CN101428211A - Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof - Google Patents
Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof Download PDFInfo
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- CN101428211A CN101428211A CNA2008100801199A CN200810080119A CN101428211A CN 101428211 A CN101428211 A CN 101428211A CN A2008100801199 A CNA2008100801199 A CN A2008100801199A CN 200810080119 A CN200810080119 A CN 200810080119A CN 101428211 A CN101428211 A CN 101428211A
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Abstract
A dimethoxy methane catalyst prepared through selective oxidation of methanol is a V2O5/TiO2 catalyst modified by an acidic compound containing chlorine, nitrogen or phosphorus, and is characterized in that components of the catalyst mainly include V and Ti, and modification components contain elements including chlorine, nitrogen or phosphorus. The method for preparing catalyst has the advantages of simple operation, good stability, and low and saved cost. When the method is applied to the preparation of dimethoxy methane by methanol one-step oxidation, the reaction temperature is greatly reduced, the conversion rate of methanol is 31.05%-60%, and the selectivity of dimethoxy methane is 86.04%-99%.
Description
Affiliated field
The invention belongs to a kind of Catalysts and its preparation method, relate in particular to a kind of Catalysts and its preparation method of methanol oxidation system dimethoxymethane.
Background technology
Along with the raising and the potential threat of oil crisis of people's quality of life, environmental protection and the energy-conservation object that becomes people's concern.Fuel oil is concerning the lifeblood of country all the time, in national product, play a part very important, but no matter be gasoline or diesel oil owing to there is the inadequate phenomenon of burning, thereby exist serious pollution.Especially the diesel oil that China produced because olefin(e) centent is low, easily deposits, and makes oil inflame insufficient, produces a large amount of soots, so improve the combustibility of fuel oil, the pollution that reduces air is the target of researcher all the time always.Recent studies show that adds additive in fuel oil, can improve fuel oil performance significantly, and with regard to additive, studying maximum at present is dimethyl ether, dimethoxymethane.Because dimethyl ether has higher vapour pressure, thereby limited it and used, and dimethoxymethane advantage in some aspects is deeply also obvious day by day along with what study.The dimethoxymethane that adds 5%-10% in diesel oil can improve the performance of diesel oil, significantly reduce the discharging of NOx, and the thermal efficiency is greatly improved also.Thereby in a single day dimethoxymethane is promoted as oil dope, extraordinary application prospect will be arranged.
Dimethoxymethane is dimethoxym ethane again, and English name dimethoxymethane (DMM) is a kind of important chemical material.Remove and can be used as oil dope, it still is a good organic solvent in the products such as cosmetics, pharmacy, paint and rubber industry; As cleaning agent, dimethoxymethane can substitute chlorinated solvents, reduces the discharging of volatile organic matter; In addition, dimethoxymethane can also be used to synthetic high-purity formaldehyde.
The industrial production of dimethoxymethane realizes by two-step method at present: methanol oxidation is a formaldehyde, and formaldehyde and methyl alcohol condensation generate dimethoxymethane.This process first step reaction is a catalyst with silver (873k-923K) or iron molybdenum (573-703K), reaction temperature is higher, the second step reaction is with inorganic acid, and Lewis acid or acid cation exchange resin are catalyst, and the condensation by methyl alcohol and formaldehyde generates dimethoxymethane.Shujuan WANGs etc. once carried out screening to the technology and the catalyst of the second step reaction, think that H-ZSM-5 also can catalysis second step reaction (referring to: Liaoning University's journal (natural science edition), volume was the 157th page in 2003 the 30th).Because first step reaction temperature is too high, and the reaction of second step used inorganic acid as catalyst, thereby exists etching apparatus, and two-step process is longer, is difficult to realize continuous production on technology.And the synthetic dimethoxymethane of one-step method can be avoided the problems referred to above.
