Patent Application
20240149255
The present invention belongs to the technical field of petrochemical industry, and relates to an alkali metal ion modified titanium silicalite zeolite TS-1 for gas phase epoxidation of propylene and hydrogen peroxide and a preparation method thereof.
A titanium silicalite zeolite is a kind of silicate zeolite containing titanium heteroatoms in a crystal framework. TS-1 is a very important member of a titanium silicalite zeolite family MarcoTaramasso et al. first reported the synthesis method of TS-1 (GB2071071A, U.S. Pat. No. 4,410,501, 1983). It has an MFI topological structure, and has a ten-membered ring cross-channel system like the well-known silica-alumina zeolite ZSM-5.
A large number of basic researches show that the titanium heteroatoms exist in the TS-1 zeolite framework in isolated tetra-coordinate form. The titanium heteroatoms generate characteristic absorption of electronic transition from oxygen ligand to titanium site atom near 210 nm in the UV-visible diffuse reflectance spectroscopy and generate characteristic resonance absorption near 1120 cm−1 in the UV Raman spectroscopy. In addition, framework titanium also generates characteristic absorption of Si—O—Ti antisymmetric stretching vibration (or Si—O bond stretching vibration disturbed by framework titanium) near 960 cm−1 in the intermediate infrared region of the infrared spectrum. The local environment of the framework titanium can be changed. According to the report of J. Catal., 1995,151, 77-86, after sodium exchange is conducted on TS-1 zeolite with 1 M NaOH solution at 25° C., the infrared characteristic peak of the framework titanium of TS-1 zeolite near 960 cm−1 disappears, and at the same time, new infrared characteristic absorption appears at 985 cm−1. Some literature suggests that the sodium exchange that occurs in the strong alkaline solution is essentially the reaction of sodium hydroxide and the silicon hydroxyl near the framework titanium (NaOH+Si—OH═Si—O−Na++H2O), which changes the local environment of the framework titanium, thereby influencing the infrared spectrum characteristics of the framework titanium.
A large number of application researches show that the TS-1 zeolite obtained by introducing the titanium heteroatoms into the MFI framework has unique catalytic oxidation performance and many uses. In short, the TS-1 zeolite can catalyze the epoxidation of low-concentration hydrogen peroxide and a series of olefins to form epoxides. In addition, the TS-1 zeolite can also be used as a catalyst for hydroxylation of phenol, ammoxidation of cyclohexanone and oxidation of alcohols to produce aldehydes and ketones, and oxidation of alkane to produce alcohols and ketones. Neri et al. first reported a liquid phase epoxidation method of propylene by taking methanol as a solvent and 30 wt. % hydrogen peroxide as an oxidant (U.S. Pat. No. 4,833,260, 1989), and obtained the result that the hydrogen peroxide conversion rate and the propylene oxide (PO) selectivity are larger than 90%. Clerici et al. systematically studied the reactions of various lower olefins and hydrogen peroxides catalyzed by the TS-1 zeolite (J Catal, 1993, 140(1): 71), and pointed out the order of the liquid phase epoxidation rate of olefins in various solvents is: methanol>ethanol>tert-butanol. In 2008, the combination of the propylene liquid phase epoxidation (HPPO) technology based on TS-1 titanium silicalite zeolite and methanol solvent with the anthraquinone method for producing hydrogen peroxide to build a green factory for producing propylene oxide was first commercialized by Degussa and Uhde, and BASF and Dow, respectively (Ind. Eng. Chem. Res. 2008, 47, 2086-2090).
Although the TS-1 titanium silicalite zeolites synthesized by different methods can have the catalytic performance of olefin epoxidation, almost all of the practical TS-1 catalysts for the propylene liquid phase epoxidation (HPPO) technology are prepared by using a nano TS-1 zeolite with agglomerate particle size of 200-300 nm as a matrix. This kind of zeolite is generally synthesized with high purity tetrapropylammonium hydroxide (TPAOH) templating agent and according to the hydrothermal synthesis method (classical method) introduced by Taramasso et al. (U.S. Pat. No. 4,410,501. 1983) and Thangaraj et al. (J Chem Soc Chem Commun, 1992: 123). In order to achieve a reaction performance, literature also has developed the so-called secondary hydrothermal treatment technology for the nano TS-1 zeolite matrix by using an aqueous solution containing a low concentration TPAOH templating agent.
The nano TS-1 zeolite synthesized by the classical method in the propylene liquid phase epoxidation (HPPO) technology has the following advantages: non-framework titanium is less, which is beneficial to reduce the decomposition of the hydrogen peroxide by the non-framework titanium; the crystal size is small and the porous channel is short, which is beneficial to reduce the resistance effect of the ten-membered ring micropores on the diffusion of reactants and products in the liquid phase reaction. However, those skilled in the art know that the synthesis of TS-1 zeolite by the classical method requires the use of high purity templating agent TPAOH and silicon ester and titanium ester raw materials to prevent the introduction of impurity metal ions, especially sodium, potassium and other alkali metal ions. It is found that, even if a very small amount of alkali metal ions present in the hydrothermal synthesis of TS-1 zeolite, the amount of titanium entering the zeolite framework will be obviously reduced, thereby obviously reducing the liquid phase oxidation activity of the catalyst. J. Catal., 1995,151, 77-86 has systematically shown the influence of sodium ion content on the TS-1 zeolite by adding sodium salt to the synthetic gel of TS-1 zeolite. The data provided by the literature show that when the sodium ion content in the gel is too high (Na/Si molar ratio≥0.05), the synthesized TS-1 zeolite has no catalytic activity for n-octane oxidation; and only when the sodium ion content in the gel is very low (Na/Si molar ratio≤0.01), the catalytic activity of the synthesized TS-1 zeolite can close to a normal level. The data provided by the literature also show that although high sodium content can obviously reduce or even completely deactivate the epoxidation catalytic activity of the TS-1 zeolite, it can significantly promote the decomposition of hydrogen peroxide. Based on the results of the liquid phase oxidation reactions, the empirical value with the maximum allowable value of the alkali metal ions of 0.01 in the gel during the hydrothermal synthesis of the TS-1 zeolite is suggested (indicated by the molar ratio of the alkali metal ions to Si atoms, see J. Catal., 1995,151, 77-86; Stud. Surf. Sci. Catal., 1991,69, 79-92; Stud. Surf. Sci. Catal., 1991,60, 343-352; Appl. Catal. A-gen., 2000, 200, 125-134; Front. Chem. Sci. Eng., 2014,8, 149-155.). According to this standard, the content of alkali metal ion impurities of many commercial templating agent TPAOH solutions exceeds the standard. Therefore, the practice of adding cation exchange resin to the synthetic gel during hydrothermal synthesis of the TS-1 zeolite has been proposed. This is because cation exchange resins can capture alkali metal cations in the synthetic gel through ion exchange (RSC Adv., 2016, DOI: 10.1039/C5RA23871D.).
In the liquid phase epoxidation of propylene with methanol solvent (low temperature and high pressure reaction conditions), the main problem to be solved when preparing the catalyst is to reduce as much as possible the negative influence of the microporous diffusion resistance on the reaction conversion rate. Therefore, the secondary hydrothermal treatment of the TS-1 zeolite matrix by using aqueous solution of the TPAOH templating agent is a common knowledge in the area of the modification of the TS-1 zeolite matrix. In this treatment, partial dissolution-recrystallization process occurs on the TS-1 zeolite matrix. The method aims to use the partial dissolution-recrystallization process to produce mesopores or/and hollow cavities in the crystals of the TS-1 zeolite and communicate with the micropores, so as to achieve the purposes of further improving the microporous diffusion of the nano TS-1 zeolite and enhancing the catalytic activity of the nano TS-1 zeolite in the liquid phase epoxidation.
For example, Chinese invention patents (application numbers) 98101357.0, 98117503.1, 99126289.1 and 01140182.6 disclose a modification method of secondary hydrothermal treatment for the TS-1 zeolite matrix with aqueous solution of organic bases, including quaternary ammonium base. Through the research by nitrogen physical adsorption, transmission electron microscopy, UV-visible diffuse reflectance spectroscopy and other methods, the publication literature Microporous and Mesoporous Materials 102 (2007) 80-85 shows that, the partial dissolution-recrystallization process truly occurs during the process of hydrothermal modification of the TS-1 with the TPAOH solution. The process produces two direct modification effects on the TS-1 zeolite: first, cavities are produced inside the crystals; and second, part of the non-framework titanium (guest titanium species, such as anatase) is converted as framework titanium. The former is helpful to the reaction by shortening the length of the micropores and reducing the microporous diffusion resistance of the TS-1 zeolite; and the latter is beneficial to the reaction by removing the guest species in the micropores, unclogging the microporous channels, increasing the number of active sites and reducing the number of titanium oxide species of decomposing hydrogen peroxide. In addition, Chinese invention patent (application number) 201010213605.0 also discloses a method of modifying TS-1 zeolite with water vapor of organic base. The modification effect is described by the phenol hydroxylation reaction (liquid phase) to synthesize diphenol. The purpose of the invention is to overcome the defect of large wastewater discharge of the hydrothermal modification method which uses the organic base solution.
In addition to the above secondary hydrothermal modification (also called partial dissolution-recrystallization modification) method intended to solve the problem of microporous diffusion limitation, the following literature also reports several titanium silicalite zeolite modification methods aimed at the framework titanium active sites and their local environment.
