CN113457700B - Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof - Google Patents
Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof Download PDFInfo
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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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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a vanadium-phosphorus-oxygen catalyst for aldol condensation and a preparation method and application thereof, which are mainly used for further improving the reaction performance of the existing catalyst. Firstly preparing VOPO under the condition of water-phase stirring 4 ·2H 2 O, and then preparing the VOHPO with a lamellar structure in a hydrothermal reaction kettle by using alcohol as a reducing agent 4 ·0.5H 2 And O precursor, and finally activating the precursor in air atmosphere to prepare the vanadium phosphorus oxide catalyst with high reaction activity. The invention has the advantages of providing a method for modulating delta-VOPO by modulating the type of alcohol used 4 The crystal is screened to obtain delta-VOPO 4 High reactivity (111) crystal face. Prepared delta-VOPO 4 The conversion rate of the catalyst can reach 95.1 percent, the selectivity reaches 92.5 weight percent, and the yield reaches 88.0 weight percent. The modification method of the catalyst is simple to operate, low in cost, free of additional requirements for equipment and easy to implement.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for improving the selectivity of a target product of a catalyst for preparing an acrylic compound by an aldol condensation reaction, and a preparation method and application thereof.
Background
The acrylic acid industry has over a thousand downstream products that are spread over various areas of national economy. In recent years, the import quantity and the consumption quantity of acrylic acid in China rapidly rise. However, the existing propylene oxidation production process is difficult to get rid of the dependence on imported crude oil. The novel process for preparing the acrylic acid by the gas-phase aldol condensation reaction of the acetic acid formaldehyde relieves the problem of surplus acetic acid in China, has low cost and meets the strategic task requirement of enhancing the autonomous energy guarantee capability in China.
At present, the preparation method has a great deal of research on the production process and the preparation of the high-efficiency catalyst. Patents CN109232247B, CN109293511B, CN106674010B, etc. have been studied around the fixed bed reactor or the internal circulating fluidized bed reactor, and the reaction process and separation process thereof, respectively. However, the lower yield of the target product acrylic acid and esters still brings difficulties for process development. Therefore, the development of highly efficient catalysts is also a hot issue.
Three types of catalysts, namely a metal-supported type, a vanadium phosphorus oxygen active center type and a pore material type, are reported in patents of CN109364908B, CN106423159B, CN105772057B, CN103143375B and the like. The vanadium-phosphorus-oxygen catalyst shows obviously improved conversion rate and target product selectivity in aldol condensation reaction due to acid-base active sites simultaneously provided by the vanadium-phosphorus-oxygen catalyst.
CN106582749B discloses a silicon-supported catalyst Cs-VPO/SiO of metal-doped vanadium phosphorus oxygen compound 2 The preparation method of (1). The catalyst is prepared by adding metal cesium and a silicon dioxide carrier into a vanadium phosphorus oxygen system prepared by an oil phase method, and the liquid phase space velocity is 0.5h -1 Under the reaction conditions of normal pressure and 360 ℃, the conversion per pass of formaldehyde is up to 78%, the selectivity of acrylic acid is up to 93%, and the yield is up to 72.5%.
CN109174164A discloses a method for preparing a catalyst of a vanadium phosphorus oxide compound prepared by a mesoporous MCM-41 molecular sieve carrier impregnation loading water phase method. The cost is low, the mesoporous carrier is convenient for secondary modification, the one-way conversion rate of the prepared catalyst is up to 73.93% under the reaction conditions of the sample injection flow rate of 8ml/h, the carrier gas oxygen flow rate of 20ml/min, normal pressure and 380 ℃, and the selectivity of acrylic acid and methyl acrylate based on acetic acid reaches 53.94%.
