CN113117732A - Active carbon composite material with three-dimensional pore channel structure and preparation method thereof - Google Patents

Active carbon composite material with three-dimensional pore channel structure and preparation method thereof Download PDF

Info

Publication number
CN113117732A
CN113117732A CN202011603587.7A CN202011603587A CN113117732A CN 113117732 A CN113117732 A CN 113117732A CN 202011603587 A CN202011603587 A CN 202011603587A CN 113117732 A CN113117732 A CN 113117732A
Authority
CN
China
Prior art keywords
composite material
activated carbon
dimensional pore
silicate
pore channel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011603587.7A
Other languages
Chinese (zh)
Other versions
CN113117732B (en
Inventor
蒋广安
赵越
单广波
李宝忠
郭宏山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Publication of CN113117732A publication Critical patent/CN113117732A/en
Application granted granted Critical
Publication of CN113117732B publication Critical patent/CN113117732B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7003—A-type
    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7053—A-type
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7607—A-type
    • 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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • 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
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic 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
    • B01J2220/4812—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
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/30—Organic compounds

Abstract

The invention provides an active carbon composite material with a three-dimensional pore structure and a preparation method thereof, wherein the composite material comprises active carbon, inorganic oxide composite soil, a 4A molecular sieve and a binder component; the composite material is provided with three-dimensional pore canals which are communicated with each other through cross-linking and intercommunicating pore canals. The preparation method comprises the steps of uniformly mixing various materials, treating the materials with a sodium hydroxide solution, and separating, drying and roasting to obtain the composite material. The composite material prepared by the preparation method has a stable three-dimensional pore structure, and can well adsorb and remove organic pollutants.