For example, Chem. Eur. J. 2012, 18, 13854-13860 reports the research work of the first characterization of a new hexa-coordinate framework titanium active site (Ti(OSi)2(OH)2(H2O)2) using UV Raman spectroscopy. It involves modification of the TS-1 zeolite at 80° C. with a low concentration NH4HF2 solution containing a small amount of hydrogen peroxide. As a result, the isolated tetra-coordinate framework titanium active site (Ti(OSi)4) in the conventional TS-1 zeolite is converted into isolated hexa-coordinate framework-like titanium active site (Ti(OSi)2(OH)2(H2O)2). The novel hexa-coordinate framework-like titanium active site produces characteristic absorption at 695 cm−1 in the UV Raman spectrum, and exhibits good catalytic activity in the liquid phase epoxidation reaction of propylene. It can be confirmed from the spectrogram supplied by the literature that, the modification method only converts part of the tetra-coordinate framework titanium active site (the absorption position is at 960 cm−1) into the framework-like active site, but does not change the local environment of the remaining tetra-coordinate framework titanium (the characteristic absorption at 960 cm−1 does not undergo a shift). In fact, the modification method based on hydrogen peroxide and NH4HF2 solution has been reported in the following literature: Angew. Chem. 2003, 115, 5087-5090; Angew. Chem. Int. Ed. 2003, 42, 4937-4940; Adv. Synth. Catal. 2007, 349, 979-986; Appl. Catal. A 2007, 327, 295-299. The catalyst modified by the method can improve the catalytic activity and the selectivity for the benzene hydroxylation reaction (liquid phase).
Phys. Chem. Chem. Phys., 2013, 15, 4930-4938 mentions a method for preparing a framework fluorine-containing titanium silicalite zeolite (F—Ti-MWW) by treating layered titanium silicalite zeolite Ti-MWW (treatment temperature of 40-150° C.) with a 2 M nitric acid solution containing NH4F. When the fluorine atom is connected with the silicon adjacent to the framework titanium, that is, SiO3/2F appears beside the framework titanium, the local environment of the framework titanium is changed. SiO3/2F enhances the electropositivity of the titanium site through the electron-withdrawing effect, and the titanium site with the enhanced electropositivity improves the epoxidation reaction activity of olefins (liquid phase) by producing more electrophilic Oα(Ti—Oα—Oβ—H). Chinese invention patent (application number) 201210100532.3 also discloses a framework-containing-fluorine MWW zeolite, and its preparation and application methods. In addition, ACS Catal., 2011, 1, 901-907 illustrates that NH4F modification can reduce the hydrophilic hydroxyl groups on the surface of the TS-1, thereby enhancing the surface hydrophobicity of the catalyst.
Chem. Commun., 2016, 52, 8679 provides a modification method for hydrothermal treatment of TS-1 (170° C.) with a solution containing both ethylamine and tetrapropylammonium bromide. The method converts part of the tetra-coordinate framework titanium (Ti(OSi)4) into hexa-coordinate active titanium species (Ti(OSi)2(OH)2(H2O)2) which is still linked to the framework. This method is a hydrothermal reaction process characterized by a forward reaction of selectively dissolves silicon and a backward reaction of recrystallizing the dissolved silicon. This method has the same modification effect as the abovementioned modification with a low concentration NH4HF2 solution containing a small amount of hydrogen peroxide. However, it is believed that, compared with the F-containing method, the F-free method is easier to optimize the ratio of the tetra-coordinate and the hexa-coordinate active titanium species in the TS-1. Besides, the F-free method can avoid the problem of dissolving titanium by fluoride. Therefore, the F-free method has obvious advantages. Moreover, the modified TS-1 zeolite exhibits the modification effects of pronouncedly improving the activity and selectivity in the epoxidation of cyclohexene (liquid phase).
In addition, there are also a few reports on the ion modification method of the titanium silicalite zeolite.
For example, Chinese invention patent (application number) 201480052389.2 discloses a method for preparing a zinc-modified titanium silicalite zeolite catalyst, which involves the impregnation (100° C.) of TiMWW zeolite with an aqueous solution containing zinc acetate to obtain a ZnTiMWW zeolite with Zn content of 0.1-5 wt. % (1.6 wt. % in the embodiment). Said method also involves such post treatment of the impregnated sample as filtration, washing, and spray drying. The Zn-containing TiMWW zeolite can be used as catalyst for the synthesis of propylene oxide in the liquid phase propylene epoxidation system, but it needs acetonitrile as solvent.
In addition, Applied Catalysis A: General 200 (2000) 125-134 reports the practice of performing alkali metal ion exchange treatment on the TS-1 zeolite by using the potassium carbonate solution at room temperature. As the sodium exchange effect on TS-1 with 1 M NaOH solution reported by J. Catal., 1995,151, 77-86, the potassium ion in the strong alkaline potassium carbonate solution can also conduct similar ion exchange reaction with the silicon hydroxyl near the framework titanium, which replaces the hydrogen ion on the silicon hydroxyl, thereby changing the local environment of the framework titanium and influencing the infrared spectrum characteristics of the framework titanium. However, from the provided results of the liquid phase oxidation reaction of hexane and 2-hexene, the alkali metal ion exchange treatment at room temperature reduces the catalytic activity of treated TS-1 zeolite.
Because people have known in the TS-1 zeolite synthesis research that the presence of the alkali metal ions in the hydrothermal synthesis system is unfavorable for the introduction of titanium into the framework of TS-1, and people have also discovered through ion exchange research that the introduction of the alkali metal ions into the TS-1 zeolite in the post-synthesis process is also unfavorable to the liquid phase oxidation reaction based on hydrogen peroxide oxidant, therefore people do not know the real catalytic application of the alkali metal ion modified TS-1 zeolite so far.
Nevertheless, some literatures such as Catal. Lett., 8, 237 (1991) and Stud. Surf. Sci. Catal., 84, 1853 (1994) have reported that the TS-1 zeolite framework often contains very low content of trivalent metal ion impurities (such as Al3+ and Fe3+) which may produce bridging hydroxyl groups with strong proton acidity. The very small amount of strong acid sites will cause acid-catalyzed side reactions in the liquid phase oxidation reactions catalyzed by the TS-1 zeolite, thereby reducing the selectivity of the reaction. The introduction of a very low content of alkali metal ions into such TS-1 zeolite can effectively prevent the acid sites from destroying the catalyst selectivity. However, in this case, the role of the very small content of alkali metal ions in TS-1 zeolite is counter cation which neutralizes the zeolitic acid sites. For the liquid phase oxidation reaction, if the alkali metal ions introduced into the TS-1 zeolite exceed the amount required to neutralize the acid sites, then side effects such as reduction of catalyst activity would be caused.
In addition, those who skilled in the art know that, various low-temperature selective oxidation reactions catalyzed by the titanium silicalite zeolite use aqueous hydrogen peroxide solution as oxidant. The commercial hydrogen peroxide solution often contains 200-300 ppm acid stabilizer (50 wt. % H2O2 has a pH value of about 1-2). The acid stabilizer enters the titanium silicalite zeolite catalytic reaction system together with hydrogen peroxide, which will acidify the reaction medium (in the propylene epoxidation reaction medium, the pH value of the hydrogen peroxide-methanol feed (3 molH2O2/L) is about 3.0), and will also reduce the reaction selectivity. In addition, when hydrogen peroxide molecules are activated on the titanium active site of the titanium silicalite zeolite through a “five-membered ring” manner, a transient peroxy proton (Ti(η2)-O—O−H+) with strong acidity is produced. In order to neutralize these acidic substances and proven their negative influence on the selectivity of the propylene epoxidation, many patents adopt the strategy of adding alkaline substances to the reaction medium. For example, the alkaline additives mentioned in the Chinese invention patent (application number) 201410512811.x are ammonia, amine, quaternary ammonium base and M1(OH)n. M1 is alkali metal or alkaline earth metal. The additives mentioned in Chinese invention patent (application number) 00124315.2 are alkali metal hydroxide, alkali metal carbonate and bicarbonate, alkali metal carboxylate and ammonia. Chinese invention patent (application number) 03823414.9 claims the introduction into the reaction medium of less than 100 wppm alkali metal and alkaline earth metal, or alkali and alkali cation with a pKB value of less than 4.5, or the combination of alkali and alkali cation, wherein wppm is based on the total weight of hydrogen peroxide in the reaction mixture. Chinese invention patent (application number) 201180067043.6 claims that the addition of 110-190 micromoles potassium cations and phosphorus with at least one hydroxy acid anion into the reaction medium. The micromoles level loading of additive is based on 1 mole of hydrogen peroxide in the feed. Therefore, the existing literature tells us that the way to deal with the extrinsic acidity of the catalyst is to add alkaline substances to the reaction medium or mixture, including alkali metal hydroxides or weak acid salts that can release hydroxide ion via hydrolysis. The loadings of the alkaline substances are generally determined based on the amount of hydrogen peroxide in the feed. According to the information disclosed in the Chinese invention patent (application number) 201480052389.2, at least most of the alkaline substances added to the reaction medium can flow out of the reactor outlet along with the reaction products.
However, Applied Catalysis A: General 218 (2001) 31-38 pointed out that, in a batchwise propylene liquid phase epoxidation test, the attempt of introducing a small amount of sodium carbonate into the reactant, in order to increase the pH value of the reaction liquid, and consequently to further inhibit the side reaction between the epoxidation product and the solvent, so as to enhance the selectivity of propylene oxide, can easily cause the deactivation of the catalyst due to the accumulation of sodium carbonate on the catalyst. The results in Table 5 in the literature show that if the loading of Na2O on TS-1 zeolite reaches 1.36 wt. % (approximately equivalent to Na/Si=0.027) by sodium carbonate impregnation, the catalyst activity (hydrogen peroxide conversion rate) may be reduced by nearly a half.
