CN109647353A - A kind of heavy metal containing sewage composite treating agent and its preparation method and application - Google Patents

A kind of heavy metal containing sewage composite treating agent and its preparation method and application Download PDF

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CN109647353A
CN109647353A CN201910094365.8A CN201910094365A CN109647353A CN 109647353 A CN109647353 A CN 109647353A CN 201910094365 A CN201910094365 A CN 201910094365A CN 109647353 A CN109647353 A CN 109647353A
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heavy metal
parts
quartz sand
metal containing
agent
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CN109647353B (en
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刘华
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Changzhou new future Chemical Co.,Ltd.
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刘华
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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 kind of heavy metal containing sewage composite treating agent and its preparation method and application, which be prepared by 20-30 parts of agricultural waste materials, 10-30 parts of humic acid, 20-30 parts of xanthic acid Modified Quartz Sands, 4-6 parts of sodium alginates, 4-6 parts of chitosans, 4-10 parts of calcium mercaptoacetates and 3-6 parts of calcium chloride.The inorganic agent includes various heavy reactive group, the efficient absorption simultaneously to various heavy can be achieved, sinking speed is fast, treatment effeciency is high, stabilization is strong, environment resistance is strong and solves the problems, such as that agricultural waste material processing is difficult, turn waste into wealth, realizes the resource utilization of agricultural waste material.Under optimum conditions, to the removal rate of heavy metal up to 99%.The heavy metal treatment agent raw material sources are extensive, preparation process is simple, have a good application prospect in terms of heavy metal processing.

Description

A kind of heavy metal containing sewage composite treating agent and its preparation method and application
Technical field
The invention belongs to heavy metal-polluted water-treatment technology fields, and in particular to a kind of heavy metal containing sewage composite treating agent, together When be related to a kind of preparation method and application of heavy metal containing sewage composite treating agent.
Background technique
Heavy metal is different from other organic pollutants, cannot be degraded by modes such as chemistry or biologies, once it generates, just Understand long-term existence in the environment, and constantly accumulate, our human bodies can be also entered by modes such as breathing, skin contact, food chains, And threaten to our health, heavy metal containing sewage be even more it is closely bound up with our life, can by it is various directly or Indirect approach enters our human bodies, and if the waste water of heavy metal pollution enters rivers and lakes, heavy metal can be in aquatile body Accumulation enrichment, and human body is entered by food chain, underground water can be also entered by seepage effect, polluted drinking water, using sewage Irrigation makes heavy metal enter agricultural land soil and to be plant absorption enter us in vivo by food chain.Therefore heavy metal polluted waste water Improvement it is very urgent.
Process for treating heavy-metal waste water mainly has chemical precipitation method, ion-exchange, solvent extraction, electrolysis method, absorption Method, flocculence, bioanalysis etc..The processing of heavy metal containing sewage usually requires to be added inorganic agent into sewage to reach change heavy metal There are position and existing forms and then purposes that the heavy metal in water body is removed.The inorganic agent of heavy metal polluted waste water at present It often include heavy metal chemical precipitation agent, chelating adsorbent, chelate resin, high polymer coagulant etc..During heavy metal precipitator includes With precipitating reagent, sulfide precipitation agent and chelating precipitating reagent, the sediment of neutralization precipitation agent and chelating precipitating reagent and heavy metal formation General particle is smaller, but all there is a problem of settling property difference, and needing additionally to add flocculant can be only achieved preferable removal effect Fruit, while causing the drawbacks of heavy mud amount is big, and heavy metal is not easily recycled；Heavy metal chelating adsorbent or chelate resin, macromolecule Flocculant etc. is chelation reaction to occur by the organic group and heavy metal on surface, and heavy metal is transferred to adsorption material from water On material, achieve the purpose that separating beavy metal.Organic synthesis heavy metal chelating adsorbent generally has that adsorption capacity is big, can inhale simultaneously The advantages of attached contents of many kinds of heavy metal ion, but have the shortcomings that adsorbent price is high, regeneration is costly, service life is short.Current There is the alumen ustum sinking speed that heavy metal adsorption type is single, adsorption efficiency is low, is formed after absorption more in heavy metal-polluted water treatment agent Slowly, defect at high cost, is restricted in practical applications, it is therefore desirable to research and develop new heavy metal-polluted water treatment agent.
