CN102423707A - 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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- CN102423707A CN102423707A CN2011104453454A CN201110445345A CN102423707A CN 102423707 A CN102423707 A CN 102423707A CN 2011104453454 A CN2011104453454 A CN 2011104453454A CN 201110445345 A CN201110445345 A CN 201110445345A CN 102423707 A CN102423707 A CN 102423707A
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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 ferrozirconium composite oxide catalysts and with the application process of this catalyst applications in carbon dioxide and the direct Synthesis of dimethyl carbonate reaction system of methyl alcohol, but be specifically related to a kind of have difunctional ferrozirconium Preparation of catalysts of modulation and method for using.
Technical background:
Dimethyl carbonate (dimethyl carbonate; DMC) be a kind of important " green " organic chemical industry intermediate; Contain carbonyl, methyl, methoxyl group and carbonyl methoxyl group in its molecular structure, thus can be widely used in carbonylation, methylate, 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 the 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, the preparation 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 the direct Synthesis of dimethyl carbonate of methyl alcohol, since discarded greenhouse gases carbon dioxide capable of using, while Coal Chemical Industry capable of using and gas chemical industry's downstream product methyl alcohol, so this route has vast potential for future development.
Being reflected on the thermodynamics of carbon dioxide and the direct Synthesis of dimethyl carbonate of methyl alcohol analyze be difficult to carry out (Δ rG in 0～800 ℃ of scope, be on the occasion of, when temperature is 353K, pressure>=2.41 * 10
4During 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; The L alkali that promptly needs corresponding power supply; And activation methyl alcohol need produce methoxyl group and methyl, and this just needs catalyst that L alkali and L acid are provided, so the ortho position soda acid is the key of this reaction.Mostly the research catalyst is alkoxide compound, alkali compounds, Cu-Ni metal and metal oxide in the document.Be easy to the water decomposition inactivation that produced in the alkoxide compound use, and the highest active tin has the characteristic of environmental pollution.Alkali compounds must have the adding of alkylating reagent iodomethane, and the iodomethane cost is higher, have corrosivity and consumption is arranged.The Cu-Ni metal active is lower, ZrO in the metal oxide
2Activity is the highest, especially the ZrO of phosphate impregnation processing
2Activity is the highest, but the ZrO that phosphate impregnation is handled
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 objective of the invention is to overcome above-mentioned deficiency of the prior art, a kind of preparation method's and methods for using them of ferrozirconium composite oxide catalysts is provided.It is characterized in that catalyst surface acid strength and acid activity number of spots are adjustable, be used for CO
2In the direct Synthesis of dimethyl carbonate of methyl alcohol synthetic, catalytic activity is high, and selectivity is high, does not run off in the use, is prone to separate with product, is prone to regeneration and reuses non-environmental-pollution.
The preparation and the application of ferrozirconium composite oxide catalysts of the present invention may further comprise the steps: adopt sol-gal process to process the compound organogel of ferrozirconium; The compound organogel of ferrozirconium obtains catalyst precursor through ageing and vacuum drying, and catalyst precursor roasting in air obtains ferrozirconium composite oxide catalysts of the present invention.This catalyst is placed autoclave, add methyl alcohol and dehydrating agent, charge into carbon dioxide.The control 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, will be dissolved in the deionized water with 1.2～2.0 times citric acid of ferrozirconium molal quantity total amount with deionized water; Adding 7～20ml does not have water glycol, and the mixed aqueous solution of water-soluble ferrozirconium salt is poured in the aqueous citric acid solution, is heated to 60～80 ℃; Reflux, constant temperature stirred 2 hours, and dropping ammonia is regulated the pH of mixed value and reached 7～8; Remove reflux, transpiring moisture is processed the compound organogel of ferrozirconium.
The ageing of the compound organogel of ferrozirconium and vacuum drying: the compound organogel of ferrozirconium is at room temperature displayed 8～12h, put into vacuum drying chamber then,, make catalyst precursor in 80～130 ℃ of freeze-day with constant temperature 4～12h.
The method of roasting of catalyst precursor: catalyst precursor is put into the Muffle furnace roasting,, make ferrozirconium composite oxide catalysts of the present invention at 400～1000 ℃ of constant temperature calcining 4～8h.
The Application of Catalyst method is following:
0.5～3g catalyst, 1～5g dehydrating agent and 20～40ml methyl alcohol are joined in the high-pressure mini stainless steel cauldron, seal and finish, with carbon dioxide replacement more than 3 times, again with CO
2Pressure transfers to 3～7MPa (room temperature), starts agitating device, rotating speed 300r/min, and temperature is controlled through temperature controller with thermocouple in the reactor.When temperature rises to 100～180 ℃, pick up counting, reaction stops heating after reaching the stipulated time, reduces to room temperature naturally.With the reaction liquid product through gas chromatographic analysis.The chromatographic run condition 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 a n-butanol.Calculate catalyst methanol conversion and dimethyl carbonate selectivity based on the chromatography result.With gas chromatograph-mass spectrometer (GC-MS) the reactant liquor component is carried out qualitative analysis.
