CN103936216A - Polycarbonate process wastewater treatment method - Google Patents
Polycarbonate process wastewater treatment method Download PDFInfo
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- CN103936216A CN103936216A CN201410097153.2A CN201410097153A CN103936216A CN 103936216 A CN103936216 A CN 103936216A CN 201410097153 A CN201410097153 A CN 201410097153A CN 103936216 A CN103936216 A CN 103936216A
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Abstract
The invention discloses a polycarbonate process wastewater treatment method using a two-stage countercurrent continuous extraction system. The two-stage countercurrent continuous extraction system comprises a mixing kettle, a peristaltic pump, a centrifuge, an evaporator, a mixing kettle, a wastewater storage pot and a resin adsorption tower. A solvent used for synthesizing polycarbonate is used as an extractant, a feeding volume ratio of the extractant to wastewater is 0.08-0.1:1, and a feeding mass-to-volume ratio of resin to wastewater is 0.025:1. The resin used for adsorption is polystyrene resin. The method has the advantages of recycling of phenol substances in wastewater, less consumption of the extractant, low wastewater treatment cost and easy industrial amplification. The recovered phenol substances can be used for synthesizing polycarbonate, and treated brine can be directly discharged, or can be discharged to high salt environment, or can be used for the preparation of sodium hydroxide, chlorine and the like through the electrolysis of the chlorine-alkali industry.
Description
Technical field:
The present invention relates to a kind of polycarbonate processing wastewater treatment process, especially adopt secondary counter current continuous extraction method to process the method for polycarbonate processing wastewater.
Background technology:
Polycarbonate (PC) is the general thermoplastic engineering plastic of a kind of tasteless, odorless, nontoxic, high comprehensive performance, there is outstanding shock resistance, creep resistance, tensile strength, thermotolerance and winter hardiness, fabulous shape and colour stability, dielectric properties are good, and light transmission is good, are unique transparent products in five large-engineering plastics.Polycarbonate is widely used in the fields such as automobile, building, packaging, health care, household supplies, and expands to rapidly many high-technology fields such as Aeronautics and Astronautics, robot calculator, CD, and having replaced ABS becomes most widely used material.
The preparation of industrialization polycarbonate at present mainly adopts interface phosgenation and melt transesterification process, wherein more than 80% adopts phosgene interface polycondensation to produce.This method technical maturity, quality product is higher.Synthetic adopt " two-step approachs " of phosgene interface polycondensation synthetic more." two-step approach " reaction equation is as follows:
Can find out from production technique, in polycarbonate production process, produce a large amount of waste water.This part waste water complicated component, mainly contains: (1) organism.Mainly that macromole intermediate product in polycarbonate production process, organic solvent dichloromethane, a small amount of unreacted raw material are as dihydroxyphenyl propane etc.; (2) ion.Derive from the ion of raw material and byproduct of reaction, as Na
+, Cl
-, CO
3 2-, OH-etc.; (3) contaminated water.Water, water generation reaction and aftertreatment washing water that raw material caustic soda is brought into.
Owing to containing a large amount of Na in polycarbonate waste water
+, Cl
-, CO
3 2-, OH-plasma and organism (dihydroxyphenyl propane, phenol, p-tert-butylphenol, triethylamine, polycarbonate oligomer etc.), single treatment process is difficult to thoroughly remove.At present, the treatment process of this waste water is mainly contained to physico-chemical processes (reverse osmosis method, osmose process, distillation method, burning method, electrochemical process), biochemical process and biological process and additive method combination (liquid/liquid extraction-membrane bioreactor combination process, activated sludge process and granulated active carbon combination process).Processing costs is high, is difficult to reach country and processes emission standard.Can process in an efficient way this class waste water recycle valuable cargo wherein, become a problem demanding prompt solution of domestic polycarbonate industry development.
