CN109647353B - Heavy metal sewage composite treating agent and preparation method and application thereof - Google Patents

Heavy metal sewage composite treating agent and preparation method and application thereof Download PDF

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CN109647353B
CN109647353B CN201910094365.8A CN201910094365A CN109647353B CN 109647353 B CN109647353 B CN 109647353B CN 201910094365 A CN201910094365 A CN 201910094365A CN 109647353 B CN109647353 B CN 109647353B
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heavy metal
quartz sand
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treating agent
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CN109647353A (en
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刘华
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Changzhou new future Chemical Co.,Ltd.
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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • 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
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • 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 discloses a heavy metal sewage composite treating agent and a preparation method and application thereof, wherein the heavy metal sewage composite treating agent is prepared from 20-30 parts of crop wastes, 10-30 parts of humic acid, 20-30 parts of xanthic acid modified quartz sand, 4-6 parts of sodium alginate, 4-6 parts of chitosan, 4-10 parts of calcium thioglycolate and 3-6 parts of calcium chloride. The treatment agent contains various heavy metal reactive groups, can realize high-efficiency adsorption of various heavy metals, has high settling speed, high treatment efficiency, high stability and strong environmental tolerance, solves the problem of difficult treatment of crop wastes, changes waste into valuable, and realizes resource utilization of the crop wastes. Under proper conditions, the removal rate of heavy metals can reach 99%. The heavy metal treating agent has wide raw material source, simple preparation process and good application prospect in the aspect of heavy metal treatment.

Description

Heavy metal sewage composite treating agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of heavy metal sewage treatment, particularly relates to a heavy metal sewage composite treating agent, and simultaneously relates to a preparation method and application of the heavy metal sewage composite treating agent.
Background
Heavy metals are different from other organic pollutants, cannot be degraded in a chemical or biological mode and the like, once generated, can exist in the environment for a long time, are accumulated continuously, can enter human bodies through breathing, skin contact, food chains and other modes, and threatens the health of people. Therefore, the treatment of the heavy metal polluted wastewater is not slow enough.
The heavy metal wastewater treatment method mainly comprises a chemical precipitation method, an ion exchange method, a solvent extraction method, an electrolysis method, an adsorption method, a flocculation method, a biological method and the like. The treatment of heavy metal sewage usually requires adding a treating agent into the sewage to achieve the purpose of changing the existing position and the existing form of heavy metals so as to remove the heavy metals in the water body. At present, the treatment agent for heavy metal polluted wastewater usually comprises a heavy metal chemical precipitator, a chelating adsorbent, chelating resin, a polymeric flocculant and the like. The heavy metal precipitator comprises a neutralization precipitator, a sulfide precipitator and a chelating precipitator, precipitates formed by the neutralization precipitator, the chelating precipitator and the heavy metal are generally small in particle size, but the precipitation performance is poor, a good removal effect can be achieved only by additionally adding a flocculating agent, and the defects that the amount of precipitated mud is large and the heavy metal is not easy to recover are caused; the heavy metal chelating adsorbent or chelating resin, polymeric flocculant, etc. transfer heavy metals from water to the adsorbing material through the chelating reaction between organic groups on the surface and the heavy metals, so as to achieve the purpose of separating the heavy metals. The organic synthetic heavy metal chelating adsorbent generally has the advantages of large adsorption capacity and capability of adsorbing various heavy metal ions at the same time, but has the defects of high price, high regeneration cost and short service life of the adsorbent. The existing heavy metal sewage treatment agent mostly has the defects of single heavy metal adsorption type, low adsorption efficiency, low settlement speed of alum floc formed after adsorption and high cost, and is limited in practical application, so that a new heavy metal sewage treatment agent needs to be researched and developed.
Quartz sand is used as a water treatment filter material, has the characteristics of strong hydrophilicity, no impurities, high density, high mechanical strength and strong dirt intercepting capability, and has long service cycle, but mainly realizes the adsorption of suspended particles in a water body by means of Van der Waals force and electrostatic acting force, reduces the turbidity of the water body, has poor adsorption stability to heavy metals and has low selectivity. Chinese patent CN105253971A provides a method for accelerating precipitation without the aid of coagulant aids. The method utilizes the precipitate or some other inert substances (such as quartz sand and the like) to accelerate the precipitation speed of the sulfide, so as to solve the defect that the sulfide precipitate is difficult to precipitate.
