CN116020503A - Shaped vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, preparation method thereof and preparation method of maleic anhydride - Google Patents
Shaped vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, preparation method thereof and preparation method of maleic anhydride Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- 230000003647 oxidation Effects 0.000 title claims abstract description 21
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
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- 238000011282 treatment Methods 0.000 claims description 19
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a formed vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, a preparation method thereof and a preparation method of maleic anhydride. The catalyst of the invention is characterized by Raman spectrum analysis, wherein the wavelength of Raman excitation light is 532nm, and the Raman shift is 1350cm ‑1 And Raman shift of 1590cm ‑1 Raman characteristic peaks appear at the positions of the graphite carbon and the defective carbon respectively, and the ratio of the peak area of the defect carbon to the peak area of the defect carbon is more than or equal to 0.8; the strength of the catalyst is more than or equal to 15N. The catalyst has higher strength, is beneficial to industrial application, and has higher raw material conversion rate and maleic anhydride selectivity when being used for catalyzing low-carbon alkane to prepare anhydride by selective oxidation.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a formed vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation and a preparation method thereof, and a preparation method of maleic anhydride.
Background
The gas phase selective oxidation of hydrocarbons is an important catalytic reaction, and can be used for preparing various oxidation products such as organic anhydride compounds and the like. One of the typical products is maleic anhydride (maleic anhydride).
Maleic anhydride, also known as Maleic Anhydride (MA), is a commonly used important organic chemical raw material, and the third largest anhydride species is consumed worldwide. Maleic anhydride is currently used mainly in the production of unsaturated polyester resins, alkyd resins, 1, 4-Butanediol (BDO), gamma-butyrolactone (GBL), and Tetrahydrofuran (THF) chemicals. In addition, it is widely used in various fine chemical fields.
The production of maleic anhydride is mainly divided into two types, and benzene is adopted as a production raw material in the earliest production method, but the proportion of the production process of the benzene method in the production of maleic anhydride is increasingly reduced due to the harm of the raw material and the environment and the influence of economic factors; the main stream production method of maleic anhydride adopts normal butane as production raw material, including fixed bed, fluidized bed and moving bed, and the processes are characterized by that they have practical industrial application, but they share a common point that these processes for preparing maleic anhydride by oxidizing normal butane all adopt the same kind of catalyst, i.e. Vanadium Phosphorus Oxide (VPO) catalyst.
VPO catalysts have been considered for many years to be the most effective catalyst system for catalyzing the production of maleic anhydride from gas phase hydrocarbons, especially n-butane. Commercial VPO catalysts typically employ an organic phase to produce a precursor, which is calcined to activate and shaped by adding a shaping lubricant (typically graphite) to form the final catalyst. It is noted that precursor powders obtained by the organic phase process typically contain residual carbon components that, together with the shaped lubricant graphite, constitute the carbon composition in the final shaped catalyst. Earlier studies found that carbon content had a significant impact on the performance of VPO catalysts (CN 100431702 and CN1353627 a). There have been studies to improve the performance of n-butane selective oxidation on VPO catalysts by modulating the solvent ratio in the organic phase process, thereby modulating the carbon content in the catalyst (CN 1353627 a). However, it should be noted that the addition of the shaped lubricant graphite also has a significant impact on the catalyst performance. The addition of too much graphite with higher graphitization degree can affect the catalyst performance, resulting in the decrease of the yield of maleic anhydride.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel formed vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation and a preparation method thereof. The catalyst has better activity in the process of preparing the acid anhydride by catalyzing the selective oxidation of the low-carbon alkane.
The first aspect of the invention provides a shaped vanadium phosphorus oxide catalyst for the selective oxidation of hydrocarbons characterized by raman spectroscopy, wherein the raman excitation wavelength is 532nm and the raman shift is 1350cm -1 And Raman shift of 1590cm -1 Raman characteristic peaks appear at the positions of the graphite carbon and the defective carbon respectively, and the ratio of the peak area of the defect carbon to the peak area of the defect carbon is more than or equal to 0.8; the strength of the catalyst is more than or equal to 15N.
In the present invention, preferably, the ratio of the peak area of ID to the peak area of IG is not less than 1. Such as, but not limited to, the ratio of the peak area of ID to the peak area of IG is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, etc.
In the present invention, the strength of the catalyst is preferably 15N to 30N.
In the present invention, preferably, the carbon content of the catalyst is 0.5 to 8 wt%. In the present invention, the analysis method of the carbon content in the catalyst is an inorganic carbon-sulfur analysis method.