Quartz sand has stronger hydrophily as a kind of water treatment filter material, and has free from admixture, density big, mechanical strong The feature that degree is high, the strong service life of retaining power is long, but it is mainly realized by Van der Waals force and electrostatic force in water body The absorption of suspended particulate reduces the turbidity of water body, and poor to the absorption stability of heavy metal, and selectivity is low.Chinese invention patent CN105253971A provides a kind of method for not accelerating precipitating by flocculation aid.This method utilizes sediment itself or one A little others inert substances (such as quartz sand) accelerate the settling velocity of sulfide, are difficult to be deposited to solve sulfide precipitation The shortcomings that falling.
China is large agricultural country, and crop genetic resource is abundant, corresponding to produce a large amount of agricultural waste material, crops The burning disposal of stalk not only causes the waste of resource, while also polluted environment, the resource utilization of agricultural waste material Become the hot spot paid close attention at present.Agricultural waste material is mainly made of cellulose substances, and structure is complicated, and stability is good, than Surface area is larger, the exploitation potential with efficient absorption, in order to realize the efficient utilization of agricultural waste material, it usually needs by it It is used as adsorbent after dusting processing, but the agricultural waste material density after dusting is small, subsequent water process easily causes dust when constructing Big problem is spent, and slow as sinking speed after adsorbent absorption, separation is difficult, and subsequent treatment process is cumbersome.
Summary of the invention
Based on the above issues, the present invention is intended to provide a kind of heavy metal containing sewage composite treating agent, is realized simultaneously to a variety of heavy The efficient absorption of metal and the rapid subsidence for adsorbing post-treatment agent reduce turbidity of sewage, improve the processing to heavy metal wastewater thereby Efficiency, while realizing to the resource utilization of agricultural waste material, turn waste into wealth, and then reduce heavy metal processing cost.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of heavy metal containing sewage composite treating agent, is prepared from the following raw materials in parts by weight: 20-30 parts of crop wastes Object, 10-30 part humic acid, 20-30 parts of xanthic acid Modified Quartz Sands, 4-6 parts of sodium alginates, 4-6 parts of chitosans, 4-10 parts of sulfydryls Calcium acetate and 3-6 parts of calcium chloride.
Further, the xanthic acid Modified Quartz Sand is by quartz sand, amino silicane coupling agent, xanthates by weight Amount is than being 1: 0.15-0.5: 0.08-1.56 to be prepared or by quartz sand, amino silicane coupling agent, CS2By weight it is 1: 0.15-0.5: 0.04-0.63 is prepared, and wherein the partial size of quartz sand is 100-200 mesh.
Preparation method, comprising the following steps:
(1) taking partial size is the quartz sand of 100-200 mesh, washing, and acid solution impregnates 6-24h, and filtering is then washed to Property, to constant weight, storage is stand-by for 105 DEG C of dryings in baking oven；
(2) it weighs the quartz sand in step (1) and is dispersed in ethanol solution and form dirty solution, then ammonia is added dropwise into dirty solution Base silane coupling agent is stirred to react 3-10h in 50-80 DEG C, wherein the content of quartz sand is 10-25%, quartz sand and amino silicone The weight ratio of alkane coupling agent is 1: 0.15-0.5；
(3) alkaline solution tune pH=9-13 is added into the dirty solution of step (2), 50 DEG C of constant temperature stir 30-60min, then CS is added into dirty solution2Or xanthates, in 50 DEG C of isothermal reaction 3-10h, wherein amino silicane coupling agent and CS2Or xanthan The molar ratio of hydrochlorate is 1: 0.5-6；
(4) step (3) products therefrom is filtered, dry to get xanthic acid Modified Quartz Sand, storage is stand-by.
Preferably, acid solution described in step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid.
Preferably, the concentration of acid solution described in step (1) is 20%-35%, and the dosage of acid solution is quartz sand quality 2 times.
Preferably, the concentration of ethanol solution described in step (2) is 20-50%.
Preferably, the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, ammonia spirit.
Preferably, the amino silicane coupling agent be one of mono amino, double amino, polyamino silane coupling agent or It is several.
Preferably, the xanthates is sodium ethylxanthate, ehtyl potassium xanthate, xanthogen sodium, propyl xanthan One or more of sour potassium, sodium n-butyl-xanthate, potassium butyl xanthate.