Description

Active carbon composite material with three-dimensional pore channel structure and preparation method thereof
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a composite material with a three-dimensional pore channel structure and a preparation method thereof.
Background
A great amount of organic pollutants generated in the industrial production process seriously affect the living state and ecological environment of human beings, and become an increasingly serious social and economic problem, especially the treatment of organic wastewater which is difficult to biodegrade is more difficult, the ozone catalytic oxidation technology is to excite ozone to generate hydroxyl radicals, then carry out a series of free radical chain reactions with the organic pollutants to gradually degrade the organic pollutants into harmless organic matters with low molecular weight and finally to CO2、H2The technology of O and other mineral salts can effectively solve the problem of reducing COD of sewage difficult to biochemically.
The key to the treatment effect of the catalytic ozonation process is the reaction activity of the catalyst. The conventional catalyst is mainly prepared by active metal loaded on carriers of active carbon, ceramsite and alumina, and the single active carbon catalyst is easy to wear and has higher loss rate in the use process; the ceramsite catalyst has lower specific surface and low activity; the alumina catalyst has a single pore structure and is not suitable for treating complex-component pollutants. When the conventional catalyst is used for treating organic pollutants, the reaction rate is low due to poor adsorption effect on complex molecular components, the driving force is insufficient, and the removal effect of the pollutants at high concentration is difficult to achieve, so that the activity of treating the organic pollutants is influenced. It is necessary to develop new catalytic materials to improve the efficient adsorption of organic pollutants, improve the mass transfer rate of pollutants and the initial concentration of catalytic treatment reactants, and realize the in-situ and real-time catalytic degradation of pollutants.
CN103657736A discloses an activated carbon/alumina composite catalyst carrier, and preparation and application thereof, wherein the preparation method of the carrier comprises the following steps: (1) acid washing and oxidation treatment of activated carbon: firstly, treating the activated carbon by hydrochloric acid, and carrying out nitric acid oxidation treatment on the acid-washed activated carbon after the acid-washed activated carbon is washed by deionized water; (2) mixing: mixing activated carbon with gamma-Al 2O3, and adding a composite auxiliary agent; (3) kneading: mixing and kneading the activated carbon, the alumina and the auxiliary agent into a cake shape under a mixer; (4) extruding strips: extruding and molding the kneaded cake-shaped object by a strip extruding machine; (5) roasting: and drying the extruded and formed carrier, and then roasting in a nitrogen protective atmosphere to prepare the active carbon/alumina composite carrier. The surface of the catalyst is alumina and activated carbon, and the strength and catalytic efficiency enhancement effect are not obvious.
CN201510296625.1 discloses a method for solid-phase synthesis of a hierarchical pore molecular sieve, comprising the steps of crushing and mixing a solid silicon source, an aluminum source, activated carbon, a template agent and an alkali source, carrying out crystallization reaction at 120-200 ℃, wherein the crystallization reaction time is at least 4 hours, cleaning and drying a reaction product, and roasting to remove the activated carbon to obtain the hierarchical pore molecular sieve. The method does not use water, burns off the mixed active carbon to obtain the hierarchical pore molecular sieve, and the most of the pore diameter is distributed within 5 nm.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an active carbon composite material with a three-dimensional pore channel structure and a preparation method thereof.
The invention provides an activated carbon composite material with a three-dimensional pore channel structure, which comprises activated carbon, inorganic oxide composite soil, a 4A molecular sieve and a binder component, wherein the relative crystallinity of the 4A molecular sieve is 30-60; the composite material is provided with three-dimensional pore channels which are communicated with each other through cross-linking and intercommunicating pore channels, wherein the pore diameter of the one-dimensional pore channel is 0.1-1.5 nm, the pore diameter of the two-dimensional pore channel is 1.5-5 nm, the pore diameter of the three-dimensional pore channel is 5-50 nm, the pore volume of the one-dimensional pore channel accounts for more than 20% and preferably 20-45% of the total pore volume, the pore volume of the two-dimensional pore channel accounts for more than 20% and preferably 20-35% of the total pore volume, and the pore volume of the three-dimensional pore channel accounts for less than 60% and preferably 30-50% of the total pore volume.