The second aspect of the invention provides a method for preparing the molded vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, which comprises the following steps:
step (1), catalyst precursor active phase powder synthesized by an organic phase method;
step (2), tabletting the active phase powder of the catalyst precursor obtained in the step (1) and a lubricant;
and (3) roasting and activating the product obtained in the step (2).
According to the method of the present invention, preferably, the lubricant is an acidified multiwall carbon nanotube, and more preferably, the lubricant is a carbon nanotube obtained by acidification with concentrated sulfuric acid and concentrated nitric acid.
According to the method of the present invention, preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:0.5-2.
According to the method of the present invention, preferably, the conditions of the acidification treatment comprise: the temperature is 40-60 ℃ and the time is 1-4 h.
According to the method of the present invention, preferably, the lubricant is acidified with concentrated sulfuric acid and concentrated nitric acid, then cooled, filtered and washed to neutrality, and dried.
According to the method of the invention, the lubricant preferably has an average tube diameter of 10 to 25nm and a length <20 μm.
According to the method of the present invention, preferably, the step (1) includes the steps of:
step (1A), mixing a vanadium compound with an organic solvent and phosphoric acid, and heating and refluxing to obtain a precipitation solution;
and (1B) filtering and washing the obtained precipitation solution to obtain a filter cake, and performing heat treatment to obtain the catalyst precursor active phase powder.
According to the method of the present invention, preferably, the vanadium compound is selected from one or more of vanadium pentoxide, ammonium metavanadate and vanadium organic acid, preferably, vanadium pentoxide.
According to the method of the present invention, preferably, the organic solvent includes an organic alcohol and a polyol, preferably, the organic solvent is a mixed solvent of isobutanol and benzyl alcohol, and more preferably, the molar ratio of isobutanol to benzyl alcohol is 2:1 to 6:1.
According to the method of the present invention, preferably, the phosphoric acid has a concentration of 85 to 110% by weight.
According to the method of the present invention, preferably, the heating reflux time is 2 to 20 hours.
Preferably, the solvent for washing is selected from the group consisting of isobutyl alcohol and/or benzyl alcohol according to the process of the present invention.
According to the method of the present invention, preferably, the conditions of the heat treatment include: the temperature is 100-160 ℃ and the time is 6-20 h.
According to the method of the present invention, preferably, the weight ratio of the vanadium compound, the organic solvent, and the phosphoric acid is 1:4 to 10:0.8 to 2.
According to the method of the present invention, preferably, the step (2) includes the steps of:
step (2A), carrying out first tabletting treatment on the active phase powder of the catalyst precursor obtained in the step (1) and a lubricant to obtain a one-step formed catalyst;
step (2B), crushing, screening and taking the catalyst with the particle size of 20-160 meshes as pre-granulating particles;
and (2C) carrying out a second tabletting treatment on the pre-granulated particles.
According to the method of the present invention, preferably, the conditions of the first tabletting treatment include: the pressure is 10-40 MPa.
According to the method of the present invention, preferably, the apparatus used for the first tabletting is a powder tabletting machine.
According to the method of the present invention, preferably, the weight ratio of the catalyst precursor active phase powder to the lubricant is 1:25 to 150.
According to the method of the present invention, preferably, the apparatus used for the second tabletting is a rotary tabletting machine. Preferably, the hollow cylindrical shaped catalyst having a height of 4 to 6mm is obtained by the second tabletting.
According to the method of the present invention, preferably, the firing is performed in an air atmosphere.
In some embodiments of the invention, the firing temperature is preferably 200 to 350 ℃ for a period of 2 to 5 hours.
According to the method of the present invention, the activation treatment process includes: the catalyst is activated by heat treatment for 1 to 20 hours at the temperature of 200 to 480 ℃ under the atmosphere formed by one or more of oxygen-containing gas, inert gas and water vapor. Preferably, the activation treatment is two activation treatments including a first activation treatment and a second activation treatment.
According to the method of the present invention, it is preferable that the first activation treatment is performed in an atmosphere having a volume content of 15% to 25% of air, 15% to 25% of nitrogen, 5% to 15% of carbon dioxide, and 45% to 55% of water vapor.
In some embodiments of the invention, the first activation treatment is preferably performed at a temperature of 300 to 450 ℃ for a time of 2 to 5 hours.
According to the method of the present invention, the second activation treatment is preferably performed in an atmosphere having a volume content of 35% to 45% nitrogen, 5% to 15% carbon dioxide and 45% to 55% water vapor.
In some embodiments of the invention, the second activation treatment is preferably carried out at a temperature of 400 to 450 ℃ for a time of 2 to 5 hours.
