CN111763144A - Method for synthesizing acrylic acid from acetic acid - Google Patents
Method for synthesizing acrylic acid from acetic acid Download PDFInfo
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- CN111763144A CN111763144A CN201911155998.1A CN201911155998A CN111763144A CN 111763144 A CN111763144 A CN 111763144A CN 201911155998 A CN201911155998 A CN 201911155998A CN 111763144 A CN111763144 A CN 111763144A
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Abstract
The invention relates to a preparation method of acrylic acid, in particular to a method for preparing acrylic acid by taking acetic acid solution as a raw material and carrying out oxidation-condensation. The catalytic reaction is carried out in a fixed bed reactor, acetic acid solution is gasified and diluted in inert atmosphere to pass through a VPO-based catalyst, carbon-carbon oxidation fracture occurs, and then acrylic acid is prepared through condensation.
Description
Technical Field
The invention relates to a method for synthesizing acrylic acid, in particular to a method for preparing acrylic acid by oxidizing acetic acid aqueous solution.
Background
Acrylic acid is an important organic compound that readily polymerizes on its own or with other polymer monomers to form polymers. The polymers are widely applied to the fields of super absorbent materials, dispersing agents, flocculating agents, thickening agents and the like. The synthesis of acrylic acid has attracted considerable attention from the industry and academia due to its important commercial value.
The production method of the acrylic acid mainly comprises the following steps: ethylene process (ethylene, CO and O)2Reaction), ethylene oxide process (ethylene oxide withCO reaction), ketene method (ketene reacts with formaldehyde), acetylene carbonylation method (Reppe method), chlorohydrin method, cyanoethanol method, propane oxidation method, propylene oxidation method, and acrylonitrile hydrolysis method. Among the above methods, the ethylene process, the ethylene oxide process and the propane oxidation process are still under development, and no large-scale production apparatus is available, and the ketene process, the acetylene carbonylation process, the chlorohydrin process, the cyanoethanol process and the acrylonitrile hydrolysis process have been eliminated due to low efficiency, large consumption and high cost. To date, propylene oxidation is used in all large-scale acrylic acid production facilities in the world. Companies possessing propylene oxidation production technologies mainly include japanese catalytic chemical company, mitsubishi chemical company, BASF company, and ohio standard petroleum Sohio company. With the increasing exhaustion of fossil resources, the cost of producing acrylic acid from propylene as a raw material will gradually increase.
The 20 th century and 70 th era have increased the price of petroleum, and a route for synthesizing acrylic acid from non-petroleum raw materials, namely acetic acid and formaldehyde, has been produced. Both acetic acid and formaldehyde can be generated from methanol, and the methanol is from synthesis gas and has rich raw material sources. With the development of the modern coal chemical industry, the route is widely concerned by researchers.
Among the reported catalysts, VPO-based catalysts are an effective class of catalysts, whose surface is mainly medium-strong Lewis acid sites and basic sites, which synergistically catalyze the process. Mamoru Ai and the like take acetic acid or methyl acetate and formaldehyde as raw materials and utilize V2O5-P2O5Acrylic acid or methyl acrylate is prepared by aldol condensation of catalysts such as binary acid oxide, vanadium-titanium binary phosphate (V-Ti-P-O) and the like. In recent years, researchers have focused on how to expose more catalytically active sites, with a series of efforts being directed to the preparation of VPO-based catalysts and their catalyzed aldol condensation to acrylic acids and esters. For example, the PEG6000 is used as a template to prepare the VPO catalyst with high specific surface area, or the VPO is loaded on SiO2SBA-15 and Al2O3On the carriers, the concentration of active sites on the surface of the catalyst is effectively improved, so that the yield of target products of acrylic acid and esters thereof is improved. Acidic molecular sieve catalyst such as HZSM-5, HZSM-35 and the like, and Cs/SiO2Or Cs/SBA-15 or the likeThe catalyst is applied to catalyzing condensation of acetic acid or methyl acetate and formaldehyde to prepare acrylic acid or methyl acrylate, but compared with a VPO catalyst, the catalyst is easier to deposit carbon, and the catalyst needs to be frequently regenerated to maintain the catalytic activity. In addition, acetic acid and acrylic acid on the strong basic catalyst are easy to generate decarboxylation side reaction to generate a large amount of COxAnd carbon deposition, which is not favorable for the generation of target products.
