CN112536018A - Preparation method and device of organic functional group modified nano zero-valent iron repairing agent - Google Patents
Preparation method and device of organic functional group modified nano zero-valent iron repairing agent Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 125000000524 functional group Chemical group 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
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- 238000006722 reduction reaction Methods 0.000 claims abstract description 17
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- 150000002505 iron Chemical class 0.000 claims abstract description 12
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- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 36
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- 229910001385 heavy metal Inorganic materials 0.000 description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 13
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 3
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/83—Mixing plants specially adapted for mixing in combination with disintegrating operations
- B01F33/831—Devices with consecutive working receptacles, e.g. with two intermeshing tools in one of the receptacles
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of an organic functional group modified nano zero-valent iron repairing agent, which comprises the steps of preparing an amino acid modified solution, and mixing and modifying the amino acid modified solution and an iron salt solution to form a chelate mixed solution; then adding a borohydride solution, carrying out liquid-phase reduction reaction to obtain a black suspension of the nano zero-valent iron, carrying out suction filtration and solid-liquid separation to obtain a black solid preparation, and preparing the black solid preparation into a suspension; and adding a copper sulfate solution into the turbid liquid to obtain modified nano bimetallic particles, and drying to obtain a nano bimetallic particle sample. The organic chelating agent is coated on the surface of the nano iron-copper bimetallic particles to form the repairing agent with certain dispersibility and stable structure, can effectively adsorb and convert hexavalent chromium in soil, and has the characteristics of simple and easy operation and high repairing efficiency.
Description
Technical Field
The invention relates to the technical field of soil treatment, in particular to a method and a device for preparing an organic functional group modified nano zero-valent iron repairing agent for treating hexavalent chromium pollution of field soil.
Background
With the rapid development of the country and the rapid promotion of industrialization and urbanization, the pollution of hexavalent chromium in the soil of the country is increasingly prominent. In particular, the pollution problem of hexavalent chromium in soil caused by chromium salt production, sewage irrigation, transportation, industrial discharge, textile printing and dyeing and atmospheric sedimentation is getting more serious. In nature, the chromium usually exists in two stable valence states of trivalent and hexavalent valence, the trivalent chromium usually exists in the form of Cr3+ cation in soil environment, the oxidation activity is low, the poisoning effect on organisms is weak, more than 90% of the trivalent chromium in water environment can be adsorbed and fixed by soil colloid, and the soil is not easily polluted. Hexavalent chromium is mostly present in the form of anions (e.g., CrO2-, Cr2O72-, and CrO42-), has a high positive charge, and has a small ionic radius
Has strong binding force with oxygen and can be mutually converted under different pH and concentration conditions. Compared with trivalent chromium, sixThe chromium has extremely high mobility, stably exists in soil, only 8.5-36.2 percent of the chromium can be adsorbed by soil colloid, has high toxicity to organisms, influences the growth of plants, causes the yield reduction of crops, is enriched in the crops and further harms the human health through a food chain.
The chromium-contaminated soil remediation technology is mainly divided into 2 methods: A. the valence state of chromium is changed, hexavalent chromium in soil is reduced into trivalent chromium, the activated state is changed into a stable state, and the toxicity is reduced; B. the hexavalent chromium is removed from the soil and recycled by technical means, so that the residual concentration approaches or reaches the background value, and the purpose of recycling is achieved. Through years of technical research by researchers at home and abroad, at present, the method for removing hexavalent chromium comprises the following steps: physical repair methods, biological repair methods, and chemical repair methods.
The phytoremediation method is suitable for heavy metal remediation with low concentration, is low in cost and beneficial to environmental protection, but has long remediation period, general remediation effect and certain limitation in practical application. Under natural conditions, the microbial remediation method has the limitations of slow remediation effect, long remediation time and the like, and easily causes the failure of a soil self-purification mechanism.
The chemical repairing method mainly comprises a chemical leaching method, a chemical reduction method and a solidification stabilization method. The chemical leaching method is to wash the polluted soil by using fluid, transfer heavy metals in the soil to a liquid phase through the actions of chelation, ion exchange, precipitation, adsorption and the like, so as to achieve the purpose of separating the heavy metals from the soil, and is suitable for the high-concentration polluted soil; the chemical reduction method belongs to an in-situ remediation technology, reduces hexavalent chromium into a form with lower migration and conversion capacity by using a reducing agent, reduces the bioavailability of chromium, and achieves the aim of remedying soil. The method is simple to operate, and the reducing agents are various in types and widely applied to the repair project; the solidification stabilization method is characterized in that a stabilizer is added into soil, and a reducing agent is added for reducing hexavalent chromium, so that the soil is fixed and stabilized, the soil does not migrate to the periphery of the soil, and the soil toxicity is reduced.
At present, the eluent with mature repairing effect is expensive and difficult to be used in large-scale repairing engineering, and in addition, the residue of the eluent is easy to cause secondary pollution and destroy the structure and the fertility of soil; chemical reduction, for example, the currently used chromium removal process, is the reduction of hexavalent chromium by ferrous sulfate under acidic conditions, followed by coprecipitation under basic conditions. The reaction process is shown in the following reaction equations 1-1 and 1-2. The method has the advantages that the acid and alkali consumption is large, the original pH and Eh of the soil are easily changed, the composition of a soil ecosystem is influenced, secondary pollution is caused, the reduction process can react with other substances in the soil, and the waste of a reducing agent is caused; the solidification and stabilization method is suitable for polluted sites with high pollution concentration and small area, can not fundamentally remove heavy metal pollution in soil, and has potential ecological environment risks.
Disclosure of Invention
The invention aims to provide a preparation method and a device of an organic functional group modified nano zero-valent iron repairing agent, which inhibit the oxidation and agglomeration of the surface of nano zero-valent iron (NZVI) through load modification and package modification, increase the specific surface area, provide more reactive sites, improve the reactivity and the adsorption performance of the NZVI, and then passivate and fix a reduction product in soil colloid by utilizing the organic chelating action of the surface active groups of nano particles, so as to solve the technical problems of low repairing efficiency and easy restoration effect rebound in the physical repairing method, the biological repairing method and the chemical repairing method in the prior art.
