CN102423707B - Preparation method and application method of iron-zirconium composite oxide catalyst - Google Patents
Preparation method and application method of iron-zirconium composite oxide catalyst Download PDFInfo
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- CN102423707B CN102423707B CN201110445345.4A CN201110445345A CN102423707B CN 102423707 B CN102423707 B CN 102423707B CN 201110445345 A CN201110445345 A CN 201110445345A CN 102423707 B CN102423707 B CN 102423707B
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Abstract
The invention belongs to the technical field of chemical industry, relates to a preparation method and application method of an iron-zirconium composite oxide catalyst, and is used for solving the problems that at present, the catalyst has low activity and is difficult for separation, recovery and reutilization in a catalytic process for direct synthesis of dimethyl carbonate from carbon dioxide and methanol. The catalyst provided by the invention is composed of iron and zirconium oxides, wherein the molar ratio of iron to zirconium is (10:1)-(0.5:1); the catalyst is prepared by adopting a sol-gel method, is used for reaction between CO2 and CH3OH for direct synthesis of dimethyl carbonate at the reaction temperature of 80-180 DEG C and CO2 pressure of 3-7MPa ( room temperature); and compared with the existing ZrO2 catalyst and H3PO4-treated ZrO2 catalyst, both the activity and selectivity of the catalyst are greatly improved.
Description
Technical field:
The invention belongs to chemical technology field, relate to a kind of preparation method of iron-zirconium composite oxide catalyst and this catalyst be applied to the application process in carbon dioxide and methyl alcohol Direct Synthesis of Dimethyl Carbonate reaction system, be specifically related to a kind of have can the difunctional ferrozirconium catalyst of modulation preparation and application.
Technical background:
Dimethyl carbonate (dimethyl carbonate, DMC) be a kind of important " green " organic chemical industry intermediate, in its molecular structure, contain carbonyl, methyl, methoxyl group and carbonyl methoxyl group, thus can be widely used in carbonylation, methylate, the organic synthesis such as methoxylation and carbonyl methylate.The phosgene of alternative severe toxicity, methylchloroformate, dimethyl suflfate etc. use as methylating reagent or carbonylation agent, improve the security of production operation, reduce environmental pollution.As highly dissoluble solvent, the alternative fluorine of DMC Lyons equal solvent.As gasoline additive, DMC can improve octane number and oxygen content, improves its anti-knock properties, prepares unleaded gas.In addition, DMC also can make the additive of cleaning agent, surfactant and softening agent.Because purposes is very extensive, DMC is described as " the new foundation stone " of current organic synthesis.The synthetic route of carbon dioxide and methyl alcohol Direct Synthesis of Dimethyl Carbonate, owing to can utilizing discarded greenhouse gases carbon dioxide, can utilize Coal Chemical Industry and gas chemical industry's downstream product methyl alcohol simultaneously, and therefore this route has vast potential for future development.
The reacting of carbon dioxide and methyl alcohol Direct Synthesis of Dimethyl Carbonate on thermodynamics, analyze be difficult to carry out (Δ rG within the scope of 0～800 ℃, be on the occasion of, when temperature is 353K, pressure>=2.41 × 10
4when Mpa, Δ rG < 0.)。The key of this process is activation carbon dioxide and methyl alcohol.Carbon dioxide has chemical inertness, the key of activation carbon dioxide is to insert electronics at the π of carbon dioxide * antibonding orbital to make its activation, need the L alkali of corresponding supplied for electronic, and activation methyl alcohol need produce methoxyl group and methyl, this just needs catalyst that L alkali and L acid are provided, and therefore ortho position soda acid is the key of this reaction.In document, Study of Catalyst mostly is alkoxide compound, alkali compounds, Cu-Ni metal and metal oxide.In alkoxide compound use procedure, be easy to the water decomposition inactivation being produced, and the highest active tin has the characteristic of environmental pollution.Alkali compounds must have adding of alkylating reagent iodomethane, and iodomethane cost is higher, have corrosivity and have consumption.Cu-Ni metal active is lower, ZrO in metal oxide
2activity is the highest, especially the ZrO of phosphate impregnation processing
2activity is the highest, but the ZrO of phosphate impregnation processing
2catalyst in use phosphoric acid is easy to run off, thereby causes catalyst activity to reduce, and is difficult to recycle.
