CN110498780B - Method for preparing tetrahydrofurfuryl acid by gas-phase hydrogenation of furoic acid - Google Patents
Method for preparing tetrahydrofurfuryl acid by gas-phase hydrogenation of furoic acid Download PDFInfo
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Abstract
The invention provides a method for preparing tetrahydrofurfuryl acid by furfuryl acid gas-phase hydrogenation, wherein the furfuryl acid is uniformly mixed with hydrogen before and after being gasified in a vaporizer, the uniformly mixed gas-phase furfuryl acid and hydrogen mixture enters a catalyst bed layer of a fixed bed reactor for catalytic hydrogenation to prepare the product tetrahydrofurfuryl acid, and a catalyst in the catalyst bed layer is Pd-M/TiO2‑Al2O3The catalyst comprises an active component Pd, an auxiliary agent M, one of Ru, Rh, Pt and Ni, and a carrier which is a composite carrier of alumina and titanium dioxide. The invention has the advantages that the conversion rate of the raw material furoic acid reaches more than 99.8 percent, and the selectivity of the product tetrahydrofurfuryl acid reaches 100 percent. In addition, the catalyst has long service life, the one-way service life of the catalyst reaches more than 2000h, and the catalyst is renewable and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing tetrahydrofurfuryl acid by gas-phase hydrogenation of furoic acid.
Background
Tetrahydrofurfuryl acid is an important medical intermediate, and can be used for preparing cephalosporin antibiotic medicaments, oxazine medicaments for treating hypertension, medicaments for treating prostate cancer and the like. At present, the tetrahydrofurfuryl acid is mainly prepared by sodium furoate or furoic acid through catalytic hydrogenation. Takes sodium furoate as raw material, and the furoate needs to be neutralized by sodium hydroxide and catalyzed by Raney NiHigh-pressure hydrogenation under the action of agent, acidification with concentrated sulfuric acid, ether extraction and other steps. The process has the defects of harsh reaction conditions, difficult product separation, large consumption of a large amount of strong acid and strong base in the preparation process, large environmental pollution, higher requirement on equipment and the like, and the operation mode can only stay in intermittent operation (J.Am.chem.Soc.,1923,45, 3029-3045). Another process is to use furoic acid as raw material and directly hydrogenate under the action of catalyst to obtain tetrahydrofurfuryl acid, which simplifies the preparation process and greatly reduces the environmental pollution. Li Zhe Qi et Al (petrochemical 2005,34, 561-) -Al with Pd-Ni/gamma-Al2O3The catalyst is water as solvent, realizes the continuous hydrogenation of the furoic acid in a fixed bed reactor, stably operates for more than 200 hours, and has the yield of the tetrahydrofurfuryl acid of 90 percent. However, the water is used as a solvent, so that the subsequent product separation is difficult, and the product yield is reduced in the purification process.
Patent application CN201810976582 discloses a composite carbon-noble metal catalyst, a preparation method thereof and application thereof in synthesizing 2-tetrahydrofurfuryl acid. The catalyst consists of graphene quantum dots, a graphene quantum dot compound and noble metal particles, wherein the noble metal particles are deposited on the surface of the graphene quantum dot compound, and the graphene quantum dot compound and the graphene quantum dots deposited with the noble metal particles are uniformly dispersed in a pure water solvent; the graphene quantum dot composite is an amorphous nano carbon-based material formed by aggregating and compounding a plurality of graphene quantum dots with the average size of 1-10nm, and the size of the amorphous nano carbon-based material is 20-100 nm; the noble metal is one of platinum, palladium, iridium, ruthenium and rhodium, and the average particle size is 1-10 nm. The invention provides the application of the catalyst aqueous solution in the synthesis of 2-tetrahydrofurfuryl acid, hydrogen does not need to be added in the synthesis process, and the characteristics of high conversion rate, high catalytic activity, high reaction rate and high stability are shown by combining the reaction conditions of photo-thermal reaction and photo-thermal reaction. Although the invention can prepare tetrahydrofurfuryl acid from furoic acid without using hydrogen, the catalyst in the invention is complicated to prepare, and in addition, the reaction requires the use of an aqueous catalyst solution and methanol, and the preparation and separation of the product are complicated, so that the method is not suitable for industrialization.
