CN111375422B - Catalyst for catalytic oxidation of formaldehyde and preparation method thereof - Google Patents

Catalyst for catalytic oxidation of formaldehyde and preparation method thereof Download PDF

Info

Publication number
CN111375422B
CN111375422B CN201811648069.XA CN201811648069A CN111375422B CN 111375422 B CN111375422 B CN 111375422B CN 201811648069 A CN201811648069 A CN 201811648069A CN 111375422 B CN111375422 B CN 111375422B
Authority
CN
China
Prior art keywords
catalyst
catalytic oxidation
formaldehyde according
formaldehyde
preparing
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.)
Active
Application number
CN201811648069.XA
Other languages
Chinese (zh)
Other versions
CN111375422A (en
Inventor
宋永一
孙晓丹
张舒冬
张庆军
刘继华
方向晨
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
Priority to CN201811648069.XA priority Critical patent/CN111375422B/en
Publication of CN111375422A publication Critical patent/CN111375422A/en
Application granted granted Critical
Publication of CN111375422B publication Critical patent/CN111375422B/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/11—Air
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for catalytic oxidation of formaldehyde and a preparation method thereof, wherein the catalyst comprises an active component, an auxiliary agent and a carrier; the active component is Mn, the auxiliary agent is one or more of Mg, ba, zn, co, ti, cu, la and Ce, and the carrier is petroleum coke-based active carbon. The preparation method comprises the steps of pretreating petroleum coke, mixing the petroleum coke, an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, uniformly mixing, and activating; washing and drying the sample obtained after activation to obtain a catalyst precursor A; treating the catalyst precursor A by using an oxidizing solution, and drying to obtain a catalyst precursor B; and (3) treating the catalyst precursor B by using a coupling agent to obtain the catalyst for catalyzing and oxidizing the formaldehyde. The catalyst prepared by the preparation method has the advantages of good dispersion of active components, high degradation efficiency, high selectivity on formaldehyde and the like.