The present invention also provides the preparation methods of heavy metal composite treating agent, comprising the following steps:
1) agricultural waste material is cleaned, dries, is smashed into fine particle, alkaline solution is added, is stirred to react at 50-100 DEG C 0.5-10h, filtering obtain filtrate and filter residue；
2) it takes the filter residue of step 1) to be washed to neutrality, after 60-105 DEG C of drying, sieves with 100 mesh sieve acquisition agricultural waste material Fine powder, storage are stand-by；
3) humic acid is added into the filtrate of step 1) to neutral humate solution is formed, seaweed is then added thereto Sour sodium and chitosan, in 50 DEG C of mixing reaction 0.5-1h to formation homogeneous latex A；
4) agricultural waste material fine powder and xanthic acid Modified Quartz Sand are added into latex A, stirs evenly acquisition mixed liquor B；
5) mixed liquid B water conservancy diversion is entered in filter screen, mixed liquid B instills the mixing of calcium mercaptoacetate and calcium chloride in droplet-like In solution, gel ball is formed, is aged 12-24h, filtering, it is compound to obtain spherical heavy metal for 60-80 DEG C of drying in a vacuum drying oven Inorganic agent.
Further, alkaline solution described in step 1) is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, carbon One or more of sour ammonium, ammonium hydrogen carbonate, ammonium hydroxide.
Preferably, the concentration of alkaline solution described in step 1) is 0.05-0.1mol/L.
Preferably, the aperture of filter screen described in step 5) is 0.5-5mm.
Preferably, calcium mercaptoacetate and calcium chloride in the mixed solution of calcium mercaptoacetate described in step 5) and calcium chloride Molar concentration be 0.5mol/L.
Further, the shape of the heavy metal treatment agent is as needed, can also be made strip, sheet, bulk and Irregular shape.
Further, the application of the heavy metal composite treating agent can be used as heavy metal precipitator and be directly added into pollution In water body or it is made the filter material layer of heavy metal sewage treatment device.
The beneficial effects of the present invention are:
1. contain a large amount of fiber substance in agricultural waste material, it, can an effective chelating huge sum of money after special activation processing Belong to, the agricultural waste material of pulverized state has a higher specific surface area, and then can more fully with heavy metal contact, but dusting Agricultural waste material density afterwards is small, not easily settled, and processing is more difficult, and agricultural waste material activation generallys use base extraction, Treated waste liquid by in humic acid and realizing secondary use, while introduce can complexing heavy metal carboxyl, carbonyl, first The functional groups such as oxygroup.Agricultural waste material and the biggish quartz sand of density are combined using the method for alginic acid cladding in the present invention It not only increases the rate of settling of inorganic agent and improves the processing speed of heavy metal, and quartz sand is dispersed in crop waste The reunion between waste powder is avoided between object and is increased the probability of agricultural waste material and heavy metal contact and then is mentioned The high adsorption efficiency of inorganic agent, while the waste of agricultural waste material resource is also avoided, realize the effective use of resource.
2. xanthic acid Modified Quartz Sand is using quartz sand as carrier, in its reactive organic group of area load heavy metal Group assigns quartz sand surface functionalization, improves common quartz sand filter media and only passes through the physical actions such as an electrostatic interaction absorption huge sum of money Belong to.For organic group by the used load of chemical bonding in quartz sand surface, Modified Quartz Sand itself has certain stablize simultaneously Property, and amino, the thiocarboxyl group of quartz sand surface load can form stable chelate with heavy metal, chemical property is stablized, no Easily cause secondary pollution.Quartz sand has biggish density, and the rate of settling of adsorbent can be improved, point after being conducive to absorption From alumen ustum is not small easily settled after solving the problems, such as precipitating reagent and small molecule chelators absorption heavy metal.
3, the present invention uses the alkaline solution of humic acid neutralisation treatment agricultural waste material activation processing, then secondary benefit With improving the utilization rate of raw material.
4. calcium mercaptoacetate can be combined with calcium ion coordination jointly by the carboxyl of one end and the carboxyl on sodium alginate surface Or by hydrogen bond action, the mercapto groups of the other end are supported on sodium alginate strand；Calcium mercaptoacetate had both played friendship Join the effect of agent, and the sulfydryl on its surface is supported on inorganic agent surface, one multipotency improves inorganic agent to the huge legendary turtle of heavy metal Conjunction ability, while also improving the utilization rate of raw material.
