CN1676635A - Process for separating and recovering sludge and heavy metals in soil - Google Patents
Process for separating and recovering sludge and heavy metals in soil Download PDFInfo
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- CN1676635A CN1676635A CNA2005100241259A CN200510024125A CN1676635A CN 1676635 A CN1676635 A CN 1676635A CN A2005100241259 A CNA2005100241259 A CN A2005100241259A CN 200510024125 A CN200510024125 A CN 200510024125A CN 1676635 A CN1676635 A CN 1676635A
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Abstract
This invention discloses a new technique that uses green polymer Asp of biological degradation to be the extractant, effectively separates the heavy metals of urban sludge and the soils, and realizes the recycling of the heavy metals and reusing of Asp. The technique is as follows: at first prepare the sludge floating liquor; then add Asp agent into the floating liquor, and the ration range of Asp to the heavy metal in the sludge is 0.1-10, adjust the floating liquor with acid alkali agent and then acentricly separate. According to the kinds of the heavy metal ions and contents in the samples, use acid alkali agent to adjust the pH value of purified liquor and implement heavy metal separation to the adjusted purified liquor with different kinds of ion exchanging resin. This invention realizes the resource utilization of heavy metals and reusing of Asp, and it has high economic benefits and environmental protection function.
Description
Technical field
The heavy metal that the present invention relates to a kind of environment-friendly type separates and the recovery friendly process, relate in particular to and a kind ofly utilize biodegradable green polymeric polyaspartic acid as extraction agent, the heavy metal in municipal sewage sludge and the soil is realized effectively separating, and realize the recovery of heavy metal and the novel process that recycles of poly aspartic acid.
Background technology
The Tandy of engineering college of Swiss Confederation, S.[Environ.Sci.Technol.2004; 38 (3); 937-944] etc. the people carried out biodegradable chelated dose of quadrol two Succinic Acid (EDDS) to the extraction of heavy metal in soil research, be intended to substitute most widely used difficult for biological degradation sequestrant EDTA at present, the ex situ that is used for the soil poisonous and harmful heavy metallic is cleaned and the chelate-enhanced plants soil remediation.The Yoshizaki of Japan Tokushima university, S.[Environ.Sci.Technol.2000; 34 (8); 1572-1575] etc. remove heavy metal in the sewage plant sludge with the phosphoric acid that adds hydrogen peroxide, studied the spent ion exchange resin method and carried out the Recycling of phosphoric acid and the recovery technology of heavy metal.Domestic stabilization, the form that at present research of heavy metal in the mud is laid particular emphasis on heavy metal in the mud distributes, mud itself to the adsorption of heavy metal, reach the pot experiment research of phytoremediation.
It is so far, international, domestic that all heavy metal in mud or the polluted soil separates and the research report of resource utilization less than being applied to about poly aspartic acid.
Summary of the invention
The object of the present invention is to provide a kind of biodegradable green polymeric polyaspartic acid (PASP) of utilizing to make extraction agent, in conjunction with extracting and separating and ion exchange process, the heavy metal in separation and recovery mud and the soil.
The present invention is achieved by the following technical solutions:
(1) sludge suspension liquid preparation
Fetch mud or contaminated pedotheque (contained heavy metal scope comprises zinc, nickel, chromium, copper, lead, cadmium, mercury etc.) 0.5～1000g from the municipal sewage plant, air-dry 1～14 day, cross 100～500 mesh sieves, for acid sludge or pedotheque, regulate suspension with alkaline solution, regulate the used alkali of suspension and comprise sodium hydroxide, potassium hydroxide, calcium hydroxide, unslaked lime, yellow soda ash, ammoniacal liquor etc.For alkaline sludge or pedotheque, regulate suspension with acid solution, regulate the used acid of suspension and comprise hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid etc.Suspension soaked 1～5 day.
(2) extraction process
Select for use three class poly aspartic acids respectively as extraction agent, comprise by the synthetic poly aspartic acid of L-aspartic acid thermal polycondensation, be raw material synthetic poly aspartic acid, be raw material synthetic poly aspartic acid with maleic anhydride and phosphoric acid with maleic anhydride and volatile salt or ammoniacal liquor, the molecular weight ranges of used poly aspartic acid is 2, between 000 to 20,000.
