CN108017242A - A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials - Google Patents

A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials Download PDF

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Publication number
CN108017242A
CN108017242A CN201711479048.5A CN201711479048A CN108017242A CN 108017242 A CN108017242 A CN 108017242A CN 201711479048 A CN201711479048 A CN 201711479048A CN 108017242 A CN108017242 A CN 108017242A
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China
Prior art keywords
heavy metal
livestock
poultry
feces
parts
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Pending
Application number
CN201711479048.5A
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Chinese (zh)
Inventor
傅剑锋
熊伟
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Anhui Lenong Environmental Protection Technology Co Ltd
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Anhui Lenong Environmental Protection Technology Co Ltd
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Priority to CN201711479048.5A priority Critical patent/CN108017242A/en
Publication of CN108017242A publication Critical patent/CN108017242A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • 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
    • 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
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry

Abstract

The invention discloses a kind of method that heavy metal in fowl and animal excrement is removed based on PAL modified materials, belong to environment and agricultural technology field, this method uses the attapulgite of high-temperature activation, cyclodextrin, charcoal, tannic acid is prepared into the circular honeycomb briquette absorption grain with suction-operated, the processing of heavy metal is carried out to fowl and animal excrement then in conjunction with electrochemical treatment, method provided by the invention has the characteristics that simple to operation, and division operation is gone not produce secondary pollution in heavy metal, electrochemistry removes free heavy metal ion, the heavy metal of circular honeycomb briquette absorption grain absorption nonionic state, have the advantages that removal efficiency is high, it is adapted to industrial production.

