CN101306849B - Modification process of fly ash zeolite and wastewater treatment process for paper making - Google Patents
Modification process of fly ash zeolite and wastewater treatment process for paper making Download PDFInfo
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- CN101306849B CN101306849B CN2008100169993A CN200810016999A CN101306849B CN 101306849 B CN101306849 B CN 101306849B CN 2008100169993 A CN2008100169993 A CN 2008100169993A CN 200810016999 A CN200810016999 A CN 200810016999A CN 101306849 B CN101306849 B CN 101306849B
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- coal ash
- ash zeolite
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- paper waste
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Abstract
The present invention relates to wastewater treatment, in particular to an application of modified fly ash zeolites in the treatment of paper making wastewater. Firstly, fly ash zeolites which are synthesized in low cost undergo the modified treatment by modifying agent; secondly, the modified fly ash zeolites are put in a reactor to fully contact the paper making wastewater; thirdly the paper making wastewater is treated; the removal rates of COD and chrominance are used to check the treatment effect of the fly ash zeolites on the paper making wastewater. The application has the advantages that the modifying agent is low in price and easily bought, and the modification process and the treatment process of the paper making wastewater are simple, and simultaneously the environmental pollution caused by fly ash solid wastes is solved, and the application range of the fly ash zeolites is widened, so that the application has the active use value.
Description
Technical field:
The present invention relates to a kind of method of wastewater treatment, the application of a kind of specifically modified coal ash zeolite in Processing Paper Wastewater belongs to environmental technology field.
Background technology
Flyash is coal-burning power plant's discarded object, and present application only limits to building material industry, but utilization rate is less than 20%, and a large amount of flyash is piled up, and has not only taken a large amount of soils, and has caused the serious environmental pollution.The flyash synthetic zeolite is the effective way that flyash is turned waste into wealth, obtained high value added product.At present, natural zeolite and commodity zeolite obtain Application and Development more widely, but its output is limited, and cost an arm and a leg.The technology of utilizing the flyash synthetic zeolite is comparative maturity, and synthetic method commonly used has hydrothermal synthesis method, alkali fusion method, mixes alkali gas phase synthesis method etc., various types of zeolites such as up to the present synthetic Na-A type, Na-P1 type, 13X type.
Chinese patent CN1296129C has authorized the preparation method and the application thereof of coal ash zeolite, and this method is to utilize the flyash synthetic zeolite to realize the synchronous denitrification dephosphorizing of sewage is handled, but this patented method only is fit to handle little molecular contaminants such as nitrogen phosphorus.
Utilize the application in handling waste water of natural and commodity zeolite more extensive both at home and abroad, but the present application of coal ash zeolite only limit to handle simple ion waste water and pernicious gas NH3 such as heavy metal ion, phosphate, NOx, SOn, the purification of Hg etc.Synthetic coal ash zeolite is not used to complex systems such as Processing Paper Wastewater.
The chromaticity of paper-making waste water height, alkalinity is big, oxygen demand is high, is important pollution sources, and to aquaculture, crop growth, animal husbandry and health constitute harm greatly.The technological process for the treatment of papermaking method mainly contains Silvola recovery, air supporting method, acid process, flocculence, bioanalysis, chemical oxidization method and membrane separation process etc. at present.These methods exist all that investment is big, equipment is many, energy consumption is high, cost is high, the big deficiency that waits of floor space.Some scope of application is less, can not generally promote, and be that the medium and small papermaking enterprise of raw material occupies sizable ratio with the grass fiber especially in China, waste water handling problem is far from fundamentally solving.The 335th～339 page of " petromineralogy magazine " magazine the 8th the 4th phase of volume of December in 1999 introduced a kind of preparation of zeolite cleanser and has been used for Processing Paper Wastewater, and terminal waste water is 450mg/L, only reaches national secondary discharge standard; Chinese patent CN1994941A discloses the technological process for the treatment of papermaking method, this method is with clear water paper waste to be diluted after the preliminary treatment again to the limewash of wherein evenly splashing, the precipitation water that precipitates after 12～48 hours enters biochemical treatment tank, regulate the pH of water with urea and calcium superphosphate, deposited 90 days, cultivate the dissolved oxygen amount of the microorganism plant raising water in the water, this method cycle of operation is long, only is applicable to the wastewater treatment of the less papermaking enterprise of part.
