CN109721481B - Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere - Google Patents
Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere Download PDFInfo
- Publication number
- CN109721481B CN109721481B CN201711048565.7A CN201711048565A CN109721481B CN 109721481 B CN109721481 B CN 109721481B CN 201711048565 A CN201711048565 A CN 201711048565A CN 109721481 B CN109721481 B CN 109721481B
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- branched
- valence
- general formula
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for increasing the selectivity of an effective product by adding carbon dioxide in an oxidizing atmosphere, which comprises the steps of mixing a branched aromatic hydrocarbon compound or/and a branched heterocyclic compound with a gas containing oxygen and carbon dioxide, and carrying out the oxidation under the action of a catalyst. Catalysts which can be used in the process according to the invention are those of the general formulae (I), (II), (III), (IV), (V), (VI) below: moaRbMcOd（I），Aga1Vb1Moc1M1d1Oe1（II），Aga2Vb2Nic2M2d2Oe2（III），Aga3Vb3Sic3M3d3Oe3（Ⅳ），Wa4Xb4Yc4Od4（Ⅴ），Wa5X'b5Y'c5Od5（Ⅵ）。
Description
Technical Field
The invention relates to a method for improving product selectivity by adding carbon dioxide in an oxidizing atmosphere. More particularly, the invention relates to a method for inhibiting the formation of deep oxidation products during the oxidation of aromatic compounds or branched heterocyclic compounds by the addition of carbon dioxide.
Background
The structure is generally considered to be quite stable, in which a carbon atom in carbon dioxide is bonded to an oxygen atom by an sp hybridized orbital, two sp hybridized orbitals of a C atom generate two sigma bonds with two O atoms, respectively, two p orbitals which do not participate in hybridization on the C atom are at right angles to the sp hybridized orbitals, and overlap with the p orbitals of the oxygen atoms from the side in a side-by-side manner, respectively. Besides participating in photosynthesis, carbon dioxide, as a chemical raw material, has only been industrially applied in a few processes such as synthesis of urea and salicylic acid. Since the last 70-80 years, carbon dioxide has been continuously concerned by academia and industry in the aspects of dry reforming of methane, oxidative dehydrogenation, synthesis of dimethyl carbonate, liquid-phase oxidation of aromatic hydrocarbon and the like. For example, Park discovered that during the liquid phase oxidation of p-xylene oxygen to terephthalic acid, CO was added2Not only can promote the conversion of p-xylene, but also can improve the selectivity of terephthalic acid, p-toluic acid and terephthalaldehyde by a plurality of carbonate species formed in the reaction process, thereby reducing the yield of other byproducts (D.R. Burri, K. -W. Jun, J.S. Yoo, C.W. Lee and S. -E.park, Catalysis Letters, "Combined Catalysisl Effect of CO2 and Ni on Co/Mn/Br Catalyst in the Liquid-Phase Oxidation of pXylene "81 volume 2002 169-. Park also observed that p-toluic acid, CO, in the presence of Co/Mn/Br catalyst2/O2The liquid phase oxidation conversion rate and the selectivity of the terephthalic acid under the atmosphere are both superior to N2/O2Atmosphere (S. -E. Park and J.S. Yoo, in stud. surf. Sci. Cat., ed. J. -S.Chang, S. -E.park and K. -W. Lee, Elsevier, Amsterdam, 2004, 153 volume 303-。
The branched aromatic compound or the branched heterocyclic compound can be oxidized to generate alcohol, aldehyde, ketone and acid under the action of molecular oxygen and a catalyst, and can also be deeply oxidized to generate carbon monoxide and carbon dioxide. For example, Eastman in US4017547 generates terephthalaldehyde by air oxidation of p-xylene, and the catalyst is selected from tungsten oxide or a mixture of silicotungstic acid and aluminum oxide and bismuth oxide, and the conversion rate of p-xylene and the yield of terephthalaldehyde can reach 41 percent and 54 percent. In US6458737 patent by Nippon company, alumina-supported oxides of antimony, iron and tungsten are used as catalysts, air oxidation is adopted, and when the reaction temperature is 550-580 ℃, the conversion rate of p-xylene is 90.9%, and the yield of terephthalaldehyde is 62.6%. The process for producing Terephthalaldehyde (TPAL) by a direct oxidation method is developed in US7429682 by LG chemical company, and adopts tungsten-containing metal composite oxide as a catalyst, wherein the conversion rate of p-xylene is 70-78% and the selectivity of terephthalaldehyde is 70-80% under the conditions of a multitubular fixed bed reactor with a tube-shell structure and atmospheric air oxidation at 550-600 ℃.
