CN108247079B - Method for large-scale continuous preparation of nano zero-valent metal material - Google Patents
Method for large-scale continuous preparation of nano zero-valent metal material Download PDFInfo
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- CN108247079B CN108247079B CN201810115054.0A CN201810115054A CN108247079B CN 108247079 B CN108247079 B CN 108247079B CN 201810115054 A CN201810115054 A CN 201810115054A CN 108247079 B CN108247079 B CN 108247079B
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- B22—CASTING; POWDER METALLURGY
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention relates to preparation of a nano material, and particularly discloses a method for continuously preparing a nano zero-valent metal material in a large scale, which comprises the following steps: (1) soaking biomass adsorption particles in a metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml for contact, filtering, separating and washing, and adding water according to a solid-to-liquid ratio of 1:1-50g/ml for size mixing to form a suspension, wherein the suspension is used as a material A; (2) preparing 0.1-1mol/L sodium borohydride aqueous solution as material B; (3) in an auger type screw mixer, A, B materials were mixed according to a volume flow ratio of 1:1-5, mixing and contacting in an auger type spiral mixer to complete reduction reaction, and quickly washing the output material to remove residual reagent to obtain the nano zero-valent metal loaded composite material. The method solves the technical problems of difficult solid-liquid separation, difficult washing and the like in the large-scale preparation of the nanometer zero-valent metal, such as easy air oxidation of the nanometer zero-valent metal, and provides a technical approach for preparing the nanometer zero-valent metal material in an engineered large-scale manner.
Description
Technical Field
The invention relates to preparation of a nano material, in particular to a method for continuously preparing a nano zero-valent metal material in a large scale.
Background
Nanometer zero-valent iron, nanometer zero-valent nickel, nanometer zero-valent copper, nanometer zero-valent silver, nanometer zero-valent iron nickel, nanometer zero-valent iron copper, nanometer zero-valent iron nickel copper, nanometer zero-valent iron silver, nanometer zero-valent iron nickel silver copper and other nanometer metal materials with one or more components are widely concerned in the fields of environment purification and restoration, sterilization and disinfection, catalytic degradation, wet metallurgy and the like. Taking the nano zero-valent iron as an example, the nano zero-valent iron has been widely paid attention to in 1997, and has been tried and explored in the aspects of heavy metal wastewater resource treatment, degradation and detoxification of residual organochlorine pesticides in water and soil, deep decomposition of oxidative toxic substances and the like, and good effects and practical prospects are obtained.
The nanometer zero-valent metal has fine granularity and large specific surface area, is easy to generate agglomeration and oxidation phenomena in the preparation, storage, transportation and use processes, and is difficult to effectively realize solid-liquid separation and washing in the preparation process, thereby seriously influencing the chemical activity of the nanometer zero-valent metal. Therefore, to avoid or reduce the occurrence of these problems, it is often prepared on site, for example, liu yi source et al uses a reactor with 1 stage of different reaction space to prepare nano zero-valent iron material, uses two pumps to rapidly pump the solution of iron salt and the solution of sodium borohydride reducing agent into the reactor, so that the nano zero-valent iron is rapidly reduced by contact and rapidly discharged (liu yi source, thunberg, wangwei, cun bright dragon. environmental engineering report, 2014(8) 10: 4233-. The research provides a good prototype design for the scale preparation of the nano zero-valent iron, but has outstanding problems, for example, the soluble iron salt is directly adopted, the aqueous solution of the soluble iron salt is often strongly acidic due to the hydrolysis of the ferric iron, which brings troubles to the effective utilization rate of a strong alkaline reducing agent such as sodium borohydride, and if the pH value of the ferric ion solution is adjusted to be higher than 2, the ferric ion can be immediately precipitated, which is not favorable for being quickly, uniformly and fully reduced into the nano zero-valent iron. In such a reduction reaction, the time of the contact reaction between the reaction reagents is short, the utilization efficiency of the reducing agent is not high, and the content and purity of the metallic iron component are not necessarily high, which affects the activity and use efficiency of the reduced iron powder.