In order to solve the technical problems, the invention specifically provides the following technical scheme:
a preparation method of an organic functional group modified nano zero-valent iron repairing agent comprises the following specific steps: the method comprises the following specific steps:
s100, hydrolyzing the biological byproducts in a high-temperature cooking mode to obtain a primary hydrolysate; performing high-temperature puffing cracking on the preliminary hydrolysate, and then dehydrating, drying and crushing to obtain the modified biological agent of the amino acid active group;
s200, preparing a modified biological agent of amino acid active groups into a solution, adding an iron salt solution into the solution for mixing and modifying, and fully stirring and uniformly mixing to form a chelate mixed solution;
s300, dropwise adding a borohydride solution into the chelate mixed solution, performing liquid-phase reduction reaction to obtain a black suspension of nano zero-valent iron, performing suction filtration and solid-liquid separation on the black suspension to obtain a black solid preparation, and preparing the black solid preparation into a suspension by using deoxygenated distilled water;
s400, dropwise adding a copper sulfate solution into the suspension to perform in-situ exchange reaction to obtain modified nano Fe/Cu bimetallic particles, removing supernatant after the reaction is finished, respectively cleaning the obtained solid substance with deoxygenated distilled water and absolute ethyl alcohol for three times, and drying to obtain a nano Fe/Cu bimetallic particle sample
In a preferred embodiment of the present invention, in S200, an amino acid modified solution with a mass fraction of 1 to 10% and an iron salt solution with a mass fraction of 0.1 to 0.2mol/L are mixed, where the iron salt is FeSO4 or FeCl3, and the volume ratio of the amino acid modified solution to the iron salt solution is 1: 1-10, fully stirring for 30min under the protection of nitrogen to form stable chelate mixed liquor;
the solution of borohydride in S300 is sodium borohydride NaBH4 or potassium borohydride KBH4, wherein the volume ratio of ferric salt to borohydride is 1:1 to 5.
In a preferred embodiment of the present invention, in S200, the process of dehydrating, drying and pulverizing the product after the high-temperature puffing and cracking further comprises a step of performing a coarse molding treatment to obtain a modified biological agent with amino acid active groups, wherein the specific steps comprise:
s201, obtaining a porous plant fiber auxiliary material by using plant fibers and cellulase;
s202, adding a porous plant fiber auxiliary material into the crushed primary hydrolysate, performing coarse crushing for 30-60 seconds to obtain a vermicelli mixture, and then performing centrifugal operation on the vermicelli mixture;
s203, maintaining the state of the vermicelli mixture after centrifugal treatment, and adding a pure water, reducing agent and hydrolase mixed solution in a dripping and permeating mode until the vermicelli mixture is completely wet;
and S204, drying the wet vermicelli mixture in a staged heating mode to obtain the amino acid active group modified biological agent.
As a preferable scheme of the present invention, in S300, after the modified biological preparation of the modified amino acid active group is cooled and washed, the gel is added to the washed black solid preparation, and after sufficient stirring and mixing, the modified organic functional group colloid fluid is formed, and then the organic functional group-hanging colloid fluid is formed into dry hollow spherical microparticles by low temperature extrusion, and then the suspension is prepared by using deoxygenated distilled water.
In a preferred embodiment of the present invention, in S202, the length of the coarsely pulverized plant fiber is controlled to be twice the length of the plant fiber after the sufficiently agitating and mixing step in S300, and in S201, the mass fraction of the cellulase is less than half of the mass fraction of the plant fiber, and the porous plant fiber auxiliary material is obtained by intermittently agitating the plant fiber during the catalytic decomposition.
As a preferred embodiment of the present invention, a specific method for obtaining hollow spherical microparticles comprises:
s301, adding the gel for multiple times into the washed intermediate product with the modified functional group, and continuously stirring while adding the gel;
s302, continuously heating in the stirring process until the gel is completely boiled, then cooling, and repeating for multiple times to obtain organic functional group colloidal fluid;
s303, blowing dry gas into the extrusion end while extruding the organic functional group colloid fluid to expand the extruded organic functional group colloid fluid, and rapidly shaping the expanded organic functional group colloid to form hollow spherical microparticles by setting the extrusion end to be a low-temperature environment.
The invention provides a preparation device of an organic functional group modified nano zero-valent iron repairing agent, which comprises a shell and a centrifugal stirring device arranged in the shell, wherein an extrusion molding device is arranged at the bottom of the centrifugal stirring device, a temperature control device is arranged at the extrusion end of the extrusion molding device, and the low-temperature control device is used for being matched with the extrusion molding device to extrude a product input by the centrifugal stirring device into hollow spherical particles.
As a preferred scheme of the invention, a main cavity and a transfer cavity are arranged in the shell, an opening and closing valve is arranged at the joint of the main cavity and the transfer cavity, the centrifugal stirring device is arranged in the main cavity, and the extrusion molding device is arranged in the transfer cavity;
the extrusion molding device comprises a mesh pipe connected to the bottom of the transfer cavity, extrusion molding holes are distributed on the surface of the mesh pipe, a main gas pipe is arranged on the axis of the mesh pipe, a plurality of gas distribution pipes are connected to the main gas pipe, exhaust heads are arranged at the tail ends of the gas distribution pipes extending to the extrusion molding holes, a sliding shovel pipe is sleeved on the mesh pipe and used for cutting off materials extruded from the extrusion molding holes in an up-and-down sliding mode;
the temperature control device is used for providing a low-temperature environment for the space in the shell where the mesh pipe is located and providing a high-temperature and low-temperature alternative control environment for the main cavity.
As a preferable scheme of the present invention, an extrusion device is disposed between the centrifugal stirring device and the inner wall of the main cavity, and the extrusion device provides a power source for the sliding shovel tube to slide up and down by connecting the sliding shovel tube, and the extrusion device is configured to change an axial stacking height of the material in the main cavity when the centrifugal stirring device performs a centrifugal motion.
As a preferable scheme of the present invention, the centrifugal stirring device includes a cylindrical barrel installed in the main cavity, a rotating shaft axially disposed inside the cylindrical barrel, and a driving motor for driving the rotating shaft to rotate to drive the cylindrical barrel to rotate, a guide knife slot fixedly connected to the cylindrical barrel is disposed on a shaft body of the rotating shaft located inside the cylindrical barrel, a stirring knife body is installed on the guide knife slot, and the stirring knife body is connected to the rotating shaft through an elastic mechanism disposed on the guide knife slot, and an opening through which the stirring knife body extends out of the cylindrical barrel is disposed on the cylindrical barrel opposite to the guide knife slot;
the end part of the stirring cutter body extending out of the cylindrical barrel is fixedly connected with a tangent plate with the same radian as the inner wall of the main cavity body.