It should be clarified that, the practice that lets the TS-1 zeolite contain a very low amount of alkali metal ions for the purpose of replacing the bridging hydroxyl (protonic acid sites) produced by the very low content of trivalent metal ion impurities (such as Al3+ and Fe3+) on the zeolite framework, so as to prevent the oxidation products from being further converted by acid-catalyzed side reactions, and the practice that adds a small amount of alkaline substances to the reaction medium, including the addition of alkali metal ions or hydroxides thereof to neutralize the acidity of the reaction medium and the transient peroxy protons produced by the activation of hydrogen peroxide by TS-1 zeolite, are all not the same alkali metal ion modification as mentioned in the present invention.
In addition, we have already known that Chinese invention patent (application number) 200910131992.0 discloses a method for hydrothermal modification of TS-1 zeolite using an aqueous solution of a mixture of organic base and inorganic base. The inorganic base involves ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide; and the organic base involves urea, quaternary ammonium base, fatty amine and alcohol amine compounds. Embodiments 2, 3, 4, 7, 8 and 11 of the patent respectively relate to the use of sodium hydroxide and ethylenediamine, potassium hydroxide and TPAOH, the potassium hydroxide and triethanolamine, sodium hydroxide and n-butylamine, the potassium hydroxide and TPAOH, and a base combination of the sodium hydroxide and TPAOH. In the above embodiments, the temperatures of hydrothermal modification are respectively 180° C. , 150° C., 180° C., 120° C., 90° C. and 180° C. The invention uses the reaction of phenol hydroxylation to diphenol (liquid phase) and the reaction of cyclohexanone ammonia oxidation (liquid phase) to demonstrate the comprehensive improvement of activity, selectivity and activity stability of the modified zeolite. However, it is worth noting that the invention uses Fourier Transform Infrared Spectroscopy (FT-IR) to confirm that the modified TS-1 zeolites, including the modifications involved by the inorganic bases, show the same infrared absorption band of framework titanium at 960 cm−1 as the unmodified matrix. Therefore, the patent uses the ratio of the absorption band intensity at 960 cm−1 (I960) to the absorption band intensity at 550 cm−1 (I550) to characterize the influence of mixed base modification on the relative content of the framework titanium. Chinese invention patent (application number) 200910131993.5 discloses a method for hydrothermal modification of the TS-1 zeolite using a pore-forming-agent containing aqueous solution of inorganic base and/or organic base. The inorganic base involves ammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide. Embodiments 2 and 3 respectively relate to a sodium hydroxide modification solution containing starch and a potassium hydroxide modification solution containing polypropylene. Similar to Chinese invention patent (application number) 200910131992.0, the invention also uses the reaction of phenol hydroxylation to diphenol (liquid phase) and the reaction of cyclohexanone ammonia oxidation (liquid phase) to demonstrate the comprehensive improvement of activity, selectivity and activity stability of the modified zeolite. Moreover, the invention also uses Fourier Transform Infrared Spectroscopy (FT-IR) to confirm that the modified TS-1 zeolites, including the modifications involved by inorganic base, show the same infrared absorption band of the framework titanium at 960 cm−1 as the matrix. Therefore, the patent also uses the ratio of absorption band intensity at 960 cm−1 (I960) to the absorption band intensity at 550 cm−1 (I550) to characterize the influence of base modification on the relative content of the framework titanium. The above invention does not mention whether the modified TS-1 contains the alkali metal ions. The purpose of the invention is actually to improve the microporous diffusivity of the TS-1 zeolite through hydrothermal modification. However, the characterization results of Fourier Transform Infrared Spectroscopy (FT-IR) provided by the inventions show that, the modified TS-1 zeolites, including the modifications involved by the inorganic base, show the infrared absorption band of the framework titanium at 960 cm−1, which is an important feature. It indicates that the use of the modification method provided by the above inventions, the alkali metal ions do not affect the asymmetric stretching vibration of the Si—O—Ti bond (or called the Si—O bond stretching vibration disturbed by the framework titanium). In other words, the alkali metal ions do not affect and change the local environment of the framework titanium. The most reasonable explanation of this phenomenon is that most of the alkali metal ions that may contain in the modified TS-1 zeolite have been eliminated by the abovementioned inventions via the generally adopted post-treatment steps, such as washing.
In addition, we also note that the following invention patents relate to alkaline solution treatment. However, the so-called alkaline solution treatment is not the same alkali metal ion modification as the one that will be provided by the present invention.
For example, the TS-1 moulding method disclosed in the Chinese invention patent (application number) 201010511572.8 relates to an alkaline solution treatment step, and the catalyst prepared by the patented method is used for propylene liquid phase epoxidation to produce propylene oxide. However, the patent has the following features, firstly, the hollow TS-1 zelite (“hollow” means TS-1 has been subjected to a secondary hydrothermal modification. The method of the secondary hydrothermal modification can be seen in Chinese invention CN1132699C with application number 99126289.1) is moulded by using a silica sol as binder, said silica sol containing a kind of silane which has at least two hydrolysable groups, to obtain a molded body. Then, the molded body is subjected to heat treatment by the alkaline solution involving the sodium hydroxide, the potassium hydroxide, the tetramethylammonium hydroxide and tetraethylammonium hydroxide, and is dried and calcined to obtain the TS-1 catalyst which has enough anti-crushing strength and extra-high zeolite content. The temperature range of heat treatment is 60-120° C.; the concentration of the used alkaline solution is within the range of 0.1-10 mol %; and the ratio of the alkaline solution to the molded body is (0.5-5)/1. It can be clarified that the alkaline solution heat treatment involved in the invention is not used to modify the molded body, but is used to promote the hydrolysis reaction of silane and/or siloxane in the binder, so that the molded body obtains enough anti-crushing strength. This can be confirmed by the proposal in paragraph [0034] of the patent text (“the volume of the alkali can be selected according to the amount of silane and/or siloxane with at least two hydrolyzable groups.”). In addition, according to the heat treatment temperature, time and index data, i.e., particle strength, hydrogen peroxide conversion rate and propylene oxide selectivity, in embodiments 1-7 for comparative analysis, the upper limit of the heat treatment temperature of 120° C. in the patent corresponds to the lower limit of the treatment time of 2 hours. Namely, in order to achieve a good molding effect, the temperature of the alkaline solution heat treatment should not be high and the time should not be long; otherwise, the reaction activity and selectivity of propylene liquid phase epoxidation may be reduced. Alkaline solution heat treatment conditions of 90° C. and 6 hours adopted in embodiment 4 are optimal values.
For another example, a preparation method of a high-performance titanium silicalite zeolite catalyst disclosed in the Chinese invention patent (application number) 201310146822.6 also relates to the step of modifying the micron-sized titanium silicalite zeolite with the alkaline solution. The main feature of the preparation method is that the micron-sized titanium silicalite zeolite catalyst is first treated with the alkaline solution for the purpose of manufacturing a large number of mesopores and macropores on the micron-sized titanium silicalite zeolite to improve the accessibility of the titanium active site inside the large-crystal titanium silicalite zeolite and facilitate the diffusion and output of product molecules from the interior of large grains. Then, the titanium-containing modification solution is used to treat the titanium silicalite zeolite catalyst containing mesopores and macropores again, for the purpose of introducing more active sites to the surface of the zeolite catalyst through the crystallization process. It can be clarified that although alkali metal hydroxide is mentioned in the alkaline solution treatment step of the invention, the patent requires that the zeolite treated in the step needs to be washed to meet the requirement of neutral pH. This means that washing in the step must be very adequate. In this way, even if the alkali metal hydroxide is used to complete the modification treatment of the alkaline solution, the alkali metal ions may not be left on the catalyst. This is because hydroxyl anions may be left if the alkali metal ions are left, causing that the harsh requirement of neutral pH cannot be satisfied. The reason that the invention proposes such a high requirement for the step of washing is that the subsequent modification step is to introduce the framework titanium active site on the surface of the zeolite. Based on the above background introduction, it is not difficult to understand that if the zeolite is allowed to contain a large amount of alkali metal ions in the first step of alkaline solution treatment of the invention, it will inevitably prevent titanium from effectively entering the framework and becoming the active site in the second step of modification.
In summary, in order to develop environmentally benign oxidation process by exploiting the hydrogen peroxide green oxidant, almost all of the existing patents and publication literatures follow the requirements of a liquid phase reaction mode to invent the preparation methods of the titanium silicalite zeolite catalyst. Generally, the liquid phase oxidation reaction is conducted at low temperature. Under this condition, the self-decomposition reaction of hydrogen peroxide is very slow. Thus, in the liquid phase reaction mode, the selectivity (utilization rate) of hydrogen peroxide for the selective oxidation reaction is higher. The main challenge of developing the titanium silicalite zeolite catalyst for the liquid phase reaction mode is how to improve the low temperature reaction activity of the catalyst. High resistance of micropores of the titanium silicalite zeolite for mass transfer and diffusion under the liquid phase reaction conditions is a major factor that limits the low temperature activity of the catalyst. This is the reason why many patents and publication literatures focus on the use of nano TS-1 zeolite synthesized by the classical method as the matrix of catalyst and conduct secondary hydrothermal recrystallization treatment for the matrix whenever possible (generally in the presence of tetrapropylammonium hydroxide) in order to produce appropriate mesopores and cavities inside the ultrafine TS-1 zeolite crystals so that the catalyst can have better catalytic performance.