In the activated carbon composite material with the three-dimensional pore channel structure, the weight of the composite material is taken as a reference, and the activated carbon accounts for 10-50%, preferably 15-30%; the inorganic oxide composite soil accounts for 10 to 60 percent, preferably 30 to 50 percent; the 4A molecular sieve accounts for 10-50%, preferably 25-40%; the binder component accounts for 2-15%, preferably 3-8%.
In the activated carbon composite material with the three-dimensional pore channel structure, the particle size of the activated carbon is 1-100 micrometers, the specific surface area is 400-3500 m2/g, the average pore diameter is 0.4-5.0 nm, and more than 90% of pores with the pore volume measuring pore diameter of 1.2-3.6 nm are used.
In the activated carbon composite material with the three-dimensional pore channel structure, the inorganic oxide composite soil is powdery particles, the particle diameter is 1-100 mu m, more than 80wt% of the particles are oxides of Si and Al, the mass ratio of the oxides of Si and Al is 1-2: 1, and the specific surface area is 5-500 m2(ii)/g, the average pore diameter is 2.0 to 30.0nm, and the content of pores having a pore diameter of 5.0 to 15.0nm is 80% or more in terms of pore volume.
In the activated carbon composite material with the three-dimensional pore structure, the binder component is an inorganic binder used in the process of preparing the composite carrier, and can be one or more selected from silicate inorganic binders and phosphate inorganic binders; the silicate inorganic binder can be one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, and sodium silicate and/or aluminum silicate are preferred; the phosphate inorganic binder can be one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and is preferably aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
In the composite material with the three-dimensional pore channel structure, the 4A molecular sieve is obtained by subjecting inorganic oxide composite soil to sodium hydroxide aqueous solution and heat treatment, and is intensively distributed on the outer surface of the composite material.
The second aspect of the invention provides a preparation method of an activated carbon composite material with a three-dimensional pore channel structure, which comprises the following steps:
(1) roasting the inorganic oxide composite soil at 600-1000 ℃;
(2) pulping the chopped fiber to obtain slurry;
(3) uniformly mixing the inorganic oxide composite soil subjected to roasting treatment in the step (1), the slurry obtained in the step (2) and activated carbon, adding a bonding component and water into the mixture, and further performing molding and curing treatment;
(4) and (4) feeding the material obtained in the step (3) into a sodium hydroxide solution for treatment, carrying out solid-liquid separation after the treatment is finished, and drying and roasting the solid particles obtained by separation to obtain the activated carbon composite material.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, in the step (1), the inorganic oxide composite soil is powdery particles, the particle diameter is 1-100 mu m, more than 80wt% of the particles are oxides of Si and Al, the mass ratio of the oxides of Si and Al is 1-2: 1, and the specific surface area is 5-500 m2(ii)/g, the average pore diameter is 2.0 to 30.0nm, and the content of pores having a pore diameter of 5.0 to 15.0nm is 80% or more in terms of pore volume.
In the preparation method of the activated carbon composite material with the three-dimensional pore structure, the chopped fiber filaments in the step (2) are alkali-soluble fibers, have the length of 2-5 mm and the monofilament diameter of 10-70 nm, and can be selected from one or more of polyester fibers, carboxymethyl cellulose fibers and hydroxyethyl cellulose fibers.
In the preparation method of the activated carbon composite material with the three-dimensional pore structure, the specific operation of pulping the chopped fiber in the step (2) is to put the chopped fiber into a container and stir and fully mix the chopped fiber according to the solid-liquid ratio of 5-20.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, in the step (3), the average pore diameter of the activated carbon is 0.4-5.0 nm, and the specific surface area is 400-3500 m2A particle diameter of 1 to 100 μm per g, and a pore volume of 90% or more of pores having a pore diameter of 1.2 to 3.6 nm. The activated carbon may be selected from ground wood, coal or nut shell granular activated carbon.
In the preparation method of the activated carbon composite material with the three-dimensional pore structure, the bonding component in the step (3) is an inorganic bonding agent, preferably one or more of silicate inorganic bonding agents and phosphate inorganic bonding agents; the silicate inorganic binder can be one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, and sodium silicate and/or aluminum silicate are preferred; the phosphate inorganic binder can be one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and is preferably aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, the curing temperature in the step (3) is 150-450 ℃, and preferably 200-350 ℃.
