CN102249383A - Compound degreasing agent for removing tar oil from residual ammonia water of coked wastewater - Google Patents
Compound degreasing agent for removing tar oil from residual ammonia water of coked wastewater Download PDFInfo
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- CN102249383A CN102249383A CN 201110116732 CN201110116732A CN102249383A CN 102249383 A CN102249383 A CN 102249383A CN 201110116732 CN201110116732 CN 201110116732 CN 201110116732 A CN201110116732 A CN 201110116732A CN 102249383 A CN102249383 A CN 102249383A
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Abstract
The invention discloses a compound degreasing agent for removing tar oil from residual ammonia water of coked wastewater, belonging to the technical filed of sewage treatment. The compound degreasing agent consists of the following components in percentage by mass: 2-8.5 percent of demulsifying agent, 83-93 percent of flocculating agent and 4.5-11.5 percent of coagulant aid, wherein the demulsifying agent is propanediol block polyether (DM6); the flocculating agent is polyaluminium chloride (PAC); and the coagulant aid is polyacrylamide (PAM). According to the compound degreasing agent, the tar oil content of the residual ammonia water can be lowered remarkably. By taking the residual ammonia water of a certain coke-oven plant in the northern region of China as an example, the tar oil content is 420-600 mg/L. After the compound degreasing agent is added for emulsion breaking, flocculating and settling, the removal rate of the tar oil is up to 60-84 percent. Moreover, the treatment cost on every ton of water is low, and good economic and social benefits are achieved.
Description
Technical field
The invention belongs to technical field of sewage, particularly a kind of coal-tar middle oil composite degreaser of coking chemical waste water remained ammonia of removing.
Background technology
In recent years, along with the high speed development of Chinese national economy, coke output heightens.Coke output was about 34,500 ten thousand tons in 2009, accounted for 60% of world's coke output.Coking industry is the important auxiliary industry of Iron And Steel Industry, also is the serious industry of environmental pollution simultaneously.According to China Environmental statistics result in 2009, China's coking industry COD in 2009 quantity discharged accounted for national industrial total release 1.26%, and the ammonia nitrogen quantity discharged accounts for national industrial total release 3.25%.The coking chemical waste water water yield is big, the water quality complexity.Not only contain ammonia nitrogen, phenol, the prussiate of high density, and contain multiple many rings such as indoles, naphthalene, pyridine, quinoline, condensed ring organism etc.The Pollutant levels height, toxicity is big, is typical difficult trade effluent (Wang, J.L., Quan, X.C., Wu, L.B., Qian, Y., Hegemann, W., 2002.Bioaugmentation as a tool to enhance the removal of refractory compound in coke plant wastewater.Process Biochemistry 38 (5): 777-781).
The waste water that produces in the gas purification process accounts for more than 80% of coking chemical waste water total amount.Just formed a large amount of ammoniacal liquor in the cold process at coke-oven gas, wherein most of as cyclic ammonia water, the unnecessary part that effluxes is called remained ammonia.Containing detrimental impurity such as coal tar, phenol, ammonia, prussiate in the remained ammonia, is the main source of coking industry waste water.The remained ammonia oil removing is the important step of Treatment of Coking Effluent.After coking chemical waste water was generally at first removed coal tar, ammonia still process dephenolize again entered biological processing unit at last.The coal-tar middle oil class substances content of remained ammonia is too high, can cause ammonia still, dephenolize tower to stop up, and influences the recovery of ammonia, phenol.And can cause in coke oven ammoniacal liquor spray nozzle clogging and the system thereof equipment scaling stop up (study of the Chinese classic literary composition, Zhu Qinyong, Zhang Guanglian, Chen Tong, the applied research of 2008. emulsion splitters in ammonia water and tar oil separates. fuel and chemical industry 39 (6): 35-36).
Remained ammonia is one and contains emulsion droplet and colloidal complex system that wherein contained tar is water insoluble.Tar is a kind of very complicated multicomponent mixture.Particularly organism wherein such as materials such as phenols, pyridine base play a part emulsifying agent.Both contain oleophilic group in its molecular structure, contained hydrophilic group again.Can form oleophilic group to oil droplet inside on tiny oil droplets, hydrophilic group aligns to the water side, and oil droplet is protected.Therefore, common settlement separate means be difficult to ammoniacal liquor and tar separation (Ma Lirong, Zhang Yanmiao, the discussion of 1999. remained ammonia deoiling methods. coal gas and heating power 19 (5): 16-17).