Despite the metal doping,The way of further improving the catalyst reactivity by carrier modification and the like has been studied, however, the influence of vanadium phosphorus oxide itself on the aldol condensation reaction is not sufficiently studied at present. At present, the variety of the vanadium phosphorus oxide compounds which are proved to be up to dozens of compounds, wherein the common active component comprises alpha I -VOPO 4 、α II -VOPO 4 、β-VOPO 4 、γ-VOPO 4 、δ-VOPO 4 、VOPO 4· ·2H 2 O, etc. CN109293495A discloses a method for mixing different crystal phases in different proportions by ball milling, consisting of (VO) 2 P 2 O 7 And delta-VOPO 4 Or with gamma-VOPO 4 Or delta-VOPO 4 And gamma-VOPO 4 The highest yield of acrylic acid and esters thereof in the aldol condensation reaction of the composite phase VPO catalyst formed by mixing the two phases in a mass ratio of 1:3-3:1 reaches 84.2%. Therefore, the research on the high-activity crystalline phase of vanadium, phosphorus and oxygen can achieve the purpose of improving the performance by using a simple modification means for the traditional preparation method, thereby having important significance.
Disclosure of Invention
The invention aims to provide a catalyst for improving the reaction yield of preparing acrylic acid by aldol condensation, and a preparation method and application thereof. The vanadium phosphorus oxygen catalyst prepared by the method has higher high-activity crystal face composition, thereby showing higher selectivity and yield of acrylic acid and acrylic ester in the reaction. The present invention focuses on delta-VOPO exhibiting high activity in aldol condensation reactions 4 The crystal phase delta-VOPO being influenced by the introduction of different types of alcohols during the preparation 4 The crystal shows the characteristic of oriented growth of different crystal faces, and the delta-VOPO is obtained by screening 4 The high activity (111) crystal face and further improves the yield of the reaction to 88.0 wt%.
In one aspect, the invention provides a delta-VOPO for aldol condensation 4 Vanadium phosphorus oxide catalyst, said delta-VOPO 4 In an X-ray diffraction pattern of the vanadium-phosphorus oxide catalyst, the proportion of the peak area of a 22-degree diffraction peak to the sum of peak areas within the range of 15-40 degrees is 60-78%.
The second aspect of the present invention providesThe delta-VOPO 4 The preparation method of the vanadium phosphorus oxide catalyst comprises the following steps:
step 1: will V 2 O 5 And H 3 PO 4 Stirring and mixing the mixture in deionized water under the heating condition, and separating to obtain a solid-phase product VOPO 4· ·2H 2 O；
And 2, step: taking the VOPO in the step 1 4· ·2H 2 O, using alcohol as a reducing agent, reducing in a hydrothermal reaction kettle, and separating to obtain a solid phase product VOHPO 4 ·0.5H 2 O precursor;
and step 3: taking the VOHPO in the step 2 4 ·0.5H 2 And O, roasting and activating for 6-18h at the temperature of 420-480 ℃ in a dry air atmosphere, tabletting the prepared sample, and screening into the vanadium-phosphorus-oxygen catalyst.
As a preferred embodiment of the present invention, in step 1, the raw material V is 2 O 5 And H 3 PO 4 The molar ratio of V/P is 0.95-1.30, the mass ratio of deionized water to vanadium pentoxide is 5-50, the reaction temperature is 60-100 ℃, and the reaction time is 2-12 hours.
In a preferred embodiment of the present invention, in step 2, the alcohol is a monohydric alcohol, a dihydric alcohol, a trihydric alcohol or a mixture thereof, preferably ethanol, propanol, butanol, pentanol, hexanol, isopropanol, isobutanol, isoamyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, polyethylene glycol (MW) or a mixture thereof<1000) One or more of the above; alcohol and VOPO 4· ·2H 2 The mass ratio of O is 3-20; the reaction temperature is 100 ℃ and 200 ℃, and the reduction time is 6-24 hours.
As a preferable scheme of the invention, in the step 3, the tabletting and forming process is completed in a dry atmosphere, and the mesh number of the vanadium phosphorus oxide catalyst obtained by screening is 20-40 meshes.