In the preparation method of the activated carbon composite material with the three-dimensional pore structure, the mass ratio of the activated carbon, the inorganic oxide composite soil, the chopped fiber filaments and the bonding component in the step (3) is 10-40: 30-85: 5-15: 2 to 5.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, the adding amount of the sodium hydroxide solution in the step (4) is determined according to the ratio of Si: the ratio of the amount of NaOH substances is 1: 3-4, and the concentration of the sodium hydroxide solution is 7-10 wt%.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, the drying temperature in the step (4) is 50-150 ℃, preferably 60-120 ℃, and the drying time is 2-12 hours.
In the preparation method of the activated carbon composite material with the three-dimensional pore channel structure, the roasting in the step (4) is carried out under the protection of nitrogen or inert gas, the roasting temperature is 300-1000 ℃, and preferably 400-800 DEG C
In the above method for preparing an activated carbon composite material with a three-dimensional pore structure, the molding technique may be any one of the existing molding methods in the field, and a person skilled in the art may freely select the molding technique according to the actual needs, and the selection belongs to the common knowledge of the person skilled in the art, such as any one of a strip shape, a spherical shape, a clover shape and a clover shape.
Compared with the prior art, the active carbon composite material with the three-dimensional pore channel structure and the preparation method thereof have the following advantages:
1. according to the preparation method of the active carbon composite material with the three-dimensional pore channel structure, firstly, alkali-soluble fiber short shreds and active carbon and other raw materials are mixed when a carrier precursor is prepared, the alkali-soluble fiber short shreds are not dissolved in distilled water and can completely exist in the formed composite material precursor, a cross-linked reticular structure of fiber filaments is reserved, then when the composite material precursor is treated and modified by adopting a sodium hydroxide solution, the alkali-soluble fiber short shreds which are uniformly distributed are dissolved and removed to form a cross-linked and intercommunicated micron-sized pore channel, the generated molecular sieve nano pore channel is communicated with the original micron pore channel of the active carbon, the mass transfer process of organic pollutants in a composite carrier is enhanced, and the capacity of treating the organic pollutants is improved.
2. According to the preparation method of the active carbon composite material with the three-dimensional pore channel structure, when a precursor is treated by a sodium hydroxide solution, the silicon-aluminum clay on the surface layer is subjected to crystal transformation under the action of alkali liquor to generate a 4A molecular sieve, a pore channel structure with the pore diameter of 0.1-1.5 nm is formed, the proportion of microporous channels in a carrier is increased while the proportion of macropores is reduced, the rapid adsorption capacity of the material is improved through the nano channels, the initial concentration of a surface reactant during reaction is increased, the adsorption reaction rate is improved, and the problem of slow mass transfer rate of the traditional carrier is well solved. Meanwhile, after the activated carbon in the carrier precursor is treated by alkali liquor, the active sites of surface hydroxyl groups are increased, and the catalytic activity of the hydroxylated activated carbon is greatly improved due to the increase of the number of the hydroxylated activated carbon.
Detailed Description
The preparation process of the present invention is further illustrated below with reference to specific examples, but the scope of the present invention is not limited to these examples.
In the examples and comparative examples of the present invention, the pore volume, specific surface area, and pore distribution were measured by a low-temperature liquid nitrogen physical adsorption method. In the present invention, wt% is a mass fraction. In the examples and comparative examples of the present invention, the relative crystallinity was obtained by X-ray diffraction method (Xuren, Pongwenqin, etc. molecular sieves and porous materials, chemistry Beijing, science publishers, 2014).
The specific surface area of the commercial powdery coconut shell activated carbon used in the invention is 920m2G, pore volume 1.0cm3(ii)/g, average pore radius of 1.1nm, iodine adsorption value of 700mg/g, and particle diameter of 45 μm. The specific surface area of the inorganic oxide composite soil used in the present invention is 105m2(ii)/g, the mass ratio of silica to alumina is 3:2, and the particle diameter is 45 μm.
Example 1
