CN107954510A - Method for reducing chemical oxygen demand in wastewater - Google Patents
Method for reducing chemical oxygen demand in wastewater Download PDFInfo
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- CN107954510A CN107954510A CN201611064349.7A CN201611064349A CN107954510A CN 107954510 A CN107954510 A CN 107954510A CN 201611064349 A CN201611064349 A CN 201611064349A CN 107954510 A CN107954510 A CN 107954510A
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- waste water
- cod
- chlorine
- alkaline
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- 239000002351 wastewater Substances 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000000126 substance Substances 0.000 title abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 16
- 239000001301 oxygen Substances 0.000 title abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 44
- 239000000460 chlorine Substances 0.000 claims description 44
- 229910052801 chlorine Inorganic materials 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 16
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000006298 dechlorination reaction Methods 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 55
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 23
- 239000000920 calcium hydroxide Substances 0.000 description 23
- 235000011116 calcium hydroxide Nutrition 0.000 description 23
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000005660 chlorination reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 159000000011 group IA salts Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Substances [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver nitrate Substances [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 241001214714 Niea Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 epoxy resin) Chemical compound 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- YXVJNOXXPKIWIM-UHFFFAOYSA-N n-(2-hydroxyethyl)-n-(2-hydroxypropyl)nitrous amide Chemical compound CC(O)CN(N=O)CCO YXVJNOXXPKIWIM-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000276457 Gadidae Species 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010998 test method 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
- C02F1/72—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
- C02F1/763—Devices for the addition of such compounds in gaseous form
-
- 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
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
-
- 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
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)
- Epoxy Compounds (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for reducing chemical oxygen demand in wastewater, which comprises the following steps: introducing chlorine gas in an amount of 1 to 7 wt% based on the total weight of the wastewater into the wastewater with a Chemical Oxygen Demand (COD) of more than 3000ppm to subject the wastewater to a oxychlorination reaction; and adding alkali into the waste water introduced with the chlorine gas. The method of the invention can effectively reduce the chemical oxygen demand in the wastewater and can effectively save the sewage treatment cost.
Description
Technical field
The present invention is in relation to a kind of method for handling waste water, espespecially a kind of method for reducing COD in waste water.
Background technology
Epoxychloropropane (epichlorohydrin, ECH) is usually used in manufacturing glycerine, plastics, artificial rubber and resin
(e.g., epoxy resin), is important industrial chemicals.In general, epoxychloropropane can pass through propylene high-temperature chlorination, propenyl chlorination
And three kinds of techniques of glycerin chlorination are made；In the technique of propenyl chlorination, propenyl and chlorine are first subjected to chlorination reaction, obtained
Alkalize the dichloro third to dichlorohydrin (dichloropropanol, DCH), then with sodium hydroxide or calcium hydroxide (milk of lime)
Alcohol, finally by isolating and purifying to obtain epoxychloropropane.Which kind of technique dichlorohydrin either is produced using, must all carry out alkali
Change is reacted to give epoxychloropropane.
But wastewater flow rate is very big caused by quaternization, and there is high chemical oxygen demand (Chemical Oxygen
Demand, COD) can not directly it discharge, it is necessary to by sewage disposal, the COD in waste water is down to below standard value, is just able to
Discharge.
For caused waste water in chemical process, organic matter degradation is carried out with activated sludge process more.However, it is different from
General wastewater treatment process, the alkalization waste water is because of the characteristic with high villaumite, to avoid suppressing the microorganism that can digest organic matter
Growth, it is necessary to add substantial amounts of dilution water, cause greatly improving for equipment and cost.
Therefore, the COD in alkalization waste water how is effectively reduced, actually the urgent problem to be solved of industry.
The content of the invention
In order to overcome the shortcomings that above-mentioned, the present invention provides a kind of method for reducing COD in waste water, including：In
COD (COD) is passed through gross weight meter with the waste water in the waste water more than 3000ppm, the chlorine of 1 to 7 weight %, with
The waste water is made to carry out oxychloride reaction；And add alkali in the waste water for being connected with chlorine.
