CN108607519B - Sludge passivator and application thereof - Google Patents
Sludge passivator and application thereof Download PDFInfo
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- CN108607519B CN108607519B CN201810547200.7A CN201810547200A CN108607519B CN 108607519 B CN108607519 B CN 108607519B CN 201810547200 A CN201810547200 A CN 201810547200A CN 108607519 B CN108607519 B CN 108607519B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to a sludge passivator and application thereof, which can effectively solve the problems of limited application range, poor passivation effect, complex preparation method, high recycling difficulty and low heavy metal treatment load and removal efficiency of a heavy metal passivator, and adopts the following technical scheme: a sludge passivator comprises the following components in percentage by weight: 85-94% of modified lignin mixture, 1-3% of quicklime and 5-12% of sodium alginate; firstly, mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3, preparing a modified lignin mixture; the sludge passivator is prepared by mixing quicklime and sodium alginate and adding the modified lignin mixture to prepare embedded pellets.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a sludge passivator and application thereof.
Background
With the improvement of the living standard of residents in China and the development of urban economy, the construction of urban sewage treatment equipment is continuously strengthened. After large scale treatment of sewage, the treatment of heavy metals in municipal sludge becomes a major problem for sludge reuse.
The lignin is cheap and easy to use as papermaking waste, has certain adsorption capacity and can be used for removing heavy metal ions, dyes and organic pollutants. Lignin molecules contain a large number of oxygen-containing functional groups, and can be directly used as an adsorbent to perform ion exchange or chelation reaction with heavy metals in wastewater. The lignin is the waste of the pulp and paper industry, and the direct discharge not only pollutes the environment but also wastes resources. The research and development of the economical and efficient lignin-based adsorbent not only comprehensively utilizes the lignin resources in the papermaking black liquor, but also provides a new technology for the treatment of heavy metal wastewater. In addition, because the lignin is nontoxic and is easy to degrade by microorganisms, the lignin-based flocculant is an environment-friendly heavy metal adsorbent and can solve the problem of secondary pollution caused by a common sewage treatment agent in the sewage treatment process. Based on the advantages of lignin, the lignin-based adsorbent has wide application prospect in the heavy metal wastewater treatment process. Lignin is a three-dimensional high-molecular reticular aromatic polymer in plant cells, has aromatic characteristics, and has functional groups such as hydroxyl, carboxyl and the like in molecules, so that the lignin can be directly used as an adsorbent but is limited by an amorphous structure of the lignin. The difference of the adsorption performance of different types of industrial lignin on metal ions is obvious, which is mainly caused by the change of the chemical structure of the lignin due to different separation methods. The adsorption performance of the industrial lignin can be greatly improved after the industrial lignin is chemically modified.
The natural high molecular sodium alginate in nature has the advantages of biocompatibility, biodegradability and the like, and is widely applied to the fields of wastewater treatment, medical treatment and the like. Dissolving in alkaline solution to make the solution viscous. The sodium alginate powder becomes wet in water, and the surface of the sodium alginate powder has viscosity due to the hydration of the particles. The lignin/sodium alginate blending crosslinking microspheres can fix lignin, increase the contact area, effectively adsorb and recover heavy metal ions and rare earth ions in sludge, and are chemical products conforming to green chemistry.
The results show that: the pH and ionic strength have a significant impact on the heavy metal ion adsorption process. The adsorption of lignin in acid solutions is partly desorbed, but not in alkaline solutions. The quicklime in the sludge passivator can improve the pH value of the sludge, improve the adsorption capacity and performance of the lignin adsorbent and convert effective heavy metals in an ionic state into precipitates in invalid states such as hydroxides and the like. Compared with the traditional adsorbent, the microspheres provide larger surface area, have better diffusion, dispersion and mass transfer behaviors, are beneficial to mud-water separation in a precipitation process, can keep high concentration and high activity of the adsorbent by immobilization, and are beneficial to improving the treatment load and removal efficiency of heavy metals. Therefore, the innovation of the sludge passivator by utilizing the substances is imperative.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention aims to provide the sludge passivating agent and the application thereof, which can effectively solve the problems of limited application range, poor passivation effect, complex preparation method, high recycling difficulty, low heavy metal treatment load and low heavy metal removal efficiency of the heavy metal passivating agent.