5. cellulose, humic acid, chitosan and sodium alginate belong to large biological molecule, cellulose belongs to polysaccharide object A large amount of hydroxyl is contained on matter, surface；The basic structure of humic acid macromolecular is aromatic ring and alicyclic ring, be connected on ring carboxyl, hydroxyl, The functional groups such as carbonyl, quinonyl, methoxyl group；Chitosan is the first order derivatives of chitin, and chemical structure is the height with cation Molecule alkaline polysaccharide polymer, surface have the amino that chelating effect can occur with various heavy；Contain on sodium alginate surface A large amount of hydroxyl and carboxyl；Pass through the physically or chemically bonding action phase such as Electrostatic Absorption, hydrogen bond, amido bond between large biological molecule The structure for forming compact structure is mutually combined, the stability of inorganic agent itself is improved.Large biological molecule surface is contained not simultaneously It is different with the binding ability of active group and different heavy metals, such as the nitrogen-containing groups such as hydroxyl, carboxyl oxygen-containing group and amido with Heavy metal lead, the binding ability of copper are stronger, and sulfur-containing group and cadmium, mercury binding ability are stronger, therefore by large biological molecule and xanthan The compound composite treating agent that may be implemented of sour Modified Quartz Sand, calcium mercaptoacetate all has the various heavies such as lead, copper, cadmium, mercury Stronger capturing ability, while a heavy metal species are captured with the strong group of its binding ability while, can also be caught by other groups It catches, and realizes that a heavy metal species are captured by various active group, form more stable chelate, and then improve inorganic agent counterweight The adsorption capacity and absorption stability of metal.
6. heavy metal composite treating agent of the invention is by sodium alginate using calcium mercaptoacetate and calcium chloride as crosslinking agent packet It covers xanthic acid Modified Quartz Sand and agricultural waste material powder and spherical heavy metal combined processing is prepared in boiomacromolecule Agent.The advantage of alginate, xanthic acid Modified Quartz Sand, agricultural waste material, boiomacromolecule, calcium mercaptoacetate is combined, High mechanical strength is obtained, adsorption capacity is big, sinking speed is fast, the heavy metal of preparation process and processing heavy metal simple process Sewage-treating agent.Group containing various active in inorganic agent, can chelating various heavy simultaneously, and various active group can also be common Heavy metal is acted on, heavy metal ion is complexed on the active group of different molecular, and more stable structure is formed, and improves weight The chelating stability of metal, and then inorganic agent is improved to the adsorbance and absorption stability of heavy metal.The compound place of heavy metal It is biggish spherical in density to manage agent, is conducive to later separation, simplifies aftertreatment technology, and improves the processing effect of adsorbent material Rate.It also solves the problems, such as the processing of agricultural waste material simultaneously, realizes the resource utilization of agricultural waste material, turn waste into wealth.
7. the heavy metal composite treating agent in the present invention is not only able to achieve the absorption of combined pollution Heavy Metals in Waters, and can Other impurities in absorption effluent reduce the turbidity of sewage.
8, heavy metal treatment agent of the invention can according to need adjustment shape, and it is straight to serve not only as heavy metal absorbent It connects and is added in polluted-water, the filter material layer of heavy metal processing unit can also be made, and expand its application range.
Specific embodiment
Embodiment 1
A kind of heavy metal containing sewage composite treating agent, is made of raw material from the following weight: 20 parts of cushaw stems, 20 parts of xanthic acid Modified Quartz Sand, 4 parts of sodium alginates, 10-30 parts of humic acid, 4 parts of chitosans, 4 parts of calcium mercaptoacetates, 3 parts of calcium chloride.
The xanthic acid Modified Quartz Sand is by quartz sand, amino silicane coupling agent, CS2By weight it is 1: 0.2: 0.14 is prepared.
The partial size of the quartz sand is 100-200 mesh.