Uniformly mixing activated carbon and inorganic oxide composite soil treated at 700 ℃, adding 10 mass percent of alkali-soluble carboxymethyl cellulose fiber short-cut pulp, uniformly mixing, adding 30 mass percent of sodium silicate binder, uniformly kneading, extruding into strips, molding, drying at 90 ℃ for 4 hours, and curing for 3 hours at 270 ℃ under the protection of nitrogen to obtain the precursor. Adding the precursor into a sodium hydroxide solution with the mass concentration of 8.0%, circularly treating the mixture for 3 hours by using the sodium hydroxide solution, filtering, drying solid particles for 6 hours at 90 ℃, and roasting the dried solid particles for 3 hours at 750 ℃ under the protection of nitrogen to obtain an activated carbon composite carrier A1, wherein the amount of used reagents is listed in Table 1. The properties of the composite carrier are shown in table 2.
The composite carrier A1 is taken and impregnated by impregnation liquid containing Ce-Cu, then dried for 10 hours at 110 ℃, and roasted for 5 hours at 550 ℃ under the protection of nitrogen, thus obtaining the catalyst A, and the physicochemical properties of the catalyst A are shown in Table 3.
Example 2
Uniformly mixing activated carbon and inorganic oxide composite soil treated at 800 ℃, adding alkali-soluble polyester cellulose fiber short-cut pulp with the mass content of 20% to be uniformly mixed, adding a sodium silicate binder with the mass content of 25% to be uniformly kneaded, extruding and forming, drying at 110 ℃ for 4h, and curing for 3 hours at 270 ℃ under the protection of nitrogen to obtain the precursor. Adding the precursor into a sodium hydroxide solution with the mass concentration of 7.0%, circularly treating the mixture for 3 hours by using the sodium hydroxide solution, filtering, drying the solid particles at 110 ℃ for 4 hours, and roasting the dried solid particles at 650 ℃ for 5 hours under the protection of nitrogen to obtain an activated carbon composite carrier B1, wherein the amount of used reagents is listed in Table 1. The properties of the composite carrier are shown in table 2.
And (3) taking the composite carrier B1, soaking the composite carrier B1 in a Ce-Fe-containing impregnation solution, drying the composite carrier B for 10 hours at 110 ℃, and roasting the composite carrier B for 5 hours at 550 ℃ under the protection of nitrogen to obtain the catalyst B, wherein the physicochemical properties of the catalyst B are shown in Table 3.
Example 3
Uniformly mixing activated carbon and inorganic oxide composite soil treated at 900 ℃, adding alkali-soluble hydroxyethyl cellulose fiber chopped slurry with the mass content of 15% to be uniformly mixed, adding a sodium silicate binder with the mass content of 30% to be uniformly kneaded, extruding and forming, drying at 100 ℃ for 6h, and curing for 3 hours under the protection of nitrogen at 300 ℃ to obtain the precursor. Adding the precursor into a sodium hydroxide solution with the mass concentration of 8.0%, circularly treating the mixture for 4 hours by using the sodium hydroxide solution, filtering, drying the solid particles at 110 ℃ for 8 hours, and roasting the dried solid particles at 700 ℃ for 5 hours under the protection of nitrogen to obtain an activated carbon composite carrier C1, wherein the amount of used reagents is listed in Table 1. The properties of the composite carrier are shown in table 2.
And (3) taking the composite carrier C1, impregnating the composite carrier C1 with an impregnation solution containing Ce-Mn, drying the composite carrier C for 10 hours at 110 ℃, and roasting the composite carrier C for 5 hours at 550 ℃ under the protection of nitrogen to obtain the catalyst C, wherein the physicochemical properties of the catalyst C are shown in Table 3.
Example 4
The synthesis of example 2 was repeated without adding alkali-soluble polyester cellulose fiber chopped strand slurry during the gelling process to obtain activated carbon composite carrier D1. The properties of the composite carrier are shown in table 2.
Catalyst preparation catalyst D was obtained as in example 2 and had the physico-chemical properties shown in Table 3.
Comparative example 1
The carrier DA1 and the catalyst DA were prepared by the method of example 2 using activated carbon, inorganic oxide composite soil and 4A molecular sieve, but not using sodium hydroxide solution, and the properties of the composite carrier are shown in Table 2, and the physicochemical properties are shown in Table 3.
Table 1 preparation of carrier reagent amounts
Figure DEST_PATH_IMAGE001
TABLE 2 Carrier Properties
Figure DEST_PATH_IMAGE002
TABLE 3 physicochemical Properties of the catalyst
Figure DEST_PATH_IMAGE003
As can be seen from the catalyst properties in table 3, the overall properties of the catalyst obtained with the addition of the chopped fibers are improved compared to the catalyst obtained without the addition.
Evaluation test: the performance of the carrier and the catalyst was examined by the results of treating wastewater with the catalyst prepared with the above carrier.
The catalyst is filled in a fixed bed, the continuous ozone catalytic oxidation reaction is carried out on the wastewater, the treatment condition is normal temperature and normal pressure, the COD of the raw water is 500 mg/L, and the airspeed is 0.5h-1The adding amount of ozone is 1000 mg/L. The results of the treatment after 100h are shown in Table 4.
TABLE 4 catalytic ozonation results of wastewater
Figure DEST_PATH_IMAGE004
As can be seen from the results in table 4, the catalyst prepared using the present method has good activity stability.