Different from the previous inventions, the alkali metal ion modified TS-1 zeolite and the preparation method thereof provided by the present invention are specially targeted at the gas phase epoxidation of propylene and hydrogen peroxide. The gas phase epoxidation of propylene is conducted without the participation of any solvent under normal pressure and temperature above 100° C. Under this condition, the reactants of propylene and hydrogen peroxide directly contact with each other in the form of gas molecules, and penetrate through a catalyst bed together to conduct the epoxidation. It is not difficult to understand that due to the change of the reaction phases and the conditions and the absence of methanol solvent, the reaction mechanism of gas phase epoxidation of the propylene is impossible the same as that of the liquid phase epoxidation; the active sites required are also different from those of the liquid phase epoxidation; and the main challenges and the main problems to be solved in the preparation and modification of the catalyst will consequently be different from those of the liquid phase epoxidation.
But compared with the known liquid phase epoxidation technology, it is clear that the gas phase epoxidation technology of propylene and hydrogen peroxide has huge potential advantages. This is the significant value of the present invention. It is well known that the liquid phase epoxidation technology (HPPO) of propylene must use a large amount of solvents to ensure that the propylene (oily) and hydrogen peroxide aqueous solution can become a stable homogeneous phase through liquid-liquid mixing, so that the epoxidation can be conducted safely. At present, commercial production lines of the HPPO technology use methanol as the solvent. Methanol is easily available and very cheap, and the methanol solvent is believed to have additional promotion effect in hydrogen peroxide activation and propylene epoxidation, probably via the formation of a so-called “five-membered ring” transition state with hydrogen peroxide molecules and the active site of the framework titanium. However, methanol solvent also brings big trouble to the practical application of the HPPO technology. Firstly, methanol easily causes solvolysis side reactions with the propylene oxide product, which results in high-boiling propylene glycol monomethyl ether and other by-products. These by-products not only remarkably reduce the selectivity of the propylene oxide, but also increase the difficulty of wastewater treatment. Secondly, the methanol solvent must be recycled and needs complex purifying treatment (including hydrogenation, rectification and resin adsorption) before recycled, this makes the HPPO technology complicated and investment and energy consumption increased. In addition, although the recycled methanol solvent will be treated by a complex purification process, more than ten or even 20 or 30 kinds of trace impurities (including fusel, aldehyde, ether, ester and acetals) are still difficult to be removed. These trace impurities will be recycled back to the reactor together with methanol solvent, consequently accelerate the deactivation of the epoxidation catalyst and greatly shortens the service cycle and life of the catalyst. The gas phase epoxidation of propylene and hydrogen peroxide can thoroughly avoid the above problems because no solvent is used, and thus has a very good development potential.
Since 2002, we have been engaged in the research related to the gas phase epoxidation of propylene and hydrogen peroxide. First, we have developed a dielectric barrier discharge plasma technology that can directly synthesize high-purity gaseous hydrogen peroxide from the mixture of hydrogen and oxygen, which has been documented by the following literature: Chem. Commun., 2005, 1631-1633; Modern Chemical Industry, Vol. 26 Supplement, 2006, P194-197; AIChE J, 53: 3204-3209, 2007; Advanced Technology of Electrical Engineering and Energy, Vol 28, 2009, No. 3, P73-76; Chin. J. Catal., 2010, 31: 1195-1199; CIESC Journal Vol 63, 2012, No. 11, P3513-3518; Journal of Catalysis 288 (2012) 1-7; Angew. Chem. Int. Ed. 2013, 52, 8446-8449; AIChE J, 64: 981-992, 2018; Chinese invention patents (application numbers) 200310105210.9, 200310105211.3 and 200310105212.8. We have realized an in-situ continuous synthesis of hydrogen peroxide gas by using the plasma technology, and completed the first stage of research work of gas phase epoxidation of propylene by 2007 (Zhou Juncheng. Direct synthesis of hydrogen peroxide by hydrogen and oxygen plasma method and its application in the gas phase epoxidation of propylene [D]. Dalian: Dalian University of Technology, 2007). Specifically, a specially designed two-stage integrated reactor was used in the research work. The first stage reactor was a dielectric barrier discharge (DBD) plasma reactor for providing continuous and stable gaseous hydrogen peroxide feed for the epoxidation reaction stage by taking the mixture of hydrogen and oxygen as raw material (the concentration of the oxygen in the hydrogen is less than 6 v %). The second stage reactor was a gas phase epoxidation reactor of propylene and gaseous hydrogen peroxide, it contained TS-1 zeolite particles. In the research, the results of the gas phase epoxidation reaction obtained at 90° C. and 1 atm were: about 7% of propylene conversion rate, 93% of propylene oxide (PO) selectivity, and 0.24 kg PO kgPO kg TS-1 −1h−1 propylene oxide yield. Later, we carried out a more comprehensive research work by use the same epoxidation system and a micron-sized large-crystal TS-1 zeolite (unmodified) synthesized with a non-classical method (also known as the cheap method) as catalyst. The results published on Chin. J. Catal., 2010, 31: 1195-1199 indicate that at the reaction temperature of 110° C., the selectivity of the propylene oxide is increased to about 95%, and the yield of the propylene oxide is maintained to about 0.25 kg PO kg TS-1 −1h−1. The reaction activity of the catalyst is stable for at least 36 h in the gas phase epoxidation. However, the epoxidation selectivity, i.e., the utilization rate, of the hydrogen peroxide is only about 36%.
We have already noted that Klemm et al. also reported the research work of gas phase epoxidation of propylene in 2008 [Ind. Eng. Chem. Res. 2008, 47, 2086-2090]. They used a special glass carburetor or a micro-channel falling-film evaporator and 50 wt % aqueous hydrogen peroxide solution to provide gaseous hydrogen peroxide raw material for the gas phase epoxidation. The gas phase epoxidation reactor was a micro-channel reactor with TS-1 zeolite coated inside. The reaction results obtained at 140° C. and 1 atm were: selectivity of propylene oxide was larger than 90%, and the yield of propylene oxide was larger than 1 kg PO kgTS-1−1h−1. However, the utilization rate of the hydrogen peroxide was only about 25%.
The above preliminary research work about the gas phase epoxidation of propylene indicates that in the absence of the methanol solvent, the direct contact of propylene and hydrogen peroxide gas can effectively conduct the epoxidation on TS-1 zeolite, a considerable yield of the propylene oxide product can be obtained. Moreover, the selectivity of the propylene oxide can be as high as about 90%, which is very close to the result of liquid phase epoxidation. However, the utilization rate of hydrogen peroxide at the normal feed ratio of propylene and hydrogen peroxide in the gas phase epoxidation reaction is very low, generally falls in the range of 20-40%. The value is much lower than that of the liquid phase epoxidation (which is generally 85-95%). The researches of Su Ji et al. (Journal of Catalysis 288 (2012) 1-7) and Fernandez et al. [Ind. Eng. Chem. Res. 2013, 52, 10126-10132] indicate that, the reason why the utilization rate of the hydrogen peroxide in the gas phase epoxidation is very low is that, the self-decomposition side reaction of hydrogen peroxide and the main reaction of epoxidation are highly competitive at high temperature (e.g., 110-140° C.). The decomposition reaction of hydrogen peroxide (to produce water and oxygen) can occur on both the material surface of the reactor and the surface of catalyst.
It is obvious that, the first challenge of the gas phase epoxidation technology of propylene is the severe problem of hydrogen peroxide self-decomposition at high temperature. The rapid decomposition of hydrogen peroxide at high temperature not only reduces the utilization rate of hydrogen peroxide and the conversion rate of propylene, but also produces oxygen which easily makes the organic gas in the reactor system and the downstream separation system have an explosive composition and thus increases the risk of explosion accidents.
In the previous invention patent applications, we have disclosed two TS-1 zeolite modification methods which are mainly used for the gas phase epoxidation of propylene and hydrogen peroxide. The first method is to treat the TS-1 zeolite using a mixed solution of tetrapropylammonium hydroxide (TPAOH) and inorganic salt (lithium, sodium, potassium and mixtures thereof) (Chinese invention patent (application number) 201110338224.x); and the second method is to treat the TS-1 zeolite using a mixed solution of tetrapropyl quaternary ammonium cation halide and inorganic base (alkali metal hydroxides of lithium, sodium and potassium) (Chinese invention patent (application number) 201110338451.2 and U.S. Pat. No. 9,486,790B2). In the follow-up research, we realized that the two disclosed TS-1 zeolite modification methods in the abovementioned inventions have limitations in improving the gas phase epoxidation performance of propylene and hydrogen peroxide (the highest conversion rate of propylene for the modified TS-1 zeolite in the gas phase epoxidation reaction is ≤9%), this is because that, in these inventions we pursue for the dual applicability of the catalyst in both the liquid phase and gas phase epoxidations of propylene and hydrogen peroxide. Therefore, the two disclosed modification methods cannot lead to the TS-1 zeolite catalyst that is especially suitable for the gas phase epoxidation of propylene and hydrogen peroxide. The above invention patents have a common feature, which underlines that the residual alkali metal ions in the modified TS-1 zeolite are not conducive to achieving the modification effect. Therefore, it clearly states in the technical solutions that, during the post-treatments, the TS-1 zeolite hydrothermally treated with a mixed solution containing the alkali metal ions must be fully washed with deionized water and the pH value of the filtrate should be less than 9 (the embodiment points out the pH is preferably 7).