Disclosure of Invention
Aiming at the problems, the invention provides a method which directly uses furoic acid as a raw material, does not adopt any solvent, vaporizes the furoic acid as the raw material, obtains a tetrahydrofurfuryl acid crude product by vaporization and hydrogenation of the furoic acid, obtains a qualified product by simple distillation, and has green and environment-friendly process. In addition, Al is used for catalyst preparation2O3-TiO2The composite carrier can greatly prolong the service life of the catalyst.
In the invention, the furoic acid is white crystal at room temperature, the melting point of the furoic acid is 129-133 ℃, so that the furoic acid is firstly heated to the temperature above the melting point to be melted, and then the liquid furoic acid and hydrogen are mixed and vaporized in a vaporizer, wherein the temperature in the vaporizer is generally higher than the boiling point 232.14 ℃ of the furoic acid under the atmospheric pressure, but the partial pressure of the furoic acid in the system is lower than the atmospheric pressure due to the existence of the hydrogen, so that the furoic acid can be partially or completely vaporized into the gaseous furoic acid at the temperature below 232 ℃ in the vaporizer.
The invention develops a catalyst for furfuryl acid hydrogenation, which has high activity, good stability and good selectivity to tetrahydrofurfuryl acid for furfuryl acid hydrogenation reaction. The invention provides a method for preparing tetrahydrofurfuryl acid by furfuryl acid gas phase hydrogenation on a fixed bed reactor, which has high yield (> 99%), avoids using a large amount of solvent, is easy to separate and purify subsequent products, has high product quality, green and environment-friendly process and has good industrial application value.
Therefore, the invention provides a method for preparing tetrahydrofurfuryl acid by furfuryl acid gas-phase hydrogenation, wherein the furfuryl acid is uniformly mixed with hydrogen before and after being gasified in a vaporizer, the uniformly mixed gas-phase furfuryl acid and hydrogen mixture enters a catalyst bed layer of a fixed bed reactor to be subjected to catalytic hydrogenation to prepare the product tetrahydrofurfuryl acid, and a catalyst in the catalyst bed layer is Pd-M/TiO2-Al2O3The catalyst comprises an active component Pd, an auxiliary agent M, one of Ru, Rh, Pt and Ni, and a carrier which is a composite carrier of alumina and titanium dioxide.
Wherein, the furoic acid and the hydrogen can be both introduced into a preheated vaporizer for uniform mixing, or the furoic acid is firstly vaporized in the vaporizer and then introduced into the hydrogen for uniform mixing.
In a specific embodiment, the method also comprises the process of heating and melting the raw material furoic acid and converting the raw material furoic acid from a solid phase to a liquid phase before the furoic acid is gasified.
In a specific embodiment, the preheating temperature of the material in the vaporizer is 200-300 ℃, preferably 230-280 ℃.
In a specific embodiment, the hydrogenation pressure is 1.0-5.0 MPa, preferably 2.0-4.0 MPa, the hydrogenation reaction temperature is 150-300 ℃, preferably 230-280 ℃, and the molar ratio of hydrogen to furoic acid is 1-50: 1, preferably 3-20: 1, more preferably 5 to 15: 1, the volume space velocity of the solid furoic acid is 0.1-1.0 h-1Preferably 0.2 to 0.4h-1。
In a specific embodiment, in the catalyst, the mass percent of palladium is 0.4-1.5%, the auxiliary agent M is Ru or Rh, and the mass percent of the auxiliary agent M is 0.01-0.5%, preferably 0.05-0.2%.
In a specific embodiment, the composite support is a TiO support2The mass fraction of (A) is 10-50%, preferably 20-45%.
In a specific embodiment, the catalyst is prepared by an impregnation method, and specifically comprises the steps of impregnating active metal palladium and auxiliary metal M on the composite carrier.
In a specific embodiment, Al is added2O3Mixing with pure water, stirring, and adding dropwise ethanol solution of tetrabutyl titanate to obtain mixed solution containing Ti (OC)4H9)4And CH3CH2The volume ratio of OH is 1: and 2-8, drying and roasting the mixed solution to obtain the composite carrier.
In a specific embodiment, before the catalyst in the fixed bed reactor participates in the hydrogenation reaction, hydrogen is firstly used for reducing for 2-8 hours at 200-400 ℃ to obtain an activated catalyst, so that the active metal and the auxiliary metal in the activated catalyst are both in a reduced state.
