CN101543775B - VOx/CeO2/TiO2 composite oxide, preparation and application thereof - Google Patents
VOx/CeO2/TiO2 composite oxide, preparation and application thereof Download PDFInfo
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- CN101543775B CN101543775B CN2008100107910A CN200810010791A CN101543775B CN 101543775 B CN101543775 B CN 101543775B CN 2008100107910 A CN2008100107910 A CN 2008100107910A CN 200810010791 A CN200810010791 A CN 200810010791A CN 101543775 B CN101543775 B CN 101543775B
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Abstract
The invention relates to a methanol low-temperature selective oxidation one-step method for preparing dimethoxymethane, in particular to a VOx/CeO2/TiO2 composite oxide and the preparation and application thereof. The mass percentage content of V accounts for 5-20% of V2O5 in the VOx/CeO2/TiO2 composite oxide, the CeO2 content accounts for 3-30%, and the TiO2 content accounts for 50-90%. The VOx/CeO2/TiO2 composite oxide has the advantages that the composite oxide has acidity and oxidizing function, can simultaneously catalyze the selective oxidation of methanol to form formaldehydeand catalyze the condensation of the formaldehyde and methanol to form DMM at a low temperature, realizes the one-step transformation from methanol to DMM, is low in reaction temperature without generation of COor CO2, and is high in atom utilization ratio and process efficiency.
Description
Technical field
The present invention relates to low-temperature methanol selective oxidation one-step method and produce dimethoxymethane, specifically VOx/CeO
2/ TiO
2Composite oxides and preparation thereof and produce catalytic applications in the dimethoxymethane (DMM) in low-temperature methanol selective oxidation one-step method.
Background technology
Dimethoxymethane (Dimethoxymethane, DMM) popular name dimethoxym ethane, 42 ℃ of boiling points.Be used as the solvent except main at present, also be used for selective oxidation and produce high-concentration formaldehyde.Recent study finds that DMM and diesel oil have good intersolubility, can be used as diesel fuel additives, therefore has been subjected to paying close attention to widely.Because oxygen content is added a certain proportion of DMM up to 42% among the DMM in diesel oil, not only can promote the completing combustion of diesel oil, improves energy efficiency, but also can significantly reduce the discharging of NOx in the tail gas, hydro carbons and solid particulate matter.
At present, dimethoxym ethane mainly with methyl alcohol and formaldehyde under the acidic catalyst effect by contracting and prepared in reaction.Traditional handicraft is used inorganic acid (as sulfuric acid, hydrochloric acid), and lewis acid (as ferric trichloride, alchlor etc.) is made catalyst.But these catalyst separation reclaim difficulty, and corrosivity is strong and catalyst activity is not high yet.At present, research mainly concentrates on solid acid catalyst, as acidic molecular sieve, cationic ion-exchange resin etc.Japan company of Asahi Chemical Industry adopts novel solid acid catalyst to obtain to use in industrial production.Chinese patent CN1301688 once disclosed and has a kind ofly made catalyst with the HZSM-5 molecular sieve and produce dimethoxym ethane with methyl alcohol and formaldehyde by catalytic rectification method.