In order to further improve the technical level of the gas phase epoxidation of propylene and hydrogen peroxide, the present invention provides an alkali metal ion modified titanium silicalite zeolite TS-1 capable of selectively promoting the epoxidation of propylene and hydrogen peroxide in a gas phase reaction without the participation of any solvent and a preparation method thereof.
The core of the present invention is the use of the alkali metal hydroxide solution containing a small amount of tetrapropylammonium (TPA+) cations to perform the degree controlled hydrothermal treatment on the titanium silicalite zeolite TS-1. After the hydrothermal treatment, alkali metal cations must remain on the titanium silicalite zeolite, and at least part of the alkali metal cations are on the silicon hydroxyls near the framework titanium in the form of counter cations to modify the local environment of the framework titanium. The small amount of tetrapropylammonium (TPA+) cations contained in the alkali metal hydroxide solution is used to recrystallize a large amount of titanium silicalite zeolite solutes produced in the hydrothermal modification process of the alkali metal hydroxide into the titanium silicalite zeolite. The TPA+ ions which remain in the modified zeolite can be removed by calcination. The connotation of the local environment includes at least the electron cloud distribution and geometric spatial factors of the framework titanium. The alkali metal hydroxides are preferably sodium hydroxide and potassium hydroxide, and less preferably lithium hydroxide. The TPA+ ions can be conveniently introduced through chloride (TPACl) and bromide (TPABr). After repeated researches, we are surprised to find that the alkali metal ion modification has almost no effect on the liquid phase epoxidation of propylene at low temperature with methanol solvent, but has an unexpected improvement effect on the gas phase epoxidation of propylene and hydrogen peroxide in the absence of solvent and at high temperature (which is generally higher than 100° C. under normal pressure). For the gas phase epoxidation of propylene and hydrogen peroxide, a framework titanium active site modified with alkali metal ions enables the catalyst to obviously inhibit the self-decomposition side-reaction of hydrogen peroxide at a normal propylene/hydrogen peroxide feed ratio and increase the conversion rate of propylene, so as to increase the utilization rate of hydrogen peroxide and reduce the generation of oxygen, thereby greatly improving the economy and safety of the gas phase epoxidation.
The specific implementation solutions and embodiments of the present invention mainly focus on TS-1 zeolite. This is mainly because TS-1 is the most popular representative in the family of the titanium silicalite zeolite. TS-1 is relatively easier to synthesize, it is widely reported in the literature, and used widely in industry. At present, it is the TS-1 zeolite which is commercially used in the HPPO technology of the liquid phase epoxidation of propylene and hydrogen peroxide. It is worth mentioning that in the present invention, the use of a small amount of TPA+ ions reduces the modification loss of the titanium silicalite zeolite, and greatly reduces the content of the silicate solutes in the alkali metal hydroxide waste solution produced after modification, so that the discharged wastewater is easier to treat and discharge after meeting the standards, and the modification method of the present invention is relatively easy to implement. More meaningfully, the use of a small amount of TPA+ ions also solves the applicability problem of the nano TS-1 zeolite matrix, and expands the application range of hydrothermal modification of the alkali metal hydroxide solution. Namely, the present invention is not only suitable for the micron-size TS-1 titanium silicalite zeolite or the small-crystal TS-1 zeolite matrix synthesized by the non-classical method, but also suitable for the nano TS-1 zeolite (the aggregate size is generally below 200-300 nanometers) synthesized by the classical method introduced by Taramasso et al. (U.S. Pat. No. 4,410,501. 1983) or Thangaraj et al. (J Chem Soc Chem Commun, 1992: 123).
In the alkali metal ion modified TS-1 zeolite prepared by the present invention, the framework titanium active site modified by the alkali metal ions has unique infrared spectral characteristics, and the characteristic absorption peak of the vibrational spectrum appears in a range above 960 cm−1 and below 980 cm−1, which is a novel framework titanium active site different from the known tetra-coordinate framework titanium active site (infrared absorption is at 960 cm−1) and the hexa-coordinate framework-like titanium active site (Ti(OSi)2(OH)2(H2O)2) (UV Raman absorption peak is at 695 cm−1). The literature (J. Catal., 1995,151, 77-86) has reported that the sodium exchange of TS-1 with 1 M NaOH solution at 25° C. can also change the infrared spectral characteristics of TS-1 zeolite framework titanium (the absorption peak at 960 cm−1 is shifted to a shoulder peak at 985 cm−1), and that the sodium exchange conducted in the strong alkaline solution is also the exchange reaction between the sodium ion in the sodium hydroxide and the hydrogen proton on the silicon hydroxyl near the framework titanium (NaOH+Si—OH═Si—O−Na++H2O), the consequence of the exchange reaction is that the sodium ion exists on the silicon hydroxyl near the framework titanium in the form of counter cation , and naturally changes the local environment of the framework titanium. However, in the present invention, the infrared characteristic absorption of the framework titanium active site modified by the alkali metal ion appears in the range above 960 cm−1 and below 980 cm−1, which is different from the value (985 cm−1) reported in the literature by at least 5 wave numbers (cm−1). It is not difficult for people familiar with infrared spectroscopy to understand that two infrared absorptions with such a large difference in the wave numbers should belong to the vibration of different framework titanium sites. In addition, it will be seen from the reference embodiment provided by the present invention that the sodium exchange TS-1 zeolite prepared according to the method reported J. Catal., 1995, 151, 77-86 (the framework titanium infrared characteristic absorption appears near 985 cm−1, which is consistent with the literature report) is basically inactive for the gas phase epoxidation of propylene and hydrogen peroxide. In sharp contrast to this, the sodium ion modified TS-1 zeolite obtained according to the present invention (the infrared characteristic absorption of the framework titanium appears in the range above 960 cm−1 and below 980 cm−1) has high activity and high selectivity for the gas phase epoxidation. People familiar with the titanium silicalite zeolite know that four framework silicons are first adjacent to the framework titanium. The four framework silicons are not equivalent in space, have 16 possible hydroxyl positions. The relative positions of these silicon hydroxyls are quite different relative to the framework titanium site. We conclude from the study of quantum chemistry calculation that the difference of infrared spectral characteristics of the framework titanium of the alkali metal ion modified TS-1 zeolite provided by the present invention from the room temperature sodium exchange TS-1 zeolite reported in the literature, should be caused by the different silicon hydroxyl positions occupied by the alkali metal countercations.
Briefly speaking, the present invention discloses a method which tells how to use the alkali metal hydroxide solution containing a small amount of TPA+ ions to hydrothermally treat a zeolite of titanium silicalite with controlled degree. The phrase “controlled degree” is mainly used to explain that the hydrothermal treatment method provided by the present invention can ensure that the alkali metal ion is always located in the most favorable silicon hydroxyl position, so as to most favorably modify the local environment of the framework titanium site of the modified TS-1 zeolite, thereby more effectively promoting the gas phase epoxidation of propylene and hydrogen peroxide.
Therefore, in general, the present invention has the following features: the hydrothermal treatment of the TS-1 zeolite by the alkali metal hydroxide solution containing a small amount of TPA+ ions is carefully controlled, and the alkali metal cations must remain in the TS-1 zeolite after the hydrothermal treatment, and at least part of the alkali metal cations are on the proper silicon hydroxyls near the framework titanium in the form of counter cations to appropriately modify the local environment of the framework titanium. Moreover, the framework titanium active site modified by the alkali metal ions produces infrared characteristic absorption above 960 cm−1 and below 980 cm−1.
To realize the degree controlled hydrothermal treatment in the present invention, firstly, a low-concentration alkali metal hydroxide solution is selected for the hydrothermal treatment. Secondly, when TS-1 zeolite is subjected to the hydrothermal treatment with the low-concentration alkali metal hydroxide solution, proper hydrothermal treatment temperature, time and liquid-solid ratio must also be adopted. In other words, the concentration of the alkali metal hydroxide solution, the temperature and time of the hydrothermal treatment, and the liquid-solid ratio are the basic parameters that control the degree of the hydrothermal treatment.
As described above, the present invention is not only suitable for the micron-size TS-1 titanium silicalite zeolite or the small-crystal TS-1 zeolite matrix synthesized by the non-classical method, but also suitable for the nano TS-1 zeolite (the aggregate size is generally below 200-300 nanometers) synthesized by the classical method introduced by Taramasso et al. (U.S. Pat. No. 4,410,501. 1983) or Thangaraj et al. (J Chem Soc Chem Commun, 1992: 123). The scientific principle obtained by research is that the hydrothermal modification effect of the alkali metal hydroxide solution is fundamentally dissolution modification. Therefore, the modification using only the alkali metal hydroxide solution is not suitable for the nano TS-1 zeolite synthesized by the classical method which has too small crystal size. This is because the TS-1 zeolite with too small crystal size is likely to be dissolved excessively or even thoroughly in the modification, so that the required alkali metal modified framework titanium active site cannot be produced. In the present invention, a small amount of TPA+ ions contained in the alkali metal hydroxide solution are enriched on the outer surfaces of the zeolite crystals in the hydrothermal modification process and act as a templating agent. As a result, the silicate species dissolved by the alkali metal hydroxide inside the zeolite is migrated to the outer surface of the zeolite for recrystallization, so as to establish a dynamic equilibrium process between the internal dissolution and external recrystallization of the crystals, thereby not only avoiding the problem of excessive loss of the micron-size TS-1 zeolite due to hydrothermal modification of the alkali metal hydroxide solution, but also solving the problem that the nano TS-1 zeolite is excessively dissolved or even completely dissolved in the modification and is inapplicable to the present invention.
