CN1231991A - Method for treatment of oil-bearing waste water - Google Patents
Method for treatment of oil-bearing waste water Download PDFInfo
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- CN1231991A CN1231991A CN 99116032 CN99116032A CN1231991A CN 1231991 A CN1231991 A CN 1231991A CN 99116032 CN99116032 CN 99116032 CN 99116032 A CN99116032 A CN 99116032A CN 1231991 A CN1231991 A CN 1231991A
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Abstract
A process for treating waste water containing oil includes such technological steps as preparing a high-absorption oil-absorbing resin from emulsifier, monomer, cross-linking agent and initiator in a weight ratio of (350-450) : 100 : (0.1-3) : (0.1-2) through emulsion polymerization at 45-95 deg.C for 6-10 hr, putting the oil-absorbing resin in the waste water containing oil and recovering oil by distillation of the resin. Said resin can be reused. Its advantages are simple process, low cost and no environmental pollution.
Description
The present invention relates to a kind of treatment process of oily(waste)water, the present invention especially relates to a kind of greasy dirt trade effluent (comprise and contain surperficial oil slick, oil in water emulsion, mechanical dispersion wet goods trade effluent), treatment process of catering trade oil-polluted water of containing.
The processing of oily(waste)water, because of its BOD, COD is higher, and the degraded of part oils is difficult, is a difficult problem in the wastewater treatment always; And existing treatment process generally is by after the pre-treatment, carry out oil removal, carry out advanced treatment with biochemical process then, this method floor space is big, and the oil removal method can only the treat surface oil slick, then must be for dispersed oil or oil in water emulsion by handling than complex apparatus, oil removal is also incomplete in addition, and follow-up biochemical treatment is difficulty.High oil absorbing resin is the new research direction that the nineties just occurs, and studies show that high oil absorbing resin has that to absorb oils wide in variety, and oil suction does not absorb water, and volume is little, reclaims after convenient and the oil suction no longer advantage such as leakage of oil of pressurized, is a kind of self swelling type oil absorption material.For this reason, its exploitation, utilization are carried out systematic research, but all located the laboratory study stage both at home and abroad.High oil absorbing resin is applied to oily(waste)water handles, do not see any report at present both at home and abroad as yet.
The objective of the invention is to overcome the deficiencies in the prior art part, develop a kind of processing method of utilizing high oil absorbing resin to handle oily(waste)water,, reduce processing costs to simplify the oily(waste)water treatment process of still continuing to use at present; Valuable oil product is able to reclaiming, and resin is reusable, non-secondary pollution; It is big because of its oils viscosity to solve the catering trade oil-polluted water, and all kinds of detergent surfactants are many, the problem that intractability is big.
A kind of treatment process of oily(waste)water may further comprise the steps and processing condition:
Step 1: high oil absorbing resin synthetic
A, nonionogenic tenside is dissolved in the water, is prepared into concentration and is 0.1～0.5% emulsifying agent;
B, under 55 ± 5 ℃ of temperature, in emulsifying agent: monomer: linking agent: the initiator weight ratio is 350～450: 100: 0.1～3: 0.1～2 ratio is reinforced successively; At this, monomer nail base CALCIUM ACRYLATE fatty alcohol (carbonatoms 4～18) is or/and methacrylic acid, linking agent refers to 1,4 butyleneglycol double methacrylates or 1,6 hexylene glycol double methacrylates, initiator refers to benzoyl peroxide or cyclohexanone peroxide, and nonionogenic tenside refers to polyvinyl alcohol or gelatin or methyl fiber;
C, under 45～95 ℃ of temperature, carried out emulsion polymerization 6～10 hours, promptly synthetic high oil absorbing resin;
Step 2: oily(waste)water is handled
The high oil absorbing resin of 5～20% (weight) of waste water oleaginousness is invested in the oily(waste)water, selects according to the changed condition of oil in waste water that to leave standstill or stir or stir earlier the back static for use, the greasy dirt in the waste water is absorbed, BOD COD reduce;
Step 3: Oil Recovery and resin regeneration
High oil absorbing resin after the oil suction can distill down at 100～200 ℃ and reclaim the oil product regenerating resin, reuses; Also can directly make fuel uses.
