CN1634655A - Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof - Google Patents
Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof Download PDFInfo
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- CN1634655A CN1634655A CN200410065321.6A CN200410065321A CN1634655A CN 1634655 A CN1634655 A CN 1634655A CN 200410065321 A CN200410065321 A CN 200410065321A CN 1634655 A CN1634655 A CN 1634655A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 234
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims description 79
- 238000002360 preparation method Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 27
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 3
- -1 sulfate radical Chemical class 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 36
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- YPBUJEGTLXNVDH-UHFFFAOYSA-N dimethoxymethane;formaldehyde Chemical compound O=C.COCOC YPBUJEGTLXNVDH-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101100114490 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cox-13 gene Proteins 0.000 description 1
- 101100061020 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cox-9 gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KTFJRKWUACQCHF-UHFFFAOYSA-N dimethoxymethane;methanol Chemical compound OC.COCOC KTFJRKWUACQCHF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
This invention relates to carbinol selection oxidation to process dimethoxym ethane catalyzer, which is loaded with vanadium on the modified titania with sulfur in acid environment, wherein the modified titania sulfur content is countered as the sulfate radical mass of 1.0-4.5 %, and the vanadium load is countered as vanadic anhydride mass of 5-20 %. The catalyzer in this invention has the conversion rate as 17.6-62.8 % and the dimethoxym ethane selection rate as 67.8-97.9 %.
Description
One, the technical field
The invention relates to a catalyst for directly producing methylal by methanol oxidation under mild conditions, a preparation method thereof and a method for preparing methylal by using the catalyst.
Second, background Art
Methylal is also called dimethoxymethane, and can be used as a solvent for producing spices and synthetic medicines due to very low toxicity, and also can be used as an intermediate for producing polyformaldehyde, and polyformaldehyde is an important engineering plastic and has wide application in the automobile industry, and in addition, because of the potential application of methylal in the field of diesel additives, methylal is more and more concerned by people.
At present, methylal is mainly produced by a method of dehydrating methanol and formaldehyde on an acid catalyst, common acid catalysts comprise inorganic acid, an acid molecular sieve, macroporous cation acid resin and the like, for example, Chinese patent CN 1301688 discloses a method for producing methylal by using HZSM-5 molecular sieve as a catalyst and methanol and formaldehyde in a liquid phase; US patent US4967014 uses macroporous cationic resin packed in a reactor to produce methylal. The raw materials for producing methylal by the two methods are methanol and formaldehyde, and the formaldehyde is also produced by partial oxidation of the methanol. The typical formaldehyde production process is to oxidize methanol with oxygen or air in the presence of a silver catalyst or an iron-molybdenum catalyst to produce formaldehyde. Therefore, in order to obtain methylal, methanol must be oxidized into formaldehyde, and the formaldehyde must be reacted with methanol to produce methylal. Thus, the methanol to the methylal are subjected to two-step reaction, and the process route is long. Obviously, the process for producing methylal by directly oxidizing methanol reduces investmentand production cost compared with the prior process for producing methylal by two steps of methanol. Thus, several inventors have patented direct synthesis of methylal by oxidation of methanol, one of the more effective methods being in SbRe2O6The oxidation of methanol with oxygen-containing gases with catalysis of (2) gives satisfactory conversion of methanol and selectivity to methylal (U.S. Pat. No. 5, 6,403,841). For example, according to the content of the specification, at the reaction temperature of 300 ℃ and 400 ℃, the methanol conversion rate can reach 50%, and the methylal selectivity approaches to 90%. However, since Re is expensive, the method is limited in use, and further, the higher oxides of Re are volatile at high temperatures and are practically usedDifficulties may exist, while higher reaction temperatures place higher demands on the production equipment.
