CN113231041B - Preparation method and application of artificial humus/iron mineral coprecipitation composite material - Google Patents

Preparation method and application of artificial humus/iron mineral coprecipitation composite material Download PDF

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CN113231041B
CN113231041B CN202110658943.3A CN202110658943A CN113231041B CN 113231041 B CN113231041 B CN 113231041B CN 202110658943 A CN202110658943 A CN 202110658943A CN 113231041 B CN113231041 B CN 113231041B
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iron mineral
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humus
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CN113231041A (en
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杨帆
兰依博
程魁
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Northeast Agricultural University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds

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Abstract

A preparation method and application of an artificial humus/iron mineral coprecipitation composite material relate to a preparation method of an iron mineral composite material. The invention aims to solve the problems of single composition and solidification, single synthesis mode, high preparation cost and unfavorable popularization and application of the existing iron mineral composite material. 1. Preparing a hydrothermal humified liquid product; 2. preparing an iron mineral precursor; 3. and carrying out hydrothermal reaction to obtain the artificial humus/iron mineral coprecipitation composite material. The maximum adsorption capacity of the artificial humus/iron mineral coprecipitation state composite material for removing P, which is prepared by the invention, is 19.394mg/g. An artificial humus/iron mineral coprecipitation composite material is used for removing phosphate in eutrophic water. The invention can obtain the artificial humus/iron mineral coprecipitation composite material.

Description

Preparation method and application of artificial humus/iron mineral coprecipitation composite material
Technical Field
The invention relates to a preparation method of an iron mineral composite material.
Background
As a precious mineral resource, the iron mineral has the characteristics of large specific surface area, high reactivity, variable charge surface area, ubiquitous existence in natural water and soil and the like, and is usually combined with natural organic matters to form an inorganic-organic complex, so that the adsorption and fixation performance on oxygen anions is directly or indirectly influenced. Humus (HS) is a typical representative of natural organic matters and is considered as a 'deep-sleeping giant person', can be formed for thousands of years under natural conditions and comprises biological and non-biological reactions, and the reaction rate can be greatly accelerated by utilizing a hydrothermal humification technology to prepare artificial humus with similar physicochemical properties. Meanwhile, the phosphorus is used as the most common oxygen anion, is not only a limiting factor for water eutrophication, but also a nonrenewable resource mainly derived from phosphate ore.
At present, relevant researches on iron minerals and humus and iron minerals, humus and phosphorus are mainly focused on a surface adsorption process, namely humic acid is coated on the surface of the iron minerals as an adsorption state complex or the humic acid and phosphorus compete for adsorption on the surface of the iron minerals, and the obvious defects of material composition solidification, single synthesis mode, high preparation cost, inconvenience for popularization and application and the like exist. Therefore, the simulation of the geological transformation process, the preparation of the coprecipitation multi-phase iron mineral composite material generated by the reaction of the iron mineral and the artificial humus and the recovery of the excessive phosphorus in the water body have important environmental and geological significance.
Disclosure of Invention
The invention provides a preparation method of an artificial humus/iron mineral coprecipitation state composite material, aiming at solving the problems of single composition and solidification, single synthesis mode, high preparation cost and unfavorable popularization and application of the existing iron mineral composite material.
The preparation method of the artificial humus/iron mineral coprecipitation composite material comprises the following steps:
1. firstly, washing, drying and grinding biomass waste, then adding biomass powder into a strong alkaline aqueous solution, and transferring the biomass powder into a high-pressure reaction kettle to carry out hydrothermal humification reaction to obtain a reaction product I; filtering the reaction product I, and collecting liquid to obtain a hydrothermal humification liquid product;
2. firstly, dissolving iron metal salt solid in water, and then dropwise adding a strong alkaline solution until the pH value of the solution is 12-14 to obtain an iron mineral precursor;
3. dropwise adding the hydrothermal humus liquid product into the iron mineral precursor, stirring, and then performing water bath constant-temperature ageing to obtain a reaction product II; and centrifuging the reaction product II, collecting solids, washing the collected solids until the solids are neutral, and finally drying to obtain the artificial humus/iron mineral coprecipitation composite material.