In summary, the conventional nanoscale zero-valent iron has several outstanding problems in the preparation and production process, such as: the problems of agglomeration, quick and uniform mixing reaction, difficult solid-liquid separation and washing, easy oxidation by air and the like all bring great challenges and restrictive technical bottlenecks to the engineering scale-up preparation of nano zero-valent iron and other nano zero-valent metal powder. Although ordinary atomized iron powder or carbonyl iron powder can be used to replace part of the nano zero-valent iron to achieve the same effect, the particle size of the iron powder is more in the order of micron to tens of microns, and the reaction activity of the iron powder is several times lower than that of the nano zero-valent iron, so the usage amount of the iron powder is greatly increased, the raw material cost is increased, and serious secondary iron pollution can be caused. Therefore, the activity safety of the nano zero-valent iron in the synthesis, storage, transportation and application processes is strictly controlled, and the method is very important for efficiently and greenly applying and playing the advantages of the nano zero-valent iron powder.
In order to realize the large-scale preparation of the nano zero-valent iron and iron-based series composite multi-element metal nano material, a new method for preparing the nano zero-valent metal material with excellent reduction activity by more sufficient contact reaction, convenience, easiness and continuity needs to be developed, and a sufficient new functional material with excellent performance is provided for the large-scale application of the nano zero-valent metal material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a floatable nano zero-valent iron material and a preparation method thereof.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for large-scale continuous preparation of nano zero-valent metal material, comprising the following steps:
(1) soaking biomass adsorption particles in a metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml for contact, filtering, separating and washing, and adding water according to a solid-to-liquid ratio of 1:1-50g/ml for size mixing to form a suspension, wherein the suspension is used as a material A;
(2) preparing 0.1-1mol/L sodium borohydride aqueous solution as material B;
(3) in an auger-type screw mixer (long-tube reactor with a spiral screw shaft rotating to have a mechanism for mixing and continuously propelling materials to separate them into a plurality of relatively independent reaction small spaces), A, B materials were mixed in a volume flow rate ratio of 1:1-5, mixing and contacting in an auger type spiral mixer to complete reduction reaction, and quickly washing the output material to remove residual reagent to obtain the nano zero-valent metal material.
Further, in the step (1), the metal salt ion solution may be one or more.
When the metal salt ion solution is various, the steps are carried out:
firstly, soaking biomass adsorption particles in a first metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml, and filtering, separating and washing to obtain first metal ion-loaded biomass adsorption particles;
soaking and contacting the biomass adsorption particles loaded with the first metal ions with a second metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml, filtering, separating and washing to obtain the biomass adsorption particles loaded with the first metal ions and the second metal ions simultaneously;
and so on;
until all needed metal ions are loaded, the biomass adsorption particles are mixed according to a solid-liquid ratio of 1: adding water into 1-20g/ml to be slurried into suspension to be used as material A.
Preferably, the metal salt ion solution is ferric salt ion solution, soluble silver, nickel and copper salt ion solution.
More preferably, when the metal salt ion solution is a ferric salt ion solution, the initial pH of the solution is 1.5-4.5, and the concentration of iron ions is 0.005-1 mol/L; when the metal salt ion solution is soluble silver, nickel and copper salt ion solution, the initial pH of the solution is 3.2-7.0, and the concentration of metal ions is 0.001-1 mol/L.
Further, the preparation method of the biomass adsorption particles comprises the following steps: crushing the biomass material, sieving with a 40-100 mesh sieve to obtain powder particles, placing in water, stirring and infiltrating, collecting the particles floating on the water surface, adding into an alkaline aqueous solution with the pH value of more than 9, stirring, and collecting the particles to obtain the biomass material. In order to ensure good modification effect, soluble alkali reagents are preferred, such as alkali metal hydroxide salt or carbonate, alkaline earth metal hydroxide salt or bicarbonate or carbonate, ammonia water, heated urea and other alkali reagents can be selected, and the alkali reagents are the modification reagents with good modification effect and can be used alone or in combination.