Description

Catalyst for catalytic oxidation of formaldehyde and preparation method thereof
Technical Field
The invention belongs to the field of chemical industry, relates to a material for purifying formaldehyde and a preparation method thereof, and particularly relates to a catalyst for catalyzing and oxidizing formaldehyde and a preparation method thereof.
Background
Formaldehyde (HCHO) is a common indoor air pollutant, and has various sources, mainly including various adhesive glues, various synthetic panels, wallpaper, coatings, foam materials, chemical fiber products, and the like. Formaldehyde has high toxicity, and chronic respiratory diseases are increased due to long-term contact or inhalation of low-concentration formaldehyde gas, and toxic symptoms comprise headache, neurasthenia, anxiety, dizziness, reduction of nervous system function and the like; the high-concentration formaldehyde has certain toxic action on human nervous system, liver, skin and immune system. More seriously, formaldehyde is carcinogenic. Therefore, the purification of formaldehyde is the key to ensure the cleanness of indoor air.
At present, an adsorption method is mostly adopted for removing formaldehyde gas, and commonly used adsorbents mainly comprise activated carbon, activated carbon fibers, molecular sieves, porous clay ores, silica gel and the like. The method has the advantages of simplicity, low cost and easy popularization; however, the adsorption method is limited by the capacity of the adsorbent, and the adsorbent only adsorbs formaldehyde but does not eliminate the formaldehyde, so that the adsorption method has poor effect in a high-temperature environment and causes secondary pollution. The catalytic oxidation method uses oxygen in the air as an oxidant, and can convert formaldehyde into harmless CO under the conditions of normal temperature and normal pressure 2 And H 2 O, the catalyst has a long service life, and the amount of the active component supported and the form of the catalyst can be controlled in consideration of the concentration of formaldehyde in the indoor air and the cost, which is an effective and practical technique. The key to the catalytic oxidation process is to find a catalyst that can maintain the long-term, high-efficiency decomposition of formaldehyde while maintaining high activity.
Catalysts for the catalytic oxidation of formaldehyde generally include noble metal catalysts and non-noble metal catalysts.
CN105289593A discloses a preparation method of micro-nano silver-loaded activated carbon for long-acting elimination of formaldehyde at room temperature, in the technology, a formaldehyde purification material is prepared by using ultrapure water cleaning and activated carbon treated by ammonia water as a carrier and loading micro-nano silver active components, and the formaldehyde purification material utilizes the adsorption and the reducibility of the activated carbon, the catalytic oxidation performance of the micro-nano silver on formaldehyde and an enrichment and conversion synergistic mechanism between the micro-nano silver and the activated carbon, so that the micro-nano silver-loaded activated carbon has high decomposition rate and stable performance of the catalytic oxidation of formaldehyde, but the silver application cost is high, and large-scale application is difficult to realize.
CN105435740A discloses a preparation method of a manganese dioxide-loaded activated carbon formaldehyde adsorbent, which comprises the steps of etching carbon on the surface of activated carbon by potassium permanganate to realize active carbon pore reconstruction, adjusting the pore structure and pore size of the surface of the activated carbon, improving the formaldehyde adsorption capacity, and enabling the formaldehyde adsorption amount of each gram of modified product to reach 195mg/g after being modified by loaded manganese dioxide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a catalyst for catalytic oxidation of formaldehyde and a preparation method thereof, in the preparation method of the catalyst, active metal is introduced in the petroleum coke activation process, an activating agent enters a diffusion path generated by petroleum coke bulk phase, and is combined with amorphous carbon defects or graphite carbon sheet layers under the action of microwave catalysis to form a high-dispersion and stable-state structure, and the prepared catalyst has the advantages of good dispersion of active components, high degradation efficiency, high selectivity on formaldehyde and the like.
The invention provides a catalyst for catalyzing and oxidizing formaldehyde, which comprises an active component, an auxiliary agent and a carrier; the active component is Mn, the auxiliary agent is one or more of Mg, ba, zn, co, ti, cu, la and Ce, and preferably one or more of Co, cu and Ce; the carrier is petroleum coke-based activated carbon, wherein the content of the active component is 1-15%, preferably 3-12%, the content of the auxiliary agent is 1-10%, preferably 3-8%, and the content of the carrier is 76-97%, preferably 81-92%, based on the weight of the catalyst.
In the catalyst for catalyzing and oxidizing formaldehyde, the specific surface area of the catalyst is 1000-2800 m 2 A ratio of 1200 to 2500 m/g is preferred 2 /g。
In the catalyst for catalytic oxidation of formaldehyde, the active component is embedded into the amorphous defect of the petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of the active metal crystal grain is 1.1-6.3 nm, preferably 1.5-5 nm.
In a second aspect, the present invention provides a method for preparing a catalyst for catalytic oxidation of formaldehyde, the method comprising:
(1) Pretreating petroleum coke;
(2) Mixing the petroleum coke obtained in the step (1), an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, and activating after uniformly mixing;
(3) Washing and drying the sample obtained in the step (2) to obtain a catalyst precursor A;
(4) Treating the catalyst precursor A by using an oxidizing solution, and drying to obtain a catalyst precursor B;
(5) And (3) treating the catalyst precursor B by using a coupling agent to obtain the catalyst for catalyzing and oxidizing the formaldehyde.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the pretreatment in the step (1) comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
In the method, the ammonium phosphate salt in the step (1.1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and is preferably ammonium phosphate.
In the above method, the method for introducing the ammonium phosphate salt into the petroleum coke in the step (1.1) is performed according to a method known in the art, and comprises one or more of an equal volume impregnation method, a supersaturated impregnation method and a kneading method, and is preferably a supersaturated impregnation method.