According to a specific embodiment of the present invention, a method for preparing a shaped vanadium phosphorus oxide catalyst for the selective oxidation of hydrocarbons comprises: the catalyst precursor active phase powder synthesized by the organic phase method is added with lubricant to be pressed into tablets to form the reactivating formed catalyst; the lubricant added in the tabletting and forming process is multi-wall carbon nano tubes.
According to a specific embodiment of the present invention, a method for preparing a shaped vanadium phosphorus oxide catalyst for the selective oxidation of hydrocarbons comprises:
1) Mixing a vanadium compound with an organic solvent serving as a reducing agent and a solvent and phosphoric acid, and then heating and refluxing for 2-20 h;
2) Filtering the obtained precipitation solution and washing with the same organic solvent as in 1), and then carrying out heat treatment on the filter cake at 100-160 ℃;
3) Uniformly mixing the precursor powder obtained after heat treatment with a tabletting lubricant (acidified multiwall carbon nanotubes), and carrying out pre-granulation and secondary tabletting treatment to obtain a hollow cylindrical formed catalyst with the height of 4-6 mm;
4) And (3) roasting and activating the obtained formed catalyst at a certain temperature under a certain atmosphere.
In a third aspect, the invention provides a method for preparing anhydride by hydrocarbon selective oxidation, comprising the following steps: and (3) oxidizing hydrocarbons to prepare maleic anhydride by adopting a gas-phase catalyst, wherein the catalyst is the catalyst or the catalyst obtained by the preparation method.
Preferably, according to the method of the present invention, the hydrocarbon is n-butane.
According to the process of the present invention, preferably, the catalyst is reacted with n-butane feedstock having a molar concentration of 1 to 1.7% in a fixed bed reactor to produce maleic anhydride.
According to the method of the present invention, preferably, the process conditions of the reaction include: space velocity of 1000-3000 hr -1 The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
The invention has the beneficial effects that:
(1) The inventor of the invention discovers through researches that the selectivity of maleic anhydride is poor due to the addition of excessive graphite with higher graphitization degree, and the catalyst has the characteristic of high yield of maleic anhydride prepared by gas-phase oxidation of n-butane.
(2) The vanadium phosphorus oxide catalyst for hydrocarbon selective oxidation, which is obtained by adopting the preparation method, has high catalyst strength and is suitable for industrial application, and the catalyst has the advantage of good reaction performance, can improve the selectivity of maleic anhydride, and under the preferred condition, the catalyst prepared by adopting the carbon nano tube obtained by the acidification treatment of concentrated sulfuric acid and concentrated nitric acid has higher selectivity of maleic anhydride.
Drawings
FIG. 1 is a Raman spectrum of the catalyst of example 1 with the addition of the acidified multiwall carbon nanotubes as a lubricant.
Fig. 2 is a Raman spectrum of the catalyst of comparative example 1 to which graphite was added as a lubricant.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method and the equipment used in the test are as follows:
(1) Carbon Nanotubes (CNTs) were purchased from Jiangsu Tianney technologies Inc., and the average tube diameter and length of CNTs were as described in preparation examples 1 to 4 with purity >98%.
(2) Graphite powder is purchased from Shanghai Ala Biochemical technology Co., ltd, and has a purity of 99.95%, and the result of chemical analysis on trace metals shows that the content of trace gold is less than 0.05%. The size is more than or equal to 325 meshes.
(3) Graphene was purchased from Shanghai Meilin Biochemical technologies Co., ltd and was 97% pure.
(4) Carbon powder was purchased from Shanghai Meilin Biochemical technologies Co., ltd., 99.5%,30nm.
(5) Inorganic carbon sulfur analysis is carried out by adopting CS-600 type high-frequency infrared carbon sulfur instrument of American LECO company, the measurement range is 0.001-100 percent (weight) C, the sensitivity is 0.0001 percent (weight) C, the sample is 0.1-0.3 gram, the furnace temperature is 400-1400 ℃, oxygen is introduced for combustion, a high-carbon content detector is selected, and standard samples with known carbon content are used for correction.
(6) The strength of the catalyst is the compressive strength of the catalyst, the catalyst is carried out by adopting a ZQJ-II intelligent particle strength tester connected with an intelligent tester factory, and the test standard method is based on the application of a ZQJ intelligent particle strength tester of China Petroleum and chemical industry standards and quality (pages 31-33,28 in 3 rd 1991).