Further, the biomass waste in the step one is leaves, rice straws, corn straws or soybean straws.
Further, the strong alkaline aqueous solution in the step one is formed by dissolving strong alkali into deionized water, wherein the mass ratio of the strong alkali to the deionized water is (1 g-6 g) to (100 mL-220 mL);
further, the strong base is NaOH or KOH.
Furthermore, the volume ratio of the mass of the biomass powder to the strong alkaline aqueous solution in the step one is (10-25 g): 100-220 mL).
Further, the temperature of the hydrothermal humification reaction in the step one is 180-200 ℃, the pressure is 1.5-3 MPa, and the reaction time is 10-24 h.
Further, the solid of the iron metal salt in the second step is Fe (NO) 3 ) 3 ·9H 2 O or FeCl 3 ·6H 2 O；
Furthermore, the ratio of the mass of the iron metal salt solid to the volume of the water is (5 g-15 g): 100 mL-250 mL.
Further, the strong alkaline solution in the second step is a KOH solution or a NaOH solution, and the concentration is 2 mol/L-2.5 mol/L.
Furthermore, the volume ratio of the hydrothermal humation liquid product to the iron mineral precursor is (5 mL-20 mL): (145 mL-160 mL);
further, the stirring speed in the third step is 150r/min to 200r/min, and the stirring time is 30min to 60min.
Further, the temperature of the water bath constant temperature ageing in the third step is 60-80 ℃, and the time is 24-48 h.
Further, in the third step, the collected solid is washed by using deionized water and absolute ethyl alcohol alternately until the solid is neutral;
further, the drying in the third step is vacuum drying, the temperature of the vacuum drying is 40-60 ℃, and the time of the vacuum drying is 72-96 hours.
The invention has the beneficial effects that:
1. the invention takes biomass waste and iron metal salt as raw materials, and prepares the artificial humus/iron mineral coprecipitation composite material by a hydrothermal humification technology and a coprecipitation method; the micro-morphology of the composite material presents a regular cluster-shaped structure with larger grain size and a precipitation-state appearance, so that the dispersibility of the material is reduced, and the recovery efficiency is improved;
2. the artificial humus/iron mineral coprecipitation composite material prepared by the invention increases the number of functional groups on the surface of the iron mineral to a great extent, particularly-COO, -OH, C-O and the like, not only improves the physical and chemical properties, but also provides a large number of active sites for subsequent reactions;
3. the artificial humic acid liquid mainly serves as an inhibitor for inhibiting the nucleation growth of goethite crystal forms and promoting the generation of ferrihydrite; as a reducing agent, reducing a small amount of Fe (III) in the solution into Fe (II), and reacting to generate an intermediate product of basic iron carbonate (Fe) 2 (OH) 2 CO 3 ) And continuously oxidizing to generate stable minerals of goethite and lepidocrocite; as an accelerator, promoting the transformation of part of the crystal form from goethite to hematite; the artificial humus/iron mineral coprecipitation state composite material prepared by the invention is a multi-phase composite state material composed of various iron minerals such as goethite, ferrihydrite, lepidocrocite, hematite and the like;
4. the artificial humus/iron mineral co-precipitation state composite material prepared by the invention combines the advantages of artificial humus and iron mineral, and increases the application effect in the environment, and the maximum adsorption capacity of the artificial humus/iron mineral co-precipitation state composite material prepared by the invention to phosphorus in eutrophicated water is 2-5 times of that of single iron mineral;
5. the artificial humus/iron mineral coprecipitation composite material prepared by the invention is beneficial to better understanding of the action mechanism and potential value of the artificial humus participating in iron mineral conversion, phosphate biogeochemical cycle and environmental water and soil pollution remediation;
6. the biomass waste is wide in material source, low in price and easy to obtain, and the manufacturing cost of the artificial humus/iron mineral coprecipitation composite material is reduced; the operation is simple, the separation is easy after the use, and the wide application in the actual production is facilitated;
7. the maximum adsorption capacity of the artificial humus/iron mineral coprecipitation state composite material for removing P, which is prepared by the invention, is 19.394mg/g.