Chinese patent CN1402749A discloses the method and apparatus of a kind of preparation PC under brine recycling.This method is by the organism in oxidized waste water, makes waste water obtain that purifying further effectively utilizes.But the complete oxidized decomposition of the aldehydes matter in water, is not utilized effectively.US Patent No. 0226078A discloses and has utilized containing the organism in the organic solvent extraction water of amine coupling catalyst, and the water after extraction is removed after residual organic solvent and amine substance by vaporizing extract process, can carry out electrolysis application.After extraction, directly turn back in the building-up process of polycarbonate containing organic organic phases such as dihydroxyphenyl propane, phenol, p-tert-butylphenol, polycarbonate oligomers, participate in the polyreaction of polycarbonate.This method has effectively been utilized the aldehydes matter in water, but it is large to extract organic solvent amount used, causes the cost of wastewater treatment high.
Summary of the invention:
Polycarbonate processing wastewater treatment process provided by the invention, to adopt the processing of secondary counter current continuous extraction method, send into and comprise that the secondary counter current continuous extraction system of mixing kettle, peristaltic pump, whizzer, vaporizer, mixing kettle, wastewater storage tank, resin absorption tower composition processes continuously by polycarbonate processing wastewater, extraction agent is the conventional methylene chloride or 1 of polycarbonate synthesis, 2-ethylene dichloride, the volume ratio that feeds intake of extraction agent and waste water is 0.08～0.1:1.The synthesizing section that can be back to polycarbonate containing phenol material after concentrated of extraction phase, extraction agent can be recycled.Water after extraction detects, and carries out resin absorption while recording COD value >=100mg/L, when COD value≤100mg/L without carrying out resin absorption.Described resin is polystyrene resins.The mass volume ratio that feeds intake of described resin and waste water is 0.025:1.Resin after absorption is reusable after desorb, and after processing, the high density salt solution of COD value≤100mg/L is directly discharged in high saline environment or as the salt of using of chlorine industry.
Concrete operation step of the present invention is as follows:
Polycarbonate waster water process waste water enters mixing kettle, add and after extraction agent stirs fully, deliver to whizzer with peristaltic pump and separate, the extraction phase of separating is concentrated through vaporizer, after concentrated, extraction phase is directly back to the synthesizing section of polycarbonate, extraction agent enters mixing kettle and recycles, water enters another mixing kettle and adds fresh solvent, after stirring fully, delivering to another whizzer with peristaltic pump filters, the reextraction refiltering is directly back to the synthesizing section of polycarbonate mutually, gained waste water enters secondary wastewater storage tank, while recording secondary wastewater COD value >=100mg/l and phenol content >=0.5mg/L, adopt adsorption treatment, send into and polystyrene resins adsorption tower is housed carries out resin absorption, after resin absorption, the high density salt solution of COD value≤100mg/l is directly discharged in high saline environment in seawater or as the raw material salt of chlorine industry.
Waste water is after continuous extraction is processed, and aldehydes matter is complete by dichloromethane extraction, there is no aldehydes matter through liquid chromatographic detection, and the rate of recovery is 97%.
Polycarbonate processing wastewater of the present invention mainly refers to the waste water that phosgene interfacial polycondensation " two-step approach " polycarbonate synthesis produces.Salts contg >=4% in waste water, content of bisphenol A >=300mg/L, phenol content >=0.25mg/L, N content >=300mg/L, COD value >=7000mg/L, pH value > 7.
The present invention is a kind of method that continuous secondary counter-current extraction is processed polycarbonate processing wastewater, waste water after treatment can reach country's " integrated wastewater discharge standard " GB8978-1996 first discharge standard, can make the aldehydes matter in waste water be recycled utilization, and extraction agent consumption is less, the cost of wastewater treatment is low, is easy to industry and amplifies.The aldehydes matter reclaiming can be used for the synthetic of polycarbonate, and salt solution after treatment can directly discharge in paramount saline environment or for chlorine industry electrolytic preparation caustic soda, chlorine etc.Waste water is after continuous extraction is processed, and aldehydes matter is complete by methylene dichloride or the extraction of 1,2-ethylene dichloride, there is no aldehydes matter through liquid chromatographic detection, and the rate of recovery is 97%.