How to further improve the selectivity of the target product and reduce the carbon oxides (including CO and CO)2) The formation of (2) can be started from two aspects of catalyst and process.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and found that the oxidation of a branched aromatic compound or a branched heterocyclic compound to alcohols, aldehydes, ketones and acids can be further improved by supplementing carbon dioxide in an oxygen-containing reaction atmosphere, thereby completing the present invention.
Specifically, the present invention oxidatively converts a branched aromatic compound or a branched heterocyclic compound into an alcohol, an aldehyde, a ketone and an acid with high efficiency by supplementing carbon dioxide in a reaction atmosphere.
The invention provides a method for oxidizing hydrocarbons, which comprises the steps of mixing a branched aromatic hydrocarbon compound or/and a branched heterocyclic compound with a gas containing oxygen and carbon dioxide, and oxidizing the mixture to generate alcohol, aldehyde, ketone and/or acid under the action of a catalyst. According to the method, the carbon dioxide is added into the oxidizing atmosphere to carry out oxidation, so that the selectivity of an effective product can be improved, and the selectivity of byproducts such as COx and the like can be reduced.
In one embodiment, the branched aromatic hydrocarbon compound refers to a compound in which two or more hydrogens on the aromatic ring are substituted with two or more C1 to C12 chain alkyl groups, preferably C1 to C6 alkanes, such as methane, ethane, propane, n-butane, isobutane, tert-butane, n-pentane, isopentane, n-hexane, and the like, more preferably toluene, p-xylene, o-xylene, m-xylene, mesitylene, pseudocumene, and durene.
In one embodiment, the branched heterocyclic compound chain refers to a compound in which two or more hydrogens on the heterocyclic ring are substituted with two or more C1 to C12 alkyl groups, preferably C1 to C6 alkanes, such as alkyl compounds such as methane, ethane, propane, n-butane, isobutane, tert-butane, n-pentane, isopentane, n-hexane, and the like, more preferably picoline, lutidine, collidine.
The heterocyclic compound refers to a compound in which one or more carbons of a cyclic carbon compound are substituted by oxygen, nitrogen, or sulfur, and may be, for example, a compound such as pyridine or thiophene.
In one embodiment, the branched aromatic hydrocarbon compound or/and branched heterocyclic compound is mixed with a gas comprising oxygen and carbon dioxide, and the concentration of the branched aromatic hydrocarbon compound or/and branched heterocyclic compound in the gas is about 10 to about 110gm-3。
In one embodiment, the reaction is carried out using a gas space velocity of from about 1000 to about 50000h-1(ii) a The pressure is from atmospheric pressure to about 5MPa, for example from about 0.1 to about 5 MPa. In one embodiment, the reaction is externally heated, preferably with a molten salt in a salt temperature range of about 300 to about 550 ℃.
In one embodiment, the gas comprising oxygen and carbon dioxide comprises CO2/O2Is about 10: about 1 to about 0.5: about 1. The molar ratio is preferably not higher than about 8; and/or the molar ratio is preferably not less than about 1, and still more preferably not less than about 2.
In one embodiment, the gas comprising oxygen and carbon dioxide comprises CO2/O2Is about 8: about 1 to about 0.5: about 1, and at least one selected from the group consisting of nitrogen, helium and argon may be used as a make-up gas, the molar ratio of make-up gas to carbon dioxide being about 0: about 1 to about 15: about 1.