In a third aspect the invention provides the above delta-VOPO 4 The application of vanadium phosphorus oxygen catalyst in catalyzing aldol condensation reaction.
As a preferred embodiment of the present invention, the application specifically is: the feedstock first passed through a vaporization chamber and then passed into a reactor containing the delta-VOPO of claim 1 4 Fixed bed reactor of vanadium phosphorus oxygen catalystCarrying out aldol condensation reaction; the raw materials at least comprise a first raw material and a second raw material, wherein the first raw material is trioxymethylene or formaldehyde, and the second raw material is acetic acid, methyl acetate or propionic acid.
Further, the temperature of the vaporization chamber is 320-400 ℃.
Further, the aldol condensation reaction is carried out under normal pressure, and the reaction temperature is 320-400 ℃; the carrier gas is dry nitrogen or a mixture of nitrogen and oxygen, wherein O 2 The volume fraction is 0.2-2%.
Furthermore, in the reaction process, the mass space velocity WHSV of formaldehyde or trioxymethylene decomposed by heating is 0.05-1h -1 。
The catalyst provided by the invention is used for modifying high-activity crystalline phase delta-VOPO 4 The relative composition content of the medium-high activity crystal face is the core, the prepared catalyst has high formaldehyde conversion rate and higher acrylic acid (and ester thereof) selectivity, and shows higher activity and target product yield in aldol condensation reaction.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the process of comparative example 1 and the process of the example of the present invention;
FIG. 2 is an X-ray diffraction pattern of the products obtained in comparative example 1 and example 1.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a view to making and evaluating the present invention, and are intended to be merely exemplary of the present disclosure and are not intended to limit the scope thereof. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise specified, temperature is in units of ° c or at ambient temperature, and pressure is at or near atmospheric pressure.
The invention takes VPO compound as active component, modifies the VPO compound, reduces pentavalent vanadium element by using solvothermal method in the synthesis step, specially selects alcohol, and controls delta-VOPO change 4 The orientation of each crystal face in the crystal is grown to obtain delta-VOPO 4 (111) crystal of (2)And (5) kneading. Resulting delta-VOPO 4 The vanadium phosphorus oxide catalyst can improve the selectivity of a target product in the conventional reaction product of the reaction for preparing the acrylic acid by the aldol condensation method, and finally achieves the purpose of improving the yield of the product.
As shown in FIG. 1, the VPO compounds of the present invention require first preparing VOPO 4· ·2H 2 O, followed by reduction thereof under conditions to produce VOHPO 4 ·0.5H 2 And O precursor, and finally activating under certain conditions.
VOPO in the above process 4· ·2H 2 The raw materials used for preparing the O are vanadium pentoxide and phosphoric acid, the molar ratio of V/P is controlled to be 0.95-1.30, and the raw materials are dissolved in a certain amount of deionized water, wherein the mass ratio of the water to the vanadium pentoxide needs to be controlled to be more than 5. In the preparation process, the reaction temperature is required to be controlled to be more than 60 ℃ till boiling, and the reaction time is 2-12 hours. Separating the product in a suction filtration mode to obtain solid-phase VOPO therein 4· ·2H 2 And repeatedly leaching the filtrate by using acetone until the filtrate is clear, and drying the separated solid in an oven at 60 ℃ overnight. Obtaining yellow-green VOPO 4· ·2H 2 And (4) O powder.