Celanese corporation disclosed a combined process of methanol carbonylation to produce acetic acid and reaction of acetic acid with formaldehyde to produce acrylic acid (US20140073812), where acetic acid conversion can reach 50% and acrylic acid selectivity can reach 70%. The advantage of this process is that formaldehyde is easily removed from the crude acrylic acid. BASF corporation discloses a combined process for preparing acetic acid by oxidizing ethanol and preparing acrylic acid by condensing acetic acid and formaldehyde (CN 104817450). The process for preparing acrylic acid by using methanol and acetic acid as raw materials is also protected in the granted patent CN201180054828.X, and a new patent CN201580053093.7 is newly applied to protect the process after the patent right is ended. Eastman discloses a process for preparing acrylic acid from aqueous acetic acid and formaldehyde solutions (US20130237724) in which the mixed oxides of V, Ti and P are used as catalysts and which have a relatively good space-time yield. The southwest institute of chemical engineering design Co., Ltd discloses TiO2、SiO2Or the catalyst of active components such as V, Ti, Zr, P and the like loaded by the molecular sieve catalyzes formaldehyde aqueous solution or paraformaldehyde and acetic acid to synthesize acrylic acid (and methyl acrylate), or catalyzes methylal and methyl acetate to synthesize methyl acrylate, and the catalyst has higher activity and selectivity (CN20140795266, CN201210502752 and CN 201210491886). Asahi chemical technology research institute Limited company reported a method for preparing a catalyst for the synthesis of methyl acrylate and co-production of methyl methacrylate from methyl acetate and formaldehyde, wherein SiO is used as the catalyst2As the catalyst carrier, metal salts of Cs and Zr, and an oxide of Sb (CN201410022889) are also included. A Yangjiang research team, Zhang-Jordan institute of Process engineering, of the Chinese academy of sciences, reports a catalyst for synthesizing acrylic acid from formaldehyde aqueous solution and acetic acid, and a preparation and application method thereof (CN201310566202), wherein the catalyst is prepared from activated carbon and Al2O3、SiO2Or one or more than two of the molecular sieves are used as carriers to load phosphorus pentoxide and one or more than two alkaline earth metal oxides. The Nanjing Daichi-Chongji team reported a VPO catalyst and its application in the preparation of acrylic acid (esters) by reacting acetic acid (esters) with formaldehyde (CN201410103826), in which the active VPO catalyst was prepared by refluxing V in a mixed alcohol solution2O5The preparation method comprises the steps of adding polyethylene glycol (PEG6000) as a surfactant, and activating the prepared active catalyst in a butane-air mixed atmosphere of 1.5 percent (volume fraction).
In summary, in the reported literature, two raw materials (acetic acid (ester) and formaldehyde or formaldehyde precursor as raw materials) are used for preparing acrylic acid, but the process of preparing acrylic acid by using only acetic acid solution as raw materials is not reported. The acrylic acid is prepared only by taking the acetic acid solution as the raw material, so that the experimental process is simplified, the formaldehyde solution can be avoided being directly used, and the process is more economic.
Disclosure of Invention
The invention aims to provide a method for synthesizing acrylic acid, which starts from cheap, easily obtained and stable acetic acid solution, and realizes the effective synthesis of acrylic acid by carrying out the oxidative cracking and the self condensation of acetic acid through a proper catalytic system.
The technical scheme is as follows:
a process for synthesizing acrylic acid includes such steps as gasifying acetic acid or its solution, diluting in oxygen-contained inertial atmosphere, oxidizing-condensing by VPO-base catalyst to obtain acrylic acid, and features simple process, low cost and high output rate.
The mass fraction of acetic acid in the acetic acid or the acetic acid solution is 50-100%; the solvent is one or a mixture of water, acetonitrile, cyclohexane, benzene, toluene, xylene, dioxane and tetrahydrofuran;
the gasification temperature is 200 ℃ and 400 ℃; the volume fraction of acetic acid in the diluted gas phase is 5-50%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-5);
inert atmosphere is N2In Ar, HeOne or a mixture of several of them;
the reaction temperature in the catalysis process is not lower than 280 ℃;
the mass space velocity (mass of acetic acid/mass of catalyst in unit time) of the catalyst is 0.5-5 h-1；
The reaction pressure of the catalytic process is 0.5 atm-30 atm.