In the method, the drying temperature in the step (1.1) is 60-120 ℃, preferably the drying temperature is 80-100 ℃, the drying time is 2-8 h, preferably the drying time is 4-6 h; the drying is further preferably carried out under vacuum conditions.
In the method, the weight ratio of the ammonium phosphate salt to the petroleum coke in the step (1.1) is 0.1-1: 1, preferably 0.3 to 0.8.
In the above method, in step (1.2), the water vapor-containing gas is water vapor or a mixed gas of water vapor and a carrier gas, and the volume ratio of water vapor to carrier gas in the mixed gas is 1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the method, the pretreatment process in the step (1.2) comprises a first-stage pretreatment process, a second-stage pretreatment process and a cooling process, wherein the temperature of the first-stage pretreatment process is 150-250 ℃, preferably 180-220 ℃, and the pretreatment time is 1-6 hours, preferably 2-4 hours; the temperature of the second stage of pretreatment is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 h, preferably 2-4 h, and the second stage of pretreatment is cooled to 20-100 ℃, preferably 40-80 ℃ after the second stage of pretreatment is finished; the cooling process is preferably carried out under nitrogen protection.
In the method, the volume space velocity of the vapor-containing gas in the step (1.2) is 500 to 2000h -1 。
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the active metal-containing compound in the step (2) can be one or more of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate, and potassium permanganate is preferred.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the metal compound containing the auxiliary agent in the step (2) can be one or more of nitrate, sulfate and hydrochloride, preferably nitrate, specifically can be one or more of magnesium nitrate, barium nitrate, zinc nitrate, cobalt nitrate, titanium nitrate, copper nitrate, cerium nitrate and lanthanum nitrate, and preferably is one or more of cobalt nitrate, copper nitrate and cerium nitrate. The auxiliary agent is one or more of Mg, ba, zn, co, ti, cu, la and Ce, and preferably one or more of Co, cu and Ce.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the activating agent in the step (2) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and preferably potassium hydroxide.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the mass ratio of the active metal-containing compound (calculated by the mass of active metal elements), the auxiliary agent-containing metal compound (calculated by the mass of auxiliary agent metal oxides), the activator and the petroleum coke in the step (2) is 0.004-0.08: 0.004-0.06: 0.5 to 4:1, preferably 0.014 to 0.062:0.014 to 0.042:1 to 3:1.
in the preparation method of the catalyst for catalytic oxidation of formaldehyde, the activation process in the step (2) is as follows: uniformly mixing the petroleum coke obtained in the step (1), an active metal compound, an auxiliary agent-containing metal compound and an activating agent, heating to an activation temperature in a nitrogen or inert atmosphere, and cooling to 20-100 ℃ after activation for subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 400-1000 ℃, preferably 700-900 ℃, and the activation time is 5-240 min, preferably 10-120 min. The activation process is further preferably carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915MHz; the microwave power is 1-10 kw, preferably 2-4 kw per kg of petroleum coke. When the activation is carried out under the microwave radiation condition, the method further preferably comprises two-stage activation, wherein the first stage is activated for 10 to 60min at 400 to 600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700 to 900 ℃ under the microwave radiation condition for activation for 10 to 30min.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the washing in the step (3) is water washing, and the sample obtained in the step (2) is firstly mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (2) to the deionized water is 1.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the drying temperature in the step (3) is 100-200 ℃, preferably 120-180 ℃, and the drying time is 2-10 hours, preferably 4-8 hours. The drying is preferably carried out under vacuum conditions.
The preparation of the catalyst for catalyzing and oxidizing formaldehydeIn the method, the oxidizing solution in the step (4) contains HNO 3 、HClO、H 2 O 2 The concentration of the aqueous solution is 1 to 10 weight percent, preferably 1 to 5 weight percent; the process of treating the catalyst precursor A obtained in the step (3) with an oxidizing solution is as follows: mixing the catalyst precursor A with an oxidizing solution for 0.5-1 h, and then carrying out solid-liquid separation, wherein the mass ratio of the catalyst precursor A to the oxidizing solution is 1:5 to 1:30, preferably 1: 10-1: 20.
in the preparation method of the catalyst for catalytic oxidation of formaldehyde, the drying temperature in the step (4) is 100-200 ℃, preferably the drying temperature is 120-180 ℃, the drying time is 2-10 h, preferably the drying time is 4-8 h; the drying is preferably carried out under vacuum.
In the preparation method of the catalyst for catalytic oxidation of formaldehyde, the coupling agent in the step (5) can be one or more of dichlorodimethylsilane, trimethylchlorosilane, hexamethyldisilazane, aminopropyltriethoxysilane, methyltriethoxysilane and mercaptopropyltrimethoxysilane, and preferred is mercaptopropyltrimethoxysilane. The specific process for treating the catalyst precursor B by using the coupling agent in the step (5) is as follows: supersaturating ethanol solution containing coupling agent to impregnate catalyst precursor B, fully reacting for 1-3 h at 40-70 ℃, evaporating ethanol solution to dryness at 80-120 ℃, and roasting the obtained sample at 500-700 ℃ for 4-8 h in nitrogen atmosphere to obtain the catalyst for catalytic oxidation of formaldehyde. Wherein, in the ethanol solution containing the coupling agent, the mass ratio of the coupling agent to the ethanol is 1.
The third aspect of the present invention provides a catalyst for the catalytic oxidation of formaldehyde, which is obtained by the above-mentioned preparation method. The catalyst comprises an active component, an auxiliary agent and a carrier; the active component is Mn, the auxiliary agent is one or more of Mg, ba, zn, co, ti, cu, la and Ce, and preferably one or more of Co, cu and Ce; the carrier is petroleum coke-based activated carbon, wherein the content of active components is 1 to 15 percent, preferably 3 to 12 percent, and the content of auxiliaries is 1 to up to e, based on the weight of the catalyst10 percent, preferably 3 to 8 percent, and the content of the carrier is 76 to 97 percent, preferably 81 to 92 percent. In the catalyst for catalyzing and oxidizing formaldehyde, the specific surface area of the catalyst is 1000-2800 m 2 A ratio of 1200 to 2500 m/g is preferred 2 /g。