In one embodiment, the catalyst has one of the following general formulae (I), (II), (III), (iv), (v), (vi):
MoaRbMcOd（I）
wherein b/a = about 0.02 to about 1.5, c/a = about 0.05 to about 6, d is a value required to satisfy the valence of an element other than oxygen atoms In the general formula (I), R is a rare earth element selected from at least one of La, Ce and Nd, M is an additive and at least one element selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi, Si;
Aga1Vb1Moc1M1d1Oe1（II）
wherein b1/a1= about 1.0 to about 2.5, c1/a1= about 0.05 to about 1.1, d1/a1= about 0.01 to about 0.58, e1 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M1 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Sb, Bi, La, Ce, Pb;
Aga2Vb2Nic2M2d2Oe2（III）
wherein b2/a2= about 1.0 to about 2.5, c2/a2= about 0.05 to about 1.2, d2/a2= about 0.01 to about 0.58, e2 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M2 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi, La, Ce, Nd;
Aga3Vb3Sic3M3d3Oe3（Ⅳ）
wherein b3/a3= about 1.0 to about 2.5, c3/a3= about 0.05 to about 0.8, d3/a3= about 0.01 to about 0.58, e3 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M3 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Sb, Bi, La, Ce, Nd, Mo;
Wa4Xb4Yc4Od4（Ⅴ）
wherein B4/a4= about 0.1 to about 1.3, c4/a4= about 0.05 to about 0.8, d4 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), W is tungsten, X is selected from P, Sb, Bi and Si, Y is at least one metal selected from Fe, Co, Ni, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Tl, Sn, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs;
Wa5X'b5Y'c5Od5（Ⅵ）
wherein B5/a5= about 0.1 to about 1.3, c5/a5= about 0.05 to about 1.2, d5 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), W is tungsten, X 'is selected from Li, Na, K, Rb and Cs, and Y' is at least one metal selected from Fe, Co, Ni, Cu, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Sn, Mg, Ca, Sr and Ba.
The invention has the obvious technical characteristics that the conversion rate of the aromatic compound with the branched chain or the heterocyclic compound with the branched chain can be effectively improved by adding carbon dioxide in the reaction atmosphere, and the selectivity of the oxidation to alcohol, aldehyde, ketone and acid can be effectively improved.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
10.0g of ammonium molybdate heptahydrate was dissolved in 100ml of water to prepare a molybdenum solution, and 0.5mol L of Mo, La, Mn and Mo were added in a mass ratio of 1.0:0.1:0.19-1Aqueous lanthanum nitrate solution and 0.1mol L-1Mixing the manganese nitrate solution, adding 28% ammonia water solution to adjust pH =13, adding monoethanolamine according to the mass ratio of 70:1 of ammonia water to monoethanolamine, precipitating, crystallizing at 130 ℃, filtering, roasting at 500 ℃ for 3 hours to obtain Mo1La0.1Mn0.19Ox catalyst, measured to have a surface area of 4m2g-1. In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the para-xylene concentration was 55gm-3，N2/CO2/O2The molar ratio is 0/4/1, the gas space velocity is 40000h-1Under normal pressure, the conversion rate of p-xylene is 14.8%, the selectivity of effective products is 99.9%, and the selectivity of COx is 0.1%.
Comparative example 1
The catalyst of example 1 was used. In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the para-xylene concentration was 55gm-3The space velocity of air gas is 40000h-1Under normal pressure, the conversion rate of p-xylene is 12.4%, the selectivity of effective products is 99.6%, and the selectivity of COx is 0.4%.
Example 2
Dissolving 10.0g of ammonium molybdate heptahydrate in 20 mass percent of hydrogen peroxide and 5 mass percent of salicylic acid solution to prepareAdding 0.5mol L of molybdenum solution according to the mass ratio of Mo, La and Cd being 1.0:0.2:0.07-1Aqueous lanthanum nitrate solution and 0.1mol L-1Adding 28% ammonia water solution to adjust pH =13 after fully mixing, adding triethanolamine according to the mass ratio of 40:1 of ammonia water to triethanolamine, precipitating, crystallizing at 130 ℃, filtering, roasting at 550 ℃ for 3 hours to obtain Mo1La0.2Cd0.07Ox catalyst, measured as a surface area of 3m2g-1。
In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the mesitylene concentration was 40gm-3，N2/CO2/O2The molar ratio is 1/4/1, the gas space velocity is 40000h-1Under the condition of normal pressure, the conversion rate of the mesitylene is 13.2 percent, the selectivity of the effective product is 98.7 percent, and the selectivity of the COx is 1.3 percent.
Comparative example 2
The catalyst of example 2 was used. In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the mesitylene concentration was 40gm-3The air space velocity is 40000h-1Under normal pressure, the conversion rate of mesitylene is 10.1%, the selectivity of effective products is 97.6%, and the selectivity of COx is 2.4%.