Compared with the prior art, the invention has the following beneficial effects:
the amino acid modifier mainly takes functional groups such as sulfydryl (-SH), amino (-NH2), hydroxyl (-OH) and the like as main materials, and is coated on the surface of the nano iron-copper bimetallic particle through the organic chelating action to form a repairing agent with certain dispersibility and stable structure, so that a new way is provided for the treatment of chromium pollution in soil.
The invention adopts active groups in amino acid to chelate and modify ferrous sulfate to form a stable dispersed structure repairing system, reduces Cr (VI) in soil into nontoxic Cr (III), and then converts free chromium ions into organic complex state or residue state, thereby effectively reducing the migration and bioavailability of the chromium ions in the environment, avoiding secondary pollution, and belonging to environment-friendly biological agents.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
FIG. 1 is a schematic configuration diagram of a longitudinal section of a production apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of an extrusion molding apparatus according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a centrifugal stirring apparatus according to an embodiment of the present invention;
fig. 4 is a schematic flow chart of a preparation method of the organic functional group modified nano zero-valent iron repairing agent according to the embodiment of the invention.
The reference numerals in the drawings denote the following, respectively:
1-a shell; 2-a centrifugal stirring device; 3-extrusion molding device; 4-a temperature control device; 5-an extrusion device; 6-an elastic mechanism;
101-a main cavity; 102-a transfer chamber;
201-cylindrical barrel; 202-rotating shaft; 203-guide knife grooves; 204-stirring cutter body; 205-a tangent plate;
301-mesh tube; 302-extrusion molding holes; 303-main gas pipe; 304-gas distribution pipe; 305-gas head; 306-sliding shovel tube.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 4, the invention provides a preparation method of an organic functional group modified nano zero-valent iron repairing agent, which comprises the following specific steps:
s100, hydrolyzing the biological byproducts in a high-temperature cooking mode to obtain a primary hydrolysate; performing high-temperature puffing cracking on the preliminary hydrolysate, and then dehydrating, drying and crushing to obtain the modified biological agent of the amino acid active group;
s200, preparing a modified biological agent of amino acid active groups into a solution, adding an iron salt solution into the solution for mixing and modifying, and fully stirring and uniformly mixing to form a chelate mixed solution;
s300, dropwise adding a borohydride solution into the chelate mixed solution, performing liquid-phase reduction reaction to obtain a black suspension of nano zero-valent iron, performing suction filtration and solid-liquid separation on the black suspension to obtain a black solid preparation, and preparing the black solid preparation into a suspension by using deoxygenated distilled water, wherein the specific reaction is as follows:
s400, dropwise adding a copper sulfate solution into the suspension to perform in-situ exchange reaction to obtain modified nano Fe/Cu bimetallic particles, removing supernatant after the reaction is finished, respectively cleaning the obtained solid substance with deoxygenated distilled water and absolute ethyl alcohol for three times, and drying to obtain a nano Fe/Cu bimetallic particle sample
In S200, mixing 1-10% by mass of an amino acid modified solution and 0.1-0.2 mol/L of an iron salt solution, wherein the iron salt is FeSO4 or FeCl3, and the volume ratio of the amino acid modified solution (namely AA solution) to the iron salt solution is 1: 1-10, and fully stirring for 30min under the protection of nitrogen to form stable AA-Fe0/Fe2+Chelate mixed liquor;
the solution of borohydride in S300 is sodium borohydride NaBH4 or potassium borohydride KBH4, wherein the volume ratio of ferric salt to borohydride is 1:1 to 5.
According to the invention, the amino acid biological agent is adopted to modify the nano zero-valent iron, so that the amino acid biological agent can improve the agglomeration phenomenon of the nano zero-valent iron and improve the reaction activity and the adsorption performance of the nano zero-valent iron; meanwhile, the composite material is used as a repairing medium to be chelated and adsorbed with the reduction product Cr (III) and the Cr (VI) which is in a free state and is not reduced, and double repairing is carried out, so that the treatment effect is effectively prevented from rebounding.
After the surface of the nano zero-valent iron is coated with catalytic metal Cu, amino acid active groups are grafted, and the modified nano iron-based bimetallic particles with good dispersibility, high stability and strong reducibility are self-assembled, so that the nano zero-valent iron is an environment-friendly material for treating soil hexavalent chromium pollution with a good application prospect.
A catalytic metal Cu is loaded on the surface of the NZVI to form a nano iron-based bimetallic system, so that the specific surface area and the adsorption capacity of particles are increased, and the surface oxidation of the NZVI is effectively relieved. Meanwhile, the Fe/Cu bimetallic nanoparticles form a miniature galvanic cell by Cu load, electron transfer is accelerated, iron core electrons are transferred to the surface through the metal Cu attached to the surface of the NZVI to react with a target pollutant Cr (VI), and the reduction efficiency of the NZVI to Cr (VI) in soil is remarkably improved.
The main reaction formula of the process is as follows:
xCr3++(1-x)Fe3++3H2O→CrxFe1-x(OH)3+3H+ (4)
xCr3++(1-x)Fe3++2H2O→CrxFe1-xOOH+3H+ (5)
Cu2++OH-→Cu(OH)2 (6)。
the amino acid modifier in the technology is prepared by adopting biological wastes which are easily obtained, such as poultry feathers, hoof shells and hair of livestock and the like, and performing a series of processes of high-temperature hydrolysis, puffing, cracking and the like. The organic chelating action of active groups such as sulfydryl (-SH), hydroxyl (-OH) amino (-NH2) and the like contained in amino acid and iron ions is utilized to form nano iron-copper bimetallic particles with dispersed and stable structures, so that reactive sites are increased, and the reactivity is improved. Meanwhile, amino acid on the surface of the nano particles can provide an adsorption site for heavy metal to form an organic-metal macromolecular chelate, so that the heavy metal is firmly adsorbed and fixed in soil colloid. The technology treats soil pollution by a method of treating waste by waste, carries out resource utilization on biological waste and industrial byproducts, and establishes a benign ecological economic cycle.
The reaction process mainly comprises three stages, wherein the first stage mainly takes adsorption effect, the second stage mainly takes reduction effect, and the third stage mainly takes organic matter boiling and fixing.
Aiming at water-soluble Cr (VI) ions, the water-soluble Cr (VI) ions are adsorbed on the surfaces of the nano Fe/Cu bimetallic particles, the Cr (VI) is reduced into Cr (III) with lower toxicity by utilizing the bimetal reducing capability of Fe and Cu, and then the organic-metal macromolecular chelate complexes of Cr (Cr) are generated and are firmly adsorbed and fixed on the soil colloid without participating in ecological cycle, thereby achieving the purpose of removing the Cr (VI).
