CN111589461B - Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by methanol oxidation - Google Patents

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

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CN111589461B
CN111589461B CN202010440901.8A CN202010440901A CN111589461B CN 111589461 B CN111589461 B CN 111589461B CN 202010440901 A CN202010440901 A CN 202010440901A CN 111589461 B CN111589461 B CN 111589461B
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catalyst
water
methyl formate
methanol
solid
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CN111589461A (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 Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J27/198—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J35/50—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
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Catalysts (AREA)

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; dropping ammonia water solution into the mixed solution under the condition of ice water bath and intense stirring until the pH value is 7-11, so as to obtain slurry containing yellow brown 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 roasting. 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 long service life at a lower temperature, is easier to form in industrial reaction, and has more excellent reaction performance than a V-Ti-S catalyst.

Description

Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by methanol oxidation
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 carbon-chemistry-paramount intermediate, having a wide range of uses, and can be used directly as a fumigant and bactericide for the treatment of tobacco, dried fruits, grains, and the like; also commonly used as solvents for nitrocellulose, cellulose acetate; in medicine, the synthetic materials are commonly used as the synthetic materials of medicines such as methyl pyrimidine sulfonate, methoxy pyrimidine sulfonate, anti-cough agent mesafen and the like. The existing industrial production methods of methyl formate mainly comprise a methanol dehydrogenation method, a formate method, a methanol liquid phase-carbonylation method and a direct synthesis of methyl formate from synthesis gasEtc. The formate method has high cost and serious equipment corrosion; the yield of the methanol dehydrogenation method is low, and the selectivity of the product is poor; 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 method for preparing methyl formate 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 broad application prospect. Catalyst S-V used for preparing methyl formate by one-step oxidation of methanol at present 2 O 5 /TiO 2 The (VTS) has excellent reaction performance, but the catalyst has low specific surface area and small 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 V 2 O 5 /TiO 2 The catalyst synthesizes methylal and methyl formate, but the preparation process of the catalyst is complex. The catalyst has large particle size, poor reaction performance and low productivity.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the existing catalyst has the problem of low reaction performance caused by large particle size.
In order to solve the technical problems, 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:
step 1): dissolving a vanadium source, a titanium source and a phosphorus source in deionized water to prepare a mixed solution;
step 2): dropping ammonia water solution into the mixed solution under the condition of ice water bath and intense stirring until the pH value is 7-11, so as to obtain slurry containing yellow brown 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): and (3) 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 VOPO 4 、NH 4 VO 3 And any one or a mixture of a plurality of acetyl vanadyl acetonates; the titanium source is tetrabutyl titanate, tetraethyl titanate and Ti 3 (PO 4 ) 4 Any one or a mixture of a plurality of the above materials; the phosphorus source is H 3 PO 4 、H 3 PO 3 Or NaH 2 PO 4 Any one or a mixture of a plurality of them.
Preferably, the mass concentration of the vanadium source in the mixed solution in the step 1) is 10-25%, the mass concentration of the titanium source is 60-80%, and the mass concentration of the phosphorus source is 5-25%.
Preferably, the mass concentration of the ammonia water solution in the step 2) is 28%.
Preferably, the ageing time in step 3) is 1 to 8 hours.
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 V-Ti-P nano catalyst obtained in the step 5) has a particle size of 10-20 nm.
The invention also provides application of the V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol, which is characterized in that the V-Ti-P nano catalyst is filled into a reactor, firstly, mixed gas of oxygen and nitrogen is introduced at the speed of 10-100 mL/min, and the catalyst is activated 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 a flow rate of 0.002-0.020mL/min, and simultaneously, mixed gas of oxygen and nitrogen is introduced at a flow rate of 10-100 mL/min for the second time, the pressure is 0.1-2.0 MPa, and the reaction space velocity is 600-60000 mL.g -1 ·h -1 Under the condition, the reaction of preparing methyl formate by oxidizing methanol is carried out. The conversion rate of methanol is 70-99%, the selectivity of methyl formate is 85-99%, and the single-pass service life of the catalyst is more than 1000h.
Preferably, the volume ratio of oxygen to nitrogen in the mixed gas which is introduced 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 long service life at a lower temperature, is easier to form in industrial reaction, and has more excellent reaction performance than a V-Ti-S catalyst. In the reaction of preparing methyl formate by oxidizing methanol, the space velocity is 600-60000 mL.g -1 ·h -1 When the conversion rate of methanol is 70-99%, the selectivity of methyl formate is 85-99.1%, and the single-pass service life of the catalyst is more than 1000h; at a space velocity of 12000 mL.g -1 ·h -1 At 140 ℃, the conversion rate of methanol is 99 percent, and the selectivity of 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 accompanied with figures are described in detail below.
Example 1
(1) 1.17g of vanadyl acetylacetonate, 9.36g of tetrabutyl titanate and 1.17. 1.17g H 3 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH=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 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 6h;
(5) And (3) roasting the solid obtained in the step (4) at 300 ℃ for 2 hours to obtain the V-Ti-P catalyst.
The catalyst thus obtained was charged in an amount of 0.1g into the reactor, and 10% O was introduced at a flow rate of 10mL/min 2 And 90% N 2 Is activated for 0.5h at 200 ℃. Activation ofAfter completion, the reactor temperature was lowered to 100deg.C and methanol was introduced at a flow rate of 0.002mL/min while 10% O was introduced at a flow rate of 100mL/min 2 And 90% N 2 The pressure of the mixed gas (volume percent) is 0.1MPa, and the reaction space velocity is 60000 mL.g -1 ·h -1 . The reactivity is shown in Table 1.
Example 2