The present invention in waste water through chlorine is passed to, by the characteristic of gas-liquid mixed and chlorine with high oxidation power, by waste water
In oxidation operation degraded, effectively reduce the COD in waste water.
The method of the present invention can with equal proportion reduce the COD in waste water through the control of chlorine and alkali, then can be according to
COD in waste water to be handled, drafts removal target, and the degree of degraded needed for carries out ratio degradation reaction, side of the invention
Method has wider opereating specification, is able to grasp under room temperature or middle low temperature (i.e. less than 100 DEG C, such as 30 DEG C to 100 DEG C) environment
Make, finally the COD of caused alkaline waste water in epoxychloropropane technique can be very down to and meet environmental protection standard.
The method of the present invention is not only restricted to for example known when being degraded through microorganism, is subject to strain growth environment to limit
System, must first tame or dilute waste water；And it must additionally add and urge different from known chemical treatment method (such as Fenton methods)
Agent, can have good removal effect, have wider opereating specification.
Embodiment
Illustrate embodiments of the present invention by particular specific embodiment below, field technology personnel can be by this theory
The bright revealed content of book understands advantages of the present invention and effect easily.The present invention also can be by other different embodiment party
Formula is implemented or applied, and the various details in this specification can also be based on different viewpoints and application, not depart from institute of the present invention
Different modification and change are assigned under the spirit of announcement.
In this specification, alleged " COD ", it is intended that the oxygen for being consumed oxidation operation in waste water it is suitable
Amount.
In the present invention, the test method of COD and alkaline salt is as follows：
COD：
First detection method (villaumite detection method-silver nitrate in NIEA W407.51C water according to Taiwan mechanism bulletin
Titration) detection water sample chlorine ion concentration, the alkaline waste water of comparative example 1 to 2 and embodiment 1 to 2 is diluted to chlorion accordingly
Concentration is less than 2,000mg/L.
According to No. 0960058228 bulletin NIEA W515.54A of Taiwan mechanism (method for detecting chemical oxygen demand in water
- potassium dichromate feedback method) measure, that is, excessive potassium bichromate solution is added in water sample, returned in about 50% sulfuric acid solution
Stream, remaining potassium bichromate, is titrated with l ferrous ammonium sulfate solution, by the potassium bichromate amount consumed, you can is tried to achieve chemical in water sample
Oxygen demand (Chemical Oxygen Demand, abbreviation COD), being represented with this can be by the content of oxidation of organic compounds in sample.
Alkaline salt：
According to CNS1625K7125 standard test calcium hydroxide concentrations, calcium carbonate is then with HCl and AgNO3Tried as titration
Material, is measured and the concentration for the calcium carbonate that converts with titration.
The method that the present invention reduces COD in waste water, including：It is more than the waste water of 3000 ppm in COD
In be passed through gross weight meter with the waste water, the chlorine of 1 to 7 weight %, to make the waste water carry out oxychloride reaction；And in this
It is connected with the waste water of chlorine and adds alkali.
In the present invention, the COD of the waste water can be 3000ppm, 9000ppm, 10000ppm, 20000ppm and
The scope that its wantonly two concentration is included.In addition, in an example, the COD of the waste water is 3000ppm to 20000ppm
Waste water.Specifically, method of the invention is suitable for the waste water of foregoing different CODs, that is, which can be warp
Cross general wastewater treatment process, by pretreatment (such as preliminary sedimentation separation or pH value adjust) or undressed waste water.
In the example of the present invention, which is epoxychloropropane manufacture (for example, it is anti-to carry out saponification to dichlorohydrin
Answering the technique of (quaternization), (wherein, which includes, but are not limited to by propylene high-temperature chlorination, propenyl chlorination and sweet
Person obtained by oily three kinds of techniques of chlorination) in caused waste water, such waste water has the spy of high chemical oxygen demand and high villaumite
Property.
In the example of the present invention, which is the waste water by pretreatment, for example, the waste water passes through preliminary sedimentation
Separation, adjustment pH value and dilution.For example, this separates by preliminary sedimentation, adjusts pH value and the COD value of diluted waste water
For 3000ppm to 9000ppm, acid-base property is weak base, neutrality or faintly acid, for example, this is by preliminary sedimentation separation, adjustment pH
Value and diluted pH value of waste water are 6 to 7.