In order to improve the agglomeration and treatment effect rebound in the process of treating soil hexavalent chromium by nano zero-valent iron, the technology of the invention utilizes active groups in amino acid to modify nano iron-copper bimetallic particles, and amino acid modification liquid contains a large amount of-NH2Active groups such as-SH, -OH, -COOH and the like form stable organic-metal Fe/Cu chelate through organic chelation with the nano Fe/Cu particles, so that organic coating of the nano Fe/Cu bimetallic particles by amino acid is realized. The steric hindrance and the electrostatic effect of the amino acid are utilized to ensure that the nano Fe/Cu particles are uniformly dispersed, more active sites are exposed, and the reaction activity is improved. Meanwhile, the amino acid also provides an adsorption site for the reduction product, forms an organic-metal macromolecular chelate with the reduction product, is firmly adsorbed and fixed on the soil colloid, and is not easy to release along with the change of environmental conditions.
The structural formula of a reaction product in the process is as follows:
m: fe. Cr metal ions; r: an amino acid chelating exocyclic group; ￤: a coordination bond;
FIG. 1 is a diagram showing a molecular structure of a typical amino acid chelate
The iron element is generally present in the nature, plays an important role in environmental remediation due to the adsorbability and the reducibility of the iron element, and particularly shows a unique effect in chromium pollution treatment. The nano zero-valent iron is influenced by interparticle magnetic force and van der waals force, so that the agglomeration phenomenon is easy to occur, the iron nano-scale particles are agglomerated into micron-scale particles, and the reaction activity is greatly reduced. The invention utilizes amino acid and copper sulfate solution to modify the nano zero-valent iron, weakens the oxidation and agglomeration phenomena of the nano zero-valent iron and improves the reaction activity. The micro primary battery formed by Cu load and Fe accelerates the electron transfer rate, so that the adsorption and reduction efficiency of the nano zero-valent iron is maximized, and the efficiency and the effect of soil hexavalent chromium treatment are greatly improved.
The repairing agent of the invention mainly adopts biological byproducts which are easy to obtain, such as animal hair, hoof shell, nail, and the like, as raw materials, and is processed into powdery repairing agent by combining biochemical reaction with ferrous sulfate.
The repairing agents contain abundant cystine, glutamic acid, glycine and other amino acids, wherein the content of the cystine is about 3 percent, the cystine can be converted into cysteine, carboxyl (-COOH), amino (-NH2), sulfydryl (-SH) and hydroxyl (-OH) functional groups contained in the cysteine, particularly the sulfydryl (-SH) has strong chelation effect on heavy metals, and can form a metal organic complex with a certain stable structure with ferrous sulfate through biochemical reaction, so that the bioavailability of hexavalent chromium pollution in soil is reduced, and the soil fertility is enhanced.
The main technical principle is as follows: the keratin in the organic matter of the raw material organism is subjected to hydrolysis reaction to generate amino acid residues, Cysteine (Cysteine) is a common amino acid containing free sulfydryl, disulfide bonds among polypeptide chains in a protein molecular structure can be broken through high-temperature hydrolysis and puffing processes, a large number of sulfydryl (-SH) functional groups are formed, and the sulfydryl functional groups have strong chelation property and can form stable complexes with heavy metals.
Ferrous sulfate is the most common method for treating soil chromium pollution, and is combined with cysteine, and a proper component of coupling agent is matched, so that a large amount of sulfydryl functional groups (-SH) are exposed, the circulation of ferrous iron and ferric iron can be accelerated, the relatively stable ferrous iron concentration can be maintained, more hydroxyl free radicals are generated, and Fe2+ is uniformly distributed in a stable repair system. The active compound is applied to hexavalent chromium polluted soil, Cr6+ is effectively reduced into Cr3+ through ion exchange and redox reaction, the active compound is converted into a stable state, and the migration and bioavailability of the active compound in the environment are effectively reduced.
The method provided by the invention is simple and easy to implement, and the remediation agent can be uniformly scattered on the soil or ploughed on a base fertilizer and irrigated to keep the water content of the soil to be more than 30%, or the remediation agent is put into water to directly irrigate the soil, so that the soil is completely soaked.
The method has the advantages of simple operation mode, low cost of the remediation agent, no toxicity, environmental friendliness, soil fertility improving effect, no secondary pollution and good application prospect for remediation of chromium pollution in soil.
Wherein, the high-pressure heating and cooking conditions are controlled as follows: the pressure is 200-700 KPa, the temperature is 120-200 ℃, and the cooking time is 25-70 min, so that the biological byproducts of the keratin are hydrolyzed and softened, the hydrolysis and softening of the biological byproducts containing the keratin are promoted, the keratin is hydrolyzed into usable smaller components, namely peptides, and the disulfide bonds (-S-S-) in the amino acid are promoted to be opened.
The temperature of high-temperature puffing cracking is controlled to be 150 ℃, the keratin structure is changed in the state, disulfide bonds (-S-S-) in the structure are broken, and a large amount of organic functional groups (-SH) are formed.
The ferrous sulfate and the cracked product are fully and uniformly mixed according to the coordination ratio of 1: 2, and the ferrous sulfate is chelated and modified by adopting an organic functional group (-SH) to form a stable structure repairing system, so that hexavalent chromium ions in soil can be converted from an activated state to a stable state, the mobility and bioavailability of the hexavalent chromium ions in the environment are effectively reduced, and the obtained repairing agent has good biocompatibility, cannot cause secondary pollution, and meets the indexes of environment-friendly repairing agents.
The preparation method of the unmodified Fe/Cu bimetallic nano-particles comprises the following steps:
preparing ferrous sulfate solution, copper sulfate solution, sodium borohydride solution and amino acid modified solution with certain concentration. Under the nitrogen atmosphere, a proper amount of sodium borohydride with the concentration of 0.4mol/l is slowly added into a ferrous sulfate solution with the concentration of 0.2mol/l through a peristaltic pump, the mixture is stirred for 30min, a nano zero-valent iron suspension is prepared by utilizing liquid-phase reduction reaction, solid-liquid separation is carried out on the black suspension in a suction filtration mode, the obtained solid is washed with deoxygenated distilled water for three times, and the deoxygenated distilled water is added to prepare the suspension.
Under the nitrogen atmosphere, adding a proper amount of copper sulfate solution with the concentration of 0.02mol/l into the suspension dropwise, stirring for 30min, preparing simple substance copper by using an in-situ exchange reaction, loading copper on the surface of the nano zero-valent iron to form modified iron-copper double-metal nano particles, removing supernatant, washing the obtained solid with deoxygenated distilled water and absolute ethyl alcohol for three times, and finally placing the solid in a drying box for drying.