Providing a scheme that:
the mass fraction of acetic acid in the acetic acid solution is 50-90%; the solvent is one or a mixture of water, acetonitrile, cyclohexane, toluene and dioxane;
the gasification temperature is 200-350 ℃; the volume fraction of acetic acid in the gas-diluted phase is 5-40%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-4);
inert atmosphere is N2And one or a mixture of more of Ar; wherein the oxygen is derived from air;
the reaction temperature of the catalytic process is 280-450 ℃;
the mass space velocity (mass of acetic acid/mass of catalyst in unit time) of the catalyst is 0.5-3 h-1；
The reaction pressure of the catalytic process is 0.5 atm-20 atm.
Providing a scheme that:
the mass fraction of acetic acid in the acetic acid solution is 50-80%; the solvent is one or a mixture of water, acetonitrile and dioxane;
the gasification temperature is 200 ℃ and 300 ℃; the volume fraction of acetic acid in the diluted gas phase is 5-30%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-3);
inert atmosphere is N2；
The reaction temperature in the catalytic process is 280-400 ℃;
catalyst mass space velocity (acetic acid per unit time)Mass of (b)/mass of catalyst) is from 1 to 3h-1；
The reaction pressure of the catalytic process is 0.5 atm-10 atm.
The preparation process of the VPO-based catalyst is as follows:
putting vanadium pentoxide into benzyl alcohol or isobutyl alcohol or a mixed alcohol solution of the benzyl alcohol and the isobutyl alcohol for refluxing, adding 5-15 g of vanadium pentoxide into every 100mL of the alcohol solution, then adding 85% by mass of phosphoric acid and a catalyst carrier (or not) and a catalyst auxiliary agent (or not) for refluxing, adding the phosphoric acid according to the P/V molar ratio of 0.5-3 or simultaneously adding a surfactant, and finally drying, roasting and activating to obtain the VPO catalyst.
The volume ratio of the benzyl alcohol to the isobutanol in the mixed alcohol is 3: 1-1: 3;
the reflux temperature in the alcohol is 120-140 ℃; the reflux time is 3-6 h;
the reflux temperature is 120-140 ℃; the reflux time is 12-24 h;
the surfactant is: PVPK30 (average molecular weight of K30 40000), PVPK150 (average molecular weight 80000), PVPK90 (average molecular weight of 630000), PEG200, PEG2000, PEG 8000; (the concentration is 10-40 mg/mL);
the temperature of the drying process is 100-140 ℃; air-blast drying or vacuum drying;
the drying time is 6-12 h;
the temperature in the roasting process is 400-800 ℃; the atmosphere is air, nitrogen or hydrogen;
the roasting time is 4-12 h; the temperature of the activation process is 400-800 ℃; the atmosphere is a mixed gas of butane and air (the volume fraction of the butane is 0.5-3%); the activation time is 4-24 h;
the carrier of the VPO-based catalyst is: SiO 22,Al2O3,SiO2-Al2O3One or a mixture of more of SiC, MgO, aluminum silicate and magnesium silicate; during the reflux, it was added.
The auxiliary agent of the VPO-based catalyst is as follows: oxides of Sc, Y, La, Ti, Nb, Ge, Ta, Mo, W, Bi, Sb or mixtures thereof; during the reflux, it was added.
The reactions involved in the present invention can be represented by the following reaction equation:
CH3COOH+O2→HCHO+H2O+CO2
advantageous technical effects
1. The raw materials of the catalyst used in the invention are cheap and easy to obtain, the preparation process is controllable and easy to operate, and the oxidation-Aldol condensation reaction of the acetic acid solution can be effectively generated;
2. the catalyst has good stability and hydrothermal stability, the reaction process is simple, controllable and easy to operate, and the yield of the acrylic acid can reach 60 percent at most.
3. The acrylic acid is prepared by reacting formaldehyde generated in situ by the oxidative decomposition reaction of acetic acid with acetic acid.
Drawings
FIG. 1 is a gas phase analysis spectrum of the product of example 3, wherein the retention time at 11.47min is the product acrylic acid.