Above-described method need be a raw material with formaldehyde and methyl alcohol, and industrial formol is to make by the selective oxidation of methyl alcohol high temperature with silver catalyst (greater than 600 ℃) or molybdenum-iron catalyst (270-350 ℃), therefore this arts demand of DMM of producing by methyl alcohol and formaldehyde is by two steps, first step selective oxidation of methanol is made formaldehyde, and the pure and mild formaldehyde condensation of second ground beetle obtains DMM.If can on a catalyst, realize contracting and will shortening production process route of oxidization of methanol and methyl alcohol and formaldehyde, might reduce investment, cut down the consumption of energy.It is less to go on foot the bibliographical information of producing DMM by methanol oxidation one at present.Yuan etc. reported once that rhenium catalyst [Chem.Comm. (2000) 1421] that a kind of di-iron trioxide supports can realize 48% methanol conversion and 91% DMM selectivity under 240 ℃ of reaction conditions.Iglesia etc. [Angew.Chem.Int.Ed.42 (2003) 5072] are with SiO
2The H that supports
3+nPV
nMo
12-nO
40Heteropolyacid catalyst is applied to this reaction, discovery is by utilizing 2,6-di-tert-butyl pyridine or pyridine are regulated the distribution that can change reactive activity and product to the acidity of heteropoly acid, wherein the ratio of DMM and dimethyl ether all increases on the acidic site of moderate strength, methanol conversion can reach 20%, DMM selectivity 80%.Recently, Shen etc. [Chem.Commun., 2007,2172-2174] utilizes SO
4 2-Modify VO
x-TiO
2The acidity of catalyst can realize 60% methanol conversion and nearly 90% DMM selectivity.In addition, Chinese patent CN1634655A also discloses by S and has added enhancing VOx-TiO
2The acidity of catalyst also improves DMM and optionally reports.
Summary of the invention
The object of the present invention is to provide a kind of VOx/CeO
2/ TiO
2Composite oxides and preparation thereof and application, described VOx/CeO
2/ TiO
2Composite oxides have acidity and oxidative function, and (120-200 ℃) catalysis methanol selective oxidation simultaneously generates formaldehyde and formaldehyde and contracts with methyl alcohol and generates DMM under lower temperature, realizes going on foot conversion by methyl alcohol to one of DMM.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of VOx/CeO
2/ TiO
2Composite oxides, the mass content of V is with V in the composite oxides
2O
5Count 5-20%, x=1.5-2.5, CeO
2Mass content be 3-30%, TiO
2Mass content be 50-90%, it has acid and the catalytic oxidation function simultaneously.
Described VOx/CeO
2/ TiO
2The preparation of composite oxides:
1) CeO
2/ TiO
2The preparation of oxide: by the metering ratio, ammonium ceric nitrate and titanium sulfate mixed solution are dropped in the urea liquid of heating, the concentration of ammonium ceric nitrate is 0.03-0.3mol/L in ammonium ceric nitrate and the titanium sulfate mixed solution, the concentration of titanium sulfate is 1-2mol/L, the concentration of urea liquid is 1-3mol/L, and the volume ratio of ammonium ceric nitrate and titanium sulfate mixed solution and urea liquid is 1: 4-1: 10, dropwised the back aging 2-6 hour, suction filtration, washing, oven dry, 300-600 ℃ of calcination 4-10h; It can make in the composite oxides dispersion of ceria and titanium dioxide more even;
2) VOx/CeO
2/ TiO
2The preparation of composite oxides: ammonium metavanadate and 1: 2 in molar ratio ratio of oxalic acid is mixed, under 30-80 ℃ of heating, be dissolved in water and get black-and-blue solution, the concentration in the solution is counted 0.5-4mol/L with V; The step 1) gained CeO that in above-mentioned solution, adds metering
2/ TiO
2Oxide stirs, oven dry, the VOx/CeO that obtains behind temperature 300-600 ℃, 4-10 hour roasting
2/ TiO
2Composite oxides.
With step 2) resulting VOx/CeO
2/ TiO
2It is the Ti (SO of 0.3-1.5mol/L that composite oxides immerse amount concentration
4)
2The aqueous solution, the mass ratio of the composite oxides and the aqueous solution is 2: 1-1: 1, stir, oven dry, roasting obtains SO
4 2-The VOx/CeO of ion modification
2-TiO
2Catalyst.Described VOx/CeO
2/ TiO
2Composite oxides are through SO
4 2-Behind the ion modification, SO
4 2-The mass content of ion in catalyst is 0.5%-5%, and its acidity improves, and produces in methanol oxidation-contract and one-step method and shows good performance aspect the DMM, can further improve the selectivity of methanol conversion and DMM.
Described bake out temperature 90-150 ℃, time 12-48 hour; Sintering temperature 300-600 ℃, time 4-10 hour.
