WO2024055515A1 - 一种污泥基六价铬复合吸附剂及其制备方法 - Google Patents

一种污泥基六价铬复合吸附剂及其制备方法 Download PDF

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WO2024055515A1
WO2024055515A1 PCT/CN2023/077445 CN2023077445W WO2024055515A1 WO 2024055515 A1 WO2024055515 A1 WO 2024055515A1 CN 2023077445 W CN2023077445 W CN 2023077445W WO 2024055515 A1 WO2024055515 A1 WO 2024055515A1
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sludge
pyrolysis
hexavalent chromium
composite adsorbent
chromium composite
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PCT/CN2023/077445
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English (en)
French (fr)
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陈勇
仇雅丽
刘勇奇
周启
巩勤学
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024055515A1 publication Critical patent/WO2024055515A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Definitions

  • the invention belongs to the technical fields of waste reuse and environmental protection, and in particular relates to a sludge-based hexavalent chromium composite adsorbent and a preparation method thereof.
  • the pyrolysis method takes advantage of the high carbon content of sludge to heat and distill it under anaerobic or anoxic conditions, so that the microbial residues, organic pollutants, and pathogenic bacteria in it can be rendered harmless and reduced. , the remaining solid residue can effectively retain the carbon element in it, forming combustible gas, liquid tar, and sludge coke products with high added value.
  • trace amounts of heavy metal elements in the sludge are transformed into a residue state with a special structure during high-temperature pyrolysis, which is inert and cannot be absorbed and utilized by organisms and cannot accumulate in the human body through the food chain. It is the safest form of heavy metals.
  • the present invention provides a preparation method of sludge-based hexavalent chromium composite adsorbent, which includes:
  • the pyrolysis product is subjected to amination modification to introduce -NH 2 onto the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorbent.
  • the pyrolysis product is subjected to amination modification to introduce -NH 2 onto the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorbent, which includes:
  • the pyrolysis product is subjected to an amination modification reaction through a silane compound under the conditions of ammonia solution and water, so that -NH 2 is introduced into the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorption agent.
  • reaction process of the amination modification reaction includes:
  • the silane compound is hydrolyzed under the catalysis of an ammonia solution to produce Si-OH groups attached to the surface of the pyrolysis product;
  • the Si-OH groups generate condensation reactions with each other and condense into Si-O-Si bonds;
  • the amino group covers and wraps the Si-O-Si bonds on the surface of the pyrolysis product to form an introduced -The sludge-based hexavalent chromium composite adsorbent of -NH2 .
  • the amination modification reaction also includes:
  • the Si-OH group can also undergo a condensation reaction with the carboxyl group on the surface of the pyrolysis product.
  • the silane compound is a silane compound that can be hydrolyzed to produce Si-OH groups under the catalysis of ammonia solution;
  • the silane compound includes one or a combination of both TEOS and APTES;
  • the ammonia solution is ammonia water.
  • the pyrolysis product is subjected to an amination modification reaction through a silane compound under the conditions of ammonia solution and water, so that -NH 2 is introduced into the surface of the pyrolysis product to obtain the sludge base.
  • Hexavalent chromium composite adsorbent including:
  • TEOS and APTES are added to perform an amination modification reaction to introduce -NH 2 to the surface of the pyrolysis product;
  • the sludge-based hexavalent chromium composite adsorbent is obtained through filtration, ethanol washing and drying;
  • the reaction temperature of the amination modification reaction is 15-35°C;
  • the reaction time of the amination modification reaction is 24-48 hours.
  • the mixture of aerobic sludge and graphite slag is added to the activator, impregnated, and pyrolytically modified to obtain pyrolysis products, including:
  • the aerobic sludge and graphite slag mixture and the activator are mixed according to a solid-liquid ratio of 1: (1-5.5);
  • the concentration of the activator is 1-5mol/L;
  • the stirring time is 24 hours;
  • the temperature during high-temperature drying of the filter residue is 105°C;
  • the time for drying the filter residue at high temperature is 24 hours;
  • the temperature of the high-temperature tube furnace pyrolysis is 350-650°C;
  • pyrolysis is performed under the protection of nitrogen atmosphere
  • the pyrolysis time is 1-4 hours
  • the flow rate of nitrogen during pyrolysis is 0.5L/min;
  • the heating rate of the high-temperature tube furnace is 5°C/min.
  • the activator is any one of ZnCl 2 solution, KOH solution and H 3 PO 4 solution;
  • the concentrations of ZnCl 2 solution, KOH solution and H 3 PO 4 solution are all 1-5 mol/L;
  • the filter residue is taken after the vacuum filtration, and the filter residue is dried at high temperature.
  • the method further includes:
  • the stirring and mixing time is 5 minutes.
  • the process further comprises:
  • the dried aerobic sludge and graphite slag are crushed separately and passed through a 100-mesh sieve to obtain sludge particles and graphite slag particles. grain;
  • an electric blast drying oven is used for drying
  • the drying time is 24 hours;
  • the drying temperature is 105°C;
  • the sludge and graphite slag are crushed separately, using a swing crusher;
  • the mixing ratio of sludge particles and graphite slag particles is (5-10):1.
  • the particle size in the mixture of aerobic sludge and graphite slag is 0.05-0.15 mm.
  • the present application also provides a sludge-based hexavalent chromium composite adsorbent, which is prepared according to the above preparation method of the sludge-based hexavalent chromium composite adsorbent.
  • each particle monomer of the sludge-based hexavalent chromium composite adsorbent has a composite structure
  • the composite structure of the particle monomer is: with the pyrolysis product particles after pyrolysis of a mixture of aerobic sludge and graphite slag as the core, with multiple groups of Si-O-Si bonds covering the outer surface of the pyrolysis product particles.
  • the middle layer has a composite structure with -NH 2 molecules connected to Si in the Si-O-Si bond as the outer layer;
  • connection between Si and -NH 2 molecules in the Si-O-Si bond is as shown in the following chemical formula:
  • the invention provides a sludge-based hexavalent chromium composite adsorbent and a preparation method thereof.
  • the preparation method includes: adding a mixture of aerobic sludge and graphite slag into an activator, impregnating it, and performing pyrolysis modification to obtain a pyrolysis product; performing amination modification on the pyrolysis product to make the pyrolysis product -NH 2 is introduced into the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorbent.
  • the present invention fully mixes two solid wastes, the remaining sludge in the aerobic pool and the graphite slag generated during the lithium battery recycling process, and uses chemical activation, bonding and pyrolysis technology to prepare a composite adsorbent, and then further uses the amine function Chemical modification improves surface activity and the ability to selectively adsorb Cr(VI), and the obtained adsorbent can quickly and efficiently adsorb Cr(VI) in acidic wastewater.
  • the preparation method of the sludge-based hexavalent chromium composite adsorbent provided by the present invention has the following beneficial effects:
  • the present invention introduces -NH 2 on the particle surface of the pyrolysis product through amine functional modification, which can be protonated to form -NH 3 + under acidic conditions, and strengthens the adhesion to Cr(VI) through ion exchange and electrostatic attraction. selective adsorption;
  • the sludge-based hexavalent chromium composite adsorbent After the sludge-based hexavalent chromium composite adsorbent is saturated, it can be desorbed with a 1 mol/L NaOH and NaCl mixed solution, and the adsorption rate can reach more than 60% after being recycled 5 times.
  • Figure 1 is a schematic flow chart of the preparation method of the sludge-based hexavalent chromium composite adsorbent in the embodiment
  • Figure 2 is a reaction diagram of the sludge-based hexavalent chromium composite adsorbent obtained by the amination modification reaction of the hot bond product;
  • Figure 3 is a composite structure diagram of the monomer particles of the sludge-based hexavalent chromium composite adsorbent
  • Figure 4 is a molecular level composite structure diagram of the monomer particles of the sludge-based hexavalent chromium composite adsorbent
  • Figure 5 is a schematic flow chart of the preparation method of the sludge-based hexavalent chromium composite adsorbent in the embodiment including step S300, step S400 and step S500;
  • Figure 6 is an overall preparation flow chart of the preparation method of the sludge-based hexavalent chromium composite adsorbent in the embodiment.