VOHPO in the above process 4 ·0.5H 2 The O precursor is prepared by reduction through the following steps of firstly taking a certain amount of VOPO 4· ·2H 2 Placing O powder in a hydrothermal reaction kettle, adding a certain amount of alcohol to construct a reducing solvent atmosphere, wherein the alcohol and VOPO 4· ·2H 2 The mass ratio of the O precursor is 3-20: wherein the alcohol is selected from monohydric alcohol, dihydric alcohol, trihydric alcohol or mixtures thereof, preferably ethanol, propanol, butanol, pentanol, hexanol, isopropanol, isobutanol, isoamyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, polyethylene glycol (MW)<1000) And more preferably one or more of ethanol, propanol and isopropanol. Sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for reduction reaction at the temperature of 100 ℃ and 200 ℃ for 6-24 hours. After the reaction, the hydrothermal reaction kettle is naturally cooled, the contents are dissolved in acetone for ultrasonic dispersion and washing, a high-speed centrifuge is used for separating solid phase and liquid phase, and the solid phase product is taken for continuous washingAfter the washing solution is clarified for 3 times, the solid phase product is placed in a 60 ℃ oven to be dried overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
The activation step involved in the above scheme is via the prepared VOHPO 4 ·0.5H 2 The O precursor powder is oxidized in a muffle furnace at a certain temperature and in a certain atmosphere for a certain time to prepare the O precursor powder. Wherein the temperature range is 420-480 ℃, the atmosphere is dry air, and the time is 6-18 hours. Prepared delta-VOPO with high-activity (111) crystal face 4 The catalyst has higher aldol condensation reaction catalytic activity and acrylic acid selectivity.
The delta-VOPO prepared according to the process 4 In an X-ray diffraction pattern of the vanadium-phosphorus-oxygen catalyst, the proportion of the peak area of a 22-degree diffraction peak to the sum of peak areas in a range of 15-40 degrees is 60-78%.
The catalyst of the invention is formed by the following method before catalytic evaluation: and tabletting the catalyst powder in a grinding tool with the diameter of 20mm under the pressure of 30MPa for 30s, grinding the obtained tablet sample in an agate mortar, and sieving to obtain 20-40 mesh catalyst particles. The tabletting and forming process needs to be finished in a dry atmosphere, and the formed sample is stored in a drying dish.
In the catalyst evaluation described in the present invention, the aldehyde as a raw material used is supplied from trioxymethylene or a formaldehyde (e.g., aqueous methanol solution) raw material, and the hydroxyl group is supplied from acetic acid, methyl acetate or propionic acid. The reaction is carried out at the temperature of 320-400 ℃ and the reaction pressure of normal pressure, the mass space velocity WHSV of formaldehyde (1 molecule of trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde, the same applies below) is 0.05-1h -1 The molar ratio of acetic acid, methyl acetate or propionic acid to trioxymethylene is 18-1.5, and the molar ratio of acid, methyl acetate or propionic acid to formaldehyde is 6-0.5; the volume ratio of the carrier gas to the formaldehyde in the reaction system is 2-15, the carrier gas is dry nitrogen or the mixed gas of nitrogen and oxygen, wherein O 2 The volume fraction is 0.2-2%.
The preparation method of the catalyst according to the present invention is further explained in detail by the following examples in combination with comparative examples, and it is noted that the scope of the present invention includes, but is not limited to, the following examples.
Comparative example 1
1. Preparation of the catalyst
Referring to fig. 1, comparative example 1 employs a conventional oil phase synthesis method.
(1) 10g of vanadium pentoxide is dissolved in a mixed solvent of 75mL of benzyl alcohol and 75mL of isobutanol, the mixture is heated to 140 ℃ and reacts for 3 hours, and the solution is changed from an orange suspension to a black suspension. After stopping the heating and naturally cooling to 70 ℃, 13.432g of phosphoric acid was added, followed by continuing the heating to 140 ℃ for 4 hours. Filtering the reaction solution, separating to obtain solid, drying in a 60 deg.C oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(2) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 12h at 450 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
As shown in FIG. 2, in the X-ray diffraction peaks of the above samples, the proportion of the peak area of the 22 ℃ diffraction peak to the total of the peak areas in the range of 15 to 40 ℃ was 38%, i.e., the proportion of the (111) crystal face was low.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
Evaluation condition 1: in a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant temperature section of a reaction tube, ceramic Raschig rings are filled in an upper layer and a lower layer for fixing, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by taking m (acetic acid)/m (trioxymethylene) as 6 and is introduced into a reaction system by a metering pump. Then, introducing 10mL/min nitrogen for purging, heating to 370 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.02mL/min, and keeping the airspeed of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 0.971h -1 The sampling airspeed of the methyl acetate is 1.029h -1 The reaction temperature was maintained at 370 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 64.4%, the selectivity for acrylic acid and methyl acrylate was 72.9% by weight, and the yield was 47.1% by weight.