(1) 1.17g of vanadyl acetylacetonate, 2.81g of tetrabutyl titanate and 0.70. 0.70g H 3 PO 3 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water solution into the mixed solution A under the condition of ice water bath and vigorous stirring until the pH value is=11, so as to obtain slurry containing yellow brown precipitate;
(3) Aging the yellow brown slurry at room temperature for 8 hours, and washing with water to obtain 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 24h;
(5) And (3) roasting the solid obtained in the step (4) at 600 ℃ for 10 hours to obtain the V-Ti-P catalyst.
1g of the catalyst thus obtained was charged into a reactor, and 10% O was introduced at a rate of 100mL/min 2 And 90% N 2 Is activated for 6 hours at 600 ℃. After activation, the reactor temperature was reduced to 180℃and methanol was introduced at a flow rate of 0.020mL/min and 10% O was introduced at a flow rate of 10mL/min 2 And 90% N 2 The pressure of the mixed gas (volume percent) is 2.0MPa, and the reaction space velocity is 600 mL.g -1 ·h -1 . The reactivity is shown in Table 1.
Example 3
(1) 2g of vanadyl phosphate, 8g of titanium phosphate and 3.33g of NaH 2 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water solution into the mixed solution A under the condition of ice water bath and intense stirring until the pH value is=10, so as to obtain slurry containing yellow brown precipitate;
(3) Aging the yellow brown slurry at room temperature for 6 hours, and washing with water to obtain 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 12h;
(5) And (3) roasting the solid obtained in the step (4) at 400 ℃ for 6 hours to obtain the V-Ti-P catalyst.
The reactor was charged with 0.5g of the catalyst prepared, and 10% O was introduced at a rate of 30mL/min 2 And 90% N 2 Is activated for 2 hours at 400 ℃. After the activation, the temperature of the reactor was reduced to 135℃and methanol was introduced at a flow rate of 0.002mL/min, an inert gas containing oxygen (20%) was introduced at a flow rate of 16.6mL/min, a pressure of 0.5MPa, and a reaction space velocity of 2400mL g -1 ·h -1 . The reactivity is shown in Table 1.
Example 4
(1) 1.6g of ammonium vanadate, 8.53g of titanium phosphate and 0.53g of NaH2PO4 were dissolved in 340mL of deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water 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 4 hours, and washing with water to obtain 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 10h;
(5) And (3) roasting the solid obtained in the step (4) at 500 ℃ for 4 hours to obtain the V-Ti-P catalyst.
The reactor was charged with 0.2g of the catalyst prepared, and 10% O was introduced at a rate of 15mL/min 2 And 90% N 2 Is activated for 2 hours at 400 ℃. After activation was complete, the reactor temperature was reduced to 140℃and methanol was introduced at a flow rate of 0.004mL/min, while 10% O was introduced at a flow rate of 8.8mL/min 2 And 90% N 2 The pressure is 1.0MPa, and the reaction space velocity is 3000 mL-gg -1 ·h -1 . The reactivity is shown in Table 1.
Example 5
(1) 1.8g of ammonium vanadate, 7.2g of tetrabutyl titanate and 1.0g of NaH 2 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water 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 6 hours, and washing with water to obtain 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 18h;
(5) The solid obtained in step 4 was calcined at 400℃for 8 hours to obtain a V-Ti-P catalyst (see FIG. 1).
The reactor was charged with 0.2g of the catalyst thus obtained, and 10% O was introduced at a rate of 50mL/min 2 And 90% N 2 Is activated for 2 hours at 400 ℃. After activation, the reactor temperature was reduced to 140℃and methanol was introduced at a flow rate of 0.002mL/min while 10% O was introduced at a flow rate of 33.2mL/min 2 And 90% N 2 The working pressure is 1.0MPa, and the reaction space velocity is 12000 mL.g -1 ·h -1 . The reactivity is shown in Table 1.
Example 6
(1) 1.4g of vanadyl acetylacetonate, 6.25g of titanium phosphate and 2.35. 2.35g H 3 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water solution into the mixed solution A under the condition of ice water bath and intense stirring until the pH value is=10, so as to obtain slurry containing yellow brown precipitate;
(3) Aging the yellow brown slurry at room temperature for 7 hours, and washing with water to obtain 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 12h;
(5) And (3) roasting the solid obtained in the step (4) at 500 ℃ for 5 hours to obtain the V-Ti-P catalyst.
The reactor was charged with 0.3g of the catalyst prepared, and 10% O was introduced at a rate of 20mL/min 2 And 90% N 2 Is activated for 2 hours at 350 ℃. After activation, the reactor temperature was reduced to 150℃and methanol was introduced at a flow rate of 0.005mL/min while 10% O was introduced at a flow rate of 24.9mL/min 2 And 90% N 2 The working pressure is 1.0MPa, and the reaction space velocity is 8000 mL.g -1 ·h -1 . The reactivity is shown in Table 1.
Example 7
(1) 2.0g of ammonium vanadate, 7.0g of tetraethyl titanate and 1.0. 1.0g H 3 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water 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 3 hours, and washing with water to obtain 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 10h;
(5) And (3) roasting the solid obtained in the step (4) at 600 ℃ for 3 hours to obtain the V-Ti-P catalyst.
The reactor was charged with 0.1g of the catalyst thus obtained, and 10% O was introduced at a rate of 30mL/min 2 And 90% N 2 Is activated for 2 hours at 300 ℃. After activation, the reactor temperature was reduced to 140℃and methanol was introduced at a flow rate of 0.002mL/min while 10% O was introduced at a flow rate of 33.2mL/min 2 And 90% N 2 The working pressure is 1.0MPa, and the reaction space velocity is 24000 mL.g -1 ·h -1 。
The catalyst has stable service life, can stably run for more than 1000 hours, and the reaction stability is shown in table 2.
Comparative example 1
(1) 1.5g of vanadyl sulfate, 8.0g of titanium sulfate and 1.5. 1.5g H 2 SO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
(2) Dropping 28wt% ammonia water solution into the mixed solution A under the condition of ice water bath and intense stirring until the pH value is=10, so as to obtain slurry containing yellow brown precipitate;
(3) Aging the yellow brown slurry at room temperature for 6 hours, and washing with water to obtain 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 12h;
(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 catalyst thus obtained was charged into a fixed bed reactor, and 10% O was introduced at a rate of 30mL/min 2 And 90% N 2 Is activated for 2 hours at 300 ℃. After activation was completed, the reactor temperature was reduced to 140℃and methanol was introduced at a flow rate of 0.002mL/min while at the same time at 16.6
Flow rate of mL/min was 10% O 2 And 90% N 2 The working pressure is 0.1MPa, and the reaction space velocity is 1200 mL.g -1 ·h -1 . The reactivity is shown in Table 1.
TABLE 1 Performance of the catalyst for the preparation of methyl formate by methanol oxidation
Table 2 evaluation of lifetime of catalyst for methyl formate by oxidation of methanol