In the example of the present invention, the waste water be epoxychloropropane technique saponification in caused alkalescence it is useless
Water.For example, the saponification is the quaternization of dichlorohydrin, the pH value of alkaline waste water caused by the saponification
Typically larger than 10, such as pH value is 10 to 13.
In previous examples, which is alkaline waste water, and it is anti-which contains dichlorohydrin, villaumite and alkalization
The remaining alkali of institute is answered, and there is high chemical oxygen demand；Wherein, the COD in the waste liquid is more than 3000ppm.In addition, should
Also contain glycerine in alkaline waste water.In previous examples, which includes calcium hydroxide or calcium carbonate, with the waste water
Total restatement, which is 1 to 3 weight %.
In an example, with total restatement of the alkaline waste water, the content of the glycerine is 0.5 to 0.8 weight %, and this two
The content of chloropropyl alcohol is 0.02 to 0.06 weight %.
In the example of the present invention, with the gross weight meter of the waste water, the chlorine is with the flow velocity of 1 to 7 weight % per hour
It is passed through in the waste water.For example, the chlorine is passed through in the waste water with 19 kilograms per hour of flow velocity.In previous examples, the chlorine
Purity be more than 99%.
In the example of the present invention, when oxychloride reaction progress 1 to 2 is small.
In the example of the present invention, the step of adding alkali in the waste water of chlorine is connected with this, is with solid or liquid shape
Formula adds in the waste water that alkali is connected with chlorine to this, such as the alkali is dissolved in the water, and adds this in liquid form and is connected with chlorine
In waste water.In this example, with the gross weight meter of the waste water, the amount which is added is 5 to 10 weight %.Also, the alkali is gold
Belong to hydroxide, for example, alkali metal hydroxide or alkaline earth metal hydroxide, more specifically sodium hydroxide or hydroxide
Calcium.
In the example of the present invention, it is during the chlorine is passed through, while adds the alkali and be connected with the useless of chlorine to this
In water, to maintain this to be connected with the pH of the waste water of chlorine as 4 to 10.
In previous examples, the rate of descent of the COD of the processed waste water is more than 94%, and the more preferably removal rate is reachable
99%, in foregoing more preferably example, the COD of the processed waste water is less than 100ppm.
In the reduction waste water of the present invention in an example of chemical oxygen demand method, further include anti-in carrying out the oxychloride
Ying Hou, carries out dechlorination reaction.In this present embodiment, which is to add to take off in this is by the waste water of oxychloride reaction
Chlorine agent, for example, the antichlor are hydrogen peroxide, sodium sulfite, sulfur dioxide, sodium thiosulfate or activated carbon.
In the reduction waste water of the present invention in the yet another embodiment of chemical oxygen demand method, further include before chlorine is passed through,
Sedimentation separation processing is carried out to the waste water, and the pH value for adjusting the waste water is 6 to 7.
Below with epoxychloropropane technique, in dichlorohydrin saponification step exemplified by caused alkaline waste water, Yu Hou
In the exemplary embodiments of described this case, in each embodiment, the content of the COD of alkaline waste water, calcium hydroxide and calcium carbonate
It is recorded in each embodiment.
Comparative example 1
In comparative example 1, pending alkaline waste water pH value is 11.57 and COD is 13,391ppm, and the alkaline waste water
In comprising 0.94 weight % calcium hydroxide and 1.22 weight % calcium carbonate.
The alkaline waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, with 7.9 kilograms per hour
Flow velocity is passed through chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system), is passed through in the alkaline waste water
Chlorine content is 31,600ppm, under the conditions of 75 ± 5 DEG C, be detained 2 it is small when after, measure water in pH value, COD, calcium hydroxide
With the content of calcium carbonate, and table 1 is recorded in.
Comparative example 2
In comparative example 2, the pH value of pending alkaline waste water is 11.63, and COD is 12,500 ppm, and the alkalescence
The calcium carbonate of calcium hydroxide comprising 0.16 weight % and 1.75 weight % in waste water.
