CN108275846A - A kind of processing method of anthraquinone waste water - Google Patents
A kind of processing method of anthraquinone waste water Download PDFInfo
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- CN108275846A CN108275846A CN201810240333.XA CN201810240333A CN108275846A CN 108275846 A CN108275846 A CN 108275846A CN 201810240333 A CN201810240333 A CN 201810240333A CN 108275846 A CN108275846 A CN 108275846A
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
A kind of processing method of the anthraquinone of nitrite containing low concentration waste water, comprises the steps of：(1) pH of waste water is adjusted to acidity；(2) active constituent is added, 0.5~1h is stirred；(3) autoclave is inputted, air or oxygen is passed through, carries out 1~5h of oxidation reaction at moderate temperatures；(4) water outlet is separated by solid-liquid separation, and liquid enters biochemical treatment, and solid is submicron order iron oxide, wherein the content of anthraquinone waste water Nitrite is 0.01%~1wt%, and total content of organic carbon is 2000~30000mg/L, active constituent Fe2+Inorganic/organic salt.The processing method of the present invention can remove nitrite and total organic carbon in waste water simultaneously, and easy to operate and operating cost is low, be suitable for industrial applications, environmental-friendly.
Description
Technical field
The present invention relates to water pollution control and wastewater processing technology, especially a kind of processing method of anthraquinone waste water.
Background technology
Anthraquinone and its derivative are a kind of important intermediates in dyestuff, medicine synthesis.Currently, only in China's anthraquinone dye
The annual output of mesosome alreadys exceed 60,000 tons, and a large amount of high chromas, high chemical oxygen demand (COD), high salinity can be discharged in production process
Waste water.Since anthraquinone and its derivant structure are stablized, solubility is big, and conventional physico-chemical process treatment effect is not very managed
Think.
By taking 1- nitroanthraquinone -5- sodium sulfonate production process as an example, synthetic route is as follows：
By said synthesis route it is found that in 1- nitroanthraquinone -5- sodium sulfonates production waste water, raw material, product containing remnants,
By-product and sodium nitrite.
Since the removal difficulty of nitrate in water is much larger than nitrite, existing sewage water treatment method would generally
It is carried out in two steps：Before using oxidizing process degradation of organic substances, nitrite is removed in advance.Common reagent have sulfamic acid,
The reducing agents such as the reducing substances such as urea, ammonium salt, metal powder, wherein sulfamic acid, urea are since reaction condition is mild, does not produce
Raw solid waste etc., often uses in high concentration nitrite wastewater treatment.After removing nitrite, subsequent oxidation means are for removing
Total organic matter (TOC).
CN103964634A Chinese patent literatures disclose the work of a kind of high nitrite, high-carbon hydrochlorate and high COD concentration
Industry wastewater treatment method after first being removed nitrite with sulfamic acid, then passes through precipitation+light electrolysis+Fenton oxygen
The COD of change+light electrolysis+flocculated technique removal waste water.This method is of high cost, and solid waste amount is big, it is difficult to competitive superiority.
CN105130062A Chinese patent literatures disclose a kind of wet oxidation processing method of anthraquinone waste water.It is high in embodiment
The nitrite of concentration (16% mass concentration) is removed before wet oxidation by electrodialysis；Or after wet oxidation
It is converted into nitrate, then is removed by condensing crystallizing.The anthraquinone that both modes are only suitable for handling the nitrite containing high concentration is useless
Water, no matter and electrodialysis or condensing crystallizing, operating cost it is high.
Invention content
The present invention provides the processing methods that a kind of nitroanthracene quinones intermediate produces waste water, and especially one kind is by adding
Active constituent makes the nitrite of low concentration and the removal rate of total organic carbon in waste water obtain the method that collaboration is promoted.
