CN111589461A - Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol - Google Patents

Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol Download PDF

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CN111589461A
CN111589461A CN202010440901.8A CN202010440901A CN111589461A CN 111589461 A CN111589461 A CN 111589461A CN 202010440901 A CN202010440901 A CN 202010440901A CN 111589461 A CN111589461 A CN 111589461A
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catalyst
methyl formate
methanol
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CN111589461B (en
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孙予罕
王慧
曾高峰
吴平
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
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Shanghai Advanced Research Institute of CAS
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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Abstract

The invention discloses a preparation method and application of a V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol. The preparation method comprises the following steps: dissolving a vanadium source, a titanium source and a phosphorus source in deionized water to prepare a mixed solution; under the conditions of ice water bath and vigorous stirring, dripping an ammonia water solution into the mixed solution until the pH value is 7-11 to obtain serous fluid containing a tawny precipitate; aging the slurry at room temperature, and then washing with water to obtain a tan solid; dispersing the obtained solid in water containing n-butanol, stirring, filtering, drying the obtained solid, and calcining. The catalyst provided by the invention has the advantages of small particle size, large specific surface area, high porosity, uniform nano size, good sintering resistance, high methanol conversion rate, high methyl formate selectivity and longer service life at lower temperature, is easier to form in industrial reaction, and has better reaction performance than a V-Ti-S catalyst.

Description

Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol
Technical Field
The invention relates to a preparation method and application of a nano catalyst for preparing methyl formate by one-step oxidation of methanol.
Background
Methyl Formate (MF) is a chemically very important intermediate of carbon, and has wide application, and can be directly used as fumigant and bactericide for processing tobacco, dried fruit, grain, etc.; also commonly used as solvents for nitrocellulose, cellulose acetate; in medicine, it is commonly used as a raw material for synthesizing drugs such as sulfonic acid methylpyrimidine, sulfonic acid methoxypyrimidine, antitussive, and methaphen. The existing industrial production methods of methyl formate mainly comprise a methanol dehydrogenation method, a formic acid esterification method, a methanol liquid phase-carbonylation method, direct synthesis of methyl formate by synthesis gas and the like. The formic acid esterification method has high cost and serious corrosion to equipment; the methanol dehydrogenation method has low yield and poor product selectivity; the direct synthesis method of the synthesis gas has low efficiency and high equipment requirement; the methanol carbonylation process requires the use of relatively expensive anhydrous methanol and high concentrations of CO greater than 80%. The methyl formate prepared by one-step oxidation of methanol overcomes the defects of the method, can be developed into a green and economic method for preparing methyl formate, and has very wide application prospect. Catalyst S-V used for preparing methyl formate by one-step oxidation of methanol2O5/TiO2(VTS) has excellent reaction performance, but the catalyst has low specific surface area and low space velocity, so that the productivity is low, and the S component in the catalyst is easy to pollute the environment.
Chinese patent CN101327444A adopts V2O5/TiO2The catalyst is used for synthesizing methylal and methyl formate, but the preparation process of the catalyst is complicated. The catalyst has large particle size, poor reaction performance and low productivity.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior catalyst has the problem of low reaction performance caused by large particle size.
In order to solve the technical problem, the invention provides a preparation method of a V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol, which is characterized by comprising the following steps of:
step 1): dissolving a vanadium source, a titanium source and a phosphorus source in deionized water to prepare a mixed solution;
step 2): under the conditions of ice water bath and vigorous stirring, dripping an ammonia water solution into the mixed solution until the pH value is 7-11 to obtain serous fluid containing a tawny precipitate;
step 3): aging the slurry at room temperature, and then washing with water to obtain a tan solid;
step 4): dispersing the obtained solid in water containing n-butanol, stirring, filtering, and drying the obtained solid;
step 5): roasting the solid obtained in the step 4) to obtain the V-Ti-P nano catalyst.
Preferably, the vanadium source in the step 1) is VOPO4、NH4VO3And vanadyl acetylacetonate; the titanium source is tetrabutyl titanate, tetraethyl titanate and Ti3(PO4)4Any one or a mixture of several of them; the phosphorus source is H3PO4、H3PO3Or NaH2PO4Any one or a mixture of several of them.