As described above, raw materials for the synthesis of TS-1 zeolite by the classical method have the features that the tetrapropylammonium hydroxide is used as the templating agent, and silicon ester and titanium ester are used as a silicon source and a titanium source, respectively. The morphology of the product observed on an electron microscope is characterized by irregular aggregates; the particle size of the aggregates is generally 200-300 nanometers; and the crystal size of the primary crystals which form the aggregates is generally below 100 nanometers. Although later people have done a lot of meaningful improvement work on the basis of Taramasso et al. and Thangaraj et al., the above basic features of the TS-1 zeolite synthesized by the classical method are not changed and many relevant literature can be found. The following literature can be used as reference: U.S. Pat. No. 4,410,501; J Chem Soc Chem Commun, 1992: 123; J. Catal., 1995,151, 77-86; Chinese invention patent (application number) 02125738.8; Chinese invention patent (application number) 201610160261.9.
Those skilled in the art know that the cheap TS-1 can be synthesized by different methods. For example, the following literature has reported the hydrothermal synthesis methods of the cheap TS-1: Zeolites and Related Microporous Materials: State of the Art 1994, Studies in Surface Science and Catalysis, Vol. 84; Zeolites 16: 108-117, 1996; Zeolites 19: 246-252,1997; Applied Catalysis A: General 185 (1999) 11-18; Catalysis Today 74 (2002) 65-75;| Ind. Eng. Chem. Res. 2011, 50, 8485-8491; Microporous and Mesoporous Materials 162 (2012) 105-114; Chinese invention patents (application numbers) 201110295555.x and 201110295596.9. The raw materials of the cheap synthesis technology are characterized by using the tetrapropylammonium bromide as the templating agent, and using ammonium hydroxide or organic amines such as methylamine, ethylamine, ethylenediamine, diethylamine, n-butylamine and hexamethylenediamine as an alkali source. Silica sol and titanium tetrachloride are mainly used as the silicon source and the titanium source, and sometimes titanium ester is also used as the titanium source. The morphology of the product observed on the electron microscope is characterized by monodisperse crystals with regular crystal edges and planes, including large-crystal thin plate crystals of several microns, or coffin-shaped small-grained crystals of 300-600 nanometers.
The present invention has no limitation on the crystal size of the matrix of the titanium silicalite zeolite, but requires the titanium silicalite zeolite to have a relatively low silicon-titanium ratio and minimal non-framework titanium content. The two requirements are easy to understand. Firstly, the gas phase epoxidation of propylene and hydrogen peroxide requires the titanium silicalite zeolite to have high-density titanium active sites, which is beneficial to avoid the ineffective thermal decomposition of the hydrogen peroxide. Secondly, as described above, in the hydrothermal modification method provided by the present invention, the controlled dissolution effect of the alkali metal hydroxide solution occurs inside the crystals, and the structure-directing effect of the templating agent generated by the addition of a small amount of TPA+ ions during the recrystallization occurs on the outer surfaces of the crystals. Therefore, if the matrix of the titanium silicalite zeolite contains too much non-framework titanium species, especially when a large amount of the non-framework titanium species is distributed inside the crystals of the zeolite, even though the total silicon-titanium ratio seems appropriate, it is not conducive to enable the modified titanium silicalite zeolite to contain sufficient framework titanium active sites modified by the alkali metal ions.
In addition, the present invention also requires the matrix of the titanium silicalite zeolite to have high enough relative crystallinity. This is not difficult to understand. After all, the crystal framework is the support of the framework titanium.
An alkali metal ion modified titanium silicalite zeolite TS-1 for gas phase epoxidation of propylene and hydrogen peroxide is provided. In the alkali metal ion modified titanium silicalite zeolite TS-1, the alkali metal ions are reserved on the silicon hydroxyls of the modified TS-1 zeolite; an infrared characteristic absorption band of a framework titanium active site modified by the alkali metal ion is in a range above 960 cm−1 and below 980 cm−1; a TS-1 zeolite matrix of the alkali metal ion modified titanium silicalite zeolite TS-1 meets the following requirements: the silicon-titanium molar ratio is ≤200; an index value of the framework titanium content is ≥0.40; and relative crystallinity is ≥85%.
Further, the silicon-titanium molar ratio of the TS-1 zeolite matrix is ≤100; the index value of the framework titanium content is ≥0.45; and the relative crystallinity is ≥90%.
The silicon-titanium molar ratio refers to the total average silicon-titanium ratio of bulk phase of the sample. X-ray fluorescence spectroscopy (XRF) can be used with reference sample to obtain silicon-titanium molar ratio data. Those skilled in the art can measure in person or entrust others to measure the silicon-titanium ratio data of the TS-1 matrix according to the instructions of an XRF instrument.
The index value of the framework titanium content is defined as I960 cm−1/I550 cm−1, that is, the ratio of the absorption peak intensity of Ti—O—Si antisymmetric stretching vibration characterized at 960 cm−1 on the framework vibration infrared spectrum of the TS-1 zeolite to the absorption peak intensity of the five-membered ring vibration of MFI structure characterized at 550 cm−1. Those skilled in the art know that the ratio has been generally accepted by researchers in the field and used to reflect the relative amount of the framework titanium in the TS-1 zeolite (for example, CATAL. REV.-SCI. ENG, 39(3). 209-251 (1997) uses the value of I960 cm−1/I550 cm−1 to give the correlation diagram P217
The relative crystallinity refers to the ratio (expressed by percentage) of the sum of the intensity of five characteristic diffraction peaks (2θ=7.8°, 8.8°, 23.0°, 23.9° and 24.3°) of the TS-1 zeolite matrix measured by the X-ray powder diffraction method (XRD) to that of a reference sample. Those skilled in the art can obtain the XRD patterns of the TS-1 zeolite matrix and the reference sample according to the XRD experimental methods reported in any publication literature. The present invention recommends using embodiment 1 in the Chinese invention patent (application number) 201110295555.x to prepare the reference sample. Specifically: 220 ml of deionized water is added to 225 g of silica sol (20% wt); after stirring for 10 minutes, 18.4 g of tetrapropylammonium bromide and 5.1 g seed crystals are added to the diluted silica sol; after continuing stirring for 20 minutes, a silicon solution is obtained; tetrabutyl titanate and acetylacetone are mixed at a mass ratio of 1:0.8, and stirred for 15 minutes to prepare a titanium solution; 19.7 ml of the prepared titanium solution is added to the silicon solution; after stirring for 30 minutes, 57 ml of n-butylamine is added and continuously stirred for 15 minutes to obtain uniform gel; then 6.0 g of Na2SO4 is added and stirred for 10 minutes; then the obtained gel is added to a 2 l stainless steel autoclave reactor and crystallized under autogenous pressure and 170° C. for 24 hours; after crystallization the product is filtered, washed to be neutral, and dried at 110° C. It is emphasized herein that before measuring the XRD patterns of the TS-1 zeolite matrix and the reference samples, the two samples to be measured must be calcined to ensure that the organic templating agents in the samples are removed completely and more than 95%, preferably more than 98% of dry basis content of the zeolite is achieved. Thus, it is recommended to dry about 2 g of TS-1 zeolite matrix and about 2 g of reference sample overnight at 110° C., and then place the samples in a muffle furnace for temperature-programmed calcination. The temperature-programmed calcination starts at room temperature, and the temperature is raised to 300° C. at a temperature rise rate of 10° C./min, and then the temperature is raised from 300° C. to 500° C. at a temperature rise rate of 1° C./min and kept constant until the sample is completely white.
The TS-1 zeolite which satisfies the above indexes can be used as the modified matrix of the present invention. The TS-1 zeolite suitable for the present invention can be purchased from the market, or can be synthesized by engineers familiar with the field according to the relevant publication literature and patent documents. If the TS-1 zeolite is synthesized by the engineers, the present invention recommends adopting the hydrothermal synthesis method of the TS-1 zeolite reported in the following publication literature and patent documents:
The micron-size TS-1 zeolite can be synthesized by the methods reported in the following literature: Zeolites and Related Microporous Materials: State of the Art 1994, Studies in Surface Science and Catalysis, Vol. 84; Zeolites 16: 108-117, 1996; Zeolites 19: 246-252,1997; Applied Catalysis A: General 185 (1999) 11-18; Catalysis Today 74 (2002) 65-75;| Ind. Eng. Chem. Res. 2011, 50, 8485-8491; Microporous and Mesoporous Materials 162 (2012) 105-114; Chinese invention patents (application numbers) 201110295555.x and 201110295596.9.
The nano TS-1 zeolite can be synthesized by the methods reported in the following literature: U.S. Pat. No. 4,410,501; J Chem Soc Chem Commun, 1992: 123; J. Catal., 1995,151, 77-86; Chinese invention patent (application number) 02125738.8; Chinese invention patent (application number) 201610160261.9.
Of course, the engineers familiar with the field can synthesize the TS-1 zeolite matrix used in the present invention according to other appropriate known methods.
A qualified TS-1 zeolite matrix must remove the organic templating agent before modification. It is the common knowledge in the art to remove the organic templating agent from a zeolite. The present invention provides the following reference practice: drying an appropriate amount of TS-1 zeolite matrix overnight at 110° C., and then placing the sample in the muffle furnace for temperature-programmed calcination. The temperature-programmed calcination starts at room temperature, and the temperature is raised to 300° C. at a temperature rise rate of 5° C./min, and then the temperature is raised from 300° C. to 400° C. at a temperature rise rate of 1° C./min and kept constant for 12 hours; then the temperature is raised to 450° C. at the same temperature rise rate and kept constant for 12 hours; and finally, the temperature is raised to 500° C. at the same temperature rise rate and kept constant until the sample is completely white.