  • the terms “comprises”, “comprising”, “having”, “containing” or “involving” are inclusive or open-ended and do not exclude other unrecited elements or method steps. .
  • the term “consisting of” is considered to be a preferred embodiment of the term “comprising”. If in the following a certain group is defined as containing at least a certain number of embodiments, this is also to be understood as revealing that a group preferably consists only of these embodiments.
  • a method for preparing a sludge-based hexavalent chromium composite adsorbent is provided. Refer to Figure 1, which includes:
  • Step S100 Add the mixture of aerobic sludge and graphite slag into the activator, impregnate it, and perform pyrolysis modification to obtain a pyrolysis product;
  • Step S200 Amination modification is performed on the pyrolysis product to introduce -NH 2 onto the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorbent.
  • the sludge referred to in this application is aerobic sludge, which refers to the sludge waste remaining after sewage treatment in the sewage treatment plant, which is the remaining sludge in the aerobic pool, including new energy companies. A large amount of aerobic sludge waste is generated during the production of batteries.
  • graphite is an allotrope of carbon. It is a gray-black, opaque solid with stable chemical properties, corrosion resistance, and does not easily react with chemicals such as acids and alkalis. Natural graphite comes from graphite deposits, and artificial graphite can also be made from petroleum coke, pitch coke, etc. through a series of processes. Graphite burns in oxygen to produce carbon dioxide, which can be oxidized by strong oxidants such as concentrated nitric acid, potassium permanganate, etc.
  • the graphite slag referred to in the application refers to the large amount of graphite slag produced during the recycling process of lithium batteries in the new energy automobile industry.
  • activation is chemical activation.
  • a chemical reaction for a chemical reaction to occur between the reactants, first their molecules and other particles must collide with each other. Experiments have shown that among countless collisions between molecules, most of them are ineffective; only a few of them can trigger chemical reactions. Such collisions that can produce chemical reactions are called effective collisions. Molecules that undergo effective collisions are called activated molecules. Molecules have energy due to thermal motion. The average energy of all molecules is low. Some molecules have greater energy due to various reasons. They are so-called activated molecules. Therefore, the activation process is a process in which a catalyst is added to a chemical reaction to increase the number of activated molecules in the entire chemical reaction and reduce the activation energy.
  • CN108479702 discloses a method for preparing a sludge-based activated carbon adsorbent.
  • the method uses municipal sludge as raw material, and after drying, grinding, screening, and washing, it is passed through a tube furnace at a certain temperature. Roasting, carbonizing, adding activator, mixing evenly, and then roasting in a tubular furnace.
  • the sludge-based activated carbon adsorbent obtained after the activation treatment is used to remove indoor polluting gas formaldehyde.
  • this preparation method modifies municipal sludge through pyrolysis and realizes the resource utilization of sludge, this preparation method requires multiple high-temperature roasting pyrolysis for preparation, and the prepared adsorbent has maximum adsorption of formaldehyde. Lower capacity and longer adsorption time.
  • the first raw materials used are aerobic sludge and graphite slag. These two wastes are worthless waste produced in the production process of new energy enterprises. After recycling, they can produce good waste materials. Economic benefits.
  • Graphite slag which has rich carbon content, can produce a positive synergistic effect when pyrolyzed together with sludge. After being introduced, it can not only make up for the shortcomings of small specific surface area and insufficient porosity of sludge pyrolysis products alone, but also can It reduces the proportion of heavy metals in the raw materials to a certain extent and enhances the safety of the use of adsorbents.
  • the preparation method used is to mix the raw materials (a mixture of aerobic sludge and graphite slag) first and then impregnate it with an activator. That is, the mixture of aerobic sludge and graphite slag is mixed as a raw material. , then add different activators to impregnate the mixture of aerobic sludge and graphite slag using the post-impregnation activation method, which can simultaneously disperse the activator on the sludge and graphite to enhance the active sites, which is beneficial to microbial sludge during subsequent pyrolysis.
  • pore etching is strengthened and the specific surface area is increased.
  • this embodiment uses amine functional modification to introduce -NH 2 , which can be protonated to form -NH 3 + under acidic conditions, and the selectivity for Cr(VI) is enhanced through ion exchange and electrostatic attraction. Adsorption.
  • the present invention fully mixes two solid wastes, the remaining sludge in the aerobic pool and the graphite slag generated during the lithium battery recycling process, and uses chemical activation, bonding and pyrolysis technology to prepare a composite adsorbent, and then further uses the amine function Chemical modification improves surface activity and the ability to selectively adsorb Cr(VI), and the obtained adsorbent can quickly and efficiently adsorb Cr(VI) in acidic wastewater.
  • the preparation method of the sludge-based hexavalent chromium composite adsorbent provided by the present invention, after dipping the raw material aerobic sludge and graphite slag mixture into an activator for activation, a large specific surface area adsorbent material can be obtained with only one pyrolysis. , the preparation process is simpler; -NH 2 is introduced on the particle surface of the pyrolysis product through amine functional modification, which can be protonated to form -NH 3 + under acidic conditions.
  • Ion exchange and electrostatic attraction enhance the selective adsorption of Cr(VI); after the sludge-based hexavalent chromium composite adsorbent is saturated, it can be desorbed with a 1 mol/L NaOH and NaCl mixed solution and can be recycled for 5 The adsorption rate can reach more than 60% after the second time.
  • the pyrolysis product is subjected to amination modification to introduce -NH 2 onto the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorbent, which includes:
  • the pyrolysis product is subjected to an amination modification reaction through a silane compound under the conditions of ammonia solution and water, so that -NH 2 is introduced into the surface of the pyrolysis product to obtain the sludge-based hexavalent chromium composite adsorption agent.
  • Silane is a compound of silicon and hydrogen. It is a general name for a series of compounds, including monosilane (SiH 4 ), disilane (Si 2 H 6 ) and some higher-level silicon hydrogen compounds. The general formula is Sin H 2n+2 . Among them, monosilane is the most common, and monosilane is sometimes referred to simply as silane.
  • Silane compounds refer to compounds with four substituents on the silicon atom, such as tetramethylsilane (Si(CH 3 ) 4 ), trichlorosilane (SiHCl 3 ), etc.
  • the silane compounds referred to in this application specifically refer to compounds that can undergo amination modification reaction under the conditions of ammonia solution and water.
  • the premise of the amination modification reaction is that the silane compound can undergo hydrolysis reaction under the conditions of ammonia solution and water, so that -NH 2 can be introduced onto the surface of each particle of the pyrolysis product.
  • ammonia solution mentioned above may refer to ammonia water, industrial ammonia water or other forms of ammonia aqueous solutions.
  • reaction process of the amination modification reaction includes:
  • the silane compound is hydrolyzed under the catalysis of an ammonia solution to produce Si-OH groups attached to the surface of the pyrolysis product;
  • the Si-OH groups generate condensation reactions with each other and condense into Si-O-Si bonds;
  • amino groups cover and wrap the Si-O-Si bonds on the surface of the pyrolysis product to form the sludge-based hexavalent chromium composite adsorbent that introduces -NH2 .
  • the amination modification reaction is a process of hydrolysis, condensation and replacement to form a coating.
  • silane compounds can produce Si-OH groups attached to the surface of the pyrolysis product after hydrolysis;
  • a sludge-based hexavalent chromium composite adsorbent with a composite structure is prepared (see Figure 3).
  • the composite structure of the sludge-based hexavalent chromium composite adsorbent has pyrolysis product particles as the core, with multiple Si-O-Si bonds connected to the outside of the core as an intermediate layer, and between each Si-O-Si bond The Si molecules are connected to the introduced -NH 2 as a multi-layer structure of the peripheral layer.
  • the amination modification reaction also includes:
  • the Si-OH group can also undergo a condensation reaction with the carboxyl group on the surface of the pyrolysis product.
  • Si-OH groups will also undergo condensation and other reactions with active groups such as carboxyl groups on the surface of the pyrolysis product. After the reaction, a sludge-based hexavalent chromium composite adsorbent is finally obtained.
  • the silane compound is a silane compound that can be hydrolyzed to generate Si-OH groups under the catalysis of ammonia solution.
  • the silane compound includes one or a combination of TEOS and APTES;
  • TEOS is tetraethoxysilane
  • APTES is aminopropyltriethoxysilane
  • a combination of two silane compounds, tetraethoxysilane and aminopropyltriethoxysilane, is used in this embodiment.
  • ammonia solution is ammonia water.
  • Hexavalent chromium composite adsorbent including:
  • TEOS and APTES are added to perform an amination modification reaction to introduce -NH 2 to the surface of the pyrolysis product;
  • the sludge-based hexavalent chromium composite adsorbent is obtained through filtration, ethanol washing and drying;
  • the Si-O-Si bonds on the surface of the particles are aminated, so that a -NH 2 is connected to the Si molecule of each Si-O-Si bond, so that on the surface of the particles
  • the surface forms a layer covering it Peripheral structure of molecules.
  • the final product formed is the sludge-based hexavalent chromium composite adsorbent.
  • each particle of the sludge-based hexavalent chromium composite adsorbent formed is a composite structure.
  • the composite structure is based on the pyrolysis product particles of the mixture of aerobic sludge and graphite slag as the core.
  • the molecular structure composed of Si-O-Si bond and -NH 2 after connection is
  • reaction temperature of the amination modification reaction is 15-35°C;
  • reaction time of the amination modification reaction is 24-48 hours.
  • the mixture of aerobic sludge and graphite slag is added to the activator for impregnation, and pyrolysis modification is performed to obtain pyrolysis products, including:
  • the dried filter residue is placed into a high-temperature tube furnace for pyrolysis to obtain the pyrolysis product.
  • the aerobic sludge and graphite slag mixture and the activator are mixed according to a solid-liquid ratio of 1: (1-5.5);
  • the concentration of the activator is 1-5mol/L;
  • the stirring time is 24 hours;
  • the temperature during high-temperature drying of the filter residue is 105°C;
  • the time for drying the filter residue at high temperature is 24 hours;
  • the temperature of the high-temperature tube furnace pyrolysis is 350-650°C;
  • pyrolysis is performed under the protection of nitrogen atmosphere
  • the pyrolysis time is 1-4 hours
  • the flow rate of nitrogen during pyrolysis is 0.5L/min;
  • the heating rate of the high-temperature tube furnace is 5°C/min.
  • the activator is any one of ZnCl 2 solution, KOH solution and H 3 PO 4 solution;
  • the concentrations of ZnCl 2 solution, KOH solution and H 3 PO 4 solution are all 1-5 mol/L;
  • the filter residue is taken after the vacuum filtration, and the filter residue is dried at high temperature.
  • the method further includes:
  • the stirring and mixing time is 5 minutes.
  • the above pyrolysis step can be as follows: take the pyrolysis product, add it to an activator of 1-5 mol/L at a solid-liquid ratio of 1: (1-5.5), and immerse it in it. After stirring for 24 hours, press the pyrolysis product: carboxymethyl The base cellulose is (18-20): 1 ratio, add carboxymethyl cellulose and stir for 5 minutes. After vacuum filtration, take the filter residue and place it in an oven to dry at 105°C for 24 hours, and then place it in a high-temperature tube furnace at 350- Pyrolysis at 650°C for 1-4h under the protection of nitrogen atmosphere.
  • carboxymethylcellulose introduces a large number of hydroxyl groups, which can significantly enhance the hydrophilicity of the adsorbent and accelerate the adsorption rate of Cr(VI).
  • step S100 the mixture of aerobic sludge and graphite slag is added to the activator, impregnated, and subjected to pyrolysis modification.
  • the mixture of aerobic sludge and graphite slag is added to the activator, impregnated, and subjected to pyrolysis modification.
  • the pyrolysis product it also includes:
  • Step S300 take aerobic sludge and graphite slag and dry them separately;
  • Step S400 crush the dried aerobic sludge and graphite slag respectively, and pass them through a 100-mesh sieve to obtain sludge particles and graphite slag particles;
  • Step S500 mix the sludge particles and the graphite slag particles to obtain the aerobic sludge and graphite slag mixture;
  • an electric blast drying oven is used for drying
  • the drying time is 24 hours
  • the drying temperature is 105°C;
  • the sludge and graphite slag are crushed separately, using a swing crusher;
  • the mixing ratio of sludge particles and graphite slag particles is (5-10):1.
  • the particle size in the mixture of aerobic sludge and graphite slag is 0.05-0.15 mm.
  • the above steps are pretreatment steps.
  • the aerobic remaining sludge and graphite slag are taken from the workshop and put into an electric blast drying box to dry at 105°C for 24 hours; the dried sludge and graphite slag are sealed respectively.
  • the swing crusher crushes and passes through a 100 mesh sieve to obtain sludge particles and graphite slag particles respectively.
  • the sludge particles and graphite slag particles are fully mixed at a ratio of (5-10):1 to obtain oxygen sludge and graphite slag. mixture.
  • steps S100 and S200 refer to Figure 6 for an overall flow chart.
  • this application also provides a sludge-based hexavalent chromium composite adsorbent, which is prepared according to the above preparation method of the sludge-based hexavalent chromium composite adsorbent.
  • each particle monomer of the sludge-based hexavalent chromium composite adsorbent has a composite structure
  • the composite structure of the particle monomer can be regarded as a three-layer structure from the perspective of the molecular level: a composite structure with the pyrolysis product particles after the pyrolysis of the aerobic sludge and graphite slag mixture as the core, multiple groups of Si-O-Si bonds as the middle layer covering the outer surface of the pyrolysis product particles, and -NH2 molecules connected to Si in the Si-O-Si bonds as the outer layer;
  • connection between Si and -NH 2 molecules in the Si-O-Si bond is as shown in the following chemical formula:
  • a method for preparing a sludge-based hexavalent chromium composite adsorbent including the following steps:
  • a method for preparing a sludge-based hexavalent chromium composite adsorbent including the following steps:
  • a method for preparing a sludge-based hexavalent chromium composite adsorbent including the following steps:
  • a method for preparing a sludge-based hexavalent chromium composite adsorbent including the following steps:
  • An adsorbent, its preparation method includes:
  • An adsorbent, its preparation method includes:
  • the sludge-based hexavalent chromium composite adsorbents in Examples 1-4 were prepared by using the preparation method provided in this application, and the sludge-based hexavalent chromium composite adsorbents that did not undergo amination modification reaction and did not form a composite were prepared respectively.
  • the adsorbents in the above examples and comparative examples were added to the Cr(VI)-containing wastewater and stirred for 3 hours. After the adsorption was completed, the adsorbent was filtered out and measured. The remaining Cr(VI) content in the water body was calculated, and the Cr(VI) adsorption rate was calculated.
  • Comparative Example 1 is only pyrolysis reaction is performed after raw material pretreatment.
  • Comparative Example 2 is pyrolysis reaction is performed after adding carboxymethylcellulose after raw material pretreatment. Both groups of adsorbents have no Amination modification reaction was carried out, and the Cr(VI) adsorption rates of Comparative Examples 1 and 2 were 4.68% and 31.76% respectively; among them, due to the addition of carboxymethyl fiber before the pyrolysis reaction in Comparative Example 2 Compared with Comparative Example 1, the adsorption rate has increased, indicating that the addition of carboxymethylcellulose can improve the bonding effect of sludge and graphite slag, improve the stability of the composite material structure, and improve the stability of the composite material structure.
  • the adsorbent can still maintain its original structure after recycling.
  • the addition of carboxymethylcellulose can provide the technical effect of introducing a large number of hydroxyl groups, enhancing the hydrophilicity of the adsorbent, and accelerating the adsorption rate of Cr(VI).
  • Examples 1-4 are all sludge-based hexavalent chromium composite adsorbents prepared according to the preparation method provided in this application, and the particle monomers of the adsorbents are all Composite structure, it can be seen from the experimental data that Examples 1-4 can all achieve a Cr(VI) adsorption rate of 63.51% and above.