The technical scheme of the invention is that the sludge passivator comprises the following components in percentage by weight: 85-94% of modified lignin mixture, 1-3% of quicklime and 5-12% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3, mixing in proportion;
the lignin is: adding 0.1-0.5mg/L coagulant aid into the alkaline papermaking black liquor, wherein the coagulant aid is one or a mixture of two of polyacrylamide, fly ash and kaolin which are mixed in equal amount, taking a sulfuric acid solution with the mass concentration of 13-17% as an acid precipitation agent, adjusting the pH value to 2-3, controlling the temperature to be 60-70 ℃, filtering after flocculation and stratification of the black liquor to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the ligninThe sulfonic acid is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 92-97 deg.C for 28-32min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 45-50% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 85-95 deg.C for 1.5-2.5 hr until no precipitate is formed, converting calcium lignosulfonate into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling, and crystallizing to obtain lignosulfonic acid; the weight volume refers to solid in g and liquid in ml;
the glutamic acid-lignin is: dissolving 1.5-2.5g of lignin in 15-25mL of alkali liquor, adding 3-4mL of 35-40% formaldehyde solution after stirring, stirring for 8-12min, dripping 18-22mL of 8-12% sodium glutamate solution within 30min, adjusting the pH value to 9-10, placing in a 50-70 ℃ water bath for reaction for 3.5-4.5h, adding 8-12mL of sulfuric acid into the product, centrifuging at 5500r/min for 8-12min, washing the precipitate for 3-5 times by using 18-22% sulfuric acid, fully washing by using water until the pH value is 7.3-7.7, drying at 45-55 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate:
adding 1-2.2% of water by weight volume of quick lime and 4-15% of sodium alginate by weight volume of water by weight volume of sodium alginate into quick lime, and stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), stirring for 8-12min,
and (3) homogenizing to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 80-92%.
(4) Preparing the solution in the step (3) into embedded pellets:
sucking 20-25ml of the mixed solution prepared in the step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/l2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice by using sterile normal saline to prepare immobilized colloidal beads with the diameter of 1.5-2.5mm, and embedding the modified lignin in calcium alginate gel to obtain the sludge passivator.
The preparation method is simple, novel, unique, energy-saving, environment-friendly, wide in application range, good in passivation effect, convenient to recycle, high in heavy metal treatment load and removal efficiency, stable and reliable, and remarkable in economic and social benefits.
Detailed Description
The following examples are provided to explain the present invention in detail.
In specific practice, the present invention is realized by the following examples.
Example 1
In the specific implementation, the invention is realized by the following steps:
the invention relates to a sludge passivator, which comprises the following components in percentage by weight: 85% of modified lignin mixture, 3% of quicklime and 12% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3, mixing in proportion;
the lignin is: adding 0.1mg/L coagulant aid polyacrylamide into the alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 13% as an acid precipitation agent, adjusting the pH value to 2, controlling the temperature to be 60 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the lignosulfonic acid is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 92 deg.C for 32min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 45% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 85 ℃ for 2.5 hours until no precipitate is generated, so that calcium lignosulfonate is converted into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling and crystallizing to obtain lignosulfonic acid; the weight volume refers to solid in g and liquid in ml;
the glutamic acid-lignin is: dissolving 1.5g of lignin in 15mL of alkali liquor, stirring, adding 3mL of 35% formaldehyde solution, stirring for 8min, dropwise adding 18mL of 8% sodium glutamate solution within 30min, adjusting the pH value to 9, placing in a 50 ℃ water bath for reaction for 4.5h, adding 8mL of sulfuric acid into the product, centrifuging at 4500r/min for 12min, washing the precipitate with 18% sulfuric acid for 3 times, fully washing with water until the pH value is 7.3, drying at 45 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding 1% of water by weight and volume into quick lime, adding 4% of water by weight and volume into sodium alginate, and stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), stirring for 8min, and homogenizing to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 80%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 20ml of the mixed solution prepared in the step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/l2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 1.5mm, and embedding the modified lignin in calcium alginate gel to obtain the sludge passivator.