Preferably, the biomass material is naturally rich in functional groups-COOH, and/or-phenolic hydroxyl, and/or-SH, and/or-NH2The porous biomass raw material of (2) is preferably a biomass raw material having a porosity of 60% or more and a relatively developed porous structure as a preferred biomass-adsorbing particulate material.
Further preferably, the preparation method of the biomass adsorption particles comprises the following steps: weighing biomass waste, crushing, screening through 40-100 meshes, throwing into water, stirring and infiltrating for 24 hours; the biomass waste particles floating on the water surface are collected and can be used as biomass adsorption particles for load modification.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The beneficial effects of the invention are at least reflected in the following points:
1. the invention solves the problems of short mixing contact time, low utilization rate of reaction reagents and easy agglomeration and activity reduction of nano metal powder products in the traditional nano zero-valent iron reaction preparation. Thereby obviously improving the utilization efficiency of the raw material reagent and obviously improving the dispersibility and the reduction activity of the nano metal. The technology disclosed by the invention skillfully utilizes the adsorption capacity of the biomass material on iron and various metal ions which can form a multi-component composite catalytic effect with the iron, such as copper, nickel, silver and the like, so as to realize the adsorption loading of the iron, copper, nickel, silver and the like in advance, and avoid the problem that in the reduction stage, soluble iron salt is directly adopted as an iron source to present acidity and consume expensive reducing agent, such as sodium borohydride. The segmented treatment technology disclosed by the invention can also accurately control the content of metal ions loaded on the biomass material, remove the hydrolysis acid production of ferric iron, provide a powerful guarantee for the subsequent efficient utilization of a sodium borohydride reagent in the metal reduction process, and obviously save and improve the utilization efficiency of a reduction reagent. In addition, the technology disclosed by the invention optimizes the reduction reaction conditions by changing the form of the supported metal ion source, provides effective precaution measures for the dispersibility and agglomeration avoidance of the nano zero-valent iron and the iron-based multi-element composite metal nano material, and avoids the difficult problem that the reduction activity is reduced due to the agglomeration growth of metal particles when the soluble ferric iron and other soluble metal salts are directly used as iron sources for reduction in the prior art.
2. The invention solves the bottleneck problems that the traditional reaction preparation method of the nano zero-valent iron is not uniform in mixing, is not rapid and obviously limits the difficulty in ensuring stable and reliable engineering amplification during large-scale production expansion. The mixing contact process is obviously strengthened, the contact time of the reduction reaction of the nano metal is obviously prolonged, the sufficiency of the reduction is ensured, and the full and uniform mixing and the yield are ensured not to be limited when the large-scale expanded continuous preparation is carried out. In the traditional reduction preparation of the nano zero-valent iron, two reaction reagents are mixed and added into a common reactor, the yield is influenced if the retention time is too long, and the reaction is insufficient if the retention time is too short, so that the yield of metal materials such as the nano zero-valent iron prepared by the reduction reaction and the utilization rate of the reagents are obviously influenced. The technology disclosed by the invention adopts a forward-push reactor which automatically rotates, mixes and continuously cuts and separates spaces in multiple stages, so that the contact reaction of reaction materials has enough time and opportunity to generate reduction reaction, and the whole process is continuously conveyed and strongly mixed for reaction, so that the reaction time is longer than that of the traditional reactor, the mixing is more uniform, and the back mixing phenomenon does not exist, the space of the whole reactor is closed, thereby ensuring that the high-activity nano-scale metal powder material of a reaction product cannot be oxidized by air, therefore, the problem of oxidation failure of nano zero-valent iron caused by excessive contact with air can be effectively avoided through industrial equipment (auger) which is closed and provided with a movable part and cuts a tubular reactor into a plurality of reaction spaces with fixed volumes, and the reaction materials can be ensured to be fully and powerfully uniformly mixed and continuously reacted, therefore, the yield can be easily enlarged, and the sufficient reaction rate of reactants can be ensured.