Brief description of the drawings:
Fig. 1 is that secondary counter current continuous extraction method is processed polycarbonate processing wastewater schema.
In Fig. 1,1 mixing kettle, 2 peristaltic pumps, 3 whizzers, 4 vaporizers, 5 mixing kettles, 6 peristaltic pumps, 7 whizzers, 8 secondary wastewater storage tanks, 9 resin absorption towers, 10 fresh solvents, 11 waste water, 12 distillate solvent, 13 concentrated rear extraction phases, 14 high density salt solution, 15 reextraction phases.
Embodiment:
Described in embodiment 1 and 2, polycarbonate processing wastewater is all processed by following flow process.
Polycarbonate processing wastewater enters mixing kettle 1 from a waste water 11, after stirring fully with extraction phase, deliver to whizzer 3 with peristaltic pump 2, concentrated through vaporizer 4 from whizzer 3 extraction phase out, after concentrated containing phenol extraction 13 synthesizing sections that are directly back to polycarbonate mutually, extraction agent enters mixing kettle 1 and recycles, water enters mixing kettle 5 and adds fresh solvent 10, after stirring fully, delivering to whizzer 7 with peristaltic pump 6 filters, the reextraction phase 15 of filtering through whizzer 7 is directly back to the synthesizing section of polycarbonate, gained waste water is that secondary wastewater enters secondary wastewater storage tank 8, then enter resin absorption tower 9 and carry out resin absorption, high density salt solution 14 after resin absorption is directly discharged in high saline environment or as the salt of using of chlorine industry.Discharge water reaches country's " integrated wastewater discharge standard " GB8978-1996 first discharge standard.
Embodiment 1
Recording waste water composition is NaCl5%, dihydroxyphenyl propane 395mg/L, and phenol 0.25mg/L, N content 350mg/L, COD is 7800mg/L, waste water ph is about 10.2.As stated above at room temperature, 1000ml waste water is sent into mixing kettle 1 from a waterwater entrance 11.The extraction agent methylene dichloride 70ml of waste water and inflow is after under abundant agitation condition, continuous countercurrent contacts, sent into whizzer 3 by peristaltic pump 2 centrifugal, be admitted to again mixing kettle 5, comprise the fresh solvent methylene dichloride of adding and the methylene chloride steaming by vaporizer with fresh solvent methylene dichloride 30ml() fully mix, be evacuated to whizzer 7 by peristaltic pump 6 again and carry out centrifugation, the dihydroxyphenyl propane of gained waste water is down to 12mg/L, phenol 0.005mg/L, and COD value is 800mg/L.Adsorb with polystyrene resin 25g, the water COD value after resin absorption is reduced to 96mg/L again, and ammonia nitrogen is 15mg/L, and TOC is 18mg/L.Meet regulation in GB26451-2011 and " integrated wastewater discharge standard " GB8978-1996, meet or exceed in line standard completely.From whizzer 3 extraction phase dihydroxyphenyl propane 3830mg/L out, phenol 2.45mg/L, dihydroxyphenyl propane 38300mg/L after vaporizer 4 is concentrated, phenol 24.5mg/L, returns to the synthesizing section of PC.Resin after absorption is reused after desorb.Experimental results show that applying mechanically solution that this phenols content is higher does not affect the quality of polycarbonate.Waste water is after continuous extraction is processed, and aldehydes matter is complete by methylene dichloride or the extraction of 1,2-ethylene dichloride, there is no aldehydes matter through liquid chromatographic detection, and the rate of recovery is 97%.