High oil absorbing resin also is to utilize the cancellated stretching, extension of its molecule to realize the performance of oil suction guarantor oil.Therefore, oiliness is protected in the oil suction of high oil absorbing resin can all have bigger getting in touch with the oleophylic ability of its side group lipophilic group and the space reticulated structure of molecular resin.Particularly, the oleophylic ability of the ester class group on the resin side group is strong more, and the molecule reticulated structure is big more, and impellent is just bigger and sterically hindered less, and the store oil ability is also strong more, and then its oil suction oil-retaining is higher; Otherwise ester class group oleophylic ability is poor more on the resin side group, and the reticulated structure of molecule is more little, and impellent is just little, and the store oil space is less, and the oil suction oil-retaining of resin is just poor more.Therefore, this patent emphasis is the influences of factors such as the kind of the character of research side group ester class group and kind, linking agent and consumption, monomer ratio, initiator amount to the resin oil absorptiveness.The present invention is a main raw with efficient oil-absorbing resins of raw material synthetic such as methacrylic acid high-carbon (8-18 carbon atom) aliphatic alcohol ester class, vinylformic acid, linking agents, utilize the characteristic of its quick oil suction, in waste water, directly absorb oil product, effectively reduce BOD, alleviated the difficulty of follow-up advanced treatment, and can directly reclaim for most of oils.
The present invention compared with prior art has following advantage:
1, first high oil absorbing resin is applied to contain greasy dirt trade effluent (comprising surperficial oil slick, oil in water emulsion and mechanical dispersion wet goods) and catering trade oil-polluted water and handles, aspects such as anti-oil product seepage.Reduce effectively BOD COD, alleviated the difficulty of follow-up advanced treatment; Simplify existing treatment process, solved the problem of difficulty of incomplete, the follow-up biochemical treatment of existing treatment process oil removal, overcome weakness such as existing treatment process equipment complexity, required area are big.
2, the present invention is according to the result of theoretical investigation, select the kind and the consumption of monomer ratio, linking agent and initiator, can (no matter being that adsorptive type or gel type oil absorption material all have easy oil leakage after the oil suction promptly to protect the shortcoming of oiliness difference) from guarantor's oiliness of having improved traditional oil absorption material, the high oil absorbing resin of this law preparation still can remain on more than 90% when pressurized owing to be to utilize the space reticulated structure of molecule to protect oil.
3, this law synthetic high oil absorbing resin steady quality, oil number is 5～20 times of weight resin part, and synthesis technique and waste water treatment process are simple, and the reaction times is short, and speed of oil absorption is fast, and it is low to handle comprehensive cost.
4, the high oil absorbing resin oil suction of the present invention's preparation does not absorb water, therefore widely applicable, applicable to oil in water emulsion and mechanical dispersion wet goods Industrial Wastewater Treatment, be suitable for the recovery of oil slick especially, valuable oil product is reclaimed, the also renewable repeated use of resin, the oil product of Hui Shouing not only, can directly make fuel usefulness, not produce secondary environmental pollution, and become the useless secondary resource that is.
5, because oil-polluted water treatment unit floor space of the present invention is little, and be specially adapted to the wastewater treatment of urban restaurant trade oils, and oil slick can all directly absorb at short notice, and specific absorption is up to more than 97%, waste water oil-containing after the processing can reach direct emission standard less than 15mg/l.
Fig. 1 is the treatment process main technique flow diagram of oily(waste)water.
The present invention is described in further detail for combined process flow diagram and embodiment:
Embodiment 1: the washes that contains useless machinery oil is handled
At first 1.2 gram gelatin are dissolved in the 500 gram tap water, fully dissolving under refluxing, be cooled to 55 ℃, add 100 gram methacrylic acid aliphatic alcohol esters (12 carbon 40% wherein, 14 carbon 30%, all the other are 16 to 18 carbon), 5 gram butyl methacrylate, two vinylformic acid butanediol esters of 1 gram and 1 gram benzoyl peroxide, reaction made high oil absorbing resin A in 6 hours under 85 ℃; Then with the washes that contains the useless machinery oil of 3～5% (weight) after this plastic resin treatment machinery removal of impurities, after per kilogram waste water drops into high oil absorbing resin 10 grams, left standstill 15 minutes, oil slick all absorbs, there is not obvious greasy dirt, resin gathers into the grume shape after the oil suction, leach resin with 80 mesh filter screens, resin reclaims machinery oil, after the waste water chemical examination 150 ℃ of following underpressure distillation regeneration, oil-containing is less than 5mg/l, the pick up the oil rate is greater than 99.5% (when so waste water does not have other refuse, need not advanced treatment), but qualified discharge.