In the catalyst for catalyzing and oxidizing formaldehyde, the active component is embedded into the amorphous defects of the petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of the active metal crystal grain is 1.1-6.3 nm, preferably 1.5-5 nm.
The invention also provides the application of the catalyst in the catalytic oxidation reaction of formaldehyde. The formaldehyde catalytic oxidation reaction is carried out in a continuous flow fixed bed device, the raw material is the mixed gas of formaldehyde and air, the reaction pressure is normal pressure to 1atm, the total flow of the gas is 300 to 500mL/min, and the concentration of the formaldehyde is 50 to 500ppm.
Compared with the prior art, the catalyst for catalyzing and oxidizing formaldehyde and the preparation method thereof have the following advantages:
1. according to the preparation method of the catalyst for catalytic oxidation of formaldehyde, active metal and auxiliary agent are introduced in the petroleum coke activation process, the active agent enters a diffusion path generated by petroleum coke phase, and is combined with amorphous carbon defects or graphite carbon sheet layers under the action of microwave catalysis to form a high-dispersion and stable-state structure.
2. According to the preparation method of the catalyst for catalytic oxidation of formaldehyde, an active metal precursor is introduced in the petroleum coke activation process, so that active metal molecules can be better dispersed in a molten state activator, and the active metal is further promoted to enter the petroleum coke; when the active metal precursor exists in an acid radical form, the active metal precursor can more easily enter the petroleum coke-based active carbon. The reason is that under the action of an activator, active sites of petroleum coke react to generate positive charged cavities, and acid radical anions are more easily combined and intercalated.
3. The preparation method of the catalyst for catalytic oxidation of formaldehyde comprises the steps of pretreating petroleum coke, introducing ammonium phosphate into the petroleum coke, and then carrying out two-stage treatment on the petroleum coke by using steam-containing gas, so that the ammonium phosphate is promoted to be decomposed in the petroleum coke to generate ammonia gas and phosphoric acid, the generated ammonia gas provides more primary pores for further activation of the petroleum coke, and meanwhile, the generated phosphoric acid can also be used as an activating agent for carrying out primary activation on the petroleum coke to create a developed pore structure and reduce the consumption of a subsequent alkali activating agent, so that the production cost is low, and the environmental pollution is small. Solves the problems that the petroleum coke used has compact structure, high crystallinity and lacks of primary pores required by activation, and needs to be activated to form pores by strong alkali with the alkali-coke ratio of more than 3/1 in inert atmosphere, which causes serious corrosion of equipment and higher production cost and restricts the development and application of the petroleum coke.
4. In the catalyst for catalytic oxidation of formaldehyde and the preparation method thereof, the raw materials used by the catalyst are cheap and easy to obtain, the preparation method is simple, formaldehyde can be converted into harmless carbon dioxide and water through low-temperature catalytic oxidation, and secondary pollution is avoided. The coupling agent is adopted to treat the catalyst precursor, so that the hydrophobicity of the activated carbon carrier is effectively improved, the desorption of product water from the carrier is accelerated, the catalytic oxidation reaction is promoted, and the catalyst is not easy to inactivate. In the catalyst, the active metal is highly dispersed on the surface of the carrier, and is not easy to agglomerate in the reaction process, so that the anti-sintering capability is improved, and the catalytic reaction capability of the catalyst on formaldehyde is enhanced.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
The specific surface and pore size distribution of the catalyst in the following examples and comparative examples are shown by using low temperature N 2 Measuring by an adsorption method; the grain size of the active component of the catalyst is measured by an X-ray broadening method.
Example 1
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; grinding 100g petroleum coke into powder, adding into the solution A, standing for 1.5h, filtering, and drying the obtained solid sample in an oven at 110 deg.CAnd 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 16.18g of potassium permanganate, 9.87g of cobalt nitrate and 300g of potassium hydroxide, placing in a tube furnace, and heating to 800 ℃ in nitrogen atmosphere for activation for 40min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
The obtained catalyst precursor B was weighed and mixed in a mass ratio of 1:15 and 3wt% of H 2 O 2 And mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
The catalyst precursor C is supersaturated and impregnated by an ethanol solution of mercaptopropyltrimethoxysilane (the mass ratio of the mercaptopropyltrimethoxysilane to the ethanol is 1: 30), and after the catalyst precursor C fully reacts for 2 hours at the temperature of 60 ℃, evaporating the ethanol solution to dryness at 100 deg.C, calcining the sample at 600 deg.C under nitrogen atmosphere for 6h to obtain a dry mass fraction of 10% Mn, 5% Co 2 O 3 The catalyst of (4), noted C-1.
Example 2
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 16.18g of potassium permanganate, 8.56g of copper nitrate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, and heating to 800 ℃ under the condition of microwave power of 0.3kw and activating for 40min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
The obtained catalyst precursor B was weighed and mixed in a mass ratio of 1:15 and 3wt% of H 2 O 2 And mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
The catalyst precursor C is supersaturated and impregnated with an ethanol solution of mercaptopropyltrimethoxysilane (the mass ratio of mercaptopropyltrimethoxysilane to ethanol is 1: 30), the mixture is fully reacted at 60 ℃ for 2 hours, the ethanol solution is evaporated at 100 ℃, the obtained sample is roasted at 600 ℃ for 6 hours in a nitrogen atmosphere, and the catalyst with the mass accounting for 10% of Mn and 5% of CuO in the adsorbent is prepared and recorded as C-2.
Example 3