The preparation method of the modified Fe/Cu bimetallic nano-particles comprises the following steps:
the preparation method of the modified Fe/Cu bimetallic nano-particles comprises the steps of adding 3% amino acid modified solution into ferrous sulfate solution at the early stage, and forming stable AA-Fe/Fe (II) organic metal chelate by utilizing the organic chelating action of active groups in amino acid and Fe (II), so as to disperse the nano-iron particles and improve the reaction activity.
Further, the repairing method provided by the modified Fe/Cu bimetallic nanoparticle repairing agent comprises the following steps:
step one, adjusting the pH value of soil to 3-5;
step two, applying a modified Fe/Cu bimetallic particle repairing agent;
and step three, adjusting the soil temperature to be 20-25 ℃.
The soil remediation method comprises the following specific examples (remediation of hexavalent chromium pollution in soil) of the soil remediation agent which is not modified and is modified by amino acid:
test field: burying chromium slag in a landfill site in Shandong; type of contamination: cr (VI) contamination of the soil; the pollution degree: cr (VI) contamination concentration about 1X 104 mg/kg; pollution sources are as follows: the chromium slag is randomly stacked and is leached by rainfall to enter the soil; the repairing method comprises the following steps: iron-copper bimetallic nanoparticles (Fe/Cu) and modified iron-copper bimetallic nanoparticles (AA-Fe/Cu) are respectively adopted to be uniformly mixed with soil with the pH value being adjusted to 3 and the initial Cr (VI) pollution concentration being 9610mg/kg according to the proportion of 1:10, and the soil is repaired at the constant temperature of 25 ℃.
After standing and waiting for the restoration, respectively sampling and detecting the residual concentration of Cr (VI) in the soil, and calculating the removal rate of Cr (VI) in the soil by different materials, wherein the results are shown in the following table:
TABLE 1 repairing Effect of different materials on hexavalent Cr (VI) in soil
| Repair material | Fe/Cu | AA-Fe/Cu |
| Repair time d/removal Rate% | 49/80.3％ | 34/99.9％ |
The implementation case shows that in a proper pH and temperature range, the amino acid modified Fe/Cu bimetal nano has a good repairing effect on soil Cr (VI), and the removal rate of hexavalent chromium is up to more than 99%, which is superior to that of the traditional ferrous sulfate or nano zero-valent iron.
The second specific embodiment of the invention (treatment of hexavalent chromium pollution in water):
test samples: chromium-contaminated water samples; sample source: yuxing chromium slag landfill; the pollution degree: cr (VI) concentration 1370 mg/kg; the repairing method comprises the following steps: mixing the amino acid biological agent (nano zero-valent iron modifier) and the chromium-polluted water sample according to the mass ratio of 1:15, and repairing at normal temperature.
Standing for repairing, filtering and taking supernatant to detect the residual concentration of Cr (VI) in the water sample, and analyzing the chelating effect of the amino acid biological agent (nano zero-valent iron modifier) on hexavalent chromium.
And (3) displaying a detection result: cr (VI) is not detected in a water sample, and a preliminary result shows that the amino acid biological agent has a strong chelating effect on Cr (VI), can form a stable macromolecular organic-Cr chelate with Cr (VI) in water in a short time, and is precipitated from an aqueous solution in a flocculent manner, so that the aim of removing 100% of Cr (VI) is fulfilled.
In S200, the powdery and granular remediation agent is usually present in the soil, and if the water content of the soil is high or the soil structure is too fluffy, the remediation agent is likely to migrate or accumulate without complete remediation, and the bonding between the remediation agent and the soil is poor.
Therefore, the process of dehydrating, drying and crushing the product after high-temperature puffing and cracking also comprises the step of carrying out rough forming treatment to obtain the modified biological preparation of the amino acid active group, and the specific steps comprise:
s201, obtaining a porous plant fiber auxiliary material by using plant fibers and cellulase, and performing incomplete degradation on the plant fibers by using the cellulase to form porous pores and holes on the surfaces of the plant fibers and provide adhesive points of effective functional groups in a hydrolysate;
s202, adding porous plant fiber auxiliary materials into the crushed primary hydrolysate, and then carrying out coarse crushing for 30-60 seconds to obtain a vermicelli mixture, wherein the diameter of the porous plant fiber auxiliary materials is far larger than the particle size of the powder, so that the mixture of the porous plant fiber auxiliary materials and the powder is a powder and strip mixed product, and then carrying out centrifugal operation on the vermicelli mixture, so that the porous plant fiber auxiliary materials are kept in a certain state in the hydrolysate to prepare for subsequent operation;
s203, maintaining the state of the vermicelli mixture after centrifugal treatment, adding a mixed solution of pure water, a reducing agent and hydrolase in a dripping and permeating mode, further hydrolyzing the primary hydrolysate until the vermicelli mixture is completely wet, and further adsorbing the functional group structure, the reducing agent and the hydrolase in the hydrolysate with the surface of the plant fiber;
s204, drying the wet vermicelli mixture in a stage heating mode to avoid damage to hydrolysis products caused by rapid heating, and also to avoid slow evaporation of water and severe evaporation effect to influence the surface structure of the plant fibers, thereby obtaining the amino acid active group modified biological agent.
The porous plant fiber is added to provide an adhesion point for the soil repairing agent, the distribution uniformity of the porous plant fiber can be improved after the porous plant fiber is spread in soil at the later stage, the plant fiber can be jointed with the soil and is connected with the soil, invalid migration of the plant fiber under the influence of the natural state is avoided, meanwhile, the plant fiber also provides rich nutrient elements for the soil in the later degradation process, and the foundations of later-stage bioremediation and other forms of repairing of the soil are improved.
In order to further improve the structural form of the organic functional group product, in step S300, after the modified biological preparation of the modified amino acid active group is cooled and washed, adding a gel into the washed black solid preparation, fully stirring and mixing to form a modified organic functional group colloidal fluid, then extruding the organic functional group colloidal fluid at a low temperature to form dry hollow spherical microparticles, and then preparing a suspension with deoxygenated distilled water.
In S202, the length of the coarsely crushed plant fiber is controlled to be one time of the length of the plant fiber after the fully stirring and uniformly mixing step in S300, in S201, the mass part of the cellulase is less than half of the mass part of the plant fiber, and intermittent stirring is carried out in the process of catalytic decomposition to obtain the porous plant fiber auxiliary material.