Summary of the invention
The present invention is directed to the coal-tar middle oil separation difficulty of remained ammonia, easily cause ammonia still and dephenolize tower to stop up, influence the problem of its operational efficiency, invented a kind of composite degreaser.Its action principle is to destroy the equilibrium state of the coal-tar middle oil emulsion layer of ammoniacal liquor, and the natural separation state of tar and ammoniacal liquor is improved, and separation surface is more clear, reduces the residence time of ammoniacal liquor in clarifying tank.
Composite degreaser provided by the invention, form by emulsion splitter, flocculation agent and coagulant aids, each component and mass percent thereof are as follows: emulsion splitter: 2-8.5%, flocculation agent: 83-93%, coagulant aids: 4.5-11.5%, described emulsion splitter is propylene glycol block polyether (DM6), and described flocculation agent is polymerize aluminum chloride (PAC), and described coagulant aids is polyacrylamide (PAM).
Above-mentioned composite degreaser directly can be added in the remained ammonia grease removal tank, supernatant liquor is delivered to ammonia still behind the flocculating settling.
As hydrophile-lipophile balance value (HLB value) scope of the propylene glycol block polyether (DM6) of emulsion splitter at 20-30.
The molecular weight of described polyacrylamide is at (preferred 300-1500 ten thousand) more than 3,000,000.
Composite degreaser is removed the coal-tar middle oil ultimate principle of remained ammonia: after being added to composite degreaser in the remained ammonia, emulsion splitter in the degreaser combines with tar in the remained ammonia, by breakdown of emulsion, dispersion and visbreaking effect, make the attenuation of ammonia water and tar oil emulsion layer, destroy the equilibrium state of tar emulsion layer.And, strengthen the velocity of separation and the separating effect of tar and ammoniacal liquor further by the effect of flocculation agent and coagulant aids.Can reduce on the one hand the suspended substance carried secretly in the ammoniacal liquor and the content of tar, reduce the blockage problem of remained ammonia subsequent disposal ammonia still; Can quicken separating of tar and coke tar refuse on the other hand, to obtain moisture and the lower tar of residue.
Compared with prior art, composite degreaser of the present invention can significantly reduce the tar content of remained ammonia.With northern China coke-oven plant remained ammonia is example, and its tar content is at 420-600mg/L.After adding composite degreaser breakdown of emulsion flocculation sediment, the clearance of tar can reach 60-84%.And the processing cost of ton water is lower, has good economic and social benefit.
Description of drawings
The COD concentration contrast of supernatant liquor after the accompanying drawing 1 remained ammonia employing different ingredients chemicals treatment.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Used experiment material among the following embodiment if no special instructions, is conventional chemical reagent shop and buys and to obtain.
The mensuration of tar content adopts weighting method, and the mensuration of COD adopts potassium dichromate process.
Remained ammonia is taken from sewage work of northern China Coal Chemical Industry company, and its character index is as shown in table 1.The content of its COD, total phenol, ammonia nitrogen and tar is all very high.
The character index of table 1 remained ammonia
Embodiment 1
Get a certain amount of remained ammonia, be heated to 45-50 ℃.Reactor 1 adds remained ammonia 300mL, emulsion splitter propylene glycol block polyether (DM6, the HLB value is 30) 3mg; Reactor 2 adds remained ammonia 300mL, emulsion splitter propylene glycol block polyether (DM6, the HLB value is 30) 3mg and flocculant poly aluminum chloride (PAC) 60mg; Reactor 3 adds remained ammonia 300mL and composite degreaser, wherein, described composite degreaser is composed as follows: emulsion splitter propylene glycol block polyether (DM6, the HLB value is 30) 3mg, flocculant poly aluminum chloride (PAC) 60mg and coagulant aids polyacrylamide (PAM, molecular weight 3,000,000) 6mg.Stir.