[ PREPARATION EXAMPLE 1 ]
Preparing acidified multiwall carbon nanotubes:
taking original carbon nano tubes (average tube diameter is 10-25 nm, length is 10 μm), adding concentrated sulfuric acid and concentrated nitric acid with volume ratio of 1:1 into the original multi-wall carbon nano tubes, and carrying out water bath reaction for 2h at 60 ℃. After the reaction, cooling, filtering, washing to neutrality, and drying the product at 80 ℃ to obtain the multiwall carbon nanotube with the surface rich in oxygen-containing functional groups.
[ PREPARATION EXAMPLE 2 ]
Preparing acidified multiwall carbon nanotubes:
taking original carbon nano tubes (average tube diameter is 10-25 nm, length is 10 μm), adding concentrated sulfuric acid and concentrated nitric acid with volume ratio of 1:2 into the original multi-wall carbon nano tubes, and carrying out water bath reaction for 2h at 60 ℃. After the reaction, cooling, filtering, washing to neutrality, and drying the product at 80 ℃ to obtain the multiwall carbon nanotube with the surface rich in oxygen-containing functional groups.
[ PREPARATION EXAMPLE 3 ]
Preparing acidified multiwall carbon nanotubes:
taking original carbon nano-tubes (average tube diameter is 10-25 nm, length is 10 μm), adding concentrated sulfuric acid and concentrated nitric acid with volume ratio of 1:1 into the original multi-wall carbon nano-tubes, and carrying out water bath reaction for 2h at 50 ℃. After the reaction, cooling, filtering, washing to neutrality, and drying the product at 80 ℃ to obtain the multiwall carbon nanotube with the surface rich in oxygen-containing functional groups.
[ PREPARATION EXAMPLE 4 ]
Preparing acidified multiwall carbon nanotubes:
taking original carbon nano tubes (average tube diameter is 7-11 nm, length is 5-250 μm), adding concentrated sulfuric acid and concentrated nitric acid with volume ratio of 1:1 into the original multi-wall carbon nano tubes, and carrying out water bath reaction for 2h at 60 ℃. After the reaction, cooling, filtering, washing to neutrality, and drying the product at 80 ℃ to obtain the multiwall carbon nanotube with the surface rich in oxygen-containing functional groups.
[ example 1 ]
250g of vanadium pentoxide is added into a mixed solution of 2500ml of isobutanol and 1000ml of benzyl alcohol, stirring is started, about 300g of 100 wt% phosphoric acid is slowly added, the mixed solution is heated to reflux for 16 hours, the mixed solution is filtered and washed by the isobutanol after stopping heating, and the obtained filter cake is dried at 120 ℃ for 16 hours to obtain a precursor. The powdered catalyst precursor is sieved, 250g of precursor smaller than 200 meshes is taken.
5g of multi-walled carbon nanotubes (obtained in preparation example 1) were thoroughly mixed with 250g of a catalyst precursor to form a mixture 1A. Tabletting the mixture under the pressure of 20MPa to obtain the one-step formed catalyst product. Then crushing, screening and taking 20-160 mesh parts, transferring the pre-granulated particles to a rotary tablet press, carrying out rotary tablet pressing on the catalyst structure with the height of 5mm to obtain the formed vanadium-phosphorus oxide catalyst 1B.
The catalyst B was calcined at 250℃for 3 hours in an air atmosphere. Then heating to 425 ℃ for activation for 3 hours in an atmosphere with the volume ratio of 20% of air/20% of nitrogen/10% of carbon dioxide/50% of water vapor, and finally activating for 3 hours at 450 ℃ in an atmosphere with the volume ratio of 40% of nitrogen/10% of carbon dioxide/50% of water vapor, thus obtaining the active catalyst 1C.
Inorganic carbon sulfur analysis was performed on catalyst 1C, which was found to have a carbon content of 4.2%. Catalyst 1C was analyzed for intensity and found to have an intensity of 24N.
As a result of Raman characterization of the catalyst 1C, as shown in FIG. 1, it was found that in the Raman analysis spectrum of the catalyst, the Raman shift was 1350cm -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 1.2.
[ example 2 ]
250g of vanadium pentoxide is added into a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 320g of 110 wt% phosphoric acid is slowly added, the mixed solution is heated to reflux for 16 hours, the mixed solution is filtered and washed by the isobutanol after stopping heating, and the obtained filter cake is dried at 120 ℃ for 16 hours to obtain a precursor. The powdered catalyst precursor is sieved, 250g of precursor smaller than 200 meshes is taken.