China is a big agricultural country, crop resources are rich, a large amount of crop wastes are correspondingly generated, the incineration treatment of crop straws not only causes resource waste, but also pollutes the environment, and the resource utilization of the crop wastes becomes a hot spot concerned at present. The crop waste is mainly composed of cellulose substances, is complex in structure, good in stability, large in specific surface area and high in development potential of efficient adsorption, and is generally required to be used as an adsorbent after being pulverized in order to realize efficient utilization of the crop waste, but the pulverized crop waste is low in density, so that the problem of high dust content is easily caused during subsequent water treatment construction, the settlement speed is low after the crop waste is adsorbed as the adsorbent, the separation is difficult, and the subsequent treatment process is complicated.
Disclosure of Invention
Based on the problems, the invention aims to provide a heavy metal sewage composite treating agent, which can realize the high-efficiency adsorption of various heavy metals and the quick sedimentation of the treating agent after adsorption, reduce the sewage turbidity, improve the treatment efficiency of heavy metal wastewater, realize the resource utilization of crop wastes, change waste into valuable and further reduce the heavy metal treatment cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a heavy metal sewage composite treatment agent is prepared from the following raw materials in parts by weight: 20-30 parts of crop waste, 10-30 parts of humic acid, 20-30 parts of xanthic acid modified quartz sand, 4-6 parts of sodium alginate, 4-6 parts of chitosan, 4-10 parts of calcium thioglycolate and 3-6 parts of calcium chloride.
Furthermore, the xanthic acid modified quartz sand is prepared by quartz sand, aminosilane coupling agent and xanthate according to the weight ratio of 1: 0.15-0.5: 0.08-1.56 or is prepared by quartz sand, aminosilane coupling agent and CS2Prepared according to the weight ratio of 1: 0.15-0.5: 0.04-0.63, wherein the particle size of the quartz sand is 100-200 meshes.
The preparation method comprises the following steps:
(1) taking 100-mesh 200-mesh quartz sand, washing with water, soaking in an acid solution for 6-24h, filtering, washing with water to neutrality, drying in an oven at 105 ℃ to constant weight, and storing for later use;
(2) weighing the quartz sand in the step (1), dispersing the quartz sand in an ethanol solution to form a turbid solution, then dropwise adding an aminosilane coupling agent into the turbid solution, and stirring and reacting for 3-10 hours at 50-80 ℃, wherein the content of the quartz sand is 10-25%, and the weight ratio of the quartz sand to the aminosilane coupling agent is 1: 0.15-0.5;
(3) adding alkaline solution into the turbid solution of step (2) to adjust pH to 9-13, stirring at 50 deg.C for 30-60min, and adding into the turbid solutionInto CS2Or xanthate, reacting at 50 deg.C for 3-10h, wherein the aminosilane coupling agent reacts with CS2Or the molar ratio of the xanthate is 1: 0.5-6;
(4) and (4) filtering and drying the product obtained in the step (3) to obtain the xanthic acid modified quartz sand, and storing for later use.
Preferably, the acid solution in step (1) is one or more of hydrochloric acid, nitric acid and sulfuric acid.
Preferably, the concentration of the acid solution in the step (1) is 20-35%, and the amount of the acid solution is 2 times of the mass of the quartz sand.
Preferably, the concentration of the ethanol solution in the step (2) is 20-50%.
Preferably, the alkaline solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water solution.
Preferably, the aminosilane coupling agent is one or more of monoamino, diamino and polyamino silane coupling agents.
Preferably, the xanthate is one or more of sodium ethyl xanthate, potassium ethyl xanthate, sodium propyl xanthate, potassium propyl xanthate, sodium butyl xanthate and potassium butyl xanthate.
The invention also provides a preparation method of the heavy metal composite treating agent, which comprises the following steps:
1) cleaning crop waste, sun drying, pulverizing into powder, adding alkaline solution, stirring at 50-100 deg.C for reaction for 0.5-10 hr, and filtering to obtain filtrate and residue;
2) washing the filter residue obtained in the step 1) with water to be neutral, drying at 60-105 ℃, sieving with a 100-mesh sieve to obtain fine powder of crop wastes, and storing for later use;
3) adding humic acid into the filtrate obtained in the step 1) until a neutral humate solution is formed, then adding sodium alginate and chitosan into the solution, and mixing and stirring the solution at 50 ℃ for reaction for 0.5 to 1 hour until a homogeneous emulsion A is formed;
4) adding the fine powder of the crop wastes and the xanthic acid modified quartz sand into the emulsion A, and uniformly stirring to obtain a mixed solution B;
5) and guiding the mixed solution B into a filter sieve, dripping the mixed solution B into a mixed solution of calcium thioglycolate and calcium chloride in a droplet shape to form a gel ball, aging for 12-24h, filtering, and drying in a vacuum drying oven at 60-80 ℃ to obtain the spherical heavy metal composite treating agent.