Example 3
Dissolving 10.0g of ammonium metavanadate in 10 mass percent of hydrogen peroxide and 5 mass percent of citric acid solution to prepare a vanadium solution, and adding 0.5mol L of the vanadium solution according to the mass ratio of V to Ag to Ni to W of 1.8 to 1.0 to 0.7 to 0.14-1Silver nitrate aqueous solution, 0.4 mol L-1And 0.1mol L of aqueous nickel nitrate solution-1Mixing the ammonium metatungstate solution, adding 28% ammonia water solution to adjust pH =13, adding cyclohexylamine according to the mass ratio of 50:1 of ammonia water to ethanolamine, precipitating, crystallizing at 130 ℃, filtering, and roasting at 530 ℃ for 3 hours to obtain Ag1V1.8Ni0.7W0.14Ox catalyst, measured as a surface area of 3m2g-1. In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the para-xylene concentration was 55gm-3，N2/CO2/O2The molar ratio is 1/5/1, gas airThe speed is 43000h-1Under normal pressure, the conversion rate of p-xylene is 15.1%, the selectivity of p-benzene dicarbaldehyde and p-tolualdehyde is 99.8%, and the selectivity of COx is 0.2%.
Comparative example 3
The catalyst of example 3 was used. In a 28mm diameter tubular reactor, the salt temperature was 430 ℃ and the para-xylene concentration was 55gm-3The space velocity of air gas is 43000h-1Under normal pressure, the conversion rate of p-xylene is 12.8%, the selectivity of effective products is 99.3%, and the selectivity of COx is 0.7%.
Example 4
Dissolving 10.0g of ammonium metavanadate in 20 mass percent of hydrogen peroxide and 5 mass percent of citric acid solution to prepare a vanadium solution, and adding 0.5mol L of the vanadium solution according to the mass ratio of V to Ag to Ni to Ru of 1.3:1.0:0.4:0.21-1Silver nitrate aqueous solution, 0.4 mol L-1Nickel acetate and 0.1mol L-1Mixing the ruthenium chloride solution, adding 28% ammonia water solution to adjust the pH to be =13, adding cyclohexylamine according to the mass ratio of 45:1 of ammonia water to ethanolamine, precipitating, crystallizing at 130 ℃, filtering, roasting at 550 ℃ for 3 hours to obtain Ag1V1.3Ni0.4Ru0.21OxCatalyst, surface area of the catalyst measured 7m2g-1The dispersion of vanadium was 17%. In a tubular reactor with a diameter of 30mm, the salt temperature was 435 ℃ and the o-xylene concentration was 40gm-3，N2/CO2/O2The molar ratio is 1/8/1, and the gas space velocity is 42000h-1Under normal pressure, the conversion rate of o-xylene is 13.2%, the selectivity of effective products is 99.8%, and the selectivity of COx is 0.2%.
Comparative example 4
The catalyst of example 4 was used. In a tubular reactor with a diameter of 30mm, the salt temperature is 435 ℃, and the concentration of o-xylene is 40gm-3The air space velocity is 42000h-1Under normal pressure, the conversion rate of o-xylene is 10.1%, the selectivity of effective products is 99.4%, and the selectivity of COx is 0.6%.
Example 5
10.0g of ammonium metavanadate is dissolved in the mass fractionAdding 10% oxalic acid solution to obtain vanadium solution, adding 0.5mol L according to the weight ratio of V: Ag: Mo: Cr of 1.8:1.0:1.0:0.11-1Silver nitrate aqueous solution, 0.4 mol L-1And 0.1mol L of an aqueous solution of ammonium molybdate heptahydrate-1Mixing the chromium nitrate solution, adding 28% ammonia water solution to adjust pH =13, crystallizing the precipitate at 130 deg.C, filtering, and calcining at 530 deg.C for 3 hr to obtain Ag1V1.8Mo1Cr0.11Ox catalyst, measured as a surface area of 3m2g-1. In a tubular reactor with a diameter of 30mm, the salt temperature is 435 ℃, and the concentration of 2, 5-lutidine is 40gm-3，N2/CO2/O2The molar ratio is 1/6/1, and the gas space velocity is 42000h-1Under normal pressure, the conversion rate of the o-2, 5-dimethylpyridine is 17.3%, the selectivity of the effective product is 97.4%, and the selectivity of the COx is 2.6%.
Comparative example 5
The catalyst of example 5 was used. In a tubular reactor with a diameter of 30mm, the salt temperature was 435 ℃ and the 2, 5-lutidine concentration was 40gm-3The air space velocity is 42000h-1Under normal pressure, the conversion rate of the o-2, 5-dimethylpyridine is 13.1%, the selectivity of the effective product is 95.4%, and the selectivity of the COx is 4.6%.