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 3:1, the heating reflux is carried out for 3h at the temperature of 120 ℃, then phosphoric acid with the mass fraction of 85% is added, the reflux is continued for 12h, and the adding amount of the phosphoric acid is 0.5 according to the molar ratio of P/V in the phosphoric acid and the vanadium pentoxide. At the same time, the surfactant PVP-K30 (10 mg/mL final concentration) was added. The obtained solid is filtered, dried by blowing at 100 ℃ for 6h, roasted at 400 ℃ for 12h, and activated in 0.5 volume percent butane air mixed gas for 4h for use.
Tabletting the obtained sample to 20-60 meshes, and adding the obtained sample into a fixed bed reactorIn the process, 5 wt% acetic acid aqueous solution is gasified at 200 deg.C and then passed through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 5%, and the molar ratio of acetic acid to oxygen is 2; reacting at 280 ℃ and the mass space velocity of acetic acid on the catalyst is 0.5h-1The gas pressure in the reaction process is 0.5atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 2
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (10g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the mixture is heated and refluxed for 3 hours at the temperature of 130 ℃, and then phosphoric acid and SiO with the mass fraction of 85 percent are added2And continuously refluxing for 12h, wherein the adding amount of the phosphoric acid is 1.2 of the molar ratio of the phosphoric acid to the P/V in the vanadium pentoxide. At the same time, the surfactant PVP-K90 (10 mg/mL final concentration) was added. The obtained solid is filtered, dried by blowing at 120 ℃ for 6h, roasted at 600 ℃ for 12h by nitrogen, and activated in butane air mixed gas with volume fraction of 1.5% for 4 h. SiO 22The mass fraction in the catalyst was 80%.
Tabletting and molding the obtained sample to 20-60 meshes, adding the sample into a fixed bed reactor, gasifying a 20 wt% acetic acid acetonitrile solution at 300 ℃, and diluting the solution by oxygen-containing Ar, wherein the volume fraction of acetic acid in a gas phase is 10%, and the molar ratio of acetic acid to oxygen is 3; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 1h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 3
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:3, the mixture is heated and refluxed for 3 hours at the temperature of 140 ℃, and then phosphoric acid and SiO with the mass fraction of 85 percent are added2And continuously refluxing the scandium oxide for 12h, wherein the adding amount of the phosphoric acid is 3 according to the molar ratio of the phosphoric acid to the P/V in the vanadium pentoxide. At the same time, the surfactant PVP-K150 (10 mg/mL final concentration) was added. And carrying out suction filtration on the obtained solid, carrying out vacuum drying at 140 ℃ for 6h, carrying out roasting reduction at 800 ℃ for 4h, and activating in 3.0 volume percent butane air mixed gas for 4h for use. SiO 22The mass fraction of scandium oxide in the catalyst was 50%, and the mass fraction of scandium oxide in the catalyst was 1%.
Tabletting and molding the obtained sample to 20-60 meshes, adding the sample into a fixed bed reactor, gasifying 100 wt% of acetic acid at 400 ℃, and diluting the acetic acid by using oxygen-containing He, wherein the volume fraction of the acetic acid in a gas phase is 50%, and the molar ratio of the acetic acid to oxygen is 5; reacting at 450 ℃, and the mass space velocity of acetic acid on the catalyst is 3h-1The gas pressure in the reaction process is 30atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 4
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the mixture is heated and refluxed for 3 hours at the temperature of 130 ℃, and then phosphoric acid and Al with the mass fraction of 85 percent are added2O3And continuously refluxing the yttrium oxide for 12 hours, wherein the adding amount of the phosphoric acid is 1.2 of the molar ratio of the phosphoric acid to the P/V in the vanadium pentoxide. At the same time, the surfactant PEG200 (final concentration of 10mg/mL) was added. The obtained solid is filtered, dried by blowing at 120 ℃ for 6h, roasted at 600 ℃ for 8h, and activated in butane air mixed gas with volume fraction of 1.5% for 12 h. Al (Al)2O3The mass fraction of the yttrium oxide in the catalyst is 95%, and the mass fraction of the yttrium oxide in the catalyst is 2%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 50 wt% of acetic acid cyclohexane solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 10atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 5