In suspension, add a certain amount of poly aspartic acid solution, the concentration ratio scope of total metals is 0.1～10 in poly aspartic acid and the mud (or polluted soil), shake up, regulate suspension with acid-base solution again, regulate used acid and comprise hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid etc., regulate used alkali and comprise sodium hydroxide, potassium hydroxide, calcium hydroxide, unslaked lime, yellow soda ash, ammoniacal liquor etc.PH value scope after the adjusting is 1～10, and wherein extracting best pH scope is 4～8.Above-mentioned mixed solution is placed on the constant temperature oscillator, and the temperature range of constant temperature vibration is 0～40 ℃, and the constant temperature duration of oscillation is 0.5～72 hour.The centrifugation on whizzer of extraction suspension, rotating speed is 1000～5000rpm, and the centrifugation time is 10～100min, and clear liquid uses for next step ion-exchange, and the solid part separation utilizes as soil constituent again.
(3) ion-exchange Separation and Recovery heavy metal and poly aspartic acid (PASP) recycle
The clear liquid that previous step is provided, regulate the pH value of clear liquid with acid-base solution, regulate used acid and comprise hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid etc., regulate used alkali and comprise sodium hydroxide, potassium hydroxide, calcium hydroxide, unslaked lime, yellow soda ash, ammoniacal liquor etc.Select the three class ion exchange resin that comprise strong acid ion exchange resin, weak-acid ion exchange resin, chelating ion exchange resin for use, respectively above-mentioned clear liquid through regulating the pH value is carried out the separation of heavy metal.Heavy metal is adsorbed by ion exchange column, and poly aspartic acid is stayed in the solution, recycles as extraction agent.Then, with acid solution ion exchange resin is carried out manipulation of regeneration again, reclaim heavy metal.Ion exchange resin after the regeneration continues on for the separation of heavy metal.The used acid of ion exchange resin regeneration comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc.
The present invention has adopted degradable green polymeric polyaspartic acid (PASP) to make extraction agent, in conjunction with extracting and separating and ion exchange process, heavy metal in separation and recovery mud and the soil, technology of the present invention has realized the recycling of heavy metal and recycling of poly aspartic acid, have increase economic efficiency, advantage such as environmental protection.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
How further specify the present invention below in conjunction with concrete embodiment realizes:
Embodiment 1
(1) is raw material with the L-aspartic acid, under the condition of catalyst-free, carries out polycondensation and prepare poly aspartic acid that step is as follows: get 40g L-aspartic acid and put into four neck flasks, flask is placed methyl-silicone oil oil bath heating.Oil bath temperature is controlled in the 170-270 ℃ of scope, feeds N
2, mechanical stirring is reacted 2-3 hour postcooling to room temperature, obtains yellow powder shape compound polysuccinimide (PSI); Get 3g PSI, and drip the NaOH solution of a certain amount of 2.5mol/L, place the 100ml small beaker, magnetic agitation 1 hour makes its hydrolysis under 0 ℃ of condition, promptly gets clarifying poly aspartic acid sodium salt red tan solution.Dropwise 35 %HCl solution, regulator solution pH value; Add 50mL methyl alcohol, regulate hydrophilic-lipophilic balance, PASP is separated out with precipitation forms.Precipitation filtered, in 40 ℃ of following drying under reduced pressure 12 hours.Be ground into powder, promptly get poly aspartic acid (PASP), its weight-average molecular weight is 8,000.
(2) fetch mud sample (contained heavy metal mainly comprises zinc, nickel, chromium, copper, cadmium etc.) 5g from municipal sewage plant, Quyang, Shanghai, air-dry 7 days, cross 200 mesh sieves, regulate pH of suspension value 4～5 with hydrochloric acid and sodium hydroxide solution.Suspension soaked 2 days.
(3) be 8 with above-mentioned weight-average molecular weight of synthesizing by L-aspartic acid thermal polycondensation, 000 poly aspartic acid, in suspension, add a certain amount of extraction agent solution that contains poly aspartic acid, the concentration ratio of total metals is 2 in poly aspartic acid and the mud, shake up, regulate suspension with hydrochloric acid, sodium hydroxide solution again, the pH value scope of adjusting is 4～5.Above-mentioned mixed solution is placed on the constant temperature oscillator, and the temperature range of constant temperature vibration is 30 ℃, and the constant temperature duration of oscillation is 24 hours.The centrifugation on whizzer of extraction suspension, rotating speed is 2000rpm, and the centrifugation time is 50min, and clear liquid uses for next step ion-exchange, and the solid part separation utilizes as soil constituent again.