The alkaline waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, with 3.8 kilograms per hour
Flow velocity is passed through chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system), is passed through the chlorine of the alkaline waste water
Gas content is 15,200ppm, under the conditions of 75 ± 5 DEG C, be detained 2 it is small when after, measure water in pH value, COD, calcium hydroxide with
The content of calcium carbonate, and it is recorded in table 1.
Table 1
※ ND represent that the content of calcium hydroxide and calcium carbonate is less than quantitation limit value, therefore do not detect (Non-detected)
Calcium hydroxide or calcium carbonate.
In comparative example 1 and 2, the pH value of processed alkaline waste water is changed into 4.26 and 3.29 respectively.
Although calcium hydroxide and calcium carbonate, alkaline salt are not all detected with the method processing alkaline waste water of comparative example 1 and 2
Removal rate be 100%, COD is still respectively 8,318 ppm and 9 in water in the alkaline waste water after processing, 843ppm, COD removal
Rate only 38% and 21%.
The method that the present invention of embodiment 1 reduces COD in waste water
In this present embodiment, the pH value of pending alkaline waste water is 11.34, and COD is 11,632ppm, and the alkalescence is useless
Calcium hydroxide, the calcium carbonate of 1.03 weight % of 0.86 weight % is included in water.In addition, with high performance liquid chromatograph (high
Performance liquid chromatography, HPLC) to analyze, in the undressed alkaline waste water, glycerine contains
The content for measuring the 0.519 weight % and dichlorohydrin that account for the alkaline waste water is 0.0436 weight %.
The alkaline waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, and with 19 kilograms per hour of stream
Speed is passed through chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system), with 80 kilograms per hour of flow velocity
Sodium hydroxide solution (concentration is 32 weight %, Yi Fang chemical industry limited companies production system) is passed through, is passed through the alkaline waste water
In the content of the chlorine gross weight that accounts for the alkaline waste water be 6.3 weight %, and the sodium hydroxide in the alkaline waste water being passed through accounts for
8.5 weight % of the gross weight of the alkaline waste water, under the conditions of 95 ± 5 DEG C, be detained 1.6 it is small when after, measure water in pH value,
The content of COD, calcium hydroxide and calcium carbonate, and it is recorded in table 2.
The method that the present invention of embodiment 2 reduces COD in waste water
In this present embodiment, the pH value of pending alkaline waste water is 11.29, and COD is 11,862 ppm, and the alkalescence
0.63% calcium hydroxide, 1.69% calcium carbonate are included in waste water.In addition, with high performance liquid chromatograph (high
Performance liquid chromatography, HPLC) to analyze, in the undressed alkaline waste water, glycerine contains
The content for measuring the 0.510 weight % and dichlorohydrin that account for the alkaline waste water is 0.0431 weight %.
The alkaline waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, and with 19 kilograms per hour of stream
Speed is passed through chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system), with 60 kilograms per hour of flow velocity
Sodium hydroxide solution (concentration 32%, Yi Fang chemical industry limited company production system) is passed through, is passed through in the alkaline waste water
Chlorine accounts for 3.8 weight % of the gross weight of the alkaline waste water, and the sodium hydroxide being passed through in the alkaline waste water accounts for the alkaline waste water
4 weight % of gross weight, under the conditions of 95 ± 5 DEG C, be detained 1 it is small when after, measure water in pH value, COD, calcium hydroxide and carbonic acid
The content of calcium, and it is recorded in table 2.
The method that the present invention of embodiment 3 reduces COD in waste water
In this present embodiment, separated, exemplified by the waste water after pH adjustment and dilution by by preliminary sedimentation, first will be by dichloro
Alkaline waste liquor caused by propyl alcohol saponification (quaternization) is pre-processed, and (e.g., preliminary sedimentation separates, pH is adjusted and dilute
Release), the pH value of pretreated waste water is 6.59, and COD is 3,285 ppm, and does not detect calcium hydroxide and carbon in the waste water
Sour calcium (i.e. the content of the calcium hydroxide and calcium carbonate is less than test limit, about all 0.0 weight %).
The waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, and with 4.8 kilograms per hour of flow velocity
Chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system) is passed through, the flow velocity with 57 kilograms per hour leads to
Enter sodium hydroxide solution (concentration 10%, Yi Fang chemical industry limited company production system), the chlorine being passed through in the waste water accounts for
1.9 weight % of the gross weight of the waste water, and the sodium hydroxide being passed through in the waste water accounts for 2.3 weight % of the gross weight of the waste water, in
Under the conditions of 75 ± 5 DEG C, be detained 2 it is small when after, measure pH value, COD, the content of calcium hydroxide and calcium carbonate in water, and be recorded in
Table 2.
The method that the present invention of embodiment 4 reduces COD in waste water
In this present embodiment, separated, exemplified by the waste water after pH adjustment and dilution by by preliminary sedimentation, this is preprocessed
The pH value of waste water be 6.82, and COD is 3,491ppm, and does not detect calcium hydroxide and calcium carbonate (i.e. hydrogen-oxygen in the waste water
The content for changing calcium and calcium carbonate is less than test limit, all about 0.0 weight %).
The waste water is imported into 500 liters of reactive tanks with cyclic absorption blender, and with 4.8 kilograms per hour of flow velocity
Chlorine (purity is more than 99%, Yi Fang chemical industry limited company production system) is passed through, the flow velocity with 75 kilograms per hour leads to
Enter sodium hydroxide solution (concentration 10%, Yi Fang chemical industry limited company production system), the chlorine being passed through in the waste water accounts for
1.9 weight % of the gross weight of the alkaline waste water, and the sodium hydroxide being passed through in the waste water accounts for the 3.0 of the gross weight of the alkaline waste water
Weight %, under the conditions of 75 ± 5 DEG C, be detained 2 it is small when after, measure pH value in water, COD, calcium hydroxide and calcium carbonate contain
Amount, and it is recorded in table 2.
Table 2
As shown in Table 2, in embodiment 1,2,3 and 4, the pH value of processed alkaline waste water is changed into 5.01 respectively,
4.9th, 5.9 and 5.09, the COD of processed alkaline waste water is respectively 100ppm, 339ppm, 164ppm and 46ppm, COD removals
Rate is 99%, 97%, 94% and 98%, and in processed waste water, does not all detect calcium hydroxide and calcium carbonate, basic salt
The removal rate of class is 100%.
Moreover, by embodiment 3 and 4 as it can be seen that being neutral or acid (calcium hydroxide and calcium carbonate even in waste water
All do not detect) in the case of, still there is more than 94% removal rate using the method for the present invention.
In addition, the method used in can also finding the present invention as embodiment 3 with 4 result still has good when COD is opposite low
Good removal rate, it is seen that method energy sustaining degradation organic matter of the invention, can't decline because of COD tends to COD removal rates
Gently, i.e., the COD in waste water is reduced with being able to equal proportion there is no the removal limit of known degraded, then can be according to being intended to handle
Waste water in COD, draft removal target, and the degree of degraded needed for carries out ratio degradation reaction.
In addition, being analyzed with HPLC, after the method processing by the present invention, the content of glycerine and dichlorohydrin is substantially reduced,
Such as the content of glycerine and dichlorohydrin is respectively 0.00% and 0.00% in the alkaline waste water.Therefore use the side of the present invention
Method, can effectively reduce the COD in waste water, achieve the purpose that organic matter degradation.
The method that the present invention of embodiment 5 reduces COD in waste water
In the reduction waste water of the present invention in an example of chemical oxygen demand method, further include anti-in carrying out the oxychloride
Ying Hou, dechlorination reaction is carried out to the waste water by oxychloride reaction.
In this present embodiment, using the waste water after the method processing by embodiment 1 as sample, and titrated through potassium iodide KI
Method detects, in the waste water that embodiment 1 is reacted by oxychloride, the residual concentration of free chlorine (free chlorine) molecule
For 0.033 weight %.