An artificial humus/iron mineral coprecipitation composite material is used for removing phosphate in eutrophic water.
The invention can obtain the artificial humus/iron mineral coprecipitation composite material.
Drawings
FIG. 1 is an SEM photograph of an artificial humus/goethite co-precipitated composite prepared in example 1;
FIG. 2 is an SEM photograph of the artificial humus/goethite co-precipitated composite prepared in example 2;
FIG. 3 is a FTIR chart in which 1 is a FTIR profile of the iron mineral precursor obtained in step two of example 1 and 2 is a FTIR profile of the composite in the state of artificial humus/goethite coprecipitation prepared in example 1;
FIG. 4 is an XRD pattern in which 1 is an XRD pattern of the iron mineral precursor obtained in step two of example 1 and 2 is an XRD pattern of the humus prosthesis/goethite co-precipitated composite prepared in example 1;
FIG. 5 is a TEM image of the artificial humus/goethite co-precipitated composite prepared in example 1;
FIG. 6 is a HRTEM image of the co-precipitated humus/goethite composite prepared in example 1;
FIG. 7 is a SAED diagram of the artificial humus/goethite co-precipitated composite prepared in example 1;
FIG. 8 is a low-power and high-power Element mapping chart of the artificial humus/goethite coprecipitation composite prepared in example 1 after adsorbing phosphorus.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first specific implementation way is as follows: the embodiment is a preparation method of the artificial humus/iron mineral coprecipitation composite material, which is completed by the following steps:
1. firstly, washing, drying and grinding biomass waste, then adding biomass powder into a strong alkaline aqueous solution, and transferring the mixture into a high-pressure reaction kettle to perform hydrothermal humification reaction to obtain a reaction product I; filtering the reaction product I, and collecting liquid to obtain a hydrothermal humification liquid product;
2. firstly, dissolving iron metal salt solid in water, and then dropwise adding a strong alkaline solution until the pH value of the solution is 12-14 to obtain an iron mineral precursor;
3. dropwise adding the hydrothermal humus liquid product into the iron mineral precursor, stirring, and then performing water bath constant-temperature ageing to obtain a reaction product II; and centrifuging the reaction product II, collecting solids, washing the collected solids until the solids are neutral, and finally drying to obtain the artificial humus/iron mineral coprecipitation composite material.
The first step of the present embodiment is to hydrothermally humify biomass in order to obtain an artificial humus liquid rich in surface functional groups and having redox ability.
In the second step of the embodiment, the strongly alkaline solution is dropwise added into the iron metal salt solution to form an iron mineral precursor, so as to provide a base material for the subsequent addition of the artificial humic acid.
In the third step of the embodiment, the liquid artificial humic acid is dripped into the rapidly stirred iron mineral precursor, so that the two can fully and uniformly react or coprecipitate, and the water bath ageing can accelerate the reaction progress and promote the reaction to be carried out in the forward direction.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the biomass waste in the step one is leaves, rice straws, corn straws or soybean straws. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is: the strong alkaline aqueous solution in the step one is formed by dissolving strong alkali into deionized water, wherein the mass ratio of the strong alkali to the deionized water is (1 g-6 g) to (100 mL-220 mL); the strong base is NaOH or KOH. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the volume ratio of the mass of the biomass powder to the strong alkaline aqueous solution in the step one is (10-25 g): 100-220 mL. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: the temperature of the hydrothermal humification reaction in the step one is 180-200 ℃, the pressure is 1.5-3 MPa, and the reaction time is 10-24 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the solid of the iron metal salt in the second step is Fe (NO) 3 ) 3 ·9H 2 O or FeCl 3 ·6H 2 O; the ratio of the mass of the iron metal salt solid to the volume of the water is (5 g-15 g) to (100 mL-250 mL). The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the strong alkaline solution in the second step is KOH solution or NaOH solution, and the concentration is 2 mol/L-2.5 mol/L. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode eight: the difference between this embodiment and the first to seventh embodiments is: the volume ratio of the hydrothermal humification liquid product to the iron mineral precursor in the third step is (5 mL-20 mL): 145 mL-160 mL; the stirring speed in the third step is 150 r/min-200 r/min, and the stirring time is 30 min-60 min; the temperature of the water bath constant temperature ageing in the third step is 60-80 ℃, and the time is 24-48 h. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the third step, the collected solid is washed by using deionized water and absolute ethyl alcohol alternately until the solid is neutral; the drying in the third step is vacuum drying, the temperature of the vacuum drying is 40-60 ℃, and the time of the vacuum drying is 72-96 hours. The other steps are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the embodiment is that the artificial humus/iron mineral coprecipitation composite material is used for removing phosphate in eutrophic water.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: the preparation method of the artificial humus/goethite coprecipitation state composite material is completed according to the following steps:
1. firstly, washing biomass waste for 5 times, then drying at 60 ℃, and grinding into powder with the particle size of 0.1-1 mm by using powder to obtain biomass powder; then adding 20g of biomass powder into 220mL of strong alkaline aqueous solution, transferring the mixture into a 500mL high-pressure reaction kettle, and carrying out hydrothermal humification reaction to obtain a reaction product I; filtering the reaction product I, and collecting liquid to obtain a hydrothermal humification liquid product;
the biomass waste in the step one is leaves;
dissolving strong alkali in deionized water in the strong alkali aqueous solution in the step one, wherein the volume ratio of the mass of the strong alkali to the volume of the deionized water is 5 g; the strong base is KOH;
the temperature of the hydrothermal humification reaction in the step one is 200 ℃, the pressure is 2.0MPa, and the reaction time is 24h;
2. firstly, 10g of FeCl 3 ·H 2 Dissolving O in 165mL of water, and then dropwise adding a strong alkaline solution until the pH value of the solution is 12 to obtain an iron mineral precursor;
the strong alkaline solution in the step two is 2.5mol/L KOH solution;
3. dropwise adding 20mL of hydrothermal humation liquid product into 145mL of iron mineral precursor, stirring at the stirring speed of 180r/min for 30min, and then aging in a water bath at the temperature of 60 ℃ for 24h at constant temperature to obtain a reaction product II; and centrifuging the reaction product II, collecting solids, washing the collected solids by using deionized water and absolute ethyl alcohol alternately until the solids are neutral, and finally drying in vacuum at 60 ℃ for 96 hours to obtain the artificial humus/goethite coprecipitation state composite material.
The maximum adsorption capacity of the artificial humus/iron mineral coprecipitation composite material prepared in the example 1 for removing P is as high as 19.394mg/g under the conditions that the temperature is 25 ℃, the addition amount of the adsorbent is 10mg, the volume of the solution is 40mL, and the concentration of P in the solution is 50 mg/L.
The SEM of the composite material in the state of artificial humus/goethite coprecipitation prepared in example 1 is shown in FIG. 1.
FIG. 1 is an SEM photograph of an artificial humus/goethite co-precipitated composite prepared in example 1;
from a scanning electron microscope image with low magnification, the coprecipitation state composite material is in a cluster structure with a regular and larger grain diameter, the dispersity is obviously reduced, and obvious precipitated compounds are gathered, so that the crystal form conversion of iron minerals and the generation of new substances are promoted.
FIG. 3 is a FTIR chart in which 1 is a FTIR profile of the iron mineral precursor obtained in step two of example 1 and 2 is a FTIR profile of the composite in the state of artificial humus/goethite coprecipitation prepared in example 1;
1 in FIG. 3 at 3393cm -1 And 3112cm -1 Peaks at 888cm associated with OH stretching vibration in the H-O-H and Fe-OH-Fe groups in goethite -1 (delta-OH) and 795cm -1 The (. Gamma. -OH) points are-OH inward and outward vibrations, respectively, and are also designated as Fe-OH-Fe bending vibrations. In addition, a distinct peak appears at 1654cm -1 And 1770cm -1 631cm artificial humus vibrations at COO and C = O due to asymmetry -1 Due to symmetric Fe-O stretching. The artificial humus/iron mineral coprecipitation composite material has typical goethite characteristic peaks at corresponding positions, but the characteristic peaks are obviously weakened and slightly shifted. Meanwhile, the artificial humus/iron mineral coprecipitation state composite material is at 1042, 1365 and 1560cm -1 Where the representatives C-O, COO and CO appear 3 2- The new characteristic peak value of the functional groups is equal, the physical and chemical properties of the artificial humus/iron mineral coprecipitation composite material are improved, and a large number of active sites are provided for the reaction.