Claims (15)

1. An activated carbon composite material with a three-dimensional pore channel structure comprises activated carbon, inorganic oxide composite soil, a 4A molecular sieve and a binder component, wherein the relative crystallinity of the 4A molecular sieve is 30-60; the composite material is provided with three-dimensional pore channels which are communicated with each other through cross-linking and intercommunicating pore channels, wherein the pore diameter of the one-dimensional pore channel is 0.1-1.5 nm, the pore diameter of the two-dimensional pore channel is 1.5-5 nm, the pore diameter of the three-dimensional pore channel is 5-50 nm, the pore volume of the one-dimensional pore channel accounts for more than 20% and preferably 20-45% of the total pore volume, the pore volume of the two-dimensional pore channel accounts for more than 20% and preferably 20-35% of the total pore volume, and the pore volume of the three-dimensional pore channel accounts for less than 60% and preferably 30-50% of the total pore volume.
2. The activated carbon composite material having a three-dimensional pore structure according to claim 1, wherein: based on the weight of the composite material, the active carbon accounts for 10-50 percent, preferably 15-30 percent; the inorganic oxide composite soil accounts for 10 to 60 percent, preferably 30 to 50 percent; the 4A molecular sieve accounts for 10-50%, preferably 25-40%; the binder component accounts for 2-15%, preferably 3-8%.
3. The activated carbon composite material having a three-dimensional pore structure according to claim 1, wherein: the inorganic oxide composite soil is a powdery particle with the particle diameter of 1-100 mu m, more than 80wt% of the particles are oxides of Si and Al, and the mass ratio of the oxides of Si and Al is 1-2: 1.
4. The activated carbon composite material having a three-dimensional pore structure according to claim 1, wherein: the binder component is an inorganic binder and is selected from one or more of silicate inorganic binders and phosphate inorganic binders.
5. The activated carbon composite material with a three-dimensional pore channel structure according to claim 4, wherein: the silicate inorganic binder is one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, and preferably sodium silicate and/or aluminum silicate; the phosphate inorganic binder is one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and preferably aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
6. A preparation method of an activated carbon composite material with a three-dimensional pore channel structure comprises the following steps:
(1) roasting the inorganic oxide composite soil at 600-1000 ℃;
(2) pulping the chopped fiber to obtain slurry;
(3) uniformly mixing the inorganic oxide composite soil subjected to roasting treatment in the step (1), the slurry obtained in the step (2) and activated carbon, adding a bonding component and water into the mixture, and further performing molding and curing treatment;
(4) and (4) feeding the material obtained in the step (3) into a sodium hydroxide solution for treatment, carrying out solid-liquid separation after the treatment is finished, and drying and roasting the solid particles obtained by separation to obtain the activated carbon composite material.
7. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (1), the inorganic oxide composite soil is powdery particles, the particle diameter is 1-100 mu m, more than 80wt% of the particles are oxides of Si and Al, and the mass ratio of the oxides of Si and Al is 1-2: 1.
8. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: the chopped fiber filaments in the step (2) are alkali-soluble fibers, have the length of 2-5 mm and the monofilament diameter of 10-70 nm, and are selected from one or more of polyester fibers, carboxymethyl cellulose fibers and hydroxyethyl cellulose fibers.
9. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: the bonding component in the step (3) is an inorganic bonding agent, preferably one or more of silicate inorganic bonding agents and phosphate inorganic bonding agents.
10. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 9, is characterized in that: the silicate inorganic binder is one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, and preferably sodium silicate and/or aluminum silicate; the phosphate inorganic binder is one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and preferably aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
11. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (3), the curing temperature is 150-450 ℃, and preferably 200-350 ℃.
12. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (3), the mass ratio of the activated carbon to the inorganic oxide composite soil to the chopped fiber filaments to the bonding component is 10-40: 30-85: 5-15: 2 to 5.
13. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (4), the adding amount of the sodium hydroxide solution is determined according to the following steps of Si: the ratio of the amount of NaOH substances is 1: 3-4, and the concentration of the sodium hydroxide solution is 7-10 wt%.
14. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (4), the drying temperature is 50-150 ℃, preferably 60-120 ℃, and the drying time is 2-12 hours.
15. The method for preparing the activated carbon composite material with the three-dimensional pore channel structure according to claim 6, is characterized in that: in the step (4), the roasting is carried out under the protection of nitrogen or inert gas, and the roasting temperature is 300-1000 ℃, preferably 400-800 ℃.
CN202011603587.7A 2019-12-31 2020-12-30 Active carbon composite material with three-dimensional pore channel structure and preparation method thereof Active CN113117732B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2019114177870 2019-12-31
CN201911417787 2019-12-31