The synthetic dimethoxymethane of one-step method mainly concentrates on dimethyl ether oxidizing process and the methanol oxidation method at present.Especially with the research of methanol oxidation method at most, mainly concentrate on the heteropolyacid catalyst at present for dimethyl ether oxidation system dimethoxymethane, but the selectivity of dimethyl ether conversion rate and dimethoxymethane is all generally on the low side.And domestic in China, be that the synthetic dimethoxymethane of methyl alcohol or single step dimethyl ether process all still is in the starting stage.For methanol by one-step method oxidation system dimethoxymethane, researcher is at SbRe
2O
6, Re/ γ-Fe
2O
3, heteropoly acid, RuO
x/ SiO
2And attempt on the Cu-ZSM-5 catalyst, find Re/ γ-Fe
2O
3Catalyst has preferably active, and methanol conversion has reached 48.4%, selectivity reach 90% (referring to: the 1421st page of Chem Commun2000).But Re costs an arm and a leg, and at high temperature volatile, limited its application, and other catalyst reaction activity is on the low side, also is unfavorable for industrialized production.
Summary of the invention
It is low to the purpose of this invention is to provide a kind of price, the Catalysts and its preparation method of the producing dimethoxymethane with methanol selective oxidation that reactivity is high
Catalyst of the present invention is by V
2O
5, TiO
2Form with modifying element,
Modifying element is chlorine element, nitrogen element or P elements, and wherein the load capacity of vanadium is with V
2O
5Meter, V
2O
5: V
2O
5And TiO
2The quality sum be 5-25:100, the chlorine element is with Cl
-1Meter, the nitrogen element is with NO
3 -1Meter, P elements is with PO
4 3-Meter, modifying element and TiO
2Mass ratio be 1-15:100.
Preparation method of the present invention is divided into two kinds:
First kind of preparation method:
Ammonium metavanadate is added solvent to be dissolved, the mass ratio of ammonium metavanadate and solvent is 1:4-15, after treating that the vanadium source is all dissolved, under ultrasonic situation, be impregnated into then on the 20-40 purpose titania support, dip time is 2-7 hour, 100-150 ℃ dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V that content of vanadium is 5-25wt%
2O
5/ TiO
2System is then with the nitrogen-containing compound of acid chlorine-containing compound, acidity or the phosphorus-containing compound immersion-V of acidity
2O
5/ TiO
2System 2-7 hour, 100-150 ℃ dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V of modification
2O
5/ TiO
2Catalyst.
Second kind of preparation method:
With the titania support compression molding is the 20-40 order, uses the chloride of acidity then, and nitrogenous or phosphorous compound soaked 2-7 hour, wherein modifying element and TiO
2Mass ratio be 1-15:100, at 100-150 ℃ of dry 5-10 hour, ammonium metavanadate is added solvent to be dissolved, the mass ratio of ammonium metavanadate and solvent is 1:4-15, be impregnated into then on the titania support of above-mentioned modification, flooded 2-7 hour, at 100-150 ℃ of dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V of modification
2O
5/ TiO
2Catalyst.
Described solvent is oxalic acid solution or water.
Advantage of the present invention is as follows:
The present invention is by utilizing the chloride of acidity, and nitrogenous or phosphorous acid or compound are to V
2O
5/ TiO
2Catalyst is regulated and control modification, or to TiO
2Carrier carries out modification, made the bifunctional catalyst that has acid catalysis center and oxidation catalysis center concurrently, this catalyst can be controlled the direction of reaction, make methanol oxidation carry out to the direction that generates dimethoxymethane, wherein conversion of methanol is 31.05%-60%, and the selectivity of dimethoxymethane is 86.04%-99%.Suppressed the generation of other accessory substance greatly.
Specific embodiments
Embodiment 1
Take by weighing the 20.3g ammonium metavanadate, then it is dissolved in the 81.2g oxalic acid solution, stir, treat that dissolving fully, under ultrasonic situation, vanadium liquid is impregnated on the 20-40 purpose 300g titania support, dip time is 2h, 100 ℃ of dry 10h, 400 ℃ of roasting 8h obtain content of vanadium and are 5% V
2O
5/ TiO
2System is designated as 1#.Get the 1# system, it is immersed in the hydrochloric acid that 410ml concentration is 1mol/L, soak time is 7h, 150 ℃ of dry 5h, and 450 ℃ of roasting 3h make the V of hydrochloric acid modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 5%, Cl
-1With TiO
2Mass ratio be 4.8%, be designated as 2#.