Further, the alkaline solution in the step 1) is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia water.
Preferably, the concentration of the alkaline solution in step 1) is 0.05-0.1 mol/L.
Preferably, the aperture of the filter sieve in the step 5) is 0.5-5 mm.
Preferably, the molar concentrations of the calcium thioglycolate and the calcium chloride in the mixed solution of the calcium thioglycolate and the calcium chloride in the step 5) are both 0.5 mol/L.
Furthermore, the heavy metal treatment agent can be made into strips, sheets, blocks and irregular shapes according to the needs.
Furthermore, the heavy metal composite treating agent can be used as a heavy metal precipitator and directly added into polluted water or prepared into a filter material layer of a heavy metal sewage treatment device.
The invention has the beneficial effects that:
1. the crop waste contains a large amount of fiber substances, and can effectively chelate heavy metals after special activation treatment, the crop waste in a pulverized state has a higher specific surface area and can be fully contacted with the heavy metals, but the pulverized crop waste has low density, is not easy to settle and is difficult to treat, the crop waste is usually activated by adopting alkali liquor, the treated waste liquid is neutralized by humic acid to realize secondary utilization, and functional groups capable of complexing the heavy metals such as carboxyl, carbonyl, methoxyl and the like are introduced. According to the invention, the alginic acid coating method is adopted to combine the crop wastes with the quartz sand with higher density, so that the sedimentation rate of the treating agent is increased, the treatment rate of heavy metal is increased, the quartz sand is dispersed among the crop wastes, the agglomeration of waste powder is avoided, the probability of contact between the crop wastes and the heavy metal is increased, the adsorption efficiency of the treating agent is further improved, the waste of crop waste resources is also avoided, and the effective utilization of resources is realized.
2. The xanthic acid modified quartz sand takes quartz sand as a carrier, and organic groups with heavy metal reactivity are loaded on the surface of the quartz sand, so that the surface of the quartz sand is functionalized, and the condition that a common quartz sand filter material adsorbs heavy metals only through physical actions such as electrostatic action and the like is improved. Meanwhile, organic groups are loaded on the surface of the quartz sand through the action of chemical bonding, the modified quartz sand has certain stability, and amino and thiocarboxyl loaded on the surface of the quartz sand can form stable chelate with heavy metal, so that the chemical property is stable, and secondary pollution is not easy to cause. The quartz sand has higher density, can improve the sedimentation rate of the adsorbent, is beneficial to separation after adsorption, and solves the problem that the alumen ustum is small and not easy to settle after the precipitator and the micromolecular chelating agent adsorb heavy metals.
3. The invention adopts humic acid to neutralize the alkaline solution for activating the crop wastes, and then the alkaline solution is reused, thereby improving the utilization rate of the raw materials.
4. Calcium thioglycollate can be coordinated and combined with calcium ions through carboxyl at one end and carboxyl on the surface of sodium alginate or can load a sulfhydryl group at the other end on a sodium alginate molecular chain through the action of hydrogen bonds; calcium thioglycolate not only plays a role of a cross-linking agent, but also loads sulfydryl on the surface of the treating agent, and one agent has multiple functions, so that the chelating capacity of the treating agent for heavy metals is improved, and the utilization rate of raw materials is also improved.
5. Cellulose, humic acid, chitosan and sodium alginate belong to biomacromolecules, the cellulose belongs to polysaccharide substances, and the surfaces of the cellulose contain a large number of hydroxyl groups; the basic structure of the humic acid macromolecule is aromatic ring and alicyclic ring, and the ring is connected with functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl and the like; chitosan is a first-order derivative of chitin, has a chemical structure of a high-molecular basic polysaccharide polymer with cations, and has amino groups on the surface capable of chelating with various heavy metals; the surface of the sodium alginate contains a large amount of hydroxyl and carboxyl; biological macromolecules are combined with each other through physical or chemical bonding actions such as electrostatic adsorption, hydrogen bonds, amido bonds and the like to form a structure with a compact structure, so that the stability of the treating agent is improved. Meanwhile, different active groups contained on the surface of the biomacromolecule have different binding capacities with different heavy metals, such as oxygen-containing groups such as hydroxyl and carboxyl, nitrogen-containing groups such as amino and the like, and heavy metals such as lead and copper, and sulfur-containing groups such as cadmium and mercury, so that the biomacromolecule is compounded with xanthic acid modified quartz sand and calcium thioglycolate to realize that the compound treating agent has stronger capturing capacity for various heavy metals such as lead, copper, cadmium and mercury, and one heavy metal is captured by the group with strong binding capacity and can also be captured by other groups, so that one heavy metal is captured by various active groups to form a more stable chelate, and further the adsorption capacity and the adsorption stability of the treating agent for the heavy metals are improved.