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (15g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the mixture is heated and refluxed for 3 hours at the temperature of 130 ℃, and then phosphoric acid and SiO with the mass fraction of 85 percent are added2-Al2O3And continuously refluxing the lanthanum oxide for 12h, wherein the adding amount of the phosphoric acid is 1.2 of the molar ratio of the P/V in the phosphoric acid to the vanadium pentoxide. At the same time, PEG2000 (final concentration of 30mg/mL) was added as a surfactant. The obtained solid is filtered, dried by blowing at 120 ℃ for 6h, roasted at 600 ℃ for 8h, and activated in butane air mixed gas with volume fraction of 1.5% for 12 h. SiO 22-Al2O3The mass fraction of lanthanum oxide in the catalyst is 70%, and the mass fraction of lanthanum oxide in the catalyst is 10%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 50 wt% of toluene acetate solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 6
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the heating reflux is carried out for 3h at the temperature of 130 ℃, then phosphoric acid with the mass fraction of 85%, SiC and titanium oxide are added for continuous reflux for 12h, and the adding amount of the phosphoric acid is 1.2 according to the molar ratio of P/V in the phosphoric acid and the vanadium pentoxide. Simultaneously, the surfactant PEG8000 (with the final concentration of 10mg/mL) is added. The obtained solid is filtered, dried by blowing at 120 ℃ for 6h, roasted at 600 ℃ for 8h, and activated in butane air mixed gas with volume fraction of 1.5% for 12 h. The mass fraction of SiC in the catalyst was 70%, and the mass fraction of titanium oxide in the catalyst was 5%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 50 wt% of acetic acid dioxane solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 7
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the heating reflux is carried out for 3h at the temperature of 130 ℃, then phosphoric acid with the mass fraction of 85%, MgO and niobium oxide are added, the reflux is continued for 12h, and the adding amount of the phosphoric acid is 1.2 according to the molar ratio of P/V in the phosphoric acid and vanadium pentoxide. At the same time, PEG2000 (final concentration of 30mg/mL) was added as a surfactant. The obtained solid is filtered, dried by blowing at 120 ℃ for 6h, and air-roasted at 600 ℃ for 8h for direct use. The mass fraction of MgO in the catalyst is 70%, and the mass fraction of niobium oxide in the catalyst is 5%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid tetrahydrofuran solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 8
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the heating reflux is carried out for 3h at the temperature of 140 ℃, then phosphoric acid with the mass fraction of 85%, aluminum silicate and germanium oxide are added, the reflux is continued for 12h, and the adding amount of the phosphoric acid is 1.6 according to the molar ratio of P/V in the phosphoric acid and vanadium pentoxide. At the same time, the surfactant PVP-K90 (10 mg/mL final concentration) was added. The obtained solid is filtered, dried by blowing at 140 ℃ for 9h, roasted at 800 ℃ for 4h, and activated in 3.0 volume percent butane air mixed gas for 24h for use. The mass fraction of aluminum silicate in the catalyst is 70%, and the mass fraction of germanium oxide in the catalyst is 5%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; at 350 ℃ to reactThe mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 9
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the heating reflux is carried out for 6h at the temperature of 140 ℃, then phosphoric acid with the mass fraction of 85 percent, magnesium silicate and tantalum oxide are added, the reflux is continued for 12h, and the adding amount of the phosphoric acid is 1.6 according to the molar ratio of P/V in the phosphoric acid and vanadium pentoxide. At the same time, PEG2000 (final concentration of 40mg/mL) was added as a surfactant. The obtained solid is filtered, dried by blowing at 140 ℃ for 6h, roasted at 800 ℃ for 4h, and activated in 3.0 volume percent butane air mixed gas for 12h for use. The mass fraction of the magnesium silicate in the catalyst is 70%, and the mass fraction of the tantalum oxide in the catalyst is 5%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 10
Putting vanadium pentoxide into mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5And 100mL of alcoholic solution), the volume ratio of the benzyl alcohol to the isobutanol is 1:1, the mixture is heated and refluxed for 3 hours at the temperature of 140 ℃, and then phosphoric acid and SiO with the mass fraction of 85 percent are added2And continuously refluxing the molybdenum oxide for 24 hours, wherein the adding amount of the phosphoric acid is 1.6 of the molar ratio of the phosphoric acid to the P/V in the vanadium pentoxide. The obtained solid is filtered, dried by blowing at 140 ℃ for 12h, roasted at 800 ℃ for 4h, and activated in butane air mixed gas with volume fraction of 3.0% for 12 h. SiO 22The mass fraction of the molybdenum oxide in the catalyst is 70 percent, and the mass fraction of the molybdenum oxide in the catalyst is 5 percent.