Summary of the invention:
The method that the purpose of this invention is to provide a kind of modified coal ash zeolite treatment paper waste.Promptly be raw material, with modifier it carried out modification and handle, with the coal ash zeolite Processing Paper Wastewater after the modification with the coal ash zeolite.Water outlet can not be up to standard when overcoming the prior art Processing Paper Wastewater, can not directly discharge, and treatment effect is relatively poor, and the cost height such as is unfavorable for generally promoting at defective, provides a kind of cost low, and is simple to operate, the paper waste processing method that water outlet can be up to standard.
The particular content of invention comprises following step:
A) prepare hydrochloric acid and sulfuric acid solution respectively, with hydrochloric acid solution and sulfuric acid solution proportioning 1 by volume: X mixes, and promptly gets modifier; The concentration of hydrochloric acid is 0.5～2.0mol/L before wherein mixing, and the concentration of sulfuric acid is 0.3～2.0mol/L before mixing, and the value of X is 0.1～6;
B) be 1 with coal ash zeolite and modifier by the quality volume proportion: 4Kg/L mixes, and obtains the solidliquid mixture of coal ash zeolite and modifier; Then with the solidliquid mixture that mixes stirring reaction at normal temperatures;
C) with the oven dry of the solidliquid mixture behind the stirring reaction, porphyrize obtains the modified coal ash zeolite;
D) take by weighing the modified coal ash zeolite and add in the paper waste, regulate the pH value, after vibration at normal temperatures or the stirring, standing sedimentation 30～60min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures.
The concentration of sulfuric acid and hydrochloric acid is respectively 1.0～2.0mol/L and 0.5～2.0mol/L before mixing in the aforesaid step a), and the value of X is 1～6.
Coal ash zeolite is the solid waste coal ash of coal-burning power plant in the aforesaid step b), [CN101164884] that makes by microwave multistage synthetic method; During the modified coal ash zeolite, the time of mixing stirring reaction is 0～12h, and mixing speed is 110～300r/min.
In the aforesaid step c) solidliquid mixture behind the stirring reaction was dried 6～8 hours down at 80～120 ℃,, obtain the modified coal ash zeolite with being ground to 100～200 orders.
The consumption of modified coal ash zeolite is (1～10) Kg/t paper waste in the aforesaid step d), and regulating pH value scope is 1～9, and vibration or stir process time are 0～180min.
Preferably, in above-mentioned step a), when with modifier the coal ash zeolite modification being handled, the value of X is 2～4.
Preferably, in above-mentioned step b), when with modifier the coal ash zeolite modification being handled, the stirring reaction time is 3～7h.
Preferably, in above-mentioned step d), regulating the pH value during Processing Paper Wastewater is 5.10～7.10.
Preferably, in above-mentioned step d), the consumption of modified coal ash zeolite is (2～4) Kg/t paper waste during Processing Paper Wastewater.
Preferably, in above-mentioned step d), vibration or mixing time are 1～30min during Processing Paper Wastewater.
Advantage of the present invention:
The present invention utilizes the synthetic zeolite of flyash cheaply to be mainly reflected in for raw material and with the advantage of its modification post processing paper waste: (1). and synthetic coal ash zeolite is a kind of environment-friendly materials newly developed, can effectively improve the purification efficiency of paper waste, reduce processing cost; (2). reaction unit is simple, and investment and operating cost are low, safe, workable, are suitable for practical application; (3). coal ash zeolite is fabulous to the decolorizing effect of paper waste since the existence of flyash adsorbed a large amount of suspensions and combine with floccule body that coagulation produces, net is caught, adsorb more suspended particulate, makes water quality that bigger change be arranged; (4). with the coal ash zeolite is that the raw material Processing Paper Wastewater is not only saved industrial chemicals, and effectively utilized industrial waste flyash, for the comprehensive utilization of coal ash zeolite provides an economical and practical approach, improved the economic benefit and the social benefit of power system.