  • the sludge-based hexavalent chromium composite adsorbent prepared by the method provided in the embodiment is modified by amine functionalization to introduce -NH 2 on the particle surface of the pyrolysis product, which can be protonated to form -NH 3 + under acidic conditions.
  • the selective adsorption of Cr(VI) is enhanced through ion exchange and electrostatic attraction.
  • the main raw materials of the adsorbent are residual sludge and graphite slag, which are worthless wastes produced in the production process of a certain enterprise and have good economic benefits after recycling.
  • graphite slag has rich carbon content, and can produce a positive synergistic effect when pyrolyzed together with sludge. After being introduced, it can not only make up for the shortcomings of small specific surface area and insufficient porosity of sludge pyrolysis products alone, but also can It reduces the proportion of heavy metals in the raw materials to a certain extent and enhances the safety of the use of adsorbents.
  • the raw materials are mixed first and then impregnated with the activator: first mix the sludge and graphite slag thoroughly, and then add different activators for impregnation.
  • the activator can be dispersed on the sludge and graphite at the same time to enhance the active sites.
  • subsequent pyrolysis which is conducive to strengthening pore etching and increasing the specific surface area during the formation of micropores.
  • a 1 mol/L NaOH and NaCl mixed solution can be used for desorption. After five cycles, the adsorption rate can reach more than 60%.

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Abstract

本发明提供一种污泥基六价铬复合吸附剂及其制备方法。其中，所述制备方法包括：将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物；对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。本发明通过将原料混合为好氧污泥和石墨渣混合物后，将其浸渍于活化剂中，只需一次热解就能得到大比表面积吸附材料，制备过程更为简洁；利用胺基功能化改性在热解产物的颗粒表面引入-NH2，在酸性条件下能质子化形成-NH3 +，通过离子交换和静电吸引加强了对Cr(VI)的选择性吸附。

Description

一种污泥基六价铬复合吸附剂及其制备方法 技术领域
本发明属于废弃物再利用和环境保护技术领域，尤其涉及一种污泥基六价铬复合吸附剂及其制备方法。
背景技术
近年来，污水处理厂的数量大幅增加，使得市政污水、工业废水得以有效地控制。然而，污水处理厂产生的大量污泥得不到妥善处理，带来了严重的环境问题和安全隐患。传统的污泥处理方法主要有农业利用、卫生填埋、焚烧和海洋倾倒等。但这些方法均存在一定的缺陷和不足，如农业利用时污泥中的有害成分不能超过受施土壤的环境容量、填埋污泥中的有毒有害物质经雨水的侵蚀和渗漏会污染地下水环境、污泥焚烧过程易产生二次污染、海洋倾倒破坏生态环境等，这些方法难以满足日益严格的环保要求。
热解法，利用污泥碳元素含量高的特点，在无氧或缺氧条件下对其加热干馏，使其中的微生物残体、有机污染物、致病菌得以无害化、减量化处理，剩余固态残渣能有效保留其中的碳元素，形成具有高附加值的可燃气、液态焦油、污泥焦炭产物。同时，污泥中的微量重金属元素在高温热解中转变为特殊结构残渣态，呈惰性，不能被生物所吸收利用，也不能通过食物链在人体内积累，是一种最安全的重金属形态。
新能源汽车行业目前发展迅猛，在锂电池回收过程中会产生大量的剩余好氧污泥和石墨渣，这些固废每年都需要花费大量成本进行处理，如能通过污泥热解技术，将其制作成吸附剂，回用于含铬废水处理，有助于为污泥处理无害化、资源化、减量化，变废为宝提供借鉴经验。
因此，如何通过高效率低成本的污泥热解技术，对污泥和石墨渣进行同时处理并形成含铬废水处理的吸附剂，成为当今废弃物再利用和环境保护技术领域的重要课题。
发明内容
为解决上述问题，本发明提供一种污泥基六价铬复合吸附剂的制备方法，包括：
将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物；
对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
优选地，所述对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
优选地，所述氨基化改性反应的反应过程包括：
所述硅烷类化合物在氨溶液催化下水解产生附着于所述热解产物表面的Si-OH基团；
所述Si-OH基团之间相互产生缩合反应，缩合成Si-O-Si键；
在氨溶液条件下，氨基覆盖并包裹在所述热解产物的表面的所述Si-O-Si键上，形成引入 -NH2的所述污泥基六价铬复合吸附剂。
优选地，所述氨基化改性反应，还包括：
所述Si-OH基团还能与所述热解产物表面的羧基发生缩合反应。
优选地，所述硅烷类化合物为能在氨溶液催化下水解产生Si-OH基团的硅烷类化合物；
优选地，所述硅烷类化合物包括TEOS和APTES中的一种或两种组合；
优选地，所述氨溶液为氨水。
优选地，所述将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
将所述热解产物分散于乙醇中，加入氨水和水混合；
加入TEOS和APTES进行氨基化改性反应，使所述热解产物的表面引入-NH2；
反应结束后依次经过滤、乙醇洗涤和干燥，即得到所述污泥基六价铬复合吸附剂；
优选地，所述氨基化改性反应的反应温度为15-35℃；
优选地，所述氨基化改性反应的反应时长为24-48小时。
优选地，所述将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物，包括：
将所述好氧污泥和石墨渣混合物，加至所述活化剂中浸渍，搅拌混合，得到浸渍混合物；
减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣；
将所述干燥滤渣置入高温管式炉热解，即得到所述热解产物；
优选地，所述好氧污泥和石墨渣混合物与所述活化剂，按照固液比1：(1-5.5)混合；
优选地，所述活化剂的浓度为1-5mol/L；
优选地，所述搅拌混合过程中，搅拌的时间为24小时；
优选地，对所述滤渣高温干燥时的温度为105℃；
优选地，对所述滤渣高温干燥时的时间为24小时；
