WO2017088216A1 - Magnetic solid polyamine adsorbent particle material, preparation method and application thereof - Google Patents

Abstract

A magnetic solid polyamine adsorbent particle material having a surface coated with a polyamine group, having a particle diameter range of 0.5-500.0 µm, having a core-shell structure having a plurality of inorganic/organic shell layers, and a carbon-nitrogen bond-linked polyamine adsorption group for stabilizing the structure. The preparation method thereof mainly comprises the following basic steps: (1) preparing an inorganic substance coating layer; (2) surface double bond modification; (3) preparing an organic substance coating layer; and (4) preparing a magnetic solid polyamine adsorbent particle material. The adsorbent particle material can selectively chemically adsorb a heavy metal substance within a wide pH range, and can be recycled and reused.

Description

Magnetic solid polyamino adsorbent particle material, preparation method and application thereof Technical field

The invention relates to a magnetic solid polyamino sorbent particle material, a preparation method and application thereof, and belongs to the field of new materials and resources and environment.

Background technique

The current problem of managing heavy metal pollution has become an environmental problem that needs to be solved globally. Among them, water pollution mainly refers to the pollution of heavy metal pollutants, including cadmium, lead, mercury, chromium, arsenic, etc., from water bodies (including rivers, lakes, reservoirs, marine and industrial water, discharged water and drinking water). Mainly industrial wastewater, such as wastewater from concentrating plants, electroplating plants, steel plants, etc.

In addition to the heavy metals contained in the heavy metals in the soil, the heavy metals in the soil are contaminated to cause heavy metals to enter the soil. The heavy metal pollution in the soil mainly comes from three aspects: the settlement of heavy metals in the atmosphere, for example, exhaust gas from industrial production, tail gas from leaded vehicles, etc., entering the soil through natural sedimentation and rain-sinking; irrigation with heavy metal-containing sewage, resulting in soil heavy Cd Increase in the content of As, Cu, etc.; in addition, plastic film for daily use and fertilizers for agricultural applications also cause soil pollution.

At present, there are four main types of heavy metal pollution control methods. In addition to traditional chemical methods, physical methods, and biological management methods, the “environmental material method” that uses the special structure and properties of environmental materials to control soil heavy metal pollution is a type of soil heavy metal that is developing. Pollution control methods have shown advantages. In particular, the new magnetic solid chelating agent granular material technology can not only selectively adsorb heavy metal substances in a multi-phase system, but also utilize the magnetic properties of the material itself to separate it from the multi-phase system by a magnet to achieve the purpose of removing heavy metals.

Similar to soil multiphase systems, other issues such as industrial waste, agricultural and livestock waste, and urban waste are widely removed from heavy metal pollution. At the same time, there are also a large number of heavy metals, valuable metals, and precious metals in other resources and environmental materials. It is necessary to use a new magnetic solid chelating agent material for extraction and recycling.

The applicant has applied for a number of invention patents in the field of new magnetic solid chelating agent materials. In the invention patent CN201210045129, a magnetic expansion adsorption composite material and a preparation method thereof are provided. The composite material is compounded by a magnetic powder, a non-metal mineral powder, a water-soluble ethylenically unsaturated monomer and a crosslinking agent by a polymerization reaction, and has a network structure, has a large adsorption capacity for a heavy metal substance, a simple manufacturing method, and a cost. Low advantage. In the invention patent CN201410080511, a magnetic aminocarboxylate chelate adsorption particulate material and a preparation method thereof are provided, which adopts SiO ₂ particles coated with magnetic material as a core-shell structure, and introduces an amino group on the shell SiO ₂ by surface modification. And obtained by carboxymethylation on an amino group. In the invention patent application 200510062264.4, a magnetic solid organic sulfur adsorbent particulate material containing an organic sulfur adsorption group is provided, and the organic sulfur adsorption group may be a mercapto group, a sulfide group, an ammonia acid group or the like. In the invention patent application 201510010306.X, a magnetic separation separation purification treatment process for removing heavy metal pollution of soil is provided, which is characterized in that it adsorbs and captures heavy metals in the soil by reactive or adsorbing magnetic carrier particle materials. Then magnetic separation and soil separation are carried out, which in turn include: 1 step of preparing soil and preparing mud; 2 step of adsorbing and collecting heavy metal by magnetic carrier; 3 step of magnetic separation; 4 step of material regeneration; 5 step of collecting concentrated metal for centralized treatment . The invention can make up for the deficiencies of existing soil repairing methods by the local soil method, the chemical method, the physical method and the biological method, and has the advantages of simple method, the magnetic carrier particle material can be recycled and recycled, the treatment cost is low, and the beneficiation technology and the beneficiation machine can be utilized. Advantages: It can carry out heavy metal removal and reduction purification of large, medium and small polluted soils. No large amount of sewage (waste) water is produced in the whole process, no secondary pollution or pollution in different places, and heavy metals can be recovered.

In addition, Hu Jianbang and others published the paper "Preparation of Aminated Modified Fe ₃ O ₄ @SiO ₂ Composite Magnetic Materials and Adsorption of Uranium (VI) by Applied Chemistry" in 2012 (12). Surface preparation of surface-aminated modified Fe ₃ O by surface precipitation of ferroferric oxide magnetic nanoparticles by surface modification with tetraethyl orthosilicate (TEOS) and 3-aminopropyltriethoxysilane (APTES) ₄ / SiO ₂ composite particles. Since the amino group is directly introduced by the silylation method, the amount of amino groups grafted on the surface of the particles is too small (the nitrogen content is usually less than 0.05% by weight) and exists in isolation from each other, resulting in low adsorption capacity; meanwhile, the main problem in terms of materials is nanometers. The particle size is too small, and it is easy to strongly adsorb with other solid materials, resulting in poor magnetic responsiveness and difficulty in separating from multiphase systems.