Preparation method, comprising the following steps:
(1) it taking 100g to cross the quartz sand of 100-200 mesh, washes, 20% sulfuric acid solution of 200g impregnates filtering for 24 hours, and After be washed to neutrality, to constant weight, storage is stand-by for 105 DEG C of dryings in baking oven；
(2) the quartz sand 50g in step (1) is weighed, is dispersed in ethanol solution and forms dirty solution, then dripped into dirty solution Add 10g gamma-aminopropyl-triethoxy-silane, is stirred to react 10h in 50 DEG C of constant temperature；
(3) it is added ammonia spirit tune pH=9 into the dirty solution of step (2), 50 DEG C of constant temperature stir 30min, then to muddiness 6.88g CS is added in liquid2, 4h is stirred to react in 50 DEG C of constant temperature；
(4) by the filtering of step (3) products therefrom, drying, xanthic acid Modified Quartz Sand is obtained, storage is stand-by.
The present invention also provides the preparation methods of heavy metal composite treating agent, comprising the following steps:
1) cushaw stem is cleaned, dries, is smashed into fine particle, the sodium hydroxide solution of 0.05mol/L is added, stirred at 50 DEG C 10h is reacted, filtering obtains filtrate and filter residue；
2) it takes the filter residue of step 1) to be washed to neutrality, is dried in 60 DEG C of drying boxes, then sieve with 100 mesh sieve acquisition cushaw stem Fine powder, storage are stand-by；
3) humic acid is added into the filtrate of step 1) to neutral humate solution is formed, seaweed is then added thereto Sour sodium and chitosan, in 50 DEG C of mixing reaction 1h to formation homogeneous latex A；
4) cushaw stem fine powder and xanthic acid Modified Quartz Sand are added into latex A, stirs evenly acquisition mixed liquid B；
5) mixed liquid B water conservancy diversion is entered in the filter screen that aperture is 0.5mm, mixed liquid B instills 0.5mol/L mercapto in droplet-like In the mixed solution of guanidine-acetic acid calcium and 0.5mol/L calcium chloride, gel ball is formed, is aged 12h, filtering, in a vacuum drying oven 60 DEG C drying, obtains inorganic agent.
Embodiment 2
A kind of heavy metal containing sewage composite treating agent, is prepared from the following materials: 25 parts of cushaw stem wastes, 25 parts of xanthan Sour Modified Quartz Sand, 5 parts of sodium alginates, 10-30 parts of humic acid, 5 parts of chitosans, 7 parts of calcium mercaptoacetates, 4.5 parts of calcium chloride.
The xanthic acid Modified Quartz Sand be by quartz sand, amino silicane coupling agent, sodium ethylxanthate by weight It is prepared for 1: 0.2: 0.13.
The partial size of the quartz sand is 100-200 mesh.
Preparation method, comprising the following steps:
(1) it taking 100g to cross the quartz sand of 100-200 mesh, washes, 30% sulfuric acid solution of 200g impregnates 15h, it filters, and After be washed to neutrality, to constant weight, storage is stand-by for 105 DEG C of dryings in baking oven；
(2) the quartz sand 50g in step (1) is weighed, is dispersed in ethanol solution and forms dirty solution, then dripped into dirty solution Add 10g gamma-aminopropyl-triethoxy-silane, is stirred to react 10h in 50 DEG C of constant temperature；
(3) it is added ammonia spirit tune pH=9 into the dirty solution of step (2), 50 DEG C of constant temperature stir 30min, then to muddiness 6.50g sodium ethylxanthate is added in liquid, is stirred to react 4h in 50 DEG C of constant temperature；
(4) step (3) products therefrom is filtered, it is dry, xanthic acid Modified Quartz Sand is obtained, storage is stand-by.
