CN101450828B - Method for processing VC wastewater by catalytic ozonation - Google Patents
Method for processing VC wastewater by catalytic ozonation Download PDFInfo
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- CN101450828B CN101450828B CN2008102361780A CN200810236178A CN101450828B CN 101450828 B CN101450828 B CN 101450828B CN 2008102361780 A CN2008102361780 A CN 2008102361780A CN 200810236178 A CN200810236178 A CN 200810236178A CN 101450828 B CN101450828 B CN 101450828B
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Abstract
The invention discloses a method for performing catalytic ozonization treatment on VC wastewater, wherein a solid catalyst, namely catalytic ozone, is utilized to oxidize the VC wastewater, and organic substances in the VC wastewater are deeply oxidized and degraded into CO2; and the generated CO2 makes Ca ion deposit in the wastewater separated out. The method comprises: firstly, adding the solid catalyst into an oxidation reactor, and injecting the VC wastewater from an upper opening of the oxidation reactor; secondly, injecting the catalytic ozone from a gas distributor at the bottom of the inside of the oxidation reactor, wherein the treatment temperature in the oxidation reactor is controlled to be between 15 and 95 DEG C, and the residence time of the VC wastewater in the oxidation reactor is between 5 and 180 minutes; and thirdly, discharging the VC wastewater after oxidative degradation from the bottom of the oxidation reactor, and discharging reaction tail gas from a tail gaswasher on the upper part of the oxidation reactor. The COD value of effluent water can be less than 80 mg/L; the decolorization ratio reaches 100 percent; the effluent water does not give out peculiar smell; the total hardness removal rate reaches more than 85 percent; the removal rate of the organic substances is more than 95 percent; secondary pollution does not exist; and the treated VC wastewater can reach the national first class emission standard or be taken as process water for recycling.
Description
Technical field
The present invention relates to field of waste water treatment, be specifically related to the treatment process of vitamins C (Vitamine C is hereinafter to be referred as VC) factory effluent.
Background technology
VC waste water is the waste water that the VC production process produces, and in the actual industrial, 1 ton of VC of every production just produces 150～200 tons of waste water, and China produces VC10 per year more than ten thousand tons at present, so the about 2,000 ten thousand tons of waste water of the annual discharging of VC industry.VC waste water main component is VC, the acid of ancient dragon, sorbyl alcohol, methyl alcohol, polymerization carbohydrate, protein, calcium ion etc., and this waste water has characteristics such as high salt, high COD, high rigidity, and color is sorrel, contains pungency peculiar smell toxic chemical substances such as methyl alcohol.
The VC wastewater treatment is the difficult problem in the VC production process always, and corresponding wastewater processing technology comes into one's own.What study more and industrial practical application is biological degradation method.Hou Aidong etc. have reported that adopting filtration neutralization-UASB-oxidation ditch is the waste water of art breading day quantity discharged more than ten thousand tons of main body, the water outlet COD value 200-400mg/L that this art breading is crossed, the color sorrel, other water quality parameters also all can not satisfy emission request (Hou Aidong Wang Fei etc., filter neutralization-UASB-oxidation ditch [J]. environment Leader 2003,9:30-31.).Li Xiaona introduces certain pharmaceutical factory and adopts bio-contact oxidation art breading VC waste water, this technology water outlet COD can not satisfy emission request, and need high-concentration waste water is diluted, waste former water (Li Xiaona vitamins C Industrial Wastewater Treatment summary [J]. the Yunnan environmental science, 2006,25 (supplementary issues): 140-142.).
Yet biological degradation method can not efficient degradation VC waste water.Because some protein of VC itself and fermenting process bacterial metabolism generation all is fungistat on the one hand, the polymerization carbohydrate will be the height inert substance to bacterium on the other hand, be difficult to biochemical degradation, so present industrial VC produces waste discharge COD value generally at COD200-400mg/L, and color is darker.