3. The invention solves the problems of difficult solid-liquid separation, slow separation, difficult washing, slow washing, water waste in washing, high risk probability of oxidation caused by long time of exposing the nano powder to the air and the like in the wet preparation process of the metal materials such as the nano zero-valent iron and the like due to fine granularity. The traditional metal materials such as the nanometer zero-valent iron and the like are high in preparation speed and fine in granularity, are difficult to separate and remove from water and are difficult to wash clean, so that much inconvenience is brought to subsequent use, and even research and public system reports on solid-liquid separation and washing problems of the nanometer zero-valent iron are not developed. The method disclosed by the invention can conveniently solve the problem of difficult washing, and because the biomass material is used as the load matrix of the metal materials such as the nano zero-valent iron and the like, the particle size of the biomass material is in the millimeter or even centimeter level, the dehydration separation and washing of the coarse particle material are not problems and can be easily solved, so that the method is more practical and efficient compared with the traditional powder separation and washing under the size of the pure naked nano zero-valent metal material. The unit operations of solid-liquid separation and repeated washing are not at all a problem for ordinary large-size powder materials, but are very difficult for nano-size metal powder materials, and the nano-metals are easily oxidized by air, so the operation time of the solid-liquid separation and washing process is required to be as short as possible. As the nano metal prepared by the method is loaded on a millimeter-level or even centimeter-level large-size particle carrier, the rapid solid-liquid separation and washing of the large-size material are not problems, so that the output of a dozens to hundreds of kilograms of nano zero-valent iron and nickel-copper-silver compounded iron-based nano material product every day can be easily realized, and the technical selection of industrial preparation is provided for realizing the large-scale production of the nano zero-valent iron and nano iron-based copper-nickel-silver compounded material.
In summary, the technology disclosed by the invention solves a plurality of technical problems encountered in the large-scale preparation of the nano metal powder of traditional nano zero-valent iron and other related nano zero-valent metals such as copper, nickel, silver and the like which are easily oxidized by air, specifically comprises the problems of easy agglomeration and air oxidation of the nano metal powder material, the problems of sufficient, uniform, rapid, stable and continuous mixing of large-volume flow reaction materials, and the problems of difficult solid-liquid separation and difficult washing of the nano metal powder, and provides a technical approach for preparing the nano zero-valent metal powder material in an engineered large scale.
Drawings
FIG. 1 is a schematic diagram of the structure of a horizontal centrifugal machine (i.e., an auger-type screw mixer) used in the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Weighing garlic waste, crushing, screening through 40 meshes, throwing into water, stirring and soaking for 24 hours; collecting garlic waste particles floating on the water surface, adding a mixed solution of magnesium hydroxide and sodium hydroxide to adjust the pH value to be 13, keeping stirring for 12 hours, and collecting the particles;
preparing 50 liters of ferric chloride ion solution with the concentration of 0.01M, wherein the initial pH is 2.5, adding 2000 grams (dry basis) of the garlic waste particles (adsorbent) prepared in the previous step, stirring and reacting for 30 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 100 liters of water to prepare uniform slurry;
preparing 100 liters of 0.1M sodium borohydride solution, respectively pumping the sodium borohydride solution and the garlic waste particle slurry adsorbed and loaded with iron ions into an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the garlic waste particle slurry in a spaced isolation space, controlling the rotating speed of a screw propeller of an auger, allowing the sodium borohydride solution and the garlic waste particle slurry to stay in the auger reactor for 10 minutes, discharging the mixture from the other end, allowing the mixture to fall into a 1-cubic stirring reaction tank, stirring and cleaning the mixture for 5 minutes, fishing out the particle materials by using a screen, putting the particle materials into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron composite material.