Example 6
Dissolving 10.0g of ammonium metavanadate in 20 mass percent hydrogen peroxide and 5 mass percent ethylenediamine solution to prepare a vanadium solution, and adding 0.5mol L of the solution according to the mass ratio of V to Ag to Si to La to Bi of 1.2:1.0:1.0:0.18:0.08-1Silver nitrate aqueous solution and SiO with the mass fraction of 10%2Hydrosol, 0.1mol L-1And 0.1mol L of lanthanum nitrate-1After the basic bismuth nitrate aqueous solution is fully mixed, adding 28% ammonia water solution to adjust the pH to be =13, wherein the mass ratio of ammonia water to N-methylformamide is 55: 1, adding N-methylformamide, crystallizing at 130 deg.C, filtering, and calcining at 450 deg.C for 3 hr to obtain Ag1V1.2Si1La0.18Bi0.08OxCatalyst having a measured surface area of 13m2g-1. In a row with a diameter of 30mmIn the tube reactor, the salt temperature was 435 ℃ and the concentration of 2, 5-lutidine was 40gm-3，N2/CO2/O2The gas space velocity is 42000h with the molar ratio of 1/5/1-1Under normal pressure, the conversion rate of 2, 5-lutidine is 16.3%, the selectivity of effective product is 98.6%, and the selectivity of COx is 1.4%.
Comparative example 6
The catalyst of example 6 was used. In a tubular reactor with a diameter of 30mm, the salt temperature was 435 ℃ and the 2, 5-lutidine concentration was 40gm-3The air space velocity is 42000h-1Under normal pressure, the conversion rate of 2, 5-lutidine is 12.8%, the selectivity of effective product is 96.8%, and the selectivity of COx is 3.2%.
Claims (8)
1. A process for oxidizing hydrocarbons, comprising mixing a branched aromatic hydrocarbon compound or/and a branched heterocyclic compound with a gas containing oxygen and carbon dioxide, and carrying out the oxidation under the action of a catalyst;
wherein the branched aromatic compound is toluene, p-xylene, o-xylene, m-xylene, mesitylene, pseudomesitylene or durene;
the branched heterocyclic compound chain is picoline, lutidine, or collidine; and
the catalyst is one or more of the following general formulas (I), (II), (III), (IV), (V), (VI):
MoaRbMcOd（I）
wherein b/a = 0.02-1.5, c/a = 0.05-6, d is a numerical value required for satisfying the valence of an element except oxygen atoms In the general formula (I), R is at least one rare earth element selected from La, Ce and Nd, M is an auxiliary agent and at least one element selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi and Si;
Aga1Vb1Moc1M1d1Oe1（II）
wherein b1/a1=1.0 to 2.5, c1/a1=0.05 to 1.1, d1/a1=0.01 to 0.58, e1 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M1 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi, La, Ce, Nd;
Aga2Vb2Nic2M2d2Oe2（III）
wherein b2/a2= 1.0-2.5, c2/a2= 0.05-1.2, d2/a2= 0.01-0.58, e2 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M2 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi, La, Ce, Nd;
Aga3Vb3Sic3M3d3Oe3（Ⅳ）
wherein b3/a3= 1.0-2.5, c3/a3= 0.05-0.8, d3/a3= 0.01-0.58, e3 is a value required to satisfy the valence of an element other than an oxygen atom In the general formula (I), M3 is an auxiliary agent and at least one metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Nb, Cr, W, Mn, Re, Fe, Ru, Co, Ni, Pd, Pt, Cu, Au, Zn, Cd, Al, Ga, In, Sn, Pb, Sb, Bi, Ce, Nd, and Mo;
Wa4Xb4Yc4Od4（Ⅴ）
wherein B4/a4=0.1 to 1.3, c4/a4=0.05 to 0.8, d4 is a numerical value required for satisfying the valence of an element except for an oxygen atom in the general formula (I), W is tungsten, X is selected from P, Sb, Bi and Si, Y is at least one metal selected from Fe, Co, Ni, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Tl, Sn, Mg, Ca, Sr, Ba, Li, Na, K, Rb and Cs;
Wa5X'b5Y'c5Od5（Ⅵ）
wherein B5/a5= 0.1-1.3, c5/a5= 0.05-1.2, d5 is a numerical value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), W is tungsten, X 'is selected from Li, Na, K, Rb and Cs, and Y' is at least one metal selected from Fe, Co, Ni, Cu, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Sn, Mg, Ca, Sr and Ba.
2. The method according to claim 1, wherein the branched aromatic hydrocarbon compound or/and the branched heterocyclic compound is mixed with a gas containing oxygen and carbon dioxide, and the concentration of the branched aromatic hydrocarbon compound or/and the branched heterocyclic compound in the gas is 10 to 110gm-3。
3. The method as claimed in claim 1, characterized in that the gas space velocity used for the reaction is 1000-50000h-1The pressure is normal pressure to 5 MPa.
