CN104710291A - Method for preparing formaldehyde by methane photocatalytic oxidation - Google Patents
Method for preparing formaldehyde by methane photocatalytic oxidation Download PDFInfo
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- CN104710291A CN104710291A CN201310682116.3A CN201310682116A CN104710291A CN 104710291 A CN104710291 A CN 104710291A CN 201310682116 A CN201310682116 A CN 201310682116A CN 104710291 A CN104710291 A CN 104710291A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing formaldehyde by methane photocatalytic oxidation and belongs to the technical field of chemical engineering. The method is characterized in that in a fixed bed photochemical reactor, under the action of a high-pressure mercury lamp as a light source (linear light source), loading molecular sieve-loaded zinc-molybdenum oxide photocatalysts prepared by a hydrothermal method are uniformly arranged in the middle of a gas phase photocatalysis reaction instrument, under normal pressure, methane and air are fed into the reaction instrument according to a certain ratio, and the reaction system is heated to a set temperature of 80-110 DEG C and then undergoes an irradiation reaction after adsorption balance. The method has the advantages of simple processes, small investment, high formaldehyde yield and low reaction temperature.
Description
Technical field
The present invention relates to a kind of method that formaldehyde is prepared in methane photochemical catalytic oxidation, belong to chemical technology field.
Background technology
Methane is the strong greenhouse gas that a kind of global warming potential (GWP) is very high, is rich in coal-seam gas.If do not made full use of, certain impact is all produced on environment and the energy.Meanwhile, methane is also widely used in catalyzed oxidation and prepares formaldehyde.The main formaldehyde prepration process of China is " silver-colored method ", and refined methanol generates formaldehyde through peroxidation, dehydrogenation reaction under silver catalyst effect.If be directly formaldehyde by Catalytic methane oxidation, cost will reduce greatly.But it is very low that Catalytic methane oxidation prepares formaldehyde conversion, and general temperature of reaction is very high.Therefore, find a kind of more efficiently catalysis process and become study hotspot.
Photocatalysis technology causes the attention of numerous researchers due to its feature such as efficient, energy-conservation.Photochemical catalytic oxidation methane is simple for formaldehyde technique, and formaldehyde conversion is high, and temperature of reaction is low, can also be greatly cost-saving.Therefore, find a kind of effective photochemical catalytic oxidation methanation catalyst and become the most important thing.
Summary of the invention
The defects such as the object of this invention is to provide a kind of method that formaldehyde is prepared in methane photochemical catalytic oxidation, this method solving Catalytic methane oxidation, to prepare formaldehyde conversion low, and temperature of reaction is high.The invention provides the processing method that methane photocatalytic-oxidation is turned to formaldehyde by a kind of molecular sieve carried zinc, molybdenum oxide catalyst, this processing method is simple, and formaldehyde conversion is high, and temperature of reaction is low.
The feature of present method is that to prepare formaldehyde reaction be carry out in gas-phase photocatalysis reaction instrument in methane photochemical catalytic oxidation; With high voltage mercury lamp (500W) for light source (linear light sorurce); With molecular sieve carried zinc, molybdenum oxide for catalyzer; Photocatalyst is evenly placed in the middle part of fixed-bed reactor; Closed system; Can react at ambient pressure; Methane and volume of air are than being 1:99; Need to control temperature of reaction, General reactions temperature range is 80 ~ 110 DEG C; Reaction time range is 0 ~ 1000min; Before illumination, need to reach adsorption equilibrium.
The invention provides a kind of method that formaldehyde is prepared in methane photochemical catalytic oxidation, its step is as follows:
1, hydrothermal method prepares molecular sieve carried zinc, molybdenum oxide catalyst
(1) zinc sulfate weighing certain mass is dissolved in the water of certain volume, adds in reactor; The mass range of general zinc sulfate is 0.1g ~ 1g; The volume of general water is 0 ~ 20ml;
(2) aniline or the ethylenediamine solution that measure certain volume join in still, vigorous stirring; General aniline or ethylenediamine solution volume are 5 ~ 20ml; The volume ratio of general aniline or quadrol and water is 0 ~ 10;
(3) ammonium molybdate weighing certain mass is soluble in water, wiring solution-forming; General ammonium molybdate aqueous solution concentration is 0 ~ 1mol/L;
(4) ammonium molybdate solution measuring certain volume joins reaction attached middle school, stirs; General ammonium molybdate solution volume is 0 ~ 5ml;
(5) molecular sieve of certain mass is added in reactor; General molecular sieve mass range is 0 ~ 10g;
(6) seal, make reaction system become closed system;
(7) be warmed up to assigned temperature T, and the reaction times is at the reaction temperatures set; General reactions temperature range is 100 ~ 180 DEG C; General reactions time range is 1 ~ 24h;
(8) after reaction terminates, question response product is down to room temperature, takes out reactant;
(9) reaction product is washed several times, vacuum-drying;
(10) after product drying, 300 ~ 700 DEG C of calcining and activating 1 ~ 5h.