The specific embodiment:
Embodiment 1:
Prepare 1.0mol/L hydrochloric acid and 1.0mol/L sulfuric acid solution respectively, with hydrochloric acid and sulfuric acid be by volume mix at 1: 6 modifier; Take by weighing coal ash zeolite 0.003Kg, add 0.012L modifier and mix, obtain solidliquid mixture; The solidliquid mixture for preparing is reacted 1h with 240r/min rotating speed stirring at normal temperature; Solidliquid mixture behind the stirring reaction is dried 8h down at 100 ℃, grind to 200 orders, obtain the modified coal ash zeolite; Take by weighing modified coal ash zeolite 0.002Kg, add the 0.5L paper waste, regulate pH value 5.10, oscillating reactions 1min at normal temperatures, solution after the vibration is poured in the 100mL graduated cylinder, and standing sedimentation 30min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures.The result shows: the water outlet absorbance is 0.030, and the COD value is 360mg/L, and COD value clearance reaches 58.09%, and the colourity rate of going out reaches 92.02%, and the COD value reaches industrial pollution caused by paper manufacturing thing discharge standard.
Embodiment 2:
Prepare 1.0mol/L hydrochloric acid and 1.0mol/L sulfuric acid solution respectively, with hydrochloric acid and sulfuric acid be by volume mix at 1: 3 modifier; Take by weighing coal ash zeolite 0.2g, add 0.8L modifier and mix, obtain solidliquid mixture; The solidliquid mixture for preparing is reacted 4h with 300r/min rotating speed stirring at normal temperature; Solidliquid mixture behind the stirring reaction is dried 8h down at 100 ℃, grind to 200 orders, obtain the modified coal ash zeolite; Take by weighing modified coal ash zeolite 0.1Kg, add the 100L paper waste, regulate pH value 6.10, oscillating reactions 180min at normal temperatures, solution after the vibration is poured in the 1000mL graduated cylinder, and standing sedimentation 30min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures.The result shows: the water outlet absorbance is 0.027, and the COD value is 345mg/L, and COD value clearance reaches 59.84%, and the colourity rate of going out reaches 92.82%, and the COD value reaches industrial pollution caused by paper manufacturing thing discharge standard.
Embodiment 3:
Prepare 1.0mol/L hydrochloric acid and 1.0mol/L sulfuric acid solution respectively, with hydrochloric acid and sulfuric acid be by volume mix at 1: 1 modifier; Take by weighing coal ash zeolite 1Kg, add 4L modifier and mix, obtain solidliquid mixture; The solidliquid mixture for preparing is reacted 4h with 150r/min rotating speed stirring at normal temperature; Solidliquid mixture behind the stirring reaction is dried 8h down at 100 ℃, grind to 200 orders, obtain the modified coal ash zeolite; Take by weighing modified coal ash zeolite 500g, add the 125L paper waste, regulate pH value 5.10, stirring reaction 30min pours the solution after stirring in the settling tank at normal temperatures, and standing sedimentation 30min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures.The result shows: the water outlet absorbance is 0.053, and the COD value is 387mg/L, and COD value clearance reaches 56.76%, and the colourity rate of going out reaches 85.90%, and the COD value reaches industrial pollution caused by paper manufacturing thing discharge standard.
Embodiment 4:
Prepare 1.0mol/L hydrochloric acid and 1.0mol/L sulfuric acid solution respectively, with hydrochloric acid and sulfuric acid be by volume mix at 1: 3 modifier; Take by weighing coal ash zeolite 3Kg, add 12L modifier and mix, obtain solidliquid mixture; The solidliquid mixture for preparing is reacted 1h with 200r/min rotating speed stirring at normal temperature; Solidliquid mixture behind the stirring reaction is dried 8h down at 100 ℃, grind to 200 orders, obtain the modified coal ash zeolite; Add the 670L paper waste, regulate pH value 6.10, enter adding modified coal ash zeolite 2Kg behind the stirring pool, stirring reaction 10min at normal temperatures, solution after the stirring enters in the settling tank, and standing sedimentation 30min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures.The result shows: the water outlet absorbance is 0.014, and the COD value is 321mg/L, and COD value clearance reaches 62.63%, and the colourity rate of going out reaches 96.28%, and the COD value reaches industrial pollution caused by paper manufacturing thing discharge standard.