4. Method according to claim 1, characterized in that the gas containing oxygen and carbon dioxide comprises CO2/O2In a molar ratio of 10: 1-0.5: 1.
5. process according to claim 4, characterized in that the gas containing oxygen and carbon dioxide comprises CO2/O2Is not higher than 8.
6. Process according to claim 4, characterized in that the gas containing oxygen and carbon dioxide comprises CO2/O2Is not less than 1.
7. Process according to claim 4, characterized in that the gas containing oxygen and carbon dioxide comprises CO2/O2Is not less than 2.
8. The method according to any one of claims 4 to 7, wherein at least one selected from the group consisting of nitrogen, helium and argon is further used as a make-up gas, and the molar ratio of the make-up gas to carbon dioxide is 0: 1-15: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711048565.7A CN109721481B (en) | 2017-10-31 | 2017-10-31 | Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711048565.7A CN109721481B (en) | 2017-10-31 | 2017-10-31 | Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109721481A CN109721481A (en) | 2019-05-07 |
| CN109721481B true CN109721481B (en) | 2022-06-14 |
Family
ID=66293237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711048565.7A Active CN109721481B (en) | 2017-10-31 | 2017-10-31 | Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109721481B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491745A (en) * | 2002-10-01 | 2004-04-28 | ��������ķ������ | Mo-V-M-Nb-X oxide catalyst for selective hydrocarbon oxidation synthesied by water heat |
-
2017
- 2017-10-31 CN CN201711048565.7A patent/CN109721481B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491745A (en) * | 2002-10-01 | 2004-04-28 | ��������ķ������ | Mo-V-M-Nb-X oxide catalyst for selective hydrocarbon oxidation synthesied by water heat |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109721481A (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4809531B2 (en) | Catalytic oxidation of alkanes to the corresponding acids | |
| JP4346822B2 (en) | Molybdenum-vanadium catalyst for the low temperature selective oxidation of propylene, its production and use | |
| US4035418A (en) | Process for producing unsaturated aldehydes and unsaturated carboxylic acids | |
| KR102121079B1 (en) | Process for making ethylene and acetic acid | |
| MXPA02005875A (en) | Hydrothermally synthesized mo-v-m-x oxide catalysts for the selective oxidation of hydrocarbons. | |
| US4111985A (en) | Process for producing unsaturated aldehydes and unsaturated carboxylic acids | |
| JP4346823B2 (en) | Catalyst for oxidation of ethane to acetic acid | |
| JP2000037625A (en) | Catalyst for oxidative dehydrogenation of lower alkanoic acid and production of olefin | |
| JP5982214B2 (en) | Method for producing oxidation product | |
| JP4182237B2 (en) | Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same | |
| CN109721481B (en) | Method for improving selectivity of effective product by adding carbon dioxide in oxidizing atmosphere | |
| JP2010260793A (en) | Catalyst for oxidative dehydrogenation of alkane, method for producing the catalyst, and method for producing unsaturated hydrocarbon compound and/or oxygen-containing hydrocarbon compound with the catalyst, or method for producing unsaturated acid | |
| EP1276561B1 (en) | Catalysts for the oxidation of lower olefins to unsaturated aldehydes; methods of making and using the same | |
| JP4809532B2 (en) | Catalyst for catalytic oxidation of propane to acrylic acid, its production and use | |
| JP2558036B2 (en) | Method for producing methacrolein and / or methacrylic acid | |
| JP4331433B2 (en) | Catalyst for oxidizing unsaturated aldehydes to produce carboxylic acids, methods for making and using the same | |
| JPH0222243A (en) | Production of methacrylic acid | |
| US4113769A (en) | Process for preparing unsaturated carboxylic acids by gas phase catalytic oxidation of the corresponding aldehydes | |
| CN110963897A (en) | Method for improving selectivity of effective product by adding water vapor in oxidizing atmosphere | |
| CN109721476B (en) | Method for changing selectivity of oxidation products through reaction pressure | |
| JP3913074B2 (en) | Catalyst for oxidation of alkylbenzenes and method for producing aromatic aldehyde | |
| JP3728762B2 (en) | Nitrile production method | |
| CN110963896B (en) | Method for producing aromatic aldehyde ketone through gas phase oxidation reaction | |
| JP3859397B2 (en) | Catalyst for production of methacrolein and methacrylic acid | |
| JPH07215925A (en) | Production of nitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |