CN101250017A - Purification technique for methyl stannum mercaptide industrial sewage - Google Patents
Purification technique for methyl stannum mercaptide industrial sewage Download PDFInfo
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- CN101250017A CN101250017A CNA2008101032818A CN200810103281A CN101250017A CN 101250017 A CN101250017 A CN 101250017A CN A2008101032818 A CNA2008101032818 A CN A2008101032818A CN 200810103281 A CN200810103281 A CN 200810103281A CN 101250017 A CN101250017 A CN 101250017A
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- methyl stannum
- stannum mercaptide
- waste water
- industrial sewage
- purification process
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Abstract
The invention discloses a purification process of industrial wastewater of methyltin mercaptide, in which the condensation wastewater in the production of methyltin mercaptide is mixed with raw wastewater after sequentially via oil separating, coagulating, adsorbing and rectifying, further via anaerobic biological treatment, when COD in the water is lower than 500mg/L, mixture of the condensation wastewater and the raw wastewater is sent into domestic sewage via pipelines and purified with the domestic sewage. The invention purifies the industrial wastewater of methyltin mercaptide with the domestic sewage through classifying and preprocessing the industrial wastewater of methyltin mercaptide to the certain extent, then combining for biochemical treatment and meeting discharge requirement of class III, thereby not only saving investment and reducing operation costs, but also facilitating management.
Description
Technical field
The present invention relates to the water field of purification, be specifically related to the purification process of trade effluent in the Methyl stannum mercaptide production.
Background technology
Organotin becomes the most important stablizer of a class in the current PVC goods with its good photo and thermal stability and mutual solubility, wherein be most widely used in the PVC goods with Methyl stannum mercaptide again, because of its stability, the transparency and mutual solubility, weathering resistance all are better than other organotin, so the good reputation of " king of stablizer " is arranged.
The synthetic of Methyl stannum mercaptide mainly contained for two steps, and the first step is that reaction product is the mixture of dimethyl tin dichloride and trichloromethyl tin by methyl chloride and the synthetic chloromethyl tin of glass putty.This mixture adopts the reaction of appropriate acid binding agent and isooctyl mercaptoacetate to generate Methyl stannum mercaptide under appropriate solvent, temperature, pressure.
The waste water that Methyl stannum mercaptide produces in process of production can be divided into two classes according to the treatment process difference, and a class is the condensation waste water from the condensation reaction generation of methyl chloride tin and thiol esters, another kind of crude product waste water for producing in the product purification process.This two classes waste water all contains thiol esters, Methyl stannum mercaptide, ammonia and a large amount of Cl
-, NH
4 +Plasma.Compare with crude product waste water, condensation waste water have salinity height (more than 10%), COD concentration height (10,000-210,000mg/L), NH
4 +-N concentration height (20,000-40,000mg/L) small scale (5-20m
3/ day) etc. characteristics, the existence of thiol esters and ammonia makes waste water not only unpleasant unusually, and poisonous and harmful, is the emphasis and the difficult point of Methyl stannum mercaptide manufacturer process for producing waste water.
The processing of relevant this type of waste water, investigation is found, the main mode of taking at present, the one, oxidation-dilution method exactly with oxygenant waste water COD is dropped to 3000mg/L earlier, is delivered to then and is handled together with sewage after large-scale or medium-sized sewage work dilutes.This method is handled owing to delivering to large-scale or medium-sized sewage work, and shipment distance is far away relatively, and manageability does not have the high processing cost.The 2nd, the wet oxidation method is exactly under high temperature (125-320 ℃) high pressure (0.5-20Mpa) condition, with airborne oxygen or H
2O
2Being oxygenant, is inorganics or small organic molecules such as carbonic acid gas, water with the oxidation operation in the waste water, handles comparatively thorough.But this method needs pressurized, heated, the energy consumption height, so expense is also higher.