Evaluation condition 2: in the micro-size of 10mm internal diameterIn the fixed bed catalytic reactor, 1.0g of the above-mentioned catalyst is filled in the constant-temperature section of the reaction tube, the upper and lower layers are filled with ceramic raschig rings for fixing, and the reaction solution is prepared by using m (methyl acetate)/m (trioxymethylene) ═ 37/5 and is fed into the reaction system by means of metering pump. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, enabling the liquid injection speed to be 0.03mL/min, and keeping the space velocity of formaldehyde to be 0.214h -1 The sampling airspeed of the methyl acetate is 1.586h -1 The reaction temperature was maintained at 360 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 61.3%, the selectivity for acrylic acid and methyl acrylate was 75.0 wt%, and the yield was 46.0 wt%.
Comparative example 2
1. Preparation of the catalyst
(1) Dissolving 5g of vanadium pentoxide in 50mL of ethanol mixed solvent, transferring the solution to a hydrothermal reaction kettle, and reacting for 5 hours at the constant temperature of 140 ℃. After stopping heating and cooling to room temperature, 6.716g of phosphoric acid was added to the reaction vessel, followed by further holding at 140 ℃ for 6 hours. Filtering the reaction solution, separating to obtain solid, drying in a 60 deg.C oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(2) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 12 hours at 450 ℃ in a dry air atmosphere, tabletting, crushing and sieving the obtained catalyst powder to 20-40 meshes for later use.
In the X-ray diffraction peaks of the above samples, the proportion of the peak area of the 22 DEG diffraction peak to the total of the peak areas in the range of 15 to 40 DEG was 41%, that is, the proportion of the (111) crystal face was low.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
Evaluation conditions are as follows: in a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by taking m (acetic acid)/m (trioxymethylene) as 6 and is introduced into a reaction system by a metering pump. Then, 10mL/min nitrogen gas is introduced for purging, the temperature is raised to 370 ℃, after 1 hour of activation, the carrier gas is adjusted to be 20mL/min nitrogen gas, and the liquid injection speed is 0.02mL/min, keeping the space velocity of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde) at 0.971h -1 The sampling airspeed of the methyl acetate is 1.029h -1 The reaction temperature was maintained at 370 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 67.3%, the selectivity for acrylic acid and methyl acrylate was 67.6 wt%, and the yield was 45.5 wt%.
Example 1
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 15g of phosphoric acid in 100mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) 5g of the above VOPO were taken 4 ·2H 2 And adding 50mL of ethanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 120 ℃ oven, and taking out the reaction kettle after 12 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a drying oven at 60 ℃ overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 12h at 450 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
As shown in FIG. 2, in the X-ray diffraction peaks of the above samples, the proportion of the peak area of the 22 ℃ diffraction peak to the total peak area in the range of 15 to 40 ℃ was 78%, i.e., the sample had a high (111) face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by taking m (acetic acid)/m (trioxymethylene) as 6 and is introduced into a reaction system by a metering pump. Then, introducing 10mL/min nitrogen for purging, heating to 370 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, adjusting the liquid injection speed to be 0.02mL/min, and keeping the space velocity of formaldehyde (1 minute)Trioxymethylene decomposed by heating at 160 ℃ and regarded as 3 molecules of formaldehyde) for 0.971h -1 The sampling airspeed of the methyl acetate is 1.029h -1 The reaction temperature was maintained at 370 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 95.1%, the selectivity for acrylic acid and methyl acrylate was 92.5 wt%, and the yield was 88.0 wt%.