So people attempt the waste water by chemical method degraded VC.Rivers and mountains, Jiangsu drugmaker is with ClO
2Chemical oxidation combines with biochemical treatment, improved VC waste water degree of degradation (Chen Honglin, Zhang Changshou. the application [J] of dioxide peroxide in the wastewater treatment of fourth industry. Treatment of Industrial Water .1999.19(6)：5-7)。Jiang Zhanpeng etc. have proposed with Ti-Ce-Bi as catalyzer, about 200 ℃ of temperature, and oxygen partial pressure 3.5MPa handles VC waste water, COD clearance 80～90% under stagnation pressure 4～8MPa condition.This technical matters condition harshness, processing costs are higher, be not suitable for handling on a large scale lot of V C waste water, be only applicable to laboratory study (Jiang opens up the experimental study [J] of Catalytic Wet Oxidation technical finesse VC pharmacy waste waters such as roc poplar magnificence. water supply and drainage 2004, NO.3:41-44.).
In view of VC waste water is difficult to degrade with aforesaid method, when pre-treatment VC wastewater processing technology can not satisfy environmental requirement (as requiring water outlet COD less than 80mg/L), so needing to demand urgently a kind of effective technology of exploitation to handle VC waste water, make water quality parameters such as water outlet COD, colourity all can reach the standard of first grade discharging or reuse.
Summary of the invention
The objective of the invention is for overcoming the defective of prior art, a kind of economy, the method for processing VC wastewater by catalytic ozonation efficiently are provided, make the water after the processing can safety dumping or reuse, save water resources, reduce VC industrial production cost.
The technical scheme that the inventive method adopts is: utilize catalysis of solid catalyst ozone oxidation VC waste water, make organic deep oxidation wherein be degraded to CO
2, the CO of generation
2Ca ion precipitation in the waste water is separated out, specifically adopts following steps:
(A) add solid catalyst in oxidation reactor, make the suitable for reading injection of VC waste water from oxidation reactor, catalysis ozone enters from the gas distributor of oxidation reactor inner bottom part.
(B) treatment temp in the controlled oxidation reactor is 15～95 ℃, and the residence time of VC waste water in oxidation reactor is 5～180 minutes.
(C) the VC waste water after the oxidative degradation is emitted from the bottom of oxidation reactor.
(D) reaction end gas is discharged from the exhaust scrubber on oxidation reactor top.
The invention has the beneficial effects as follows:
1, the oxidation reactor of the present invention's employing can adopt bubbling column reactor, also can adopt common tray column or packing tower, or employing loop reactor or plural serial stage bubbling column reactor, purpose is to improve the utilization ratio of ozone as much as possible, make and do not have ozone in the tail gas basically, do not produce secondary pollution, reduce running cost.
2, the present invention can reach the purpose that reduces discharge water COD and hardness simultaneously.
3, treatment process of the present invention is effective, water outlet COD value can reach 100% less than 80mg/L, percent of decolourization, water outlet free from extraneous odour, total hardness clearance more than 85%, organic removal rate greater than 95%, non-secondary pollution.VC waste water after the processing can reach national grade one discharge standard (less than 80mg/L), perhaps as the process water reuse.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Fig. 1 is a structure connection diagram of the present invention.
Fig. 2 is an one embodiment of the invention structure connection diagram.
Among the figure: 1. fresh feed pump; 2. oxygen/air under meter; 3. oxygen/air under meter; 4. ozone generator; 5. gas distributor; 6. oxidation reactor; 7. thermoindicating controller; 8. exhaust scrubber; 9. discharge tail gas ozone telltale.
Embodiment
As shown in Figure 1: the present invention at VC waste water can be the high-concentration waste water of Vc production plant, comprise and extract mother liquor, transform mother liquor and refinement mother liquor, be sorrel, transparent thick, pH between 2-6, COD
CrValue contains fermented hypha albumen, polymerization carbohydrate, methyl alcohol, organic heteroacid, sodium salt class etc. at 6000-12000mg/l, also can be three sinking pool effluents after, the secondary aerobic treatment aerobic through anaerobism, one-level, COD
Cr: 289mg/l, colourity: 140 times, calcium ion concn 1080mg/l.VC wastewater feed pump 1 is connected oxygen/air under meter 2 backs to be communicated with oxidation reactor 6 tops, oxygen/air under meter 3 connection ozone generators 4 back bottoms from oxidation reactor 6 enter and connect gas distributor 5, and exhaust scrubber 8 is communicated with oxidation reactors 6 tops.On oxidation reactor 6, connect thermoindicating controller 7, the temperature of reaction of controlled oxidation reactor 6.On exhaust scrubber 8, connect discharging tail gas ozone telltale 9.
