CN102513067A - Adsorbent for adsorbing heavy metal ions in wastewater and adsorption process - Google Patents
Adsorbent for adsorbing heavy metal ions in wastewater and adsorption process Download PDFInfo
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- CN102513067A CN102513067A CN2012100163620A CN201210016362A CN102513067A CN 102513067 A CN102513067 A CN 102513067A CN 2012100163620 A CN2012100163620 A CN 2012100163620A CN 201210016362 A CN201210016362 A CN 201210016362A CN 102513067 A CN102513067 A CN 102513067A
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Abstract
The invention relates to the technical field of wastewater purification, in particular to an adsorbent for adsorbing heavy metal ions in wastewater, i.e., waste residues obtained after xylitol is prepared by using corncobs. An adsorption process for heavy metal ions in wastewater comprises the following steps of: placing the adsorbent into wastewater containing heavy metal ions; adsorbing at a certain pH value and temperature for a certain time; and after the adsorption is ended, filtering to obtain filtrate, adjusting the filtrate to be neutral and discharging. The adsorbent for adsorbing heavy metal ions in wastewater has high adsorption capacity and can be directly filtered and removed after the adsorption process is ended, therefore, the cost is low, and the process is simple; and after being used, the adsorbent can be directly filtered and separated from the water, burned or further treated so as to play very important roles in solving the problem of environment pollution and promoting the recycle of wastes.
Description
Technical field
The present invention relates to the wastewater purification technology field, particularly a kind of heavy metal ions in wastewater adsorbent also relates to a kind of absorbing process that uses this adsorbent.
Background technology
A large amount of chromate waste water severe contaminations that industries such as plating, process hides, printing and dyeing, mining produce environment, only electroplating wastewater just discharges 4,000,000,000 m every year
3Chromate waste water is very harmful, and Cr VI especially is in case be absorbed by the body, accumulate; Various diseases such as meeting cause cancer; The trivalent chromium concentration height can cause fish kills in the water body, and contaminated water source can not be used, and must handle chrome waste water to make it reach discharge standard.At present bioanalysis, electrolysis, ion-exchange, oxidation-reduction method, absorption method etc. are mainly adopted in the processing of chromate waste water.The biomaterial absorption method is cheap with it, selectivity good, the source is wide and come into one's own.
Corncob is the discarded object of agricultural production, is again China's xylitol and the topmost raw materials for production of fuel ethanol production industry.Only with regard to xylitol, about about 200,000 tons of the gross annual output amount in the whole world, China's xylitol output accounts for about half of world wide production.Producing 1 ton of xylitol needs 10-12 ton corncob, and annual xylitol manufacturing enterprise has the few hundred thousand tonnes of waste residue to need to handle approximately.At present the processing method to the production waste residue of xylitol industry only limits to as fuel, edible mushroom cultivations, fertilizer etc., awaits opening and more utilizes method.
Corncob, peanut shell, sawdust, eucalyptus skin, orange peel etc. all are common biological adsorption agents.As; " water technology " 2010 the 36th volumes the 5th phase 58-62 page or leaf " typical agricultural wastes are to the characterization of adsorption research of Cr_VI_ in the water " has been reported peanut shell, shaddock skin, straw, corncob directly as adsorbent; Adsorption rate to 20mg/L Cr VI solution reaches 97%; Their optimal adsorption pH is at 1-2, adsorption capacity from 3.19 to 1.20mg/g; Walnut shell powder is that 1 o'clock adsorption rate to 50mg/L Cr VI solution is 95.39% at pH; Every gram walnut powder has adsorbed 4.76mg chromium (" agricultural environment science journal " approximately; 2009,28 volumes the 8th phase 1693-1700 page or leaf " the agricultural wastes walnut shell powder is to the adsorpting characteristic research of Cr (VI) ").