Described VOx/CeO
2/ TiO
2Composite oxides are produced application in the dimethoxymethane in low-temperature methanol selective oxidation one-step method, and methyl alcohol is directly produced the technical process of DMM under this composite oxide catalytic low-temp reaction condition.
Described VOx/CeO
2/ TiO
2Composite oxides are through SO
4 2-Catalyst behind the ion modification can be used for methanol oxidation-contract and one-step method is produced DMM, feeds the CH that does not add dilution in continuous fixed bed reactor
3OH/O
2Reacting gas, CH
3OH and O
2Mol ratio be 3/7-7/3, the air speed of reacting gas is 1000-3000ml/gh, reaction bed temperature is controlled at 120-200 ℃, can obtain DMM; Product carries out on-line analysis by gas-chromatography.
The present invention has following advantage:
VOx/CeO of the present invention
2/ TiO
2Composite oxides have acidity and oxidative function, and (120-200 ℃) catalysis methanol selective oxidation simultaneously generates formaldehyde and formaldehyde and contracts with methyl alcohol and generates DMM under lower temperature, realizes going on foot conversion by methyl alcohol to one of DMM.Described VOx/CeO
2/ TiO
2Composite oxides are through SO
4 2-After modifying, ion (content 0.5-5%) can further improve the selectivity of DMM.Conversion of methanol is 30-80%, and the selectivity of DMM is 80-90%, a small amount of methyl formate of by-product.Compare with two-step method in the past, promptly methyl alcohol elder generation high-temperature oxydation on Mo/Fe oxide or Ag catalyst generates formaldehyde, and formaldehyde carries out acid catalysis with methyl alcohol again and contracts and (catalytic distillation), and the new process reaction temperature that one step of methyl alcohol is catalytically conveted to DMM is low, no CO and CO
2Generate, atom utilization and process efficiency are all higher.
Description of drawings
The present invention is further detailed explanation below in conjunction with accompanying drawing and table and embodiment:
Fig. 1 is 20%V
2O
5/ 4%CeO
2/ 76%TiO
2Selective oxidation of methanol system DMM reaction on the composite oxides, methanol conversion and selectivity of product are with the variation diagram in reaction time.(423K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%)
Fig. 2 is SO
4 2-20%V
2O
5/ 4%CeO
2/ 76%TiO
2Selective oxidation of methanol system DMM reaction on the catalyst, methanol conversion and selectivity of product are with the variation diagram in reaction time.(423K, GHSV=1600, V
Methyl alcohol/ V
O2=44%/56%)
Fig. 3 is SO
4 2-20%V
2O
5/ 8%CeO
2/ 72%TiO
2Selective oxidation of methanol system DMM reaction on the catalyst, methanol conversion and selectivity of product are with the variation diagram in reaction time.(423K, GHSV=1600ml/gh, V
Methyl alcohol/ V
O2=44%/56%)
Fig. 4 is SO
4 2-20%V
2O
5/ 12%CeO
2/ 68%TiO
2Selective oxidation of methanol system DMM reaction on the catalyst, methanol conversion and selectivity of product are with the variation diagram in reaction time.(453K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%)
Fig. 5 is SO
4 2-20%V
2O
5/ 24%CeO
2/ 56%TiO
2Selective oxidation of methanol system DMM reaction on the catalyst, methanol conversion and selectivity of product are with the variation diagram in reaction time.(reaction condition: 453K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%; DMM represents dimethoxymethane, and MF represents methyl formate)
The specific embodiment
Embodiment 1
CeO
2/ TiO
2The preparation of (weight content 5% and 95%)
With 2.14g (NH
4)
2Ce (NO
3)
62H
2O and 36g Ti (SO
4)
2It is standby to be dissolved in the 100ml deionized water.Urea 60g adds in the 1000ml deionized water, and heating makes the solution boiling, then with 100ml (NH
4)
2Ce (NO
3)
62H
2O and Ti (SO
4)
2Mixed solution in 10-40min, be added drop-wise in the urea liquid, dropwise and continue to add thermal agitation 3h.Filter, with the washing of 2000ml deionized water for several times, use the 250ml absolute ethanol washing then three times, 110 ℃ of oven dry 12h, 400 ℃ of roasting 4h.