The wastewater treatment method of the present invention comprises the steps of：(1) pH of waste water is adjusted to acidity；(2) activity is added
Ingredient stirs 0.5~1h；(3) input autoclave, be passed through air or oxygen into, at moderate temperatures row oxidation reaction 1~
5h；(4) water outlet is separated by solid-liquid separation, and liquid enters biochemical treatment, and solid is submicron order iron oxide, wherein in the anthraquinone waste water
The content of nitrite anions is 0.01%~1wt%, and the content of total organic carbon (TOC) is：2000~30000mg/L, the activity
Ingredient is Fe2+Inorganic/organic salt.
Preferably, the molar ratio of the active constituent dosage and the waste water Nitrite is 1:1~10.
In the method for the present invention, the pH value for adjusting waste water is acidity, ensures Fe2+It is not precipitated.
The active constituent of the present invention is Fe2+Inorganic/organic salt, only contain Fe2+One metal ion species, not cupric etc. its
Its metal or metal ion.
Hydrogen peroxide need not be added in the method for the present invention.
Preferably, Fe of the invention2+Inorganic/organic salt be ferrous sulfate, frerrous chloride, ferrous gluconate；Into
One step is preferably ferrous sulfate.
Preferably, anthraquinone waste water of the invention is nitroanthracene quinones waste water, such as produces the life of nitroanthracene quinones intermediate
Produce waste water, further preferably the production waste water of nitroanthraquinone sulfonic acid class intermediate.
Preferably, the temperature in step (3) is 220~260 DEG C.
Preferably, the nitrite anions removal rate in method processed waste water through the present invention is in 80% or more, TOC removal rates
90% or more.
Preferably, submicron order iron oxide obtained by step (4) can after rinsing recycling.
Fe3+Compare Fe2+Stablize, general catalyst requirement has certain stability.The application is it was unexpectedly observed that waste water
Middle addition Fe2+Even if Fe2+Addition far below removal nitrite needed for theoretical molar amount, at moderate temperatures, energy
The nitrite of nitroanthracene quinones intermediate production waste water and TOC are reduced to the level of suitable subsequent processing simultaneously.
Nitrate content and TOC are extremely low in water outlet obtained by the wastewater treatment method of the application, are substantially free of nitrite,
Water outlet can be separated by solid-liquid separation.Liquid can be diluted according to the salt content of water outlet, and biochemistry pool aerobic sigestion is entered after dilution
Processing is until qualified discharge.It is preferred that the bacterium of 2%~5% salinity of tolerance carries out biochemical treatment, to reduce the dilute of the water outlet
Release multiple.Solid is that submicron order iron oxide can be used as the progress such as ferric oxide red colorant and other raw materials after detaching, rinsing
Recycling, rinse water are used as latter step biochemistry dilution water.
Compared with the existing technology, the processing method of nitroanthracene quinones intermediate production waste water provided by the invention can be simultaneously
Remove the nitrite and TOC in waste water；With easy to operate, flow is short, repeatability is strong between batch, effect stability, operation at
The features such as this is low；Solid waste and waste water will not be additionally generated in whole flow process, it is environmentally friendly.
Specific implementation mode
The present invention is further understood below in conjunction with specific example help, but protection scope of the present invention is not limited to this.
In the present invention, nitrite, nitrate content ion chromatography, TOC are measured with TOC analyzers, and granularity is used
Laser fineness gage measures.
Embodiment 1
1- nitro -5- sulfonic group anthraquinone intermediates produce waste water, and color is atropurpureus, TOC=14215mg/L, pH=12,
c(NO2 -)=4157mg/L.Organic matter in waste water is mostly the isomer of 1- nitro -5- sulfonic group anthraquinones.
(1) concentrated sulfuric acid is slowly added dropwise into waste water, wastewater pH is adjusted to 3.
(2) ferrous sulfate heptahydrate is added into waste water, the molar ratio of dosage and nitrite anions is 1:5.There is gas after adding
Bubble generates.Stirring is opened, 0.5h is continued.