An important aspect of the research in the literature concerning the oxidation of methanol is the research of the oxidation of methanol on supported or unsupported vanadium pentoxide, mainly for the purpose of obtaining oxygen-containing organic compounds, such as formaldehyde, methyl formate, etc., as disclosed in the US 6,281,378 patent. In studying these reactions methylal was considered as a by-product of partial oxidation of methanol, especially at lower temperatures, methylal selectivity was higher, up to 50%, but the corresponding methanol conversion was less than 30% (Tronconi E, Ind. Eng. chem. Res., Vol 26 1987, p 1369). The temperature is increased, the conversion rate of methanol is increased, but the selectivity of methylal is sharply reduced, and the selectivity of formaldehyde and methyl formate is increased to become main products; the further increase of the temperature gradually increases the selectivity of carbon monoxide and carbon dioxide in the product, and the deep oxidation of methanol occurs, so the biggest difficulty in preparing methylal by the methods is that the methylal has low selectivity when the conversion rate of methanol is high, and therefore, the method has no practical value.
Third, the invention
Through the intensive research on the selective oxidation reaction of methanol on the supported vanadium pentoxide catalyst, the invention discovers that the selectivity of the generated methylal has a close relationship with the oxidability and the acidity of the catalyst. The reaction of direct oxidation of methanol to methylal can be considered as a coupling of two reactions, that is, oxidation of methanol to formaldehyde (reaction 1) and condensation of formaldehyde with methanol (reaction 2), and the oxidation of methanol to formaldehyde requires a catalyst having suitable oxidizing property, while the condensation of formaldehyde with methanol requires a catalyst having suitable acidity.
By suitable oxidation is meant that the oxidation product of methanol over the catalyst at a certain temperature is predominantly formaldehyde, rather than further oxidation to formic acid or carbon oxides (COx); proper acidity means that dehydration condensation reaction on the catalyst at a certain temperature mainly reacts between methanol and formaldehyde to produce methylal, but not methanol molecules to produce dimethyl ether by dehydration. The oxidation capacity and dehydration capacity of the catalyst are closely related to the reaction temperature. For oxidation reactions, an increase in temperature tends to increase the selectivity to deep oxidation products; for the dehydration reaction, the temperature is increased to favor the generation of dehydration reaction products with higher activation energy, and the activation energy for methanol dehydration to generate dimethyl ether is much higher than that of the reaction (2). According to the above analysis, if the oxidizability and acidity of the catalyst can be properly matched, methanol can be oxidized into methylal under mild conditions, and the methanol conversion rate and the methylal selectivity are higher.
It is an object of the present invention to provide a high efficiency bifunctional catalyst for the direct production of methylal by the oxidation of methanol and a process for the preparation thereof, and it is another object of the present invention to provide a process for the production of methylal by using the catalyst prepared by the process of the present invention.
The technical scheme of the invention is as follows:
a catalyst for producing methylal by selective oxidation of methanol is prepared by loading vanadium on acidic sulfur-containing modified titanium dioxide, wherein the sulfur content of the modified titanium dioxide is 1.0-4.5% by mass of sulfate radical, the vanadium loading on the modified titanium dioxide is 5-20% by mass of vanadium pentoxide, and the preferable vanadium loading is 10-15% by mass of vanadium pentoxide.
The modified sulfur-containing titanium dioxide having acidity can be produced by the following method: titanium sulfate is dissolved in water, and then titanium dioxide powder is added, stirred, dried and roasted to obtain modified titanium dioxide containing sulfur and having acidity (see: journal of catalysis 20, 321, 1999; J.Catal., 1997, 168, 482). The modified titanium dioxide obtained in the way has certain acidity, but is not strong in acidity, and is remarkably characterized in that the conversion rate of the modified titanium dioxide for catalyzing the dehydration of methanol to dimethyl ether at the temperature of below 200 ℃ is lower than 5%, and the conversion rate of the modified titanium dioxide for catalyzing the dehydration of methanol to dimethyl ether at the temperature of below 150 ℃ is negligible.
The invention relates to a preparation method of a catalyst for producing methylal by selective oxidation of methanol, which comprises the steps of mixing ammonium metavanadate and oxalic acid in a mass ratio of 1: 2, adding water to dissolve the ammonium metavanadate and the oxalic acid to obtain a dark green solution, adding metered acidic sulfur-containing modified titanium dioxide powder into the dark green solution, stirring the acidic sulfur-containing modified titanium dioxide powder into a paste, drying and roasting the paste to obtain the catalyst for producing methylal by selective oxidation of methanol, wherein the modified titanium dioxide is loaded with 5 to 20 mass percent of vanadium pentoxide.