The specific method for obtaining the hollow sphere microparticles comprises the following steps:
s301, adding the gel for multiple times into the washed intermediate product with the modified functional group, and continuously stirring while adding the gel;
s302, continuously heating in the stirring process until the gel is completely boiled, then cooling, and repeating for multiple times to obtain organic functional group colloidal fluid;
s303, blowing dry gas into the extrusion end while extruding the organic functional group colloid fluid to expand the extruded organic functional group colloid fluid, and rapidly shaping the expanded organic functional group colloid to form hollow spherical microparticles by setting the extrusion end to be a low-temperature environment.
Wherein, porous plant fiber auxiliary material can for hollow spheroid microparticle provides skeleton texture improves the stability of its structure to in-process becoming the spheroid granule, organic functional group is attached to the surface of spheroid mostly, increases the area of contact with soil.
Further, the specific embodiment of the invention for treating the hexavalent chromium pollution in the field by using the modified Fe/Cu bimetallic nano-particle repairing agent further comprises the following steps:
1. qinghai pilot test case in certain place
The category: heavy metal pollution of the site; type of contamination: heavy metal hexavalent chromium (Cr6+) contamination; pollution characteristics: stacking certain chromium salt and chromium slag; the pollution degree: the content of hexavalent chromium in the soil is 1500-1350 mg/kg; the repairing method comprises the following steps: 1/60 the repairing agent and the soil are dry, the site is flooded to ensure the water content is more than or equal to 30%.
The repairing effect is as follows: the medicine is applied for 5 days, and the repairing amount is 10.7%; 15d, the repair amount is 30.5%; 50 days, the repair amount is 99.2%
2. Test cases in some places in Jiangsu:
the category: heavy metal pollution of the site; type of contamination: heavy metal hexavalent chromium (Cr6+) contamination; pollution characteristics: air sedimentation and leaching; the pollution degree: the hexavalent chromium content of the soil with the depth of 0.5m is 24 mg/kg; the repairing method comprises the following steps: 1/100 the repairing agent and the soil are dry, the site is flooded to ensure the water content is more than or equal to 30%.
The repairing effect is as follows: type A repairing agent 25d, repairing amount 74%; type B repairing agent 25d, repairing amount 79%
3. Case of treating certain place in Henan:
the category: heavy metal pollution of the site; type of contamination: heavy metal hexavalent chromium (Cr6+) contamination; pollution characteristics: chromium salt production, high diffusivity and high concentration; the pollution degree: the average value of the hexavalent chromium content of the soil with the depth of 0-5 m is 1300mg/kg, and the average value of the hexavalent chromium content of the superficial surface exceeds 3000 mg/kg; the repairing method comprises the following steps: high throwing ratio, 1/10 dry weight ratio of the repairing agent to soil, and flooding of the field to ensure that the water content is more than or equal to 30%.
The repairing effect is as follows: repairing for 4d, and reducing the content of hexavalent chromium by 60.2 percent; 15d, the hexavalent chromium content is reduced by 98 percent.
As shown in fig. 1, fig. 2 and fig. 3, the present invention provides a preparation apparatus of an organic functional group modified nano zero-valent iron repairing agent, including a casing 1, an opening for conveying powder to the inside of the casing 1 is arranged on the top of the casing 1, a cover for sealing the casing 1, and a centrifugal stirring apparatus 2 installed in the casing 1, an extrusion molding apparatus 3 is arranged on the bottom of the centrifugal stirring apparatus 2, a temperature control apparatus 4 is arranged at an extrusion end of the extrusion molding apparatus 3, and the low temperature control apparatus 4 is used for extruding a product input by the centrifugal stirring apparatus 2 to form hollow spherical particles in cooperation with the extrusion molding apparatus 3.
The inside main cavity 101 and the cavity 102 that relays that is provided with of casing 1, wherein the diameter of main cavity 101 is greater than the diameter of cavity 102 relays to smooth excessively through the round platform tubular construction between the two, main cavity 101 and the cavity 102 junction that relays are provided with the valve that opens and shuts, and centrifugal stirring device 2 installs in main cavity 101, and extrusion moulding device 3 installs in cavity 102 that relays.
The extrusion molding device 3 comprises a mesh pipe 301 connected with the bottom of the transfer cavity 102, extrusion molding holes 302 are distributed on the surface of the mesh pipe 301, a main air pipe 303 is arranged on the axis of the mesh pipe 301, the main air pipe 303 supplies air through an external air source, a plurality of air distribution pipes 304 are connected to the main air pipe 303, the air distribution pipes 304 are of a needle-tube-shaped structure, the diameter of which is controlled to 1/5 of the extrusion hole 302, the end of the gas distribution pipe 304 extending to the extrusion hole 302 is provided with a gas discharge head 305, wherein the exhaust head 305 comprises an end vent and a side ring vent, wherein the exhaust head 305 uses the end vent to blow air to make the material entering the extrusion molding hole 302 expand spherically, and the end of giving vent to anger of lateral part annular venthole just is to on the inner wall that extrusion moulding hole 302 is close to the export, utilizes annular air curtain to form in the material and cuts off the thin layer, the shaping of the later stage of being convenient for.
Furthermore, the mesh pipe 301 is sleeved with a sliding shovel pipe 306, the sliding shovel pipe 306 is used for cutting off the material extruded from the extrusion forming hole 302 in an up-and-down sliding manner, cutting holes corresponding to the extrusion forming hole 302 are distributed on the surface of the sliding shovel pipe 306, the width of each cutting hole is the same as that of the extrusion forming hole, and the length of each cutting hole is three times that of the extrusion forming hole 302, so that the mesh pipe 301 can be conveniently subjected to reciprocating cutting, and efficient mass production is realized.
The temperature control device 4 is used for providing a low-temperature environment for the space in the shell 1 where the mesh pipe 301 is located and providing a high-temperature and low-temperature alternative temperature control environment for the main cavity 101, and the specific temperature control device 4 specifically adopts the working principle of the existing semiconductor refrigeration and heating.
Be provided with extrusion device 5 between centrifugal stirring device 2 and the main cavity body 101 inner wall, and extrusion device 5 provides the power supply of upper and lower slip for slip shovel pipe 306 through connecting slip shovel pipe 306, and extrusion device 5 is used for changing the piling up height of the interior material of main cavity body 101 on the axial when centrifugal stirring device 5 is centrifugal motion.