5g of multi-walled carbon nanotubes (obtained in preparation example 1) were taken and thoroughly mixed with 250g of the catalyst precursor powder to form a mixture 2A. Tabletting the mixture under the pressure of 20MPa to obtain the one-step formed catalyst product. Then crushing, screening and taking 20-160 mesh parts, transferring the pre-granulated particles to a rotary tablet press, carrying out rotary tablet pressing on the catalyst structure with the height of 5mm to obtain the formed vanadium-phosphorus oxide catalyst 2B.
The catalyst 2B was calcined at 250℃for 3 hours in an air atmosphere. Then heating to 425 ℃ for activation for 3 hours in an atmosphere with the volume ratio of 20% of air/20% of nitrogen/10% of carbon dioxide/50% of water vapor, and finally activating for 3 hours at 450 ℃ in an atmosphere with the volume ratio of 40% of nitrogen/10% of carbon dioxide/50% of water vapor, thus obtaining the final catalyst 2C.
Inorganic carbon sulfur analysis was performed on catalyst 2C, which was found to have a carbon content of 4.1%. Catalyst 2C was analyzed for intensity, and the intensity was found to be 23N.
The Raman characterization of catalyst 2C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 1.2.
[ example 3 ]
250g of vanadium pentoxide is added into a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 320g of 110 wt% phosphoric acid is slowly added, the mixed solution is heated to reflux for 16 hours, the mixed solution is filtered and washed by the isobutanol after stopping heating, and the obtained filter cake is dried at 120 ℃ for 16 hours to obtain a precursor. The powdered catalyst precursor is sieved, 250g of precursor smaller than 200 meshes is taken.
7.5g of multi-walled carbon nanotubes (obtained in preparation example 1) were taken and thoroughly mixed with 250g of the catalyst precursor powder to form a mixture 3A. Tabletting the mixture under the pressure of 20MPa to obtain the one-step formed catalyst product. Then crushing, screening and taking 20-160 mesh parts, transferring the pre-granulated particles to a rotary tablet press, carrying out rotary tablet pressing on the catalyst structure with the height of 5mm to obtain the formed vanadium-phosphorus oxide catalyst 3B.
Roasting the catalyst 3B at 250 ℃ for 3 hours in an air atmosphere, heating to 425 ℃ for activation for 3 hours in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor, and finally activating for 3 hours at 450 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the final catalyst 3C.
Inorganic carbon sulfur analysis was performed on catalyst 3C, which was found to have a carbon content of 6.0%. The intensity analysis was performed on the catalyst 3C, and the intensity was 22N.
The Raman characterization of catalyst 3C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 1.2.
[ example 4 ]
250g of vanadium pentoxide is added into a mixed solution of 2500ml of isobutanol and 800ml of benzyl alcohol, stirring is started, about 320g of 110 wt% phosphoric acid is slowly added, the mixed solution is heated to reflux for 16 hours, the mixed solution is filtered and washed by the isobutanol after stopping heating, and the obtained filter cake is dried at 120 ℃ for 16 hours to obtain a precursor. The powdered catalyst precursor is sieved, 250g of precursor smaller than 200 meshes is taken.
2.5g of multi-walled carbon nanotubes (obtained in preparation example 1) were taken and thoroughly mixed with 250g of the catalyst precursor powder to form a mixture 4A. Tabletting the mixture under the pressure of 20MPa to obtain the one-step formed catalyst product. Then crushing, screening and taking 20-160 mesh parts, transferring the pre-granulated particles to a rotary tablet press, carrying out rotary tablet pressing on the catalyst structure with the height of 5mm to obtain the formed vanadium-phosphorus oxide catalyst 4B.
Roasting the catalyst 4B at 250 ℃ for 3 hours in an air atmosphere, heating to 425 ℃ for activation for 3 hours in an atmosphere of 20% air/20% nitrogen/10% carbon dioxide/50% water vapor, and finally activating for 3 hours at 450 ℃ in an atmosphere of 40% nitrogen/10% carbon dioxide/50% water vapor to obtain the final catalyst 4C.
Inorganic carbon sulfur analysis was performed on catalyst 4C, which was found to have a carbon content of 2.2%. Catalyst 4C was analyzed for intensity and 22N was measured.
The Raman characterization of catalyst 4C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 1.2.
[ example 5 ]
The method of example 1 was used, except that the multi-walled carbon nanotube obtained in preparation example 1 was replaced with the multi-walled carbon nanotube obtained in preparation example 2. To obtain the final catalyst 5C.
Inorganic carbon sulfur analysis was performed on catalyst 5C, which was found to have a carbon content of 4.3%. The catalyst 5C was subjected to an intensity analysis, and the intensity was found to be 23N.