Example 2
Weighing garlic waste, crushing, screening through 80 meshes, throwing into water, stirring and soaking for 12 hours; collecting garlic waste particles floating on the water surface, adding a mixed solution of calcium hydroxide and sodium hydroxide to adjust the pH value to 11, keeping stirring for 24 hours, and collecting the particles;
preparing 100 liters of ferric chloride ion solution with the concentration of 0.02M, wherein the initial pH is 2.5, adding 10 kilograms (measured on a dry basis) of garlic waste particles (adsorbent) prepared in the previous step, stirring and reacting for 30 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 500 liters of water to prepare uniform slurry;
preparing 500 liters of 0.2M sodium borohydride solution, respectively pumping the sodium borohydride solution and the garlic waste particle slurry adsorbed and loaded with iron ions into an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the garlic waste particle slurry in a spaced isolation space, controlling the rotating speed of a screw propeller of an auger, staying the sodium borohydride solution and the garlic waste particle slurry in the auger reactor for 15 minutes, discharging the mixture from the other end, falling into a stirring reaction tank with the volume of 1 cube, stirring and cleaning for 5 minutes, fishing out the particle materials by using a screen, filling the particle materials into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron composite material.
Example 3
Weighing garlic waste, crushing, screening through 80 meshes, throwing into water, stirring and soaking for 12 hours; collecting garlic waste particles floating on the water surface, adding a mixed solution of calcium hydroxide and sodium hydroxide to adjust the pH value to 11, keeping stirring for 24 hours, and collecting the particles;
preparing 200 liters of nickel chloride ion solution with the concentration of 0.05M, wherein the initial pH is 6.5, adding 10 kilograms (measured on a dry basis) of garlic waste particles (adsorbent) prepared in the previous step, stirring and reacting for 30 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 100 liters of water to prepare uniform slurry;
preparing 100 liters of 0.05M sodium borohydride solution, respectively pumping the sodium borohydride solution and the garlic waste particle slurry adsorbed and loaded with iron ions into an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the garlic waste particle slurry in a spaced isolation space, controlling the rotating speed of a screw propeller of an auger, staying the sodium borohydride solution and the garlic waste particle slurry in the auger reactor for 15 minutes, discharging the mixture from the other end, falling into a stirring reaction tank with the volume of 1 cube, stirring and cleaning for 5 minutes, fishing out the particle materials by using a screen, filling the particle materials into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent nickel composite material.
Example 4
Weighing orange waste, crushing, screening through 80 meshes, throwing into water, stirring and soaking for 12 hours; collecting waste particles, adding a mixed solution of sodium hydroxide and ammonia water to adjust the pH value to 12, keeping stirring for 24 hours, and collecting the particles;
preparing 100 liters of ferric chloride ion solution with the concentration of 0.12M, wherein the initial pH is 2.0, adding 8 kilograms (measured on a dry basis) of the citrus waste particles (adsorbent) prepared in the previous step, stirring and reacting for 560 minutes, filtering the adsorbent, and washing with distilled water for 3 times to obtain the citrus waste particles loaded with the ferric ions.
Preparing 100 liters of nickel chloride ion solution with the concentration of 0.05M, wherein the initial pH is 6.5, adding 8 kilograms (measured on a dry basis) of the citrus waste particles (adsorbent) prepared in the previous step, stirring and reacting for 600 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 100 liters of water to prepare uniform slurry, so as to obtain the citrus waste particle slurry loaded with iron and nickel ions.
Preparing 100 liters of 0.15M sodium borohydride solution, respectively pumping the sodium borohydride solution and the citrus waste particle slurry adsorbed and loaded with iron and nickel ions into an auger reactor with the total reaction space of 500 liters by using a liquid delivery pump, mixing, contacting and reducing the sodium borohydride solution and the citrus waste particle slurry in an interval isolation space, controlling the rotating speed of a screw propeller of the auger, allowing the sodium borohydride solution and the citrus waste particle slurry to stay in the auger reactor for 15 minutes, discharging the mixture from the other end, allowing the mixture to fall into a 1-cubic stirring reaction tank, stirring and cleaning the mixture for 5 minutes, fishing out the particle materials by using a screen, putting the particle materials into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron-nickel composite material.