In the preparation method of the catalyst for producing methylal by selective oxidation of methanol, the mass of the added water is 3.75-17 times of that of the ammonium metavanadate.
In the preparation method of the catalyst for producing methylal by selective oxidation of methanol, the drying is carried out at 100-120 ℃.
In the preparation method of the catalyst for producing methylal by selective oxidation of methanol, the calcination is carried out at 390-460 ℃ for 5-10 hours.
The method for producing methylal by using the catalyst for producing methylal by selective oxidation of methanol is characterized by filling the catalyst for producing methylal by selective oxidation of methanol, which is disclosed by the invention, in a reactor, heating, controlling the temperature of the reactor at 130-160 ℃, introducing mixed gas of methanol vapor and oxygen-containing gas preheated to 130-160 ℃, wherein the mass ratio of the methanol vapor to the oxygen-containing gas is 5: 1-5: 10, and the total flow rate of the introduced gas is 1.1 x 10 per gram of the catalyst4And (5) obtaining methylal after ml/h.
The oxygen-containing gas in the above production process is pure O2Air or containing molecules O2Nitrogen or helium.
Because the molar reaction heat of the reaction is larger, inert gas such as nitrogen or helium is added into the reaction mixed gas in a certain proportion, which is beneficial to controlling the reaction temperature. The reaction should generally avoid operating within the explosive limits of methanol.
The reactor used for producing methylal by the method for producing methylal by using the catalyst for producing methylal by selective oxidation of methanol can be a fixed bed gas-solid phase reactor and also can be a fluidized bed gas-solid phase reactor.
The catalyst for producing methylal by selective oxidation of methanol has the advantages of simple preparation method and low cost, and the catalyst can be used for directly producing methylal by one-step reaction of methanol, thereby greatly reducing the production cost and the investment cost for producing methylal. The conversion rate of methylal methanol produced by using the catalyst for producing methylal by selective oxidation of methanol can reach 17.6-62.8%, the methylal selectivity can reach 67.8-97.9%, and the catalyst is obviously superior to the unmodified catalyst of titanium dioxide loaded with vanadium.
Fourth, detailed description of the invention
The invention is further illustrated by the following examples:
example 1:
mixing 71.0g ammonium metavanadate and 142.0g oxalic acid, adding 600.0ml water, stirring to dissolve to obtain dark green solution, adding 500.0g powdered titanium dioxide into the dark green solution, stirring to obtain light green paste, standing for 2 hr, oven drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 6 hr to obtain V-containing solution2O5The yellow powdery vanadium-titanium catalyst A. Pressing a part of the prepared powdery vanadium-titanium catalyst A into a sheet shape, smashing the sheet vanadium-titanium catalyst, and sieving to obtain a particle size of 20-40 meshes for activity detection. Analysis of the catalyst composition, V2O5The content is 9.8%. This sample was designated as #1 catalyst for comparison.
Example 2:
77.2g of ammonium metavanadate and 154.4g of oxalic acid are mixed, 290.0ml of water is added, the mixture is stirred and dissolved to obtain a dark green solution, 240.0g of powdery titanium dioxide is added into the dark green solution, the mixture is stirred into a light green paste, the paste is dried for 12 hours at 110 ℃ after being placed for 2 hours, and the paste is roasted for 6 hours in the air at 400 ℃ to obtain a yellow powdery vanadium-titanium catalyst B. Pressing a part of the prepared powdery vanadium-titanium catalyst B into a sheet shape, smashing the sheet vanadium-titanium catalyst, and sieving to obtain a particle size of 20-40 meshes for activity detection. Analysis of the catalyst composition, V2O5The content is 20.1%. This sample was designated as #2 catalyst for comparison.