Further, the extruding device 5 comprises a pneumatic telescopic rod installed on the cover body and a piston plate connected to the tail end of the pneumatic telescopic rod, wherein the pneumatic telescopic rod and the piston plate are both of an existing structure, and the width of the piston plate is the same as the width between the centrifugal stirring device 2 and the main cavity 101.
In order to realize the multi-functionality of the centrifugation, stirring and material reaction of the main cavity 101 of the present invention, the centrifugation stirring apparatus 2 comprises a cylindrical barrel 201 installed in the main cavity 101, a rotating shaft 202 axially arranged inside the cylindrical barrel 201, and a driving motor for driving the rotating shaft 202 to rotate and drive the cylindrical barrel 201 to rotate, a guide knife slot 203 fixedly connected with the cylindrical barrel 201 is arranged on a shaft body of the rotating shaft 202 located inside the cylindrical barrel 201, a stirring knife body 204 is installed on the guide knife slot 203, and the stirring knife body 204 is connected to the rotating shaft 202 through an elastic mechanism 6 arranged on the guide knife slot 203, wherein the elastic mechanism 6 may be specifically a spring, and the stirring knife body 204 is installed on an axis of the spring, and the stirring knife body 204 is not fixedly connected with the rotating shaft 202, so that the spring can guide the stirring knife body 204 while obtaining elastic potential energy, the stirring blade body 204 is always kept stable.
Further, the end of the stirring blade body 204 facing the rotating shaft 202 is fixedly connected to the end of the elastic mechanism 6, the end of the elastic mechanism far from the rotating shaft 202 is fixedly connected to the inner wall of the cylindrical barrel 201, and when the elastic mechanism 6 obtains the centrifugal force to compress the spring, the stirring blade body 204 moves along the axial direction of the elastic mechanism 6 and synchronously compresses the elastic mechanism 6, so that the elastic mechanism 6 obtains elastic potential energy.
An opening through which the stirring blade body 204 extends out of the cylindrical barrel 201 is provided on the cylindrical barrel 201 right opposite to the guide blade groove 203.
The specific working principle is that when the material needs to be chopped and stirred, when the driving motor drives the rotating shaft 202 to reach a certain rotating speed, the stirring cutter body 204 extends out through the opening on the cylindrical barrel 201 along the guide cutter groove 203 due to the centrifugal effect, and the material in the main cavity 101 is chopped and stirred.
When centrifugal stirring is required, the rotating speed of the rotating shaft 202 can be reduced or the stirring cutter body 204 can be fixed, and the squeezing device 5 is utilized, so that the pneumatic telescopic rod drives the piston plate to move to the tangent plate 205 of the stirring cutter body 204, and thus, the centrifugal stirring can be carried out without ejecting the stirring cutter body 204.
When the material reaction is performed, the extruding device can change the state of the material in the main cavity 101, or increase the pressure in the main cavity 101 to pressurize the material, thereby realizing the pressurization in the transfer cavity 102 and providing a pressure source for the extrusion forming device 3.
Further, the end portion of the stirring cutter body 204 extending out of the cylindrical barrel 201 is fixedly connected with a tangent plate 205 which has the same radian as the inner wall of the main cavity 101, the tangent plates 205 of the stirring cutter body 204 in the same axial direction can be fixedly connected together, on one hand, the extrusion device 5 can be conveniently utilized, the pneumatic telescopic rod drives the piston plate to move to the tangent plate 205 of the stirring cutter body 204, the ejection of the stirring cutter body 204 is controlled, the working mode of the main cavity 101 is changed, and in addition, the stirring cutter body 204 can be contacted with the inner wall of the main cavity 101 when being completely ejected through the tangent plate 205, so that the inner wall can be cleaned.
When the stirring cutter body 204 is completely received in the cylindrical barrel 201, the opening can be covered, and the material is prevented from entering the cylindrical barrel 201.
The above embodiments are only exemplary embodiments of the present application, and are not intended to limit the present application, and the protection scope of the present application is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present application and such modifications and equivalents should also be considered to be within the scope of the present application.
Claims (10)
1. A preparation method of an organic functional group modified nano zero-valent iron repairing agent is characterized by comprising the following specific steps:
s100, hydrolyzing the biological byproducts in a high-temperature cooking mode to obtain a primary hydrolysate; performing high-temperature puffing cracking on the preliminary hydrolysate, and then dehydrating, drying and crushing to obtain the modified biological agent of the amino acid active group;
s200, preparing a modified biological agent of amino acid active groups into a solution, adding an iron salt solution into the solution for mixing and modifying, and fully stirring and uniformly mixing to form a chelate mixed solution;
s300, dropwise adding a borohydride solution into the chelate mixed solution, performing liquid-phase reduction reaction to obtain a black suspension of nano zero-valent iron, performing suction filtration and solid-liquid separation on the black suspension to obtain a black solid preparation, and preparing the black solid preparation into a suspension by using deoxygenated distilled water;
s400, adding a copper sulfate solution into the suspension dropwise, carrying out in-situ exchange reaction to obtain modified nano Fe/Cu bimetallic particles, removing supernatant after the reaction is finished, respectively cleaning the obtained solid substance with deoxygenated distilled water and absolute ethyl alcohol for three times, and drying to obtain a nano Fe/Cu bimetallic particle sample.
2. The preparation method of the organic functional group modified nano zero-valent iron repairing agent according to claim 1, wherein in S200, 1-10% by mass of amino acid modified solution and 0.1-0.2 mol/L of iron salt solution are mixed, wherein the iron salt is FeSO4Or FeCl3The volume ratio of the amino acid modified solution to the ferric salt solution is 1: 1-10, fully stirring for 30min under the protection of nitrogen to form stable chelate mixed liquor;
the solution of borohydride in S300 is sodium borohydride NaBH4 or potassium borohydride KBH4, wherein the volume ratio of ferric salt to borohydride is 1:1 to 5.
3. The method for preparing the organic functional group modified nano zero-valent iron repairing agent according to claim 1, wherein in S200, the processes of dehydration, drying and crushing of the product after the high-temperature swelling and cracking further comprise a step of coarse molding treatment to obtain a modified biological agent of amino acid active groups, and the specific steps comprise:
s201, obtaining a porous plant fiber auxiliary material by using plant fibers and cellulase;
s202, adding a porous plant fiber auxiliary material into the crushed primary hydrolysate, performing coarse crushing for 30-60 seconds to obtain a vermicelli mixture, and then performing centrifugal operation on the vermicelli mixture;
s203, maintaining the state of the vermicelli mixture after centrifugal treatment, and adding a pure water, reducing agent and hydrolase mixed solution in a dripping and permeating mode until the vermicelli mixture is completely wet;
and S204, drying the wet vermicelli mixture in a staged heating mode to obtain the amino acid active group modified biological agent.