Description

A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials
Technical field
The invention belongs to environment and agricultural technology field, and in particular to one kind removes feces of livestock and poultry based on PAL modified materials The method of middle heavy metal.
Background technology
With the development of intensive culture industry, the heave metals trace elements such as copper, zinc, cadmium, arsenic are added to animal feeding extensively In material, and livestock and poultry are low to the utilization rate of trace element, and plurality of heavy metal is discharged with excrement, and such as copper and zinc, the excretion in excrement accounts for More than 95%, livestock and poultry are only 1%-3% to the absorptivity of inorganic cadmium in feed, and 10%- is also only to the absorptivity of organic cadmium 25%, as country is to the pay attention to day by day of ecological environment, the problem of centralization-breeding factory feces of livestock and poultry heavy-metal residual, and it is right The environmental risk that water body, soil are brought increasingly attracts attention, and becomes an environmental problem for needing to solve in a hurry.
At present, the method for heavy metal based on aerobic compost, passes through physical chemistry in birds and livestocks faces are handled both at home and abroad Biotechnology realizes the efficient passivation of heavy metal, reduces the validity of heavy metal, using physical method to heavy metal in compost Absorption, the cost of adsorbent is low, source is wide, absorption principle is simple, but removal rate is not high, and adsorbent is difficult to separate with compost, this And heavy metal is based on being passivated, it is difficult to the reason for removing.The chemical technology of birds and livestocks faces compost heavy metal passivation, mainly Using acidification and add surfactant, the environmental benefit harm of surfactant is larger.Acidation treatment method is simple, effect Substantially, but because the consuming cost of acid is higher, fail to be used widely；The biotechnology of birds and livestocks faces compost heavy metal passivation Mainly heavy metal changes into the weight of soluble state by microbial action under high oxidation-reduction potential and the effect of low pH value Metal, reaches the removal of heavy metal in leaching process, and the heavy metal woods filtrate of high concentration is generally gone by electrolysis Remove, but this method cost is higher, not can apply to production practices.With advances in technology, new heavy metal absorbent is not yet Disconnected standby developmental research comes out, and is combining new treatment technology, the heavy metal in physical absorption fowl and animal excrement is still to be answered at present With most wide, as Chinese patent publication No. CN107253814A using sodium silicate aqueous solution wraps up attapulgite, then The attapulgite of parcel and acetone semicarbazone thiocarbamide are modified, modified attapulgite filters fowl and animal excrement Absorption, removes the heavy metal ion in fowl and animal excrement, likewise, Chinese patent publication No. CN105732130A uses concave convex rod The compound adsorbent of soil, charcoal and sodium thiosulfate composition adsorbs the heavy metal ion in excrement, therefore concave convex rod Soil is widely used in adsorbing domain due to its special Rotating fields.
The content of the invention
According to above the deficiencies in the prior art, the technical problems to be solved by the invention are to propose that a kind of PAL that is based on is modified The method that material removes heavy metal in feces of livestock and poultry, in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, is comprised the following steps that：
1) by attapulgite at 300-350 DEG C of temperature high-temperature activation 1.5-2.5h, obtain activation attapulgite；
2) it is by weight, that 30-35 parts of activation attapulgites, 5-8 parts of charcoals, 1-2.5 parts of tannic acid ball milling mixings are equal It is even, honeycomb extruder grain is carried out, obtains honeycomb absorption grain；
3) honeycomb absorption grain is placed in the 4-6V electrochemical appliances equipped with excrement solution, carries out adsorption treatment 3-5h.
2. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature It is, the particle diameter of the attapulgite is 150-200 mesh.
Preferably, the rotating speed of the ball milling is 500-600r/min, and Ball-milling Time 40-60min, comes into full contact with, do not break The layer structure of bad attapulgite.
Preferably, the electrode of the electrochemical appliance is graphite, electrode spacing 8-10cm.
Preferably, the particle diameter of the honeycomb absorption grain is 0.5-0.8cm, and additive amount is the 5%- of dry stool quality 10%, be conducive to fully absorption contact, improve adsorption efficiency.
Preferably, the ratio of the molten fluid drying excrement of the excrement and water is 1:10.
A kind of mixture in method for heavy metal in the removal feces of livestock and poultry based on PAL modified materials, institute State mixture by weight, 30-35 parts of activation attapulgites, 5-8 parts of charcoals, 1-2.5 parts of tannic acid ball milling mixings are uniform It is made.
Preferably, the mixture further includes following parts by weight ingredient：10-15 parts of cyclodextrin, increases the ability of absorption.
Compared with prior art, beneficial effects of the present invention：
1. the present invention removes the weight in excrement using the method that high-temperature activation pretreatment attapulgite and electrochemistry are combined Metal, electrochemistry make, and mineral particle, heavy metal ion and its compound, organic matter inside excrement etc. are in DC electric field Under effect, the reaction of a series of complex occurs, is migrated by modes such as electromigration, convection current, free diffusings, in the mistake of migration Concave convex rod carries out concentration absorption to it in journey, improves the adsorption capacity to heavy metal.
2. the present invention can be removed in crystal structure not when heated using high-temperature activation pretreatment attapulgite, attapulgite With state water, internal structure becomes loose porous, increases specific surface area, lifts the adsorption capacity to heavy metal.
3. the present invention is easy to operate, high to the adsorption rate of heavy metal, and will not produce secondary pollution.
Embodiment
Below by the description to embodiment, it is described in further detail, to help those skilled in the art to this hair Bright inventive concept, technical solution have more complete, accurate and deep understanding.
Embodiment 1
A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, is comprised the following steps that：
1) it is 40% that attapulgite, which needs to be dried to water content, before activating, and crosses 150 mesh sieves, then by attapulgite It is placed in activation furnace, the high-temperature activation 2h at 300 DEG C of temperature, obtains activation attapulgite；150 mesh sieves excessively after grinding, circulate operation, Until all activation attapulgites all pass through sieve；
2) 30 parts of activation attapulgites by weight, are weighed, 12 parts of cyclodextrin, 7 parts of charcoals, 2 parts of tannic acid are in rotating speed Ball milling mixing is uniform in the ball mill of 600r/min, during ball milling, first adds 30 parts of activation attapulgites and 12 parts of rings Dextrin, 7 parts of charcoals are added after ball milling 10min, are continued ball milling 10min, are eventually adding 2 parts of tannic acid and are further continued for ball milling 25min, the mixed powder after ball milling mixing carry out honeycomb extruder grain, obtain the circular honeycomb absorption grain of particle diameter 0.8cm；
3) circular honeycomb absorption grain is added three times in the electrochemical appliance equipped with excrement solution graphite electrode, be separated by In the two graphite electrodes insertion excrement solution of 10cm, excrement solution presses dry excrement and water weight ratio 1:10 are configured, then The voltage of 5V is added on electrochemical appliance, carries out handling 4.5h to excrement solution electrochemistry, in electrochemical treatment process, often 1.5h additions once remaining circular honeycomb absorption grain is spaced, ensures that the orientation of the heavy metal ion in electrochemical treatment process is moved Dynamic and heavy metal adsorption efficiency, improves heavy metal removal rate.
Embodiment 2
The present embodiment is with embodiment 1, the difference is that circular honeycomb absorption grain is disposably to add in the present embodiment.
Embodiment 3
The present embodiment is with embodiment 1, the difference is that circular honeycomb absorption grain includes following component in the present embodiment：35 parts of work Change attapulgite, 10 parts of cyclodextrin, 5 parts of charcoals, 1 part of tannic acid.
Embodiment 4
The present embodiment is with embodiment 1, the difference is that being not added with circular honeycomb absorption grain in the present embodiment.
Embodiment 5
The present embodiment, the difference is that only adding circular honeycomb absorption grain in the present embodiment, is not powered on pressing with embodiment 1.
Pass through Cu in the excrement solution after high performance liquid chromatography detection process2+Concentration, then not do any processing Excrement solution in Cu2+On the basis of, as a comparison, 1 is denoted as, calculates after embodiment 1-5 processing Cu in excrement2+Concentration, Test result see the table below：
Contrast Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Cu2+Concentration 1 0.14 0.2 0.28 0.38 0.34
Can be seen that method provided by the invention by the detection of above-described embodiment, comparative example can effectively remove fowl Animal manure just in heavy metal.
The present invention is exemplarily described above in conjunction with specific embodiment, it is clear that the present invention implements and from upper The limitation of mode is stated, if the improvement of the various unsubstantialities of inventive concept and technical scheme of the present invention progress is employed, or It is not improved by the present invention design and technical solution directly apply to other occasions, protection scope of the present invention it It is interior.Protection scope of the present invention should be determined by the scope of protection defined in the claims.

