CN106732522A - The preparation method of carrying transition metal oxide catalyst - Google Patents

The preparation method of carrying transition metal oxide catalyst Download PDF

Info

Publication number
CN106732522A
CN106732522A CN201611226704.6A CN201611226704A CN106732522A CN 106732522 A CN106732522 A CN 106732522A CN 201611226704 A CN201611226704 A CN 201611226704A CN 106732522 A CN106732522 A CN 106732522A
Authority
CN
China
Prior art keywords
carrier
solution
transition metal
alcohol
constant temperature
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.)
Pending
Application number
CN201611226704.6A
Other languages
Chinese (zh)
Inventor
赵东
赵亮
田振邦
张馨月
张永军
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.)
Institute of Chemistry Henan Academy of Sciences Co Ltd
Original Assignee
Institute of Chemistry Henan Academy of Sciences Co Ltd
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 Institute of Chemistry Henan Academy of Sciences Co Ltd filed Critical Institute of Chemistry Henan Academy of Sciences Co Ltd
Priority to CN201611226704.6A priority Critical patent/CN106732522A/en
Publication of CN106732522A publication Critical patent/CN106732522A/en
Pending legal-status Critical Current

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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/72—Copper
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of method for preparing carrying transition metal oxide catalyst, belong to technical field of inorganic material synthesis.First in the aqueous solution of transition metal inorganic salts be sufficiently impregnated carrier by the present invention, it is sufficiently impregnated in the alcohol/aqueous solution of NaOH after drying, water miscible slaine is set to be converted into water-insoluble metal hydroxides, it is calcined after washing, drying again, loaded hydroxide kinetics is generated oxide, obtain the catalyst of carrying transition metal oxide.The method can avoid the pernicious gases such as the conventional method nitrogen oxides produced in roasting, and advantageously reduce sintering temperature, realize cleaning, the preparation technology of energy-conservation.