Claims (6)
1. a modified coal ash zeolite is used for the method that paper waste is handled, and it is characterized in that comprising the steps:
1) prepare hydrochloric acid and sulfuric acid solution respectively, with hydrochloric acid solution and sulfuric acid solution proportioning 1 by volume: X mixes, and promptly gets modifier;
2) be 1 with coal ash zeolite and modifier by the quality volume proportion: 4Kg/L mixes, and obtains the solidliquid mixture of coal ash zeolite and modifier; Then with the solidliquid mixture that mixes stirring reaction at normal temperatures;
3) with the oven dry of the solidliquid mixture behind the stirring reaction, porphyrize promptly gets the modified coal ash zeolite;
4) take by weighing the modified coal ash zeolite and add in the paper waste, regulate the pH value, after vibration at normal temperatures or the stirring, standing sedimentation 30～60min carries out relevant water quality parameter to the waste water that discharges after the sedimentation and measures;
The concentration of sulfuric acid and hydrochloric acid is respectively 0.5～2.0mol/L and 0.3～2.0mol/L before mixing in the described step 1), and the value of X is 1～6; Described step 2) coal ash zeolite is the solid waste coal ash of coal-burning power plant in, makes by microwave multistage synthetic method; During the modified coal ash zeolite, the time of mixing stirring reaction is 0～12h, and mixing speed is 110～300r/min; In the described step 3) solidliquid mixture behind the stirring reaction is dried 6～8h under 80～120 ℃ of temperature; And the coal ash zeolite of modification is ground to 100～200 orders, obtain the modified coal ash zeolite; Modified coal ash zeolite and paper waste amount ratio are (1～10) Kg/t paper waste in the described step 4), and regulating pH value scope is 1～9, and vibration or stir process time are 0～180min.
2. a kind of modified coal ash zeolite as claimed in claim 1 is used for the method that paper waste is handled, and the value that it is characterized in that X is 2～4.
3. a kind of modified coal ash zeolite as claimed in claim 1 is used for the method that paper waste is handled, and it is characterized in that the stirring reaction time is 3～7h.
4. a kind of modified coal ash zeolite as claimed in claim 1 is used for the method that paper waste is handled, and regulating the pH value when it is characterized in that Processing Paper Wastewater is 5.10～7.10.
5. a kind of modified coal ash zeolite as claimed in claim 1 is used for the method that paper waste is handled, and the consumption that it is characterized in that the modified coal ash zeolite is (2～4) Kg/t paper waste.
6. a kind of modified coal ash zeolite as claimed in claim 1 is used for the method that paper waste is handled, and it is characterized in that vibration or mixing time are 1～30min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100169993A CN101306849B (en) | 2008-07-03 | 2008-07-03 | Modification process of fly ash zeolite and wastewater treatment process for paper making |
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| CN2008100169993A CN101306849B (en) | 2008-07-03 | 2008-07-03 | Modification process of fly ash zeolite and wastewater treatment process for paper making |
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| CN101306849A CN101306849A (en) | 2008-11-19 |
| CN101306849B true CN101306849B (en) | 2011-07-06 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428983B (en) * | 2008-12-11 | 2011-08-17 | 上海电力学院 | Method for modification treatment of coal ash |
| CN102225815B (en) * | 2011-04-15 | 2012-09-05 | 四川省环保科技工程有限责任公司 | New method for removing volatile phenol from wastewater of pulping and papermaking with boiler fly ashes |
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN102964025B (en) * | 2012-10-26 | 2014-10-29 | 陕西科技大学 | Method for prevention and elimination of scaling in papermaking wastewater closed circulation system |
| CN104478029B (en) * | 2014-10-20 | 2017-05-31 | 中国矿业大学(北京) | A kind of water treatment agent and preparation method thereof |
| CN104370413A (en) * | 2014-10-24 | 2015-02-25 | 无锡伊佩克科技有限公司 | Papermaking wastewater treatment method by use of modified fly ash zeolite |
| CN104692593A (en) * | 2015-02-28 | 2015-06-10 | 江苏高科物流科技股份有限公司 | Treatment method applied to industrial wastewater |
| CN106237977A (en) * | 2016-08-18 | 2016-12-21 | 国网天津市电力公司 | The preparation of modified coal ash and use for advanced treating refinery(waste) water |
| CN107376881A (en) * | 2017-08-16 | 2017-11-24 | 国网天津市电力公司电力科学研究院 | A kind of modification of flyash for treatment of Power waste water and application method |
| CN108176350A (en) * | 2018-01-26 | 2018-06-19 | 上海理工大学 | A kind of technique for preparing Low Cost Sorbents using coal quality flying dust |
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