The catalyst 5C was fed with 1.5% by volume butane at 400℃under normal pressure for 2000hr -1 Butane conversion was determined to be 85.3% and maleic anhydride selectivity to 65.0% by examination in a fixed bed reactor at space velocity.
The Raman characterization of catalyst 5C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) was 1.1.
[ example 6 ]
The method of example 1 was used, except that the multi-walled carbon nanotube obtained in preparation example 1 was replaced with the multi-walled carbon nanotube obtained in preparation example 3. To obtain the final catalyst 6C.
Inorganic carbon sulfur analysis was performed on catalyst 6C, which was found to have a carbon content of 4.2%. Catalyst 6C was analyzed for intensity and 22N was measured.
The Raman characterization of catalyst 6C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) was 1.1.
[ example 7 ]
The method of example 1 was used, except that the multi-walled carbon nanotube obtained in preparation example 1 was replaced with the multi-walled carbon nanotube obtained in preparation example 4. The final catalyst 7C was obtained, which was difficult to mold after Cheng Tuomo and had weak compressive strength.
Inorganic carbon sulfur analysis was performed on catalyst 7C, which was found to have a carbon content of 4.3%. The catalyst 7C was subjected to an intensity analysis, and the intensity was found to be 15N.
The Raman characterization of catalyst 7C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 1.0.
[ example 8 ]
The procedure of example 1 was used, except that the multiwall carbon nanotubes obtained in preparation example 1 were replaced with original wall carbon nanotubes that were not subjected to acidification treatment. To obtain the final catalyst 8C.
Inorganic carbon sulfur analysis was performed on catalyst 8C, which was found to have a carbon content of 4.3%. The intensity analysis was performed on catalyst 8C, and the intensity was measured to be 15N.
The Raman characterization of catalyst 8C, similar to that of fig. 1, shows a Raman shift of 1350cm in the Raman analysis spectrum of the catalyst -1 And Raman shift of 1590cm -1 The raman characteristic peak appears at the position of the samplePeaks other than defective carbon (I) D ) Peak with graphitic carbon (I G ) And the ratio of the peak area of ID to the peak area of IG (the peak area ratio I of the two peaks D /I G Peak area ratio) of 0.8.
Comparative example 1
The method of example 1 was used, except that the multi-walled carbon nanotube obtained in preparation example 1 was replaced with graphite powder. To obtain the final catalyst 1DC.
Inorganic carbon sulfur analysis was performed on catalyst 1DC, which was found to have a carbon content of 4.8%. Catalyst 1DC was analyzed for intensity and found to have an intensity of 25N.
The Raman characterization of the catalyst 1DC, as shown in FIG. 2, shows that in the Raman analysis spectrum of the catalyst, the Raman shift is 1350cm -1 And Raman shift of 1590cm -1 At which raman characteristic peaks appear, respectively peaks of defective carbon (I D ) Peak with graphitic carbon (I G ) And the peak area ratio I of two peaks D /I G The peak area ratio of (2) is only 0.2.
Comparative example 2
The method of example 1 was used, except that the multi-walled carbon nanotube obtained in preparation example 1 was replaced with graphene. The final catalyst 2DC is obtained, the catalyst is difficult to mold after Cheng Tuomo, and the compressive strength of the catalyst is weak.
Inorganic carbon sulfur analysis was performed on catalyst 2DC, which was found to have a carbon content of 4.2%. The catalyst 2DC was subjected to an intensity analysis, and the intensity was found to be 12N.
[ comparative example 3 ]
The procedure of example 1 was used, except that the multiwall carbon nanotubes obtained in preparation example 1 were replaced with carbon powder. The final catalyst 3DC is obtained, the catalyst is difficult to mold after Cheng Tuomo, and the compressive strength of the catalyst is weak.
Inorganic carbon sulfur analysis was performed on catalyst 3DC, which was found to have a carbon content of 4.4%. The catalyst 3DC was subjected to an intensity analysis, and the intensity was found to be 11N.