The preparation method of the alkali metal ion modified titanium silicalite zeolite TS-1 for the gas phase epoxidation of propylene and hydrogen peroxide comprises the following steps:
At first step: preparing an alkali metal hydroxide modification solution containing a small amount of TPA+ ions. In order to achieve the effect of degree controlled hydrothermal modification, the present invention requires that:
The preferred range of the concentration of the alkali metal hydroxide solution is: a lower limit of 0.01 mol/L and an upper limit of 0.20 mol/L (at room temperature), and a more preferred range is: the lower limit of 0.05 mol/L and the upper limit of 0.15 mol/L (at room temperature).
The alkali metal hydroxide is preferably lithium hydroxide, sodium hydroxide and potassium hydroxide; and more preferably sodium hydroxide and potassium hydroxide.
When the modification solution is prepared, any one of the alkali metal hydroxides recommended above can be used alone, or a mixture of any two of the alkali metal hydroxides in any ratio can be used, or a mixture of three hydroxides in any ratio can also be used. When more than two alkali metal hydroxides are used to prepare the modification solution, the solution concentration refers to the sum of the molar concentrations of various hydroxides.
The preferred range of the concentration of the TPA+ ions is: a lower limit of 0.05 mol/L and an upper limit of 0.50 mol/L (at room temperature), and a more preferred range is: the lower limit of 0.10 mol/L and the upper limit of 0.3 mol/L (at room temperature).
The TPA+ ions are preferably provided by tetrapropylammonium chloride (TPACl) or tetrapropylammonium bromide (TPABr). When the modification solution is prepared, any one of the quaternary ammonium salts recommended above can be used alone, or a mixture of two quaternary ammonium salts in any ratio can be used.
It is hereby declared that it is also feasible to provide TPA+ by other tetrapropyl quaternary ammonium salt precursor compounds such as tetrapropyl ammonium fluoride (TPAF) and tetrapropylammonium iodide (TPAI). However, the TPAF and the TPAI may bring about the trouble of treating F− and I− ions, and thus are not recommended in the present invention. In addition, tetraethylammonium (TEA+) and tetrabutylammonium (TBA+) also act as the templating agents for the synthesis of the MFI zeolite topology, but are not better than the TPA+ ions in price or capability of structure-directing crystallization of an all-silicon MFI zeolite framework, and thus are also not recommended.
Considering that commercially available alkali metal hydroxides contain a certain amount of impurities, the purity of the raw materials of the alkali metal hydroxides should be analyzed by chemical titration before the modification solution is prepared. Those skilled in the art can perform the titration operation according to a conventional chemical analysis method. Similarly, after the modification solution is prepared, the same conventional chemical analysis method should be used to calibrate the hydroxide concentration of the modification solution. Because the alkali metal hydroxides release a large amount of heat in the dissolution process, the concentration is calibrated only when the solution is cooled to room temperature.
During modification, the concentration of the alkali metal hydroxide in the modification solution will decrease as a result of the reaction of the alkali solution with the zeolite framework (for example, NaOH+Si—OH═Si—O−Na++H2O). Meanwhile, the used alkali metal hydroxide solution will also contain low concentrations of silicate, titanate and silicotitanate due to the framework dissolution and desilication reaction (a small amount of framework titanium is inevitably dissolved in the process). Meanwhile, the TPA+ ions also act as a templating agent in the recrystallization of the zeolite crystal surface, and part of the TPA+ ions are encapsulated in the newly grown zeolite framework, thereby reducing the concentration in the modification solution. However, undoubtedly, the used alkali metal hydroxidesolution can be recycled conditionally, which can reduce the modification cost and waste solution discharge. Before the used solution is recycled, the concentration of the alkali metal hydroxide and the TPA+ ions needs to be accurately measured in order to restore their initial concentrations by supplementing the alkali metal hydroxide and TPA+ ions; and the concentrations of the silicate, the titanate and the silicotitanate contained in the solution also need to be measured in order to control the number of cycles. In order to avoid too complicated and lengthy description of the present invention and to make it easier for the colleagues to understand the gist of the present invention, the present invention will not provide detailed illustration for the recycling of the used modification solution herein and in subsequent embodiments. The engineers in the art can recycle the used modification solution according to the common sense.
However, it should be stated that, just as the used modification solution can be recycled, it is beneficial that a certain amount of alkali metal silicate, titanate and titanium silicate is added deliberately into the fresh modification solution in order to control the degree of dissolution modification. We have even found that the introduction of suitable amount of alkali metal carbonate and bicarbonate into the fresh modification solution can also assist in controlling the degree of dissolution modification. The commonality of the above salts is that they belong to strong alkali and weak acid salts, and can be hydrolyzed in the aqueous solution to provide alkali metal cations and hydroxyl anions, that is, alkali metal hydroxides are actually produced by hydrolysis. The difference from the direct addition of the alkali metal hydroxides is that the weak acid salt produces weak acid after hydrolysis, which can adjust the pH value of the modification solution to a certain extent, thereby helping to control the degree of dissolution modification. In terms of the strong alkali and weak acid salts, alkali metal phosphates and hydrogen phosphates should also be candidates, but the phosphates and the hydrogen phosphates are easy to accumulate in the recycling of the modification solution, which is not conducive to multiple recycling of the modified solution. The engineers familiar with the field can select other strong alkali and weak acid salts for the present modification purpose under the guidance of the above principles described in the present invention, and will not be repeated.
At second step: conducting degree controlled hydrothermal treatment on the TS-1 zeolite matrix by using the alkali metal hydroxide solution containing a small amount of TPA+ ions. The hydrothermal treatment can be conducted under static and stirring states. In order to achieve the effect of degree controlled hydrothermal treatment, the present invention requires that:
The preferred ratio range of the volume of the modification solution to the weight of the titanium silicalite zeolite matrix is from the lower limit of 5 ml/g to the upper limit of 15 ml/g, and a more preferably ratio range is from the lower limit of 8 ml/g to the upper limit of 12 ml/g.
The preferred range of the hydrothermal modification temperature is from the lower limit of 100° C. to the upper limit of 200° C., and a more preferred range is from the lower limit of 150° C. to the upper limit of 190° C.
The preferable range of the hydrothermal modification time from the lower limit of 10 hours to the upper limit of 20 hours, and a more preferable range is from the lower limit of 15 hours to the upper limit of 20 hours.
It should be specially explained that, in order to achieve the effect of degree controlled hydrothermal treatment, all the parameters such as the concentration of the alkali metal hydroxide modification solution, the ratio of the volume of the modification solution to the weight of the titanium silicalite zeolite matrix, the modification temperature and the time need to be taken into consideration together. It is not difficult for those skilled in the art to understand that the lower limit values of all the hydrothermal modification parameters involved in the first step and the second step can produce the weakest degree of modification effect, and the upper limit values of the hydrothermal modification parameters can produce the strongest degree of modification effect. Therefore, the modification conditions defined by the combination of the lower limit values of all the parameters inevitably generate the lowest degree of modification result, and the modification conditions defined by the combination of the upper limit values of all the parameters inevitably generate the highest degree of modification result. Therefore, it is not difficult to understand that the hydrothermal modification result between the lowest degree and the highest degree will be obtained by selecting the lower limit value of a certain parameter and the intermediate values and the upper limit values of other parameters. Of course, it is not difficult to understand that the modification conditions defined by the combination of different values of various parameters can generate different degrees of hydrothermal modification results. When the values of the parameters are designed for a given titanium silicalite zeolite matrix to reach a desired modification degree which guarantees a satisfactory catalytic performance in the gas phase epoxidation of propylene and hydrogen peroxide, it is the exact meaning of the degree controlled hydrothermal modification in the present invention. Clearly, the lowest degree of modification effect and the highest degree of modification effect herein shall not be mistakenly understood as the worst modification effect and the best modification effect. Some titanium silicalite zeolite matrices need the lowest degree of hydrothermal modification, while some titanium silicalite zeolite matrices need higher degree of hydrothermal modification. Therefore, the present invention clarifies that the combination conditions for the hydrothermal modification for a specific titanium silicalite zeolite matrix should be determined through experiments, and shall be judged based on the position of the infrared vibration absorption peak of the active site, especially based on the gas phase epoxidation data of propylene and hydrogen peroxide. The engineers in the field can determine specific modification conditions suitable for the specified titanium silicalite zeolite within the parameter value range recommended by the present invention according to specific considerations such as equipment use efficiency, modification cost and wastewater discharge.
At third step: conducting post-treatment on the hydrothermally modified TS-1 zeolite. Specifically, the third step comprises conventional solid-liquid separation, washing, drying and calcining steps. However, for the present invention, correct washing of the wet material of the zeolite after solid-liquid separation is the key. The present invention recommends using a low-concentration alkali metal hydroxide solution to wash the wet material of the modified zeolite obtained by solid-liquid separation, and the degree of washing is satisfactory when no precipitate appears after the washing solution is neutralized with acid. The present invention requires that the preferred range of the concentration of the alkali metal hydroxide solution used for the washing purpose is from the lower limit of 0.001 mol/l to the upper limit of 0.05 mol/l (calibrated at room temperature), and a more preferred range is from the lower limit of 0.005 mol/l to the upper limit of 0.04 mol/l (calibrated at room temperature). A further preferred range is from the lower limit of 0.005 mol/l to the upper limit of 0.03 mol/l (calibrated at room temperature). The alkali metal hydroxide is preferably lithium hydroxide, sodium hydroxide and potassium hydroxide; and more preferably sodium hydroxide and potassium hydroxide.