6. The heavy metal composite treating agent is prepared by coating xanthic acid modified quartz sand, crop waste powder and biological polymer with sodium alginate by using calcium thioglycolate and calcium chloride as cross-linking agents. The advantages of alginate, xanthic acid modified quartz sand, crop wastes, biological macromolecules and calcium thioglycolate are combined, and the heavy metal sewage treatment agent which has high mechanical strength, large adsorption capacity, high settling speed, simple preparation process and heavy metal treatment process is obtained. The treating agent contains various active groups, can chelate various heavy metals at the same time, and the various active groups can also act on the heavy metals together, so that heavy metal ions are complexed on the active groups of different molecules to form a more stable structure, the chelating stability of the heavy metals is improved, and the adsorption capacity and the adsorption stability of the treating agent on the heavy metals are further improved. The heavy metal composite treating agent is spherical with high density, which is beneficial to subsequent separation, simplifies post-treatment process and improves the treatment efficiency of the adsorbing material. Meanwhile, the problem of treatment of the crop wastes is solved, the resource utilization of the crop wastes is realized, and the wastes are changed into valuables.
7. The heavy metal composite treating agent disclosed by the invention can realize the adsorption of heavy metals in a composite polluted water body, can adsorb other impurities in sewage, and reduces the turbidity of the sewage.
8. The heavy metal treating agent can be adjusted in shape according to needs, can be used as a heavy metal adsorbent to be directly added into polluted water, and can also be used for manufacturing a filter material layer of a heavy metal treating device, so that the application range of the heavy metal treating agent is expanded.
Detailed Description
Example 1
A heavy metal sewage composite treatment agent is prepared from the following raw materials in parts by weight: 20 parts of pumpkin vine, 20 parts of xanthic acid modified quartz sand, 4 parts of sodium alginate, 10-30 parts of humic acid, 4 parts of chitosan, 4 parts of calcium thioglycolate and 3 parts of calcium chloride.
The xanthic acid modified quartz sand is prepared from quartz sand, aminosilane coupling agent and CS2Prepared according to the weight ratio of 1: 0.2: 0.14.
The particle size of the quartz sand is 100-200 meshes.
The preparation method comprises the following steps:
(1) taking 100g of quartz sand which is sieved by a 100-mesh and 200-mesh sieve, washing with water, soaking in 200g of 20% sulfuric acid solution for 24 hours, filtering, washing with water to be neutral, drying in an oven at 105 ℃ to constant weight, and storing for later use;
(2) weighing 50g of quartz sand in the step (1), dispersing the quartz sand in an ethanol solution to form a turbid solution, then dropwise adding 10g of gamma-aminopropyltriethoxysilane into the turbid solution, and stirring and reacting at the constant temperature of 50 ℃ for 10 hours;
(3) adding ammonia water solution into the turbid solution of the step (2) to adjust the pH value to 9, stirring at the constant temperature of 50 ℃ for 30min, and adding 6.88g of CS into the turbid solution2Stirring and reacting for 4 hours at the constant temperature of 50 ℃;
(4) and (4) filtering and drying the product obtained in the step (3) to obtain the xanthic acid modified quartz sand, and storing for later use.