Example 3:
6.2g of crystalline titanium sulfate was placed in a 200ml crucible, 150.0ml of distilled water was added thereto and stirred to dissolve it, 135.0g of titanium dioxide powder was weighed and added to the above solution, stirred for 10 minutes, left to stand for 5 hours, dried overnight at 110 ℃ and then calcined at 400 ℃ for 5 hours to obtain modified titanium dioxide.
Example 4:
2.14g of crystalline titanium sulfate was placed in a 200ml crucible, 150.0ml of distilled water was added thereto and stirred to dissolve it, 135.0g of titanium dioxide powder was weighed and added to the above solution, stirred for 10 minutes, left to stand for 5 hours, dried overnight at 110 ℃ and then calcined at 400 ℃ for 5 hours to obtain modified titanium dioxide.
Example 5:
6.64g of crystalline titanium sulfate was placed in a 200ml crucible, 150.0ml of distilled water was added thereto and stirred to dissolve it, 135.0g of titanium dioxide powder was weighed and added to the above solution, stirred for 10 minutes, left to stand for 5 hours, dried overnight at 110 ℃ and then calcined at 400 ℃ for 5 hours to obtain modified titanium dioxide.
Example 6:
after 35.1g of ammonium metavanadate and 70.2g of oxalic acid are mixed, 600.0ml of water is added, stirring is carried out to dissolve the mixture to obtain a dark green solution, 500.0g of modified titanium dioxide powder prepared in example 3 is added into the dark green solution, the mixture is stirred into light green paste, the mixture is placed for 2 hours and then dried for 12 hours at 110 ℃, and then roasted for 6 hours in air at 400 ℃, so that the modified titanium dioxide supported yellow powdery vanadium-titanium catalyst is obtained. Pressing a part of the prepared powdery vanadium-titanium catalyst into a sheet shape, smashing the sheet vanadium-titanium catalyst, and sieving to obtain a particle size of 20-40 meshes for activity detection. Analysis of the catalyst composition, V2O5The content is 5.0 percent. This sample was designated as #3 catalyst.
Example 7:
71.0g of ammonium metavanadate and 142.0g of oxalic acid are mixed, 600.0ml of water is added, the mixture is stirred and dissolved to obtain a dark green solution, 500.0g of the modified titanium dioxide powder prepared in the example 4 is added into the dark green solution, the mixture is stirred into a light green paste, the mixture is placed for 2 hours, then dried for 12 hours at 110 ℃, and then roasted for 6 hours in the air at 400 ℃ to obtain the modified titanium dioxide supported titanium dioxideYellow powdery vanadium-titanium catalyst. Pressing a part of the prepared powdery vanadium-titanium catalyst into a sheet shape, smashing the sheet vanadium-titanium catalyst, and sieving to obtain a particle size of 20-40 meshes for activity detection. Analysis of the catalyst composition, V2O5The content is 9.9%. This sample was designated as #4 catalyst.
Example 8:
77.2g of ammonium metavanadate and 154.4g of oxalic acid are mixed, 290.0ml of water is added, the mixture is stirred and dissolved to obtain a dark green solution, 240.0g of modified titanium dioxide powder prepared in example 5 is added into the dark green solution, the mixture is stirred into a light green paste, the mixture is placed for 2 hours, then dried at 110 ℃ for 12 hours, and then roasted at 400 ℃ for 6 hours to obtain the yellow powdery vanadium-titanium catalyst loaded on the modified titanium dioxide. Pressing a part of the prepared powdery vanadium-titanium catalyst into a sheet shape, smashing the sheet vanadium-titanium catalyst, sieving, and taking the particle size of 20-40 meshes for activity detection. Analysis catalystComposition of the agent V2O5The content is 19.9%. This sample was designated as #5 catalyst.
Example 9:
weighing 0.5g of the #1 catalyst sample, placing the sample into a glass reaction tube with the inner diameter of 8 mm, preheating to 150 ℃, and mixing the sample with the volume composition of 5 percent of methanol and O26％，N289% of the feed gas was preheated to 150 ℃ and passed through the reaction tube. The reaction system is at normal pressure. The gas space velocity is 1.1X 10 per gram of catalyst4Ml/hour. The composition of the reaction raw material gas and the reaction tail gas is analyzed on line by gas chromatography. The methanol conversion and product selectivity were calculated as follows.