2, formaldehyde is prepared in methane photochemical catalytic oxidation
Photochemical catalysis experiment is carried out in gas phase photochemical reaction instrument, take high voltage mercury lamp as light source (linear light sorurce), above-mentioned prepared photocatalyst is evenly placed in the middle part of gas-phase photocatalysis reaction instrument, at ambient pressure, pass into methane and air by a certain percentage, and be warming up to design temperature (80 ~ 110 DEG C), after reaching adsorption equilibrium, carry out irradiation reaction, after for some time, methane conversion can reach more than 90%.
Embodiment
Embodiment 1:
The zinc sulfate of 0.1g ~ 1g is dissolved in 0 ~ 20ml water, measure volume ratio be 0 ~ 10 aniline-water solution 5 ~ 20ml join in reactor, be then be that the ammonium molybdate solution of 0 ~ 1mol/L adds in reactor by 0 ~ 5ml concentration, then the molecular sieve of 0 ~ 10g joined in reactor, stir, sealing, 120 DEG C, reaction 10h, after question response completes, take out reactant, use water and absolute ethanol washing respectively for several times, then 450 DEG C of calcining 2h.
Methane photochemical catalytic oxidation is prepared Formaldehyde Test and is carried out in gas phase photochemical reaction instrument, with high voltage mercury lamp (500W) for light source (linear light sorurce), above-mentioned prepared photocatalyst is evenly placed in the middle part of gas-phase photocatalysis reaction instrument, at ambient pressure, pass into methane and air by a certain percentage, and be warming up to 100 DEG C, after reaching adsorption equilibrium, carry out irradiation reaction, after for some time, methane conversion can reach 92%.
Embodiment 2:
The zinc sulfate of 0.1g ~ 1g is dissolved in 1 ~ 20ml water, measure volume ratio be 2 ~ 10 ethylenediamine solution 5 ~ 20ml join in reactor, be then be that the ammonium molybdate solution of 0 ~ 1mol/L adds in reactor by 0 ~ 5ml concentration, then the molecular sieve of 0 ~ 10g joined in reactor, stir, sealing, 120 DEG C, reaction 10h, after question response completes, take out reactant, use water and absolute ethanol washing respectively for several times, then 450 DEG C of calcining 2h.
Methane photochemical catalytic oxidation is prepared Formaldehyde Test and is carried out in gas phase photochemical reaction instrument, with high voltage mercury lamp (500W) for light source (linear light sorurce), above-mentioned prepared photocatalyst is evenly placed in the middle part of gas-phase photocatalysis reaction instrument, at ambient pressure, pass into methane and air by a certain percentage, and be warming up to 100 DEG C, after reaching adsorption equilibrium, carry out irradiation reaction, after for some time, methane conversion can reach 91%.
Embodiment 3:
The zinc sulfate of 0.1g ~ 1g is dissolved in 1 ~ 20ml water, measure volume ratio be 2 ~ 10 aniline-water solution 5 ~ 20ml join in reactor, be then be that the ammonium molybdate solution of 0 ~ 1mol/L adds in reactor by 0 ~ 5ml concentration, then the molecular sieve of 0 ~ 10g joined in reactor, stir, sealing, 150 DEG C, reaction 10h, after question response completes, take out reactant, use water and absolute ethanol washing respectively for several times, then 550 DEG C of calcining 2h.
Methane photochemical catalytic oxidation is prepared Formaldehyde Test and is carried out in gas phase photochemical reaction instrument, with high voltage mercury lamp (500W) for light source (linear light sorurce), above-mentioned prepared photocatalyst is evenly placed in the middle part of gas-phase photocatalysis reaction instrument, at ambient pressure, pass into methane and air by a certain percentage, and be warming up to 80 DEG C, after reaching adsorption equilibrium, carry out irradiation reaction, after for some time, methane conversion can reach 95%.