Example 2
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 15g of phosphoric acid in 100mL of deionized water, reacting for 6 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in an oven at 60 ℃ for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) Taking 5g of the VOPO 4 ·2H 2 Adding 25mL of ethanol and 25mL of polyethylene glycol 200 into 100mL of hydrothermal reaction kettle, sealing, transferring to a 120 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a drying oven at 60 ℃ overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 12h at 460 ℃ in dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22-degree diffraction peak to the total peak area in the range of 15-40 degrees is 68%, namely, the sample has higher (111) crystal face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with the inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in the upper layer and the lower layer for fixation, and a reaction solution is prepared by using a metering pump to introduce into a reaction system, wherein m (methyl acetate)/m (trioxymethylene) is 37/5. Then, 10mL/min nitrogen is introduced for purging, the temperature is raised to 350 ℃, after 1 hour of activation, the carrier gas is adjusted to be 20mL/min nitrogen, the liquid injection speed is 0.03mL/min, and formaldehyde is kept (1 molecule trioxymethylene is heated and decomposed at 160 ℃, and is regarded as 3 molecules formaldehyde)The space velocity is 0.214h -1 The sampling airspeed of the methyl acetate is 1.586h -1 The reaction temperature was maintained at 360 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 93.9%, the selectivity for acrylic acid and methyl acrylate was 91.2% by weight, and the yield was 85.6% by weight.
Example 3
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 49g of phosphoric acid in 100mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) 5g of the above VOPO were taken 4 ·2H 2 And adding 50mL of ethanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring the mixture into a 100 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 480 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15-40 DEG is 66%, namely, the sample has higher (111) plane content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with the inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in the upper layer and the lower layer for fixation, and a reaction solution is prepared by using a metering pump to introduce into a reaction system, wherein m (methyl acetate)/m (trioxymethylene) is 37/5. Then, introducing 10mL/min nitrogen for purging, heating to 320 ℃, activating for 1 hour, adjusting the carrier gas to be 10mL/min nitrogen, the liquid injection speed to be 0.02mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is heated and decomposed at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 1.057h -1 The sampling space velocity of the methyl acetate is 0.143h -1 The reaction temperature was maintained at 340 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 89.1%, the selectivity for acrylic acid and methyl acrylate was 95.0 wt%, and the yield was 84.6 wt%.
Example 4
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 24.5g of phosphoric acid in 100mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) 5g of the above VOPO were taken 4 ·2H 2 And adding 50mL of isopropanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 150 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 450 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15-40 DEG is 62%, namely, the sample has higher (111) crystal face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by using a metering pump, wherein m (methyl acetate)/m (trioxymethylene) is 37/5 and is introduced into a reaction system. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.2mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃, and is regarded as 3 molecules of formaldehyde) to be 1.428h -1 The sample injection space velocity of acetic acid is 10.572h -1 The reaction temperature was maintained at 360 ℃ and the operation was carried outThe pressure is slightly positive. At this time, the conversion of formaldehyde was 96.4%, the selectivity for acrylic acid and methyl acrylate was 86.7% by weight, and the yield was 83.4% by weight.
Example 5
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 13g of phosphoric acid in 50mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) 5g of the above VOPO were taken 4 ·2H 2 And adding 50mL of n-propanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 180 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 440 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15-40 DEG is 63%, namely, the sample has higher (111) plane content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by mixing m (acetic acid)/m (trioxymethylene) 12 and is introduced into a reaction system by a metering pump. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.462mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 0.714h -1 The sample injection space velocity of the methyl acetate is 5.538h -1 The reaction temperature was maintained at 350 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde is96.7%, the selectivity for acrylic acid and methyl acrylate was 84.3% by weight, and the yield was 81.5% by weight.
