CN106395969B - A method of Cd2+ or Cu2+ waste water is handled by adsorbent of animal blood meal - Google Patents

A method of Cd2+ or Cu2+ waste water is handled by adsorbent of animal blood meal Download PDF

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Publication number
CN106395969B
CN106395969B CN201611048069.7A CN201611048069A CN106395969B CN 106395969 B CN106395969 B CN 106395969B CN 201611048069 A CN201611048069 A CN 201611048069A CN 106395969 B CN106395969 B CN 106395969B
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animal blood
waste water
blood meal
ion
adsorbent
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CN106395969A (en
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李亚东
李思彤
王行国
陈红兵
李顺意
倪红
杨兰芳
李海波
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Hubei University
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Hubei University
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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
    • 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
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of methods for handling heavy metal ion-containing waste water as adsorbent using animal blood meal, cadmium, the copper ion in waste water can be efficiently removed using animal blood meal, handled waste water residual weight cadmium, copper ion concentration can be made to reach the discharge standard after wastewater treatment, animal blood powder raw material is from a wealth of sources, cheap, it has a vast market foreground, and heavy metal ions in wastewater concentration it is lower when, the animal blood meal for adsorbing heavy metal ion is alternatively arranged as the use of landscape flower soil, realizes the target of utilization of waste as resource.