Description

The preparation method of carrying transition metal oxide catalyst
Technical field
The present invention relates to a kind of preparation method of Inorganic catalyst materials, more particularly to a kind of carrying transition metal oxide Catalyst material preparation method, belong to technical field of inorganic material synthesis.
Background technology
No matter catalysis material is key High-tech Material, wherein transiting metal oxidation in industrial production or field of Environment Protection Thing is the important catalytic active substance of a major class, different with oxide structure according to its metallic element species, can be used for catalysis many Plant chemical reaction.For reduction transition metal resource consumption, avoid heavy metal pollution, raising catalytic efficiency and reduces cost etc. Consider, be typically carried on the carrier surface with certain form and good strength, the surface nature using carrier makes on a small quantity Catalyst can play obvious action.
The conventional method for preparing metal oxide supporting catalyst, is that carrier is soaked in the aqueous solution of slaine at present Stain, makes slaine be scattered in the Surface and internal structure of carrier with ionic state, dries and removes moisture, and then high-temperature roasting makes Metal cation be converted into metal oxide and with carrier strong bonded, the anion of slaine then by pyrolytic and is oxidized to Gas and remove.For example：Chinese patent CN200910186028.8 " loaded catalyst of multi-phase catalytic ozonation and its preparation Method " is with honeycomb haydite as carrier, using the oxide of transition metal Cu as active component, through carrier in copper nitrate solution Impregnate, dry, be calcined and obtain metal oxide-loaded catalyst；Chinese patent CN201210094240.3 " one kind loads The preparation method of type metal oxide ozone catalytic oxidation catalyst " is the nickel nitrate after pretreatment with ceramic filtration ball as carrier Impregnated in solution, after drying in Muffle kiln roasting, then be washed with deionized, dry and obtain metal oxide-loaded Catalyst；Chinese patent CN200610165429.1 " a kind of loaded noble metal catalyst of low-temperature catalytic oxidation benzene series thing and Its preparation method " is that carrier is stirred in the solution of precious metal salt, then rotary evaporation removal solvent, in drying box Dry, be calcined with Muffle furnace and obtain supported precious metal catalyst；Chinese patent CN201310420135.9 " one kind catalysis burnings With the preparation method of supported complex oxide catalyst " it is La, Mg, Mn and Ce soluble-salt with mesopore molecular sieve as carrier It is raw material, complex carrier CeO is prepared by dipping, dry, roasting2- mesopore molecular sieve, then used La-Mg-Mn mixed solutions Dipping, supported complex oxide catalyst is obtained through drying, roasting；Chinese patent CN201210312162.X is " a kind of more Phase catalytic ozonation loaded catalyst and preparation method thereof " is during basic copper carbonate is dissolved in into ammonium bicarbonate solution or ammoniacal liquor Complex solution is formed, is taken out after carrier is impregnated in the solution and dried, the heat preservation and dryness at a temperature of 200-250 DEG C makes oxygen Change copper to separate out in carrier surface formation Catalytic Layer, obtain loaded copper oxide catalyst.
As shown in above technical literature, many carried metals that prepared using the method being calcined after impregnating metal salt are aoxidized at present Thing catalyst, the method has the advantages that technique is easy, applied widely, it is more to prepare material category, but the nitrate for being impregnated Nitrogen oxides etc. can be produced poisonous and corrosive gas Deng in roasting, to prevent from polluting surrounding air and being made to equipment Into infringement, waste gas absorption purification facility and safeguard procedures need to be equipped with, increased relevant cost.
The content of the invention
The load of pernicious gas rationally and in can avoiding being calcined is produced it is an object of the invention to provide a kind of technique simplicity The preparation method of catalyst of transition metal oxide.
To realize the object of the invention, preparation method is concretely comprised the following steps：
1. the inorganic salts of transition metal are dissolved in deionized water, are configured to the solution that concentration of metal ions is 0.2-2mol/L, By carrier impregnation in the solution, 2-10mL solution is used per 1g carriers, in 5-50 DEG C of constant temperature oscillation or stirring 2-10h, make gold Category ion is gradually diffused into the Surface and internal structure of carrier；
2. will be separated from solution by the carrier of above-mentioned treatment, in 60-100 DEG C of freeze-day with constant temperature to constant weight；
3. NaOH is dissolved in alcohol/water volume ratio for 2-10:In 1 alcohol/water mixed solvent, NaOH is configured to dense The solution for 0.2-2mol/L is spent, in the solution, uses 2-10mL molten per 1g carriers by by the carrier impregnation of above-mentioned treatment Liquid, in 5-50 DEG C of constant temperature oscillation or stirring 2-20h, makes metal ion gradually react water insoluble and alcohol the metallic hydrogen of generation with alkali Oxide.
4. will be separated from solution by the carrier of above-mentioned treatment, soaked with deionized water, clean removing water solubility Slaine and solvent alcohol, in 60-100 DEG C of freeze-day with constant temperature to constant weight.
5. by by the carrier of above-mentioned treatment in 300-500 DEG C constant temperature calcining 2-6 hours, make the metal hydrogen-oxygen on carrier Compound decomposes generation metal oxide.
Transition metal inorganic salts employed in above-mentioned preparation method are the nitric acid of Fe, Cu, Ni, Mn, Co, Ag, La or Ce Salt, hydrochloride or sulfate, the carrier for being used are alundum (Al2O3), silica, carborundum, porous ceramics, molecular sieve, silicon Diatomaceous earth or perlite, the alcohol that alcohol/water mixed solvent is used are ethanol, isopropanol, ethylene glycol or propane diols.
Innovative point of the invention is：After carrier is sufficiently impregnated the aqueous solution of slaine and dries, using NaOH Alcohol/aqueous solution it is impregnated and is reacted, by the slaine for being used is in the alcohol/water mixed solvent containing more amount alcohol Insoluble or solubility is very low, and metal ion can be avoided to be lost in in solution, it is given birth on the surface of carrier or internal reaction with alkali Into metal hydroxides；Then washing removes alcohol and unreacted slaine, water insoluble metal hydroxides and carrier one Rise and obtain metal oxide-loaded catalyst through drying and being calcined.
The beneficial effects of the present invention are：（1）Compared with conventional method, water-soluble metal salt is converted into before roasting non- Water soluble metal hydroxide, in subsequent roasting process hydroxide dehydration can generation oxide avoid nitrate, Hydrochloride etc. produces pernicious gas under high-temperature roasting, such as nitrogen oxides, hydrogen chloride, chlorine, is advantageously implemented clean manufacturing, Disposal of pollutants is reduced, simplifies exhaust-gas treatment and protective equipment；（2）Hydroxide is easy to thoroughly be decomposed into oxide, required temperature Generally it is not required to too high, advantageously reduces sintering temperature, reduces energy resource consumption, and be conducive to preventing carrier structure at high temperature from breaking Bad and hydraulic performance decline；（3）This method reaction mechanism is clear, implementation process is easy, it is adaptable to various transition metal oxides it is negative Carry, be also applied for various artificial synthesized or natural catalyst carrier material.
Specific embodiment
It is as follows for embodiment for preferably the present invention is described in detail：
Embodiment 1
Prepare Cu2+Concentration is the copper nitrate aqueous solution of 0.5mol/L, and 10g white globules shape alumina carriers are immersed in In the 50mL solution, in 20 DEG C of constant temperature oscillation 3h, then carrier is separated from solution, 70 DEG C of freeze-day with constant temperature to constant weight；Prepare Naoh concentration is 0.5mol/L, isopropanol/water volume ratio 5:1 as mixed solvent sodium hydroxide solution, by above-mentioned place The carrier impregnation managed, in 20 DEG C of constant temperature oscillation 10h, then separates carrier in the 50mL solution from solution, spend from Sub- water immersion, cleaning remove water miscible slaine and isopropanol, in 70 DEG C of freeze-day with constant temperature to constant weight；Finally will be above-mentioned treated Carrier in Muffle furnace in 400 DEG C of constant temperature calcining 3h, obtain the spherical catalyst of the load Cu oxide of grey black, after tested The mantoquita for being loaded has been converted into cupric oxide.
Embodiment 2
Prepare Fe3+Concentration is the ferric chloride in aqueous solution of 1mol/L, and 10g white chunks cellular ceramic substrates are immersed in into 25mL should In solution, in 30 DEG C of constant temperature oscillation 8h, then carrier is separated from solution, 90 DEG C of freeze-day with constant temperature to constant weight；Prepare hydroxide Na concn is 2mol/L, ethanol/water volume ratio is 3:1 sodium hydroxide solution, 25mL is added to by above-mentioned treated carrier In the solution, in 30 DEG C of constant temperature oscillation 15h, then carrier is separated from solution, removed with deionized water immersion, cleaning water-soluble The slaine and ethanol of property, in 90 DEG C of freeze-day with constant temperature to constant weight；Finally by above-mentioned treated carrier in Muffle furnace in 450 DEG C Constant temperature calcining 5h, obtains the porous ceramic catalyst of the supported ferriferous oxide of brownish red, and the molysite for being loaded after tested has been converted It is di-iron trioxide.