Gong Hongxia et al. published a paper on the adsorption mechanism of tetraethylenepentamine functionalized nano-Fe ₃ O ₄ magnetic polymer materials in the coexistence of Cu(II) and Cr(VI) in the 69 (22) Chemical Journal of 2011. The tetraethylenepentamine functionalized nano Fe is prepared by a copolymerization reaction of methyl methacrylate with glycidyl methacrylate to form a magnetic nanoparticle material having an epoxy group on the surface, and a ring-opening reaction of recurring epoxy groups. ₃ O ₄ magnetic polymer material. The remarkable feature of this method is that the amino group in the tetraethylenepentamine molecule undergoes ring-opening aminolysis reaction with the epoxy group to form a product, but at the same time, (1) the particle size of the material is 30 nm, the characteristics of the nano-sized particles, and (2) nanometers are retained. The outer layer of the magnetic particles is not coated with inorganic substances such as silica, (3) the physical adsorption bond between the organic coating layer and the inorganic core is not conjugated by oleic acid, and (4) the monomer methyl group is polymerized. Four structural defects such as ester bonds in glycidyl acrylate. Due to the presence of the defect (1), it is difficult to apply the material to the solid-liquid suspension (mixing) system, the defect (2) causes the oxidation resistance and acid resistance of the ferroferric oxide to be weak, and the defect (3) leads to the organic coating or The amino group is easy to fall off, and the defect (4) causes the ester bond to undergo hydrolysis reaction and addition substitution reaction under acidic and basic conditions, which limits the application range of the material.

Therefore, materials and methods for the removal (purification) of heavy metal pollution in water, soil and solid-liquid suspension (mixing) systems require new inventions.

The magnetic solid polyamino adsorbent particle material prepared by the invention contains inorganic substances different from the above various inventions The multi-shell core-shell structure and the polyamino-adsorbing group have selective adsorption of valuable metals and heavy metal ions by using 1 polyamino group, and 2 magnetic particle materials have easy to be removed from water bodies and soils by magnets or magnetic separation devices. Separated from solid-liquid suspension system, renewable, low cost, easy to carry out a variety of large, medium and small multi-scale heavy metal pollution removal and purification operations, no large amount of pollution (waste) water production, no secondary pollution or pollution And can recycle heavy metals.

Summary of the invention

The technical problem to be solved by the present invention is to provide a particle diameter of moderate, stable structure, large amino content or large adsorption capacity, resistance to calcium and magnesium ions, and solid-liquid multiphase. A magnetic solid polyaminosorbent particulate material coated with a polyamine group on the surface and a wide pH range.

A magnetic solid polyamino sorbent particle material (referred to as magnetic polyamino granule) coated with a polyamine-based adsorption group, characterized in that the structure is an internal organic-inorganic multi-shell core-shell structure and a peripheral polyamino group The group composition, the polyamino group as its peripheral adsorption group, is linked to the organic-inorganic multi-shell core-shell structure by a carbon-nitrogen bond (CN).

The above magnetic polyamino particles are characterized in that the organic-inorganic multi-shell core-shell structure is composed of a magnetic powder particle core or an agglomerate thereof, an inorganic coating layer, and an organic coating layer. The core of the magnetic powder particles or the agglomerates thereof and the inorganic coating layer are connected by a covalent bond between the inorganic coating layer and the organic coating layer.

The above magnetic polyamino particles are characterized in that a polyamino group is used as a peripheral adsorption group thereof, and is bonded to the inorganic organic multi-shell core-shell structure by a carbon-nitrogen bond (C-N).

The above magnetic polyamino particles are characterized in that the carbon-nitrogen bond (C-N) is a carbon-nitrogen bond in the amide group or a carbon-nitrogen bond in the secondary or tertiary amine.

The above magnetic polyamino particles have a particle diameter ranging from 0.02 to 1000 μm, preferably from 0.5 to 500.0 μm.

The above magnetic polyamino particles, in the inorganic organic multi-shell core-shell structure: the magnetic powder core is selected from magnetite powder or Fe ₃ O ₄ powder, iron powder or other synthetic magnetic powder One or more mixtures of materials having a particle size ranging from 0.01 to 100.0 μm; the inorganic coating layer is usually silica or an oxide of titanium, aluminum or the like. The thickness of the coating layer is from 0.001 to 10.0 μm, and the particle size of the coated particles ranges from 0.021 to 500 μm, preferably from 0.4 to 200.0 μm. The organic coating layer is polymethyl methacrylate or a copolymer thereof. The thickness of the organic coating layer is from 0.010 to 200.0 μm.

The above magnetic polyamino particles are characterized in that the magnetic solid polyamino adsorbent particulate material has a nitrogen content of more than 0.01% by weight, preferably more than 1.20% by weight.

For the production of this product, the technical solution adopted by the present invention is:

1 Preparation of inorganic coating layer: using magnetic powder core (selected from one or more mixtures of magnetite powder or Fe ₃ O ₄ powder, iron powder or other synthetic magnetic powder materials, grain The diameter range is 0.02 to 100.0 μm), which is reacted with tetraethyl orthosilicate or the like to prepare an inorganic-coated magnetic powder material, and its structure can be represented by Fe ₃ O ₄ @SO ₂ or FS.

2 Surface double-bonding: The magnetic powder material coated with carbon-carbon double bonds on the surface of FS magnetic particles was prepared by reacting FS with a carbon-carbon double bond silane coupling agent. The typical preparation steps are as follows: FS is used as the core-shell structure matrix, organic solvent ethanol is added, stirred to form a uniform suspension, and then vinyl triethoxysilane and the like are added and stirred to cause silanization on the surface of the substrate. After the reaction, the particulate material is separated by a magnet to obtain a magnetic powder material FS@- double bond whose surface is covered with a carbon-carbon double bond.

3 Preparation of organic coating layer: Under the action of initiator, solid surface graft copolymerization reaction is carried out by polymerizing monomer with FS@- double bond and carbon-carbon double bond to form magnetic powder material FS@- coated with organic functional group. Organic functional group.