Example 5
Weighing mangosteen waste, crushing, screening through 100 meshes, throwing into water, stirring and soaking for 12 hours; collecting waste particles, adding sodium hydroxide for mixing and potassium hydroxide solution for adjusting the pH value to 12, keeping stirring for 24 hours, and collecting the particles;
preparing 100 liters of ferric chloride ion solution with the concentration of 0.20M, wherein the initial pH is 2.0, adding 10 kg (measured on a dry basis) of the mangosteen waste particles (adsorbent) prepared in the previous step, stirring and reacting for 360 minutes, filtering the adsorbent, and washing with distilled water for 3 times to obtain the mangosteen waste particles loaded with the ferric ions.
Preparing 100 liters of silver nitrate ion solution with the concentration of 0.005M, wherein the initial pH is 5.5, adding 8 kilograms (measured on a dry basis) of mangosteen waste particles (adsorbent) prepared in the previous step, stirring and reacting for 600 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 100 liters of water to prepare uniform slurry, namely the mangosteen waste particle slurry loaded with iron and silver ions.
Preparing 100 liters of 0.15M sodium borohydride solution, respectively pumping the sodium borohydride solution and the mangosteen waste particle slurry adsorbed and loaded with iron and silver ions into an auger reactor with the total reaction space of 500 liters by using a liquid delivery pump, mixing, contacting and reducing the sodium borohydride solution and the mangosteen waste particle slurry in a spaced isolation space, controlling the rotating speed of a screw propeller of the auger, allowing the sodium borohydride solution and the slurry to stay in the auger reactor for 15 minutes, discharging the mixture from the other end, allowing the mixture to fall into a 1 cubic stirring reaction tank, stirring and cleaning the mixture for 5 minutes, fishing out the particle material by using a screen, filling the particle material into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron-silver composite material.
Example 6
Weighing shaddock peel waste, crushing, screening through 100 meshes, throwing into water, stirring and infiltrating for 12 hours; collecting waste particles, adding sodium hydroxide for mixing and lithium hydroxide solution to adjust the pH value to 11, keeping stirring for 24 hours, and collecting the particles;
preparing 100 liters of ferric chloride ion solution with the concentration of 0.10M, wherein the initial pH is 2.0, adding 10 kg (dry basis measurement) of the shaddock peel waste particles (adsorbent) prepared in the previous step, stirring and reacting for 360 minutes, filtering the adsorbent, and washing with distilled water for 3 times to obtain the shaddock peel waste particles loaded with the ferric ions.
100 liters of copper nitrate ion solution with the concentration of 0.05M is prepared, the initial pH is 5.5, 10 kg (dry basis measurement) of the shaddock peel waste particles (adsorbent) prepared in the previous step are added, the stirring reaction is carried out for 600 minutes, then the adsorbent is filtered, and the shaddock peel waste particles loaded with iron and copper ions are obtained after the adsorbent is washed for 3 times by distilled water.
Preparing 100 liters of silver nitrate ion solution with the concentration of 0.005M, wherein the initial pH is 5.5, adding 10 kilograms (measured on a dry basis) of the shaddock peel waste particles (adsorbent) prepared in the previous step, stirring and reacting for 600 minutes, filtering the adsorbent, washing for 3 times by using distilled water, and adding 100 liters of water to prepare uniform slurry, namely the shaddock peel waste particle slurry loaded with iron, copper and silver ions.
Preparing 100 liters of 0.15M sodium borohydride solution, respectively pumping the sodium borohydride solution and shaddock peel waste particle slurry adsorbed and loaded with iron, copper and silver ions into an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the shaddock peel waste particle slurry in a separated isolated space, controlling the rotating speed of a screw propeller of the auger, staying the sodium borohydride solution and the auger reactor for 15 minutes, discharging the sodium borohydride solution and the auger reactor from the other end, falling into a 1 cubic stirring reaction tank, stirring and cleaning for 5 minutes, fishing out the particle materials by using a screen, filling the particles into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron, copper and silver composite material.