(4) ion-exchange Separation and Recovery heavy metal and PASP recycle
The clear liquid that previous step is provided, with the pH value that hydrochloric acid, sodium hydroxide solution are regulated clear liquid, the pH value scope of adjusting is 2～8, and the different sorts of the metal ion that concrete pH optimum range is contained is per sample determined, for example for institute's copper ions, pH value optimum range is 4～7.The difference of contained heavy metal ion kind and content per sample, the D113 macropore acidulous acrylic acid cation exchange resin of selecting for use TianXing, Anhui resin company to produce, or 001 * 16/14/12 strongly acidic styrene type cation exchange resin of TianXing, Anhui resin company production, or the big empty polystyrene chelating ion exchange resin of D401 of Jiangsu Qing Shui water treatment company production, (for example for cupric ion, the big empty polystyrene chelating ion exchange resin of D401 that can select for use Jiangsu Qing Shui water treatment company to produce), above-mentioned clear liquid through regulating the pH value is carried out the separation of heavy metal, heavy metal is adsorbed by ion exchange column, poly aspartic acid is stayed in the solution, recycles as extraction agent.Then, with hydrochloric acid soln ion exchange resin is carried out manipulation of regeneration again, reclaim heavy metal, the ion exchange resin after the regeneration continues on for the separation of heavy metal.Wherein the exchange rate to zinc, cadmium can reach 90%, and the reclamation rate of poly aspartic acid is greater than 95%.
Embodiment 2
(1) be raw material with maleic anhydride and volatile salt, synthesizing polyaspartic acid, step is as follows: get 49g maleic anhydride and ammonium salt in molar ratio (1: 1) mix, add in the four neck flasks, place methyl-silicone oil to bathe heating, stir simultaneously, controlled temperature reacts 170 ℃ of-260 ℃ of scopes, react after 2～3 hours, reaction mixture gets precursor yellow powder shape compound polysuccinimide (PSI); Get 3g PSI, and drip the NaOH solution of a certain amount of 2.5mol/L, place the 100ml small beaker, magnetic agitation 1 hour makes its hydrolysis under 0 ℃ of condition, promptly gets clarifying poly aspartic acid sodium salt red tan solution.Dropwise 35 %HCl solution, regulator solution pH value; Add 50mL methyl alcohol, regulate hydrophilic-lipophilic balance, PASP is separated out with precipitation forms.Precipitation filtered, in 40 ℃ of following drying under reduced pressure 12 hours.Be ground into powder, promptly get poly aspartic acid (PASP), its weight-average molecular weight is 5,000.
(2) fetch sample (contained heavy metal mainly comprises zinc, nickel, chromium, copper, cadmium, mercury) 5g from Shanghai district polluted soil, air-dry 7 days, cross 200 mesh sieves, regulate pH of suspension value 4～6 with hydrochloric acid and sodium hydroxide solution.Suspension soaked 2 days.
(3) be 5 with above-mentioned weight-average molecular weight of synthesizing by L-aspartic acid thermal polycondensation, 000 poly aspartic acid, in suspension, add a certain amount of extraction agent solution that contains poly aspartic acid, the concentration ratio of total metals is 8 in poly aspartic acid and the mud, shake up, regulate suspension with hydrochloric acid, sodium hydroxide solution again, the pH value scope of adjusting is 4～6.Above-mentioned mixed solution is placed on the constant temperature oscillator, and the temperature range of constant temperature vibration is 30 ℃, and the constant temperature duration of oscillation is 24 hours.The centrifugation on whizzer of extraction suspension, rotating speed is 2000rpm, and the centrifugation time is 50min, and clear liquid uses for next step ion-exchange, and the solid part separation utilizes as soil constituent again.