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h) -1 ) And raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, uniformly mixing with 16.18g of potassium permanganate, 7.10g of cerium nitrate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
The obtained catalyst precursor B was weighed and mixed in a mass ratio of 1:15 and 3wt% of H 2 O 2 And mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
Supersaturating and dipping the catalyst precursor C by adopting ethanol solution of mercaptopropyltrimethoxysilane (the mass ratio of the mercaptopropyltrimethoxysilane to the ethanol is 1: 30), fully reacting for 2 hours at 60 ℃, evaporating the ethanol solution to dryness at 100 ℃, roasting the obtained sample for 6 hours at 600 ℃ in nitrogen atmosphere, and finally obtaining the catalyst precursor C with the mass accounting for 10 percent of the adsorbent, wherein the mass of the catalyst precursor C accounts for 5 percent of the content of the CeO and the mass of the CeO 5 2 The catalyst of (4), noted C-3.
Example 4
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 110 ℃ for 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 500 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing the powder with 7.89g of potassium permanganate, 4.15g of cerium nitrate and 300g of sodium hydroxide, putting the mixture into a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 20min, then introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition that the microwave power is 0.3kw to activate for 10min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
Weighing the obtained catalyst precursor B, and mixing the weighed catalyst precursor B with the catalyst precursor B according to a mass ratio of 1:15 and 3wt% of H 2 O 2 And (3) mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
The catalyst precursor C is supersaturated and impregnated with an ethanol solution of mercaptopropyltrimethoxysilane (the mass ratio of the mercaptopropyltrimethoxysilane to the ethanol is 1: 30), fully reacted at 60 ℃ for 2 hours, the ethanol solution is evaporated at 100 ℃, the obtained sample is roasted at 600 ℃ for 6 hours in a nitrogen atmosphere, and the active carbon adsorbent is prepared, wherein the mass of the active carbon adsorbent accounts for 5 percent of Mn and 3 percent of CeO 2 The catalyst of (4), noted C-4.
Example 5
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 110 ℃ for 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h) -1 ) And raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, uniformly mixing with 25.22g of potassium permanganate, 11.79g of cerium nitrate, 100g of potassium hydroxide and 200g of potassium bicarbonate, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition that the microwave power is 0.3kw for activation for 30min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
The obtained catalyst precursor B was weighed and mixed in a mass ratio of 1:15 and 3wt% of H 2 O 2 And (3) mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
Supersaturating and dipping a catalyst precursor C by adopting an ethanol solution of mercaptopropyltrimethoxysilane (the mass ratio of the mercaptopropyltrimethoxysilane to the ethanol is 1: 30), fully reacting at 60 ℃ for 2 hours, evaporating the ethanol solution at 100 ℃, roasting the obtained sample at 600 ℃ for 6 hours in a nitrogen atmosphere, and thus obtaining the catalyst precursor C with the mass percentage of 15% of CeO Mn and 8% of CeO in the adsorbent 2 The catalyst of (4), noted C-5.
Example 6
Weighing 50g of ammonium dihydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 110 ℃ for 5h. And (2) pretreating the dried solid sample for 3h at 200 ℃ by using a mixed gas with the volume ratio of water vapor to nitrogen being 1 -1 ) And raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, uniformly mixing with 16.18g of potassium permanganate, 7.10g of cerium nitrate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
Weighing the obtained catalyst precursor B, and mixing the weighed catalyst precursor B with the catalyst precursor B according to a mass ratio of 1:20 and 1wt% HNO 3 And (3) mixing the aqueous solutions, fully stirring for 0.5h, then carrying out solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain a catalyst precursor C.
The catalyst precursor C is supersaturated and impregnated with an ethanol solution of methyltriethoxysilane (the mass ratio of methyltriethoxysilane to ethanol is 1 2 The catalyst of (4), denoted as C-6.
Example 7
Weighing 50g of ammonium hydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 90 ℃ for 8h. And (2) pretreating the dried solid sample for 3h at 200 ℃ by using a mixed gas with the volume ratio of water vapor to argon gas being 1 -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 16.18g of potassium permanganate, 7.10g of cerium nitrate and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain a catalyst precursor B.
The obtained catalyst precursor B was weighed and mixed in a mass ratio of 1: mixing 10 with 5wt% HClO aqueous solution, stirring thoroughly for 1h, performing solid-liquid separation, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under vacuum condition to obtain catalyst precursor C.
The catalyst precursor C was supersaturated and impregnated with an ethanol solution of hexamethyldisilazane (the mass ratio of hexamethyldisilazane to ethanol was 1 2 The catalyst of (4), noted C-7.
Comparative example
Grinding 100g of petroleum coke into powder, then uniformly mixing the powder with 300g of potassium hydroxide, placing the mixture into a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to normal pressure, and continuing heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 16.18g of potassium permanganate and 7.10g of cerous nitrate, dissolving the potassium permanganate and the cerous nitrate in 100mL of deionized water, adding the mixture into the sample obtained in the step of vacuum drying, uniformly stirring, aging for 2 hours, then placing the sample into a vacuum drying oven, drying the sample for 6 hours at 150 ℃ under a vacuum condition, roasting the dried sample for 6 hours at 700 ℃ under a nitrogen atmosphere, and thus obtaining the catalyst with the weight percentage content of 10% of Mn and 5% of CeO 2 The catalyst of (4), denoted as D-1.
Evaluation conditions were as follows: the formaldehyde catalytic oxidation reaction is carried out in a continuous flow fixed bed device, the raw material is a mixed gas of formaldehyde and air with the concentration of 220ppm, the reaction pressure is normal pressure, the temperature is room temperature, the total flow of the gas is 400mL/min, the point of 10h of reaction is taken for analysis, and the reaction results are shown in Table 1.
TABLE 1 catalyst Properties and reaction Performance
Figure 417065DEST_PATH_IMAGE002