Publications (2)

Publication Number Publication Date
CN113117732A true CN113117732A (en) 2021-07-16
CN113117732B CN113117732B (en) 2023-04-07

Family

ID=76772656

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011603587.7A Active CN113117732B (en) 2019-12-31 2020-12-30 Active carbon composite material with three-dimensional pore channel structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113117732B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114084887A (en) * 2021-11-04 2022-02-25 中欣环保科技有限公司 Preparation method of super-capacitor carbon

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5403809A (en) * 1992-12-21 1995-04-04 W. R. Grace & Co.-Conn. Composite inorganic supports containing carbon for bioremediation
US20050133051A1 (en) * 2003-12-22 2005-06-23 Philip Morris Usa Inc. Composite materials and their use in smoking articles
CN106975473A (en) * 2017-05-27 2017-07-25 苏州思美特表面材料科技有限公司 The supported materials catalyst of network structure
CN108786721A (en) * 2017-05-02 2018-11-13 中国石油化工股份有限公司 A kind of composite adsorbing material and preparation method thereof
CN109718797A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 A kind of preparation method of hydrotreating catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5403809A (en) * 1992-12-21 1995-04-04 W. R. Grace & Co.-Conn. Composite inorganic supports containing carbon for bioremediation
US20050133051A1 (en) * 2003-12-22 2005-06-23 Philip Morris Usa Inc. Composite materials and their use in smoking articles
CN108786721A (en) * 2017-05-02 2018-11-13 中国石油化工股份有限公司 A kind of composite adsorbing material and preparation method thereof
CN106975473A (en) * 2017-05-27 2017-07-25 苏州思美特表面材料科技有限公司 The supported materials catalyst of network structure
CN109718797A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 A kind of preparation method of hydrotreating catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114084887A (en) * 2021-11-04 2022-02-25 中欣环保科技有限公司 Preparation method of super-capacitor carbon

Also Published As

Publication number Publication date
CN113117732B (en) 2023-04-07

Similar Documents

Publication Publication Date Title
CN113117735B (en) Catalyst for treating hydrocarbon-containing wastewater and preparation method and application thereof
US20050214539A1 (en) Porous carbon structures and methods
CN1537075A (en) Shaped activated carbon
JP2000511864A (en) Rigid porous carbon structures, methods of making, using, and products containing the same
Lan et al. Progress on fabrication and application of activated carbon sphere in recent decade
CN113117731B (en) Composite carrier containing active carbon and preparation method thereof
CN113117732B (en) Active carbon composite material with three-dimensional pore channel structure and preparation method thereof
Anadão et al. Montmorillonite/carbon nanocomposites prepared from sucrose for catalytic applications
CN113042109A (en) Ozone catalyst carrier and preparation method thereof
CN113117730B (en) Preparation method of active carbon composite carrier
US4637908A (en) Process for manufacturing highly active, dispersed low apparent density aluminium hydrate
JP2020152902A (en) Carbon black molded body and method for producing the same
CN114762835B (en) Ozone catalytic oxidation catalyst for wastewater treatment and preparation method thereof
CN114644353B (en) Preparation method of three-dimensional through macroporous alumina
CN113181973B (en) Porous catalyst particles and forming method thereof
CN113117736B (en) Catalytic wet oxidation catalyst and preparation method thereof
CN114471743B (en) Advanced oxidation catalyst containing ferric phosphate and preparation method thereof
CN108816191A (en) A kind of compound bulky grain cleanser of graphite for air purification and preparation method
CN113117737B (en) Catalyst for treating oily sewage and preparation method and application thereof
CN114887654A (en) Molecular sieve based nano carbon coated supported advanced oxidation catalyst and preparation method thereof
CN113117733B (en) Preparation method of carbon-containing carrier containing cross-linked and intercommunicated micron pore canals
JPH0871425A (en) Ozone decomposition catalyst
KR100351624B1 (en) A manufacturing method of granulated adsorbent having multi-functions
CN113117739B (en) Catalyst for treating wastewater and preparation method and application thereof
KR102319751B1 (en) Activated carbon formed from raw materials including fly ash and method for producing same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231122

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right