4 Preparation of Magnetic Polyamino Particles: The product was obtained by mixing an FS@-organic functional group with a polyamino compound at 10 to 80 ° C to form an aminolysis reaction to form a carbon-nitrogen bond (C-N).

The use of this product, combined with magnetic separation technology, can solve the purification problem of water, farmland and site soil, livestock manure, sludge, river and lake sediments (liquid, solid-liquid suspension system) contaminated by heavy metals. It includes adsorption and capture of specific heavy metals in heavy metal-contaminated water bodies, farmland and site soils, livestock manure, sludge, river and lake sediments (liquid, solid-liquid suspension systems), and then magnetic separation and system separation. The details are as follows:

A method for removing heavy metal pollution in soil by using magnetic solid polyamino sorbent particulate material, comprising adsorbing and trapping specific heavy metals in the soil, and then performing magnetic separation and separation of soil materials. The present invention has a directivity effect on a specific heavy metal substance such as lead cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc., and the magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The method of use includes but is not limited to: 1 mud, 2 magnetic solid polyamino adsorbent mixed with mud to adsorb and capture heavy metals; 3 magnetically adsorbed heavy metal magnetic solid polyamino adsorbent and mud; 4 magnetic solids The amino sorbent material is recovered together with the heavy metal and concentrated for resource disposal.

A method for removing heavy metal pollution in livestock manure by using magnetic solid polyamino sorbent granular material, including adsorbing and trapping specific heavy metals in livestock manure, and then performing magnetic separation and separation of livestock manure. The present invention has a directivity effect on a specific heavy metal substance such as lead cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc., and the magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The method of use includes, but is not limited to: 1 mixing a magnetic solid polyamino sorbent with a livestock manure slurry to adsorb and collect heavy metals; 2 separating a magnetic solid polyamino sorbent adsorbing heavy metal from a livestock manure slurry by a magnet; The solid polyamino sorbent material is recovered together with heavy metals and concentrated for resource disposal.

A method for removing heavy metal pollution in sludge by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in the sludge, and then performing magnetic separation and separation of coal chemical sludge. The present invention has a directivity effect on a specific heavy metal substance such as lead cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc., and the magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The method of use includes but is not limited to: 1 mixing the magnetic solid polyamino adsorbent with the sludge slurry to absorb the trapping weight Metal; 2 magnetic solid multi-amino acid adsorbent adsorbing heavy metal is separated from coal chemical sludge slurry by magnet; 3 magnetic solid polyamino adsorbent material is recovered together with heavy metal, and concentrated for resource disposal.

A method for removing heavy metal pollution in river bottom mud by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in river bottom sediment, and then performing magnetic separation and river lake sediment separation. The present invention has a directivity effect on a specific heavy metal substance such as lead cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc., and the magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The method of use includes, but is not limited to, 1: sucking out the river mud to form a slurry, 2 mixing the magnetic solid polyamino adsorbent with the river bottom mud slurry to adsorb and collect heavy metals; 3 using a magnet to adsorb the heavy metal magnetic solid polyamino adsorbent and The mud slurry at the bottom of the river is separated; 4 The magnetic solid polyamino sorbent material is recovered together with the heavy metal, and concentrated for resource disposal.

The invention has a directivity effect on specific heavy metal materials such as lead cadmium, chromium, mercury, arsenic, copper, nickel, zinc, uranium and thorium, and the magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The method of use includes, but is not limited to: 1 mixing a magnetic solid polyamino adsorbent with an aqueous solution to adsorb and capture heavy metals; 2 separating a magnetic solid polyamino adsorbent adsorbing heavy metal from a water body with a magnet; 3 using a magnetic solid polyamino adsorbent material Collected together with heavy metals and concentrated on resource disposal. The invention can make up for the defects of the existing guest soil method, the chemical method, the physical method and the biological method for repairing, has the directivity effect on some metal ions, has a simple method, and the magnetic carrier particle material can be recycled and utilized, and the treatment cost Low, able to take advantage of mineral processing technology and mineral processing machinery, can carry out heavy metal removal and reduction purification of large and medium-sized pollutants of various scales, without large amount of pollution (waste) water in the whole process, without causing secondary pollution or pollution in different places, and Ability to recover heavy metals.

The invention is described below:

1. According to the above scheme, the magnetic powder in the first step mainly refers to a soft magnetic material. Soft magnetic material A magnetic material having low coercivity and high magnetic permeability. Soft magnetic materials are easy to magnetize and are also prone to demagnetization. There are many types of soft magnetic materials, and in principle, they can be used in the present invention. The soft magnetic powder material suitable for use in, but not limited to, the invention mainly refers to one or a mixture of magnetite powder, Fe ₃ O ₄ powder, iron powder, etc., and has a particle size ranging from 0.02 to 100.0 μm.

2. According to the above scheme, the carbon-carbon double bond silane coupling agent in the step 2 is a kind of a silane coupling agent, and the classical product thereof can be represented by the general formula YSiX ₃ . When the Y group contains a carbon-carbon double bond, it is called a carbon-carbon double bond silane coupling agent. Suitable carbon carbon double bond silane coupling agents for use in, but not limited to, the present invention are: vinyl triethyl (meth) oxy silane, vinyl trichloro silane, γ-(methacryloyloxy) propyl trimethoxy silane.

3. According to the above scheme, the carbon-carbon double bond polymerizable monomer in the step 3 mainly refers to a methacrylate ester and an acrylate compound. Suitable but not limited to the methacrylates of the present invention include: methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, suitable but not limited to the acrylates of the present invention include: methyl acrylate, ethyl acrylate Wait.