(3) autoclave is inputted, oxygen is passed through, sealing is warming up to 240 DEG C, oxidation processes are obtained after sustained response 2h
Liquid.It stands, supernatant is taken to survey TOC=1060mg/L, c (NO3 -)=840mg/L, is not detected nitrite.Nitrous acid known to calculating
Root removal rate is 85% (nitrate anion is converted to nitrite anions according to molecular weight when calculating), and TOC removal rates are 93%.
(4) solid phase in oxidation treatment liquid is red oxidization iron particle, and through rinsing, drying, measuring its average particle size is
557nm is submicron order.
(5) supernatant of oxidation treatment liquid, it is 8.7% to measure its salt content, and tolerance high salt concentration is used after diluting three times
Bacterium carries out biochemical treatment for 24 hours, and TOC is down to 126mg/L after processing.
Embodiment 2
Waste water described in embodiment 1 makes waste water Nitrite content be promoted to 1% by adding suitable sodium nitrite.
It is 1 that the dosage of ferrous sulfate heptahydrate, which is increased to the molar ratio of nitrite anions,:2, remaining condition is in the same manner as in Example 1.Institute
It obtains oxidation treatment liquid to stand, takes supernatant to detect, TOC=1098mg/L, c (NO3 -)=1167mg/L.Nitrite anions known to calculating
Removal rate is that 91%, TOC removal rates are 92%.
Embodiment 3
Waste water described in embodiment 1, it is 1 that the dosage of ferrous sulfate heptahydrate, which is down to the molar ratio of nitrite anions,:10,
Remaining condition is in the same manner as in Example 1.Gained oxidation treatment liquid is stood, and takes supernatant to detect, TOC=1490mg/L, c (NO3 -)=
974mg/L.It is 90% that nitrite anions removal rate known to calculating, which is 83%, TOC removal rates,.
Embodiment 4
Waste water described in embodiment 1, it is 1 that the dosage of ferrous sulfate heptahydrate, which is increased to the molar ratio of nitrite anions,:1,
Remaining condition is in the same manner as in Example 1.Gained oxidation treatment liquid is stood, and takes supernatant to detect, TOC=994mg/L, c (NO3 -)=
1130mg/L.It is 93% that nitrite anions removal rate known to calculating, which is 80%, TOC removal rates,.
Comparative example 1
Waste water described in embodiment 1 directly inputs autoclave and carries out oxidation reaction, flow of oxygen, temperature, reaction time
Etc. conditions it is in the same manner as in Example 1.Sample detection after completion of the reaction, TOC=1375mg/L, c (NO3 -)=3547mg/L.It calculates
Known to nitrite anions removal rate be 15%, TOC removal rates be 90%.
If the explanation of comparative example 1 does not add active material, nitrite anions removal rate is extremely low.
Comparative example 2
Waste water described in embodiment 1, is handled according to the following steps：
(1) suitable sulfamic acid is added, stirring is opened, reacts 0.5h, sampling measures c (NO2 -)=735mg/L.
(2) by treated waste water, input autoclave carries out oxidation reaction, when flow of oxygen, temperature, reaction
Between etc. conditions it is in the same manner as in Example 1.Sample detection after completion of the reaction, TOC=3015mg/L, c (NO3 -)=1300mg/L.Meter
It is 79% that nitrite anions removal rate known to calculating, which is 77%, TOC removal rates,.
Comparative example 2 illustrates after removing nitrite in advance that waste water TOC removal rates drastically reduce.
Comparative example 3
Waste water described in embodiment 1 will add ferrous sulfate heptahydrate and be changed to add the cupric sulfate pentahydrate of equimolar amounts, remaining
Part is in the same manner as in Example 1.Gained oxidation treatment liquid is adjusted to sample detection after pH=10 precipitation copper removals, TOC=758mg/L, c
(NO3 -)=3210mg/L.It is 95% that nitrite anions removal rate known to calculating, which is 43%, TOC removal rates,.