In addition corncob, rice husk, walnut shell etc. are carried out modification with its adsorption rate of further raising in the prior art, perhaps these biomaterials are processed active carbon as adsorbent.As; " northwest agricultural journal " 2007 the 16th volumes the 1st phase 26-29 page or leaf has been published people's such as Yu Meifang article " rice husk preparing active carbon and to the adsorption capacity research of chromium in the sewage " />; < 6 o'clock is 95.8% to the chromic adsorption rate of 10mgL, and every gram rice hull active carbon has adsorbed 0.12mg chromium at pH to process active carbon to rice husk; " environmental science and technology " 2009 the 22nd volume the 3rd phase 41-43 page or leaf " the non-living body living beings are to the absorption research of chromate waste water " corncob with phosphoric acid modification after, be the chromic adsorption rate of 20mg/L to be reached 98.16% (adsorption capacity 0.98mg/g) at 2 o'clock at pH.In addition; Modified lignin sulfonate, furfuraldehyde waste slag etc. also have relevant report as the chromium adsorbent; Can both reach than higher adsorption rate, as, modified lignin sulfonate reaches 99.0% to the chromic clearance of 100mg/L under the pH of 4-7; Make in the water chromium ion concentration less than 0.5mg/L, adsorption capacity is 3.33mg/g (seeing " process engineering journal " 2008 the 8th volumes the 5th phase 877-880 page or leaf " modified lignin mahogany sulfonate is to the absorption of CR^6+ in the water "); Furfural dregs is that the chromic clearance of 4.9mg/L is 84.2% to concentration; The furfural dregs fineness increases; Adsorption rate can bring up to 98.2%, adsorption capacity 0.24mg/g (seeing " Ningxia University's journal " 2011 the 32nd volumes the 3rd phase 262-265 page or leaf " furfural dregs is to the absorption research of Cr_3_ in the waste water ").
Can find out from these above living beings absorption reports; The general chromium solution that is adopted is the chromium solution (4.9-50 mg/L) of low concentration; The chromium concn of chromate waste water remnants after adsorbing is at 0.4-2.3mg/L; Though modified lignin sulfonate has good adsorption effect to the chromium waste liquid of high concentration, residual chromium concentration still reaches 0.5mg/L.According to the chromic discharge standard of standard GB 21900-2008; Newly-built enterprise Cr VI emission limit is 0.2mg/L, and the special emission limit of water pollutant is 0.1mg/L, and above-mentioned various adsorbents all do not reach existing wastewater discharge standard; Waste water also needs further to handle and could discharge; And various modifying process can increase production cost, bring secondary pollution, and this also is the disadvantage of modified adsorbent.
Summary of the invention
For the waste residue utilization problem that solves xylitol manufacturing enterprise and heavy metal-containing waste water adsorption treatment still can not be up to standard problem, the present invention proposes a kind of waste residue of producing behind the xylitol with corncob is the heavy metal ions in wastewater adsorbent of raw material.
Another object of the present invention provides a kind of absorbing process that uses above-mentioned adsorbent that heavy metal ions in wastewater is adsorbed.
The present invention realizes in the following manner:
A kind of heavy metal ions in wastewater adsorbent is for corncob is produced the waste residue behind the xylitol.
Corncob is produced the general technology of xylitol: the corncob raw material with 2.8% sulfuric acid 120-125 ℃ of acidolysis, hydrolyzate through decolour, remove slag, ion-exchange, concentrate, crystallization obtains wood sugar, wood sugar obtains xylitol through further hydrogenating reduction.The corncob slag that hydrolysis kettle is discharged is the waste residue of indication of the present invention.Furfural dregs is corncob and the 140-180 ℃ of reaction in hydrolysis kettle of 5% dilute sulfuric acid after pulverizing, and the gas of generation obtains furfural stoste after condensation, and the waste residue of discharging in the agitated reactor is a furfuraldehyde waste slag.The acidolysis degree of making xylitol by corn cob is different with the acidolysis degree of system furfural; So the structure of the waste residue that produces is also different; To have adsorption capacity be predictable though corncob is produced waste residue behind the xylitol, and the power of its adsorption capacity but can't be predicted.Waste residue behind the making xylitol by corn cob has exceeded those of ordinary skills' expection to the adsorption capacity of heavy metal ion, is non-obvious.
A kind of absorbing process of heavy metal ions in wastewater is put into the waste water that contains heavy metal ion with claim 1 or 2 described adsorbents, under certain pH, uniform temperature, adsorbs certain hour, filters after absorption is accomplished, and filtrating transfers to neutrality, discharging.