4. According to the above scheme, the polyamino compound in the step 4 refers to an organic compound containing two or more amino groups (including primary and tertiary amino groups) in the molecule. Suitable but not limited to the polyamino compounds of the present invention are: 1 polyethyleneimine, 2 polyallylamine (hydrochloride): molecular formula (C ₃ H ₇ N) _n · xHCl, suitable for the degree of polymerization of the invention n = 30 3 oligoethylenediamine: suitable for the present invention are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine; 4 natural product chitosan degradation product: chitosan (chitosan) The chemical name is polyglucosamine (1-4)-2-amino-β-D-glucose, which reacts with hydrochloric acid to cause cleavage of glycosidic bonds to form a number of degradants of varying degrees of polymerization.

5. According to the above scheme, the preparation method is characterized in that a stable covalent bond is formed between the organic coating layer and the inorganic coating layer by graft copolymerization to form a carbon-carbon single bond, and the structure is very stable, and the multi-shell layer is avoided. The inorganic layer and the organic layer are peeled off during use.

6. According to the above scheme, the preparation method is characterized in that the polyamino compound and the reactive group on the shell layer of the magnetic particle material undergo an aminolysis reaction to form a carbon-nitrogen bond to be grafted onto the surface of the magnetic particle material, and the structure is very stable. The disadvantage that the adsorption group is easily detached during use is avoided.

7. According to the above scheme, the magnetic polyamino particles have a particle size ranging from 0.5 to 500.0 μm. The particle size is suitable for magnetic separation in solid-liquid suspension (mixing) system, and the recovery rate of magnetic particles is over 99%, which avoids the strong magnetic particles in the solid-liquid suspension (mixing) system. Adsorption (adhesion), it is difficult to perform magnetic separation, resulting in a defect of less than 70%.

8. According to the above scheme, the adsorption group is characterized by a polyamino group, and the calcium and magnesium ions do not interfere.

9. According to the above scheme, the nitrogen content of the magnetic polyamino particles is usually greater than 1.20% by weight, and the larger adsorption capacity makes it practically useful.

According to the above scheme, the multi-shell core-shell structure is composed of a core of magnetic powder particles or agglomerates thereof, an inorganic coating layer, and an organic coating layer.

11. According to the above aspect, the inorganic coating layer to which the present invention is applied, but not limited to, is usually silica, and may be an oxide of titanium or aluminum. The thickness of the coating layer is from 0.005 to 0.05 μm, and the particle size of the coated particles ranges from 0.2 to 200.0 μm.

12. According to the above scheme, the organic coating layer is polymethacrylamide or a copolymer of methyl methacrylate and methacrylamide. The organic coating layer has a thickness of 0.05 to 0.80 μm.

13. According to the above scheme, the multi-shell core-shell structure is characterized in that the magnetic core and the inorganic coating layer are connected by a covalent bond between the inorganic coating layer and the organic coating layer.

14. According to the above scheme, the preparation method 1 is characterized in that the preparation method of the magnetic polyamino particles is characterized in that the polyamino compound is a polyethyleneimine, a polyallylamine group or an oligoethylenediamine group, and comprises the following typical preparation steps:

1 Preparation of magnetic powder matrix: using Fe ₃ O ₄ powder and ethyl orthosilicate to prepare inorganic materials such as silica coated magnetic powder material, the structure of which can be Fe ₃ O ₄ @SO ₂ Or FS said.

2 Preparation of double bond layer coated magnetic powder material: The double bond layer coated magnetic powder material is prepared by reacting FS with a carbon-carbon double bond silane coupling agent. The typical preparation steps are as follows: FS is used as the core-shell structure matrix, organic solvent ethanol is added, stirred to form a uniform suspension, and then vinyl triethoxysilane and the like are added and stirred to cause silanization on the surface of the substrate. After the reaction, the particulate material is separated by a magnet to obtain a magnetic powder material FS@- double bond whose surface is covered with a carbon-carbon double bond.

3 Preparation of a magnetic powder material such as a methyl ester layer: a monomer such as methyl methacrylate is polymerized with a FS@- double bond and a carbon-carbon double bond, and a solid surface is formed under the action of the initiator benzoyl peroxide. The branch copolymerization reaction produces a magnetic powder material FS@-carboxylate having a surface coated with an organic functional functional group such as a methyl carboxylate or the like.

4 Preparation of final product: Aminolysis reaction of a carboxylic acid ester or the like is carried out with a polyamino compound such as FS@-carboxylate or the like at 10 to 80 ° C to obtain a final product, magnetic polyamino particles.

Preparation method 2: a magnetic polyamino particle, the preparation method is characterized in that when the polyamino compound is a chitosan group, the preparation steps are as follows:

1 Preparation of magnetic powder matrix: using Fe ₃ O ₄ powder and ethyl orthosilicate to prepare inorganic materials such as silica coated magnetic powder material, the structure of which can be Fe ₃ O ₄ @SO ₂ Or FS said.

2 Preparation of double bond layer coated magnetic powder material: The double bond layer coated magnetic powder material is prepared by reacting FS with a carbon-carbon double bond silane coupling agent. The typical preparation steps are as follows: FS is used as the core-shell structure matrix, organic solvent ethanol is added, stirred to form a uniform suspension, and then vinyl triethoxysilane and the like are added and stirred to cause silanization on the surface of the substrate. After the reaction, the particulate material is separated by a magnet to obtain a magnetic powder material FS@- double bond whose surface is covered with a carbon-carbon double bond.

3 Preparation of a magnetic powder material such as a methyl ester layer or the like: a monomer such as methyl methacrylate is polymerized with a FS@- double bond and a carbon-carbon double bond, and a solid surface occurs under the action of the initiator benzoyl peroxide. The graft copolymerization reaction produces a magnetic powder material FS@-carboxylate which is coated with an organic functional functional group such as a methyl carboxylate or the like.

4 Preparation of chitosan degradation products: the acetic acid solution of chitosan is adjusted to pH=2±0.5 with hydrochloric acid, heated at 30-80 ° C for 30-120 minutes, cooled to room temperature, and then treated with sodium hydroxide solution. The pH was adjusted to 8-10 to obtain a degradation product of chitosan.