Preferably, the mixed solution in the step 1) has a vanadium source mass concentration of 10-25%, a titanium source mass concentration of 60-80%, and a phosphorus source mass concentration of 5-25%.
Preferably, the mass concentration of the ammonia water solution in the step 2) is 28%.
Preferably, the aging time in the step 3) is 1-8 h.
Preferably, the stirring time in the step 4) is 1-12 h; the drying temperature is 40-120 ℃, and the drying time is 6-24 h.
Preferably, the roasting temperature in the step 5) is 300-600 ℃, and the roasting time is 2-10 h.
Preferably, the particle size of the V-Ti-P nano catalyst obtained in the step 5) is 10-20 nm.
The invention also provides application of the V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol, which is prepared by the preparation method, and is characterized in that the V-Ti-P nano catalyst is filled into a reactor, mixed gas of oxygen and nitrogen is firstly introduced at the speed of 10-100 mL/min, and the activation is carried out for 0.5-6 h at the temperature of 200-600 ℃; after activation, reducing the temperature of the reactor to 100-200 ℃, introducing methanol at the flow rate of 0.002-0.020mL/min, simultaneously introducing mixed gas of oxygen and nitrogen at the flow rate of 10-100 mL/min for the second time, and reacting at the pressure of 0.1-2.0 MPa and the space velocity of 600-60000 mL-g-1·h-1The reaction of methanol oxidation to methyl formate is carried out under the condition. The conversion rate of the methanol is 70-99%, the selectivity of the methyl formate is 85-99%, and the one-way service life of the catalyst is more than 1000 h.
Preferably, the volume ratio of oxygen to nitrogen in the mixed gas fed twice is 1: 9.
the catalyst provided by the invention has the advantages of small particle size, large specific surface area, high porosity, uniform nano size, good sintering resistance, high methanol conversion rate, high methyl formate selectivity and longer service life at lower temperature, is easier to form in industrial reaction, and has better reaction performance than a V-Ti-S catalyst. In the reaction for preparing methyl formate by oxidizing methanol, the space velocity is 600-60000 mL-g-1·h-1In the process, the conversion rate of the methanol is 70-99%, the selectivity of the methyl formate is 85-99.1%, and the one-way service life of the catalyst is more than 1000 h; at a space velocity of 12000mL g-1·h-1And at the reaction temperature of 140 ℃, the conversion rate of the methanol is 99 percent, and the selectivity of the methyl formate is 99.1 percent.
Drawings
FIG. 1 is a TEM spectrum of the product obtained in example 5;
fig. 2 is a TEM spectrum of the product obtained in comparative example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
(1) 1.17g vanadyl acetylacetonate, 9.36g tetrabutyl titanate and 1.17g H3PO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 7 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 1h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 1h, filtering, and drying the obtained solid at 40 ℃ for 6 h;
(5) and (4) roasting the solid obtained in the step (4) at 300 ℃ for 2h to obtain the V-Ti-P catalyst.
0.1g of the prepared catalyst was charged into a reactor, and 10% O was first introduced at a flow rate of 10mL/min2And 90% N2The mixed gas (volume percentage) is activated for 0.5h at 200 ℃. After activation, the reactor temperature was reduced to 100 ℃ and methanol was fed in at a flow rate of 0.002mL/min, while 10% O was fed in at a flow rate of 100mL/min2And 90% N2The pressure of the mixed gas (volume percent) is 0.1MPa, and the reaction space velocity is 60000mL g-1·h-1. The reaction properties are shown in Table 1.
Example 2
(1) 1.17g vanadyl acetylacetonate, 2.81g tetrabutyl titanate and 0.70g H3PO3Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 11 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 8h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 12h, filtering, and drying the obtained solid at 120 ℃ for 24 h;
(5) and (4) roasting the solid obtained in the step (4) at 600 ℃ for 10 hours to obtain the V-Ti-P catalyst.