As shown in Figure 2: oxidation reactor 6 can be the plural serial stage tandem type reactor or is loop reactor, connects corresponding thermoindicating controller 7 on each oxidation reactor 6, at each oxidation reactor 6 inner bottom part corresponding gas distributor 5 is installed.
The present invention utilizes catalysis of solid catalyst ozone oxidation VC waste water, makes organic deep oxidation wherein be degraded to CO
2, the CO of generation
2Ca ion precipitation in the waste water is separated out.Earlier add solid catalyst in oxidation reactor 6, this solid catalyst can be that particulate state also can be Powdered.The catalyst activity component is that the oxide compound of following one or more elements is composited.They comprise B, Ti, Al, Si, V, Nb, Mn, Fe, Co, W, Mo, Ni, Cu, Ag, Ce, Bi etc.Make VC waste water process fresh feed pump 1 and oxygen/air under meter 2 backs in the input oxidation reactor 6 suitable for reading of oxidation reactor 6, enter in the ozone generator 4 behind the oxygen/air process oxygen/air under meter 3 and produce catalysis ozone, this catalysis ozone enters in the oxidation reactor 6 from the gas distributor 5 of oxidation reactor 6 bottoms.Reach the abundant contact reacts of gas, liquid, solid three-phase in oxidation reactor 6, with degraded organism wherein, the catalytic ozonation treatment temp in the controlled oxidation reactor 6 is 15～95 ℃, is preferably 65～85 ℃.The too low VC waste water that is difficult to degrade of temperature, temperature is too high can to reduce ozone utilization rate.The residence time of VC waste water in oxidation reactor 6 is 5～180 minutes; Be preferably 15～60 minutes.The residence time of VC waste water in reactor is too short, and it is insufficient to degrade, and water outlet COD can be too high; The residence time is oversize, and processing cost can be too high.VC waste water after the last oxidative degradation is emitted from the bottom of oxidation reactor 6; Detect the Ca ionic concn of discharge water with the COD value of COD detector mensuration discharge water, with the colourity of colorimeter mensuration discharge water, with plasma emission spectrometer (ICP).Reaction end gas is discharged from the exhaust scrubber 8 on oxidation reactor 6 tops, can be observed the exhaust emissions situation from discharging tail gas ozone telltale 9, utilizes KI solution to carry out ozone indication in the tail gas, washs tail gas with hypo solution.Measure ozone concn in the tail gas with ozone detector.
Embodiment 1
Utilize device shown in Figure 1, oxidation reactor 6 is bubble towers of circulation in having, and its effective volume is 2.5L.With TiO
2(20%)-SiO
2(80%) the mixture solid particulate is a catalyzer, and loaded catalyst is that 15g, granularity are 80～120 orders.Temperature of reaction is controlled at 75 ℃.
VC waste water is to take from Jiangsu Jiangshan Pharmaceutical Co's three sinking pool effluents, COD
Cr: 289mg/l, colourity: 140 times, calcium ion concn 1080mg/l.VC wastewater feed speed is 5L/h, and VC waste water residence time in oxidation reactor 6 is 30min.Regulate oxygen/air under meter 2 oxygen flows, observe, make the tail gas ozone content be no more than 2.5mg/L by discharging tail gas ozone telltale 9.The COD of water outlet
CrValue 63.9mg/L, COD clearance 77.9%; Go out water colorless; Calcium ion concn 49mg/L, clearance reach more than 95%.
Embodiment 2
Change the VC wastewater source, use Vc production plant waste water, be sorrel, colourity greater than 450, COD
CrValue 11270mg/l has pungent taste.Ca ion 52mg/L.Adopt device identical and identical catalyzer with embodiment 1.Temperature of reaction is controlled at 75 ℃.VC wastewater feed speed is 2.5L/h, and VC waste water residence time in oxidation reactor 6 is 60min.Regulate oxygen/air under meter 2 oxygen flows, observe, make the tail gas ozone content be no more than 2.5mg/L by discharging tail gas ozone telltale 9.
The COD of water outlet
CrValue 213.9mg/L, COD clearance 99%; Effluent color dilution 60, tasteless, Ca ion 39.6mg/L.
Embodiment 3
VC wastewater feed speed is 10L/h, and VC waste water residence time in oxidation reactor 6 is 15min.All the other operations are with embodiment 1.The results are shown in table 1.