5 Preparation of the final product: mixing with chitosan degradation products with FS@-carboxylic acid methyl ester or the like, and at 30-80 ° C, an aminolysis reaction of a carboxylic acid ester or the like occurs to obtain a final product - more chitosan Magnetic polyamino particles of an amino coating.

Compared with the prior art, the beneficial effects of the present invention are:

1. The magnetic polyamino particles of the present invention have a particle size ranging from 0.5 to 500.0 μm, which avoids the disadvantage that the nanoparticles are easily adsorbed by other solid materials, and is very suitable for magnetic separation operation using a magnetic separator, and the magnetic separation recovery of the material is greater than 99%.

2. The magnetic polyamino particles of the present invention have an inorganic-organic multi-shell core-shell structure, a magnetic powder particle core and an inorganic coating layer, and a covalent bond phase between the inorganic coating layer and the organic coating layer. The polyamino group and the magnetic powder are mainly linked by an amide bond, and the structure is very stable, and the water can be selectively adsorbed in a wide pH range, and Zn, Pb, Cd, Hg, Cr, As in a solid-liquid mixed (suspended) system, Heavy metals such as Cu and Ni and noble metals such as Au and Ag do not interfere with calcium and magnesium plasma.

3. The magnetic polyamino particles of the present invention are easily separated from water, soil, solid-liquid suspension (mixing) system by magnetic separation or filtration after being adsorbed by heavy metals and precious metals, and can be recovered by acid leaching or the like. Heavy metals, which make materials regenerate and reuse, are suitable for environmental protection, pollution control, biological separation, mineral processing, hydrometallurgical and other industries for adsorption and enrichment of heavy metals and precious metals.

DRAWINGS

1 is a schematic structural view of a core-shell structure magnetic solid polyamino sorbent particulate material;

2 is a preparation process of a core-shell structure magnetic solid polyamino sorbent particulate material;

Figure 3 is a TEM image of a magnetic solid polyamino sorbent particle material coated with a polyamino group;

Figure 4 is a TEM image of a magnetic solid polyaminosorbent particle material coated with a polyamino group on the surface.

detailed description

In order to better understand the present invention, the contents of the present invention will be further clarified by the following examples, but the present invention is not limited to the following embodiments.

Example 1

A magnetic polyamino particulate material, wherein when the polyamino group is derived from polyallylamine (hydrochloride) having a degree of polymerization of 30, the preparation method thereof is as follows:

1 40 g of an average particle diameter of 0.02 μm Fe ₃ O ₄ magnetic powder, 40 g of tetraethyl orthosilicate, 300 ml of absolute ethanol were mixed, and a mixture of 40 ml of ammonia water and 20 ml of ethanol was added dropwise at 20 ° C for 1 hour, and then 70 ° C The reaction was carried out for 10 h, filtered, washed with ethanol and dried at 110 ° C to give FS.

2 Take 40g FS, 20g vinyl triethyl (meth) oxysilane, 100ml ethanol mixed, 3ml ammonia water, stir at 50 ° C for 10h, make silanization reaction on the surface of the substrate, then separate the granular material with a magnet, wash with ethanol, Drying at 60 ° C, the magnetic powder material FS@- double bond coated with carbon-carbon double bonds on the surface.

3 Take 40g FS@- double bond, 80g methyl methacrylate, 400ml water, 2g benzoyl peroxide, react at 90 ° C for 8h, filter, wash, dry at 110 ° C, the surface coated with polymethacrylic acid Molecular magnetic powder material FS@-polymethyl methacrylate.

4 Take 40g of FS@-polymethyl methacrylate and 300g of polyallylamine (hydrochloride) containing 30g of polymerization degree 30g The aqueous solution was reacted at 80 ° C for 5 hours to cause an aminolysis reaction of a carboxylate or the like, and then the particulate material was separated by a magnet, washed with ethanol, and dried at 60 ° C to obtain a final product, magnetic polyamino particles.

The morphology of the magnetic polyamino particles obtained in this example under transmission electron microscope (TEM) observation, as shown in Fig. 3, the dark gray core is covered with a light gray outer shell, which is a core-shell structure; elemental analysis is used. It was analyzed by nitrogen, and its N content was 0.25-0.60wt%. It was magnetically analyzed and its saturation magnetization was 25.00-38.00emu/g. It showed the characteristics of soft magnetic material and was suitable for magnetic separation.

The adsorption capacity of the above products to heavy metals Hg, Cd, Pb, etc. in 100 mL, 100 mg/L aqueous solution is 30.0-60.0 mg/g, the removal rate of heavy metals is over 95%, the recovery of magnetic separation is more than 99.8%, and the use of 100 mL 0.1 mol/ L hydrochloric acid is immersed in 1.0g of heavy metal-loaded magnetic solid powder material for 1h, and the desorption rate is over 95%. The material can be regenerated and recycled.

Example 2

A magnetic polyamino particulate material, wherein when the polyamino-adsorbing group is derived from diethylenetriamine, the preparation method thereof is as follows:

1 40g of an average particle diameter of 0.20μm of ferroferric oxide powder (content greater than 99%), 10g of tetraethyl orthosilicate, 300ml of absolute ethanol mixed, 20ml of ammonia and 20ml of ethanol were added dropwise at 20 °C for 1h. The mixture was then reacted at 70 ° C for 10 h, filtered, washed with ethanol and dried at 110 ° C to give FS.

2 Take 40gFS, 20g vinyl trichlorosilane, 200ml ethanol mixed, 3ml ammonia water, stir at 55 °C for 8h, then make silanization reaction on the surface of the substrate, then separate the granular material with magnet, wash with ethanol, dry at 60 °C, A magnetic powder material FS@- double bond having a surface coated with a carbon-carbon double bond is obtained.

3 Take 40g FS@- double bond, 60g methyl methacrylate and 20g glycidyl methacrylate mixture, 400ml water, 2g benzoyl peroxide, react at 70 ° C for 12h, filtered, washed with water, dried at 110 ° C, A copolymer of FS@-methyl methacrylate and glycidyl methacrylate was produced.