1g of the prepared catalyst was charged into a reactor, and 10% O was first introduced at a rate of 100mL/min2And 90% N2The mixed gas (volume percentage) is activated for 6 hours at 600 ℃. After activation was complete, the reactor temperature was reduced to 180 ℃ and methanol was passed at a flow rate of 0.020mL/min and 10% O was passed at a flow rate of 10mL/min2And 90% N2The pressure of the mixed gas (volume percent) is 2.0MPa, and the reaction space velocity is 600mL g-1·h-1. The reaction properties are shown in Table 1.
Example 3
(1) 2g of vanadyl phosphate, 8g of titanium phosphate and 3.33g of NaH2PO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 10 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 6h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 6h, filtering, and drying the obtained solid at 100 ℃ for 12 h;
(5) and (4) roasting the solid obtained in the step (4) at 400 ℃ for 6 hours to obtain the V-Ti-P catalyst.
0.5g of the prepared catalyst was charged into a reactor, and 10% O was first introduced at a rate of 30mL/min2And 90% N2The mixed gas (volume percentage) is activated for 2 hours at 400 ℃. After activation, the reactor temperature was reduced to 135 ℃ and methanol was fed at a flow rate of 0.002mL/min, an oxygen-containing (20%) inert gas was fed at a flow rate of 16.6mL/min, the pressure was 0.5MPa, and the reaction space velocity was 2400mL · g-1·h-1. The reaction properties are shown in Table 1.
Example 4
(1) Dissolving 1.6g of ammonium vanadate, 8.53g of titanium phosphate and 0.53g of NaH2PO4 in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 9 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 4h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 3h, filtering, and drying the obtained solid at 120 ℃ for 10 h;
(5) and (4) roasting the solid obtained in the step (4) at 500 ℃ for 4h to obtain the V-Ti-P catalyst.
0.2g of the prepared catalyst was charged into the reactor, and 10% O was first introduced at a rate of 15mL/min2And 90% N2The mixed gas (volume percentage) is activated for 2 hours at 400 ℃. After activation was complete, the reactor temperature was lowered to 140 ℃ and methanol was fed at a flow rate of 0.004mL/min, while 10% O was fed at a flow rate of 8.8mL/min2And 90% N2The mixed gas (volume percentage) of (2), the pressure is 1.0MPa, and the reaction space velocity is 3000 mL. gg-1·h-1. The reaction properties are shown in Table 1.
Example 5
(1) 1.8g of ammonium vanadate, 7.2g of tetrabutyl titanate and 1.0g of NaH2PO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 9 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 6h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 5h, filtering, and drying the obtained solid at 80 ℃ for 18 h;
(5) and (3) roasting the solid obtained in the step (4) at 400 ℃ for 8h to obtain the V-Ti-P catalyst (shown in figure 1).
0.2g of the prepared catalyst was charged into the reactor, and 10% O was first introduced at a rate of 50mL/min2And 90% N2The mixed gas (volume percentage) is activated for 2 hours at 400 ℃. After activation, the reactor temperature was lowered to 140 ℃ and methanol was fed in at a flow rate of 0.002mL/min, while methanol was fed in at a flow rate of 33.2mL/min10％O2And 90% N2The working pressure of the mixed gas (volume percentage) is 1.0MPa, and the reaction space velocity is 12000mL g-1·h-1. The reaction properties are shown in Table 1.
Example 6
(1) 1.4g vanadyl acetylacetonate, 6.25g titanium phosphate and 2.35g 2.35g H3PO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 10 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 7h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 6h, filtering, and drying the obtained solid at 90 ℃ for 12 h;
(5) and (4) roasting the solid obtained in the step (4) at 500 ℃ for 5 hours to obtain the V-Ti-P catalyst.
0.3g of the prepared catalyst was charged into the reactor, and 10% O was first introduced at a rate of 20mL/min2And 90% N2The mixed gas (volume percentage) is activated for 2 hours at 350 ℃. After activation was complete, the reactor temperature was lowered to 150 ℃ and methanol was fed in at a flow rate of 0.005mL/min while 10% O was fed in at a flow rate of 24.9mL/min2And 90% N2The working pressure of the mixed gas (volume percentage) is 1.0MPa, and the reaction space velocity is 8000mL g-1·h-1. The reaction properties are shown in Table 1.