优选地，所述高温管式炉热解的温度为350-650℃；
优选地，热解时在氮气气氛保护下进行；
优选地，热解的时间为1-4小时；
优选地，热解时的氮气的流量为0.5L/min；
优选地，所述高温管式炉的升温速率为5℃/min。
优选地，所述活化剂为ZnCl2溶液、KOH溶液和H3PO4溶液中的任一种；
优选地，ZnCl2溶液、KOH溶液和H3PO4溶液的浓度均为1-5mol/L；
优选地，所述减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣之前，还包括：
根据所述浸渍混合物与羧甲基纤维素为(18-20)：1的比例条件，于所述浸渍混合物中添加羧甲基纤维素，搅拌混合；
优选地，搅拌混合的时间为5分钟。
优选地，所述将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物之前，还包括：
取好氧污泥和石墨渣分别进行干燥；
将干燥后的好氧污泥和石墨渣分别进行破碎，并过100目筛，得到污泥颗粒和石墨渣颗 粒；
将所述污泥颗粒和所述石墨渣颗粒混合，即得到所述好氧污泥和石墨渣混合物；
优选地，取好氧污泥和石墨渣分别进行干燥时，采用电热鼓风干燥箱进行干燥；
优选地，取好氧污泥和石墨渣分别进行干燥时，干燥时间为24小时；
优选地，取好氧污泥和石墨渣分别进行干燥时，干燥温度为105℃；
优选地，对污泥和石墨渣分别进行破碎，采用摇摆式粉碎机破碎；
优选地，所述好氧污泥和石墨渣混合物中，污泥颗粒和石墨渣颗粒的混合比例为(5-10)：1。
优选地，所述好氧污泥和石墨渣混合物中的颗粒粒径为0.05-0.15mm。
此外，为解决上述问题，本申请还提供一种污泥基六价铬复合吸附剂，根据上述污泥基六价铬复合吸附剂的制备方法制备而成。
优选地，所述污泥基六价铬复合吸附剂的每个颗粒单体均为复合结构；
所述颗粒单体的复合结构为：以好氧污泥和石墨渣混合物热解后的热解产物颗粒为核心，以多组Si-O-Si键为覆盖于所述热解产物颗粒外表面的中间层，以与Si-O-Si键中的Si相连接的-NH2分子为外围层的复合结构；
优选地，Si-O-Si键中的Si与-NH2分子的连接方式如下化学式所示：
本发明提供一种污泥基六价铬复合吸附剂及其制备方法。其中，所述制备方法，包括：将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物；对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
本发明通过将好氧池剩余污泥和锂电池回收过程中产生的石墨渣两种固废充分混匀，通过化学活化、粘结及热解技术制成复合吸附剂，随后进一步通过胺基功能化改性提高表面活性和选择性吸附Cr(VI)的能力，得到的吸附剂能快速高效地吸附酸性废水中的Cr(VI)。本发明所提供的污泥基六价铬复合吸附剂的制备方法具有如下有益效果：
1、本发明通过将原料混合为好氧污泥和石墨渣混合物后，将其浸渍于活化剂中，只需一次热解就能得到大比表面积吸附材料，制备过程更为简洁；
2、本发明通过胺基功能化改性在热解产物的颗粒表面引入-NH2，在酸性条件下能质子化形成-NH3 +，通过离子交换和静电吸引加强了对Cr(VI)的选择性吸附；
3、污泥基六价铬复合吸附剂在吸附饱和后，可采用1mol/L的NaOH和NaCl混合溶液进行解吸，能够在循环使用5次后吸附率还能达到60％以上。
附图说明
图1为实施例中污泥基六价铬复合吸附剂的制备方法的流程示意图；
图2为热键产物氨基化改性反应得到污泥基六价铬复合吸附剂的反应式图；
图3为污泥基六价铬复合吸附剂的单体颗粒的复合结构图；
图4为污泥基六价铬复合吸附剂的单体颗粒的分子层面的复合结构图；
图5为实施例中污泥基六价铬复合吸附剂的制备方法包括步骤S300、步骤S400和步骤S500的流程示意图；
图6为实施例中污泥基六价铬复合吸附剂的制备方法的整体制备流程图。
附图标记：
100、污泥基六价铬复合吸附剂(一个颗粒单体)；110、核心；120、中间层；130、外
围层。
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非在下文中另有定义，本发明具体实施方式中所用的所有技术术语和科学术语的含义意图与本领域技术人员通常所理解的相同。虽然相信以下术语对于本领域技术人员很好理解，但仍然阐述以下定义以更好地解释本发明。
如本发明中所使用，术语“包括”、“包含”、“具有”、“含有”或“涉及”为包含性的(inclusive)或开放式的，且不排除其它未列举的元素或方法步骤。术语“由…组成”被认为是术语“包含”的优选实施方案。如果在下文中某一组被定义为包含至少一定数目的实施方案，这也应被理解为揭示了一个优选地仅由这些实施方案组成的组。
在提及单数形式名词时使用的不定冠词或定冠词例如“一个”或“一种”，“所述”，包括该名词的复数形式。
本发明中的术语“大约”表示本领域技术人员能够理解的仍可保证论及特征的技术效果的准确度区间。该术语通常表示偏离指示数值的±10％，优选±5％。
此外，说明书和权利要求书中的术语第一、第二、第三、(a)、(b)、(c)以及诸如此类，是用于区分相似的元素，不是描述顺序或时间次序必须的。应理解，如此应用的术语在适当的环境下可互换，并且本发明描述的实施方案能以不同于本发明描述或举例说明的其它顺序实施。
除非另外定义或由背景清楚指示，否则在本公开中的全部技术与科学术语具有如本公开所属领域的普通技术人员通常理解的相同含义。
下面结合具体实施例的方式对本发明的技术方案做进一步的详细说明，但并不构成对本发明的任何限制，任何人在本发明权利要求范围内所做的有限次的修改，仍在本发明的权利要求范围之内。
本实施例中，提供一种污泥基六价铬复合吸附剂的制备方法，参考图1，包括：
步骤S100，将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物；
步骤S200，对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
上述，本申请中所指的污泥，为好氧污泥，其中，针对的是污水处理厂在进行污水处理后剩余的污泥废料，为好氧池剩余污泥，也包括新能源企业在生产电池过程中所产生的大量好氧污泥废料。
上述，需要说明的是，石墨是碳的一种同素异形体，为灰黑色、不透明固体，化学性质稳定，耐腐蚀，同酸、碱等药剂不易发生反应。天然石墨来自石墨矿藏，也可以以石油焦、沥青焦等为原料，经过一系列工序处理而制成人造石墨。石墨在氧气中燃烧生成二氧化碳，可被强氧化剂如浓硝酸、高锰酸钾等氧化。
上述，申请中的所指的石墨渣，是指新能源汽车行业在锂电池回收过程中，所产生大量的石墨渣。
上述，石墨渣和好氧污泥，两种废料均为固体废料。
上述，活化，即为化学活化，在化学反应中，反应物之间要能发生化学反应，首先它们的分子等微粒间必须发生相互碰撞。实验证明，在无数次分子间的碰撞中，大多数的碰撞是无效的；只有其中少数分子间的碰撞才能引发化学反应。这种能够发生化学反应的碰撞叫做有效碰撞。发生有效碰撞的分子叫做活化分子。分子由于热运动而具有能量，所有分子具有的平均能量是较低的，部分分子由于种种原因而具有较大的能量，它们就是所谓活化分子。所以活化的过程就是在化学反应中添加催化剂，使整个化学反应中的活化分子增多，活化能降低的一个过程。
需要说明的是，CN108479702中，公开了一种污泥基活性炭吸附剂的制备方法，所述方法以市政污泥为原材料，经干燥、研磨、筛分、洗涤后，通过管式炉在一定温度下焙烧，碳化处理，再添加活化剂混合均匀后经管式炉焙烧，活化处理后得到的污泥基活性炭吸附剂用于去除室内污染气体甲醛。上述方法虽然通过热解法改性市政污泥，实现了污泥的资源化利用，但是该制备方法，需要采用多次高温焙烧热解进行制备，并且所制备得到的吸附剂对甲醛的最大吸附容量较低、吸附时间较长。
而本实施例中，首先采用的原料即为好氧污泥和石墨渣两种废料，这两种废料均属于新能源企业生产过程中产出的无价值废弃物，资源化后能够产生良好的经济效益。
石墨渣，具有丰富的碳含量，与污泥一同热解，可以产生正向的协同效应，引入后不仅可以弥补了污泥单独热解产物比表面积小和孔隙度不足的缺点，还能在一定程度上降低原料中重金属的比重，加强了吸附剂使用的安全性。
本实施例中，采用的制备方法是，取原料(好氧污泥和石墨渣混合物)先混合再用活化剂浸渍的方法，即为先将好氧污泥和石墨渣混合物在混合后作为原料，再加入不同活化剂浸渍，采用浸渍后活化方法的好氧污泥和石墨渣混合物，能够同时实现将活化剂分散在污泥和石墨上增强活性位点，后续热解时，有利于在微孔的形成过程中加强孔隙刻蚀，增大比表面积。