The present invention also provides the preparation methods of heavy metal composite treating agent, comprising the following steps:
1) cushaw stem is cleaned, dries, is ground into powder, is added in the sodium hydroxide solution of 0.05mol/L, at 80 DEG C It is stirred to react 5h, is filtered, filtrate and filter residue are obtained；
2) filter residue of step 1) is taken to be washed to neutrality, 60 DEG C dry, sieve with 100 mesh sieve obtain cushaw stem fine powder, storage to With；
3) humic acid is added into the filtrate of step 1) to neutral humate solution is formed, seaweed is then added thereto Sour sodium and chitosan, in 60 DEG C of mixing reaction 40min to formation homogeneous latex A；
4) cushaw stem fine powder and xanthic acid Modified Quartz Sand are added into latex A, stirs evenly acquisition mixed liquid B；
5) mixed liquid B water conservancy diversion is entered in the filter screen that aperture is 0.5mm, mixed liquid B instills 0.5mol/L mercapto in droplet-like In the mixed solution of guanidine-acetic acid calcium solution and 0.5mol/L calcium chloride, gel ball is formed, is aged 18h, filtering, in vacuum oven In 60 DEG C of dryings, obtain inorganic agent；
Embodiment 3
A kind of heavy metal containing sewage composite treating agent, is prepared from the following materials: 30 parts of cushaw stem wastes, 30 parts of xanthan Sour Modified Quartz Sand, 6 parts of sodium alginates, 10-30 parts of humic acid, 6 parts of chitosans, 10 parts of calcium mercaptoacetates, 6 parts of calcium chloride.
The xanthic acid Modified Quartz Sand is by quartz sand, amino silicane coupling agent, CS2By weight it is 1: 0.4: 0.28 is prepared.
The partial size of the quartz sand is 100-200 mesh.
Preparation method, comprising the following steps:
(1) it taking 100g to cross the quartz sand of 100-200 mesh, washes, 30% sulfuric acid solution of 200g impregnates filtering for 24 hours, and After be washed to neutrality, to constant weight, storage is stand-by for 105 DEG C of dryings in baking oven；
(2) the quartz sand 50g in step (1) is weighed, is dispersed in ethanol solution and forms dirty solution, then dripped into dirty solution Add 20g gamma-aminopropyl-triethoxy-silane, is stirred to react 6h in 50 DEG C；
(3) it is added ammonia spirit tune pH=9 into the dirty solution of step (2), 50 DEG C of constant temperature stir 30min, then to muddiness 13.76g CS is added in liquid2, in 50 DEG C of isothermal reaction 4h；
(4) by the filtering of step (3) products therefrom, drying, xanthic acid Modified Quartz Sand is obtained, storage is stand-by.
The present invention also provides the preparation methods of heavy metal composite treating agent, comprising the following steps:
1) cushaw stem is cleaned, dries, is ground into powder, is added in the ammonia spirit of 1mol/L, stirred at 100 DEG C anti- 0.5h is answered, is filtered, filtrate and filter residue are obtained；
2) filter residue of step 1) is taken to be washed to neutrality, 105 DEG C drying sieve with 100 mesh sieve obtain cushaw stem fine powder, storage to With；
3) humic acid is added into the filtrate of step 1) to neutral humate solution is formed, seaweed is then added thereto Sour sodium and chitosan, in 80 DEG C of mixing reaction 30min to formation homogeneous latex A；
4) cushaw stem fine powder and xanthic acid Modified Quartz Sand are added into latex A, stirs evenly acquisition mixed liquid B；
5) mixed liquid B water conservancy diversion is entered in the filter screen that aperture is 0.5mm, mixed liquid B instills 0.5mol/L mercapto in droplet-like In the mixed solution of guanidine-acetic acid calcium and 0.5mol/L calcium chloride, form gel ball, ageing for 24 hours, filtering, in a vacuum drying oven 80 DEG C drying, obtains inorganic agent；
Comparative example 1
Comparative example 1 is substantially the same manner as Example 3, the difference is that the quartz sand equivalent that xanthic acid is modified is unmodified Quartz sand replaces.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 3, the difference is that replacing calcium mercaptoacetate with the calcium chloride of equivalent.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that the agricultural waste material of chitosan equivalent replaces.
Application examples 1
It is that raw material prepares Pb with plumbi nitras, cadmium nitrate and copper nitrate2+、Cd2+、Cu2+Concentration be respectively 80mg/L, 60mg/L, Embodiment 1, embodiment 2, embodiment 3, comparative example 1, right is then added as simulation heavy metal wastewater thereby water sample in the solution of 30mg/L The heavy metal treatment agent that ratio 2, comparative example 3 are prepared, the removal rate of heavy metal after calculation processing.