The invention also provides a preparation method of the heavy metal composite treating agent, which comprises the following steps:
1) cleaning pumpkin vine, drying in the sun, crushing into powder, adding 0.05mol/L sodium hydroxide solution, stirring and reacting at 50 ℃ for 10 hours, and filtering to obtain filtrate and filter residue;
2) washing the filter residue obtained in the step 1) with water to be neutral, drying in a drying oven at 60 ℃, then sieving with a 100-mesh sieve to obtain pumpkin vine fine powder, and storing for later use;
3) adding humic acid into the filtrate obtained in the step 1) until a neutral humate solution is formed, then adding sodium alginate and chitosan into the solution, and mixing and stirring the solution at 50 ℃ for reacting for 1 hour until a homogeneous emulsion A is formed;
4) adding the pumpkin vine fine powder and the xanthic acid modified quartz sand into the emulsion A, and uniformly stirring to obtain a mixed solution B;
5) and (3) guiding the mixed solution B into a filter sieve with the aperture of 0.5mm, dripping the mixed solution B into a mixed solution of 0.5mol/L calcium thioglycolate and 0.5mol/L calcium chloride in a droplet shape to form a gel ball, aging for 12h, filtering, and drying in a vacuum drying oven at 60 ℃ to obtain the treating agent.
Example 2
A heavy metal sewage composite treatment agent is prepared from the following raw materials: 25 parts of pumpkin vine waste, 25 parts of xanthic acid modified quartz sand, 5 parts of sodium alginate, 10-30 parts of humic acid, 5 parts of chitosan, 7 parts of calcium thioglycolate and 4.5 parts of calcium chloride.
The xanthic acid modified quartz sand is prepared from quartz sand, an aminosilane coupling agent and sodium ethyl xanthate according to the weight ratio of 1: 0.2: 0.13.
The particle size of the quartz sand is 100-200 meshes.
The preparation method comprises the following steps:
(1) taking 100g of quartz sand which is sieved by a 100-mesh and 200-mesh sieve, washing with water, soaking for 15h in 200g of 30% sulfuric acid solution, filtering, washing with water to be neutral, drying in an oven at 105 ℃ to constant weight, and storing for later use;
(2) weighing 50g of quartz sand in the step (1), dispersing the quartz sand in an ethanol solution to form a turbid solution, then dropwise adding 10g of gamma-aminopropyltriethoxysilane into the turbid solution, and stirring and reacting at the constant temperature of 50 ℃ for 10 hours;
(3) adding an ammonia water solution into the turbid solution obtained in the step (2) to adjust the pH value to 9, stirring at the constant temperature of 50 ℃ for 30min, adding 6.50g of sodium ethyl xanthate into the turbid solution, and stirring at the constant temperature of 50 ℃ to react for 4 h;
(4) and (4) filtering and drying the product obtained in the step (3) to obtain the xanthic acid modified quartz sand, and storing for later use.
The invention also provides a preparation method of the heavy metal composite treating agent, which comprises the following steps:
1) cleaning pumpkin vine, drying in the sun, crushing into powder, adding into 0.05mol/L sodium hydroxide solution, stirring and reacting for 5h at 80 ℃, and filtering to obtain filtrate and filter residue;
2) washing the filter residue obtained in the step 1) with water to be neutral, drying at 60 ℃, sieving with a 100-mesh sieve to obtain pumpkin vine fine powder, and storing for later use;
3) adding humic acid into the filtrate obtained in the step 1) until a neutral humate solution is formed, then adding sodium alginate and chitosan into the solution, and mixing and stirring the solution at the temperature of 60 ℃ for reacting for 40min until a homogeneous emulsion A is formed;
4) adding the pumpkin vine fine powder and the xanthic acid modified quartz sand into the emulsion A, and uniformly stirring to obtain a mixed solution B;
5) guiding the mixed solution B into a filter sieve with the aperture of 0.5mm, dripping the mixed solution B into a mixed solution of 0.5mol/L calcium thioglycolate solution and 0.5mol/L calcium chloride in a droplet shape to form a gel ball, aging for 18h, filtering, and drying in a vacuum drying oven at 60 ℃ to obtain a treating agent;
example 3
A heavy metal sewage composite treatment agent is prepared from the following raw materials: 30 parts of pumpkin vine waste, 30 parts of xanthic acid modified quartz sand, 6 parts of sodium alginate, 10-30 parts of humic acid, 6 parts of chitosan, 10 parts of calcium thioglycolate and 6 parts of calcium chloride.
The xanthic acid modified quartz sand is prepared from quartz sand, aminosilane coupling agent and CS2Prepared according to the weight ratio of 1: 0.4: 0.28.
The particle size of the quartz sand is 100-200 meshes.