Tabletting the obtained sample to 20-60 meshes, and then carrying out tablettingAdding into a fixed bed reactor, gasifying 30 wt% acetic acid water solution at 300 ℃, and passing through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 11
Vanadium pentoxide was placed in benzyl alcohol solution (5g V)2O5And 100mL of alcoholic solution), heating and refluxing for 3h at 130 ℃, and then adding phosphoric acid and SiO with the mass fraction of 85 percent2And tungsten oxide is continuously refluxed for 12 hours, and the adding amount of phosphoric acid is 1.2 according to the molar ratio of P/V in the phosphoric acid and the vanadium pentoxide. At the same time, PVP-K90 (final concentration 40mg/mL) was added as a surfactant. The obtained solid is filtered, dried by blowing at 120 ℃ for 12h, roasted at 600 ℃ for 4h, and activated in butane air mixed gas with volume fraction of 1.5% for 12 h. SiO 22The mass fraction of tungsten oxide in the catalyst was 70%, and the mass fraction of tungsten oxide in the catalyst was 5%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 12
Vanadium pentoxide was placed in isobutanol solution (5g V)2O5And 100mL of alcoholic solution), heating and refluxing for 6h at 120 ℃, and then adding phosphoric acid and SiO with the mass fraction of 85 percent2And continuously refluxing the bismuth oxide for 24 hours, wherein the adding amount of the phosphoric acid is 1.2 of the molar ratio of the phosphoric acid to the P/V in the vanadium pentoxide. At the same time, the surfactant PVP-K90 (10 mg/mL final concentration) was added. The obtained solid is filtered, dried by blowing at 120 ℃ for 12h, roasted at 600 ℃ for 4h, and activated in butane air mixed gas with volume fraction of 1.5% for 24 h. SiO 22In the catalyst, the mass fraction is70 percent, and the mass fraction of the bismuth oxide in the catalyst is 5 percent.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 13
Vanadium pentoxide was placed in isobutanol solution (5g V)2O5And 100mL of alcoholic solution), heating and refluxing for 6h at 120 ℃, and then adding phosphoric acid and SiO with the mass fraction of 85 percent2And antimony oxide is continuously refluxed for 24 hours, and the adding amount of the phosphoric acid is added according to the molar ratio of the P/V in the phosphoric acid and the vanadium pentoxide of 1.2. At the same time, the surfactant PVP-K90 (10 mg/mL final concentration) was added. The obtained solid is filtered, dried by blowing at 120 ℃ for 12h, roasted at 600 ℃ for 4h, and activated in butane air mixed gas with volume fraction of 1.5% for 24 h. SiO 22The mass fraction of the antimony oxide in the catalyst is 70 percent, and the mass fraction of the antimony oxide in the catalyst is 5 percent.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Example 14
Vanadium pentoxide was placed in isobutanol solution (5g V)2O5And 100mL of alcoholic solution), heating and refluxing for 6h at 120 ℃, and then adding phosphoric acid and SiO with the mass fraction of 85 percent2Titanium oxide and antimony oxide are continuously refluxed for 24 hours, and the adding amount of phosphoric acid is 1.2 of the molar ratio of P/V in the phosphoric acid and vanadium pentoxide. At the same time, the surfactant PVP-K90 (10 mg/mL final concentration) was added. Filtering the obtained solid, blowing at 120 deg.CDrying for 12h, air roasting at 600 deg.C for 4h, and activating in 1.5% volume fraction butane-air mixed gas for 24 h. SiO 22The mass fraction of the titanium oxide in the catalyst is 70%, the mass fraction of the titanium oxide in the catalyst is 2%, and the mass fraction of the antimony oxide in the catalyst is 3%.
Tabletting the obtained sample to 20-60 meshes, adding the obtained sample into a fixed bed reactor, gasifying 30 wt% acetic acid aqueous solution at 300 ℃, and passing the gasified solution through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1.