现有的方法中，众多污泥焦炭类吸附剂的表面化学官能团种类很少且含量低，使其在吸附时吸附选择性差、吸附容量有限。针对这一问题，本实施例通过胺基功能化改性来引入-NH2，在酸性条件下能质子化形成-NH3+，通过离子交换和静电吸引加强了对Cr(VI)的选择性吸附。
本发明通过将好氧池剩余污泥和锂电池回收过程中产生的石墨渣两种固废充分混匀，通过化学活化、粘结及热解技术制成复合吸附剂，随后进一步通过胺基功能化改性提高表面活性和选择性吸附Cr(VI)的能力，得到的吸附剂能快速高效地吸附酸性废水中的Cr(VI)。本发明所提供的污泥基六价铬复合吸附剂的制备方法在将原料好氧污泥和石墨渣混合物浸渍于活化剂中进行活化后，只需一次热解就能得到大比表面积吸附材料，制备过程更为简洁；通过胺基功能化改性在热解产物的颗粒表面引入-NH2，在酸性条件下能质子化形成-NH3+，通过 离子交换和静电吸引加强了对Cr(VI)的选择性吸附；污泥基六价铬复合吸附剂在吸附饱和后，可采用1mol/L的NaOH和NaCl混合溶液进行解吸，能够在循环使用5次后吸附率还能达到60％以上。
进一步的，参考图2，所述对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
硅烷即硅与氢的化合物，是一系列化合物的总称，包括甲硅烷(SiH4)、乙硅烷(Si2H6)和一些更高级的硅氢化合物，通式为SinH2n+2。其中，甲硅烷最为常见，有时也将甲硅烷简称为硅烷。硅烷类化合物，硅烷类化合物是指硅原子上具有四个取代基的化合物，如四甲基硅烷(Si(CH3)4)、三氯硅烷(SiHCl3)等。本申请中所指的硅烷类化合物，特指能在氨溶液和水的条件下进行氨基化改性反应的化合物。
上述，氨基化改性反应的前提是，硅烷类化合物能在氨溶液和水的条件下发生水解反应，从而使热解产物的每个颗粒的表面能够引入-NH2。
上述，氨溶液，可以指代的是氨水、工业氨水或者其他形式的氨的水溶液。
优选地，所述氨基化改性反应的反应过程包括：
所述硅烷类化合物在氨溶液催化下水解产生附着于所述热解产物表面的Si-OH基团；
所述Si-OH基团之间相互产生缩合反应，缩合成Si-O-Si键；
在氨溶液条件下，氨基覆盖并包裹在所述热解产物的表面的所述Si-O-Si键上，形成引入-NH2的所述污泥基六价铬复合吸附剂。
上述，氨基化改性反应，是一个水解、缩合并替换形成包覆的过程。
其中，硅烷类化合物在水解后，能够产生附着于热解产物表面的Si-OH基团；
进一步的，在每个热解产物的颗粒的表面均附着有多个以颗粒为核心的Si-OH基团，Si-OH基团之间相互进行缩合，从而形成Si-O-Si键，从而形成了表面附着有多个Si-O-Si键的热解产物颗粒；
再进一步，随着缩合反应的进行，颗粒表面的多个Si-O-Si键上在氨溶液的条件下引入了大量的胺基，导致颗粒表面在附着了Si-O-Si键的基础上，又包裹了与Si-O-Si键相连接的-NH2。
由此，即制备成了具有复合结构的污泥基六价铬复合吸附剂(参考图3)。而污泥基六价铬复合吸附剂的复合结构，为以热解产物颗粒为核心，核心外连接有多个Si-O-Si键作为中间层，并且在每个Si-O-Si键的Si分子处均连接有所引入的-NH2作为外围层的多层结构。
进一步的，所述氨基化改性反应，还包括：
所述Si-OH基团还能与所述热解产物表面的羧基发生缩合反应。
此外，部分Si-OH基团还会和热解产物的表面的羧基等活性基团进行缩合等反应，反应后最终得到污泥基六价铬复合吸附剂。
进一步的，所述硅烷类化合物为能在氨溶液催化下水解产生Si-OH基团的硅烷类化合物。
进一步的，所述硅烷类化合物包括TEOS和APTES中的一种或两种组合；
上述，TEOS，即为四乙氧基硅烷；APTES即为氨丙基三乙氧基硅烷。
优选地，本实施例中采用四乙氧基硅烷和氨丙基三乙氧基硅烷两种硅烷类化合物的组合。
进一步的，所述氨溶液为氨水。
进一步的，所述将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
将所述热解产物分散于乙醇中，加入氨水和水混合；
加入TEOS和APTES进行氨基化改性反应，使所述热解产物的表面引入-NH2；
反应结束后依次经过滤、乙醇洗涤和干燥，即得到所述污泥基六价铬复合吸附剂；
上述，加入TEOS和APTES进行氨基化改性反应，使所述热解产物的表面引入-NH2的过程中，从反应整体来说，分别进行的是两个反应过程：
1、TEOS和APTES的在氨水催化下的水解反应，以及2、针对于颗粒的氨基化改性反应，分别为：
(1)TEOS的水解反应如下反应式所示：
(2)APTES的水解反应如下反应式所示：
(3)在水解反应之后，热解产物的每一个颗粒表面，均附着有多个以颗粒为核心的Si-O-Si键，形成一种复合结构，即，颗粒的外表面附着有大量的Si-O-Si键；
(4)在进一步的反应中，针对于颗粒表面的Si-O-Si键进行氨基化，从而在每个Si-O-Si键的Si分子上均连接上一个-NH2，从而在颗粒的表面形成一层覆盖于其上的分子的外围结构。
至此，形成的终产品即为污泥基六价铬复合吸附剂。
上述，由此形成的污泥基六价铬复合吸附剂，其每一个颗粒均为复合结构，该复合结构参考图4，是以好氧污泥和石墨渣混合物的热解产物颗粒为核心，以Si-O-Si键为中间层，以-NH2为外围层的复合结构。其中，Si-O-Si键与-NH2在连接后组成的分子结构为
进一步的，所述氨基化改性反应的反应温度为15-35℃；
进一步的，所述氨基化改性反应的反应时长为24-48小时。
进一步的，所述将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物，包括：
将所述好氧污泥和石墨渣混合物，加至所述活化剂中浸渍，搅拌混合，得到浸渍混合物；
减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣；
将所述干燥滤渣置入高温管式炉热解，即得到所述热解产物。
优选地，所述好氧污泥和石墨渣混合物与所述活化剂，按照固液比1：(1-5.5)混合；
优选地，所述活化剂的浓度为1-5mol/L；
优选地，所述搅拌混合过程中，搅拌的时间为24小时；
优选地，对所述滤渣高温干燥时的温度为105℃；
优选地，对所述滤渣高温干燥时的时间为24小时；
优选地，所述高温管式炉热解的温度为350-650℃；
优选地，热解时在氮气气氛保护下进行；
优选地，热解的时间为1-4小时；
优选地，热解时的氮气的流量为0.5L/min；
优选地，所述高温管式炉的升温速率为5℃/min。
优选地，所述活化剂为ZnCl2溶液、KOH溶液和H3PO4溶液中的任一种；
优选地，ZnCl2溶液、KOH溶液和H3PO4溶液的浓度均为1-5mol/L；
优选地，所述减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣之前，还包括：
根据所述浸渍混合物与羧甲基纤维素为(18-20)：1的比例条件，于所述浸渍混合物中添加羧甲基纤维素，搅拌混合；
优选地，搅拌混合的时间为5分钟。
上述热解步骤，例如其可以为，取热解产物，以固液比1：(1-5.5)加入到1-5mol/L的活化剂中浸渍，搅拌24h后，按热解产物：羧甲基纤维素为(18-20)：1的比例，添加羧甲基纤维素搅拌5min，减压抽滤后取滤渣置于烘箱中105℃干燥24h，随后置于高温管式炉中在350-650℃、氮气气氛保护下热解1-4h。
需要说明的是，将污泥和石墨渣简单地物理混合后进行热解改性时，其烧结程度有限，羧甲基纤维素的加入可以提高污泥和石墨渣的粘结效果，提高复合材料(热解产物)结构的稳定性，在多次循环使用后吸附剂仍能保持其原有结构。
此外，羧甲基纤维素的加入引入了大量羟基，能够显著增强吸附剂的亲水性，加快了Cr(VI)的吸附速率。
进一步的，参考图5，所述步骤S100，将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物之前，还包括：
步骤S300，取好氧污泥和石墨渣分别进行干燥；
步骤S400，将干燥后的好氧污泥和石墨渣分别进行破碎，并过100目筛，得到污泥颗粒和石墨渣颗粒；
步骤S500，将所述污泥颗粒和所述石墨渣颗粒混合，即得到所述好氧污泥和石墨渣混合物；
优选地，取好氧污泥和石墨渣分别进行干燥时，采用电热鼓风干燥箱进行干燥；
优选地，取好氧污泥和石墨渣分别进行干燥时，干燥时间为24小时；
优选地，取好氧污泥和石墨渣分别进行干燥时，干燥温度为105℃；
优选地，对污泥和石墨渣分别进行破碎，采用摇摆式粉碎机破碎；
优选地，所述好氧污泥和石墨渣混合物中，污泥颗粒和石墨渣颗粒的混合比例为(5-10)：1。
优选地，所述好氧污泥和石墨渣混合物中的颗粒粒径为0.05-0.15mm。