Embodiment 2
With reference to technique shown in Fig. 1 and device, recording waste water composition is NaCl14%, dihydroxyphenyl propane 975mg/L, and phenol 0.23mg/L, N content 500mg/L, COD value of waste water is 9600mg/L, pH value is 10.6.With embodiment 1 method, adopt the waste water (1000ml) of secondary continuous countercurrent extraction polycarbonate.As stated above at room temperature, 1000ml waste water is sent into mixing kettle 1 from a waterwater entrance 11.The extraction agent 1 of waste water and inflow, 2-ethylene dichloride 50ml is under abundant agitation condition after continuous countercurrent contact, sent into whizzer 3 by peristaltic pump 2 centrifugal, be admitted to again mixing kettle 5, with fresh solvent 1,2-ethylene dichloride 30ml(comprises the fresh solvent 1 of adding, 2-ethylene dichloride and the solvent 1 steaming by vaporizer, 2-ethylene dichloride) fully mix, be evacuated to whizzer 7 by peristaltic pump 6 again and carry out centrifugation, be down to 72mg/L from the dihydroxyphenyl propane of whizzer 7 waste water out, phenol 0.01mg/L, COD is 1120mg/L.Again this waste water is sent into secondary continuous countercurrent extraction system from a waterwater entrance 11, the water dihydroxyphenyl propane after extraction is down to 0.04mg/L, phenol 0.002mg/L, and COD is 90mg/L, and ammonia nitrogen is 12mg/L, and TOC is 15mg/L.Can exempt resin absorption.Return to the synthesizing section of PC from whizzer 3 extraction phase (dihydroxyphenyl propane 9710mg/L phenol 2.28mg/L) out (dihydroxyphenyl propane 97100mg/L phenol 22.8mg/L) after vaporizer 4 is concentrated, experimental results show that applying mechanically solution that this phenols content is higher does not affect the quality of polycarbonate.
Claims (2)
1. polycarbonate processing wastewater treatment process, it is characterized in that with methylene dichloride or 1, 2-ethylene dichloride is extraction agent, the volume ratio that feeds intake of extraction agent and waste water is 0.08～0.1:1, polycarbonate processing wastewater is comprising mixing kettle, peristaltic pump, whizzer, vaporizer, mixing kettle, wastewater storage tank, in the secondary counter current continuous extraction system of resin absorption tower composition, process continuously, water after extraction treatment detects, while recording COD value >=100mg/l and phenol content >=0.5mg/L, adopt polystyrene resins to carry out adsorption treatment, when COD value≤100mg/l without carrying out resin absorption processing, the mass volume ratio that feeds intake of resin and waste water is 0.025:1, the high density salt solution of water COD value≤100mg/l after adsorption treatment is directly discharged in high saline environment or as the raw material salt of chlorine industry.
2. polycarbonate processing wastewater treatment process according to claim 1, is characterized in that the synthesizing section that is back to polycarbonate containing phenol material after concentrating of extraction phase, and extraction agent recycles, and the resin after absorption is reused after desorb.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039486A (en) * | 2019-12-30 | 2020-04-21 | 江西兄弟医药有限公司 | Method for treating o-ethoxyphenol production wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575152A (en) * | 2008-05-05 | 2009-11-11 | 上海芝东商务咨询有限公司 | Reusable method of decanedioic acid phenol-containing wastewater |
| CN102010505A (en) * | 2009-06-04 | 2011-04-13 | 拜尔材料科学股份公司 | Method for producing polycarbonate |
| CN102503010A (en) * | 2011-10-19 | 2012-06-20 | 甘肃银光聚银化工有限公司 | Method for treating polycarbonate waste water and recycling resin glue solution and solvent |
| CN102604067A (en) * | 2012-03-16 | 2012-07-25 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
-
2014
- 2014-03-14 CN CN201410097153.2A patent/CN103936216A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575152A (en) * | 2008-05-05 | 2009-11-11 | 上海芝东商务咨询有限公司 | Reusable method of decanedioic acid phenol-containing wastewater |
| CN102010505A (en) * | 2009-06-04 | 2011-04-13 | 拜尔材料科学股份公司 | Method for producing polycarbonate |
| CN102503010A (en) * | 2011-10-19 | 2012-06-20 | 甘肃银光聚银化工有限公司 | Method for treating polycarbonate waste water and recycling resin glue solution and solvent |
| CN102604067A (en) * | 2012-03-16 | 2012-07-25 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039486A (en) * | 2019-12-30 | 2020-04-21 | 江西兄弟医药有限公司 | Method for treating o-ethoxyphenol production wastewater |
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Application publication date: 20140723 |