Example 2
In the specific implementation, the invention is realized by the following steps:
a sludge passivator comprises the following components in percentage by weight: 88% of modified lignin mixture, 2% of quicklime and 10% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3, mixing in proportion;
the lignin is: adding 0.3mg/L coagulant aid fly ash into alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 15% as an acid precipitation agent, adjusting the pH value to 2.5, controlling the temperature to be 65 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the lignosulfonic acid is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 95 deg.C for 30min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 47% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 90 ℃ for 2 hours until no precipitate is generated, converting calcium lignosulfonate into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling and crystallizing to obtain lignosulfonic acid; the weight volume refers to solid in g and liquid in ml;
the glutamic acid-lignin is: dissolving 2.0g of lignin in 20mL of alkali liquor, stirring, adding 3.5mL of formaldehyde solution with the mass concentration of 38%, stirring for 10min, dropwise adding 20mL of sodium glutamate solution with the mass fraction of 10% within 30min, adjusting the pH value to 9.5, placing in a water bath with the temperature of 60 ℃ for reaction for 4.0h, adding 10mL of sulfuric acid into a product, centrifuging for 10min at the speed of 5000r/min, washing the precipitate for 4 times by using the sulfuric acid with the mass concentration of 20%, fully washing the precipitate by using water until the pH value is 7.5, drying at the temperature of 50 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding 1.8% of water by weight and volume of quicklime and 10% of water by weight and volume of sodium alginate into quicklime, and uniformly stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), stirring for 10min, and homogenizing to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 86%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 22ml of the mixed solution prepared in the step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/l2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 2.0mm, and embedding the modified lignin in calcium alginate gel to obtain the sludge passivator.
Example 3
In the specific implementation, the invention is realized by the following steps:
a sludge passivator comprises the following components in percentage by weight: 94% of modified lignin mixture, 1% of quicklime and 5% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3, mixing in proportion;
the lignin is: adding 0.5mg/L coagulant aid, namely a mixture of fly ash and kaolin which are mixed in equal amount, into the alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 17% as an acid precipitation agent, adjusting the pH value to be 3, controlling the temperature to be 70 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the lignosulfonic acid is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 97 deg.C for 28min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 50% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 95 ℃ for 1.5h until no precipitate is generated, so that calcium lignosulfonate is converted into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling and crystallizing to obtain lignosulfonic acid; the weight volume refers to solid in g and liquid in ml;
the glutamic acid-lignin is: dissolving 2.5g of lignin in 25mL of alkali liquor, stirring, adding 4mL of 40% formaldehyde solution, stirring for 12min, dropwise adding 22mL of 12% sodium glutamate solution within 30min, adjusting the pH value to 10, placing in a 70 ℃ water bath for reaction for 3.5h, adding 12mL of sulfuric acid into the product, centrifuging at 5500r/min for 8min, washing the precipitate for 5 times by using 22% sulfuric acid, fully washing by using water until the pH value is 7.7, drying at 55 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding water with the weight volume of 2.2 percent of the quicklime and water with the weight volume of 15 percent of the sodium alginate into the quicklime, and uniformly stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), stirring for 12min, and homogenizing to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 92%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 20-25ml of the mixed solution prepared in the step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/l2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 2.5mm, and embedding the modified lignin in calcium alginate gel to obtain the sludge passivator.
The product in the embodiment is effectively used for treating paper sludge.
The invention obtains consistent effect through repeated experiments, and the related test data is as follows:
experiment one
The heavy metal passivator prepared by the method is uniformly mixed with sludge according to 5 different proportions to form an experimental group, wherein the mass ratio of the passivator to the sludge is respectively 1: 20,1: 25,1: 30,1: 35,1: and 40, taking the sludge without the passivating agent as a blank control, and after the sludge is treated for 6 months, respectively detecting the heavy metal concentrations in the sludge treated by the passivating agent and the sludge of the blank control, wherein the experimental results are shown in table 1.
TABLE 1 influence of different specific gravities of passivator and municipal sludge on heavy metal passivation effect
Experiment two
The heavy metal passivator prepared by the method is uniformly mixed with sludge according to 5 different proportions to form an experimental group, wherein the mass ratio of the passivator to the sludge is respectively 1: 20,1: 25,1: 30,1: 35,1: and 40, planting 6 arabidopsis thaliana plants with the same growth vigor and the same height into pots of different experimental groups and blank control groups respectively by taking sludge without passivator as blank control, and detecting the heavy metal concentration in the arabidopsis thaliana plants of the different experimental groups and the blank control groups respectively after the arabidopsis thaliana plants grow for six months, wherein the experimental results are shown in table 2.