Summary of the invention:
The object of the invention is to overcome above-mentioned deficiency of the prior art, a kind of preparation method and application's method of iron-zirconium composite oxide catalyst is provided.It is characterized in that catalyst surface acid strength and acid activity point quantity are adjustable, for CO
2in methyl alcohol Direct Synthesis of Dimethyl Carbonate synthetic, catalytic activity is high, selectively high, in use procedure, does not run off, and easily and product separation, easily regeneration is reused, non-environmental-pollution.
Preparation and the application of iron-zirconium composite oxide catalyst of the present invention comprise the following steps: adopt sol-gal process to make the compound organogel of ferrozirconium; The compound organogel of ferrozirconium obtains catalyst precursor by ageing and vacuum drying, and catalyst precursor roasting in air obtains iron-zirconium composite oxide catalyst of the present invention.This catalyst is placed in to autoclave, adds methyl alcohol and dehydrating agent, be filled with carbon dioxide.Controlling reaction temperature is 80 ℃～180 ℃, and reaction pressure is 12.0～30.0MPa, and the reaction time is 5～30 hours.
The preparation method of the compound organogel of ferrozirconium: with Fe (NO
3)
39H
2o (or FeCl
3, or ferric acetate) and Zr (NO
3)
45H
2o (or ZrOCl
28H
2o) be raw material, be mixed with the aqueous solution by deionized water, by being dissolved in deionized water with the citric acid of 1.2～2.0 times of ferrozirconium molal quantity total amount, add 7～20ml without water glycol, the mixed aqueous solution of water-soluble ferrozirconium salt is poured in aqueous citric acid solution, be heated to 60～80 ℃, reflux, constant temperature stirs 2 hours, dripping ammoniacal liquor regulates pH of mixed value to reach 7～8, remove reflux, transpiring moisture, makes the compound organogel of ferrozirconium.
The ageing of the compound organogel of ferrozirconium and vacuum drying: compound ferrozirconium organogel is at room temperature displayed to 8～12h, then put into vacuum drying chamber, in 80～130 ℃ of freeze-day with constant temperature 4～12h, make catalyst precursor.
The method of roasting of catalyst precursor: catalyst precursor is put into Muffle furnace roasting, at 400～1000 ℃ of constant temperature calcining 4～8h, make iron-zirconium composite oxide catalyst of the present invention.
The application process of catalyst is as follows:
0.5～3g catalyst, 1～5g dehydrating agent and 20～40ml methyl alcohol are joined in high-pressure mini stainless steel cauldron, seal complete, with carbon dioxide replacement more than 3 times, then by CO
2pressure is adjusted to 3～7MPa (room temperature), starts agitating device, rotating speed 300r/min, thermocouple process temperature controller control for temperature in reactor.In the time that temperature rises to 100～180 ℃, start timing, reaction stops heating after reaching the stipulated time, is naturally down to room temperature.By reaction liquid product by gas chromatographic analysis.Operation condition of chromatogram is: Φ 30 × 0.53mm × 0.25 μ m quartz capillary column, fixer is OV-101, detects with fid detector.Adopt internal standard method to carry out quantitatively, internal standard compound is n-butanol.Selective according to chromatography result calculating catalyst methanol conversion and dimethyl carbonate.Reactant liquor component is carried out to qualitative analysis with gas chromatograph-mass spectrometer (GC-MS).
The regeneration condition of iron-zirconium composite oxide catalyst of the present invention: by post catalyst reaction in vacuum drying chamber in 80～130 ℃ of freeze-day with constant temperature 4～12h, then take out and put into Muffle furnace roasting, sintering temperature is 400-1000 ℃, roasting time 4-8h, obtain regenerated catalyst, this regenerated catalyst reusable edible.
Accompanying drawing explanation:
The different ferrozirconium comparison catalytic activitys of Fig. 1 catalyst of the present invention and impact optionally.
The specific embodiment
Further describe below by examples of implementation the catalyst method of preparation and use that the present invention proposes, provide ZrO simultaneously
2the acid-treated ZrO of catalyst and phosphorus
2the enforcement of catalyst as a comparison.
Embodiment 1
Accurately take Fe (NO
3)
3.9H
2o, 60.66g (0.15mol), Zr (NO
3)
2.5H
2o, 12.88g (0.03mol) is dissolved in deionized water, then weighs citric acid 45.39g, is dissolved in deionized water.The aqueous solution of ferrozirconium is poured in lemon aqueous acid, stirred, add 12ml ethylene glycol, in 60 ℃ of water-baths, constant temperature stirs 2h, drips ammoniacal liquor and regulates pH value to 7, at 80 ℃ of constant temperature return stirring 2h, to producing colloidal sol.Colloidal sol is taken out, at room temperature display 12h, then put into vacuum drying chamber, at 80 ℃ of freeze-day with constant temperature 12h, obtain catalyst precursor.Catalyst precursor is put into Muffle furnace roasting, at 500 ℃ of constant temperature calcining 5h, make required iron-zirconium composite oxide catalyst.
By iron-zirconium composite oxide catalyst 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into autoclave.Use CO
2gas displacement more than 3 times, is then filled with CO with gas boosting pump
2to 5MPa (normal temperature), start magnetic stirring apparatus, be warming up to 150 ℃, isothermal reaction 24h, stops reaction, and reactor is down to room temperature naturally.Reactant liquor is taken out and filtered.Reactant liquor carries out quantitative analysis by above-mentioned GC conditions, carries out qualitative analysis with gas chromatograph-mass spectrometer (GC-MS).Methanol conversion is 1.2176%, and accessory substance is dimethyl ether, and DMC is selectively 91.53%
Comparison example 1:
Market sold goods ZrO
2, roasting 4hr in 400 ℃ of Muffle furnaces, makes ZrO
2catalyst.
By ZrO
2catalyst 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into high-pressure parallel reactor, reacts by example 1 reaction condition, and methanol conversion is 0.3763%, and accessory substance is dimethyl ether, and DMC is selectively 89.12%
Comparison example 2:
Take commercial goods ZrO
212.32g (0.1mol) and 0.49g (0.005mol) phosphoric acid, be dissolved in phosphoric acid in 2.5ml deionized water, adopts equi-volume impregnating that phosphoric acid is loaded on to ZrO
2surface, more than 4h is placed in ageing under room temperature, then puts it into roasting in Muffle furnace, at 400 ℃ of constant temperature calcining 4h, makes phosphoric acid and processes ZrO
2catalyst.
Phosphoric acid is processed to ZrO
2catalyst 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into autoclave, reacts by example 1 reaction condition, and methanol conversion is 0.8509%, and accessory substance is dimethyl ether, and DMC is selectively 87.12%
Preparation method according to embodiment 1 ferrozirconium composite oxides prepares respectively Fe: Zr mol ratio is respectively 10: 1, and 5: 1, the catalyst of 2: 1 and 1: 1, adopted autoclave, according to the activity rating method of catalyst, at CO
2pressure is 5MPa (normal temperature), and 150 ℃ of reaction temperatures, react under the condition of reaction time 24h.Respectively gained reactant liquor is carried out to quantitative analysis by above-mentioned GC conditions.As shown in Figure 1, the catalytic activity of iron-zirconium composite oxide catalyst has the trend that first raises and reduce afterwards to experimental result with the addition of iron, Fe: Zr mol ratio is 5: 1 o'clock, and methanol conversion has reached peak.