Embodiment 2
Take by weighing the 42.87g ammonium metavanadate, then it is dissolved in the 342.96g water, stir, treat that dissolving fully, under ultrasonic situation, vanadium liquid is impregnated on the 20-40 purpose 300g titania support, dip time is 4h, 110 ℃ of dry 8h, 410 ℃ of roasting 5h obtain content of vanadium and are 10% V
2O
5/ TiO
2System is designated as 3#.Get the 3# system, it is immersed in 310ml concentration is in the 1mol/L hydrochloric acid, and soak time is 4h, 150 ℃ of dry 5h, and 430 ℃ of roasting 4h make the V of hydrochloric acid modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 10%, Cl
-1With TiO
2Mass ratio be 3.7%, be designated as 4#.
Embodiment 3
Take by weighing the 68.1g ammonium metavanadate, then it is dissolved in the 681g oxalic acid solution, stir, treat that dissolving fully, under ultrasonic situation, vanadium liquid is impregnated on the 20-40 purpose 300g titania support, dip time is 5h, 120 ℃ of dry 8h, 430 ℃ of roasting 3h obtain content of vanadium and are 15% V
2O
5/ TiO
2System is designated as 5#.Get the 5# catalyst, it is immersed in 510ml concentration is in the 1mol/L hydrochloric acid, and soak time is 2h, 140 ℃ of dry 6h, and 400 ℃ of roasting 8h make the V of hydrochloric acid modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 15%, Cl
-1With TiO
2Mass ratio be 6.0%, be designated as 6#.
Embodiment 4
Take by weighing the 96.47g ammonium metavanadate, then it is dissolved in the 1157g water, stir, treat that dissolving fully, under ultrasonic situation, vanadium liquid is impregnated on the 20-40 purpose 300g titania support, dip time is 6h, 150 ℃ of dry 5h, 450 ℃ of roasting 3h obtain content of vanadium and are 20% V
2O
5/ TiO
2System is designated as 7#.Get the 7# catalyst, it is immersed in 300ml concentration is in the 1mol/L hydrochloric acid, and soak time is 5h, 110 ℃ of dry 9h, and 450 ℃ of roasting 3h make the V of hydrochloric acid modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 20%, Cl
-1With TiO
2Mass ratio be 3.55%, be designated as 8#.
Embodiment 5
Take by weighing the 128.63g ammonium metavanadate, then it is dissolved in the 1929.45g water, stir, treat that dissolving fully, under ultrasonic situation, vanadium liquid is impregnated on the 20-40 purpose 300g titania support, dip time is 7h, 100 ℃ of dry 7h, 430 ℃ of roasting 5h obtain content of vanadium and are 25% V
2O
5/ TiO
2System is designated as 9#.Get the 9# catalyst, it is immersed in 700ml concentration is in the 1mol/L hydrochloric acid, and soak time is 4h, 110 ° of dry 7h, and 420 ℃ of roasting 6h make the V of hydrochloric acid modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 25%, Cl
-1With TiO
2Mass ratio be 8.3%, be designated as 10#.
Embodiment 6
Get the 3# system, it is immersed in 410ml concentration is in the 1mol/L nitric acid, and soak time is 7h, 110 ℃ of dry 8h, and 450 ℃ of roasting 3h make the V of Nitric Acid Modified
2O
5/ TiO
2/ NO
3 -1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 10%, NO
3 -1With TiO
2Mass ratio be 8.5%, be designated as 11#.
Embodiment 7
Get the 3# catalyst, join then in the phosphoric acid that 410ml concentration is 1mol/L, soak time is 3h, 140 ℃ of dry 7h, and 400 ℃ of roasting 8h make the V of phosphoric acid modification
2O
5/ TiO
2/ PO
4 3-Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 10%, PO
4 -1With TiO
2Mass ratio be 13%, be designated as 12#.