[ comparative example 4 ]
According to the method of example 1, except that the acidified multiwall carbon nanotubes were added during the synthesis of the active phase powder of the catalyst precursor by the organic phase method, namely:
250g of vanadium pentoxide was added to a mixed solution of 2500ml of isobutanol and 1000ml of benzyl alcohol, then 5g of multi-walled carbon nanotubes (obtained in preparation example 1) were added, stirring was started, about 300g of 100 wt% phosphoric acid was slowly added, the mixed solution was heated to reflux and then refluxed for 16 hours, after stopping heating, the mixed solution was filtered and washed with isobutanol, and the obtained filter cake was dried at 120 ℃ for 16 hours to obtain a precursor. Sieving the powdery catalyst precursor, and taking the precursor smaller than 200 meshes. Tabletting the mixture under the pressure of 20MPa to obtain the one-step formed catalyst product. Then crushing, screening and taking 20-160 mesh parts, transferring the pre-granulated particles to a rotary tablet press, carrying out rotary tablet pressing on the catalyst structure with the height of 5mm to obtain the formed vanadium-phosphorus oxide catalyst 4DB.
The catalyst 4DB was calcined at 250℃for 3 hours in an air atmosphere. Then heating to 425 ℃ for activation for 3 hours in an atmosphere with the volume ratio of 20% of air/20% of nitrogen/10% of carbon dioxide/50% of water vapor, and finally activating for 3 hours at 450 ℃ in an atmosphere with the volume ratio of 40% of nitrogen/10% of carbon dioxide/50% of water vapor to obtain the active catalyst 4DC, wherein the catalyst is difficult to mold after Cheng Tuomo, and the compressive strength of the catalyst is weak.
Inorganic carbon sulfur analysis was performed on catalyst 4DC, which was found to have a carbon content of 4.0%. Catalyst 4DC was analyzed for intensity and found to have an intensity of 10N.
[ test case ]
The catalysts obtained in examples 1 to 8 and comparative examples 1 to 4 were evaluated, respectively. The evaluation conditions were: 1.5% by volume butane feed at 400℃under normal pressure for 2000hr -1 Butane conversion and maleic anhydride selectivity were evaluated in a fixed bed reactor at space velocity and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the strength of the catalyst of the present invention is 15N or more, preferably 15 to 24N, which is advantageous for industrial application. The catalysts of comparative examples 2 to 4 have lower strength, are difficult to release from the mold during molding, and have weaker compressive strength, thus being unfavorable for industrial application. Compared with comparative example 1, the catalyst provided by the invention has better activity and selectivity in the process of preparing anhydride by catalyzing the selective oxidation of low-carbon alkane.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art based on the technical teaching provided herein, and are also to be considered as the scope of the present invention.
Claims (10)
1. A shaped vanadium phosphorus oxide catalyst for the selective oxidation of hydrocarbons characterized by raman spectroscopy wherein the raman excitation light wavelength is 532nm and the raman shift is 1350cm -1 And Raman shift of 1590cm -1 Raman characteristic peaks appear at the positions of the graphite carbon and the defective carbon respectively, and the ratio of the peak area of the defect carbon to the peak area of the defect carbon is more than or equal to 0.8; the strength of the catalyst is more than or equal to 15N.
2. The catalyst of claim 1, wherein the ratio of the peak area of ID to the peak area of IG is equal to or greater than 1.
3. The catalyst according to claim 1 or 2, characterized in that the strength of the catalyst is 15N-30N; and/or the carbon content of the catalyst is 0.5-8 wt%.
4. A process for preparing a shaped vanadium phosphorus oxide catalyst for the selective oxidation of hydrocarbons according to any one of claims 1 to 3, comprising:
step (1), catalyst precursor active phase powder synthesized by an organic phase method;
step (2), tabletting the active phase powder of the catalyst precursor obtained in the step (1) and a lubricant;
and (3) roasting and activating the product obtained in the step (2).
5. The method according to claim 4, wherein the lubricant is an acidified multiwall carbon nanotube, preferably the lubricant is a carbon nanotube obtained by acidification with concentrated sulfuric acid and concentrated nitric acid;
preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:0.5-2;
preferably, the conditions of the acidification treatment comprise: the temperature is 40-60 ℃ and the time is 1-4 h.
6. The method according to claim 4, wherein the lubricant has an average tube diameter of 10 to 25nm and a length of < 20. Mu.m.
7. The method of claim 4, wherein the step (1) comprises the steps of:
step (1A), mixing a vanadium compound with an organic solvent and phosphoric acid, and heating and refluxing to obtain a precipitation solution;
and (1B) filtering and washing the obtained precipitation solution to obtain a filter cake, and performing heat treatment to obtain the catalyst precursor active phase powder.