The regeneration condition of ferrozirconium composite oxide catalysts of the present invention: with post catalyst reaction in vacuum drying chamber in 80～130 ℃ of freeze-day with constant temperature 4～12h; Take out then and put into the Muffle furnace roasting; Sintering temperature is 400-1000 ℃; Roasting time 4-8h obtains regenerated catalyst, this regenerated catalyst reusable edible.
Description of drawings:
Different ferrozirconium comparison catalytic activitys of Fig. 1 catalyst of the present invention and influence optionally.
The specific embodiment
Further describe Preparation of Catalyst and the method for using that the present invention proposes through examples of implementation below, provide ZrO simultaneously
2The ZrO that catalyst and phosphoric acid are handled
2The enforcement of catalyst is as comparing.
Embodiment 1
Accurately take by weighing Fe (NO
3)
3.9H
2O, 60.66g (0.15mol), Zr (NO
3)
2.5H
2O, 12.88g (0.03mol) is dissolved in the deionized water, and weighing citric acid 45.39g is dissolved in the deionized water then.The aqueous solution of ferrozirconium is poured in the lemon aqueous acid, stirred, add 12ml ethylene glycol, constant temperature stirs 2h in 60 ℃ of water-baths, and dropping ammonia is regulated pH value to 7, at 80 ℃ of constant temperature refluxing and stirring 2h, to producing colloidal sol.Colloidal sol is taken out, at room temperature display 12h, put into vacuum drying chamber then,, obtain catalyst precursor at 80 ℃ of freeze-day with constant temperature 12h.Catalyst precursor is put into the Muffle furnace roasting,, make required ferrozirconium composite oxide catalysts at 500 ℃ of constant temperature calcining 5h.
With ferrozirconium composite oxide catalysts 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into autoclave.Use CO
2Gas displacement charges into CO with the gas boosting pump more than 3 times then
2To 5MPa (normal temperature), start magnetic stirring apparatus, be warming up to 150 ℃, isothermal reaction 24h stops reaction, and agitated reactor is reduced to room temperature naturally.Reactant liquor is taken out filtration.Reactant liquor carries out quantitative analysis with above-mentioned GC conditions, carries out qualitative analysis with gas chromatograph-mass spectrometer (GC-MS).Methanol conversion is 1.2176%, and accessory substance is a dimethyl ether, and the DMC selectivity is 91.53%
Comparison example 1:
Commodity ZrO is sold in market
2, roasting 4hr in 400 ℃ of Muffle furnaces makes ZrO
2Catalyst.
With ZrO
2Catalyst 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into high-voltage flat row agitated reactor, reacts by instance 1 reaction condition, and methanol conversion is 0.3763%, and accessory substance is a dimethyl ether, and the DMC selectivity is 89.12%
Comparison example 2:
Take by weighing commercial goods ZrO
212.32g (0.1mol) and 0.49g (0.005mol) phosphoric acid, phosphoric acid is dissolved in the 2.5ml deionized water, adopts equi-volume impregnating that phosphoric acid is loaded on ZrO
2Place more than the 4h in ageing under the room temperature on the surface, puts it into roasting in the Muffle furnace then, at 400 ℃ of constant temperature calcining 4h, makes phosphoric acid and handle ZrO
2Catalyst.
Phosphoric acid is handled ZrO
2Catalyst 1g, 4A molecular sieve 3g, methyl alcohol 20ml once puts into autoclave, reacts by instance 1 reaction condition, and methanol conversion is 0.8509%, and accessory substance is a dimethyl ether, and the DMC selectivity is 87.12%
Preparation method according to embodiment 1 ferrozirconium composite oxides prepares Fe respectively: the Zr mol ratio was respectively 10: 1, and 5: 1, the catalyst of 2: 1 and 1: 1 adopted autoclave, according to the activity of such catalysts evaluation method, at CO
2Pressure is 5MPa (normal temperature), and 150 ℃ of reaction temperatures are reacted under the condition of reaction time 24h.Respectively the gained reactant liquor is carried out quantitative analysis with above-mentioned GC conditions.Experimental result is as shown in Figure 1, and the catalytic activity of ferrozirconium composite oxide catalysts has the trend that raises and afterwards reduce earlier with the addition of iron, and Fe: the Zr mol ratio is 5: 1 o'clock, and methanol conversion has reached peak.