(4) ion-exchange Separation and Recovery heavy metal and PASP recycle
The clear liquid that previous step is provided, with the pH value that hydrochloric acid, sodium hydroxide solution are regulated clear liquid, the pH value scope of adjusting is 2～8, and the different sorts of the metal ion that concrete pH optimum range is contained is per sample determined, for example for institute's copper ions, pH value optimum range is 4～7.The difference of contained heavy metal ion kind and content per sample, select 001 * 16/14/12 strongly acidic styrene type cation exchange resin of TianXing, Anhui resin company production or the big empty polystyrene chelating ion exchange resin of D401 that Jiangsu Qing Shui water treatment company produces for use, carry out the separation of heavy metal to above-mentioned through the stillness of night of regulating the pH value, heavy metal is adsorbed by ion exchange column, poly aspartic acid is stayed in the solution, recycles as extraction agent.Then, with hydrochloric acid soln ion exchange resin is carried out manipulation of regeneration again, reclaim heavy metal, the ion exchange resin after the regeneration continues on for the separation of heavy metal.Wherein the exchange rate to zinc, copper can reach 90%, and the reclamation rate of poly aspartic acid is greater than 95%.
Claims (7)
1, a kind of novel process of separating and reclaiming mud and heavy metal in soil comprises the steps:
A, the preparation of sludge suspension liquid
Fetch mud or contaminated pedotheque from the municipal sewage plant, air-dry, screening for acid sludge or pedotheque, is regulated suspension with alkaline solution, for alkaline sludge or pedotheque, regulates suspension with acid solution, and suspension soaked 1～5 day;
B, extraction
In suspension, add poly aspartic acid solution, the concentration ratio scope of total metals is 0.1～10 in poly aspartic acid and the mud, shake up, regulate suspension with acid-base solution again, pH value scope after the adjusting is 1～10, above-mentioned mixed solution placed on the constant temperature oscillator vibrate, extract suspension then and on whizzer, carry out centrifugation.
Recycling of the recovery of C, heavy metal and poly aspartic acid
The stillness of night that the previous step centrifugation is obtained, contained heavy metal ion kind and content per sample, regulate the pH value of clear liquid with acid-base solution, again per sample in the difference of contained heavy metal ion kind and content, select for use strong acid ion exchange resin, weak-type ion exchange resin, chelating ion exchange resin at three interior class ion exchange resin, respectively above-mentioned clear liquid through regulating the pH value is carried out the separation of heavy metal.
2. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 1 is characterized in that: described biodegradable polymeric polyaspartic acid is selected one or more in the polymeric polyaspartic acid that following three kinds of different synthetic methods make for use: by the synthetic poly aspartic acid of L-aspartic acid thermal polycondensation; With maleic anhydride and volatile salt or ammoniacal liquor is raw material synthetic poly aspartic acid; With maleic anhydride and phosphoric acid is raw material synthetic poly aspartic acid.
3. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 2, it is characterized in that: the molecular weight ranges of selected poly aspartic acid is between 2,000 to 20,000.
4. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 1, it is characterized in that: regulate the used acid of suspension in the described B step and select one or more mixture in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid or the citric acid for use, regulate the used alkali of suspension and select one or more mixture in sodium hydroxide, potassium hydroxide, calcium hydroxide, unslaked lime, yellow soda ash or the ammoniacal liquor for use.
5. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 1 is characterized in that: the pH of suspension value scope after regulating with acid-base solution in the described B step is 4～8.
6. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 1 is characterized in that: the temperature range of suspension constant temperature vibration is 0～40 ℃ in the described B step, and the constant temperature duration of oscillation is 0.5～72 hour.
7. a kind of novel process of separating and reclaiming mud and heavy metal in soil according to claim 1, it is characterized in that: the rotating speed of centrifugation is 1000～5000rpm in the described C step, the centrifugation time is 10～100min.