Comparative example 4
Waste water described in embodiment 1 will add ferrous sulfate heptahydrate and be changed to add nine water ferric sulfate of equimolar amounts, remaining
Part is in the same manner as in Example 1.Gained oxidation treatment liquid is stood, and takes supernatant to detect, TOC=1269mg/L, c (NO3 -)=
1950mg/L.It is 91% that nitrite anions removal rate known to calculating, which is 65%, TOC removal rates,.
The result of comparative example 3 and comparative example 4 explanation, only Fe2+The waste water TOC and nitrite can be greatly improved simultaneously
Removal rate, this is the result is that unexpected.
Claims (7)
1. a kind of processing method of anthraquinone waste water, comprises the steps of：(1) pH of waste water is adjusted to acidity；(2) work is added
Property ingredient, stir 0.5~1h；(3) autoclave is inputted, air or oxygen is passed through, carries out oxidation reaction 1 at moderate temperatures
~5h；(4) water outlet is separated by solid-liquid separation, and liquid enters biochemical treatment, and solid is submicron order iron oxide,
Wherein, the content of the anthraquinone waste water Nitrite is 0.01%~1wt%, and the content of total organic carbon is：2000~
30000mg/L,
The active constituent is Fe2+Inorganic/organic salt.
2. according to the method described in claim 1, wherein, the active constituent dosage rubs with the waste water Nitrite
You are than being 1:1~10.
3. according to claim 1-2 any one of them methods, wherein the Fe2+Inorganic/organic salt be ferrous sulfate,
Frerrous chloride, ferrous gluconate；Preferably ferrous sulfate.
4. according to claim 1-3 any one of them methods, wherein the anthraquinone waste water is nitroanthracene quinones waste water, such as
Produce the production waste water of nitroanthracene quinones intermediate, further preferably the production waste water of nitroanthraquinone sulfonic acid class intermediate.
5. according to claim 1-4 any one of them methods, wherein the temperature in step (3) is preferably 220~260 DEG C.
6. according to claim 1-5 any one of them methods, wherein the nitrite anions removal rate in step (3) water outlet exists
80% or more, TOC removal rate are 90% or more.
7. according to claim 1-6 any one of them methods, wherein submicron order iron oxide obtained by step (4) can be through rinsing
Recycling afterwards.
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| CN201810070329 | 2018-01-24 | ||
| CN2018100703293 | 2018-01-24 |
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| CN108275846A true CN108275846A (en) | 2018-07-13 |
| CN108275846B CN108275846B (en) | 2020-08-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010492A (en) * | 2019-05-31 | 2020-12-01 | 南京绿岛环境工程有限公司 | Physicochemical and biochemical treatment process for 1-aminoanthraquinone wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030035962A (en) * | 2001-10-26 | 2003-05-09 | (주)피엠지 | Method for disposing of livestock waste water |
| CN102627361A (en) * | 2012-03-27 | 2012-08-08 | 浙江省环境保护科学设计研究院 | Method and device for removing phosphorous from glyphosate production wastewater |
| CN105130062A (en) * | 2015-09-25 | 2015-12-09 | 浙江奇彩环境科技有限公司 | Anthraquinone wastewater treatment method |
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- 2018-03-22 CN CN201810240333.XA patent/CN108275846B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030035962A (en) * | 2001-10-26 | 2003-05-09 | (주)피엠지 | Method for disposing of livestock waste water |
| CN102627361A (en) * | 2012-03-27 | 2012-08-08 | 浙江省环境保护科学设计研究院 | Method and device for removing phosphorous from glyphosate production wastewater |
| CN105130062A (en) * | 2015-09-25 | 2015-12-09 | 浙江奇彩环境科技有限公司 | Anthraquinone wastewater treatment method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010492A (en) * | 2019-05-31 | 2020-12-01 | 南京绿岛环境工程有限公司 | Physicochemical and biochemical treatment process for 1-aminoanthraquinone wastewater |
| CN112010492B (en) * | 2019-05-31 | 2022-06-14 | 南京绿岛环境工程有限公司 | Physicochemical and biochemical treatment process for 1-aminoanthraquinone wastewater |
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