Claims (2)
1. an iron-zirconium composite oxide catalyst is for the application process of carbon dioxide and methyl alcohol Direct Synthesis of Dimethyl Carbonate, concrete application process is: by 0.5～3g iron-zirconium composite oxide catalyst, 1～5g dehydrating agent and 20～40mL methyl alcohol are placed in the miniature stainless steel cauldron of high pressure, under room temperature, be filled with pressure carbon dioxide to 3～7MPa, heat up, controlling reaction temperature is 100 ℃～180 ℃, reaction pressure is 12.0～30.0MPa, reaction time is 10～30 hours, it is characterized in that: adopt sol-gal process to prepare iron-zirconium composite oxide catalyst, iron, zirconium atom mol ratio is 10: 1～0.5: 1, concrete preparation process is as follows: adopt Fe (NO
3)
39H
2o and Zr (NO
3)
45H
2o is raw material, be configured to the aqueous solution by deionized water, the citric acid of 1.2～2.0 times of ferrozirconium molal quantity total amount is dissolved in deionized water, add 7mL～20mL without water glycol, the mixed aqueous solution of water-soluble ferrozirconium salt is poured in aqueous citric acid solution, be heated to 60～80 ℃, reflux, constant temperature stirs 2h, dripping ammoniacal liquor regulates pH of mixed value to reach 7～8, remove reflux, transpiring moisture, makes the compound organogel of ferrozirconium, the compound organogel of ferrozirconium, through room temperature ageing 8～12 hours, is then put into vacuum drying chamber, in 80～130 ℃ dry 4～12 hours, make catalyst precursor, catalyst precursor is put into Muffle furnace roasting, 400～1000 ℃ of sintering temperatures, constant temperature 4～8 hours, makes iron-zirconium composite oxide catalyst.
2. iron-zirconium composite oxide catalyst as claimed in claim 1, for the application process of carbon dioxide and methyl alcohol Direct Synthesis of Dimethyl Carbonate, is characterized in that dehydrating agent is 4A molecular sieve.
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| CN108126704B (en) * | 2017-12-20 | 2021-04-02 | 中国科学院山西煤炭化学研究所 | Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof |
| TWI654178B (en) * | 2017-12-28 | 2019-03-21 | 財團法人工業技術研究院 | Method for preparing dialkyl carbonate |
| TWI722719B (en) | 2019-12-16 | 2021-03-21 | 財團法人工業技術研究院 | Catalyst and precursor thereof and method of forming dialkyl carbonate |
| CN112973778B (en) * | 2021-02-05 | 2022-03-22 | 浙江大学 | Iron-zirconium bimetal supported catalyst and preparation method and application thereof |
| CN113457723B (en) * | 2021-05-27 | 2023-12-08 | 浙江大学衢州研究院 | Ruthenium-zirconium composite alkylation catalyst and preparation method thereof |
| CN113426474B (en) * | 2021-05-27 | 2022-05-03 | 浙江大学衢州研究院 | Boric acid modified iron-zirconium shape-selective catalyst and preparation method and application thereof |
| CN113735176B (en) * | 2021-08-25 | 2023-04-21 | 北京化工大学 | Preparation method of chemical warfare agent digestion material and modified fiber material thereof |
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| CN101966460A (en) * | 2010-09-21 | 2011-02-09 | 中山大学 | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof |
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| JPH0975714A (en) * | 1995-09-07 | 1997-03-25 | Matsushita Electric Ind Co Ltd | Gaseous carbon dioxide adsorbent and gaseous carbon dioxide exchanger |
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| CN101966460A (en) * | 2010-09-21 | 2011-02-09 | 中山大学 | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof |
Non-Patent Citations (7)
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| DMC formation over Ce0.5Zr0.5O2 prepared by complex-decomposition method;Zhi-Fang Zhang et al.;《Catalysis Letters》;20081223;第129卷;第429-430页，2 Experimental * |
| Hyperfine study on sol-gel derived-hematite doped zirconia;Santiago Figueroa et al.;《Chem. Mater.》;20050524;第17卷(第13期);第3488页Experimental Procedures * |
| JP特开平9-75714A 1997.03.25 |
| Santiago Figueroa et al..Hyperfine study on sol-gel derived-hematite doped zirconia.《Chem. Mater.》.2005,第17卷(第13期),第3486-3491页. |
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