Stir the time soon: 4min; Stir speed: 350rpm soon
Slowly stir the time: 5min; Slowly stir speed: 45rpm
Sedimentation 5min pours out supernatant liquor and detects tar content and COD concentration then.
As table 2 as seen, add emulsion splitter merely, the clearance of tar can reach 78.8%.Add composite degreaser, the clearance of tar can increase by 5%.And as seen from Figure 1, the COD concentration of supernatant liquor also descends to some extent.Contrast adds degreaser front and back remained ammonia as can be known, and after remained ammonia added degreaser, its viscosity reduced greatly, and most of tar component is along with degreaser is deposited in the bottom, and the supernatant liquor good fluidity helps entering ammonia still and further handles.
The tar of table 2 composite degreaser is removed efficient
Embodiment 2
Get a certain amount of remained ammonia, be heated to 45-50 ℃.Measure 300mL, add degreaser, filling a prescription is: emulsion splitter propylene glycol block polyether (DM6, the HLB value is 30) 1.5mg, flocculant poly aluminum chloride (PAC) 60mg and coagulant aids polyacrylamide (PAM, molecular weight 1,500 ten thousand) 6mg, stir.
Stir the time soon: 4min; Stir speed: 350rpm soon
Slowly stir the time: 5min; Slowly stir speed: 45rpm
Sedimentation 5min pours out supernatant liquor and detects then.The result is: settling of floccus is better, and the clearance of tar is 60%, and supernatant C OD does not have to change substantially.
Embodiment 3
Get a certain amount of remained ammonia, be heated to 45-50 ℃.Measure 300mL, add degreaser, filling a prescription is: emulsion splitter propylene glycol block polyether (DM6, the HLB value is 20) 3mg, flocculant poly aluminum chloride (PAC) 60mg and coagulant aids polyacrylamide (PAM, molecular weight 5,000,000) 7.5mg, stir.
Stir the time soon: 4min; Stir speed: 350rpm soon
Slowly stir the time: 5min; Slowly stir speed: 45rpm
Sedimentation 5min pours out supernatant liquor and detects then.The result is: settling of floccus is better, and the clearance of tar is 65%, and supernatant C OD slightly reduces.
Embodiment 4
Get a certain amount of remained ammonia, be heated to 45-50 ℃.Measure 300mL, add degreaser, filling a prescription is: emulsion splitter propylene glycol block polyether (DM6, the HLB value is 20) 3mg, flocculant poly aluminum chloride (PAC) 30mg and coagulant aids polyacrylamide (PAM, molecular weight 3,000,000) 3mg, stir.
Stir the time soon: 4min; Stir speed: 350rpm soon
Slowly stir the time: 5min; Slowly stir speed: 45rpm
Sedimentation 5min pours out supernatant liquor and detects then.The result is: settling of floccus is general, and the clearance of tar is 58%, and supernatant C OD does not have to change substantially.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (5)
1. remove the coal-tar middle oil composite degreaser of coking chemical waste water remained ammonia for one kind, it is characterized in that: this composite degreaser is made up of emulsion splitter, flocculation agent and coagulant aids, each component and mass percent thereof are as follows: emulsion splitter: 2-8.5%, flocculation agent: 83-93%, coagulant aids: 4.5-11.5%, described emulsion splitter is a propylene glycol block polyether, and described flocculation agent is a polymerize aluminum chloride, and described coagulant aids is a polyacrylamide.
2. composite degreaser according to claim 1 is characterized in that: the hydrophile-lipophile balance value scope of described emulsion splitter propylene glycol block polyether is at 20-30.
3. composite degreaser according to claim 1 is characterized in that: the molecular weight of described polyacrylamide is more than 3,000,000.
4. composite degreaser according to claim 3 is characterized in that: the molecular weight of described polyacrylamide is 300-1500 ten thousand.