Example 7
(1) 2.0g of ammonium vanadate, 7.0g of tetraethyl titanate and 1.0g of 1.0g H3PO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 9 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 3h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 8 hours, filtering, and drying the obtained solid at 100 ℃ for 10 hours;
(5) and (4) roasting the solid obtained in the step (4) at 600 ℃ for 3h to obtain the V-Ti-P catalyst.
0.1g of the prepared catalyst was charged into a reactor, and 10% O was first introduced at a rate of 30mL/min2And 90% N2The mixed gas (volume percentage) of (2) was activated at 300 ℃ for 2 hours. After activation was complete, the reactor temperature was lowered to 140 ℃ and methanol was fed at a flow rate of 0.002mL/min while 10% O was fed at a flow rate of 33.2mL/min2And 90% N2The working pressure of the mixed gas (volume percentage) is 1.0MPa, and the reaction space velocity is 24000mL g-1·h-1。
The catalyst has stable service life, can stably run for more than 1000h, and has reaction stability shown in Table 2.
Comparative example 1
(1) 1.5g vanadyl sulfate, 8.0g titanium sulfate and 1.5g H g2SO4Dissolving in 340mL of deionized water to prepare a mixed solution A;
(2) dropping 28 wt% aqueous ammonia solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is 10 to obtain slurry containing yellow brown precipitate;
(3) aging the yellow brown slurry at room temperature for 6h, and washing with water to obtain a yellow brown solid B;
(4) dissolving the obtained solid B in a solution of 15mL of water and 35mL of n-butanol, stirring for 8h, filtering, and drying the obtained solid at 100 ℃ for 12 h;
(5) the solid obtained in step 4 was calcined at 500 ℃ for 4 hours to obtain a V-Ti-S catalyst (see FIG. 2, which had a larger particle size than the product obtained in example 5).
1g of the prepared catalyst was charged into a fixed bed reactor, and 10% O was first introduced at a rate of 30mL/min2And 90% N2The mixed gas (volume percentage) of (2) was activated at 300 ℃ for 2 hours. After activation was complete, the reactor temperature was lowered to 140 ℃ and methanol was passed through at a flow rate of 0.002mL/min while simultaneously maintaining 16.6
10% O was introduced at a flow rate of mL/min2And 90% N2The working pressure of the mixed gas (volume percentage) is 0.1MPa, and the reaction space velocity is 1200mL g-1·h-1. The reaction properties are shown in Table 1.
TABLE 1 Performance of the catalyst for the oxidation of methanol to methyl formate
Figure BDA0002504097580000071
TABLE 2 evaluation of the lifetime of the catalyst for the preparation of methyl formate by the oxidation of methanol
Figure BDA0002504097580000072
Figure BDA0002504097580000081

Claims (10)

1. A preparation method of a V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol is characterized by comprising the following steps:
step 1): dissolving a vanadium source, a titanium source and a phosphorus source in deionized water to prepare a mixed solution;
step 2): under the conditions of ice water bath and vigorous stirring, dripping an ammonia water solution into the mixed solution until the pH value is 7-11 to obtain serous fluid containing a tawny precipitate;
step 3): aging the slurry at room temperature, and then washing with water to obtain a tan solid;
step 4): dispersing the obtained solid in water containing n-butanol, stirring, filtering, and drying the obtained solid;
step 5): roasting the solid obtained in the step 4) to obtain the V-Ti-P nano catalyst.
2. The method according to claim 1, wherein the vanadium source in step 1) is VOPO4、NH4VO3And vanadyl acetylacetonate; the titanium source is tetrabutyl titanate, tetraethyl titanate and Ti3(PO4)4Any one or a mixture of several of them; the phosphorus source is H3PO4、H3PO3Or NaH2PO4Any one or a mixture of several of them.
3. The method according to claim 1, wherein the mixed solution in step 1) contains 10 to 25 mass% of a vanadium source, 60 to 80 mass% of a titanium source, and 5 to 25 mass% of a phosphorus source.
4. The method according to claim 1, wherein the ammonia aqueous solution in step 2) has a mass concentration of 28%.
5. The method according to claim 1, wherein the aging time in step 3) is 1 to 8 hours.
6. The preparation method according to claim 1, wherein the stirring time in the step 4) is 1-12 h; the drying temperature is 40-120 ℃, and the drying time is 6-24 h.