Summary of the invention
In view of this, in order to overcome the jejune problem of method for purifying treatment of industrial effluent in the present Methyl stannum mercaptide production, the invention provides a kind of purifying treatment with methyl stannum mercaptide industrial sewage and purify waste water with life and handle the sewage treatment process that combines, so that reduce investment outlay, reduce working cost, be convenient to management.
The purification process of methyl stannum mercaptide industrial sewage provided by the invention, be that the condensation waste water in the Methyl stannum mercaptide production is mixed with crude product waste water after oil removal, coagulation, absorption, rectification process successively, pass through 2-15 days anaerobic biological treatment again, when chemical oxygen demand COD in the water is lower than 500mg/L after pipeline is sent in the sanitary sewage, with the sanitary sewage purifying treatment; Described oil removal is meant removes surperficial oil slick; Coagulation is meant by stirring behind the coagulating agent that adds 500-5000mg/L, filtering; Absorption is meant and adds 80-500kg/m
3Sorbent material, fully absorption; Rectifying is meant by rectifying tower carries out gas-liquid separation, removes easy evaporable ammonia in the waste water.
Described anaerobic biological treatment is to utilize facultative anaerobe and obligatory anaerobic bacteria that larger molecular organics in the sewage is degraded to low molecular compound, and then be converted into small molecules, the easy organic wastewater treatment of resolvent, be divided into two stages of acid digestion and alkaline digest.In the acid digestion stage,, make larger molecular organics become simple organic acid and alcohols, aldehydes and carbonic acid gas etc. by acid-producing bacteria (as sulfydryl decomposer etc.) excretory exoenzyme effect; In the alkaline digest stage, the meta-bolites of acid digestion further resolves into methane, carbonic acid gas etc. under the methanogen effect.
The present invention to a certain degree, remerges biochemical treatment by pre-treatment that methyl stannum mercaptide industrial sewage is classified, and reaches behind three grades of emission requests with the sanitary sewage purifying treatment, not only reduces investment outlay, has reduced working cost, and be convenient to management.
Further, described oil removal is to remove surperficial oil slick in the waste liquid by inclined plate grease pond or water-and-oil separator are set.
Further, described coagulating agent is bodied ferric sulfate or poly-ferric chloride.
Further, described coagulation is bodied ferric sulfate or the poly-ferric chloride that adds 500-2000mg/L, behind the stirring 0.1-2h, adds coagulant aids 2-20mg/L under whipped state, continues to stir 5-15 minute, leaves standstill 0.5-3h, filters.
Further, described coagulant aids is polyacrylamide (PAM).
Further, described absorption is meant and adds 80-167kg/m
3Sawdust or 80-500kg/m
3Activated carbon.
Further, described gac specific surface is 600-1300m
2/ g, density is 470-520kg/m
3
Behind condensation waste water process oil removal-coagulation-absorption-rectification process, water outlet NH
4 +-N is less than 200mg/L, and COD is less than 2500mg/L.Wherein oil removal technology mainly is to remove surperficial oil slick, the surface oil slick is mainly formed by separating incomplete intermediates and the unreacted raw material of part, concrete separating step is for being provided with inclined plate grease pond or water-and-oil separator, to condensation waste water from condensation process, carry out oily water separation, by the oil removal operation, not only remove oil slick, COD can reduce 10-35% simultaneously.Coagulation process mainly is to remove the thiol esters compounds, mainly be by dosing coagulant bodied ferric sulfate or poly-ferric chloride, dosage is 500-5000mg/L, behind stirring reaction 0.1-2h, under whipped state, add coagulant aids such as PAM (molecular weight is 300-2000 ten thousand) 2-20mg/L, continue to stir after 5-15 minute and leave standstill 0.5-3h, filter afterwards, by this step, COD can remove 40-70%.Absorbing process mainly is to remove most of organotin and portion C OD, and sorbent material can be sawdust according to local production characteristics, also can be gac; When adopting sawdust absorption, the condensation waste water amount is 5-15m
3During/d, dosage is 2500-25000kg, can keep 30-200 days, adsorbs the sheet material that saturated sawdust can be used for producing different densities, also can directly burn; When adopting gac, the gac specific surface requires at 600-1300m
2/ g, density is at 470-520kg/m