TABLE 2 heavy metal content in Arabidopsis thaliana after sludge treatment by passivating agent
As can be seen from tables 1 and 2, the heavy metal passivator prepared by the invention has good effect of passivating heavy metals in sludge and can well reduce the content of heavy metals in plants growing in the sludge. As can be seen from Table 1, when the heavy metal passivator prepared according to the present invention is uniformly mixed with sludge in different proportions, the content of the heavy metal remaining in the sludge is different. The larger the specific gravity of the passivator is, the better the passivating effect is. From the experimental results, the heavy metals Cu, Cd, Zn and the like are in the ratio of 1: the passivation effect is better when the specific gravity is 30, so that the specific gravity is 1: 30 is preferred. In addition, compared with a blank control group, the specific gravity of the passivating agent to the sludge is 1: at 40 hours, the passivating agent has remarkable passivating effect, and the content of other heavy metals except Pb is lower than GB4284-84 pollutant control standard in agricultural sludge. When the specific gravity of the passivating agent and the sludge is 1: at 20, the Pb content is 4.97mg/kg, which is also obviously lower than the pollutant control standard in agricultural sludge. Therefore, the proper proportion can be selected according to the content of different heavy metals in the sludge.
As can be seen from Table 2, when the passivator is mixed with the sludge uniformly in different proportions, the heavy metal content in Arabidopsis is also different. Several heavy metal elements are accumulated in plants to different degrees, wherein Zn is accumulated seriously. The accumulation amount difference of the heavy metal under different treatments is small, and the variation trend fluctuation is small. The higher the passivant specific gravity, the lower the heavy metal content in arabidopsis thaliana. When the specific gravity of the passivating agent and the sludge is 1: at 20, the content of the above 6 heavy metals is lower than GB 2762-2012 limit for pollutants in food. Compared with a blank control group, the specific gravity of the passivating agent and the sludge is 1: at 40, the passivating agent has a remarkable passivating effect, and the content of other heavy metals except Pb is lower than GB 2762-2012 limit for pollutants in food. The specific gravity of the passivating agent and the sludge is 1: and 35, the content of the 6 heavy metals is lower than that of GB 2762-2012 pollutant Limit in food. The experiment shows that the plants have high accumulation of Zn, and soil and human bodies in China are generally lack of Zn, so that the sludge is used for agriculture to supply elements which are lack of the human bodies in a food chain mode. The results show that the lignin, the lignosulfonic acid, the glutamic acid-lignin, the quicklime and the sodium alginate in the passivator can be matched and act synergistically at a specific ratio to play a role in reducing the effective heavy metals in the sludge.
The invention provides a sludge passivator, which comprises a lignin mixture, quicklime and sodium alginate, wherein the soda lime in the sludge passivator can improve the pH value of sludge, improve the adsorption capacity and performance of a lignin adsorbent, convert effective heavy metals in an ionic state into precipitates in invalid states such as hydroxides and the like, the sodium alginate has a good chelating effect on heavy metals, and the lignin has a certain adsorption effect on the effective heavy metals in the ionic state, the heavy metals in the hydroxide state, the heavy metals in a complex state and the like. And different lignins in the lignin mixture can be used for adsorbing and removing different types of heavy metals, so that the limitation of heavy metal adsorption is overcome, and the mixture is low in cost and easy to obtain. The sodium lignosulfonate is a byproduct of paper pulp production, has strong dispersing capacity, can be adsorbed on the surfaces of various solid particles, and can be uniformly mixed with sodium alginate. The lignosulfonate is easy to dissolve in water and is not easy to remove from waste liquid after heavy metal is adsorbed, and the passivant beads prepared by the method are favorable for solid-liquid separation after treatment. More acid/alkali adsorption sites are loaded on the surface of the glutamic acid-lignin copolymer, so that the glutamic acid-lignin copolymer can be better suitable for different acid-alkali environments. The lignin mixture is compatible and plays a complementary coordination role among the three, and different heavy metals can be passivated. The lignin, the quicklime and the sodium alginate in the passivator can be matched and cooperated under a specific proportion, so that the passivator has the effects of reducing the content of most kinds of effective heavy metals in sludge, overcoming the defect of single kind of heavy metal passivation of the past passivator, improving the pH value of the sludge, improving the sludge function, and avoiding secondary pollution, and is suitable for heavy metal passivation treatment of sludge produced by industrial wastewater.
