zinc chloride, zinc sulfate, trbasic zinc phosphate, biphosphate
One of zinc, zinc tartrate, zinc pyrophosphate or several combinations；
It is furthermore preferred that the dosage of the catalyst is the 0.2%~1.0% of waste water weight.
6. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the oxygen-containing gas is selected from one of air or industrial pure oxygen or two kinds.
7. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the TOC of the waste water is 2000~6000mg/L.
8. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In pH=8~10 of the waste water.
9. the processing method of the waste water generated when producing epoxy chloropropane through glycerine method according to claim 1, feature exist
In the process of the recycling catalyst specifically includes following steps：
The pH of waste water after adjusting catalytic oxidation treatment is adjusted to neutrality, and is then separated by solid-liquid separation, obtain catalytic solid and
Water phase containing catalyst-solvent, the water phase containing catalyst-solvent obtain energy by cation exchange resin and chelating resin
The water of enough direct emissions.
10. a kind of device of the waste water generated when producing epoxy chloropropane through glycerine method, which is characterized in that including sequentially connected pre-
Processing system, catalytic oxidation system and catalyst recovery system；
The pretreatment system, including sequentially connected pretreatment adjuster, discharge pump, millipore filter and the first storage tank；
Preferably, the pretreatment adjuster is also connected with waste pipe and hydrochloric acid pipeline；
Preferably, the pretreatment adjuster is connected with the discharge pump by adjuster drainage line；
Preferably, the discharge pump is connected with the millipore filter by filter feed pipe；
Preferably, the millipore filter is connected with first storage tank by filter discharge pipeline；
Preferably, first storage tank includes the first storage tank drainage line and catalyst channels；
Preferably, the first storage tank drainage line is connected with the catalytic oxidation system by storage tank drainage line；
The catalytic oxidation system, including sequentially connected high-pressure pump, heat exchanger, heater, oxidizing tower, heat exchanger, cooler
With the second storage tank；
Preferably, the oxidizing tower further includes：Oxidizing tower feed pipe, oxidizing tower admission line, oxidizing tower drainage line and useless
Gas drainage line；
Preferably, the heater is connected with the oxidizing tower by oxidizing tower feed pipe；
Preferably, the oxidizing tower is logical is connected with the heat exchanger by oxidizing tower drainage line；
Preferably, second storage tank further includes the second storage tank drainage line of the second storage tank feed pipe and bottom, wherein institute
It states the second storage tank feed pipe to be connected with the heat exchanger, the second storage tank drainage line and the catalyst recovery system phase
Even；
The catalyst recovery system includes that sequentially connected pH adjusts tank, sludge dewatering equipment, water conveying pump, the first resin tower
With the second resin tower；
It includes adjusting tank feed pipe and lye feed pipe, the adjusting tank feed pipe and described second that the pH, which adjusts tank,
Storage tank drainage line is connected；
The sludge dewatering equipment includes solid phase discharge line and water phase discharge line, the solid phase discharge line and the catalyst
Pipeline is connected；
The water phase discharge line is connected with concatenated first resin tower and the second resin tower.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110255773A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in epoxy resin production process |
| CN110255772A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in glycerol method epoxychloropropane production process |
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| CN113087251A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Benzene wastewater treatment system and method |
| CN113750782A (en) * | 2020-06-05 | 2021-12-07 | 中国科学院过程工程研究所 | Purification device and method for epoxy compound-containing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110255773A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in epoxy resin production process |
| CN110255772A (en) * | 2019-07-04 | 2019-09-20 | 浙江德强科技有限公司 | A kind of processing method of the high salt organic waste water generated in glycerol method epoxychloropropane production process |
| CN114436444A (en) * | 2019-07-04 | 2022-05-06 | 浙江德强科技有限公司 | Method for treating high-salt organic wastewater generated in epoxy resin production process |
| CN114436443A (en) * | 2019-07-04 | 2022-05-06 | 浙江德强科技有限公司 | Energy-saving treatment method for high-salt organic wastewater generated in caustic soda preparation through ionic membrane |
| CN113087251A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Benzene wastewater treatment system and method |
| CN111115940A (en) * | 2019-12-31 | 2020-05-08 | 江苏远畅环保科技有限公司 | Industrial wastewater treatment system |
| CN113750782A (en) * | 2020-06-05 | 2021-12-07 | 中国科学院过程工程研究所 | Purification device and method for epoxy compound-containing material |
| CN113750782B (en) * | 2020-06-05 | 2022-08-23 | 中国科学院过程工程研究所 | Purification device and method for epoxy compound-containing material |
| CN112957770A (en) * | 2021-03-11 | 2021-06-15 | 江苏扬农化工集团有限公司 | Continuous extraction device and continuous extraction method for epichlorohydrin |
| CN112957770B (en) * | 2021-03-11 | 2023-02-21 | 江苏扬农化工集团有限公司 | Continuous extraction device and continuous extraction method for epichlorohydrin |
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