上述步骤，为预处理步骤，例如可以为，从车间分别取好氧剩余污泥和石墨渣，分别放入电热鼓风干燥箱中105℃干燥24h；干燥后的污泥和石墨渣分别经密封摇摆式粉碎机破碎并过100目筛，分别得到污泥颗粒和石墨渣颗粒，随后将污泥颗粒和石墨渣颗粒以(5-10)：1比例充分混合，即得到氧污泥和石墨渣混合物。综合预处理步骤，以及步骤S100和步骤S200，参考图6为整体的流程图。
此外，本申请还提供一种污泥基六价铬复合吸附剂，根据上述污泥基六价铬复合吸附剂的制备方法制备而成。
进一步的，参考图3和图4，所述污泥基六价铬复合吸附剂的每个颗粒单体均为复合结构；
所述颗粒单体的复合结构在分子层面的角度，可以视为三层结构：以好氧污泥和石墨渣混合物热解后的热解产物颗粒为核心，以多组Si-O-Si键为覆盖于所述热解产物颗粒外表面的中间层，以与Si-O-Si键中的Si相连接的-NH2分子为外围层的复合结构；
进一步的，Si-O-Si键中的Si与-NH2分子的连接方式如下化学式所示：
下面通过具体的实施例进一步说明本发明，但是应当理解为，这些实施例仅仅是用于更详细地说明，而不应理解为用于以任何形式限制本发明。
实施例1
一种污泥基六价铬复合吸附剂的制备方法，包括如下步骤：
(1)取剩余的污泥和石墨渣各500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛，随后称取50g过筛后的污泥与石墨渣按5：1比例充分混合。
(2)将混合物按固液比1：2.5加入到5mol/L的ZnCl2溶液中搅拌24h后，加入3g羧甲基纤维素搅拌5min，减压抽滤后取滤渣置于烘箱中105℃干燥24h，随后置于高温管式炉中在氮气氛围、500℃下热解2h。
(3)胺基功能化改性：1g热解产物经超声充分分散于200ml无水乙醇中，随后加入15ml氨水和15ml超纯水，搅拌15min后加入5ml四乙氧基硅烷(TEOS)和10ml氨丙基三乙氧基硅烷(APTES)进行反应，反应结束后过滤并用乙醇洗涤3次，真空干燥后得到目标吸附剂。
(4)取实施例1中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝2-6的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)最大吸附率为76.82％。

(5)采用1mol/L NaOH溶液和1mol/L NaCl溶液的1：1混合液对实施例1所制备的吸附剂进行解吸，将解吸附后的吸附剂过滤并洗涤，真空干燥，进行循环利用。重复该过程5次，检测每一次吸附剂的重复利用效果，测试结果如下表所示。结果表明在5个吸附-再生循环后，Cr(VI)的吸附去除率仍保持在60％以上。
实施例2：
一种污泥基六价铬复合吸附剂的制备方法，包括如下步骤：
(1)取剩余污泥和石墨渣各500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛，随后称取50g过筛后的污泥与石墨渣按7：1比例充分混合。
(2)将混合物按固液比1：5.5加入到5mol/L的H3PO4溶液中搅拌24h，加入3g羧甲基纤维素搅拌5min，减压抽滤后取滤渣置于烘箱中105℃干燥24h，随后置于高温管式炉中在氮气氛围、500℃下热解3h。
(3)胺基功能化改性：1g热解产物经超声充分分散于200ml无水乙醇中，随后加入15ml氨水和15ml超纯水，搅拌15min后加入5ml四乙氧基硅烷(TEOS)和10ml氨丙基三乙氧基硅烷(APTES)进行反应，反应结束后过滤并用乙醇洗涤3次，真空干燥后得到目标吸附剂。
(4)取实施例2中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝3的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)吸附率为48.67％。
实施例3
一种污泥基六价铬复合吸附剂的制备方法，包括如下步骤：
(1)取剩余污泥和石墨渣各500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛，随后称取50g过筛后的污泥与石墨渣按10：1比例充分混合。
(2)将混合物按固液比1：1加入到3mol/L的KOH溶液中搅拌24h，加入3g羧甲基纤维素搅拌5min，减压抽滤后取滤渣于烘箱中105℃干燥24h，随后置于高温管式炉中在氮气氛围、350℃下热解4h。
(3)胺基功能化改性：1g热解产物经超声充分分散于200ml无水乙醇中，随后加入15ml氨水和15ml超纯水，搅拌15min后加入5ml四乙氧基硅烷(TEOS)和10ml氨丙基三乙氧基硅烷(APTES)进行反应，反应结束后过滤并用乙醇洗涤3次，真空干燥后得到目标吸附剂。
(4)取实施例3中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝3的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)吸 附率为52.48％。
实施例4
一种污泥基六价铬复合吸附剂的制备方法，包括如下步骤：
(1)取剩余污泥和石墨渣各500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛，随后称取50g过筛后的污泥与石墨渣按5：1比例充分混合。
(2)将混合物按固液比1：3加入到1mol/L的ZnCl2溶液中搅拌24h，加入3g羧甲基纤维素搅拌5min，减压抽滤后取滤渣于烘箱中105℃干燥24h，随后置于高温管式炉中在氮气氛围、650℃下热解2h。
(3)胺基功能化改性：1g热解产物经超声充分分散于200ml无水乙醇中，随后加入15ml氨水和15ml超纯水，搅拌15min后加入5ml四乙氧基硅烷(TEOS)和10ml氨丙基三乙氧基硅烷(APTES)进行反应，反应结束后过滤并用乙醇洗涤3次，真空干燥后得到目标吸附剂。
(4)取实施例4中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝3的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)吸附率为63.51％。
对比例1：预处理后只进行热解反应
一种吸附剂，其制备方法包括：
(1)取剩余污泥500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛得到粒径小于0.15mm的颗粒。
(2)将50g过筛后的颗粒置于高温管式炉中在氮气氛围、500℃下热解2h，得到目标吸附剂。
(3)取对比例1中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝3的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)吸附率为4.68％。
对比例2：预处理后，加入活化剂和羧甲基纤维素后进行热解反应
一种吸附剂，其制备方法包括：
(1)取剩余污泥和石墨渣各500g于烘箱中105℃下干燥24h，经密封摇摆式破碎机破碎后过100目筛，随后称取50g过筛后的污泥与石墨渣按5：1比例充分混合。
(2)将混合后颗粒按固液比1：2.5加入到5mol/L的ZnCl2溶液中搅拌24h，加入3g羧甲基纤维素搅拌5min，减压抽滤后取滤渣于烘箱中105℃干燥24h，随后置于高温管式炉中在氮气氛围、500℃下热解2h得到目标吸附剂。
(3)取对比例2中制备的吸附剂0.05g，加入到50mL浓度为50mg/L，pH＝3的模拟含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，得Cr(VI)吸附率为31.76％。
实验结果：
本实验中，通过利用本申请中所提供的制备方法，分别制备得到实施例1-4中的污泥基六价铬复合吸附剂，并分别制备了未经过氨基化改性反应且未构成复合结构的对比例1和2，在pH＝3的环境下，将上述实施例和对比例中的吸附剂分别加入到含Cr(VI)废水中搅拌3h，吸附结束后将吸附剂滤除，测量水体中Cr(VI)剩余含量，统计Cr(VI)吸附率。
具体横向对比结果如上表所示，对比例1为原料预处理后只进行热解反应，对比例2为原料预处理后在加入羧甲基纤维素后进行热解反应，两组吸附剂均未进行氨基化改性反应，由此可得对比例1和2的Cr(VI)吸附率分别为4.68％和31.76％；其中，由于对比例2中在热解反应之前增加了加入羧甲基纤维素的步骤，其相比于对比例1的吸附率有所上升，说明了羧甲基纤维素的加入可以提高污泥和石墨渣的粘结效果，提高复合材料结构的稳定性，在多次循环使用后吸附剂仍能保持其原有结构。此外，羧甲基纤维素的加入能够提供引入大量羟基、增强吸附剂的亲水性，加快Cr(VI)的吸附速率的技术效果。