Example 6
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 49g of phosphoric acid in 100mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) Taking 5g of the VOPO 4 ·2H 2 And adding 50mL of n-propanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 150 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 480 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15-40 DEG is 62%, namely, the sample has higher (111) crystal face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by using a metering pump, wherein m (methyl acetate)/m (40% formaldehyde aqueous solution) ═ 37/25. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, enabling the liquid injection speed to be 0.1mL/min, and keeping the space velocity of formaldehyde to be 0.968h -1 The space velocity of methyl acetate injection is 3.581h -1 The reaction temperature was maintained at 350 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 94.5%, the selectivity for acrylic acid and methyl acrylate was 88.1%, and the yield was 83.3% by weight.
Example 7
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 20g of phosphoric acid in 200mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) Taking 10g of the VOPO 4 ·2H 2 And adding 50mL of isopropanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 180 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 460 ℃ in dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22-degree diffraction peak to the total peak area in the range of 15-40 degrees is 64%, namely, the sample has higher (111) crystal face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with the inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in the upper layer and the lower layer for fixation, and a reaction solution is prepared by using a metering pump to introduce into a reaction system, wherein m (methyl acetate)/m (trioxymethylene) is 37/15. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.1mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 1.731h -1 The space velocity of methyl acetate injection is 4.269h -1 The reaction temperature was maintained at 350 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 92.2%, the selectivity for acrylic acid and methyl acrylate was 90.5 wt%, and the yield was 83.4 wt%.
Example 8
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 20g of phosphoric acid in 200mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) Taking 10g of the VOPO 4 ·2H 2 And adding 25mL of n-propanol into the O powder in a 100mL hydrothermal reaction kettle, sealing, transferring to a 150 ℃ oven, and taking out the reaction kettle after 10 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a drying oven at 60 ℃ overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 480 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the above samples, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15 to 40 DEG is 61%, that is, the sample has a high (111) face content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with an inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in an upper layer and a lower layer for fixation, a quartz reaction tube is used in the experiment, and a reaction solution is prepared by m (acetic acid)/m (trioxymethylene) ═ 3 and is introduced into a reaction system by a metering pump. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.02mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is heated and decomposed at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 0.300h -1 The sampling space velocity of the methyl acetate is 0.900h -1 The reaction temperature was maintained at 360 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 96.9%, the selectivity for acrylic acid and methyl acrylate was 83.6 wt%, and the yield was 81.0 wt%.
Example 9
1. Preparation of the catalyst
(1) Dissolving 10g of vanadium pentoxide and 13g of phosphoric acid in 50mL of deionized water, reacting for 10 hours under the condition of keeping the solution slightly boiling, and then placing the solid obtained by suction filtration and separation of the reaction liquid in a 60 ℃ oven for drying overnight. Obtaining yellow-green VOPO 4 ·2H 2 And (4) O powder.
(2) Taking 15g of the VOPO 4 ·2H 2 Adding 25mL of isopropanol and 25mL of ethanol into a 100mL hydrothermal reaction kettle, sealing, transferring the mixture into a 120 ℃ oven, and taking out the reaction kettle after 6 hours. Dissolving the reaction solution in the kettle in a solid-phase product separated by an acetone ultrasonic centrifuge, and drying in a 60 ℃ drying oven overnight to obtain sky blue VOHPO 4 ·0.5H 2 O precursor powder.
(3) Taking the VOHPO 4 ·0.5H 2 Activating O powder for 6h at 480 ℃ in a dry air atmosphere, tabletting the obtained catalyst powder, crushing and sieving to 20-40 meshes for later use.
In the X-ray diffraction peaks of the sample, the proportion of the peak area of the 22 DEG diffraction peak to the total peak area in the range of 15-40 DEG is 63%, namely, the sample has higher (111) plane content.