Claims (4)

1. The preparation method of the V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol is characterized by comprising the following steps:
step 1): 1.6g of ammonium vanadate, 8.53g of titanium phosphate and 0.53g of NaH 2 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A; or 2g of vanadyl phosphate, 8g of titanium phosphate and 3.33g of NaH 2 PO 4 Dissolving in 340mL deionized water to prepare a mixed solution A;
step 2): dropping 28wt% ammonia water solution into the mixed solution A under the conditions of ice water bath and vigorous stirring until the pH value is 9-10, so as to obtain slurry containing yellow brown precipitate;
step 3): aging the yellow brown slurry at room temperature, and washing with water to obtain yellow brown solid B;
step 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 100-120 ℃ for 10-12 h;
step 5): roasting the solid obtained in the step 4) for 4-6 hours at 400-500 ℃ to obtain the V-Ti-P catalyst.
2. The method according to claim 1, wherein the V-Ti-P nanocatalyst obtained in step 5) has a particle size of 10 to 20nm.
3. 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 1-2, which is characterized in that the V-Ti-P nano catalyst is filled into a reactor, firstly, mixed gas of oxygen and nitrogen is introduced at the speed of 10-100 mL/min, and the catalyst is activated 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 a flow rate of 0.002-0.020mL/min, and simultaneously, mixed gas of oxygen and nitrogen is introduced at a flow rate of 10-100 mL/min for the second time, the pressure is 0.1-2.0 MPa, and the reaction space velocity is 600-60000 mL.g -1 ·h -1 Under the condition, the reaction of preparing methyl formate by oxidizing methanol is carried out.
4. The use according to claim 3, wherein the volume ratio of oxygen to nitrogen in the mixture of two passes is 1:9.
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