8. The preparation method according to claim 7, wherein the vanadium compound is selected from one or more of vanadium pentoxide, ammonium metavanadate and vanadium organic acid, preferably vanadium pentoxide; and/or the number of the groups of groups,
the organic solvent comprises organic alcohol and polyalcohol, preferably the organic solvent is a mixed solvent of isobutyl alcohol and benzyl alcohol, more preferably the molar ratio of the isobutyl alcohol to the benzyl alcohol is 2:1-6:1; and/or the number of the groups of groups,
the concentration of the phosphoric acid is 85-110 wt%; and/or the number of the groups of groups,
the heating reflux time is 2-20 h; and/or the number of the groups of groups,
the washed solvent is selected from isobutyl alcohol and/or benzyl alcohol; and/or the number of the groups of groups,
the conditions of the heat treatment include: the temperature is 100-160 ℃ and the time is 6-20 h; and/or the number of the groups of groups,
the weight ratio of the vanadium compound, the organic solvent and the phosphoric acid is 1:4-10:0.8-2.
9. The method according to any one of claims 4 to 8, wherein the step (2) comprises the steps of:
step (2A), carrying out first tabletting treatment on the active phase powder of the catalyst precursor obtained in the step (1) and a lubricant to obtain a one-step formed catalyst;
step (2B), crushing, screening and taking the catalyst with the particle size of 20-160 meshes as pre-granulating particles;
step (2C), carrying out a second tabletting treatment on the pre-granulated particles;
preferably, the conditions of the first tabletting process include: the pressure is 10-40 MPa, more preferably, the equipment adopted by the first tabletting is a powder tabletting machine;
preferably, the weight ratio of the lubricant to the catalyst precursor active phase powder is 1:25-150;
preferably, the apparatus used for the second tabletting is a rotary tabletting machine.
10. A method for preparing anhydride by hydrocarbon selective oxidation, comprising the following steps: oxidizing hydrocarbons to maleic anhydride using a gas phase catalyst, wherein the catalyst is a catalyst according to any one of claims 1 to 3 or a catalyst obtained by the production process according to any one of claims 4 to 9;
preferably, the hydrocarbon is n-butane;
preferably, the catalyst reacts with n-butane raw material with the molar concentration of 1-1.7% in a fixed bed reactor to produce maleic anhydride;
more preferably, the process conditions of the reaction include: space velocity of 1000-3000 hr -1 The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003078058A1 (en) * | 2002-03-15 | 2003-09-25 | Basf Aktiengesellschaft | Catalyst-precursor for the production of maleic acid anhydride and method for the production thereof |
| CN105413725A (en) * | 2014-09-09 | 2016-03-23 | 中国石油化工股份有限公司 | Vanadium-phosphorus catalyst and preparation method thereof |
| WO2016102440A1 (en) * | 2014-12-22 | 2016-06-30 | Basf Se | Carbon supported catalyst comprising a modifier and process for preparing the carbon supported catalyst |
| CN107866248A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | For catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN112174764A (en) * | 2019-07-02 | 2021-01-05 | 中国科学院大连化学物理研究所 | Application of iron-based catalyst in catalyzing carbon dioxide hydrogenation to synthesize low-carbon olefin |
| CN112939765A (en) * | 2021-02-22 | 2021-06-11 | 湘潭大学 | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane |
-
2021
- 2021-10-25 CN CN202111243326.3A patent/CN116020503B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003078058A1 (en) * | 2002-03-15 | 2003-09-25 | Basf Aktiengesellschaft | Catalyst-precursor for the production of maleic acid anhydride and method for the production thereof |
| CN105413725A (en) * | 2014-09-09 | 2016-03-23 | 中国石油化工股份有限公司 | Vanadium-phosphorus catalyst and preparation method thereof |
| WO2016102440A1 (en) * | 2014-12-22 | 2016-06-30 | Basf Se | Carbon supported catalyst comprising a modifier and process for preparing the carbon supported catalyst |
| CN107866248A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | For catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN112174764A (en) * | 2019-07-02 | 2021-01-05 | 中国科学院大连化学物理研究所 | Application of iron-based catalyst in catalyzing carbon dioxide hydrogenation to synthesize low-carbon olefin |
| CN112939765A (en) * | 2021-02-22 | 2021-06-11 | 湘潭大学 | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane |
Non-Patent Citations (2)
| Title |
|---|
| 曹丹艳;陈平;楼辉;HONG HAIPING;: "多壁碳纳米管负载的碳化钼催化剂在玉米油加氢脱氧反应中的应用", 浙江大学学报(理学版), no. 06, 15 November 2015 (2015-11-15) * |
| 许磊;樊金龙;徐亚荣;: "活化气氛对正丁烷选择性氧化制顺酐催化剂性能的影响", 工业催化, no. 11, 15 November 2013 (2013-11-15) * |
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