Claims (8)

  1. A kind of 1. method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, it is characterised in that comprise the following steps that：
    1) by attapulgite at 300-350 DEG C of temperature high-temperature activation 1.5-2.5h, obtain activation attapulgite；
    2) attapulgite by weight, is activated by 30-35 parts, 5-8 parts of charcoals, 1-2.5 parts of tannic acid ball milling mixings are uniform, into Row honeycomb extruder grain, obtains honeycomb absorption grain；
    3) honeycomb absorption grain is placed in the 4-6V electrochemical appliances equipped with excrement solution, carries out adsorption treatment 3-5h.
  2. 2. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature are existed In the particle diameter of the attapulgite is 150-200 mesh.
  3. 3. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature are existed In the rotating speed of the ball milling is 500-600r/min, Ball-milling Time 40-60min.
  4. 4. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature are existed In the electrode of, the electrochemical appliance be graphite, electrode spacing 8-10cm.
  5. 5. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature are existed In the particle diameter of the honeycomb absorption grain is 0.5-0.8cm, and additive amount is the 5%-10% of dry stool quality.
  6. 6. the method according to claim 1 that heavy metal in feces of livestock and poultry is removed based on PAL modified materials, its feature are existed In the ratio of the molten fluid drying excrement of the excrement and water is 1:10.
  7. It is 7. a kind of mixed in the method for heavy metal in feces of livestock and poultry for being removed described in claim 1 based on PAL modified materials Compound, it is characterised in that the mixture by weight, by 30-35 parts activate attapulgites, 5-8 parts of charcoals, 1-2.5 parts Tannic acid ball milling mixing is uniformly made.
  8. 8. the mixture according to claim 7 removed based on PAL modified materials in feces of livestock and poultry in the method for heavy metal, It is characterized in that, the mixture further includes following parts by weight ingredient：10-15 parts of cyclodextrin.
CN201711479048.5A 2017-12-29 2017-12-29 A kind of method that heavy metal in feces of livestock and poultry is removed based on PAL modified materials Pending CN108017242A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733076A (en) * 2009-12-31 2010-06-16 四川大学 Modified attapulgite adsorbent for tannery wastewater treatment and preparation method thereof
CN104667875A (en) * 2015-03-05 2015-06-03 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 Method for preparing charcoal/attapulgite nanocomposite from attapulgite and hogwash fat
US20150158006A1 (en) * 2011-03-24 2015-06-11 Cool Planet Energy Systems, Inc. System for making renewable fuels
CN105732130A (en) * 2016-02-02 2016-07-06 中国科学院合肥物质科学研究院 Method for reducing heavy metal toxicity in livestock and poultry feces and mixture thereof
CN106477833A (en) * 2016-11-22 2017-03-08 浙江科技学院 The electronic eliminating equipment of exceeded heavy metal and method in biogas residue feces
WO2017117633A1 (en) * 2016-01-07 2017-07-13 Commonwealth Scientific And Industrial Research Organisation Plants with modified traits
CN107349913A (en) * 2017-08-11 2017-11-17 安徽乐农环保科技有限公司 A kind of heavy metals removal method based on PAL M materials in feces of livestock and poultry

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733076A (en) * 2009-12-31 2010-06-16 四川大学 Modified attapulgite adsorbent for tannery wastewater treatment and preparation method thereof
US20150158006A1 (en) * 2011-03-24 2015-06-11 Cool Planet Energy Systems, Inc. System for making renewable fuels
CN104667875A (en) * 2015-03-05 2015-06-03 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 Method for preparing charcoal/attapulgite nanocomposite from attapulgite and hogwash fat
WO2017117633A1 (en) * 2016-01-07 2017-07-13 Commonwealth Scientific And Industrial Research Organisation Plants with modified traits
CN105732130A (en) * 2016-02-02 2016-07-06 中国科学院合肥物质科学研究院 Method for reducing heavy metal toxicity in livestock and poultry feces and mixture thereof
CN106477833A (en) * 2016-11-22 2017-03-08 浙江科技学院 The electronic eliminating equipment of exceeded heavy metal and method in biogas residue feces
CN107349913A (en) * 2017-08-11 2017-11-17 安徽乐农环保科技有限公司 A kind of heavy metals removal method based on PAL M materials in feces of livestock and poultry

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Application publication date: 20180511