In one embodiment, the catalytic hydrogenation of furoic acid in the absence of a solvent produces the product tetrahydrofurfuryl acid.
The method is carried out on a fixed bed reactor, and comprises melting raw material furoic acid in a reaction kettle, pumping into the fixed bed reactor, vaporizing by a vaporizer, feeding into a catalyst bed layer together with hydrogen, carrying out hydrogenation reaction under the action of a catalyst, and carrying out gas-liquid separation and condensation on reaction liquid to obtain a liquid-phase product. The conversion rate of the raw material furoic acid is more than 99.8 percent, the selectivity of the tetrahydrofurfuryl acid is 100 percent, the qualified product can be obtained by simply distilling the liquid phase product, and the hydrogen can be recycled.
The method for preparing the tetrahydrofurfuryl acid by the gas-phase hydrogenation of the furoic acid adopted by the invention has the following advantages:
(1) the reaction process does not need to use a solvent, the purity of the hydrogenated liquid is more than 99.8 percent, and a qualified tetrahydrofurfuryl acid product can be obtained by simple distillation; the whole process for preparing the tetrahydrofurfuryl acid product by hydrogenating the furoic acid is very simple, energy-saving and environment-friendly.
(2) The catalyst used in the invention has high activity, and when the furoic acid is subjected to solvent-free hydrogenation in a gaseous state, the selectivity of the product tetrahydrofurfuryl acid reaches 100%.
(3) The carrier of the catalyst used in the invention is a titanium oxide and alumina composite carrier, and the obtained catalyst has excellent catalytic effect, long service life, and can stably run for more than 2000h, which is more than ten times of the service life of the catalyst in the prior art; and the catalyst can be regenerated, so that the method has a good industrial application prospect.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Preparation of the catalyst:
TiO2-Al2O3preparing a composite carrier: weighing a certain mass of Al2O3Adding into a certain amount of purified water, rapidly stirring, and adding dropwise a certain amount of ethanol solution of tetrabutyl titanate, wherein Ti (OC) is4H9)4And CH3CH2The volume ratio of OH is 1: 4, drying at 110 DEG CDrying for 12h, and roasting the dried sample at 500 ℃ for 4h to obtain TiO2-Al2 O3-X (%) composite carrier. Wherein X is TiO2The mass fractions were 0, 10, 30, 50, respectively, where x is 0 is the catalyst used in comparative example A1 and x is 10, 30, 50 is the catalyst used in examples A1 to A8.
Example a 1: weighing a certain mass of palladium chloride and ruthenium chloride, dissolving the palladium chloride and the ruthenium chloride by hydrochloric acid, and adding a certain amount of TiO2-Al2O3-30 is immersed in the above solution. Dipping for 24h, drying at 120 ℃ for 12h, and roasting in a muffle furnace at 500 ℃ for 4h, wherein the loading capacity of metal Pd is 0.5%, and the loading capacity of Ru is 0.05%, so as to obtain the catalyst 1.
Example a 2: catalyst 2 was obtained by supporting metals Pd and Rh with a supported amount of Pd of 0.5% and Rh of 0.05%, and otherwise the same as in example a 1.
Example a 3: catalyst 3 was obtained by supporting metals Pd and Pt with a loading of 0.5% for metallic Pd and a loading of 0.05% for Pt in the same manner as in example a 1.
Example a 4: catalyst 4 was obtained by supporting metals Pd and Ni, with a Pd loading of 0.5% and a Ni loading of 0.05%, in the same manner as in example A1.
Example a 5: the carrier being TiO2-Al2O3-10 otherwise as in example A1, giving catalyst 5.
Example a 6: the carrier being TiO2-Al2O3-50 otherwise as in example A1, giving catalyst 6.
Example a 7: catalyst 7 was obtained in the same manner as in example A1 except that the supporting amount of Ru was 0.10%.
Example A8: catalyst 8 was obtained in the same manner as in example A1 except that the loading of Ru was 0.20%.
Comparative example a 1: weighing a certain mass of palladium chloride and ruthenium chloride, dissolving the palladium chloride and the ruthenium chloride by hydrochloric acid, and adding a certain amount of Al2O3And soaking in the solution. Dipping for 24h, drying at 120 ℃ for 12h, and roasting in a muffle furnace at 500 ℃ for 4h, wherein the loading capacity of metal Pd is 0.5%, and the loading capacity of Ru is 0.05%, so as to obtain the catalyst 9.