The weight ratio of chromium ion and adsorbent is not more than 6.3mg:1g in the waste water.
The weight ratio of lead ion and adsorbent is not more than 5.2mg:1g in the waste water.
The weight ratio of zinc ion and adsorbent is not more than 3.5mg:1g in the waste water.
The weight ratio of copper ion and adsorbent is not more than 4.5mg:1g in the waste water.
Described absorbing process, preferred pH is 1-2.
Described absorbing process, preferable reaction temperature are 70-80 ℃.
Described absorbing process, described adsorption time is preferably 60-180min.
Beneficial effect of the present invention:
1, heavy metal ions in wastewater adsorbent of the present invention can reach 99.99% to the chromium ion adsorption rate; Even all remove; And adsorption capacity is high, can reach 6.46mg/g, and heavy metals such as lead, zinc, copper are all had good adsorption effect; Adsorption rate and adsorption capacity are higher than reported other living beings class sorbing material, and embodying this adsorbent has fabulous absorption to remove ability to chromium ion in the waste water;
2, adsorbent of the present invention directly is used for the absorbing process of heavy metal ions in wastewater, does not need to pass through further process again, after adsorption process is accomplished; Direct Filtration is removed; With low cost, technology is simple, is a kind of extremely valuable novel heavy metal absorbent;
3, xylitol is produced waste residue itself and is stronger acidity, and pH value is about 3.5, and absorption also is effective under acid condition, therefore in adsorption process, need not add acid or only need the adding small amount of acid can promote adsorption effect;
4, direct isolated by filtration from water after this adsorbent is finished using; Burn or further handle; Need not sorbing material is regenerated; The waste residue that has solved xylitol enterprise is on the one hand handled problems, and removes the sorbing material that a kind of Cheap highly effective is provided for the heavy metal of waste water industry again on the other hand, for solving environmental pollution, promoting that refuse reclamation is significant.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, does not constitute any restriction of the present invention.Remove other and indicate, all umbers among the embodiment and percentage number average are by weight.
Embodiment 1:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 30 parts of concentration be 80mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:2.4mg; Using concentration is that 20% sulfuric acid solution transfers to pH2; The control temperature is 90 ℃, adsorption time 180 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of residual chromium ion in the filtrating; Getting adsorption rate is 99.98%, and the residual chromium ion concentration has only 0.016mg/L in the filtrating, is lower than discharging standards (0.1mg/L).Filtrating can be discharged with limewash neutralization, post precipitation clear liquid.
Embodiment 2:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 40 parts of concentration be 50mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:2mg; Using concentration is that 20% sulfuric acid solution transfers to pH2; The control temperature is 80 ℃, adsorption time 140 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of residual chromium ion in the filtrating; Getting adsorption rate is 99.97%, and the residual chromium ion concentration has only 0.015mg/L in the filtrating, is lower than discharging standards (0.1mg/L).
Embodiment 3:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 50 parts of concentration be 50mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:2.5mg; Using concentration is that 20% sulfuric acid solution transfers to pH2; The control temperature is 80 ℃, adsorption time 150 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of residual chromium ion in the filtrating; Getting adsorption rate is 99.98%, and the residual chromium ion concentration has only 0.01mg/L in the filtrating, is lower than discharging standards (0.1mg/L).
Embodiment 4:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 50 parts of concentration be 100mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:5mg; Using concentration is that 20% sulfuric acid solution transfers to pH1; The control temperature is 80 ℃, adsorption time 180 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of residual chromium ion in the filtrating; Getting adsorption rate is 99.99%, and the residual chromium ion concentration has only 0.01mg/L in the filtrating, is lower than discharging standards (0.1mg/L).
Embodiment 5:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 70 parts of concentration be 100mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:7mg; Using concentration is that 20% sulfuric acid solution transfers to pH2, and the control temperature is 70 ℃, adsorption time 120 minutes; Acid waste water is measured the concentration of residual chromium ion in the filtrating through filtering after the absorption completion, and getting adsorption rate is 92.29%; Residual chromium ion concentration 7.7mg/L in the filtrating; The adsorption capacity that has surpassed waste residue need be carried out further adsorption treatment or increase the adsorbent consumption waste liquid, reduces liquid-solid ratio.