Example 7
Weighing beer fermentation spent grain waste, crushing, screening and passing through 100 meshes, throwing into water, stirring and infiltrating for 12 hours; collecting waste particles, adding a sodium hydroxide solution to adjust the pH value of the waste particles to 11, keeping stirring for 24 hours, and collecting the particles;
100 liters of iron chloride ion solution with the concentration of 0.10M is prepared, the initial pH is 2.0, 10 kilograms (dry basis measurement) of the beer fermentation spent grain waste particles (adsorbent) prepared in the previous step are put into the solution, the mixture is stirred and reacts for 360 minutes, the adsorbent is filtered, and the beer fermentation spent grain waste particles loaded with iron ions are obtained after being washed for 3 times by distilled water.
100 liters of copper nitrate ion solution with the concentration of 0.05M is prepared, the initial pH is 5.5, 10 kilograms (dry basis measurement) of the beer fermentation spent grain waste particles (adsorbent) prepared in the previous step are added, the mixture is stirred and reacts for 600 minutes, then the adsorbent is filtered, and the beer fermentation spent grain waste particles loaded with iron and copper ions are obtained after being washed for 3 times by distilled water.
100 liters of silver nitrate ion solution with the concentration of 0.001M is prepared, the initial pH is 5.5, 10 kilograms (measured on a dry basis) of the beer fermentation spent grain waste particles (adsorbent) prepared in the previous step are put into the solution, the mixture is stirred and reacts for 600 minutes, then the adsorbent is filtered, and after the mixture is washed for 3 times by distilled water, 100 liters of water is added to prepare uniform slurry, namely the beer fermentation spent grain waste particle slurry loaded with iron, copper and silver ions.
Preparing 100 liters of 0.15M sodium borohydride solution, respectively pumping the sodium borohydride solution and beer fermentation spent grain waste particle slurry adsorbed and loaded with iron, copper and silver ions into an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the beer fermentation spent grain waste particle slurry in the spaced isolated space, controlling the rotating speed of a screw propeller of the auger, allowing the sodium borohydride solution and the slurry to stay in the auger reactor for 15 minutes, discharging the sodium borohydride solution from the other end, allowing the sodium borohydride solution and the slurry to fall into a 1 cubic stirring reaction tank, stirring and cleaning the mixture for 5 minutes, fishing out the particle materials by using a screen, filling the particles into a plastic film bag, and carrying out plastic package to obtain the nano zero-valent iron, copper, nickel and silver composite.
Experimental example 1
The nano zero-valent iron composite material loaded with the garlic waste particles prepared in the example 1 is mechanically stirred and washed for 1 time by using deionized water with the volume number of 3 times, and then is filtered by using a 80-mesh sieve, the filtering speed is improved by at least 100 times (compared with the volume of clean water filtered in the same time) compared with that of nano zero-valent iron suspension obtained by conventionally adopting the contact reduction of ferric chloride salt and sodium borohydride solution by using a filter membrane with the average pore size of 0.1 mu m, the turbidity of the filtrate is lower by more than 10 times than that of the traditional method, and the concentrations of borate ions and sodium ions remained in the filtrate for 1 time are also higher by more than 3 times than that of the traditional method (namely more soluble impurity ions are washed and transferred into the filtrate). Therefore, the preparation method of the supported nano metal material disclosed by the invention obviously improves the solid-liquid separation effect and the washing impurity removal effect of the material, and obviously improves the purity of a material product under the same operation condition. The effect of the technology of the invention on the production efficiency of the nano zero-valent metal material is obviously improved.
Experimental example 2
The nano zero-valent iron composite material loaded by the garlic waste particles in the example 1 is subjected to contact reduction with a conventional ferric chloride salt and sodium borohydride solution to obtain nano zero-valent iron, two forms of zero-valent iron materials are weighed according to the amount of iron, the two forms of zero-valent iron materials are respectively stirred and reacted with an atrazine solution with the initial pH of 3.0 and the initial concentration of 10mg/L for 30 hours according to the weight/volume ratio of 1:100(g/ml), and the concentrations of the residual atrazine are respectively 1.3mg/L and 3.4mg/L through sampling detection. Therefore, the effect of the loaded nano zero-valent iron on degrading the atrazine pesticide is obviously better than that of the nano zero-valent iron without any loading body. The method also shows that the nano zero-valent metal material prepared by the method has obvious improvement effect on improving and maintaining the reaction activity.