2. Evaluation of reaction for preparing acrylic acid by aldol condensation method
In a miniature fixed bed catalytic reactor with the inner diameter of 10mm, 1.0g of the catalyst is filled in a constant-temperature section of a reaction tube, ceramic raschig rings are filled in the upper layer and the lower layer for fixation, and a reaction solution is prepared by using a metering pump to introduce into a reaction system, wherein m (methyl acetate)/m (trioxymethylene) is 74/15. Then, introducing 10mL/min nitrogen for purging, heating to 350 ℃, activating for 1 hour, adjusting the carrier gas to be 20mL/min nitrogen, the liquid injection speed to be 0.05mL/min, and keeping the space velocity of formaldehyde (1 molecule trioxymethylene is decomposed by heating at 160 ℃ and is regarded as 3 molecules of formaldehyde) to be 0.506h -1 The sampling space velocity of the methyl acetate is 2.494h -1 The reaction temperature was maintained at 350 ℃ and the operating pressure was slightly positive. At this time, the conversion of formaldehyde was 91.6%, the selectivity for acrylic acid and methyl acrylate was 87.5 wt%, and the yield was 80.2 wt%.
Claims (9)
1. Delta-VOPO 4 Preparation method of vanadium phosphorus oxide catalyst, and X-ray of delta-VOPO 4 vanadium phosphorus oxide catalystIn the diffraction pattern, the proportion of the peak area of the 22-degree diffraction peak to the total peak area within the range of 15-40 degrees is 60-78%. The method is characterized by comprising the following steps:
step 1: will V 2 O 5 And H 3 PO 4 Stirring and mixing the mixture in deionized water under the heating condition, and separating to obtain a solid-phase product VOPO 4 ·2H 2 O；
Step 2: taking the VOPO in the step 1 4 ·2H 2 O, using alcohol as a reducing agent, reducing in a hydrothermal reaction kettle, and separating to obtain a solid phase product VOHPO 4 ·0.5H 2 O precursor;
and step 3: taking the VOHPO in the step 2 4 ·0.5H 2 And O, roasting and activating for 6-18h at the temperature of 420-480 ℃ in a dry air atmosphere, tabletting the prepared sample, and screening into the vanadium-phosphorus-oxygen catalyst.
2. The process according to claim 1, wherein in step 1, starting material V is 2 O 5 And H 3 PO 4 The molar ratio of V/P is 0.95-1.30, the mass ratio of deionized water to vanadium pentoxide is 5-50, the reaction temperature is 60-100 ℃, and the reaction time is 2-12 hours.
3. The method according to claim 1, wherein in step 2, the alcohol is a monohydric alcohol, a dihydric alcohol, a trihydric alcohol or a mixture thereof; alcohol and VOPO 4 ·2H 2 The mass ratio of O is 3-20; the reaction temperature is 100 ℃ and 200 ℃, and the reduction time is 6-24 hours.
4. The preparation method according to claim 1, wherein in the step 3, the tabletting and forming process is completed in a dry atmosphere, and the mesh number of the vanadium phosphorus oxide catalyst obtained by screening is 20-40 meshes.
5. delta-VOPO prepared by the process of claim 1 4 The application of vanadium phosphorus oxygen catalyst in catalyzing aldol condensation reaction.
6. Use according to claim 5, characterized in that the raw material is first passed through a vaporization chamber and subsequently passed into a reactor containing a delta-VOPO according to claim 1 4 Carrying out aldol condensation reaction in a fixed bed reactor of a vanadium phosphorus oxygen catalyst; the raw materials at least comprise a first raw material and a second raw material, wherein the first raw material is trioxymethylene or formaldehyde, and the second raw material is acetic acid, methyl acetate or propionic acid.
7. The use as claimed in claim 6, wherein the vaporization chamber temperature is 320-400 ℃.
8. The use as claimed in claim 6, wherein the aldol condensation reaction is carried out at normal pressure and the reaction temperature is 320-400 ℃; the carrier gas is dry nitrogen or a mixture of nitrogen and oxygen, wherein O 2 The volume fraction is 0.2-2%.
9. The use as claimed in claim 6, wherein the formaldehyde or trioxymethylene is decomposed by heating at a formaldehyde mass space velocity WHSV of 0.05-1h -1 。
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