Claims (51)

1. A catalyst for catalyzing and oxidizing formaldehyde comprises an active component, an auxiliary agent and a carrier; wherein the active component is Mn, the auxiliary agent is one or more of Mg, ba, zn, co, ti, cu, la and Ce, and the carrier is petroleum coke-based activated carbon, wherein the content of the active component is 1-15%, the content of the auxiliary agent is 1-10% calculated by oxide, and the content of the carrier is 76-97% based on the weight of the catalyst;
the preparation method of the catalyst for catalyzing and oxidizing the formaldehyde comprises the following steps:
(1) Pretreating petroleum coke; the pretreatment comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) by using water vapor-containing gas;
(2) Mixing the petroleum coke obtained in the step (1), an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, and activating after uniformly mixing;
(3) Washing and drying the sample obtained in the step (2) to obtain a catalyst precursor A;
(4) Treating the catalyst precursor A by using an oxidizing solution, and drying to obtain a catalyst precursor B;
(5) And (3) treating the catalyst precursor B by using a coupling agent to obtain the catalyst for catalyzing and oxidizing the formaldehyde.
2. The catalyst for catalytic oxidation of formaldehyde according to claim 1, characterized in that: the auxiliary agent is one or more of Co, cu and Ce, and based on the weight of the catalyst, the content of the active component is 3-12%, the content of the auxiliary agent is 3-8% calculated by oxide, and the content of the carrier is 81-92%.
3. The method as claimed in claim 1 for catalysisA catalyst for oxidizing formaldehyde, characterized by: the specific surface area of the catalyst is 1000-2800 m 2 /g。
4. The catalyst for the catalytic oxidation of formaldehyde according to claim 1 or 3, characterized in that: the specific surface area of the catalyst is 1200-2500 m 2 /g。
5. The catalyst for the catalytic oxidation of formaldehyde according to claim 1, characterized in that: the active components are embedded into the amorphous defect of the petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of active metal crystal grains is 1.1-6.3 nm.
6. The catalyst for the catalytic oxidation of formaldehyde according to claim 1 or 5, characterized in that: the active components are embedded into the amorphous defect of the petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of active metal crystal grains is 1.5-5 nm.
7. The method for preparing a catalyst for the catalytic oxidation of formaldehyde according to any one of claims 1 to 6, which comprises the following steps:
(1) Pretreating petroleum coke; the pretreatment comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) by using water vapor-containing gas;
(2) Mixing the petroleum coke obtained in the step (1), an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, and activating after uniformly mixing;
(3) Washing and drying the sample obtained in the step (2) to obtain a catalyst precursor A;
(4) Treating the catalyst precursor A by using an oxidizing solution, and drying to obtain a catalyst precursor B;
(5) And (3) treating the catalyst precursor B by using a coupling agent to obtain the catalyst for catalyzing and oxidizing the formaldehyde.
8. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (1.1), the ammonium phosphate salt is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
9. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 8, characterized in that: in the step (1.1), the ammonium phosphate salt is ammonium phosphate.
10. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (1.1), the drying temperature is 60-120 ℃, and the drying time is 2-8 h.
11. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 10, characterized in that: in the step (1.1), the drying temperature is 80-100 ℃, and the drying time is 4-6 h.
12. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 10, characterized in that: the drying in step (1.1) is carried out under vacuum.
13. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (1.1), the weight ratio of the ammonium phosphate to the petroleum coke is 0.1-1: 1.
14. the process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 13, characterized in that: in the step (1.1), the weight ratio of the ammonium phosphate salt to the petroleum coke is 0.3-0.8.
15. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (1.2), the vapor-containing gas is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
16. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 15, characterized in that: in the step (1.2), the vapor-containing gas is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
17. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 5, wherein: the pretreatment process in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 150-250 ℃, and the pretreatment time is 1-6 h; the second stage of pretreatment is carried out at the temperature of 300-500 ℃ for 1-6 h, and then the second stage of pretreatment is cooled to 20-100 ℃.
18. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 17, wherein: the pretreatment process in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 180-220 ℃, and the pretreatment time is 2-4 h; the temperature of the second stage of pretreatment is 350-450 ℃, the pretreatment time is 2-4 h, and the second stage of pretreatment is cooled to 40-80 ℃ after finishing the second stage of pretreatment.
19. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 17 or 18, wherein: and (3) carrying out the cooling process in the step (1.2) under the protection of nitrogen.
20. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: step (1.2)) The volume space velocity of the vapor-containing gas is 500-2000 h -1 。
21. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (2), the active metal-containing compound is one or more of lithium permanganate, sodium permanganate, potassium permanganate and ammonium permanganate.
22. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 21, wherein: in the step (2), the active metal-containing compound is high lithium manganate.
23. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (2), the metal compound containing the auxiliary agent is one or more of nitrate, sulfate and hydrochloride.
24. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 23, characterized in that: in the step (2), the metal compound containing the auxiliary agent is nitrate.
25. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 23, wherein: in the step (2), the metal compound containing the auxiliary agent is one or more of magnesium nitrate, barium nitrate, zinc nitrate, cobalt nitrate, titanium nitrate, copper nitrate, cerium nitrate and lanthanum nitrate.
26. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 23, characterized in that: in the step (2), the metal compound containing the auxiliary agent is one or more of cobalt nitrate, copper nitrate and cerium nitrate.
27. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: the activating agent in the step (2) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate.
28. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 27, characterized in that: in the step (2), the activating agent is potassium hydroxide.
29. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (2), the mass ratio of the active metal-containing compound to the auxiliary agent-containing metal compound to the activating agent to the petroleum coke is 0.004-0.08: 0.004 to 0.06:0.5 to 4:1.
30. the process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 29, wherein: in the step (2), the mass ratio of the active metal-containing compound to the auxiliary metal-containing compound to the activator to the petroleum coke is 0.014-0.062: 0.014 to 0.042:1 to 3:1.
31. the process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: the activation process in the step (2) is as follows: uniformly mixing the petroleum coke obtained in the step (1), an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, heating to an activation temperature in an inert atmosphere, cooling to 20-100 ℃ after activation is completed, and performing subsequent treatment, wherein the activation temperature is 400-1000 ℃, and the activation time is 5-240 min.
32. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 31, wherein: the activation process in the step (2) is as follows: uniformly mixing the petroleum coke obtained in the step (1), an active metal-containing compound, an auxiliary agent-containing metal compound and an activating agent, heating to an activation temperature in an inert atmosphere, cooling to 20-100 ℃ after activation is completed, and performing subsequent treatment, wherein the activation temperature is 700-900 ℃, and the activation time is 10-120 min.
33. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 31, wherein: the activation is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915MHz; the microwave power is 1-10 kW per kg of petroleum coke.
34. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 33, wherein: the microwave power is 2-4 kW in terms of petroleum coke per kg.
35. A process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 33, wherein: when the activation is carried out under the microwave radiation condition, two-stage activation is carried out, the first stage is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
36. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: and (3) washing is water washing, firstly, the sample obtained in the step (2) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral.
37. The process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (3), the drying temperature is 100-200 ℃, and the drying time is 2-10 h.
38. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 37, wherein: in the step (3), the drying temperature is 120-180 ℃, and the drying time is 4-8 h.
39. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 37, wherein: the drying in step (3) is carried out under vacuum conditions.
40. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: the oxidizing solution in the step (4) contains HNO 3 、HClO、H 2 O 2 One or more than one of the aqueous solutions, wherein the concentration of the oxidizing solution is 1wt% -10 wt%.
41. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 40, wherein: the oxidizing solution in the step (4) contains HNO 3 、HClO、H 2 O 2 One or more than one of aqueous solutions, wherein the concentration of the oxidizing solution is 1 to 5 weight percent.
42. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: the process of treating the catalyst precursor A obtained in the step (3) with an oxidizing solution is as follows: mixing the catalyst precursor A with an oxidizing solution for 0.5-1 h, and then carrying out solid-liquid separation, wherein the mass ratio of the catalyst precursor A to the oxidizing solution is 1:5 to 1:30.
43. a method for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7 or 42, wherein: the process of treating the catalyst precursor A obtained in the step (3) with an oxidizing solution is as follows: mixing the catalyst precursor A with an oxidizing solution for 0.5-1 h, and then carrying out solid-liquid separation, wherein the mass ratio of the catalyst precursor A to the oxidizing solution is 1: 10-1: 20.
44. the process for preparing a catalyst for catalytic oxidation of formaldehyde according to claim 7, wherein: in the step (4), the drying temperature is 100-200 ℃, and the drying time is 2-10 h.
45. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 44, wherein: in the step (4), the drying temperature is 120-180 ℃, and the drying time is 4-8 h.
46. The process for producing a catalyst for catalytic oxidation of formaldehyde according to claim 7 or 44, wherein: the drying in step (4) is carried out under vacuum conditions.
47. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: the coupling agent in the step (5) is one or more of dichlorodimethylsilane, trimethylchlorosilane, hexamethyldisilazane, aminopropyltriethoxysilane, methyltriethoxysilane and mercaptopropyltrimethoxysilane.
48. A process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7 or 47, characterized in that: the coupling agent in the step (5) is mercaptopropyltrimethoxysilane.
49. The process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 7, wherein: the process of treating the catalyst precursor B with the coupling agent in the step (5) is as follows: and supersaturating ethanol solution containing a coupling agent to impregnate the catalyst precursor B, fully reacting at 40-70 ℃, evaporating the ethanol solution to dryness at 80-120 ℃, and roasting the obtained sample at 500-700 ℃ in nitrogen atmosphere to obtain the catalyst for catalyzing and oxidizing formaldehyde.
50. A process for preparing a catalyst for the catalytic oxidation of formaldehyde according to claim 49, wherein: in the ethanol solution containing the coupling agent, the mass ratio of the coupling agent to the ethanol is 1.
51. Use of a catalyst according to any one of claims 1 to 6 in a catalytic oxidation reaction of formaldehyde.
CN201811648069.XA 2018-12-29 2018-12-29 Catalyst for catalytic oxidation of formaldehyde and preparation method thereof Active CN111375422B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811648069.XA CN111375422B (en) 2018-12-29 2018-12-29 Catalyst for catalytic oxidation of formaldehyde and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811648069.XA CN111375422B (en) 2018-12-29 2018-12-29 Catalyst for catalytic oxidation of formaldehyde and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111375422A CN111375422A (en) 2020-07-07
CN111375422B true CN111375422B (en) 2022-10-11