Embodiment 6:
The making xylitol by corn cob waste residue is through after nature dries, and the hexavalent chromium wastewater that to get 1 part of waste residue and 70 parts of concentration be 90mg/kg mixes, and the weight ratio of waste residue and chromium ion is 1g:6.3mg; Using concentration is that 20% sulfuric acid solution transfers to pH3; The control temperature is 100 ℃, adsorption time 60 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of residual chromium ion in the filtrating; Getting adsorption rate is 99.90%, and the residual chromium ion concentration has only 0.09mg/L in the filtrating, is lower than discharging standards (0.1mg/L).
Embodiment 7:
The making xylitol by corn cob waste residue is through after nature dries, and the lead solution that to get 1 part of waste residue and 65 parts of concentration be 80mg/kg mixes, and the weight ratio of waste residue and lead ion is 1g:5.2mg; Using concentration is that 20% sulfuric acid solution transfers to pH2; The control temperature is 80 ℃, adsorption time 120 minutes, and acid waste water was through filtering after absorption was accomplished; Measure the concentration of remaining lead ion in the filtrating; Getting adsorption rate is 99.10%, and plumbum ion concentration is 0.72mg/L in the waste water, surpasses the wastewater discharge standard (1mg/L) of national regulation
Embodiment 8:
The making xylitol by corn cob waste residue is through after nature dries, and the lead solution that to get 1 part of waste residue and 56 parts of concentration be 100mg/kg mixes, and the weight ratio of waste residue and lead ion is 1g:5.6mg; Using concentration is that 20% sulfuric acid solution transfers to pH2, and the control temperature is 80 ℃, adsorption time 150 minutes; Acid waste water is measured the concentration of remaining lead ion in the filtrating through filtering after the absorption completion, and getting adsorption rate is 98.30%; Plumbum ion concentration is 1.7mg/L in the waste water; The wastewater discharge standard (1mg/L) that surpasses national regulation needs further adsorption treatment, reduces plumbum ion concentration.
Embodiment 9:
The making xylitol by corn cob waste residue is through after nature dries, and the zinc solution that to get 1 part of waste residue and 50 parts of concentration be 70mg/kg mixes, and the weight ratio of waste residue and zinc ion is 1g:3.5mg; Using concentration is that 20% sulfuric acid solution transfers to pH2, and the control temperature is 85 ℃, adsorption time 160 minutes; Acid waste water is measured the concentration of remaining zinc ion in the filtrating through filtering after the absorption completion, and getting adsorption rate is 99.80%; Remaining zinc ion concentration is 0.14mg/L, is lower than national wastewater discharge standard (2mg/L).
Embodiment 10:
The making xylitol by corn cob waste residue is through after nature dries, and the copper solution that to get 1 part of waste residue and 45 parts of concentration be 100mg/kg is mixed, and the weight ratio of waste residue and copper ion is 1g:4.5mg; Using concentration is that 20% sulfuric acid solution transfers to pH1, and the control temperature is 75 ℃, adsorption time 170 minutes; Acid waste water was through filtering after absorption was accomplished; Measure the concentration 0.10mg/L of extraneous copper ion in the filtrating, adsorption rate is 99.90%, is lower than wastewater discharge standard 0.5mg/L.
The foregoing description 1-10 has only provided the absorbing process of the data combination of several advantages of good adsorption effect; The mass ratio of adsorbent and waste water; As long as guarantee that both mix state afterwards is liquid, it is just passable that absorption can be taken place, and is not limited in the ratio among the foregoing description 1-10.PH, temperature, time parameter about absorbing process; What provide among the foregoing description 1-10 is preferred value; PH also can realize adsorbing not in the scope of 1-2, just acidity more a little less than; Adsorption effect is poor more, and this is that those of ordinary skills can know according to existing disclosed technology.Temperature parameter, if at normal temperatures, absorption also can take place, just adsorption effect also can variation, because temperature raises, molecular motion is accelerated, so advantages of good adsorption effect.Time parameter, according to time temperature equivalence principle, adsorption time is long, and adsorption effect also can be got well.At this, all parameter combinations technology is not all enumerated one by one, because can't be exhaustive.