Claims (5)
1. The sludge passivating agent is characterized by comprising the following components in percentage by weight: 85-94% of modified lignin mixture, 1-3% of quicklime and 5-12% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3;
the lignin is: adding 0.1-0.5mg/L coagulant aid into the alkaline papermaking black liquor, wherein the coagulant aid is one or a mixture of two of polyacrylamide, fly ash and kaolin which are mixed in equal amount, taking a sulfuric acid solution with the mass concentration of 13-17% as an acid precipitation agent, adjusting the pH value to 2-3, controlling the temperature to be 60-70 ℃, filtering after flocculation and stratification of the black liquor to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the sodium lignosulfonate is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 92-97 deg.C for 28-32min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 45-50% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 85-95 deg.C for 1.5-2.5 hr until no precipitate is formed, converting calcium lignosulfonate into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling, and crystallizing to obtain sodium lignosulfonate; the weight volume refers to that the solid is measured by g, and the liquid is measured by mL;
the glutamic acid-lignin is: dissolving 1.5-2.5g of lignin in 15-25mL of alkali liquor, adding 3-4mL of 35-40% formaldehyde solution after stirring, stirring for 8-12min, dripping 18-22mL of 8-12% sodium glutamate solution within 30min, adjusting the pH value to 9-10, placing in a 50-70 ℃ water bath for reaction for 3.5-4.5h, adding 8-12mL of sulfuric acid into the product, centrifuging at 5500r/min for 8-12min, washing the precipitate for 3-5 times by using 18-22% sulfuric acid, fully washing by using water until the pH value is 7.3-7.7, drying at 45-55 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate:
adding 1-2.2% of water by weight volume of quick lime and 4-15% of sodium alginate by weight volume of water by weight volume of sodium alginate into quick lime, and stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), and stirring for 8-12min to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 80-92%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 20-25mL of the mixed solution prepared in step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/L2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice by using sterile normal saline to prepare immobilized colloidal beads with the diameter of 1.5-2.5mm, and embedding the modified lignin mixture in calcium alginate gel to obtain the sludge passivator.
2. The sludge passivating agent according to claim 1, wherein the sludge passivating agent comprises, in weight percent: 85% of modified lignin mixture, 3% of quicklime and 12% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3;
the lignin is: adding 0.1mg/L coagulant aid polyacrylamide into the alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 13% as an acid precipitation agent, adjusting the pH value to 2, controlling the temperature to be 60 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the sodium lignosulfonate is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 92 deg.C for 32min, standing for settling to obtain precipitate, and filtering to obtain precipitateWashing the supernatant with water, adding 45 vol% sulfuric acid, filtering to remove calcium sulfate, and adding Na2CO3Reacting at 85 ℃ for 2.5 hours until no precipitate is generated, so that the calcium lignosulfonate is converted into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling and crystallizing to obtain sodium lignosulfonate; the weight volume refers to that the solid is measured by g, and the liquid is measured by mL;
the glutamic acid-lignin is: dissolving 1.5g of lignin in 15mL of alkali liquor, stirring, adding 3mL of 35% formaldehyde solution, stirring for 8min, dropwise adding 18mL of 8% sodium glutamate solution within 30min, adjusting the pH value to 9, placing in a 50 ℃ water bath for reaction for 4.5h, adding 8mL of sulfuric acid into the product, centrifuging at 4500r/min for 12min, washing the precipitate with 18% sulfuric acid at a mass concentration for 3 times, fully washing with water until the pH value is 7.3, drying at 45 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding 1% of water by weight and volume into quick lime, adding 4% of water by weight and volume into sodium alginate, and stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), and stirring for 8min to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 80%;
(4) preparing the solution in the step (3) into embedded pellets:
20mL of the mixed solution prepared in step (3) was aspirated by a sterile syringe, and CaCl was slowly dropped in an amount of 0.05mol/L in terms of molar concentration2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 1.5mm, and embedding the modified lignin mixture in calcium alginate gel to obtain the sludge passivator.
3. The sludge passivating agent according to claim 1, wherein the sludge passivating agent comprises, in weight percent: 88% of modified lignin mixture, 2% of quicklime and 10% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3;
the lignin is: adding 0.3mg/L coagulant aid fly ash into alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 15% as an acid precipitation agent, adjusting the pH value to 2.5, controlling the temperature to be 65 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the sodium lignosulfonate is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 95 deg.C for 30min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 47% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3Reacting at 90 ℃ for 2 hours until no precipitate is generated, converting calcium lignosulfonate into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling and crystallizing to obtain sodium lignosulfonate; the weight volume refers to that the solid is measured by g, and the liquid is measured by mL;
the glutamic acid-lignin is: dissolving 2.0g of lignin in 20mL of alkali liquor, stirring, adding 3.5mL of formaldehyde solution with the mass concentration of 38%, stirring for 10min, dropwise adding 20mL of sodium glutamate solution with the mass fraction of 10% within 30min, adjusting the pH value to 9.5, placing in a water bath with the temperature of 60 ℃ for reaction for 4.0h, adding 10mL of sulfuric acid into a product, centrifuging for 10min at the speed of 5000r/min, washing the precipitate for 4 times by using the sulfuric acid with the mass concentration of 20%, fully washing the precipitate by using water until the pH value is 7.5, drying at the temperature of 50 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding 1.8% of water by weight and volume of quicklime and 10% of water by weight and volume of sodium alginate into quicklime, and uniformly stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), and stirring for 10min to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 86%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 22mL of the mixture prepared in step (3) with a sterile syringe, and slowly dropping CaCl at a molar concentration of 0.05mol/L2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 2.0mm, and embedding the modified lignin mixture in calcium alginate gel to obtain the sludge passivator.
