CN112266095A - Method for oxidative degradation of cyanide in wastewater - Google Patents
Method for oxidative degradation of cyanide in wastewater Download PDFInfo
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- CN112266095A CN112266095A CN202011048288.1A CN202011048288A CN112266095A CN 112266095 A CN112266095 A CN 112266095A CN 202011048288 A CN202011048288 A CN 202011048288A CN 112266095 A CN112266095 A CN 112266095A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 92
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000010525 oxidative degradation reaction Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000009423 ventilation Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 27
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000009776 industrial production Methods 0.000 claims description 3
- CCQZKUWBWPJBPY-UHFFFAOYSA-N tert-butyl 6-cyano-5-hydroxy-3-oxohexanoate Chemical compound CC(C)(C)OC(=O)CC(=O)CC(O)CC#N CCQZKUWBWPJBPY-UHFFFAOYSA-N 0.000 claims description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 2
- 229960002218 sodium chlorite Drugs 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000005070 sampling Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- OJRHUICOVVSGSY-RXMQYKEDSA-N (2s)-2-chloro-3-methylbutan-1-ol Chemical compound CC(C)[C@H](Cl)CO OJRHUICOVVSGSY-RXMQYKEDSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229960001770 atorvastatin calcium Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000037374 absorbed through the skin Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to an oxidative degradation method of cyanide in wastewater, which comprises the following steps: (1) adding strong base into cyanide-containing wastewater, adjusting the pH value of the cyanide-containing wastewater to be more than 11, stirring the cyanide-containing wastewater at 90-110 ℃ under the ventilation condition for reaction, and cooling the cyanide-containing wastewater to 50-85 ℃; (2) and (2) respectively conveying the wastewater treated according to the step (1) and an aqueous solution containing an oxidant to a microchannel reactor, and reacting for 10-60 seconds at 40-80 ℃. The method can treat cyanide-containing wastewater with cyanide ion concentration of 0.02-10 g/L, has short reaction time of no more than 1 minute, low oxidant consumption and high reaction efficiency, and reduces the residual quantity of cyanide ions in the treated wastewater to below 1 mg/L.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an oxidative degradation method of cyanide in wastewater, more particularly to an oxidative degradation method of wastewater containing sodium cyanide and potassium cyanide in industrial production of an important raw material, namely tert-butyl 3-oxo-5-hydroxy-6-cyanohexanoate, for synthesizing atorvastatin calcium.
Background
3-oxo-5-hydroxy-6-cyano-tert-butyl hexanoate, which is an essential raw material in the synthesis process of atorvastatin calcium, and the synthesis method comprises the following steps:
the cyanide in the wastewater has high toxicity and can be quickly absorbed through the skin, eyes or gastrointestinal tracts of human bodies, the cyanide waste can not only cause environmental pollution, but also cause poisoning and even death of people and animals, the cyanide waste can be discharged into the water, aquatic organisms can be endangered, the ecological balance is damaged, and the state has strict regulation on the content of the cyanide in the discharged wastewater.
Commonly used methods for degrading cyanide in wastewater are:
an electrolytic method: the simple cyanide and the complex cyanide in the wastewater generate chemical reactions on the anode and the cathode through electrolysis, and the cyanogen is electrolytically oxidized into carbon dioxide and nitrogen (firstly oxidized into cyanate). The cyanogen pollution in the wastewater can be effectively removed by utilizing the principle. The disadvantages are that: large power consumption, large consumption of electrode metal, etc.
And (3) high-temperature pressurization degradation of cyanide: the cyanide ion reacts with water to produce non-toxic ammonia and carbonate, and when the temperature reaches over 65 deg.c, its decomposition speed is accelerated, and when the temperature reaches over 200 deg.c, the cyanide hydrolysis speed is very fast. However, special high-temperature and high-pressure equipment is needed, and the content of cyanide ions in the treated wastewater can reach the standard by further oxidative degradation.
Sodium hypochlorite/bleach oxidation process: cyanide is oxidized to low-toxicity cyanate, but the method has the disadvantages that the dosage of hypochlorite is large, and the oxidant needs to be excessive, so that the method is not suitable for treating high-concentration cyanide wastewater. For example, patent CN106348426 reports a method for degrading cyanide in wastewater with sodium hypochlorite, the content of cyanide ions in wastewater is generally 8000ppm or less, the treatment time is generally 4-5 hours, and the residual content of cyanide ions in wastewater after treatment can be reduced to 5ppm or less, and experiments show that if the concentration of cyanide ions in wastewater is high, even if the treatment time is greatly prolonged, the residual content of cyanide ions in wastewater after treatment is greatly increased, for example, the content of cyanide (calculated as sodium cyanide) in wastewater reaches 18000ppm, and after 12 hours of treatment, the content of cyanide (calculated as sodium cyanide) is generally higher than 10ppm, which does not reach the standard of general wastewater, and occupies a long time for treatment equipment.