Embodiment 2: the catering trade wastewater treatment
High oil absorbing resin A's is synthetic with above-mentioned embodiment 1, contains organic substances 4～7% such as oils in certain hotel's waste water, is that 1% high oil absorbing resin A of wastewater flow rate drops into wastewater disposal basin with consumption, when room temperature is more than 25 ℃, leaves standstill 30 minutes, and oils is all directly by oil suction; Below 25 ℃ or oils viscosity greater than 20, during 000 centipoise, 3% the diesel oil that can add wastewater flow rate helps to absorb, improve processing speed, waste water oil-containing after the processing is less than 15mg/l, and the oil product specific absorption is higher than 97%, and this hotel expands under the twice situation in business, original treatment facility can be handled the waste water more than one times that has more fully, need not to increase new facility investment.
Embodiment 3: the wastewater treatment of turpentine grease
At first 1.5 gram polyvinyl alcohol (PVA-1799) are dissolved in the 500 gram water, monomer methacrylic acid aliphatic alcohol ester 100 grams, 1,6 hexylene glycol double methacrylate, 2 grams, cyclohexanone peroxide 2 grams make high oil absorbing resin B; Handle certain factory's turpentine oil wastewater with high oil absorbing resin B, waste water oil-containing 1000～1500mg/l, during processing, at first add toluene 3g/l, add resin 3g/l again, under 150rpm, stirred 10 minutes, left standstill 5 minutes, the water surface does not have obvious greasy dirt, and result of laboratory test waste water oil-containing is reduced to 15mg/l, and the greasy rate of recovery of turpentine is higher than 99%; Reclaim resin behind vacuum fractionation, reclaim toluene and turpentine grease, the resin reuse.
Claims (6)
1, a kind of treatment process of oily(waste)water is characterized in that this method may further comprise the steps and processing condition:
Step 1: high oil absorbing resin synthetic
A, nonionogenic tenside is dissolved in the water, is prepared into concentration and is 0.1～0.5% emulsifying agent;
B, under 55 ± 5 ℃ of temperature, in emulsifying agent: monomer: linking agent: the initiator weight ratio is 350～450: 100: 0.1～3: 0.1～2 ratio is reinforced successively; Described monomer nail base CALCIUM ACRYLATE fatty alcohol (carbonatoms 4～18) is or/and methacrylic acid, and linking agent refers to 1,4 butyleneglycol double methacrylate or 1,6 hexylene glycol double methacrylate, and initiator refers to benzoyl peroxide or cyclohexanone peroxide;
C, under 45～95 ℃ of temperature, carried out emulsion polymerization 6～10 hours, promptly synthetic high oil absorbing resin;
Step 2: oily(waste)water is handled
The high oil absorbing resin of 5～20% (weight) of waste water oleaginousness is invested in the oily(waste)water, left standstill 5～90 minutes, the greasy dirt in the waste water is absorbed, BOD COD reduce.
2, a kind of oily wastewater treatment method according to claim 1, it is characterized in that can be before adding high oil absorbing resin or simultaneously, adds in waste water and help lyosorption, helps lyosorption to refer to low molecular weight alkanes, the phenol hydrocarbon.
3, the treatment process of oily(waste)water according to claim 1 is characterized in that nonionogenic tenside refers to polyvinyl alcohol or gelatin or methyl fiber.
4, according to the treatment process of claim 1,2,3 described a kind of oily(waste)waters, it is characterized in that the high oil absorbing resin after the oil suction can reclaim the oil product regenerating resin in 100～200 ℃ of distillations of low temperature, reuse.
5, a kind of oily wastewater treatment method according to claim 1 is characterized in that the high oil absorbing resin of 5～20% (weight) of waste water oleaginousness is invested in the oily(waste)water, leaves standstill after stirring or stirring.