Embodiment 2
20%V
2O
5/ 4%CeO
2/ 76%TiO
2The preparation of composite oxides
With 1.29g ammonium metavanadate and 2.78g oxalic acid, be dissolved in the 6ml deionized water, in this solution, add 3.85 g5%CeO
2/ 95%TiO
2Composite oxides stir and make into pasty state, 110 ℃ of oven dry 12h, 400 ℃ of roasting 4h.Gained is 20%V
2O
5/ 4%CeO
2/ 76%TiO
2Composite oxides.
Embodiment 3
With embodiment 2 gained 20%V
2O
5/ 4%CeO
2/ 76%TiO
2Composite oxides add 6ml and contain 0.25 gTi (SO
4)
2In the solution, stir and make into pasty state, 110 ℃ of oven dry 12h, 400 ℃ of roasting 4h.Gained is SO
4 2--20%V
2O
5/ 4%CeO
2/ 76%TiO
2Catalyst.
Embodiment 4
SO
4 2--20%V
2O
5/ 8%CeO
2/ 72%TiO
2, SO
4 2-20%V
2O
5/ 12%CeO
2/ 68%TiO
2And SO
4 2-20%V
2O
5/ 24%CeO
2/ 56%TiO
2The Preparation of catalysts method is identical with embodiment 1-3, various ce O
2And TiO
2The CeO of ratio
2/ TiO
2Add (NH in the preparation process of oxide
4)
2Ce (NO
3)
62H
2The amount of O is followed successively by 4.415g, and 7.2g and 17.5g add Ti (SO
4)
2Amount be 36g, the amount that adds urea is respectively 60g, 75g, 100g.Other preparation process and embodiment 1-3 are identical.
Embodiment 5
20%V
2O
5/ 4%CeO
2/ 76%TiO
2The test of methanol oxidation on the composite oxides-contract and produce the DMM reactivity worth.With the composite oxide power compression molding, and fragmentation is screened to the 40-60 order, and consumption is 200-400mg, adds 800mg quartz sand (40-60 order) mixing.In being the continuous-flow micro fixed-bed reactor of 10mm, internal diameter carries out.Use 20vol%O before the reaction
2/ N
2Handle down 1h (flow 30ml/min) at 400 ℃, and sweep in the He air-blowing and to drop to 150 ℃, the 2ml/min purity oxygen obtains methyl alcohol/O after by 45 ℃ of methyl alcohol bubblers
2Volume ratio is 44: 56 a mixed gas, gas enters reactor bed under 150 ℃ of insulations, bed temperature is 150 ℃, reacted mixture enters the HP-6890 gas-chromatography and carries out on-line analysis under 150 ℃ of insulations, adopt Porapack N packed column to be connected thermal conductivity detector (TCD) quantitative analysis O with the 5A molecular sieve column
2, CO, CO
2And formaldehyde, the INNOWAX capillary column connects FID and is used to analyze methyl alcohol, dimethyl ether, methyl formate and DMM.Reaction test the results are shown in Figure 1.Methanol conversion 75%, DMM accounts for 55% in the product, and MF accounts for 35%, and the DMM yield is 41%.
Embodiment 6
20%V
2O
5/ 4%CeO
2/ 76%TiO
2, 20%V
2O
5/ 8%CeO
2/ 72%TiO
2, 20%V
2O
5/ 12%CeO
2/ 68%TiO
2, 20%V
2O
5/ 24%CeO
2/ 56%TiO
2Composite oxides are through 0.5%SO
4 2-Reactivity worth method of testing after the processing is identical with embodiment 4, the catalyst filling amount is 200mg (40-60 order), the gas that feeds beds is followed successively by 3ml/min oxygen by 45 ℃ of methyl alcohol bubblers, 3ml/min oxygen is by 45 ℃ of methyl alcohol bubblers, 2ml/min oxygen is by 45 ℃ of methyl alcohol bubblers, the mixed gas that 2ml/min oxygen obtains after by 45 ℃ of methyl alcohol bubblers, and reaction temperature is followed successively by 150 ℃, 150 ℃, 180 ℃ and 180 ℃.Test result is listed in Fig. 2-Fig. 5 respectively.Table 1 has been listed the catalytic performance of above-mentioned composite oxides.