The catalyst is sieved into 20-40 meshes, evaluation is carried out on a fixed bed reactor with the inner diameter of 13mm, the reduction temperature of the catalyst is 300 ℃, the hydrogen pressure is 3.0MPa, the reaction temperature is 250 ℃, the molar ratio of hydrogen to furoic acid is 5.0, and the feeding volume airspeed of the furoic acid is 0.3h-1The evaluation results are shown in Table 1.
TABLE 1 evaluation of Furic acid hydrogenation Performance on different catalysts
As can be seen from examples A1-A4 of Table 1, for the catalytic hydrogenation of furoic acid to tetrahydrofurfuryl acid, the promoter metals are preferably ruthenium and rhodium, with ruthenium being the most preferred, when palladium is used as the primary catalytic metal, as compared to platinum and nickel. The promoter metal in the embodiment A3 is platinum, and the selectivity of the product tetrahydrofurfuryl acid in the embodiment is low because platinum easily leads furan ring to be cracked; however, it is possible that the catalyst containing the promoter platinum has a better catalytic effect at lower reaction temperature and pressure or at lower catalyst amount and promoter platinum content in the catalyst. From examples A1, A5-A6 and comparative example 1 of Table 1, TiO was used in the present invention2And Al2O3When the carrier is compounded, the furoic acid hydrogenation conversion rate of the obtained catalyst is higher, especially TiO2When the catalyst accounts for 30 weight percent of the composite carrier, the obtained catalyst has better effect, and when TiO is used2When the weight portion of the composite carrier is 10 percent and 50 percent, the TiO will be used2The occupied amount is too small or too large to affect the catalytic performance of the catalyst. As can be seen from the examples A1 and A7 to A8 in Table 1, the catalyst has very good catalytic performance when the content of the auxiliary agent ruthenium in the catalyst is 0.05 to 0.2 percent.
The reaction process comprises the following steps:
example B1:
in a fixed bed reactor, 10.0g of catalyst 1 is loaded in a constant temperature area of a reaction tube, and the catalyst is reduced for 4 hours at 300 ℃ in a hydrogen atmosphere. Hydrogen and furoic acid are fed into a reactor according to the molar ratio of 10, and the hydrogen pressure is 3.0MPa, the hydrogenation reaction temperature is 250 ℃, and the feeding volume space velocity of the furoic acid is 0.3h-1. After the reacted material passes through a gas-liquid separator, gas-phase hydrogen and supplemented fresh hydrogen enter a hydrogenation reactor together. The conversion rate of the furoic acid is 99.9 percent, and the selectivity of the tetrahydrofurfuryl acid is 100 percent.
Examples B2 to B9 the results are shown in Table 2, with corresponding changes in the reaction conditions:
TABLE 2 Effect of reaction conditions on Furic acid hydrogenation Performance
As can be seen from the comparison of examples B1-B3 in Table 2, the catalyst hydrogenation reaction pressure is about 3MPa, and when the reaction pressure is as low as 1MPa, part of the furoic acid is not available to participate in the reaction, and the reaction is not complete, so the hydrogenation effect is poor; when the reaction pressure is up to 5MPa, the conversion rate of the furoic acid is also affected due to the excessive pressure. As can be seen from examples B1 and B4 of Table 2, the catalytic hydrogenation of furoic acid is very effective at reaction temperatures of 250 ℃ and 280 ℃; when the reaction temperature is as low as about 200 ℃, partial furoic acid may be liquefied to enable the liquid furoic acid to directly contact with the catalyst, the furfuric acid hydrogenation performance is affected due to uneven contact between the raw material and the catalyst, and when the reaction temperature is as high as above 300 ℃, other byproducts may be generated to affect the selectivity of the reaction. Therefore, the optimal reaction temperature of the catalyst for catalyzing the hydrogenation of the furoic acid is 250-280 ℃. As can be seen from examples B1 and B5-B6 of Table 2, the space velocity of furoic acid is 0.3h-1When the conversion of furoic acid is complete, the space velocity of furoic acid is increased to 0.4h-1And 0.5h-1In time, the conversion of furoic acid is incomplete and thus its conversion rate decreases. As can be seen from the examples B1 and B7-B9 in Table 2, if the amount of hydrogen is too large, the conversion of furoic acid is affected, and the molar ratio of hydrogen to furoic acid is optimally 5-15: 1.
example B10
The long-term stability test of catalyst 1 was carried out under the same reaction conditions as in example B1. And collecting the liquid phase product at the outlet of the hydrogenation reactor for analysis, wherein the analysis result is shown in Table 3.