Family

ID=71213111

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811648069.XA Active CN111375422B (en) 2018-12-29 2018-12-29 Catalyst for catalytic oxidation of formaldehyde and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111375422B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471456B (en) * 2020-10-27 2023-07-28 中国石油化工股份有限公司 Modified carbon material and preparation method thereof
CN114471583B (en) * 2020-10-28 2023-08-01 中国石油化工股份有限公司 Catalyst for treating low COD sewage and preparation method thereof
CN112473666A (en) * 2020-11-17 2021-03-12 上海应用技术大学 Catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method and application thereof
CN112619699B (en) * 2020-12-21 2022-08-05 山东齐鲁华信高科有限公司 Post-treatment method of SSZ-13 molecular sieve
CN113522354A (en) * 2021-07-28 2021-10-22 几唯(苏州)新材料科技有限公司 Preparation and application of molecular sieve supported composite metal oxide catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101181993A (en) * 2007-12-13 2008-05-21 中国人民解放军总后勤部军需装备研究所 Kenaf stalk activated charcoal and preparation method thereof
CN106082213A (en) * 2016-06-20 2016-11-09 山东欧铂新材料有限公司 A kind of compound petroleum coke matrix activated carbon and preparation method thereof, ultracapacitor
CN108126709A (en) * 2017-12-19 2018-06-08 如皋六维环境科技有限公司 A kind of support type formaldehyde catalyst and preparation method thereof
CN108579741A (en) * 2018-05-21 2018-09-28 西安凯立新材料股份有限公司 A kind of formaldehyde room temperature oxidation composite carried catalyst prepared using collosol and gel-infusion process
CN108855108A (en) * 2018-06-26 2018-11-23 天津工业大学 Starch-based bio activated carbon loaded nano catalysis material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2009002359A (en) * 2009-03-03 2010-10-01 Mexicano Inst Petrol Carbon supported catalyst for demetallation of heavy crude oil and residue.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101181993A (en) * 2007-12-13 2008-05-21 中国人民解放军总后勤部军需装备研究所 Kenaf stalk activated charcoal and preparation method thereof
CN106082213A (en) * 2016-06-20 2016-11-09 山东欧铂新材料有限公司 A kind of compound petroleum coke matrix activated carbon and preparation method thereof, ultracapacitor
CN108126709A (en) * 2017-12-19 2018-06-08 如皋六维环境科技有限公司 A kind of support type formaldehyde catalyst and preparation method thereof
CN108579741A (en) * 2018-05-21 2018-09-28 西安凯立新材料股份有限公司 A kind of formaldehyde room temperature oxidation composite carried catalyst prepared using collosol and gel-infusion process
CN108855108A (en) * 2018-06-26 2018-11-23 天津工业大学 Starch-based bio activated carbon loaded nano catalysis material and preparation method thereof

Also Published As

Publication number Publication date
CN111375422A (en) 2020-07-07

Similar Documents

Publication Publication Date Title
CN111375422B (en) Catalyst for catalytic oxidation of formaldehyde and preparation method thereof
CN111717902B (en) Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof
CN111375406B (en) Ozone catalytic oxidation catalyst and preparation method thereof
CN101879435B (en) High-adsorption-capacity room-temperature nitrogen oxide adsorbent and preparation method thereof
CN111375373B (en) Adsorbent using active carbon as carrier and preparation method thereof
CN104667916A (en) Method for preparing catalytic wet oxidation catalyst
CN108069497B (en) Method for treating organic wastewater by catalytic wet oxidation
CN111377443B (en) Copper-doped activated carbon composite material and preparation method thereof
CN111377523B (en) Catalytic wet oxidation treatment method for organic wastewater
CN102463030A (en) Method for removing nitric oxide in tail gas for preparing oxalate from CO
CN105712461A (en) Catalytic wet oxidation method for acrylic acid and ester wastewater
CN111375374B (en) Load type copper-based adsorbent and preparation method thereof
CN112086298B (en) Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof
CN110342580B (en) Microwave-assisted method for preparing activated carbon-manganese dioxide nanocomposite
CN111377520B (en) Organic wastewater treatment process
CN111375375B (en) Desulfurization adsorbent and preparation method thereof
CN105709746A (en) Catalytic wet oxidation catalyst and preparation method thereof
CN114130387B (en) Nitrogen defect g-C3N4Surface doped nano manganese catalyst and preparation method and application thereof
CN104667922A (en) Method for preparing noble metal catalyst for catalytic wet oxidation
CN114471146B (en) Green and odorless formaldehyde scavenger and preparation method thereof
CN105709732A (en) Noble metal catalyst for catalytic wet oxidation and preparation method thereof
CN114602446A (en) Catalyst for UV/persulfate process and preparation method and application thereof
CN105712459B (en) A kind of ozone catalytic wet oxidation method of acrylicacidandesters waste water
CN113231037A (en) Solid amine adsorbent for removing trace hydrogen sulfide and preparation method thereof
CN112588298A (en) Composite catalyst for air purification and preparation method and application thereof

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
TR01 Transfer of patent right

Effective date of registration: 20231106

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.