3, the condensation waste water amount is 5-15m
3During/d, dosage is 2500-25000kg, can keep 10-80 days, and absorption back gac is renewable, and by this step, COD can remove 40-85%; After rectification process is meant that waste water is promoted by pump, through preheating section, heating zone, wastewater temperature is risen to 50-100 ℃ by normal temperature, enter from the rectifying tower middle part, carry out gas-liquid separation, gaseous ammonia is in the condensation of cat head process, except that partial reflux (reflux ratio is 1.02-4.0), all the other recyclings, liquid enters at the bottom of the tower, heat by the bottom, temperature is 80-105 ℃, and the ammonia in the liquid is continued to be evaporated, and enters recovered overhead, after the water outlet process recovery of heat (being used for preheating), directly send into crude product waste water and mix at the bottom of the tower.By rectifying separation, the ammonia purity of recovery can be back to the condensation process neutralizing agent more than 90%, also ammoniacal liquor can be done fertilizer export trade or personal, and by this technology, ammonia nitrogen removal frank is at 80-99.5%.With after crude product waste water mixes, COD is at 1000-5000mg/L with the condensation waste water treating water, and through 2-15 days anaerobic biological treatment, COD reached " integrated wastewater discharge standard " three grades of emission standards less than 500mg/L, can handle with sanitary sewage.
Beneficial effect of the present invention is:
1. because generally speaking, manufacturer is all from having sanitary sewage disposal factory on a small scale, and mainly be biochemical processing process, processing cost is lower, and the present invention combines the purifying treatment of methyl stannum mercaptide industrial sewage with sanitary sewage disposal, handle purification of waste water to a certain degree after, deliver to sanitary sewage disposal factory by pipeline again and carry out purifying treatment, not only can reduce investment outlay, can also save working cost, be convenient to management.
2. decontamination process of the present invention, rectifying are removed the required heat of ammonia operation and can be got final product from the used heat that production process produces, and need not extra pressurized, heated, so energy consumption are low, cost saving.
3. the ammonia that reclaims in the scavenging process of the present invention can be back to the condensation process neutralizing agent, also ammoniacal liquor can be done fertilizer export trade or personal,
Although by reference some preferred embodiment of the present invention, the present invention is illustrated and describes, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Description of drawings:
Fig. 1. the purification process schema of methyl stannum mercaptide industrial sewage of the present invention
Embodiment:
Embodiment 1
Certain methyl stannum mercaptide industrial sewage, condensation waste water water yield 10m
3/ d, water-quality COD are 20000mg/L, NH
4 +-N is 40000mg/L, and organotin content is 3000mg/L, Cl
-Content is 8000mg/L, and mercaptans content is 2000mg/L, through inclined plate grease, stirs coagulation, filtration behind the input 5000mg/L iron trichloride, adds 80kg/m
3(specific surface is 600m to acticarbon
2/ g, density is 470kg/m
3), fully after the absorption, again through rectifying separation ammonia, with the water yield be 70m
3/ d, water-quality COD are 1000mg/L, NH
4 +-N is 30mg/L, Cl
-Content is that the crude product waste water of 300mg/L mixes, and handles through 15 days anaerobic biologicals, and water outlet COD is 430mg/L, NH
4 +-N is 50mg/L, and total tin is 0.8mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Embodiment 2
Certain methyl stannum mercaptide industrial sewage, condensation waste water water yield 15m
3/ d, water-quality COD are 200000mg/L, NH
4 +-N is that the condensation waste water of 20000mg/L is removed surperficial oil slick through water-and-oil separator, stirs coagulation, filtration behind the input 2000mg/L bodied ferric sulfate, adds 100kg/m
3(specific surface is 1000m to acticarbon
2/ g, density is 490kg/m
3), fully after the absorption, again through rectifying separation ammonia, with the water yield be 80m
3/ d, water-quality COD are 2000mg/L, NH
4 +-N is 20mg/L, Cl
-Content is that the crude product waste water of 350mg/L mixes, and handles through 10 days anaerobic biologicals, and water outlet COD is 475mg/L, NH
4 +-N is 41mg/L, and total tin is 0.7mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Embodiment 3
The condensation waste water of handling and crude product waste water with embodiment 1.