Then, when carrying out dechlorination reaction, hydrogen peroxide is added in embodiment 1 is by the waste water of oxychloride reaction, with order
The molar ratio of the free chlorine molecule and hydrogen peroxide is 1：1.After dechlorination is handled, the residual of free chlorine molecule in the waste water
Concentration is 0.00 weight %, therefore can solve free chlorine bad-smell problem.
In conclusion the method for COD in waste water is reduced using the present invention, through being passed through chlorine in waste water,
Organic matter in oxychloride alkaline waste water, can reduce the COD in alkaline waste water.Without using unmanageable microorganism into
Row degraded, need not also dilute the alkaline waste water of tape handling, can effectively save cost of sewage disposal.
Furthermore through the waste water after the method processing of the present invention, the removal rate of COD can be more than 94%, more than 97% or
More than 98%, 99% removal rate is very can reach, can more be less than the 100ppm of environmental protection standard institute specification.
In addition, consider it is processed by the invention after waste water in cause stink containing free chlorine (free chlorine) molecule
Problem, can also be further transmitted through removing the waste water progress dechlorination reaction by oxychloride reaction, to reduce to environment
Influence.
In addition, the method for the present invention for caused alkaline waste liquor in epoxychloropropane technique there is good remove to imitate
Fruit, can effectively reduce COD and surplus in alkaline waste water caused by the saponification step in epoxychloropropane technique
Alkaline salt.
Above-described embodiment is to be illustrated the principle of the present invention and its effect, not for the limitation present invention.It is any
Field technology personnel can modify above-described embodiment under the spirit and scope without prejudice to the present invention.Therefore this hair
Bright rights protection scope, should be as listed by claims.
Claims (11)
1. a kind of method for reducing COD in waste water, including：
The gross weight meter with the waste water, the chlorine of 1 to 7 weight % are passed through in waste water of the COD (COD) more than 3000ppm
Gas, to make the waste water carry out oxychloride reaction；And
Alkali is added in the waste water that this is connected with chlorine, to obtain the waste water reacted by oxychloride.
2. the method as described in claim 1, it is characterised in that the waste water is produced in the saponification of epoxychloropropane technique
Raw alkaline waste water.
3. method as claimed in claim 2, it is characterised in that the saponification is dichlorohydrin quaternization.
4. method as claimed in claim 2, it is characterised in that the alkaline waste water contains glycerine and dichlorohydrin.
5. the method as described in claim 1, it is characterised in that with the gross weight meter of the waste water, the chlorine is with per hour 1 to 7
The flow velocity of weight % is passed through in the waste water.
6. the method as described in claim 1, it is characterised in that with the gross weight meter of the waste water, the additive amount of the alkali is 5 to 10
Weight %.
7. method as claimed in claim 6, it is characterised in that the alkali is alkali or alkaline earth metal hydroxide.
8. method as claimed in claim 6, it is characterised in that the alkali adds this with solid or liquid form and is connected with the useless of chlorine
In water.
9. the method as described in claim 1, it is characterised in that when oxychloride reaction progress 1 to 2 is small.
10. the method as described in claim 1, further includes after the oxychloride reaction is carried out, to this by oxychloride reaction
Waste water carries out dechlorination reaction.
11. the method as described in claim 1, further includes before the chlorine is passed through, sedimentation separation processing is carried out to the waste water,
And the pH value for adjusting the waste water is 6 to 7.
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| CN108706761A (en) * | 2018-04-26 | 2018-10-26 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of chloro-pyridine class waste water |
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| CN101925539A (en) * | 2008-01-31 | 2010-12-22 | 索尔维公司 | Process for degrading organic substances in aqueous composition |
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| CN103241862A (en) * | 2013-05-28 | 2013-08-14 | 天津惠畅环保技术有限公司 | Method for treating high-sulfide high-salinity high-COD (Chemical Oxygen Demand) waste water |
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| CN108706761A (en) * | 2018-04-26 | 2018-10-26 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of chloro-pyridine class waste water |
| CN108706761B (en) * | 2018-04-26 | 2021-03-23 | 浙江奇彩环境科技股份有限公司 | Method for treating chloropyridine wastewater |
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