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| CNB2005100241259A CN100372951C (en) | 2005-03-01 | 2005-03-01 | Process for separating and recovering sludge and heavy metals in soil |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101533002A (en) * | 2008-03-10 | 2009-09-16 | 黄永 | Flat ion-exchange module |
| CN103788956A (en) * | 2014-01-12 | 2014-05-14 | 北京化工大学 | Environment-friendly eluting agent and application method thereof |
| CN103819064A (en) * | 2014-03-10 | 2014-05-28 | 中钢集团武汉安全环保研究院有限公司 | Method for removing heavy metals from sludge by pickling of composite acids |
| CN103849772A (en) * | 2012-11-28 | 2014-06-11 | 大连东泰产业废弃物处理有限公司 | Method for recovering metal cobalt by N,N'-1,2-ethanediylbis-1-aspartic acid |
| CN105524627A (en) * | 2015-12-03 | 2016-04-27 | 阜阳欣奕华材料科技有限公司 | Purification method of waste liquid crystal alignment liquid and purification device |
| CN105567975A (en) * | 2015-12-31 | 2016-05-11 | 南京工业大学 | Method for recycling Zn from electroplating sludge and disposing waste residues |
| CN105945052A (en) * | 2016-05-30 | 2016-09-21 | 青岛理工大学 | Heavily-polluted site Pb in-situ and ex-situ couplingdetoxificationmethod |
| CN106001087A (en) * | 2016-05-30 | 2016-10-12 | 青岛理工大学 | Hg in-situ and heterotopic coupling detoxifying method for heavily-contaminated site |
| CN108636996A (en) * | 2018-05-04 | 2018-10-12 | 中国农业大学 | A kind of conditioner with repairing heavy metal in soil anti-contamination function |
| CN110368896A (en) * | 2019-06-04 | 2019-10-25 | 中国地质大学（武汉） | A kind of carbon-based functional material of superhigh specific surface area and its preparation method and application |
| CN111484224A (en) * | 2020-03-09 | 2020-08-04 | 杭州埃莫森环保科技有限公司 | Method and system for manufacturing anti-hardening ecological nutrient soil by using sludge |
| CN113087325A (en) * | 2021-03-27 | 2021-07-09 | 同济大学 | Targeted clean extraction method for sludge phosphorus recovery |
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| JPWO2004037453A1 (en) * | 2002-10-24 | 2006-02-23 | 帝人ファイバー株式会社 | Soil purification method |
| CN1548382A (en) * | 2003-05-22 | 2004-11-24 | 中南大学 | Method of treating waste water containing heavy metal with waste sludge as carrier |
| CN1559711A (en) * | 2004-03-05 | 2005-01-05 | 中山大学 | Plant repairing method of agricultural land polluted by heavy metal |
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- 2005-03-01 CN CNB2005100241259A patent/CN100372951C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533002A (en) * | 2008-03-10 | 2009-09-16 | 黄永 | Flat ion-exchange module |
| CN103849772A (en) * | 2012-11-28 | 2014-06-11 | 大连东泰产业废弃物处理有限公司 | Method for recovering metal cobalt by N,N'-1,2-ethanediylbis-1-aspartic acid |
| CN103788956A (en) * | 2014-01-12 | 2014-05-14 | 北京化工大学 | Environment-friendly eluting agent and application method thereof |
| CN103819064A (en) * | 2014-03-10 | 2014-05-28 | 中钢集团武汉安全环保研究院有限公司 | Method for removing heavy metals from sludge by pickling of composite acids |
| CN105524627A (en) * | 2015-12-03 | 2016-04-27 | 阜阳欣奕华材料科技有限公司 | Purification method of waste liquid crystal alignment liquid and purification device |
| CN105567975A (en) * | 2015-12-31 | 2016-05-11 | 南京工业大学 | Method for recycling Zn from electroplating sludge and disposing waste residues |
| CN105945052A (en) * | 2016-05-30 | 2016-09-21 | 青岛理工大学 | Heavily-polluted site Pb in-situ and ex-situ couplingdetoxificationmethod |
| CN106001087A (en) * | 2016-05-30 | 2016-10-12 | 青岛理工大学 | Hg in-situ and heterotopic coupling detoxifying method for heavily-contaminated site |
| CN108636996A (en) * | 2018-05-04 | 2018-10-12 | 中国农业大学 | A kind of conditioner with repairing heavy metal in soil anti-contamination function |
| CN108636996B (en) * | 2018-05-04 | 2020-10-27 | 广东维特农业科技有限公司 | Conditioner with function of repairing heavy metal pollution of soil |
| CN110368896A (en) * | 2019-06-04 | 2019-10-25 | 中国地质大学（武汉） | A kind of carbon-based functional material of superhigh specific surface area and its preparation method and application |
| CN111484224A (en) * | 2020-03-09 | 2020-08-04 | 杭州埃莫森环保科技有限公司 | Method and system for manufacturing anti-hardening ecological nutrient soil by using sludge |
| CN113087325A (en) * | 2021-03-27 | 2021-07-09 | 同济大学 | Targeted clean extraction method for sludge phosphorus recovery |
| CN113087325B (en) * | 2021-03-27 | 2022-06-24 | 同济大学 | Targeted cleaning extraction method for sludge phosphorus recovery |
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