The preparation method comprises the following steps:
(1) taking 100g of quartz sand which is sieved by a 100-mesh and 200-mesh sieve, washing with water, soaking for 24 hours in 200g of 30% sulfuric acid solution, filtering, washing with water to be neutral, drying in an oven at 105 ℃ to constant weight, and storing for later use;
(2) weighing 50g of quartz sand in the step (1), dispersing the quartz sand in an ethanol solution to form a turbid solution, then dropwise adding 20g of gamma-aminopropyltriethoxysilane into the turbid solution, and stirring and reacting for 6 hours at 50 ℃;
(3) adding ammonia water solution into the turbid solution of step (2) to adjust pH to 9, stirring at 50 deg.C for 30min, and adding 13.76g CS into the turbid solution2Reacting for 4 hours at a constant temperature of 50 ℃;
(4) and (4) filtering and drying the product obtained in the step (3) to obtain the xanthic acid modified quartz sand, and storing for later use.
The invention also provides a preparation method of the heavy metal composite treating agent, which comprises the following steps:
1) cleaning pumpkin vine, drying in the sun, crushing into powder, adding into 1mol/L ammonia water solution, stirring and reacting for 0.5h at 100 ℃, and filtering to obtain filtrate and filter residue;
2) washing the filter residue obtained in the step 1) with water to be neutral, drying at 105 ℃, sieving with a 100-mesh sieve to obtain pumpkin vine fine powder, and storing for later use;
3) adding humic acid into the filtrate obtained in the step 1) until a neutral humate solution is formed, then adding sodium alginate and chitosan into the solution, and mixing and stirring the solution at 80 ℃ for reaction for 30min until a homogeneous emulsion A is formed;
4) adding the pumpkin vine fine powder and the xanthic acid modified quartz sand into the emulsion A, and uniformly stirring to obtain a mixed solution B;
5) guiding the mixed solution B into a filter sieve with the aperture of 0.5mm, dripping the mixed solution B into a mixed solution of 0.5mol/L calcium thioglycolate and 0.5mol/L calcium chloride in a droplet shape to form a gel ball, aging for 24 hours, filtering, and drying in a vacuum drying oven at 80 ℃ to obtain a treating agent;
comparative example 1
Comparative example 1 is substantially the same as example 3 except that the xanthic acid-modified silica sand is replaced with an equal amount of unmodified silica sand.
Comparative example 2
Comparative example 2 is essentially the same as example 3 except that the calcium thioglycolate is replaced with an equal amount of calcium chloride.
Comparative example 3
Comparative example 3 is essentially the same as example 3 except that the chitosan was replaced with an equal amount of crop waste.
Application example 1
Pb is compounded with lead nitrate, cadmium nitrate and copper nitrate as material2+、Cd2+、Cu2+Solutions with the concentrations of 80mg/L, 60mg/L and 30mg/L are used as simulated heavy metal wastewater samples, then the heavy metal treatment agents prepared in examples 1, 2, 3, 1, 2 and 3 are added, and the removal rate of the treated heavy metal is calculated.
The treatment process comprises the following steps: respectively taking 100mL of a simulated heavy metal water sample, respectively adding a heavy metal treatment agent, vibrating for 2h on a constant temperature oscillator, standing for layering, filtering, detecting the content of heavy metal in filtrate, and calculating the removal rate, wherein the specific result is shown in Table 1, the weight ratio of the heavy metal treatment agent to the detected water sample is 1:3, and the calculation result is the average value of three parallel experiments;
TABLE 1 removal rate of heavy metals from water sample by treating agent
Pb2+ Cd2+ Cu2+
Example 3 99％ 99％ 99％
Comparative example 1 80％ 65％ 85％
Comparative example 2 73％ 85％ 80％
Comparative example 3 65％ 68％ 75％
As shown in Table 1, the heavy metal-containing Pb was treated with the heavy metal-complexing agent prepared in example 3 of the present invention2+、Cd2+、Cu2+The removal rate of the solution of (1) to all three heavy metals is more than 99%, while the comparative examples 1, 2 and 3 are obtained by adjusting the raw materials based on the example 3, i.e. the quartz sand in the comparative example 1 is not xanthated, the calcium thioglycolate is not used as the cross-linking agent in the comparative example 2, the chitosan is not added in the comparative example 3, and the heavy metals Pb in the comparative examples 1, 2 and 3 are heavy metals2+、Cd2 +、Cu2+The removal rate of the composite treatment agent is lower than that of the example 3, which shows that the raw materials of the composite treatment agent have synergistic effect, and the adsorption performance of the material is greatly improved.
Application example 2
A certain turbid dark gray waste water containing heavy metals in a certain city is treated, and the content of lead, cadmium, copper, hexavalent chromium and mercury in a sample is detected by referring to a method specified in the technical Specification for environmental monitoring and the method for monitoring and analyzing water and waste water (fourth edition).