Comparative example 1
Vanadium pentoxide was dispersed in a mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5With 50mL benzyl alcohol and 50mL isobutanol solution), reflux at 150 ℃ for 2H, add 98% H3PO4The amount of the solvent is calculated according to the P/V of 1.06, the mixture is continuously refluxed for 2h, the solvent is evaporated, and the obtained sample is dried for 6h at 150 ℃, then roasted for 6h in air at 300 ℃ and further roasted for 12h at 450 ℃.
The obtained sample was V2O5-P2O5(P/V ═ 1.06), the obtained sample was tabletted and molded into 20 to 60 mesh, and then charged into a fixed bed reactor, and after vaporizing at 300 ℃ with 30 wt% aqueous acetic acid, it was passed through an oxygen-containing N column2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure is 1atm in the reaction process, the gas chromatography is used for on-line monitoring, and the main reaction products are acetone and CO2No acrylic acid was produced.
Comparative example 2
Vanadium pentoxide was dispersed in a mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5With 50mL benzyl alcohol and 50mL isobutanol solution), reflux at 150 ℃ for 2H, add 98% H3PO4Adding the mixture according to the proportion of P/V to 1.06, continuously refluxing for 2h, evaporating the solvent to dryness to obtain a sampleDrying at 150 deg.C for 6h, calcining at 300 deg.C in air for 6h, and calcining at 450 deg.C for 12 h.
Tabletting the obtained sample to 20-60 mesh, adding into fixed bed reactor, gasifying acetic acid and methanol (molar ratio of acetic acid to methanol is 1: 1) at 300 deg.C, and passing through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid or methanol to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1. A large amount of by-products, namely methyl acetate, methyl acrylate and methylal are generated, and the products are difficult to separate.
Comparative example 3
Vanadium pentoxide was dispersed in a mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5With 50mL benzyl alcohol and 50mL isobutanol solution), reflux at 150 ℃ for 2H, add 98% H3PO4The amount of the solvent is calculated according to the P/V of 1.06, the mixture is continuously refluxed for 2h, the solvent is evaporated, and the obtained sample is dried for 6h at 150 ℃, then roasted for 6h in air at 300 ℃ and further roasted for 12h at 450 ℃.
Tabletting the obtained sample to 20-60 meshes, adding into a fixed bed reactor, gasifying acetic acid and trioxymethylene (the molar ratio of acetic acid to formaldehyde is 1: 1) at 300 ℃, and passing through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1. Formaldehyde cannot react completely and can form polyoxymethylene in the reacted solution, which causes difficulties in separation and in operation of the apparatus.
Comparative example 4
Vanadium pentoxide was dispersed in a mixed alcohol solution of benzyl alcohol and isobutanol (5g V)2O5With 50mL benzyl alcohol and 50mL isobutanol solution), reflux at 150 ℃ for 2H, add 98% H3PO4Adding the active component according to the proportion of P/V ═ 1.06, continuously refluxing for 2h, evaporating the solvent, drying the obtained sample at 150 ℃ for 6h, and then baking the sample in the air at 300 DEG CThe mixture is calcined for 6 hours and then calcined at 450 ℃ for 12 hours.
Tabletting the obtained sample to 20-60 mesh, adding into fixed bed reactor, gasifying acetic acid and formalin solution (molar ratio of acetic acid to formaldehyde is 1: 1) at 300 deg.C, and passing through oxygen-containing N2Diluting, wherein the volume fraction of acetic acid in the gas phase is 25%, and the molar ratio of acetic acid to oxygen is 2; reacting at 350 ℃, wherein the mass space velocity of acetic acid on the catalyst is 2h-1The gas pressure in the reaction process is 1atm, the gas chromatography is used for on-line monitoring, and the conversion rate and the selectivity are shown in Table 1. Formaldehyde cannot react completely and can form polyoxymethylene in the reacted solution, which causes difficulties in separation and in operation of the apparatus. The operation is relatively complicated by the use of two raw materials.
TABLE 1 reaction evaluation results
Claims (6)
1. A process for synthesizing acrylic acid from acetic acid, characterized by:
in a fixed bed reactor, acetic acid or an acetic acid solution is gasified and diluted in an oxygen-containing inert atmosphere, and then is catalyzed by a VPO-based catalyst to generate oxidation-condensation to prepare acrylic acid at a certain temperature and under a certain pressure.