Disclosure of Invention
The invention aims to provide a method for oxidative degradation of cyanide in wastewater based on the prior art.
The technical scheme of the invention is as follows:
a method for oxidative degradation of cyanide in wastewater, comprising the steps of:
(1) adding strong base into cyanide-containing wastewater, adjusting the pH value of the cyanide-containing wastewater to be more than 11, stirring the cyanide-containing wastewater at 90-110 ℃ under the ventilation condition for reaction, and cooling the cyanide-containing wastewater to 50-85 ℃;
(2) and (2) respectively conveying the wastewater treated according to the step (1) and an aqueous solution containing an oxidant to a microchannel reactor, and reacting for 10-60 seconds at 40-80 ℃.
The cyanide-containing wastewater to be treated by the present invention is sodium cyanide and potassium cyanide-containing wastewater, for example, wastewater generated in industrial production of tert-butyl 3-oxo-5-hydroxy-6-cyanohexanoate. Cyanide, such as sodium cyanide, is easy to hydrolyze, but the hydrolysis speed is obviously accelerated only in aqueous solution with the temperature of more than 60 ℃ to generate ammonia and sodium formate, and the hydrolysis speed is very slow at normal temperature. According to the method, strong base is added into the cyanide-containing wastewater, the pH value of the cyanide-containing wastewater is adjusted to be more than 11, stirring reaction is carried out at 90-110 ℃ under the ventilation condition, the cyanide hydrolysis reaction is accelerated, and meanwhile, cyanide ions in the cyanide-containing wastewater are prevented from diffusing into the air in an HCN form to cause air pollution.
In a preferable scheme, the cyanide ion concentration of the cyanide-containing wastewater is 0.02-10 g/L (calculated by the amount of sodium cyanide, 0.04-18.8 g/L).
For the present invention, in step (1), a strong base is added to the cyanide-containing wastewater to adjust the pH thereof to 11 or more (including 11 and more). Preferably, the pH value is adjusted to 11-12.
In a preferred embodiment, in step (1), the temperature for performing the stirring reaction under aeration may be, but is not limited to, 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃.
Further, the stirring reaction time is 0.5 to 2 hours, for example, 0.5 hour, 1 hour or 2 hours, and may be adjusted according to the actual conditions.
In step (2), the microchannel reactor used may be one suitable for the present invention in the prior art, for example, WH-LAB684 glass microchannel reactor, corning G2 ceramic reactor.
In a preferable scheme, in the step (2), the molar ratio of the oxidant to the cyanide ions in the wastewater before treatment according to the step (1) is 1: 2-10.
In step (2), the oxidant used in the present invention may be, but is not limited to, one or more of sodium hypochlorite, calcium hypochlorite or sodium chlorite. Generally, sodium hypochlorite solutions with a concentration of 3-10% are relatively common, and when the sodium hypochlorite solution is used, the concentration after dilution is generally more than 0.7%.
In one scheme, in the step (1), the strong base is one or more of sodium hydroxide, potassium hydroxide, trisodium phosphate or tripotassium phosphate. For example, sodium hydroxide or potassium hydroxide may be used, but is not limited thereto.
In a preferred embodiment, in step (2), the temperature for performing the reaction in the microchannel reactor may be, but is not limited to, 40 ℃, 43 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃ or 80 ℃.
Further, the reaction time is 30-60 seconds.
In the step (2), the speed of conveying the wastewater treated in the step (1) is 30-60 ml/min, and preferably 40-50 ml/min.
Further, the speed of conveying the aqueous solution containing the oxidant is 5-30 ml/min, and preferably 8-25 ml/min.
By adopting the technical scheme of the invention, the advantages are as follows:
the oxidation degradation method of the invention is adopted to treat the waste water containing cyanide, the materials staying in the microchannel reactor are few, the materials are fully mixed, the reaction time is short, the reaction time and the reaction temperature can be accurately controlled, the problems of large consumption of oxidant, unsuitability for treating the waste water with high-concentration cyanide ions, long reaction time, low efficiency and the like in the oxidation degradation method of cyanide in the waste water in the prior art are solved, under the coordination of other conditions, the oxidation degradation method of the invention greatly shortens the reaction time, has high safety, small pollution, less pollutant discharge, small consumption of oxidant, low cost, and the residual quantity of cyanide ions in the treated waste water can be reduced to below 1 mg/l (reduced to 1.8ppm of residual content of sodium cyanide), and the oxidation degradation method can be used for treating the waste water with larger concentration range of cyanide ions (generally, 0.02-10 g/l).