It should be understood that the technical solutions of the above embodiments, in which the amounts of reagents or raw materials used are proportionally increased or decreased, are substantially the same as those of the above embodiments.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (2)
1. A method for large-scale continuous preparation of a nanometer zero-valent metal material is characterized by comprising the following steps:
(1) soaking biomass adsorption particles in a metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml for contact, filtering, separating and washing, and adding water according to a solid-to-liquid ratio of 1:1-50g/ml for size mixing to form a suspension, wherein the suspension is used as a material A;
in the step (1), the metal salt ion solution may be one or more;
when the metal salt ion solution is various, the steps are carried out:
firstly, soaking biomass adsorption particles in a first metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml, and filtering, separating and washing to obtain first metal ion-loaded biomass adsorption particles;
soaking and contacting the biomass adsorption particles loaded with the first metal ions with a second metal salt ion solution according to a solid-to-liquid ratio of 1:1-50g/ml, filtering, separating and washing to obtain the biomass adsorption particles loaded with the first metal ions and the second metal ions simultaneously;
and so on;
until all needed metal ions are loaded, the biomass adsorption particles are mixed according to a solid-liquid ratio of 1: adding water in 1-50g/ml to prepare suspension as material A;
the preparation method of the biomass adsorption particles comprises the following steps: crushing the biomass material, sieving with a 40-100 mesh sieve to obtain powder particles, placing the powder particles in water, stirring and infiltrating, adding the powder particles into an alkaline aqueous solution with the pH value of more than 9, stirring, and collecting the particles to obtain the biomass material; the biomass material is naturally rich in functional groups of-COOH, and/or-phenolic hydroxyl, and/or-SH, and/or-NH2The porous biomass feedstock of (a);
(2) preparing 0.1-1mol/L sodium borohydride aqueous solution as material B;
(3) in an auger type screw mixer, A, B materials were mixed according to a volume flow ratio of 1:1-5, mixing and adding, carrying out mixing and enhanced contact in an auger type spiral mixer to complete reduction reaction, and quickly washing the output material to remove residual reagent to obtain a nano zero-valent metal material;
the auger type spiral mixer is a long tube type reactor with a spiral shaft, wherein the spiral rotary shaft rotates and is provided with a mechanical device which mixes materials and separates the materials into a plurality of relatively independent small reaction spaces in the continuous forward pushing process;
the metal salt ion solution is ferric iron salt ion solution or soluble silver, nickel and copper salt ion solution;
when the metal salt ion solution is a ferric salt ion solution, the initial pH of the solution is 1.5-4.5, and the concentration of iron ions is 0.005-1 mol/L;
when the metal salt ion solution is soluble silver, nickel and copper salt ion solution, the initial pH of the solution is 3.2-7.0, and the concentration of the metal ions is 0.001-1 mol/L.
2. The method of claim 1,
preparing 50 liters of ferric chloride solution with the concentration of 0.01M, wherein the initial pH is 2.5, adding 2000 grams of biomass adsorption particles in a dry basis, stirring for reaction for 30 minutes, filtering, washing with distilled water for 3 times, and adding 100 liters of water to prepare uniform slurry which is loaded with metal ions in an adsorption manner;
preparing 100 liters of 0.1M sodium borohydride solution, respectively pumping the sodium borohydride solution and the slurry into a charging chamber of an auger reactor with the total reaction space of 500 liters by using a liquid conveying pump, mixing, contacting and reducing the sodium borohydride solution and the slurry in a separated isolated space, controlling the rotating speed of a screw propeller of an auger, allowing the sodium borohydride solution and the slurry to stay in the auger reactor for 10 minutes, discharging the sodium borohydride solution and the slurry from the other end, allowing the sodium borohydride solution and the slurry to fall into a stirring reaction tank with the volume of 1 cubic meter, stirring and cleaning the mixture for 5 minutes, fishing out the granular materials by using a screen, filling the granular materials into a plastic film bag, and carrying out plastic packaging to obtain the nano zero-valent iron.
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