Table 1
Table 1 is 1. 20%V
2O
5/ 4%CeO
2/ 76%TiO
2Composite oxides, 2. SO
4 2-20%V
2O
5/ 4%CeO
2/ 76%TiO
2Catalyst, 3. SO
4 2--20%V
2O
5/ 8%CeO
2/ 72%TiO
2Catalyst, 4. SO
4 2--20%V
2O
5/ 12%CeO
2/ 68%TiO
2Catalyst and 5. SO
4 2-20%V
2O
5/ 24%CeO
2/ 56%TiO
2Selective oxidation of methanol system DMM reaction, the conversion ratio of reaction and each selectivity of product data on the catalyst.
Reaction condition: 1. 423K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%; 2. 423K, GHSV=1600, V
Methyl alcohol/ V
O2=44%/56%; 3. 423K, GHSV=1600ml/gh, V
Methyl alcohol/ V
O2=44%/56%; 4. 453K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%; 5. 453K, GHSV=1070ml/gh, V
Methyl alcohol/ V
O2=44%/56%.DMM represents dimethoxymethane, and MF represents methyl formate, and DME represents dimethyl ether, and FA represents formaldehyde, and COx represents CO and CO
2Summation.
Claims (3)
1. SO
4 2-The VOx/CeO of ion modification
2/ TiO
2Composite oxides is characterized in that being prepared by following steps:
1) CeO
2/ TiO
2The preparation of oxide: by the metering ratio, ammonium ceric nitrate and titanium sulfate mixed solution are dropped in the urea liquid of heating, the concentration of ammonium ceric nitrate is 0.03-0.3mol/L in ammonium ceric nitrate and the titanium sulfate mixed solution, the concentration of titanium sulfate is 1-2mol/L, the concentration of urea liquid is 1-3mol/L, and the volume ratio of ammonium ceric nitrate and titanium sulfate mixed solution and urea liquid is 1: 4-1: 10, dropwised the back aging 2-6 hour, suction filtration, washing, oven dry, 300-600 ℃ of calcination 4-10h;
2) VOx/CeO
2/ TiO
2The preparation of composite oxides: ammonium metavanadate and 1: 2 in molar ratio ratio of oxalic acid is mixed, under 30-80 ℃ of heating, be dissolved in water and get black-and-blue solution, the concentration in the solution is counted 0.5-4mol/L with V; The step 1) gained CeO that in above-mentioned solution, adds metering
2/ TiO
2Oxide stirs, oven dry, the VOx/CeO that obtains behind temperature 300-600 ℃, 4-10 hour roasting
2/ TiO
2Composite oxides;
The mass content of V is with V in the prepared composite oxides
2O
5Count 5-20%, x=1.5-2.5, CeO
2Mass content be 3-30%, TiO
2Mass content be 50-90%;
3) with step 2) resulting VOx/CeO
2/ TiO
2It is the Ti (SO of 0.3-1.5mol/L that composite oxides immerse amount concentration
4)
2The aqueous solution, the mass ratio of the composite oxides and the aqueous solution is 2: 1-1: 1, stir, oven dry, roasting obtains SO
4 2-The VOx/CeO of ion modification
2-TiO
2Composite oxides.