FIG. 4 is an XRD pattern in which 1 is an XRD pattern of the iron mineral precursor obtained in step two of example 1 and 2 is an XRD pattern of the humus prosthesis/goethite co-precipitated composite prepared in example 1;
it can be seen from fig. 4 that the major XRD diffraction peaks of the iron minerals are located at 2 θ =17.796 °, 21.223 °, 26.323 °, 33.242 °, 34.701 °, 36.650 °, 39.985 °, 41.187 °, 53.238 °, 59.025 °, 61.385 °, 63.976 ° due to (020), (110), (120), (130), (021), (111), (121), (140), (221), (151), (002) and are located at 2 θ =17.796 °, 3238 ° and 53.238 °(061) Typical goethite structure, with a lattice constant of
Figure BDA0003115487920000061
No additional diffraction peaks of the second phase were detected, highlighting the high purity of the sample. An XRD curve of the artificial humus/goethite coprecipitation state composite material shows second-line ferrihydrite characteristic peaks at 2 theta =35.597 degrees and 61.345 degrees, and according to Bragg's law, the d-spacing value and Miller index (hkl) of the characteristic peaks are respectively calculated to be 0.252nm (110) and 0.151nm (115), which indicates that the artificial humus inhibits the nucleation growth of the goethite and promotes the crystallization transformation. Similarly, three new characteristic peaks of the artificial humus/iron mineral coprecipitation composite material at 23.73 degrees, 29.41 degrees and 33.95 degrees are respectively attributed to the basic iron carbonate (Fe) with crystal faces of (160), (320) and (211) 2 (OH) 2 CO 3 Lattice constant of
Figure BDA0003115487920000071
Figure BDA0003115487920000072
) Proves that the artificial humus is used as a reducing agent to reduce a small amount of Fe (III) in the solution into Fe (II), and the reaction generates an intermediate product of basic ferric carbonate (Fe) 2 (OH) 2 CO 3 ) Thereby promoting the transformation and generation of new substances.
FIG. 5 is a TEM image of the artificial humus/goethite co-precipitated composite prepared in example 1;
the presence of needle-like and lumpy species, i.e. the presence of multi-phase precipitated iron minerals, in the artificial humus/goethite co-precipitated composite is clearly observed by the highly magnified TEM image of fig. 5.
FIG. 6 is a HRTEM image of the co-precipitated humus/goethite composite prepared in example 1;
HRTEM analysis of FIG. 6 revealed that the interplanar spacings of the needle-like substances observed in TEM were
Figure BDA0003115487920000073
Corresponding to the (101) plane of goethite. BlockThe interplanar spacing of the like substances is
Figure BDA0003115487920000074
Corresponding to the (101) lattice plane of hematite, it was demonstrated that artificial humus acts as a promoter, promoting the conversion of some of the crystalline forms from goethite to hematite.
FIG. 7 is a SAED diagram of the artificial humus/goethite co-precipitated composite prepared in example 1;
analysis of the SAED spots in fig. 7 shows that the material is a polycrystalline structure, comprising goethite, hematite and lepidocrocite. It was confirmed that the humus/goethite coprecipitation state composite material prepared in this example 1 was a multi-phase composite state material composed of various iron minerals such as goethite, ferrihydrite, lepidocrocite, hematite, and the like.
FIG. 8 is a low-power and high-power Element mapping chart of the artificial humus/goethite coprecipitation composite prepared in example 1 after adsorbing phosphorus.
FIG. 8 shows that Fe, O and C are uniformly distributed on the surface of the humus/goethite coprecipitation state composite material, and C is uniformly coprecipitated in the iron mineral. Most importantly, the distribution of P on the artificial humus/goethite coprecipitation state composite material is very similar to the distribution of C on the artificial humus/goethite coprecipitation state composite material, and the chemical adsorption capacity of the goethite on the P is greatly improved after the artificial humus is doped.