Claims (2)

1. the preparation method of carrying transition metal oxide catalyst, it is characterised in that comprise the following steps that：
1. the inorganic salts of transition metal are dissolved in deionized water, are configured to the solution that concentration of metal ions is 0.2-2mol/L, By carrier impregnation in the solution, 2-10mL solution is used per 1g carriers, in 5-50 DEG C of constant temperature oscillation or stirring 2-10h, make gold Category ion is gradually diffused into the Surface and internal structure of carrier；
2. will be separated from solution by the carrier of above-mentioned treatment, in 60-100 DEG C of freeze-day with constant temperature to constant weight；
3. NaOH is dissolved in alcohol/water volume ratio for 2-10:In 1 alcohol/water mixed solvent, NaOH is configured to dense The solution for 0.2-2mol/L is spent, in the solution, uses 2-10mL molten per 1g carriers by by the carrier impregnation of above-mentioned treatment Liquid, in 5-50 DEG C of constant temperature oscillation or stirring 2-20h, makes metal ion with alkali reaction water insoluble and alcohol the metal hydroxide of generation Thing；
4. will be separated from solution by the carrier of above-mentioned treatment, soaked with deionized water, clean the water miscible gold of removing Category salt and solvent alcohol, in 60-100 DEG C of freeze-day with constant temperature to constant weight；
5. by by the carrier of above-mentioned treatment in 300-500 DEG C constant temperature calcining 2-6 hours, make the metal hydroxides on carrier Decompose generation metal oxide.
2. the preparation method of carrying transition metal oxide catalyst as claimed in claim 1, it is characterised in that used Transition metal inorganic salts are nitrate, hydrochloride or the sulfate of Fe, Cu, Ni, Mn, Co, Ag, La or Ce, the carrier for being used It is alundum (Al2O3), silica, carborundum, porous ceramics, molecular sieve, diatomite or perlite, alcohol/water mixed solvent is adopted Alcohol is ethanol, isopropanol, ethylene glycol or propane diols.
CN201611226704.6A 2016-12-27 2016-12-27 The preparation method of carrying transition metal oxide catalyst Pending CN106732522A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611226704.6A CN106732522A (en) 2016-12-27 2016-12-27 The preparation method of carrying transition metal oxide catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611226704.6A CN106732522A (en) 2016-12-27 2016-12-27 The preparation method of carrying transition metal oxide catalyst