2. The method of claim 1, wherein:
the mass fraction of acetic acid in the acetic acid or the acetic acid solution is 50-100%; the solvent is one or more of water, acetonitrile, cyclohexane, benzene, toluene, xylene, dioxane and tetrahydrofuran;
the gasification temperature is 200 ℃ and 400 ℃; the volume fraction of acetic acid in the diluted gas phase is 5-50%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-5);
the oxygen-containing inert atmosphere is N2One or more of Ar and He; the oxygen-containing inert atmosphere, wherein oxygen is derived from one or two of oxygen and air;
the reaction temperature in the catalysis process is not lower than 280 ℃; the reaction pressure is 0.5 atm-30 atm;
the mass space velocity of the acetic acid is 0.5-5 h-1。
3. The method of claim 2, wherein:
the mass fraction of acetic acid in the acetic acid solution is 50-90%; the solvent is one or more of water, acetonitrile, cyclohexane, toluene and dioxane;
the gasification temperature is 200-350 ℃; the volume fraction of acetic acid in the diluted gas phase is 5-40%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-4);
the oxygen-containing inert atmosphere is preferably N2One or two of Ar; wherein the oxygen is derived from air;
the reaction temperature of the catalytic process is 280-450 ℃; the reaction pressure is 0.5 atm-20 atm;
the mass space velocity of the acetic acid is 0.5-3 h-1。
4. A method according to claim 3, characterized by:
the mass fraction of acetic acid in the acetic acid solution is 50-80%; the solvent is one or more of water, acetonitrile and dioxane;
the gasification temperature is 200 ℃ and 300 ℃; the volume fraction of acetic acid in the diluted gas phase is 5-30%;
the oxygen content in the oxygen-containing inert atmosphere is determined according to the acetic acid content in the acetic acid solution, and the ratio of the mole number of the acetic acid to the mole number of the oxygen is ensured to be (2-3);
the reaction temperature in the catalytic process is 280-400 ℃; the reaction pressure is 0.5 atm-10 atm;
the mass space velocity of the acetic acid is 1-3 h-1。
5. The method of claim 1, wherein:
the VPO-based catalyst is VPxOy, x is 0.5-3, and y is a suitable value to satisfy the valence states of the respective elements (V and P)
Or the VPO-based catalyst consists of an active component VPxOyAn auxiliary agent and a carrier; x is 0.5 to 3, and y is a suitable value satisfying the valence of each element (V and P);
the catalyst comprises an active VPO component and a catalyst component, wherein the active VPO component comprises the following components in percentage by mass: 4 to 50 percent;
the catalyst comprises the following carriers: SiO 22,Al2O3,SiO2-Al2O3One or more of SiC, MgO, aluminum silicate and magnesium silicate; the mass fraction of the carrier in the catalyst is 50-96%;
the catalyst comprises the following auxiliary agents: one or more oxides of Sc, Y, La, Ti, Nb, Ge, Ta, Mo, W, Bi and Sb; the mass fraction of the auxiliary agent in the catalyst is 0-10%.
6. The method of claim 5, wherein:
the catalyst, wherein the mass fraction of the active VPO component is preferably: 20 to 40 percent;
the catalyst, the preferred carrier is: SiO 22,Al2O3,SiO2-Al2O3One or more of SiC and MgO; the mass fraction of the carrier in the catalyst is 60-80%;
the catalyst, preferable auxiliaries are: one or more oxides of Sc, La, Ti, Nb, Mo, W, Bi and Sb; the mass fraction of the auxiliary agent in the catalyst is 0-5%.
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| CN114605252A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
| CN114605251A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for synthesizing acrylic acid |
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| CN103842326A (en) * | 2011-10-03 | 2014-06-04 | 国际人造丝公司 | Processes for producing acrylic acids and acrylates |
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| CN114605252A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
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| CN114605251B (en) * | 2020-12-09 | 2023-04-07 | 中国科学院大连化学物理研究所 | Synthetic method of acrylic acid |
| CN114605252B (en) * | 2020-12-09 | 2023-05-26 | 中国科学院大连化学物理研究所 | Method for preparing methacrylic acid and methyl ester thereof |
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