Condensation waste water is removed surperficial oil slick through water-and-oil separator, stirs 2 hours behind the input 500mg/L poly-ferric chloride, adds polyacrylamide 20mg/L, continues to stir 10 minutes, leaves standstill 3 hours, filters, and adds 167kg/m
3The sawdust sorbent material, fully absorption behind rectifying separation ammonia, mixes with crude product waste water again, handles through 6 days anaerobic biologicals, and water outlet COD is 400mg/L, NH
4 +-N is 46mg/L, and total tin is 0.7mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Embodiment 4
The condensation waste water of handling and crude product waste water with embodiment 2.
Condensation waste water is removed surperficial oil slick through water-and-oil separator, stirs 0.1 hour behind the input 3000mg/L bodied ferric sulfate, adds polyacrylamide 10mg/L, continues to stir 5 minutes, leaves standstill 1 hour, filters, and adds 85kg/m
3The sawdust sorbent material, fully absorption behind rectifying separation ammonia, mixes with crude product waste water again, handles through 2 days anaerobic biologicals, and water outlet COD is 421mg/L, NH
4 +-N is 45mg/L, and total tin is 0.1mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Embodiment 5
The condensation waste water of handling and crude product waste water with embodiment 1.
Condensation waste water is removed surperficial oil slick through the inclined plate grease pond, stirs 1.5 hours behind the input 500mg/L bodied ferric sulfate, adds polyacrylamide 2mg/L, continues to stir 15 minutes, leaves standstill 0.5 hour, filters, and adds 500kg/m
3(specific surface is 1300m to activated carbon adsorbent
2/ g, density is 500kg/m
3), fully absorption behind rectifying separation ammonia, mixes with crude product waste water again, handles through 15 days anaerobic biologicals, and water outlet COD is 402mg/L, NH
4 +-N is 40mg/L, and total tin is 0.2mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Embodiment 6
The condensation waste water of handling and crude product waste water with embodiment 2.
Condensation waste water is removed surperficial oil slick through the inclined plate grease pond, stirs 1 hour behind the input 1000mg/L poly-ferric chloride, adds polyacrylamide 15mg/L, continues to stir 8 minutes, leaves standstill 1 hour, filters, and adds 80kg/m
3The sawdust sorbent material, fully absorption after the rectification process separation of ammonia, mixes with crude product waste water again, handles through 3 days anaerobic biologicals, and water outlet COD is 443mg/L, NH
4 +-N is 46mg/L, and total tin is 0.7mg/L, reaches " integrated wastewater discharge standard " three grades of emission requests, handles with sanitary sewage.
Claims (7)
1. the purification process of a methyl stannum mercaptide industrial sewage, it is characterized in that, condensation waste water in the Methyl stannum mercaptide production is mixed with crude product waste water after oil removal, coagulation, absorption, rectifying successively, pass through 2-15 days anaerobic biological treatment again, when chemical oxygen demand COD in the water is lower than 500mg/L after pipeline is sent in the sanitary sewage, with the sanitary sewage purifying treatment; Described oil removal is meant removes surperficial oil slick; Coagulation is meant by stirring behind the coagulating agent that adds 500-5000mg/L, filtering; Absorption is meant and adds 80-500kg/m
3Sorbent material, fully absorption; Rectifying is meant by rectifying tower carries out gas-liquid separation, removes easy evaporable ammonia in the waste water.
2. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 1, it is characterized in that described oil removal is to remove surperficial oil slick in the waste liquid by inclined plate grease pond or water-and-oil separator are set.
3. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 1, it is characterized in that described coagulating agent is bodied ferric sulfate or poly-ferric chloride.
4. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 1, it is characterized in that, described coagulation is to add 500-2000mg/L bodied ferric sulfate or poly-ferric chloride, after stirring 0.1-2h, under whipped state, add coagulant aids 2-20mg/L, continue to stir 5-15 minute, leave standstill 0.5-3h, filter.
5. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 4, it is characterized in that described coagulant aids is polyacrylamide PAM.
6. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 1, it is characterized in that described absorption is meant and adds 80-167kg/m
3Sawdust or 80-500kg/m
3Activated carbon.
7. according to the purification process of the described methyl stannum mercaptide industrial sewage of claim 6, it is characterized in that described gac specific surface is 600-1300m
2/ g, density is 470-520kg/m
3
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810103281A CN101250017B (en) | 2008-04-02 | 2008-04-02 | Purification technique for methyl stannum mercaptide industrial sewage |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810103281A CN101250017B (en) | 2008-04-02 | 2008-04-02 | Purification technique for methyl stannum mercaptide industrial sewage |
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| CN101250017A true CN101250017A (en) | 2008-08-27 |
| CN101250017B CN101250017B (en) | 2010-05-12 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402495B (en) * | 2008-11-12 | 2011-09-07 | 云南锡业集团（控股）有限责任公司 | Process for treating waste water from thiol methyl tin production |
| CN104386848A (en) * | 2014-09-25 | 2015-03-04 | 昆明理工大学 | Organic tin production wastewater treatment method |
| CN107226579A (en) * | 2016-03-24 | 2017-10-03 | 福建省三净环保科技有限公司 | A kind of sewage disposal device |
| CN108976254A (en) * | 2018-07-04 | 2018-12-11 | 湖北犇星化工有限责任公司 | A kind of dry method for waste water of reduction thiol methyl tin synthesis |
| CN114314732A (en) * | 2022-01-06 | 2022-04-12 | 绍兴上虞联谊化工有限公司 | Treatment and recycling process of sulfonated para-ester production mother liquor wastewater |
| CN114956404A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Micro-electrolysis Fenton pretreatment process for photovoltaic wastewater |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316394A (en) * | 2000-04-06 | 2001-10-10 | 刘玉伶 | Process for reclaiming sewage |
| CN101148275B (en) * | 2007-07-26 | 2010-09-22 | 滨州市隆盛宏源化工科技有限公司 | PVC centrifugal mother liquor treatment reclaiming technique and device |
-
2008
- 2008-04-02 CN CN200810103281A patent/CN101250017B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402495B (en) * | 2008-11-12 | 2011-09-07 | 云南锡业集团（控股）有限责任公司 | Process for treating waste water from thiol methyl tin production |
| CN104386848A (en) * | 2014-09-25 | 2015-03-04 | 昆明理工大学 | Organic tin production wastewater treatment method |
| CN104386848B (en) * | 2014-09-25 | 2016-02-24 | 昆明理工大学 | A kind of method processing organotin factory effluent |
| CN107226579A (en) * | 2016-03-24 | 2017-10-03 | 福建省三净环保科技有限公司 | A kind of sewage disposal device |
| CN108976254A (en) * | 2018-07-04 | 2018-12-11 | 湖北犇星化工有限责任公司 | A kind of dry method for waste water of reduction thiol methyl tin synthesis |
| CN114314732A (en) * | 2022-01-06 | 2022-04-12 | 绍兴上虞联谊化工有限公司 | Treatment and recycling process of sulfonated para-ester production mother liquor wastewater |
| CN114956404A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Micro-electrolysis Fenton pretreatment process for photovoltaic wastewater |
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| Publication number | Publication date |
|---|---|
| CN101250017B (en) | 2010-05-12 |
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