4. The sludge passivating agent according to claim 1, wherein the sludge passivating agent comprises, in weight percent: 94% of modified lignin mixture, 1% of quicklime and 5% of sodium alginate;
the preparation method comprises the following steps:
(1) preparing a modified lignin mixture: mixing lignin, sodium lignosulfonate and glutamic acid-lignin according to a mass ratio of 4: 2: 3;
the lignin is: adding 0.5mg/L coagulant aid, namely a mixture of fly ash and kaolin which are mixed in equal amount, into the alkaline papermaking black liquor, using a sulfuric acid solution with the mass concentration of 17% as an acid precipitation agent, adjusting the pH value to be 3, controlling the temperature to be 70 ℃, carrying out flocculation layering on the black liquor, filtering to obtain a filter cake, drying and grinding the filter cake to obtain lignin;
the sodium lignosulfonate is: adding lime milk 10% of the waste liquid weight volume into paper mill pulp waste liquid as raw material, heating at 97 deg.C for 28min, standing for settling to obtain precipitate, filtering out the precipitate to obtain supernatant, washing with water, adding sulfuric acid 50% of the supernatant volume, filtering, removing calcium sulfate, adding Na into the filtrate2CO3, reacting at 95 deg.C for 1.5 hr to convert calcium lignosulfonate into sodium sulfonate, standing, filtering, concentrating the filtrate, cooling, and crystallizing to obtain sodium lignosulfonate; the weight volume refers to that the solid is measured by g, and the liquid is measured by mL;
the glutamic acid-lignin is: dissolving 2.5g of lignin in 25mL of alkali liquor, stirring, adding 4mL of 40% formaldehyde solution, stirring for 12min, dropwise adding 22mL of 12% sodium glutamate solution within 30min, adjusting the pH value to 10, placing in a 70 ℃ water bath for reaction for 3.5h, adding 12mL of sulfuric acid into the product, centrifuging at 5500r/min for 8min, washing the precipitate for 5 times by using 22% sulfuric acid, fully washing by using water until the pH value is 7.7, drying at 55 ℃, and grinding to obtain glutamic acid-lignin;
(2) mixing quicklime with sodium alginate
Adding water with the weight volume of 2.2 percent of the quicklime and water with the weight volume of 15 percent of the sodium alginate into the quicklime, and uniformly stirring the two until the solution is viscous and porous to obtain viscous solution;
(3) adding the modified lignin mixture obtained in the step (1) into the viscous solution prepared in the step (2), and stirring for 12min to obtain a mixed solution, wherein the mass fraction of the modified lignin mixture is 92%;
(4) preparing the solution in the step (3) into embedded pellets:
sucking 20-25mL of the mixed solution prepared in step (3) by using a sterile syringe, and slowly dropping CaCl with the molar concentration of 0.05mol/L2And (3) in the solution, standing overnight at 4 ℃, taking out, washing twice with sterile normal saline to prepare immobilized colloidal beads with the diameter of 2.5mm, and embedding the modified lignin mixture in calcium alginate gel to obtain the sludge passivator.
5. Use of the sludge-passivating agent of any of claims 1 to 4 in sludge treatment.
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| CN112321132A (en) * | 2020-12-04 | 2021-02-05 | 河南工程学院 | Municipal sludge treatment and utilization method |
| CN112897686B (en) * | 2021-01-28 | 2022-08-02 | 海南天鸿市政设计股份有限公司 | Immobilized activated sludge and preparation method thereof |
| CN114835916A (en) * | 2022-06-14 | 2022-08-02 | 齐鲁工业大学 | Threonine modified lignin flocculant and preparation method thereof |
| CN115028247B (en) * | 2022-06-14 | 2023-12-22 | 齐鲁工业大学 | Guanidinoacetic acid modified lignin flocculant and preparation method thereof |
| CN115043476A (en) * | 2022-06-24 | 2022-09-13 | 齐鲁工业大学 | Serine modified lignin flocculant and preparation method thereof |
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