4. The preparation method of the organic functional group modified nano zero-valent iron repairing agent according to claim 1 or 3, wherein in S300, after the modified biological preparation of the modified amino acid active group is cooled and washed, the gel is added into the washed black solid preparation, after sufficient stirring and mixing, the modified organic functional group colloid fluid is formed, and then the organic functional group-hanging colloid fluid is formed into dry hollow spherical microparticles by low-temperature extrusion, and then the suspension is prepared by using deoxidized distilled water.
5. The method for preparing the organic functional group modified nano zero-valent iron restoration agent according to claim 3, wherein in S202, the length of the plant fiber after coarse crushing is controlled to be one time of the length after the step of fully stirring and uniformly mixing in S300, in S201, the mass part of the cellulase is less than half of the mass part of the plant fiber, and in the process of catalytic decomposition, intermittent stirring is carried out to obtain the porous plant fiber auxiliary material.
6. The preparation method of the organic functional group modified nano zero-valent iron repairing agent according to claim 4, wherein the specific method for obtaining the hollow spherical microparticles comprises the following steps:
s301, adding the gel for multiple times into the washed intermediate product with the modified functional group, and continuously stirring while adding the gel;
s302, continuously heating in the stirring process until the gel is completely boiled, then cooling, and repeating for multiple times to obtain organic functional group colloidal fluid;
s303, blowing dry gas into the extrusion end while extruding the organic functional group colloid fluid to expand the extruded organic functional group colloid fluid, and rapidly shaping the expanded organic functional group colloid to form hollow spherical microparticles by setting the extrusion end to be a low-temperature environment.
7. A preparation device used for the preparation method of any one of claims 1 to 6, characterized by comprising a shell (1) and a centrifugal stirring device (2) installed in the shell (1), wherein the bottom of the centrifugal stirring device (2) is provided with an extrusion molding device (3), the extrusion end of the extrusion molding device (3) is provided with a temperature control device (4), and the low-temperature control device (4) is used for matching with the extrusion molding device (3) to extrude the product input by the centrifugal stirring device (2) into hollow spherical particles.
8. A preparation device according to claim 7, characterized in that a main cavity (101) and a transfer cavity (102) are arranged inside the housing (1), an opening and closing valve is arranged at the joint of the main cavity (101) and the transfer cavity (102), the centrifugal stirring device (2) is arranged in the main cavity (101), and the extrusion molding device (3) is arranged in the transfer cavity (102);
the extrusion molding device (3) comprises a mesh pipe (301) connected to the bottom of the transfer cavity (102), extrusion molding holes (302) are distributed on the surface of the mesh pipe (301), a main gas pipe (303) is arranged on the axis of the mesh pipe (301), a plurality of gas distribution pipes (304) are connected to the main gas pipe (303), an exhaust head (305) is arranged at the tail end of each gas distribution pipe (304) extending to the corresponding extrusion molding hole (302), a sliding shovel pipe (306) is sleeved on the mesh pipe (301), and the sliding shovel pipe (306) is used for cutting off materials extruded from the extrusion molding holes (302) in an up-and-down sliding mode;
the temperature control device (4) is used for providing a low-temperature environment for the space in the shell (1) where the mesh pipe (301) is located and providing a high-temperature and low-temperature alternative control environment for the main cavity (101).
9. A preparation device according to claim 8, characterized in that a squeezing device (5) is arranged between the centrifugal stirring device (2) and the inner wall of the main cavity (101), the squeezing device (5) provides a power source for the sliding shovel tube (306) to slide up and down by connecting the sliding shovel tube (306), and the squeezing device (5) is used for changing the stacking height of the material in the main cavity (101) in the axial direction when the centrifugal stirring device (5) makes centrifugal motion.
10. A preparation device according to claim 9, characterized in that said centrifugal stirring device (2) comprises a cylindrical barrel (201) mounted inside said main cavity (101), a rotating shaft (202) axially arranged inside said cylindrical barrel (201), and a driving motor which drives the cylindrical barrel (201) to rotate by driving the rotating shaft (202), a guide knife groove (203) fixedly connected with the cylindrical barrel body (201) is arranged on the shaft body of the rotating shaft (202) positioned in the cylindrical barrel body (201), a stirring knife body (204) is arranged on the guide knife groove (203), the stirring cutter body (204) is connected to the rotating shaft (202) through an elastic mechanism (6) arranged on the guide cutter groove (203), and an opening for the stirring cutter body (204) to extend out of the cylindrical barrel (201) is formed in the cylindrical barrel (201) opposite to the guide cutter groove (203);
the end part of the stirring cutter body (204) extending out of the cylindrical barrel body (201) is fixedly connected with a tangent plate (205) with the same radian as the inner wall of the main cavity body (101).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113231104A (en) * | 2021-05-31 | 2021-08-10 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
| CN113563895A (en) * | 2021-07-27 | 2021-10-29 | 华东理工大学 | Heavy metal compound contaminated soil remediation agent and preparation method and application thereof |
| CN115634659A (en) * | 2022-10-31 | 2023-01-24 | 生态环境部南京环境科学研究所 | Soil remediation agent based on modified nano zero-valent iron and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195758A (en) * | 2015-08-27 | 2015-12-30 | 太原理工大学 | Preparation method and application of nano zero-valence iron and copper double-metal particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195758A (en) * | 2015-08-27 | 2015-12-30 | 太原理工大学 | Preparation method and application of nano zero-valence iron and copper double-metal particles |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113231104A (en) * | 2021-05-31 | 2021-08-10 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
| CN113231104B (en) * | 2021-05-31 | 2022-06-14 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
| CN113563895A (en) * | 2021-07-27 | 2021-10-29 | 华东理工大学 | Heavy metal compound contaminated soil remediation agent and preparation method and application thereof |
| CN113563895B (en) * | 2021-07-27 | 2022-04-01 | 华东理工大学 | Heavy metal compound contaminated soil remediation agent and preparation method and application thereof |
| CN115634659A (en) * | 2022-10-31 | 2023-01-24 | 生态环境部南京环境科学研究所 | Soil remediation agent based on modified nano zero-valent iron and preparation method thereof |
| CN115634659B (en) * | 2022-10-31 | 2023-06-23 | 生态环境部南京环境科学研究所 | Soil restoration agent based on modified nano zero-valent iron and preparation method thereof |
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