Claims (5)
1. the method for formaldehyde is prepared in a methane photochemical catalytic oxidation, it is characterized in that carrying out in gas-phase photocatalysis reaction instrument, take high voltage mercury lamp as light source (linear light sorurce), above-mentioned prepared photocatalyst is evenly placed in the middle part of gas-phase photocatalysis reaction instrument, at ambient pressure, pass into methane and air by a certain percentage, and be warming up to design temperature, after reaching adsorption equilibrium, carry out irradiation reaction.Described catalyst preparation step is as follows:
(1) zinc sulfate weighing certain mass is dissolved in the water of certain volume, adds in reactor;
(2) aniline or the ethylenediamine solution that measure certain volume join in still, vigorous stirring;
(3) ammonium molybdate weighing certain mass is soluble in water, wiring solution-forming;
(4) ammonium molybdate solution measuring certain volume joins reaction attached middle school, stirs;
(5) molecular sieve of certain mass is added in reactor;
(6) seal, make reaction system become closed system;
(7) be warmed up to assigned temperature T, and the reaction times is at the reaction temperatures set;
(8) after reaction terminates, question response product is down to room temperature, takes out reactant;
(9) reaction product is washed several times, vacuum-drying;
(10) after product drying, calcining and activating.
2., according to claim 1, it is characterized in that high voltage mercury lamp is 500W, and be linear light sorurce.
3., according to claim 1, it is characterized in that used catalyst preparation method is hydrothermal method preparation.
4. according to claim 1, it is characterized in that each component ratio of reaction system is as follows: the volume ratio that zinc sulfate quality is 0.1 ~ 1g, the volume of water is 0 ~ 20ml, aniline or ethylenediamine solution is 0 ~ 10, the aniline of reactor or the volume of quadrol are 5 ~ 20ml, the concentration of ammonium molybdate is 0 ~ 1mol/L, add that the volume of the ammonium molybdate of reactor is 0 ~ 5ml, the quality of molecular sieve is 0 ~ 10g.
5. according to claim 1, it is characterized in that condition is as follows: catalyst preparing is in closed system, temperature generally at 100 ~ 180 DEG C, the reaction times be generally 1 ~ 24h, activation temperature generally between 300 ~ 700 DEG C, soak time generally carries out at ambient pressure in 1 ~ 5h, light-catalyzed reaction, light-catalyzed reaction temperature is 80 ~ 110 DEG C, light-catalyzed reaction methane and air ratio are 1:99, the light-catalyzed reaction time is 0 ~ 1000min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310682116.3A CN104710291A (en) | 2013-12-16 | 2013-12-16 | Method for preparing formaldehyde by methane photocatalytic oxidation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310682116.3A CN104710291A (en) | 2013-12-16 | 2013-12-16 | Method for preparing formaldehyde by methane photocatalytic oxidation |
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| CN104710291A true CN104710291A (en) | 2015-06-17 |
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| CN201310682116.3A Pending CN104710291A (en) | 2013-12-16 | 2013-12-16 | Method for preparing formaldehyde by methane photocatalytic oxidation |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199939A (en) * | 2007-12-21 | 2008-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst of methanol and formaldehyde from methane oxidation synthesis and preparation and application thereof |
| JP2008194683A (en) * | 2007-01-18 | 2008-08-28 | Shiga Univ Of Medical Science | Decomposition method of volatile compound |
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2013
- 2013-12-16 CN CN201310682116.3A patent/CN104710291A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008194683A (en) * | 2007-01-18 | 2008-08-28 | Shiga Univ Of Medical Science | Decomposition method of volatile compound |
| CN101199939A (en) * | 2007-12-21 | 2008-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst of methanol and formaldehyde from methane oxidation synthesis and preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| KENJI WADA ET.: "Selective Photooxidation of Light Alkanes to Oxygenates using Supported Molybdenum Oxide Catalysts", 《J. CHEM. SOC. FARADAY TRANS.》 * |
| KENJI WADA ET.: "The Selective Photooxidation of Methane and Ethane with Oxygen over Zinc Oxide and Molybdena-loaded Zinc Oxide Catalysts", 《J. CHEM. SOC., CHEM. COMMUN.》 * |
| 王奂玲等: "甲烷光催化氧化制甲醇研究进展", 《分子催化》 * |
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