4 40gFS@-methyl methacrylate and glycidyl methacrylate copolymer and 300g of diethylenetriamine containing 30g of ethanol solution were reacted at 80 ° C for 4h, the aminolysis reaction of carboxylate group and epoxy group occurred. Or partial aminolysis reaction, then separate the granular material with a magnet, wash with ethanol, and dry at 60 ° C to obtain the final product - magnetic polyamino particles.

The morphology of the magnetic polyamino particles obtained in this example is observed by transmission electron microscopy (TEM). As shown in Fig. 4, the dark gray core is covered with a light gray outer shell, which is a core-shell structure; elemental analysis is used. Nitrogen analysis was carried out, and its N content was 1.20-1.40wt%. The magnetic analysis was carried out, and its saturation magnetization was 25.00-38.00emu/g, which showed the characteristics of soft magnetic material, which is suitable for magnetic separation materials.

Take 1000 g of cadmium, lead and copper composite contaminated soil, add 2000 g of natural water to be beaten, add 10 g of the above product, intermittently stir for 24 hours, and separate the slurry with magnet; the removal rate of heavy metal reaches 70%, and the recovery rate of magnetic separation is more than 99.8%. 100 g of 0.1 mol/L hydrochloric acid was used to soak the 1.0 g heavy metal-loaded magnetic solid powder material for more than 95%, and the material was recyclable and recycled.

Example 3

A magnetic polyamino particulate material, wherein the polyamino group adsorption group is derived from a chitosan degradant, and the preparation method thereof is as follows:

1 40g of an average particle size of 50.0μm magnetite powder (content greater than 90%), 10g of tetraethyl orthosilicate, 300ml of absolute ethanol were mixed, and a mixture of 40ml of ammonia and 20ml of ethanol was added dropwise at 20 °C for 1h. Then, the reaction was carried out at 70 ° C for 10 h, filtered, washed with ethanol, and dried at 110 ° C to obtain FS.

2 Take 40gFS, 20g γ-(methacryloyloxy)propyltrimethoxysilane, 200ml of toluene mixed, 3ml of ammonia water, stir at 55 °C for 8h, to cause silanization reaction on the surface of the substrate, and then separate the granular material by magnet It is washed with ethanol and dried at 60 ° C to obtain a magnetic powder material FS@- double bond whose surface is covered with a carbon-carbon double bond.

3 Take 40g FS@- double bond, 60g of glycidyl methacrylate and 10g of ethyl acrylate mixture, 400ml of water, 2g of potassium persulfate, react at 70 ° C for 12h, filtered, washed with water, dried at 110 ° C, resulting in FS@ - a copolymer of glycidyl methacrylate and ethyl acrylate.

4 Take 40g of FS@-glycidyl methacrylate and ethyl acrylate copolymer and 300g of chitosan-containing degradation product 30g solution at 80 ° C for 4h, ammonia hydrolysis reaction or partial aminolysis reaction, and then separated by magnet The particulate material was washed with ethanol and dried at 60 ° C to obtain the final product - magnetic polyamino particles.

The morphology of the magnetic polyamino particles obtained in this example under the observation of transmission electron microscope (TEM) has a morphology similar to that shown in FIG. 4, and the dark gray core is covered with a light gray outer shell, which is a core-shell structure; The elemental analysis method was used for the analysis of nitrogen. The N content was 0.30-0.40wt%. The magnetic analysis was carried out. The saturation magnetization was 15.00-18.00emu/g, and it showed the characteristics of soft magnetic material. It is suitable for magnetic application. Separate the material.

Take 1000g of zinc-copper composite contaminated poultry manure slurry (solid content 30wt%), add 10g of the above product, intermittently stir for 24 hours, separate the mud with magnet; the removal rate of heavy metal reaches 95%, the recovery rate of magnetic separation is greater than 99.8 %; 100 g of 0.1 mol/L hydrochloric acid was used to soak the 1.0 g heavy metal-loaded magnetic solid powder material for more than 95%, and the material was recyclable and recycled.

Example 4

A magnetic polyamino particulate material, wherein when the polyamino-adsorbing group is derived from polyethyleneimine, the preparation method thereof is as follows:

1 40g of an average particle size of 50.0μm iron powder (content greater than 98%), 10g of tetraethyl orthosilicate, 300ml of absolute ethanol were mixed, and a mixture of 40ml of ammonia water and 20ml of ethanol was added dropwise at 20 ° C for 1 hour, then 70 The reaction was carried out at ° C for 10 h, filtered, washed with ethanol, and dried at 110 ° C to obtain FS.

2 Take 40gFS, 20g γ-(methacryloyloxy)propyltrimethoxysilane, 200ml of toluene mixed, 3ml of ammonia water, stir at 55 °C for 8h, to cause silanization reaction on the surface of the substrate, and then separate the granular material by magnet It is washed with ethanol and dried at 60 ° C to obtain a magnetic powder material FS@- double bond whose surface is covered with a carbon-carbon double bond.

3 Take 40g FS@- double bond, 30g methyl methacrylate and 20g ethyl acrylate mixture, 400ml water, 2g potassium persulfate, react at 70 ° C for 12h, filtered, washed with water, dried at 110 ° C, resulting in FS@- A copolymer of methyl methacrylate and ethyl acrylate.

4 Take 40g of FS@-methyl methacrylate and ethyl acrylate copolymer, 500g of water, 10g of polyethyleneimine, mix and stir at 80 ° C for 4h, ammonia decomposition reaction or partial aminolysis reaction, and then separated by magnet The particulate material, washed with ethanol, and dried at 60 ° C, gave the final product - magnetic polyamino particles.

The morphology of the magnetic polyamino particles obtained in this example under the observation of transmission electron microscope (TEM) has a morphology similar to that shown in FIG. 3, and the dark gray core is covered with a light gray outer shell, which is a core-shell structure; The elemental analysis method was used for the analysis of nitrogen. The N content was 0.30-0.40wt%. The magnetic analysis was carried out. The saturation magnetization was 24.00-28.00emu/g, which showed the characteristics of soft magnetic material. It is suitable for magnetic application. Separate the material.