Treatment process: modulus intends heavy metal water sample 100mL respectively, then is separately added into heavy metal treatment agent, in constant temperature oscillation 2h is shaken on device, is filtered after stratification, the content of heavy metal in filtrate is detected, and calculates removal rate, concrete outcome such as 1 institute of table Show, the weight ratio of the heavy metal treatment agent and detection water sample is 1:3, and calculated result is the average value of parallel laboratory test three times；
Removal rate of 1. inorganic agent of table to heavy metal in water sample
Pb2+ Cd2+ Cu2+
Embodiment 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 composite treating agent processing prepared using the embodiment of the present invention 3 is containing heavy metal Pb2+、 Cd2+、Cu2+Solution, 99% or more has all been reached to the removal rate of three heavy metal species, and comparative example 1,2,3 is in embodiment 3 On the basis of carry out raw material and adjust to obtain, i.e., it is modified that the quartz sand in comparative example 1 does not carry out xanthogenation, in comparative example 2 Calcium mercaptoacetate is not used as crosslinking agent, is not added with chitosan in comparative example 3, and 1,2,3 pair of heavy metal Pb of comparative example2+、Cd2 +、Cu2+Removal rate to be lower than embodiment 3, illustrate that there is synergistic effect between each raw material of composite treating agent, and greatly increase The absorption property of material.
Application examples 2
The city Qu Mou is handled containing heavy metal in muddy shape Dark grey waste water, with reference to " environmental monitoring technology specification ", The content of the lead of method test sample as defined in " water and effluent monitoring analysis method " (fourth edition), cadmium, copper, Cr VI, mercury.
Treatment process: taking each 100mL of above-mentioned heavy metal wastewater thereby respectively, and the pH for adjusting waste water is 7~9, then by embodiment 1, it is sufficiently stirred after the heavy metal treatment agent addition that embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3 are prepared It mixes, is then 3~4 with salt acid for adjusting pH, content of beary metal, the heavy metal treatment agent and detection water sample are detected after staticly settling Weight ratio be 1:3, as a control group with the test sample of no added heavy metal treatment agent, the measurement result of heavy metal concentration is such as Shown in table 2 (unit mg/L)
The content (unit mg/L) of heavy metal in 2. water sample of table
As shown in table 2, after being handled using heavy metal treatment agent prepared by 1-3 of the embodiment of the present invention waste water, a huge sum of money Belong to the rule that content is respectively less than IV class in National Standard of the People's Republic of China water environment quality standard GB3838-2002 table 1 Fixed lead < 0.05mg/L, cadmium < 0.005mg/L, copper < 1.0mg/L, the rule of Cr VI < 0.05mg/L, mercury < 0.001mg/L It is fixed, that is, meet the regulation of IV class in National Standard of the People's Republic of China water environment quality standard GB3838-2002 table 1, And experimentation can clearly find out in treatment process that heavy metal wastewater thereby gradually becomes achromaticity and clarification by Dark grey muddiness, thus It can be seen that heavy metal treatment agent of the invention is not only a kind of good heavy metal treatment agent, also have to the suspended matter in sewage Very strong absorption property.1,2,3 couple of Cd of comparative example2+、Cu2+、Hg2+Adsorption effect it is poorer than embodiment 3, and to the adsorptivity of lead Can influence less, be because by adjust pH can remove most lead, to the absorption property indifference of Cr VI, be due to Cr VI is mainly adsorbed with physical action, further illustrating between each raw material of compound adsorbent, there is good collaboration to make With.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, those of ordinary skill in the art are to this hair Other modifications or equivalent replacement that bright technical solution is made, as long as it does not depart from the spirit and scope of the technical scheme of the present invention, It is intended to be within the scope of the claims of the invention.

Claims (10)

1. a kind of heavy metal containing sewage composite treating agent, which is characterized in that be prepared by following raw material in parts by weight: 20-30 Part agricultural waste material, 10-30 parts of humic acid, 20-30 parts of xanthic acid Modified Quartz Sands, 4-6 parts of sodium alginates, 4-6 parts of shells are poly- Sugar, 4-10 parts of calcium mercaptoacetates and 3-6 parts of calcium chloride.
2. heavy metal containing sewage composite treating agent as described in claim 1, which is characterized in that the xanthic acid Modified Quartz Sand To be by quartz sand, amino silicane coupling agent, xanthates be by weight 1: 0.15-0.5: 0.08-1.56 is prepared, described Quartz sand partial size be 100-200 mesh.