7. The preparation method according to claim 1, wherein the roasting temperature in the step 5) is 300-600 ℃, and the roasting time is 2-10 h.
8. The preparation method of claim 1, wherein the particle size of the V-Ti-P nano catalyst obtained in the step 5) is 10-20 nm.
9. The application of the V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol prepared by the preparation method of any one of claims 1 to 8 is characterized in that the V-Ti-P nano catalyst is filled into a reactor, mixed gas of oxygen and nitrogen is firstly introduced at the speed of 10-100 mL/min, and the activation is carried out for 0.5-6 h at the temperature of 200-600 ℃; after activation, the temperature of the reactor is reduced to 100-200 ℃, methanol is introduced at the flow rate of 0.002-0.020mL/min, and simultaneouslyIntroducing mixed gas of oxygen and nitrogen for the second time at the flow rate of 10-100 mL/min, and reacting at the space velocity of 600-60000 mL-g at the pressure of 0.1-2.0 MPa and the reaction space velocity of 600-60000 mL-g-1·h-1The reaction of methanol oxidation to methyl formate is carried out under the condition.
10. The use of claim 9, wherein the volume ratio of oxygen to nitrogen in the mixed gas introduced twice is 1: 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112536048A (en) * 2020-12-10 2021-03-23 上海簇睿低碳能源技术有限公司 Nano catalyst for preparing methylal through methanol oxidation, preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877330A (en) * 1995-06-08 1999-03-02 Nippon Shokubai Co., Ltd. Vanadium-containing catalysts, process for manufacturing and use of the same
CN101721991A (en) * 2008-10-31 2010-06-09 南京大学 Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal
US20130072716A1 (en) * 2011-09-16 2013-03-21 Eastman Chemical Company PROCESS FOR PREPARING MODIFIED V-Ti-P CATALYSTS FOR SYNTHESIS OF 2,3-UNSATURATED CARBOXYLIC ACIDS
US20130072715A1 (en) * 2011-09-16 2013-03-21 Eastman Chemical Company PROCESS FOR PREPARING V-Ti-P CATALYSTS FOR SYNTHESIS OF 2,3-UNSATURATED CARBOXYLIC ACIDS
CN104511275A (en) * 2013-09-26 2015-04-15 中国科学院上海高等研究院 Oxide catalyst for preparing methyl formate through oxidizing methanol, preparation method and applications thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877330A (en) * 1995-06-08 1999-03-02 Nippon Shokubai Co., Ltd. Vanadium-containing catalysts, process for manufacturing and use of the same
CN101721991A (en) * 2008-10-31 2010-06-09 南京大学 Method for preparing V-Ti-Si-O composite catalyst used in methanol oxidation for synthesizing methylal
US20130072716A1 (en) * 2011-09-16 2013-03-21 Eastman Chemical Company PROCESS FOR PREPARING MODIFIED V-Ti-P CATALYSTS FOR SYNTHESIS OF 2,3-UNSATURATED CARBOXYLIC ACIDS
US20130072715A1 (en) * 2011-09-16 2013-03-21 Eastman Chemical Company PROCESS FOR PREPARING V-Ti-P CATALYSTS FOR SYNTHESIS OF 2,3-UNSATURATED CARBOXYLIC ACIDS
CN103781545A (en) * 2011-09-16 2014-05-07 伊士曼化工公司 Process for preparing modified V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
CN103781546A (en) * 2011-09-16 2014-05-07 伊士曼化工公司 Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
CN104511275A (en) * 2013-09-26 2015-04-15 中国科学院上海高等研究院 Oxide catalyst for preparing methyl formate through oxidizing methanol, preparation method and applications thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112536048A (en) * 2020-12-10 2021-03-23 上海簇睿低碳能源技术有限公司 Nano catalyst for preparing methylal through methanol oxidation, preparation method and application
CN112536048B (en) * 2020-12-10 2023-05-23 上海簇睿低碳能源技术有限公司 Nanometer catalyst for preparing methylal by oxidizing methanol, preparation method and application

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