Embodiment 8
Get 300g20-40 purpose titania support, it is immersed in 610ml concentration is in the 1mol/L hydrochloric acid, and soak time is 7h, 100 ℃ of dry 10h, the TiO of the modification of system
2, count 13#.Take by weighing the 68.1g ammonium metavanadate, then it is dissolved in the 203g water, stir, treat that dissolving fully under ultrasonic situation, is impregnated into vanadium liquid on the titania support of the above-mentioned modification of 20-40 purpose 300g, dip time is 7h, 110 ℃ of dry 8h, 440 ℃ of roasting 3h obtain the V of modification
2O
5/ TiO
2/ Cl
-1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 15%, Cl
-1With TiO
2Mass ratio be 7.2%, be designated as 14#,
Embodiment 9
Get 300g20-40 purpose 300g titania support, it is immersed in 210ml concentration is in the 1mol/L nitric acid, and soak time is 2h, and 150 ℃ of dry 3h make the TiO of modification
2, count 15#.Take by weighing the 68.1g ammonium metavanadate, then it is dissolved in the 203g water, stir, treat that dissolving fully under ultrasonic situation, is impregnated into vanadium liquid on the titania support of the above-mentioned modification of 20-40 purpose 300g, dip time is 4h, 150 ℃ of dry 5h, 400 ℃ of roasting 8h obtain the V of modification
2O
5/ TiO
2/ NO
3 -1Catalyst, the composition of analysis of catalyst, V in the catalyst
2O
5: V
2O
5And TiO
2Quality and be 15%, NO
3 -1With TiO
2Mass ratio be 4.34%, be designated as 16#,
Get 2# respectively, 4#, 6#, 8#, 10#, 11#, 12#, 14#, 16# catalyst 1.5ml, the internal diameter of packing into is the crystal reaction tube of 6mm, is preheated to 150 ℃, and the ratio of regulating the amount of substance of methyl alcohol and oxygen then is 3:1, and reaction system is a normal pressure, and evaluation result sees Table 1.
Table 1 is implemented activity of such catalysts that the foregoing description measures and experimental result optionally
Claims (4)
1, a kind of catalyst of producing dimethoxymethane with methanol selective oxidation is characterized in that catalyst is by V
2O
5, TiO
2Form with modifying element, modifying element is chlorine element, nitrogen element or P elements, and wherein the load capacity of vanadium is with V
2O
5Meter, V
2O
5: V
2O
5And TiO
2The quality sum be 5-25:100, the chlorine element is with Cl
-1Meter, the nitrogen element is with NO
3 -1Meter, P elements is with PO
4 3-Meter, modifying element and TiO
2Mass ratio be 1-15:100.
2, the Preparation of catalysts method of a kind of producing dimethoxymethane with methanol selective oxidation as claimed in claim 1 is characterized in that comprising the steps:
Ammonium metavanadate is added solvent to be dissolved, the mass ratio of ammonium metavanadate and solvent is 1:4-15, after treating that the vanadium source is all dissolved, under ultrasonic situation, be impregnated into then on the 20-40 purpose titania support, dip time is 2-7 hour, 100-150 ℃ dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V that content of vanadium is 5-25wt%
2O
5/ TiO
2System is then with the nitrogen-containing compound of acid chlorine-containing compound, acidity or the phosphorus-containing compound immersion-V of acidity
2O
5/ TiO
2System 2-7 hour, 100-150 ℃ dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V of modification
2O
5/ TiO
2Catalyst.
3, the Preparation of catalysts method of a kind of producing dimethoxymethane with methanol selective oxidation as claimed in claim 1 is characterized in that comprising the steps:
With the titania support compression molding is the 20-40 order, uses the chloride of acidity then, and nitrogenous or phosphorous compound soaked 2-7 hour, wherein modifying element and TiO
2Mass ratio be 1-15:100, at 100-150 ℃ of dry 5-10 hour, ammonium metavanadate is added solvent to be dissolved, the mass ratio of ammonium metavanadate and solvent is 1:4-15, be impregnated into then on the titania support of above-mentioned modification, flooded 2-7 hour, at 100-150 ℃ of dry 5-10 hour, 400-450 ℃ roasting 3-8 hour, obtain the V of modification
2O
5/ TiO
2Catalyst.
4,, it is characterized in that described solvent is oxalic acid solution or water as the Preparation of catalysts method of claim 2 or 3 described a kind of producing dimethoxymethane with methanol selective oxidation.
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