Examples 10 to 13: the activity of the catalyst samples #2- #5 was measured by the method of example 9, and the measurement results are shown in Table 1.
Example 14:
weighing 0.5g of #5 catalyst sample, placing the sample into a glass reaction tube with the inner diameter of 8 mm, preheating to 130 ℃, and mixing the volume of 5 percent of methanol and O26％，N289% of the raw gas is preheated to 130 ℃ and passes through the reaction tube. The reaction system is at normal pressure. The gas space velocity is 1.1X 10 per gram of catalyst4Ml/hour. The composition of the reaction raw material gas and the reaction tail gas is analyzed on line by gas chromatography. The methanol conversion and product selectivity were calculated using the method of example 9.
Example 15:
weighing 0.5g of #5 catalyst sample, placing the sample into a glass reaction tube with the inner diameter of 8 mm, preheating to 160 ℃, and mixing the volume of 5 percent of methanol and O26％，N289% of raw gas is preheated to 160 ℃ and passes through the reaction tube. The reaction system is at normal pressure. The gas space velocity is 1.1X 10 per gram of catalyst4Ml/hour. The composition of the reaction raw material gas and the reaction tail gas is analyzed on line by gas chromatography. The methanol conversion and product selectivity were calculated using the method of example 9.
The results of the measurements of examples 14 and 15 are shown in Table 2, and the results of the measurement of example 13 are shown for comparison.
Example 16:
weighing 0.5g of #4 catalyst sample, placing the sample into a glass reaction tube with the inner diameter of 8 mm, preheating to 150 ℃, and mixing the volume of 5 percent of methanol and O210％，N285% of the feed gas was preheated to 150 ℃ and passed through the reaction tube. The reaction system is at normal pressure. The gas space velocity is 1.1X 10 per gram of catalyst4Ml/hour. The composition of the reaction raw material gas and the reaction tail gas is analyzed on line by gas chromatography. Methanol conversion and product selectivity were calculated using the method of example 9
Example 17:
0.5g of a #4 catalyst sample was weighed and charged to an internal diameter of 8 mmPreheating to150 deg.C in a glass reaction tube to obtain a mixture containing 5% methanol and O21％，N294% of the feed gas was preheated to 150 ℃ and passed through the reaction tubes. The reaction system is at normal pressure. The gas space velocity is 1.1X 10 per gram of catalyst4Ml/hour. The composition of the reaction raw material gas and the reaction tail gas is analyzed on line by gas chromatography. Methanol conversion and product selectivity were calculated using the method of example 9
The results of the measurements of examples 16 and 17 are shown in Table 3, together with the results of the measurement of example 12, for comparison.
TABLE 1 catalyst activity and selectivity results determined in examples 9-15
| Practice of Example weaving Number (C) | Catalysis Agent weaving Number (C) | V2O5Comprises Amount/wt.% | Methanol converter Percent conversion% | Selectivity/%) | ||||
| Methylal | Formaldehyde (I) | Formic acid Methyl ester | Dimethyl ether | COx | ||||
| 9 | #1 | 10 | 23.9 | 63.7 | 31.2 | 4.7 | 0.4 | 0 |
| 10 | #2 | 20 | 30.0 | 64.2 | 23.0 | 12.5 | 0.3 | 0 |
| 11 | #3 | 5 | 36.7 | 92.2 | 0.0 | 3.6 | 4.3 | 0 |
| 12 | #4 | 10 | 44.4 | 90.6 | 1.0 | 8.2 | 0.2 | 0 |
| 13 | #5 | 20 | 49.1 | 85.3 | 1.2 | 13.0 | 0.5 | 0 |
TABLE 2 catalyst activity and selectivity results determined in examples 13, 14 and 15
| Practice of Example weaving Number (C) | Catalysis Agent weaving Number (C) | Measuring the temperature Degree/. degree.C | Methanol converter Percent conversion% | Selectivity/%) | ||||