Description

One kind handling Cd by adsorbent of animal blood meal2+Or Cu2+The method of waste water
Technical field
The invention belongs to solid waste -- the recycling of slaughterhouse's blood and its application field in sewage treatment, tool Body is related to a kind of method for handling heavy metal ion-containing waste water as adsorbent using animal blood meal.
Background technique
With the development of modern industry, water containing heavy metal ion pollution problem is got worse, how to obtain it is novel, cheap, The adsorbent material of high-adsorption-capacity (or efficient removal rate) becomes one of the key content of heavy metal ion-containing waste water treatment research. The heavy metal ion-containing waste water processing method of current development and application mainly has chemical precipitation method, electrolysis method, ion-exchange, mixes Solidifying or flocculence, membrane separation process, absorption method.Chemical precipitation method is to make to be changed into not in waste water in the heavy metal ion of dissolved state It is dissolved in the method for the heavy metal compound of water, including neutralization precipitation method and sulphide precipitation etc.；Electrolysis method utilizes electrolysis Basic principle is made heavy metal ions in wastewater that redox reaction occur respectively on the negative the two poles of the earth of sun-by electrolysis, is separated with this Heavy metal contaminants；Ion-exchange is to be carried out using the cation exchange groups on ion-exchanger with the heavy metal ion in waste water Exchange reaction, the method that will be removed in heavy metal ion displacement to exchanger；Coagulation or flocculence are by waste water Mixed (wadding) is added and coagulates agent, so that colloid and particulate matter in waste water is formed alumen ustum, accelerates heavy metal ion coagulation, reach the mesh of removal 's；Membrane separation process is to utilize natural or artificial synthesized macromolecule membrane pair using outside energy or chemical potential difference as motive force A kind of method that bi-component or multi-component solute and solvent are separated, be classified, purified and be concentrated；Absorption method is using porous Property adsorbent material removal heavy metal ions in wastewater method.
These types of method has respective advantage and disadvantage, and chemical precipitation method is with easy to operate, effect is preferable, lower-cost excellent Point, but a large amount of heavy metallic salt sludge is not easy to handle, easily causes secondary pollution, at the same it is handled after waste water cannot directly arrange Put, residual concentration of heavy metal ion it is higher, cannot achieve discharge, and take up a large area, treating capacity is small, poor selectivity.Electrolysis method Technical maturity, occupied area are small, removal efficiency is high, heavy metal without secondary pollution, precipitating can recycle, but the method is not suitable for Containing the lower wastewater treatment of concentration of heavy metal ion, power consumption is big, wastewater treatment capacity is small, processing cost is high.Ion-exchange behaviour Work is simple, high treating effect, exchanger is renewable, occupied area is small, is less than 10mgL to heavy metal concentration-1Wastewater treatment Effect is good, but the method one-time investment is larger, and material and operating cost are higher, is affected by useless impurities in water, and uncomfortable Conjunction all heavy metal ion of removal and adsorbed heavy metal ion need to elute and need to regenerate with resin, to generate new give up Water.Coagulation or flocculence can handle heavy metal concentration lower than 100mgL-1Or it is higher than 1000mgL-1Waste water, between being convenient for It has a rest operation, sludge is stable is good, bacterial activity is low, effect is good, but the method operating cost is high, needs to consume a large amount of chemistry examination Agent, and have minimum concentration limit value, it is difficult to reach discharge standard.There is membrane separation process equipment to be simple and convenient to operate, it is efficient handle, The advantages that energy saving, but the easily contaminated object of film blocks, the service life is short, renewal cost is expensive, it, will if film regeneration also needs soda acid processing regeneration Generate new waste water or new waste, it is difficult to realize that a step is up to standard and other effects；Absorption method has easy to operate, treatment effeciency is high etc. Advantage, but the adsorbent price industrially used at present is generally higher, is unable to get extensive use, it is often more important that handled Waste water residual concentration of heavy metal ion is difficult to reach discharge standard.
Summary of the invention
All have that complicated for operation, operating cost is high, removal in view of common several heavy metal ion-containing waste water processing methods The disadvantages of effect is poor, the present invention propose one kind using slaughterhouse's animal blood as raw material, are processed into animal blood meal, and be used as absorption The method and application of agent processing heavy metal ion-containing waste water.
One aspect of the present invention provides a kind of new adsorbent --- animal blood meal, by slaughterhouse's animal blood through 145- The product is made in 165 DEG C of high temperature gas flow dryings, crushing, and the water content after the animal blood dried bean noodles is dry is 5-12%, crushes and is 50-200 mesh.
Another aspect of the present invention additionally provides a kind of using animal blood meal as adsorbent processing Cd2+Or Cu2+Waste water Method, specific as follows:
Processing contains Cd2+The method of waste water: by animal blood meal and contain Cd2+The waste water of ion mixes in the reactor, adjusts pH Value is 5-5.5, under room temperature stirring and adsorbing 2-4h, and mixing speed turns for 30-100 per minute, and Cd is remained in solution2+Ion Concentration is lower than 0.1mgL-1Reach wastewater discharge standard, the additive amount and Cd of the animal blood meal2+Ion total content ratio For 1:4.8-5, unit g:mg.