Take 1000g of zinc-copper-lead compound contaminated municipal sludge slurry (solid content 20wt%), add 10g of the above product, intermittently stir for 24 hours, separate the mud with magnet; the removal rate of heavy metal reaches 75%, magnetic separation recovery More than 99.8%; with 100mL 0.1mol / L hydrochloric acid on 1.0g of heavy metal-loaded magnetic solid powder material soaked for 1h desorption rate of more than 95%, the material can be regenerated, recycled.

Example 5

A magnetic polyamino particulate material, wherein when the polyamino-adsorbing group is derived from diethylenetriamine, the preparation method thereof is as follows:

1 40g of an average particle diameter of 0.20μm of ferroferric oxide powder (content greater than 99%), 10g of tetraethyl orthosilicate, 300ml of absolute ethanol mixed, 20ml of ammonia and 20ml of ethanol were added dropwise at 20 °C for 1h. The mixture was then reacted at 70 ° C for 10 h, filtered, washed with ethanol and dried at 110 ° C to give FS.

2 Take 40gFS, 20g vinyl trichlorosilane, 200ml ethanol mixed, 3ml ammonia water, stir at 55 °C for 8h, then make silanization reaction on the surface of the substrate, then separate the granular material with magnet, wash with ethanol, dry at 60 °C, A magnetic powder material FS@- double bond having a surface coated with a carbon-carbon double bond is obtained.

3 Take 40g FS@- double bond, 60g methyl methacrylate and 20g glycidyl methacrylate mixture, 400 ml of water, 2 g of benzoyl peroxide, reacted at 70 ° C for 12 h, filtered, washed with water and dried at 110 ° C to form a copolymer of FS@-methyl methacrylate and glycidyl methacrylate.

4 40gFS@-methyl methacrylate and glycidyl methacrylate copolymer and 300g of diethylenetriamine containing 30g of ethanol solution were reacted at 80 ° C for 4h, the aminolysis reaction of carboxylate group and epoxy group occurred. Or partial aminolysis reaction, then separate the granular material with a magnet, wash with ethanol, and dry at 60 ° C to obtain the final product - magnetic polyamino particles.

The morphology of the magnetic polyamino particles obtained in this example under the observation of transmission electron microscope (TEM) has a morphology similar to that shown in FIG. 3, and the dark gray core is covered with a light gray outer shell, which is a core-shell structure; The elemental analysis method was used for the analysis of nitrogen. The N content was 1.20-1.40wt%. The magnetic analysis was carried out. The saturation magnetization was 25.00-38.00emu/g, which showed the characteristics of soft magnetic material. It is suitable for magnetic application. Separate the material.

Take 1000 grams of cadmium, lead, copper and arsenic compound contaminated river sediment, add 2000 grams of natural water to be beaten, add 10 grams of the above product, intermittently stir for 24 hours, separate the mud with magnet; the removal rate of heavy metal reaches 70%, magnetic separation recovery More than 99.8%; with 100mL 0.1mol / L hydrochloric acid on 1.0g of heavy metal-loaded magnetic solid powder material soaked for 1h desorption rate of more than 95%, the material can be regenerated, recycled.

The above is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make several improvements and changes without departing from the inventive concept. The scope of protection.

Claims (14)