TABLE 3 stability test results for furoic acid hydrogenation catalysts
| Reaction time/h | Furoic acid conversion/%) | Tetrahydrofurfuryl acid Selectivity/%) |
| 10 | 99.9 | 100 |
| 500 | 99.9 | 100 |
| 750 | 99.8 | 100 |
| 1000 | 99.8 | 100 |
| 1500 | 99.7 | 100 |
| 2000 | 99.6 | 100 |
As can be seen from the data in Table 3, the catalyst 1 has good stability, the furoic acid conversion rate is still maintained above 99.6% after the catalyst is continuously used for 2000 hours, and the selectivity of the tetrahydrofurfuryl acid is as high as 100%. In the background art, Pd-Ni/gamma-Al is used2O3When the catalyst is used and water is used as a solvent, the yield of the tetrahydrofurfuryl acid is only 90 percent, and the service life of the catalyst is 200 h. The yield of the tetrahydrofurfuryl acid generated by catalyzing the furfuryl acid hydrogenation by the catalyst used in the invention can reach 99.6-99.9%, and the service life of the catalyst can reach 2000 hours, which shows that the catalyst has good industrial application prospect when being used for the furfuryl acid hydrogenation.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (6)
1. A method for preparing tetrahydrofurfuryl acid by furfuryl acid gas-phase hydrogenation comprises the steps of uniformly mixing furfuryl acid with hydrogen before and after gasification in a vaporizer, feeding the uniformly mixed gas-phase furfuryl acid and hydrogen mixture into a catalyst bed layer of a fixed bed reactor, and carrying out catalytic hydrogenation under the condition of no solvent to obtain a product tetrahydrofurfuryl acid, wherein a catalyst in the catalyst bed layer is Pd-M/TiO2-Al2O3The catalyst comprises an active component Pd, an auxiliary agent M and a carrier, wherein the mass percent of the palladium is 0.5-1.5%, the auxiliary agent M is Ru or Rh, the mass percent of the auxiliary agent M is 0.05-0.2%, the carrier is a composite carrier of alumina and titanium dioxide, and TiO in the composite carrier2The mass fraction of (A) is 30-45%; the hydrogenation pressure is 2.0-4.0 MPa, the hydrogenation reaction temperature is 230-280 ℃, and the molar ratio of hydrogen to furoic acid is 5-15: 1.
2. the method of claim 1 further comprising the step of heating the starting material furoic acid to melt and convert from a solid phase to a liquid phase prior to the step of vaporizing the furoic acid.
3. The method according to claim 1, wherein the preheating temperature of the material in the vaporizer is 230 to 280 ℃.
4. The method according to any one of claims 1 to 3, wherein the catalyst is prepared by an impregnation method, and specifically comprises impregnating an active metal palladium and an auxiliary metal M on the composite carrier.
5. The method of claim 4, wherein Al is added2O3Mixing with pure water, stirring, and adding dropwise ethanol solution of tetrabutyl titanate to obtain mixed solution containing Ti (OC)4H9)4And CH3CH2The volume ratio of OH is 1: and 2-8, drying and roasting the mixed solution to obtain the composite carrier.
6. The method according to any one of claims 1 to 3, wherein before the catalyst in the fixed bed reactor participates in the hydrogenation reaction, hydrogen is firstly used for reducing for 2 to 8 hours at 200 to 400 ℃ to obtain an activated catalyst, so that the active metal and the auxiliary metal in the activated catalyst are in a reduced state.
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| Pd-Ru/Al2O3催化剂上α-呋喃甲酸催化加氢反应的研究;敖志勇等;《石油化工》;20051231;第34卷(第4期);第368页摘要、第1.2-1.3节 * |
| 水溶剂中Pd-Ni/γ-Al2O3催化剂上糠酸加氢;李浙齐等;《石油化工》;20051231;第34卷(第6期);第561页摘要、第1.2、1.4节 * |
| 糠酸加氢负载型催化剂的制备及催化性能;李浙齐等;《分子催化》;20051231;第19卷(第6期);第436页摘要、第1.2-1.3节、第438页表3 * |
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