The treatment process comprises the following steps: respectively taking 100mL of the heavy metal wastewater, adjusting the pH value of the wastewater to 7-9, adding the heavy metal treatment agents prepared in the examples 1, 2, 3, 1, 2 and 3, fully stirring, adjusting the pH value to 3-4 with hydrochloric acid, standing for precipitation, and detecting the content of heavy metal, wherein the weight ratio of the heavy metal treatment agent to a detection water sample is 1:3, the detection sample without the heavy metal treatment agent is used as a control group, and the determination result of the concentration of the heavy metal is shown in Table 2 (unit mg/L)
TABLE 2 content of heavy metals in the Water sample (unit mg/L)
Figure BDA0001964144930000121
As shown in Table 2, after the heavy metal treatment agent prepared in examples 1-3 of the present invention is used for treating wastewater, the heavy metal content is less than the lead of < 0.05mg/L, cadmium of < 0.005mg/L, copper of < 1.0mg/L, hexavalent chromium of < 0.05mg/L and mercury of < 0.001mg/L, which are specified in the IV-type of the national standard surface water environment quality standard GB3838-2002 in Table 1 of the national standard of the people's republic of China, and the experimental process can clearly show that the heavy metal wastewater is gradually changed from dark gray turbid to colorless and clear in the treatment process, so that the heavy metal treatment agent of the present invention is not only a good heavy metal treatment agent, but also has strong adsorption performance on suspended matters in wastewater. Comparative examples 1, 2, 3 for Cd2+、Cu2+、Hg2+The adsorption effect of the composite adsorbent is poorer than that of the example 3, the influence on the adsorption performance of the lead is small because most of lead can be removed by adjusting the pH value, the adsorption performance of the composite adsorbent to hexavalent chromium is not different, and the composite adsorbent is mainly used for adsorbing the hexavalent chromium by physical action, so that the good synergistic effect of the raw materials of the composite adsorbent is further illustrated.
The above embodiments are only for illustrating the technical solutions of the present invention and are not limited, and other modifications or equivalent substitutions made by the technical solutions of the present invention by the ordinary skilled person in the art are included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The heavy metal sewage composite treating agent is characterized by being prepared from the following raw materials in parts by weight: 20-30 parts of crop waste, 10-30 parts of humic acid, 20-30 parts of xanthic acid modified quartz sand, 4-6 parts of sodium alginate, 4-6 parts of chitosan, 4-10 parts of calcium thioglycolate and 3-6 parts of calcium chloride; the preparation method specifically comprises the following steps:
1) cleaning crop waste, drying in the sun, pulverizing into powder, adding alkaline solution, stirring at 50-100 deg.C for reaction for 0.5-10 hr, and filtering to obtain filtrate and residue; the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia water;
2) washing the filter residue obtained in the step 1) with water to be neutral, drying at 60-105 ℃, sieving with a 100-mesh sieve to obtain fine powder of crop wastes, and storing for later use;
3) adding humic acid into the filtrate obtained in the step 1) until a neutral humate solution is formed, then adding sodium alginate and chitosan into the solution, and mixing and stirring the solution at 50-80 ℃ for reaction for 0.5-1h until a homogeneous emulsion A is formed;
4) adding the fine powder of the crop wastes and the xanthic acid modified quartz sand into the emulsion A, and uniformly stirring to obtain a mixed solution B;
5) and guiding the mixed solution B into a filter sieve, dripping the mixed solution B into a mixed solution of calcium thioglycolate and calcium chloride in a droplet shape to form a gel ball, aging for 12-24h, filtering, and drying in a vacuum drying oven at 60-80 ℃ to obtain the spherical heavy metal composite treating agent, wherein the aperture of a screen mesh of the filter sieve is 0.5-5 mm.
2. The heavy metal sewage composite treating agent as claimed in claim 1, wherein the xanthic acid modified quartz sand is prepared from quartz sand, aminosilane coupling agent and xanthate in a weight ratio of 1: 0.15-0.5: 0.08-1.56, and the particle size of the quartz sand is 100-200 mesh.
3. The heavy metal sewage composite treating agent as claimed in claim 1, wherein the xanthic acid modified quartz sand is prepared from quartz sand, aminosilane coupling agent, CS2Prepared according to the weight ratio of 1: 0.15-0.5: 0.04-0.63, the stoneThe grain size of the quartz sand is 100-200 meshes.