进一步的，与对比例1和2相比，实施例1-4均为根据本申请中所提供的制备方法进行制备得到的污泥基六价铬复合吸附剂，吸附剂的颗粒单体均为复合结构，从实验数据上可见，实施例1-4均能够达到63.51％及以上的Cr(VI)吸附率，相比于对比例1和2，尤其是相比于对比例2，说明采用本实施例中所提供的方法制备的污泥基六价铬复合吸附剂通过胺基功能化改性在热解产物的颗粒表面引入-NH2，在酸性条件下能质子化形成-NH3+，通过离子交换和静电吸引加强了对Cr(VI)的选择性吸附。
此外，相比于现有的需进行两次甚至多次热解的制备方法(即，通过一次热解使污泥表面形成一定孔隙，二次热解时再引入活性气体提高化学反应程度)，本实施例中通过原料预先混合，再经活化剂一起浸渍，只需一次热解就能得到大比表面积吸附材料，制备过程更为简洁。
并且，吸附剂的主要原料为剩余污泥和石墨渣，均属于某企业生产过程中产出的无价值废弃物，资源化后具有良好的经济效益。
进一步的，石墨渣具有丰富的碳含量，与污泥一同热解可以产生正向的协同效应，引入后不仅可以弥补污泥单独热解产物比表面积小和孔隙度不足的缺点，还能在一定程度上降低原料中重金属的比重，加强了吸附剂使用的安全性。
进一步的，原料先混合再活化剂浸渍：先将污泥与石墨渣充分混匀，再加入不同活化剂浸渍，可同时将活化剂分散在污泥和石墨上增强活性位点，后续热解时，有利于在微孔的形成过程中加强孔隙刻蚀，增大比表面积。
此外，吸附剂吸附饱和后，可采用1mol/L的NaOH和NaCl混合溶液进行解吸，循环使用5次后吸附率还能达到60％以上。
以上所述的是本发明的优选实施方式和相应实施例，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提，还可以做出若干变形和改进，包括但不限于比例、流程、用量的调整，这些都属于本发明的保护范围之内。

Claims (13)

  1. 一种污泥基六价铬复合吸附剂的制备方法，其特征在于，包括：
    将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物；
    对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
  2. 根据权利要求1所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述对所述热解产物进行氨基化改性，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
    将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂。
  3. 根据权利要求2所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述氨基化改性反应的反应过程包括：
    所述硅烷类化合物在氨溶液催化下水解产生附着于所述热解产物表面的Si-OH基团；
    所述Si-OH基团之间相互产生缩合反应，缩合成Si-O-Si键；
    在氨溶液条件下，氨基覆盖并包裹在所述热解产物的表面的所述Si-O-Si键上，形成引入-NH2的污泥基六价铬复合吸附剂。
  4. 根据权利要求3所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述氨基化改性反应，还包括：
    所述Si-OH基团还能与所述热解产物表面的羧基发生缩合反应。
  5. 根据权利要求2所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述硅烷类化合物为能在氨溶液催化下水解产生Si-OH基团的硅烷类化合物；
    优选地，所述硅烷类化合物包括TEOS和APTES中的一种或两种组合；
    优选地，所述氨溶液为氨水。
  6. 根据权利要求5所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述将所述热解产物在氨溶液和水的条件下，通过硅烷类化合物进行氨基化改性反应，使所述热解产物的表面引入-NH2，得到所述污泥基六价铬复合吸附剂，包括：
    将所述热解产物分散于乙醇中，加入氨水和水混合；
    加入TEOS和APTES进行氨基化改性反应，使所述热解产物的表面引入-NH2；
    反应结束后依次经过滤、乙醇洗涤和干燥，即得到所述污泥基六价铬复合吸附剂；
    优选地，所述氨基化改性反应的反应温度为15-35℃；
    优选地，所述氨基化改性反应的反应时长为24-48小时。
  7. 根据权利要求1所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物，包括：
    将所述好氧污泥和石墨渣混合物，加至所述活化剂中浸渍，搅拌混合，得到浸渍混合物；
    减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣；
    将所述干燥滤渣置入高温管式炉热解，即得到所述热解产物；
    优选地，所述好氧污泥和石墨渣混合物与所述活化剂，按照固液比1：(1-5.5)混合；
    优选地，所述活化剂的浓度为1-5mol/L；
    优选地，所述搅拌混合过程中，搅拌的时间为24小时；
    优选地，对所述滤渣高温干燥时的温度为105℃；
    优选地，对所述滤渣高温干燥时的时间为24小时；
    优选地，所述高温管式炉热解的温度为350-650℃；
    优选地，热解时在氮气气氛保护下进行；
    优选地，热解的时间为1-4小时；
    优选地，热解时的氮气的流量为0.5L/min；
    优选地，所述高温管式炉的升温速率为5℃/min。
  8. 根据权利要求7所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述活化剂为ZnCl2溶液、KOH溶液和H3PO4溶液中的任一种；
    优选地，ZnCl2溶液、KOH溶液和H3PO4溶液的浓度均为1-5mol/L。
  9. 根据权利要求7所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述减压抽滤后取滤渣，对所述滤渣进行高温干燥，得到干燥滤渣之前，还包括：
    根据所述浸渍混合物与羧甲基纤维素为(18-20)：1的比例条件，于所述浸渍混合物中添加羧甲基纤维素，搅拌混合；
    优选地，搅拌混合的时间为5分钟。
  10. 根据权利要求1所述污泥基六价铬复合吸附剂的制备方法，其特征在于，所述将好氧污泥和石墨渣混合物加入活化剂中浸渍，并进行热解改性，得到热解产物之前，还包括：
    取好氧污泥和石墨渣分别进行干燥；
    将干燥后的好氧污泥和石墨渣分别进行破碎，并过100目筛，得到污泥颗粒和石墨渣颗粒；
    将所述污泥颗粒和所述石墨渣颗粒混合，即得到所述好氧污泥和石墨渣混合物；
    优选地，取好氧污泥和石墨渣分别进行干燥时，采用电热鼓风干燥箱进行干燥；
    优选地，取好氧污泥和石墨渣分别进行干燥时，干燥时间为24小时；
    优选地，取好氧污泥和石墨渣分别进行干燥时，干燥温度为105℃；
    优选地，对污泥和石墨渣分别进行破碎，采用摇摆式粉碎机破碎；
    优选地，所述好氧污泥和石墨渣混合物中，污泥颗粒和石墨渣颗粒的混合比例为(5-10)：1；
    优选地，所述好氧污泥和石墨渣混合物中的颗粒粒径为0.05-0.15mm。
  11. 一种污泥基六价铬复合吸附剂，其特征在于，根据如权利要求1-10中任一项所述的污泥基六价铬复合吸附剂的制备方法制备而成。
  12. 根据权利要求11所述污泥基六价铬复合吸附剂，其特征在于，所述污泥基六价铬复合吸附剂的每个颗粒单体均为复合结构；
    所述颗粒单体的复合结构为：以好氧污泥和石墨渣混合物热解后的热解产物颗粒为核心，以多组Si-O-Si键为覆盖于所述热解产物颗粒外表面的中间层，以与Si-O-Si键中的Si相连接的-NH2分子为外围层的复合结构。
  13. 根据权利要求11所述污泥基六价铬复合吸附剂，其特征在于，Si-O-Si键中的Si与 -NH2分子的连接方式如下化学式所示：
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CN115318241A (zh) * 2022-09-15 2022-11-11 广东邦普循环科技有限公司 一种污泥基六价铬复合吸附剂及其制备方法

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