And in embodiment 1-10, the mass ratio of adsorbent and heavy metal ion is in a scope; In this scope, add preferred parameter such as pH, temperature, adsorption effect is best; Can reach more than 99.9% even 100%, but in adsorption process, as long as adsorbent no show adsorption capacity; Just suction-operated can take place, produce adsorption effect, therefore; Absorbing process of the present invention, the adsorbent that is not restricted to mention among the foregoing description 1-10 and the mass ratio of heavy metal ion.
Claims (9)
1. heavy metal ions in wastewater adsorbent is characterized in that producing the waste residue behind the xylitol for corncob.
2. the absorbing process of a heavy metal ions in wastewater is characterized in that the described adsorbent of claim 1 is put into the waste water that contains heavy metal ion, under certain pH, uniform temperature, adsorbs certain hour, filters after absorption is accomplished, and filtrating transfers to neutrality, discharging.
3. absorbing process according to claim 2 is characterized in that the weight ratio of chromium ion and adsorbent is not more than 6.3mg:1g in the waste water.
4. absorbing process according to claim 2 is characterized in that the weight ratio of lead ion and adsorbent is not more than 5.2mg:1g in the waste water.
5. absorbing process according to claim 2 is characterized in that the weight ratio of zinc ion and adsorbent is not more than 3.5mg:1g in the waste water.
6. absorbing process according to claim 2 is characterized in that the weight ratio of copper ion and adsorbent is not more than 4.5mg:1g in the waste water.
7. absorbing process according to claim 2 is characterized in that pH is 1-2.
8. absorbing process according to claim 2 is characterized in that reaction temperature is 70-80 ℃.
9. absorbing process according to claim 2 is characterized in that described adsorption time is 60-180min.
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| CN103508538A (en) * | 2013-09-25 | 2014-01-15 | 郑州航空工业管理学院 | Nickel-containing wastewater treatment method |
| CN104437392A (en) * | 2014-10-17 | 2015-03-25 | 广西大学 | Method for adsorbing Cr (VI) with modified eucalyptus bark |
| CN104891596A (en) * | 2014-03-06 | 2015-09-09 | 上海市南洋模范中学 | Static device for rapid purification of low-concentration lead-containing wastewater by utilizing biomass material |
| CN107986498A (en) * | 2017-12-20 | 2018-05-04 | 北京科技大学 | The method of sulphion in a kind of precipitation-biological adsorption combination removing waste water |
| CN109329898A (en) * | 2018-11-13 | 2019-02-15 | 东台市济民生物科技有限公司 | A kind of extracting method of edible fungus living being active material |
| CN110577299A (en) * | 2019-10-18 | 2019-12-17 | 河北渤海远达环境检测技术服务有限公司 | method for treating hot galvanizing pickling wastewater and preparing carbon-loaded iron-zinc binary metal composite material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508538A (en) * | 2013-09-25 | 2014-01-15 | 郑州航空工业管理学院 | Nickel-containing wastewater treatment method |
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| CN104891596A (en) * | 2014-03-06 | 2015-09-09 | 上海市南洋模范中学 | Static device for rapid purification of low-concentration lead-containing wastewater by utilizing biomass material |
| CN104437392A (en) * | 2014-10-17 | 2015-03-25 | 广西大学 | Method for adsorbing Cr (VI) with modified eucalyptus bark |
| CN107986498A (en) * | 2017-12-20 | 2018-05-04 | 北京科技大学 | The method of sulphion in a kind of precipitation-biological adsorption combination removing waste water |
| CN109329898A (en) * | 2018-11-13 | 2019-02-15 | 东台市济民生物科技有限公司 | A kind of extracting method of edible fungus living being active material |
| CN110577299A (en) * | 2019-10-18 | 2019-12-17 | 河北渤海远达环境检测技术服务有限公司 | method for treating hot galvanizing pickling wastewater and preparing carbon-loaded iron-zinc binary metal composite material |
| CN110577299B (en) * | 2019-10-18 | 2021-08-27 | 河北渤海远达环境检测技术服务有限公司 | Method for treating hot galvanizing pickling wastewater and preparing carbon-loaded iron-zinc binary metal composite material |
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Application publication date: 20120627 |