VC wastewater feed speed is 2.5L/h, and VC waste water residence time in oxidation reactor 6 is 60min.All the other operations are with embodiment 1.The results are shown in table 1.
Embodiment 5
VC wastewater feed speed is 1.25L/h, and VC waste water residence time in oxidation reactor 6 is 120min.All the other operations are with embodiment 2.The results are shown in table 1.
Embodiment 6
VC wastewater feed speed is 30L/h, and VC waste water residence time in oxidation reactor 6 is 5min.All the other operations are with embodiment 1.The results are shown in table 1.
Embodiment 7
Temperature of reaction is controlled to be 15 ℃, and all the other are operated with embodiment 1.The results are shown in table 1.
Temperature of reaction is controlled to be 45 ℃, and all the other are operated with embodiment 1.The results are shown in table 1.
Temperature of reaction is controlled to be 65 ℃, and all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 10
Temperature of reaction is controlled to be 95 ℃, and all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 11
Use γ-Al
2O
3(pore volume 0.72ml/g, specific surface area 135m
2/ g) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 12
Use Fe
2O
3(18%)/γ-Al
2O
3(82%) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 13
Use MoO
3(25%)/γ-Al
2O
3(75%) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 14
Use CuO (20%)/SiO
2(80%) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 15
Use Ni (10%)-B
2O
3(8%)/γ-Al
2O
3(82%) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 16
Use CuO (18%)-Ce
2O
3(6%)/SiO
2(76%) be catalyzer, all the other are operated with embodiment 1.The results are shown in table 1.
Embodiment 17
Use three grades of series connection oxidation reactors 6 as shown in Figure 2, the VC retention time of sewage is 180min, and all the other are operated with embodiment 2.The results are shown in table 1.
Embodiment 18
Use tertiary oxidation reactor 6 as shown in Figure 2, the VC retention time of sewage is 90min, and all the other are operated with embodiment 2.The results are shown in table 1.
Table 1 O3 catalytic oxidation method is handled VC waste water result
Claims (2)
1. the method for a processing VC wastewater by catalytic ozonation is characterized in that: utilize catalysis of solid catalyst ozone oxidation VC waste water, make organic deep oxidation wherein be degraded to CO
2, the CO of generation
2Ca ion precipitation in the waste water is separated out, specifically adopts following steps:
(A) add solid catalyst in oxidation reactor (6), make the suitable for reading injection of VC waste water from oxidation reactor (6), catalysis ozone enters from the gas distributor (5) of oxidation reactor (6) inner bottom part; Solid catalyst is a particulate state or Powdered, and the catalyst activity component is that the oxide compound of one or more elements among B, Ti, Al, Si, V, Nb, Mn, Fe, Co, W, Mo, Ni, Cu, Ag, Ce, the Bi is composited;
(B) treatment temp in the controlled oxidation reactor (6) is 15～95 ℃, and the residence time of VC waste water in oxidation reactor (6) is 5～180 minutes;
(C) the VC waste water after the oxidative degradation is emitted from the bottom of oxidation reactor (6);
(D) reaction end gas is discharged from the exhaust scrubber (8) on oxidation reactor (6) top.
2. the method for a kind of processing VC wastewater by catalytic ozonation according to claim 1 is characterized in that: the residence time of VC waste water in oxidation reactor (6) is 15～60 minutes in the step (B); Treatment temp in the oxidation reactor (6) is 65～85 ℃.
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| CN101955307A (en) * | 2010-10-27 | 2011-01-26 | 同济大学 | Method for treating vitamin B1 production waste water |
| CN102863071B (en) * | 2012-10-23 | 2014-05-07 | 北京市环境保护科学研究院 | Advanced treatment method for decolorizing yeast wastewater |
| CN107064420B (en) * | 2017-02-14 | 2023-11-28 | 中国科学院化学研究所 | Online monitoring system and method for medium-volatile organic compounds in atmosphere |
| CN107051176A (en) * | 2017-06-02 | 2017-08-18 | 中化重庆涪陵化工有限公司 | The ardealite solid waste processing reutilization system and processing method of environmental protection |
| CN109364937A (en) * | 2018-09-25 | 2019-02-22 | 威水星空（北京）环境技术有限公司 | A kind of nanoporous crude boron stone load ferrimanganic composite depth processing catalyst for catalytic ozonation |
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