Claims (3)
1. preparation method's and methods for using them of a ferrozirconium composite oxide catalysts; The composition and the proportioning thereof of ferrozirconium composite oxide catalysts are following: the ferrozirconium composite oxide catalysts is made up of the oxide of iron and zirconium; Iron, zirconium atom mol ratio are 10: 1～0.5: 1; This Preparation of catalysts may further comprise the steps, and adopts sol-gal process to process the compound organogel of ferrozirconium; Compound organogel ageing of ferrozirconium and vacuum drying obtain catalyst precursor; Catalyst precursor roasting in air obtains ferrozirconium composite oxide catalysts of the present invention; The catalyst applications method is: this catalyst is placed autoclave, add methyl alcohol and dehydrating agent, charge into carbon dioxide; The control reaction temperature is 80 ℃～180 ℃, and reaction pressure is 12.0～30.0MPa.
2. the preparation method of the compound organogel of said ferrozirconium is meant the (NO with Fe in requiring like right 1
3)
39H
2O and Zr (NO
3)
45H
2O is a raw material, is mixed with the aqueous solution with deionized water, will be dissolved in deionized water with 1.2～2 times citric acid of ferrozirconium molal quantity total amount, and adding 7～20ml does not have water glycol; Pour the water-soluble ferrozirconium aqueous solution into stirring, be heated to 60～80 ℃, reflux; Constant temperature stirred 2 hours, regulated the pH value with ammoniacal liquor and reached 7～8, removed reflux; Transpiring moisture is processed the compound organogel of ferrozirconium, the Fe (NO here
3)
39H
2O also can be FeCl
3Or ferric acetate, the Zr (NO here
3)
45H
2O also can be ZrOCl
28H
2O, the citric acid here also can be EDTA.
3. said catalyst applications method is in requiring like right 1: 0.5～3g catalyst, 1～5g dehydrating agent and 20～40ml methyl alcohol are joined in the miniature stainless steel cauldron of high pressure, charge into CO
2Pressure to 3～7MPa (room temperature) is warming up to 100～180 ℃, and reaction pressure is 12.0～30.0MPa, and the reaction time is 10～30 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126704A (en) * | 2017-12-20 | 2018-06-08 | 中国科学院山西煤炭化学研究所 | A kind of cerium iron-zirconium composite oxide catalyst and preparation method and application |
| CN109970561A (en) * | 2017-12-28 | 2019-07-05 | 财团法人工业技术研究院 | The preparation method of dialkyl carbonate |
| CN112973778A (en) * | 2021-02-05 | 2021-06-18 | 浙江大学 | Iron-zirconium bimetal supported catalyst and preparation method and application thereof |
| CN113426474A (en) * | 2021-05-27 | 2021-09-24 | 浙江大学衢州研究院 | Boric acid modified iron-zirconium shape-selective catalyst and preparation method and application thereof |
| CN113457723A (en) * | 2021-05-27 | 2021-10-01 | 浙江大学衢州研究院 | Ruthenium-zirconium composite alkylation catalyst and preparation method thereof |
| CN113735176A (en) * | 2021-08-25 | 2021-12-03 | 北京化工大学 | Chemical warfare agent digestion material and preparation method of fiber material modified by chemical warfare agent digestion material |
| US11400440B2 (en) | 2019-12-16 | 2022-08-02 | Industrial Technology Research Institute | Catalyst and precursor thereof and method of forming dialkyl carbonate |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108126704A (en) * | 2017-12-20 | 2018-06-08 | 中国科学院山西煤炭化学研究所 | A kind of cerium iron-zirconium composite oxide catalyst and preparation method and application |
| CN109970561B (en) * | 2017-12-28 | 2022-02-22 | 财团法人工业技术研究院 | Process for the preparation of dialkyl carbonates |
| CN109970561A (en) * | 2017-12-28 | 2019-07-05 | 财团法人工业技术研究院 | The preparation method of dialkyl carbonate |
| US10696619B2 (en) | 2017-12-28 | 2020-06-30 | Industrial Technology Research Institute | Method for preparing dialkyl carbonate |
| US11565244B2 (en) | 2019-12-16 | 2023-01-31 | Industrial Technology Research Institute | Catalyst precursor |
| US11400440B2 (en) | 2019-12-16 | 2022-08-02 | Industrial Technology Research Institute | 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 |
| CN112973778A (en) * | 2021-02-05 | 2021-06-18 | 浙江大学 | Iron-zirconium bimetal supported catalyst and preparation method and application thereof |
| CN113457723A (en) * | 2021-05-27 | 2021-10-01 | 浙江大学衢州研究院 | Ruthenium-zirconium composite alkylation catalyst and preparation method thereof |
| CN113426474A (en) * | 2021-05-27 | 2021-09-24 | 浙江大学衢州研究院 | Boric acid modified iron-zirconium shape-selective 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 |
| CN113735176A (en) * | 2021-08-25 | 2021-12-03 | 北京化工大学 | Chemical warfare agent digestion material and preparation method of fiber material modified by chemical warfare agent digestion material |
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