Processing contains Cu2+The method of waste water: by animal blood meal and contain Cu2+The waste water of ion mixes in the reactor, adjusts pH Value is 7-8, under room temperature stirring and adsorbing 15-18h, and mixing speed turns for 30-100 per minute, and Cu is remained in solution2+Ion Concentration is lower than 0.5mgL-1Reach wastewater discharge standard；The additive amount and Cu of the animal blood meal2+Ion total content ratio For 1:6.6-10, unit g:mg.
When processing contains Cd2+Electroplating wastewater when, discharge standard require it is higher, processing method be two-step method: first according to The additive amount and heavy metal ion total content ratio of animal blood meal are that 1:4.8-5 (g:mg) carries out first step processing, reach solution Middle residual concentration of heavy metal ion is 0.1mgL-1Left and right, then the filtrate of first step processing is subjected to second step processing, i.e., it will filter Liquid is added animal blood meal according to the ratio of 1% (percent weight in volume) and carries out second of absorption, i.e. two-step method.By two-step method After adsorption treatment, residue Cd in solution2+Concentration is down to 0.006mgL-1, it is lower than discharge standard for electroplating pollutants (GB-21900- 2008) to Cd2+Emission limit (0.05mgL-1)。
Animal blood meal adsorbent prepared by the present invention has the advantage that the blood meal can efficiently remove the weight in waste water Metal ion can make handled waste water remain concentration of heavy metal ion and reach the discharge standard after electroplating wastewater processing Treated the heavy metals ion residues amount of realization is in 0.05mgL-1Hereinafter, this is current all adsorbent (ion exchanges Except resin) be difficult to realize, and the raw material sources of animal blood meal are extensive, cheap (about 6000-8000 member per ton), and When heavy metal ions in wastewater concentration is lower (when meeting landscape flower soil heavy metal ion content requirement), heavy metal was adsorbed The blood meal of ion can be used as the use of landscape flower soil, realize the target of utilization of waste as resource.
Specific embodiment
With reference to embodiments, a specific embodiment of the invention is described in more details, so as to more preferably Ground understands the advantages of the solution of the present invention and its various aspects.However, specific embodiments described below and embodiment are only It is for illustrative purposes, rather than limiting the invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1: the preparation method of animal blood meal
The animal blood that slaughterhouse is discarded is dry as thick blood meal particle through 155 DEG C of high temperature gas flows, aqueous after drying Amount is 10%, using the animal blood meal adsorbent for being ground into 100 mesh, becomes efficient absorption adsorbent for heavy metal.
Embodiment 2: one-step method handles Cd2+The method of concentration waste water
1. being 20mgL equipped with 10 tons of initial concentrations in 12 tons of reaction kettles-1Cd2+Above-mentioned preparation is added in solution 40kg animal blood meal adsorbent, adjusting pH value is 5.0, under room temperature stirring and adsorbing 2h, and mixing speed is 80 turns per minute, Filtering obtains the filtrate of low-concentration heavy metal ions.
2. the filtrate 50mL of step 1. is taken to be placed in 150mL conical flask, 2.5mL nitric acid is added, is heated on electric hot plate Resolution, it is ensured that sample does not boil, and steams to 5mL or so, and 2.5mL nitric acid and 1 mL perchloric acid are added again, then steam to 1mL or so, Cooling is removed, adds ultrapure water to be settled to 50mL, then this constant volume liquid is measured with WYS2200 type atomic absorption spectrophotometer and is remained Concentration of cadmium ions.
Measurement result is residue Cd in filtering solution2+Ion concentration is 0.1mgL-1, reach integrated wastewater discharge standard (GB8978-1996) Cd in2+Ion emission limit 0.1mgL-1。
Embodiment 3: two-step method handles Cd in electroplating wastewater2+Method
1. due to electroplating wastewater be usually pass through chemical precipitation processing to discharge using common adsorbents treatment process, but It is generally unattainable discharge standard, thus technique or adsorbent need to be improved, first by chemical precipitation treated high concentrations of Cd2+Waste water It is handled by the first step, i.e., is that 1:5 (g:mg) carries out the according to the additive amount of animal blood meal and heavy metal ion total content ratio The processing of one step inputs 10 tons of chemical precipitations treated Cd specifically, in 12 tons of reaction kettles or reaction tank2+Solution, Cd2+ Concentration is 20mgL-1, it is added the 40kg animal blood meal adsorbent of above-mentioned preparation, adjusting pH value is 5.0, stirring and adsorbing 2h, Mixing speed is 80 turns per minute, and filtering obtains remaining Cd2+Ion concentration is 0.1mgL-1The treatment fluid of left and right.
2. the filtrate by first step processing carries out second step processing again, i.e., by filtrate according to 1% (percent weight in volume) Ratio animal blood meal be added carry out second absorption (two-step method), other process conditions are identical as embodiment 2.
3. after two-step method adsorption treatment, residue Cd in solution2+Concentration is down to 0.006mgL-1, lower than plating pollution Object discharge standard (GB-21900-2008) is to Cd2+Emission limit (0.05mgL-1), analysis determining method is with embodiment 2 It is identical.
Embodiment 4: contain Cu2+The processing method of waste water
1. being 20mgL equipped with 10 tons of initial concentrations in 12 tons of reaction kettles-1Cu2+Above-mentioned preparation is added in solution 30kg animal blood meal adsorbent, adjusting pH value is 7, stirs 15h under room temperature, and mixing speed is 80 turns per minute, filtering Obtain the filtrate of low-concentration heavy metal ions.
2. the filtrate 50mL of step 1. is taken to be placed in 150mL conical flask, 2.5mL nitric acid is added, is heated on electric hot plate Resolution, step is same as Example 2, then measures residual Cu with WYS2200 type atomic absorption spectrophotometer2+ ion concentration. Residue Cu in solution2+Ion concentration is 0.411mgL-1, lower than discharge standard for electroplating pollutants (GB-21900-2008) to Cu2 +Emission limit (0.5mgL-1)。