3. heavy metal containing sewage composite treating agent as described in claim 1, which is characterized in that the xanthic acid Modified Quartz Sand It is by quartz sand, amino silicane coupling agent, CS2It is prepared by weight for 1: 0.15-0.5: 0.04-0.63, the stone The partial size of sand is 100-200 mesh.
4. heavy metal containing sewage composite treating agent as claimed in claim 2 or claim 3, which is characterized in that the modified stone of the xanthic acid The preparation method of sand, comprising the following steps:
(1) taking partial size is the quartz sand of 100-200 mesh, is washed, and acid solution impregnates 6-24 h, and filtering is then washed to neutrality, in To constant weight, storage is stand-by for 105 DEG C of dryings in baking oven；
(2) it weighs the quartz sand in step (1) and is dispersed in ethanol solution and form dirty solution, then amino silicone is added dropwise into dirty solution Alkane coupling agent is stirred to react 3-10 h in 50-80 DEG C, wherein the content of quartz sand is 10-25%, and quartz sand and amino silane are even The weight ratio for joining agent is 1: 0.15-0.5；
(3) it is added alkaline solution tune pH=9-13 into the dirty solution of step (2), 50 DEG C of constant temperature stir 30-60 min, then to mixed CS is added in turbid2Or xanthates, in 50 DEG C of isothermal reaction 3-10 h, wherein amino silicane coupling agent and CS2Or xanthic acid The molar ratio of salt is 1: 0.5-6；
(4) step (3) products therefrom is filtered, it is dry, xanthic acid Modified Quartz Sand is obtained, storage is stand-by.
5. heavy metal containing sewage composite treating agent as described in claim 1, which is characterized in that the humic acid is water-soluble rotten Grow acid.
6. heavy metal containing sewage composite treating agent as described in claim 1, which is characterized in that the agricultural waste material includes jade Rice stalk, corncob, wheat stalk, wheat shell, rice straw, rice husk, peanut vine, peanut shell, cushaw stem, rapeseed plants, One or more of garlic root, stem, leaf, skin.
7. a kind of preparation method of any one of -6 heavy metal containing sewage composite treating agents according to claim 1, which is characterized in that Specific step is as follows:
1) agricultural waste material is cleaned, dries, is ground into powder, alkaline solution is added, is stirred to react at 50-100 DEG C 0.5-10 h, filtering obtain filtrate and filter residue；The alkaline solution is sodium hydroxide, potassium hydroxide, sodium carbonate, bicarbonate One or more of sodium, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydroxide；
2) it takes the filter residue of step 1) to be washed to neutrality, after 60-105 DEG C of drying, it is thin to sieve with 100 mesh sieve acquisition agricultural waste material Powder, storage are stand-by；
3) humic acid is added into the filtrate of step 1) to neutral humate solution is formed, sodium alginate is then added thereto And chitosan, in 50-80 DEG C of mixing reaction 0.5-1 h to formation homogeneous latex A；
4) agricultural waste material fine powder and xanthic acid Modified Quartz Sand are added into latex A, stirs evenly acquisition mixed liquid B；
5) mixed liquid B water conservancy diversion is entered in filter screen, mixed liquid B instills calcium mercaptoacetate and calcium chloride mixed solution in droplet-like In, gel ball is formed, 12-24 h, filtering are aged, 60-80 DEG C of drying in a vacuum drying oven obtains spherical heavy metal combined processing Agent, the mesh size of the filter screen are 0.5-5 mm.
8. the preparation method of heavy metal containing sewage composite treating agent according to claim 7, which is characterized in that described in step 5) In calcium mercaptoacetate and calcium chloride mixed solution, the molar concentration of calcium mercaptoacetate and calcium chloride is 0.5 mol/L.
9. the preparation method of heavy metal containing sewage composite treating agent according to claim 7, which is characterized in that heavy metal is compound The shape of inorganic agent is as needed, and strip, sheet, bulk and irregular shape can also be made.
10. a kind of application of any one of -6 heavy metal containing sewage composite treating agents according to claim 1, which is characterized in that make Heavy metal sewage treatment device filter material layer is directly added into polluted-water or prepared for heavy metal absorbent.
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CN113263805B (en) * 2021-01-07 2023-08-11 湖南盛业土工材料制造有限公司 Heavy metal-blocking fiber net/high polymer composite waterproof coiled material and preparation method thereof

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