Example 2: the difference between this example and example 1 is: in the third step: 10mL of the hydrothermal humification liquid product was added dropwise to 155mL of the iron mineral precursor. The other steps and parameters were the same as in example 1.
FIG. 2 is an SEM photograph of the co-precipitated humus/goethite composite prepared in example 2;
as can be seen from the scanning electron microscope image with low magnification, the artificial humus/goethite co-precipitated composite material prepared in example 2 is composed of regular needle-shaped and blocky clusters, the surface is loose and porous, compared with example 1, the artificial humus doping amount is small, the mineral conversion is incomplete, and a large amount of intermediate products and unconverted substances exist.

Claims (7)

1. A preparation method of an artificial humus/iron mineral coprecipitation state composite material is characterized in that the artificial humus/iron mineral coprecipitation state composite material is a multiphase composite state material consisting of goethite, ferrihydrite, lepidocrocite and hematite, and the preparation method is completed according to the following steps:
1. firstly, washing, drying and grinding biomass waste, then adding biomass powder into a strong alkaline aqueous solution, and transferring the mixture into a high-pressure reaction kettle to perform hydrothermal humification reaction to obtain a reaction product I; filtering the reaction product I, and collecting liquid to obtain a hydrothermal humification liquid product;
the temperature of the hydrothermal humification reaction in the step one is 180-200 ℃, the pressure is 1.5MPa-3MPa, and the reaction time is 10h-24h;
2. firstly, dissolving iron metal salt solid in water, and then dropwise adding a strong alkaline solution until the pH value of the solution is 12-14 to obtain an iron mineral precursor;
the solid of the iron metal salt in the second step is Fe (NO) 3 ) 3 ·9H 2 O or FeCl 3 ·6H 2 O; the volume ratio of the mass of the iron metal salt solid to the water is (5 g-15g): 100mL-250mL);
the strong alkaline solution in the second step is a KOH solution or a NaOH solution, and the concentration is 2-2.5 mol/L;
3. dropwise adding the hydrothermal humification liquid product into the iron mineral precursor, stirring, and then performing water bath constant-temperature aging to obtain a reaction product II; centrifuging the reaction product II, collecting solids, washing the collected solids until the solids are neutral, and finally drying to obtain the artificial humus/iron mineral coprecipitation composite material;
the volume ratio of the hydrothermal humification liquid product to the iron mineral precursor in the third step is 20mL.
2. The method for preparing the artificial humus/iron mineral co-precipitated composite material as claimed in claim 1, wherein the biomass waste in the first step is leaves, rice straw, corn straw or soybean straw.
3. The preparation method of the artificial humus/iron mineral co-precipitation composite material as claimed in claim 1, wherein the strongly alkaline aqueous solution in the step one is formed by dissolving strong alkali into deionized water, wherein the volume ratio of the mass of the strong alkali to the deionized water is (1g to 6 g): (100mL to 220mL); the strong base is NaOH or KOH.
4. The preparation method of the artificial humus/iron mineral co-precipitation composite material as claimed in claim 1, wherein the volume ratio of the mass of the biomass powder to the volume of the strongly alkaline aqueous solution in the step one is (10 g) - (25g) - (100mL) - (220mL).
5. The preparation method of the artificial humus/iron mineral co-precipitated composite material as claimed in claim 1, wherein the stirring speed in the third step is 150r/min to 200r/min, and the stirring time is 30min to 60min; and the temperature of the water bath constant-temperature ageing in the third step is 60-80 ℃, and the time is 24h-48h.
6. The method for preparing the artificial humus/iron mineral co-precipitated composite material as claimed in claim 1, wherein the collected solid is washed by using deionized water and absolute ethyl alcohol alternately in the third step until the solid is neutral; the drying in the third step is vacuum drying, the temperature of the vacuum drying is 40-60 ℃, and the time of the vacuum drying is 72h to 96h.
7. The application of the artificial humic substance/iron mineral co-precipitation state composite material obtained by the preparation method according to claim 1, wherein the artificial humic substance/iron mineral co-precipitation state composite material is used for removing phosphate in eutrophic water.
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