| Methylal | Formaldehyde (I) | Formic acid Methyl ester | Dimethyl ether | COx | ||||
| 13 | #5 | 150 | 49.1 | 85.3 | 1.2 | 13.0 | 0.5 | 0 |
| 14 | #5 | 130 | 17.6 | 97.9 | 0.0 | 1.4 | 0.7 | 0 |
| 15 | #5 | 160 | 62.8 | 67.8 | 1.9 | 29.0 | 1.1 | 0.2 |
TABLE 3 catalyst activity and selectivity results determined in examples 12, 16 and 17
| Practice of Example weaving Number (C) | Catalysis Agent weaving Number (C) | Raw material gas O2/CH3OH Volume ratio of | Methanol converter Percent conversion% | Selectivity/%) | ||||
| Methylal | Formaldehyde (I) | Formic acid Methyl ester | Dimethyl ether | COx | ||||
| 12 | #4 | 1.2∶1 | 44.4 | 90.6 | 1.0 | 8.2 | 0.2 | 0 |
| 16 | #4 | 2∶1 | 50.5 | 84.2 | 1.9 | 13.6 | 0.2 | 0 |
| 17 | #4 | 1∶5 | 36.1 | 91.4 | 0.6 | 7.8 | 0.2 | 0 |
Claims (9)
1. A catalyst for producing methylal by selective oxidation of methanol is characterized in that: vanadium is loaded on acidic sulfur-containing modified titanium dioxide, wherein the sulfur content of the modified titanium dioxide is 1.0-4.5% by mass of sulfate radical, and the loading amount of the vanadium on the modified titanium dioxide is 5-20% by mass of vanadium pentoxide.
2. The catalyst of claim 1, wherein: the loading amount of the vanadium is 10-15% by mass of the vanadium pentoxide.
3. A process for producing a catalyst for producing methylal by selective oxidation of methanol according to claim 1, which comprises: mixing ammonium metavanadate and oxalic acid in a mass ratio of 1: 2, adding water to dissolve the mixture to obtain a dark green solution, adding metered acidic sulfur-containing modified titanium dioxide powder into the dark green solution, stirring the mixture into paste, drying and roasting the paste to obtain the catalyst for producing methylal by selective oxidation of methanol, wherein the modified titanium dioxide is loaded with 5 to 20 mass percent of vanadium calculated by the mass of vanadium pentoxide.
4. The process for producing a catalyst for producing methylal by selective oxidation of methanol according to claim 3, wherein: the mass of the addedwater is 3.75-17 times of the mass of the ammonium metavanadate.
5. The process for producing a catalyst for producing methylal by selective oxidation of methanol according to claim 3, wherein: the drying is carried out at the temperature of 100-120 ℃.
6. The process for producing a catalyst for producing methylal by selective oxidation of methanol according to claim 3, wherein: the roasting is carried out at 390-460 ℃ for 5-10 hours.
7. A process for producing methylal by using the catalyst for producing methylal by selective oxidation of methanol according to claim 1, characterized by comprising: the catalyst for producing methylal by selective oxidation of methanol is filled in a reactor and heated, the temperature of the reactor is controlled to be 130-160 ℃, mixed gas of methanol vapor and oxygen-containing gas preheated to 130-160 ℃ is introduced, and the mass ratio of the methanol vapor to the oxygen is 5: 1-5: 10, so that the methylal is obtained.
8. The method of claim 7, wherein: the oxygen-containing gas is pure O2Air or containing molecules O2Nitrogen or helium.
9. The process for producing methylal according to claim 7, wherein: the reactor used for producing the methylal can be a fixed bed gas-solid phase reactor or a fluidized bed gas-solid phase reactor.
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| CN101322943B (en) * | 2007-06-15 | 2010-12-22 | 南京大学 | Ti2O nano tube supported V2O5 composite catalyst |
| CN101396667B (en) * | 2007-09-28 | 2010-12-22 | 南京大学 | V2O5 composite catalyst loaded by Ce-V-Ti-O meso-material |
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