Detailed Description
The oxidative degradation process of the present invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Example 1:
taking 1L of wastewater generated in the synthesis of the 3-oxo-5-hydroxy-6-cyano-tert-butyl hexanoate, sampling and measuring CN-The total content is up to 5 g (0.19mol), adding 1 g of sodium hydroxide into the wastewater, adjusting the pH value to 12, heating to 100 ℃ in a fume hood, stirring for half an hour, and cooling to 50 ℃ by air (air) blowing for later use.
195 g of sodium hypochlorite solution (with the effective chlorine content being 7 percent) is taken and diluted to 500 ml by adding water, and the sodium hypochlorite and CN in the wastewater before treatment-In a molar ratio of 2: 1.
And (3) respectively conveying the treated wastewater and the sodium hypochlorite aqueous solution into a microchannel reactor (WH-LAB684 glass microchannel reactor) by using a metering pump at the conveying speeds of 50 ml/min and 25 ml/min, at the reaction temperature of 43 ℃ and for the reaction time of 30 seconds. Sampling and detecting CN from discharge port of micro-channel reactor-Content of (a), results: 0.3 mg/l.
Example 2:
taking 500 ml of waste water containing cyanide, sampling and measuring CN-The content is 10mmol (converted to NaCN content, 0.49 g), sodium hydroxide is added to adjust the pH value to 11.0, the mixture is heated to 100 ℃ in a ventilated fume hood, stirred for half an hour, and then cooled to 85 ℃ by air blowing for standby.
Taking 10.2 g of sodium hypochlorite solution (the content of available chlorine is measured to be 7 percent), adding water to dilute the sodium hypochlorite solution to 100 ml, and adding CN in the wastewater before treatment-The molar ratio of the raw materials is 2:1, the raw materials are preheated to 50 ℃, and the raw materials are used in time.
And respectively conveying the treated wastewater and the sodium hypochlorite aqueous solution into a microchannel reactor (Corning G2 ceramic reactor) through a metering pump, wherein the injection speeds are respectively 40 ml/min and 8 ml/min, the reaction time is 10 seconds, and the reaction temperature is 70-80 ℃. Sampling and detecting CN from outlet of micro-channel-Content of (a), results: 0.17 mg/l.
Example 3:
500 ml of waste water containing cyanide is taken and is passed through CN-The content was determined as 1.8% NaCN (9 g total NaCN, CN)-Content of 0.18mol), adding sodium hydroxide to adjust pH to 11.5, heating to 100 deg.C in a fume hood with good ventilation, stirring for half an hour, and cooling to 85 deg.C by air blowing.
Taking 186 g of sodium hypochlorite solution (with the measured available chlorine content of 7 percent), adding water to dilute the solution to 300 ml, and adding CN in the sodium hypochlorite and the wastewater before treatment-The molar ratio of the raw materials is 2:1, the raw materials are preheated to 50 ℃, and the raw materials are used in time.
And respectively conveying the treated wastewater and the sodium hypochlorite aqueous solution into a micro-channel reactor (Corning G2 ceramic reactor) through a metering pump, wherein the injection speeds are 40 ml/min and 24 ml/min, the reaction time is 30 seconds, and the reaction temperature is 75-80 ℃. Sampling and detecting CN from outlet of micro-channel-Content of (a), results: 0.27 mg/l (0.5 ppm sodium cyanide remaining).
Example 4:
500 ml of waste water containing cyanide is taken, and the total amount of the waste water is 9 g (CN)-Content of 0.18mol), adding sodium hydroxide to adjust pH to 11.8, heating to 110 deg.C in a fume hood with good ventilation, stirring for half an hour, and cooling to 85 deg.C by air blowing.
Taking 280 g (3.0 equivalent) of sodium hypochlorite solution (with the measured available chlorine content of 7 percent), adding water to dilute the sodium hypochlorite solution to 300 ml, wherein the sodium hypochlorite and CN in the wastewater before treatment-The molar ratio of the raw materials is 2:1, the raw materials are preheated to 50 ℃, and the raw materials are used in time.
And respectively conveying the treated wastewater and the sodium hypochlorite aqueous solution into a microchannel reactor (Corning G2 ceramic microreactor) through a metering pump, wherein the injection speeds are 40 ml/min and 24 ml/min respectively, the reaction time is 60 seconds, and the reaction temperature is 75-80 ℃. Sampling and detecting CN from outlet of micro-channel-Content of (a), results: 0.17 mg/l (0.32 ppm of residual NaCN).