6, a kind of oily wastewater treatment method according to claim 1 is characterized in that leaching resin through filter screen, can directly make fuel and use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116032 CN1112326C (en) | 1999-01-28 | 1999-01-28 | Method for treatment of oil-bearing waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116032 CN1112326C (en) | 1999-01-28 | 1999-01-28 | Method for treatment of oil-bearing waste water |
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| Publication Number | Publication Date |
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| CN1231991A true CN1231991A (en) | 1999-10-20 |
| CN1112326C CN1112326C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99116032 Expired - Fee Related CN1112326C (en) | 1999-01-28 | 1999-01-28 | Method for treatment of oil-bearing waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301914C (en) * | 2005-02-02 | 2007-02-28 | 大同市煤气化总公司 | Technology for treating waste water generated by coking |
| CN100336733C (en) * | 2005-12-31 | 2007-09-12 | 朱守诚 | Application of down for preventing and treating pollution of oil |
| CN100391571C (en) * | 2006-08-18 | 2008-06-04 | 南京大学 | High performance deoiling method through adsorption of resin |
| CN100534917C (en) * | 2007-08-21 | 2009-09-02 | 马冬兰 | Composite emulsion breaking scavenging agnet and preparation method thereof |
| US7695697B2 (en) | 2004-12-23 | 2010-04-13 | Franco D'Orazio Pessia | Devices for crude oil treatment and upgrading |
| CN101785947B (en) * | 2009-01-23 | 2012-07-04 | 国立云林科技大学 | Oil-fume extraction and biological treatment method and device |
| CN105642256A (en) * | 2016-01-29 | 2016-06-08 | 江苏科技大学 | Hydrophobic resin oil adsorption material and preparation method |
| CN106745506A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of preparation method of the super hydrophilic oil-water separating net of antipollution |
-
1999
- 1999-01-28 CN CN 99116032 patent/CN1112326C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7695697B2 (en) | 2004-12-23 | 2010-04-13 | Franco D'Orazio Pessia | Devices for crude oil treatment and upgrading |
| CN1301914C (en) * | 2005-02-02 | 2007-02-28 | 大同市煤气化总公司 | Technology for treating waste water generated by coking |
| CN100336733C (en) * | 2005-12-31 | 2007-09-12 | 朱守诚 | Application of down for preventing and treating pollution of oil |
| CN100391571C (en) * | 2006-08-18 | 2008-06-04 | 南京大学 | High performance deoiling method through adsorption of resin |
| CN100534917C (en) * | 2007-08-21 | 2009-09-02 | 马冬兰 | Composite emulsion breaking scavenging agnet and preparation method thereof |
| CN101785947B (en) * | 2009-01-23 | 2012-07-04 | 国立云林科技大学 | Oil-fume extraction and biological treatment method and device |
| CN105642256A (en) * | 2016-01-29 | 2016-06-08 | 江苏科技大学 | Hydrophobic resin oil adsorption material and preparation method |
| CN106745506A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of preparation method of the super hydrophilic oil-water separating net of antipollution |
| CN106745506B (en) * | 2016-12-30 | 2020-12-04 | 常州碳星科技有限公司 | Preparation method of anti-pollution super-hydrophilic oil-water separation net |
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| Publication number | Publication date |
|---|---|
| CN1112326C (en) | 2003-06-25 |
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Owner name: LI YINGTING Free format text: FORMER OWNER: DONGGUAN CITY TRADE AND INDUSTRY CO., LTD. Effective date: 20060210 Owner name: DONGGUAN CITY TRADE AND INDUSTRY CO., LTD. Free format text: FORMER OWNER: SOUTH CHINA UNIVERSITY OF TECHNOLOGY; DONGGUAN CITY TRADE AND INDUSTRY CO., LTD. Effective date: 20060210 |
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Effective date of registration: 20060210 Address after: 523000 Guangdong province Dongguan City Wanjiang pailou base Lian Guan control box factory Patentee after: Li Yingting Address before: 511705 Guangdong Province, Dongguan city two floor building Yinli loop Patentee before: Dongguan Industrial and Trade Corp. Effective date of registration: 20060210 Address after: 511705 Guangdong Province, Dongguan city two floor building Yinli loop Patentee after: Dongguan Industrial and Trade Corp. Address before: 510641 Guangdong city of Guangzhou province Tianhe District Wushan Co-patentee before: Dongguan Industrial and Trade Corp. Patentee before: South China University of Technology |
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