2. described SO of claim 1
4 2-The VOx/CeO of ion modification
2/ TiO
2The preparation method of composite oxides is characterized in that:
1) CeO
2/ TiO
2The preparation of oxide: by the metering ratio, ammonium ceric nitrate and titanium sulfate mixed solution are dropped in the urea liquid of heating, the concentration of ammonium ceric nitrate is 0.03-0.3mol/L in ammonium ceric nitrate and the titanium sulfate mixed solution, the concentration of titanium sulfate is 1-2mol/L, the concentration of urea liquid is 1-3mol/L, and the volume ratio of ammonium ceric nitrate and titanium sulfate mixed solution and urea liquid is 1: 4-1: 10, dropwised the back aging 2-6 hour, suction filtration, washing, oven dry, 300-600 ℃ of calcination 4-10h;
2) VOx/CeO
2/ TiO
2The preparation of composite oxides: ammonium metavanadate and 1: 2 in molar ratio ratio of oxalic acid is mixed, under 30-80 ℃ of heating, be dissolved in water and get black-and-blue solution, the concentration in the solution is counted 0.5-4mol/L with V; The step 1) gained CeO that in above-mentioned solution, adds metering
2/ TiO
2Oxide stirs, oven dry, the VOx/CeO that obtains behind temperature 300-600 ℃, 4-10 hour roasting
2/ TiO
2Composite oxides;
3) with step 2) resulting VOx/CeO
2/ TiO
2It is the Ti (SO of 0.3-1.5mol/L that composite oxides immerse amount concentration
4)
2The aqueous solution, the mass ratio of the composite oxides and the aqueous solution is 2: 1-1: 1, stir, oven dry, roasting obtains SO
4 2-The VOx/CeO of ion modification
2-TiO
2Composite oxides.
3. described SO of claim 1
4 2-The VOx/CeO of ion modification
2/ TiO
2Composite oxides are produced application in the dimethoxymethane in low-temperature methanol selective oxidation one-step method, it is characterized in that: described SO
4 2-The VOx/CeO of ion modification
2/ TiO
2Composite oxides are used for methanol oxidation-condensation one-step method and produce DMM, feed the CH that does not add dilution in continuous fixed bed reactor
3OH/O
2Reacting gas, CH
3OH and O
2Mol ratio be 3/7-7/3, the air speed of reacting gas is 1000-3000ml/gh, reaction bed temperature is controlled at 120-200 ℃, promptly obtains DMM.
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| CN103933965B (en) * | 2014-04-23 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | For the methanol oxidation synthesis catalyst of dimethoxymethane and method for making and application |
| CN104498114B (en) * | 2014-11-19 | 2016-07-06 | 四川省大气投资有限公司 | A kind of automobile-used ethers mixes fuel burning and its preparation method and application |
| CN109806881A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol |
| CN108772055A (en) * | 2018-05-31 | 2018-11-09 | 合肥神舟催化净化器股份有限公司 | A kind of preparation method of unformed composite oxides for SCR reactions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782039A (en) * | 1986-05-19 | 1988-11-01 | Johnson Matthey, Inc. | Selective catalytic reduction catalyst and a process for preparing the catalyst |
| CN1265383A (en) * | 2000-02-28 | 2000-09-06 | 南京大学 | Composite nanometer-level Ce-V-Ti oxide and its preparation and application |
| CN1565724A (en) * | 2003-07-08 | 2005-01-19 | 浙江大学 | Cerium-titanium solid solution and its preparing method |
-
2008
- 2008-03-28 CN CN2008100107910A patent/CN101543775B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4782039A (en) * | 1986-05-19 | 1988-11-01 | Johnson Matthey, Inc. | Selective catalytic reduction catalyst and a process for preparing the catalyst |
| CN1265383A (en) * | 2000-02-28 | 2000-09-06 | 南京大学 | Composite nanometer-level Ce-V-Ti oxide and its preparation and application |
| CN1565724A (en) * | 2003-07-08 | 2005-01-19 | 浙江大学 | Cerium-titanium solid solution and its preparing method |
Non-Patent Citations (2)
| Title |
|---|
| 李健等.Ti1-xCexO2体系纳米粉体的制备及其结构表征.《高压物理学报》.2006,第20卷(第2期),211-216. * |
| 许波连等.V2O5/TiO2催化剂表面钒氧物种的分散状态和催化性能.《中国科学(B辑)》.2002,第32卷(第3期),235-242. * |
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