5. the application of the described composite degreaser of any one claim of claim 1 to 4, it is characterized in that: described composite degreaser directly is added in the remained ammonia grease removal tank, and supernatant liquor is delivered to ammonia still behind the flocculating settling.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627344A (en) * | 2012-04-11 | 2012-08-08 | 中国海洋石油总公司 | Method for treating polymer-driven oilfield sewage |
| CN102765767A (en) * | 2012-07-12 | 2012-11-07 | 天津市瑞德赛恩新材料开发有限公司 | Delay coking coke cooling water demulsifier composition and preparation method and application thereof |
| JP2015520017A (en) * | 2012-04-18 | 2015-07-16 | ゼネラル・エレクトリック・カンパニイ | Processing method of flushing liquid system in coke plant |
| WO2015123825A1 (en) * | 2014-02-19 | 2015-08-27 | 张征北 | Purification assistant for coal chemical industry production, and uses thereof in coal chemical industry production |
| WO2015186459A1 (en) * | 2014-06-06 | 2015-12-10 | 栗田工業株式会社 | Oil-water separation method |
| CN105502574A (en) * | 2015-12-16 | 2016-04-20 | 杭州富阳伟文环保科技有限公司 | Treating agent for tar-containing wastewater |
| CN105692780A (en) * | 2016-02-24 | 2016-06-22 | 中国海洋石油总公司 | Water clarifier mixed system for treating sewage containing polymer |
| CN104817150B (en) * | 2015-05-22 | 2016-07-20 | 华东理工大学 | A kind of compound demulsifying flocculant |
| CN108218034A (en) * | 2018-01-18 | 2018-06-29 | 苏州永峰联环保科技有限公司 | The processing method and its processing system of coke oven cycle ammonium hydroxide |
| CN108299593A (en) * | 2017-12-25 | 2018-07-20 | 威海翔泽新材料科技有限公司 | A kind of method of preparation and use of ammonium hydroxide detersive |
| CN108793555A (en) * | 2018-06-13 | 2018-11-13 | 苏州永峰联环保科技有限公司 | Remained ammonia treatment process and its processing system |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627344B (en) * | 2012-04-11 | 2013-11-06 | 中国海洋石油总公司 | Method for treating polymer-driven oilfield sewage |
| CN102627344A (en) * | 2012-04-11 | 2012-08-08 | 中国海洋石油总公司 | Method for treating polymer-driven oilfield sewage |
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| JP2015520017A (en) * | 2012-04-18 | 2015-07-16 | ゼネラル・エレクトリック・カンパニイ | Processing method of flushing liquid system in coke plant |
| CN102765767A (en) * | 2012-07-12 | 2012-11-07 | 天津市瑞德赛恩新材料开发有限公司 | Delay coking coke cooling water demulsifier composition and preparation method and application thereof |
| CN102765767B (en) * | 2012-07-12 | 2015-07-01 | 天津市瑞德赛恩新材料开发有限公司 | Delay coking coke cooling water demulsifier composition and preparation method and application thereof |
| WO2015123825A1 (en) * | 2014-02-19 | 2015-08-27 | 张征北 | Purification assistant for coal chemical industry production, and uses thereof in coal chemical industry production |
| WO2015186459A1 (en) * | 2014-06-06 | 2015-12-10 | 栗田工業株式会社 | Oil-water separation method |
| CN104817150B (en) * | 2015-05-22 | 2016-07-20 | 华东理工大学 | A kind of compound demulsifying flocculant |
| CN105502574A (en) * | 2015-12-16 | 2016-04-20 | 杭州富阳伟文环保科技有限公司 | Treating agent for tar-containing wastewater |
| CN105692780A (en) * | 2016-02-24 | 2016-06-22 | 中国海洋石油总公司 | Water clarifier mixed system for treating sewage containing polymer |
| CN105692780B (en) * | 2016-02-24 | 2018-05-25 | 中国海洋石油集团有限公司 | A kind of polymer-bearing waste-water processing water cleaning agent compound system |
| CN108299593A (en) * | 2017-12-25 | 2018-07-20 | 威海翔泽新材料科技有限公司 | A kind of method of preparation and use of ammonium hydroxide detersive |
| CN108218034A (en) * | 2018-01-18 | 2018-06-29 | 苏州永峰联环保科技有限公司 | The processing method and its processing system of coke oven cycle ammonium hydroxide |
| CN108793555A (en) * | 2018-06-13 | 2018-11-13 | 苏州永峰联环保科技有限公司 | Remained ammonia treatment process and its processing system |
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Application publication date: 20111123 |