Comparative example 1:
500 ml of waste water containing cyanide is taken, and the total amount of the waste water is 9 g (CN)-Content of 0.18mol), adding sodium hydroxide to adjust pH to 11.8 for later use.
Taking 280 g (3.0 equivalent) of sodium hypochlorite solution (with the measured available chlorine content of 7 percent), adding water to dilute the sodium hypochlorite solution to 300 ml, wherein the sodium hypochlorite and CN in the wastewater before treatment-The molar ratio of the raw materials is 2:1, the raw materials are preheated to 50 ℃, and the raw materials are used in time.
The treated water is treated by a metering pumpThe wastewater and the sodium hypochlorite aqueous solution are respectively conveyed into a microchannel reactor (Corning G2 ceramic microreactor), the injection speeds are respectively 40 ml/min and 24 ml/min, the reaction time is 60 seconds, and the reaction temperature is 75-80 ℃. Sampling and detecting CN from outlet of micro-channel-Content of (a), results: 3.4 mg/l.
Comparative example 2:
taking 500 ml of waste water containing cyanide, sampling and measuring CN-The content was 10mmol (converted to NaCN content, 0.49 g), the pH was adjusted to 9.0 by adding NaOH, and the mixture was stirred in a well-ventilated hood at 60 ℃ for half an hour.
Taking 10.2 g of sodium hypochlorite solution (the content of available chlorine is measured to be 7 percent), adding water to dilute the sodium hypochlorite solution to 100 ml, and adding CN in the wastewater before treatment-The molar ratio of the raw materials is 2:1, the raw materials are preheated to 50 ℃, and the raw materials are used in time.
And respectively conveying the treated wastewater and the sodium hypochlorite aqueous solution into a micro-channel reactor (Corning G2 ceramic reactor) through a metering pump, wherein the injection speeds are 40 ml/min and 8 ml/min, the reaction time is 10 seconds, and the reaction temperature is 20-30 ℃. Sampling and detecting CN from outlet of micro-channel-Content of (a), results: 2.8 mg/l.
In general, by adopting the method, the cyanide wastewater with higher concentration can be treated, the treatment speed is high, and the residual quantity of the cyanide in the treated wastewater is lower.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for oxidative degradation of cyanide in wastewater, which is characterized by comprising the following steps:
(1) adding strong base into cyanide-containing wastewater, adjusting the pH value of the cyanide-containing wastewater to be more than 11, stirring the cyanide-containing wastewater at 90-110 ℃ under the ventilation condition for reaction, and cooling the cyanide-containing wastewater to 50-85 ℃;
(2) and (2) respectively conveying the wastewater treated according to the step (1) and an aqueous solution containing an oxidant to a microchannel reactor, and reacting for 10-60 seconds at 40-80 ℃.
2. The method for the oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein in the step (1), a strong base is added to the cyanide-containing wastewater to adjust the pH value thereof to 11 to 12.
3. The method for oxidative degradation of cyanide in wastewater according to claim 1 or 2, wherein in the step (1), the cyanide-containing wastewater is wastewater produced in industrial production of tert-butyl 3-oxo-5-hydroxy-6-cyanohexanoate; preferably, the concentration of cyanide ions in the cyanide-containing wastewater is 0.02-10 g/L.
4. The method for oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein in step (2), the molar ratio of the oxidizing agent to cyanide ions in wastewater before treatment according to step (1) is 1:2 to 10.
5. The method for oxidative degradation of cyanide in wastewater as claimed in claim 4, wherein in step (2), the oxidant is one or more of sodium hypochlorite, calcium hypochlorite or sodium chlorite; preferably sodium hypochlorite.
6. The method for oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein in step (1), the strong base is one or more of sodium hydroxide, potassium hydroxide, trisodium phosphate or tripotassium phosphate; sodium hydroxide is preferred.
7. The method for the oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein, in the step (1), the temperature of the agitation reaction is 100 ℃; the stirring reaction time is 0.5 to 2 hours, preferably 0.5 hour.
8. The method for oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein the reaction temperature in step (2) is 50-60 ℃.
9. The method for oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein the reaction time in step (2) is 30 to 60 seconds.
10. The method for the oxidative degradation of cyanide in wastewater as claimed in claim 1, wherein in the step (2), the wastewater treated in the step (1) is conveyed at a speed of 30-60 ml/min, preferably 40-50 ml/min; the speed of conveying the aqueous solution containing the oxidant is 5-30 ml/min, and preferably 8-25 ml/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011048288.1A CN112266095A (en) | 2020-09-29 | 2020-09-29 | Method for oxidative degradation of cyanide in wastewater |
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