4. The heavy metal sewage composite treating agent as claimed in claim 2 or 3, wherein the preparation method of the xanthic acid modified quartz sand comprises the following steps:
(1) taking 100-mesh 200-mesh quartz sand, washing with water, soaking in an acid solution for 6-24h, filtering, washing with water to neutrality, drying in an oven at 105 ℃ to constant weight, and storing for later use;
(2) weighing the quartz sand in the step (1), dispersing the quartz sand in an ethanol solution to form a turbid solution, then dropwise adding an aminosilane coupling agent into the turbid solution, and stirring and reacting for 3-10 hours at 50-80 ℃, wherein the content of the quartz sand is 10-25%, and the weight ratio of the quartz sand to the aminosilane coupling agent is 1: 0.15-0.5;
(3) adding alkaline solution into the turbid solution of step (2) to adjust pH =9-13, stirring at 50 deg.C for 30-60min, and adding CS into the turbid solution2Or xanthate, reacting at 50 deg.C for 3-10h, wherein the aminosilane coupling agent reacts with CS2Or the molar ratio of the xanthate is 1: 0.5-6;
(4) and (4) filtering and drying the product obtained in the step (3) to obtain the xanthic acid modified quartz sand, and storing for later use.
5. The heavy metal sewage composite treatment agent as claimed in claim 1, wherein the humic acid is water-soluble humic acid.
6. The heavy metal sewage composite treating agent as claimed in claim 1, wherein the crop wastes comprise one or more of corn stalks, corncobs, wheat stalks, wheat husks, rice stalks, rice hulls, peanut vines, peanut husks, pumpkin vines, rape plants, garlic roots, stems, leaves and skins.
7. The heavy metal sewage composite treating agent of claim 1, wherein in the mixed solution of calcium thioglycolate and calcium chloride in the step 5), the molar concentrations of the calcium thioglycolate and the calcium chloride are both 0.5 mol/L.
8. The composite heavy metal sewage treatment agent as claimed in claim 1, wherein the composite heavy metal sewage treatment agent can be made into a strip shape, a sheet shape, a block shape or an irregular shape as required.
9. The application of the heavy metal sewage composite treating agent according to any one of claims 1 to 8, which is used as a heavy metal adsorbent directly added into a polluted water body or used for preparing a filter material layer of a heavy metal sewage treatment device.
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CN111018244B (en) * 2019-12-12 2021-05-07 清华大学 Heavy metal sewage treatment system
CN111018177B (en) * 2019-12-12 2021-03-16 清华大学 Heavy metal sewage treatment process
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940912A (en) * 2010-09-27 2011-01-12 浙江农林大学 Method for producing adsorbent by coupling chitosan and bamboo charcoal with sodium alginate
CN102161781A (en) * 2011-02-18 2011-08-24 中国广州分析测试中心 Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof
CN105413660A (en) * 2015-12-17 2016-03-23 山东大学 Nanosilicon dioxide structure-based high-heavy metal ion adsorption chelating agent and preparation method thereof
CN106563417A (en) * 2016-12-22 2017-04-19 浙江海洋大学 Heavy-metal biological absorbent and preparation method thereof
CN106824104A (en) * 2017-01-04 2017-06-13 华中科技大学 A kind of compound heavy metal absorbent and preparation method thereof
CN106984282A (en) * 2017-05-04 2017-07-28 凤台县双利生物科技有限公司 A kind of preparation method of the magnetic green substance adsorber of sulfydryl lignocellulosic montmorillonite Composite

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940912A (en) * 2010-09-27 2011-01-12 浙江农林大学 Method for producing adsorbent by coupling chitosan and bamboo charcoal with sodium alginate
CN102161781A (en) * 2011-02-18 2011-08-24 中国广州分析测试中心 Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof
CN105413660A (en) * 2015-12-17 2016-03-23 山东大学 Nanosilicon dioxide structure-based high-heavy metal ion adsorption chelating agent and preparation method thereof
CN106563417A (en) * 2016-12-22 2017-04-19 浙江海洋大学 Heavy-metal biological absorbent and preparation method thereof
CN106824104A (en) * 2017-01-04 2017-06-13 华中科技大学 A kind of compound heavy metal absorbent and preparation method thereof
CN106984282A (en) * 2017-05-04 2017-07-28 凤台县双利生物科技有限公司 A kind of preparation method of the magnetic green substance adsorber of sulfydryl lignocellulosic montmorillonite Composite

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