Claims (3)

1. a kind of handle Cd by adsorbent of animal blood meal2+Or Cu2+The method of waste water, which is characterized in that this method includes as follows Step:
1. prepared by animal blood meal: discarded animal blood being become thick blood meal particle through 145-165 DEG C of high temperature gas flow drying, is passed through again The animal blood meal adsorbent for being ground into 50-200 mesh is crossed, the water content after the animal blood dried bean noodles is dry is 5-12%；
2. processing contains Cd2+The method of waste water: by animal blood meal and contain Cd2+The waste water of ion mixes in the reactor, adjusts pH value For 5-5.5, stirring and adsorbing 2-4h, mixing speed turn under room temperature for 30-100 per minute, and Cd is remained in solution2+Ion is dense Degree is lower than 0.1 mgL-1Reach wastewater discharge standard；
The additive amount and Cd of the animal blood meal2+Ion total content ratio is 1:4.8-5, unit g:mg；
Or:
2. processing contains Cu2+The method of waste water: by animal blood meal and contain Cu2+The waste water of ion mixes in the reactor, adjusts pH value For 7-8, stirring and adsorbing 15-18h, mixing speed turn under room temperature for 30-100 per minute, and Cu is remained in solution2+Ion is dense Degree is lower than 0.5 mgL-1Reach wastewater discharge standard；
The additive amount and Cu of the animal blood meal2+Ion total content ratio is 1:6.6-10, unit g:mg.
2. as described in claim 1 a kind of using animal blood meal as adsorbent processing Cd2+Or Cu2+The method of waste water, feature exist In: contain Cd2+When waste water is electroplating wastewater, 2. solution that above-mentioned steps are handled need to carry out second adsorption, i.e., 2. handle step Solution is added animal blood meal according to the ratio of percent weight in volume 1% and carries out second of absorption, by two-step method adsorption treatment Afterwards, residue Cd in solution2+Concentration is lower than 0.05 mgL-1Reach wastewater discharge standard.
3. as claimed in claim 1 or 2 a kind of using animal blood meal as adsorbent processing Cd2+Or Cu2+The method of waste water, feature It is: Cd in the waste water2+Or Cu2+The initial concentration of ion is lower than 20mgL-1。
CN201611048069.7A 2016-11-25 2016-11-25 A method of Cd2+ or Cu2+ waste water is handled by adsorbent of animal blood meal Active CN106395969B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87100511A (en) * 1987-01-28 1988-08-10 山西大学 Be used to handle the resin and the method for making thereof of mercury-containing waste water
JPH0347535A (en) * 1989-07-12 1991-02-28 Teruo Tomota Preparation of granule for adsorbing cyan and heavy metal compound

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US7291271B2 (en) * 2003-12-09 2007-11-06 Separation Design Group, Llc Meso-frequency traveling wave electro-kinetic continuous adsorption system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87100511A (en) * 1987-01-28 1988-08-10 山西大学 Be used to handle the resin and the method for making thereof of mercury-containing waste water
JPH0347535A (en) * 1989-07-12 1991-02-28 Teruo Tomota Preparation of granule for adsorbing cyan and heavy metal compound

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