A magnetic solid polyaminosorbent particle material coated with a polyamine-based adsorbing group, characterized in that its structure is composed of an inner inorganic organic multi-shell core-shell structure and a peripheral polyamino group. The surface-coated polyamine-based adsorption group-containing magnetic solid polyamino adsorbent particle material according to claim 1, wherein the inorganic-organic multi-shell core-shell structure comprises magnetic core particles or agglomerates thereof, inorganic substances The coating layer is composed of an organic coating layer, and the core of the magnetic powder particles or the agglomerates thereof and the inorganic coating layer are connected by a covalent bond between the inorganic coating layer and the organic coating layer. The surface-coated polyamine-based adsorption group-containing magnetic solid polyamino adsorbent particle material according to claim 1 or 2, characterized in that the polyamino group is used as a peripheral adsorption group thereof, and the inorganic organic multi-shell core shell The structure is connected by a carbon-nitrogen bond (CN). The surface-coated polyamine-based absorbing group-containing magnetic solid polyamino sorbent particulate material according to claim 3, wherein the carbon-nitrogen bond (CN) is a carbon-nitrogen bond in the amide group, or a secondary or tertiary amine Carbon-nitrogen bond. The magnetic solid polyamino adsorbent particulate material according to claim 1 or 2, which has a particle size ranging from 0.02 to 1000 μm, preferably from 0.5 to 500.0 μm. The magnetic solid polyamino adsorbent particle material according to claim 1 or 2, wherein in the inorganic-organic multi-shell core-shell structure, the magnetic powder core is selected from magnetite powder or Fe ₃ O ₄ powder. One or more mixtures of iron powder or other synthetic magnetic powder materials having a particle size ranging from 0.01 to 100.0 μm; the inorganic coating layer is usually silica or titanium or aluminum. The oxide of the same, the thickness of the coating layer is 0.001 to 10.0 μm, the particle diameter of the coated particles is in the range of 0.021 to 500 μm, preferably 0.4 to 200.0 μm, and the organic coating layer is polymethyl methacrylate or The copolymer, the thickness of the organic coating layer is from 0.010 to 200.0 μm. The magnetic solid polyaminosorbent particulate material according to claim 1 or 2, wherein the magnetic solid polyamino adsorbent particulate material has a nitrogen content of more than 0.01% by weight, preferably more than 1.20% by weight. A magnetic solid polyamino sorbent particulate material, the preparation method of which is characterized in that the peripheral polyamine group is obtained by amination reaction of a polyamino compound with a reactive functional group on the organic coating layer, comprising the following steps: 1 Preparation of inorganic coating layer: using magnetic powder core (selected from one or more mixtures of magnetite powder or Fe3O4 powder, iron powder or other synthetic magnetic powder materials, the particle size range is 0.02-100.0 μm) reacted with tetraethyl orthosilicate to prepare an inorganic coated magnetic powder material, the structure of which can be represented by Fe ₃ O ₄ @SO ₂ or FS; 2 surface double bond: using FS and carbon The carbon double bond silane coupling agent is reacted to prepare a magnetic powder material coated with carbon-carbon double bonds on the surface of the FS magnetic particles; the typical preparation steps are as follows: FS is a core-shell structure matrix, organic solvent ethanol is added, and stirring is performed to form a uniform suspension. After the liquid, vinyl triethoxysilane and the like are further added to the catalyst to be stirred to cause a silylation reaction on the surface of the substrate, and then the particulate material is separated by a magnet to obtain a magnetic powder material having a surface coated with a carbon-carbon double bond. FS@-double bond; 3 preparation of organic coating: under the action of initiator, FS@- double bond and carbon-carbon double bond polymerization monomer solid surface graft copolymerization reaction to form magnetic surface coated with organic functional group Powder material FS@-organic function 4; Preparation of magnetic solid polyamino adsorbent granule material: mixed with a polyamino compound at FS@-organic functional group at 10-80 ° C, and an aminolysis reaction to form a carbon-nitrogen bond (CN) to obtain a product. The magnetic solid polyamino adsorbent particle material according to claim 8, wherein the preparation method is characterized in that the peripheral polyamino group is obtained by amination reaction of a polyamino compound with a reactive functional group on the organic coating layer, and the following steps are included. : 3 Preparation of organic coating layer: The monomer is polymerized by FS@- double bond and carbon-carbon double bond, and under the action of initiator, solid surface graft copolymerization reaction occurs to form magnetic powder material FS@ with surface coated with organic functional group. - an organic functional group, such as potassium persulfate, FS@- double bond copolymerization with methyl methacrylate to form FS@-polymethyl methacrylate; 4 Preparation of magnetic solid polyamino adsorbent granule material: mixing with FS@-organic functional group and polyamino compound at 10-80 ° C, amino acid reaction to form carbon-nitrogen bond (CN) to obtain product; FS@-poly Methyl methacrylate or the like is mixed with ethylenediamine to form an amino-decomposition reaction of an N-substituted amide bond, thereby obtaining a final product, a magnetic solid polyamino sorbent particle material coated with a polyamine-based adsorption group. A method for removing heavy metal pollution in a water body by using a magnetic solid polyamino sorbent particle material, comprising adsorbing and trapping a specific heavy metal in an aqueous solution, and then performing magnetic separation and water separation, the specific heavy metal substance such as lead cadmium chromium mercury Arsenic, copper, nickel, zinc, uranium, plutonium and the like have a directivity effect. The magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The methods include, but are not limited to: 1 mixing the magnetic solid polyamino adsorbent with an aqueous solution. Heavy metal; 2 using a magnet to separate the magnetic solid polyamino adsorbent adsorbing heavy metal from the water; 3 recycling the magnetic solid polyamino adsorbent material together with the heavy metal, and centralized resource disposal. A method for removing heavy metal pollution in soil by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in soil, and then performing magnetic separation and separation of soil materials, and the present invention treats specific heavy metal substances such as lead cadmium chromium mercury Arsenic copper, nickel, zinc and the like have a directivity effect. The magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The use methods include, but are not limited to, 1 mud slurry, 2 magnetic solid polyamino adsorbent and mud mixed adsorption trapping. Heavy metal; 3 using a magnet to separate the magnetic solid polyamino sorbent adsorbing heavy metal from the slurry; 4 recycling the magnetic solid polyamino sorbent material together with the heavy metal, and centralized resource disposal. A method for removing heavy metal pollution in livestock manure by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in livestock manure, and then performing magnetic separation and separation of livestock manure, the present invention is for specific heavy metals Substances such as lead, cadmium, chromium, mercury, arsenic, copper, nickel and zinc have a directing effect. The magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The methods include, but are not limited to: 1 magnetic solid polyamino sorbent and livestock manure Slurry mixing adsorption to capture heavy metals; 2 using a magnet to separate heavy metal-loaded magnetic solid polyamino sorbent from livestock and poultry manure slurry: 3 The magnetic solid polyamino sorbent material is recovered together with heavy metals and concentrated for resource disposal. A method for removing heavy metal pollution in sludge by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in sludge, and then performing magnetic separation and separation of coal chemical sludge to invent specific heavy metal materials such as Lead, cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc. have a directivity effect. The magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The methods include, but are not limited to: 1 mixing the magnetic solid polyamino adsorbent with the sludge slurry. The heavy metal is captured; 2 the magnetic solid polyamino adsorbent adsorbing heavy metal is separated from the coal chemical sludge slurry by a magnet; 3 the magnetic solid polyamino adsorbent material is recovered together with the heavy metal, and concentrated for resource disposal. A method for removing heavy metal pollution in river bottom mud by using magnetic solid polyamino sorbent granular material, comprising adsorbing and trapping specific heavy metals in river bottom sediment, and then performing magnetic separation and river lake sediment separation, the present invention is for specific heavy metals Substances such as lead, cadmium, chromium, mercury, arsenic, copper, nickel, zinc, etc. have a directivity effect. The magnetic solid adsorbent can be recycled and recycled, and can recover heavy metals. The methods of use include, but are not limited to: 1 pumping out river mud to form mud, 2 magnetic The solid polyamino sorbent is mixed with the river mud slurry to adsorb and collect heavy metals; 3 the magnet is used to separate the magnetic solid polyamino sorbent adsorbing heavy metal from the river bottom mud slurry; 4 the magnetic solid polyamino sorbent material is recycled together with the heavy metal , centralized resource disposal.

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