Publications (1)

Publication Number Publication Date
CN106732522A true CN106732522A (en) 2017-05-31

Family

ID=58921628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611226704.6A Pending CN106732522A (en) 2016-12-27 2016-12-27 The preparation method of carrying transition metal oxide catalyst

Country Status (1)

Country Link
CN (1) CN106732522A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109675560A (en) * 2018-12-29 2019-04-26 广州市金龙峰环保设备工程股份有限公司 A kind of ceramsite catalyst and its preparation method and application that low-temperature plasma is modified
CN112844443A (en) * 2020-12-14 2021-05-28 北京航天试验技术研究所 Ortho-para hydrogen conversion catalyst using ordered mesoporous material and preparation method thereof
CN115121279A (en) * 2021-03-25 2022-09-30 河南省高新技术实业有限公司 Solid catalyst, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549273A (en) * 2014-12-31 2015-04-29 北京北华中清环境工程技术有限公司 Metal oxide loading active carbon catalyst and preparation method thereof
CN104841429A (en) * 2015-04-05 2015-08-19 浙江大学 Supported copper-based catalyst for synthetic gas-to-methanol, and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549273A (en) * 2014-12-31 2015-04-29 北京北华中清环境工程技术有限公司 Metal oxide loading active carbon catalyst and preparation method thereof
CN104841429A (en) * 2015-04-05 2015-08-19 浙江大学 Supported copper-based catalyst for synthetic gas-to-methanol, and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109675560A (en) * 2018-12-29 2019-04-26 广州市金龙峰环保设备工程股份有限公司 A kind of ceramsite catalyst and its preparation method and application that low-temperature plasma is modified
CN112844443A (en) * 2020-12-14 2021-05-28 北京航天试验技术研究所 Ortho-para hydrogen conversion catalyst using ordered mesoporous material and preparation method thereof
CN115121279A (en) * 2021-03-25 2022-09-30 河南省高新技术实业有限公司 Solid catalyst, preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN104888806B (en) A kind of regeneration method that inactivation vanadium titanium-based Faveolate denitration catalyst combined denitration demercuration is modified
CN101690888B (en) Method for preparing chemical absorbent with porous mineral
KR100668936B1 (en) Method of regenerating Honeycomb type SCR catalyst by air lift loop reactor
CN102814201A (en) Cleaning and regeneration method for SCR denitration catalyst poisoned by arsenic component in flue
CN105056882A (en) Preparation method of modified charcoal-based adsorbent for removing hydrogen sulfide
CN104646020A (en) Ozone catalyst and preparation method
CN111939896B (en) Liquid catalyst for catalyzing ozonolysis at normal temperature and preparation method and application thereof
CN100528345C (en) Denitration catalyst, and preparation method
CN106732522A (en) The preparation method of carrying transition metal oxide catalyst
CN108380214B (en) A kind of preparation of modified meerschaum and method applied to wastewater treatment
CN107649176B (en) Catalyst for catalytic hydrolysis of hydrogen cyanide and preparation method thereof
CN107552067A (en) A kind of material for water treatment and its application
CN109092328A (en) A kind of method of SCR denitration spent catalyst recovery
CN107138168A (en) Ozone catalyst for high concentration organic nitrogen wastewater treatment
CN111013601A (en) Preparation method of manganese ozone catalyst and method for treating coal chemical industry wastewater
CN106964333B (en) Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone
CN113104928B (en) Application of CuO @ nitrogen doped carbon composite catalytic material in photo-thermal catalysis for producing non-free radicals
CN106552644B (en) Ozone catalyst for difficult biochemical wastewater and preparation method thereof
CN109433217A (en) A kind of red mud denitrating catalyst and preparation method thereof
CN112642495A (en) Realize low SO2Catalyst regeneration and modification method for conversion rate and high zero-valent mercury oxidation performance
TWI488690B (en) The method of preparation of cerium oxide-manganese oxide supported nano-palladium catalysts and its application in destruction of volatile organic compounds in air
CN112007650A (en) Method for preparing porous cerium oxide-copper oxide composite material by chemical corrosion method
CN111939924A (en) Composite catalyst for ozone oxidation and preparation method thereof
CN114308052A (en) Preparation method of strong-effect water-resistant and sulfur-resistant denitration catalyst
CN107803205A (en) A kind of manufacture method of material for water treatment

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20170531

RJ01 Rejection of invention patent application after publication