The necessity of washing is that, on one hand, the wet material of the zeolite obtained from solid-liquid separation still has a considerable amount of residual used modification solution existed in the form of a surface liquid film and a capillary condensate, roughly account for 40-50 wt. % of the weight of the wet material. The residual used modification solution mainly contains free alkali metal hydroxides, it also contains silicate ions, titanate ions and titanium silicate ions and larger zeolite framework fragments dissolved from the zeolite framework. Excessive free alkali may continue to react with the silicon hydroxyl in the drying process and destroy an expected modification degree, while other species may become blockages of the porous channels of the zeolite and even become the active sites that cause various side reactions. On the other hand, improper washing method and degree may easily lead to the loss of useful alkali metal ions balanced on the silicon hydroxyl. Therefore, it is very important to select correct washing method and degree. The alkali metal hydroxide solution used for the washing purpose in the present invention is an alkali metal hydroxide solution having a concentration much lower than that of the modified solution. The simplest practice is to use a lower-concentration alkali metal hydroxide solution with the same type as the modification solution as the washing solution. The present invention provides the following reasons for selecting the alkali metal hydroxide as the washing solution: firstly, the use of the alkali metal hydroxide solution as the washing solution is beneficial to supplement the lost of the useful alkali metal ions balanced on the silicon hydroxyls in the washing process. Secondly, the alkali metal hydroxide solution is strongly alkaline. The fall off and runoff of the useful alkali metal ions balanced on the silicon hydroxyl can be prevented by maintaining the strong alkalinity of the washing solution in the washing process. Otherwise, if deionized water is selected as the washing solution, the useful alkali metal ions balanced on the silicon hydroxyls are easy to lose in the form of NaOH due to the reverse reaction of NaOH+Si—OH═Si—O−Na++H2O. That is, the hydrolysis reaction of strong alkali and weak acid salt (Si—O−Na+). This is exactly the reason that the existing patents involving inorganic base modification can remove the alkali metal ions in the washing step. Therefore, in order to obtain the alkali metal ion modified TS-1 zeolite, the deionized water is not suitable for the present invention, and a solution with an acidic pH value also cannot be used as the washing solution for the wet material after solid-liquid separation. The truth is self-evident.
Of course, it is entirely feasible in principle, but is not desirable from the perspective of environmental protection and cost that low-concentration quaternary ammonium alkali solutions or other organic alkali aqueous solutions with strong alkalinity are used as the washing solution.
In addition, the purpose of the present invention emphasizing the use of the alkali metal hydroxide solution with a concentration lower than that of the modification solution as the washing solution, is to reduce the residual amount of free alkali metal hydroxide in the modified TS-1 after washing. The shortcomings of excessive free alkali metal hydroxide remaining in the modified TS-1 has been explained above.
The simplest way for the solid-liquid separation in the present invention is centrifugation and filtration. However, when centrifugation and filtration are used, it is preferably not to introduce additives such as flocculants and filter aids to prevent the pH value of the solution from changing or even causing the precipitate. Other solid-liquid separation modes are allowed to be used as long as obvious liquid phase concentration, precipitation of precipitates and pH change are not caused in the separation process.
The drying and calcining in the present invention can be conducted in an air atmosphere according to conventional practices. The reference practice recommended by the present invention is as follows: the drying temperature range is 80-120° C., and the drying time is decided based on the dry basis content of the sample not less than 90%. The recommended final calcining temperature range is 400-550° C., and the constant temperature time at the final temperature is not less than 3 hours.
The implementation effects of the present invention can be evaluated by the following means:
Firstly, infrared spectroscopy is used to characterize the absorption peak position of the active site of the modified TS-1 zeolite catalyst. The method comprises: putting an appropriate amount of sample from the modified TS-1 zeolite treated by the third step into a small beaker, putting an appropriate amount of spectral purity KBr into another small beaker, and putting the two small beakers into an oven at 110° C. simultaneously for pre-drying for 4 hours; then mixing and grinding KBr and TS-1 zeolite into powder at a ratio of 200:1, and pressing into wafers under a pressure of 6 MPa; putting the wafers into an infrared sample cell for testing to obtain an infrared spectra; and finally, using the second derivative spectrum in the infrared software to accurately locate the infrared characteristic absorption peak position of the framework titanium active site modified by the alkali metal ions.
Secondly, the X-ray fluorescence spectroscopy (XRF) method is used to obtain the silicon-titanium molar ratio and sodium ion content data of the modified sample.
In addition, a small fixed bed reactor is used to evaluate the gas phase epoxidation performance of the modified TS-1 zeolite catalyst. It is recommended to refer to the experimental devices and methods described in the previously published journal papers and authorized Chinese invention patents to evaluate the gas phase epoxidation of propylene and hydrogen peroxide. References recommended by the present invention include: Chem. Commun., 2005, 1631-1633; Modern Chemical Industry, Vol. 26 Supplement, 2006, P194-197; AIChE J, 53: 3204-3209, 2007; Advanced Technology of Electrical Engineering and Energy, Vol 28, 2009, No. 3, P73-76; Chin. J. Catal., 2010, 31: 1195-1199; CIESC Journal Vo163, 2012, No. 11, P3513-3518; Journal of Catalysis 288 (2012) 1-7; Angew. Chem. Int. Ed. 2013, 52, 8446-8449; AIChE J, 64: 981-992, 2018; Chinese invention patents (application numbers) 200310105210.9, 200310105211.3 and 200310105212.8.
The characteristic of the evaluation method is the use of the integrated reactor. The upper segment of the integrated reactor is a self-cooling dielectric barrier discharge reactor for in-situ synthesis of gaseous hydrogen peroxide from hydrogen and oxygen plasma. The lower segment of the integrated reactor is a conventional fixed bed reactor which contains titanium silicalite zeolite particles (20-40 meshes) for the gas phase epoxidation of propylene and hydrogen peroxide. The working principle of the integrated reactor is: hydrogen and oxygen are mixed at 170 ml/min and 8 ml/min respectively under the control of a mass flow controller, and then enter the self-cooling dielectric barrier discharge reactor in the upper segment of the integrated reactor to synthesize gaseous hydrogen peroxide. The yield of the hydrogen peroxide is 0.35 g/h. The synthesized hydrogen peroxide gas is carried by excess hydrogen to enter the epoxidation reactor in the lower segment from a gas hole between the two segments of reactors, and is fully mixed with the propylene gas (18 ml/min) which enters the segment of reactor from a side line to jointly enter the TS-1 catalyst bed for the epoxidation.
The reaction conditions are: the loading of the TS-1 catalyst is 0.5 g (the catalyst powder is tableted and then crushed and sieved to obtain 20-40 meshes); the actual molar ratio of propylene to hydrogen peroxide is about 5:1; and the gas phase epoxidation is conducted at atmospheric pressure and 130° C.
The beneficial effects of the present invention are: the present invention uses the alkali metal hydroxide solution containing a small amount of tetrapropylammonium (TPA+) cations to perform the degree controlled hydrothermal treatment on the titanium silicalite zeolite TS-1. After the hydrothermal treatment, alkali metal cations must remain in the titanium silicalite zeolite, and at least part of the alkali metal cations are on the silicon hydroxyls near the framework titanium in the form of counter cations to modify the local environment of the framework titanium. The alkali metal ion modification has an unexpected improvement effect on the gas phase epoxidation of propylene and hydrogen peroxide in the absence of solvent and at high temperature (which is generally higher than 100° C. under normal pressure). For the gas phase epoxidation of propylene and hydrogen peroxide, a framework titanium active site with alkali metal ions enables the catalyst to obviously inhibit the self-decomposition side reaction of the hydrogen peroxide at a normal propylene/hydrogen peroxide feed ratio and increase the conversion rate of the propylene, so as to increase the utilization rate of the hydrogen peroxide and reduce the generation of oxygen, thereby greatly improving the economy and the safety of the gas phase epoxidation. In addition, the introduction of a small amount of TPA+ ions in the hydrothermal modification solution reduces the modification loss of the titanium silicalite zeolite, and greatly reduces the content of the silicate solutes in the alkali metal hydroxide waste solution produced after modification, so that the discharged wastewater is easier to treat and discharge after meeting the standards, and the modification method of the present invention is relatively easy to implement. More meaningfully, the use of a small amount of TPA+ ions also solves the applicability problem of the nano TS-1 zeolite matrix, and expands the application range of hydrothermal modification of the alkali metal hydroxide solution.
The following embodiments only serve to further illustrate the present invention, but shall not be used to limit the contents of the present invention. The reagents and drugs involved in all the embodiments are commercially available and analytically pure.
The SEM images are obtained with the NOVA NanoSEM 450 field emission scanning electron microscope from American FEI Company. The voltage is 230 kV, the frequency is 60 Hz, the current is 8 A, and the magnification is 800,000 to 1,600,000. Samples are dispersed into anhydrous alcohol, and dripped on silicon wafers with a capillary. Then, after fixed on the conductive adhesive, the samples are subjected to metal spraying treatment and the image is observed.
X-ray powder diffraction (XRD) crystal structure analysis: D/max·2400 X-ray powder diffractometer from Japanese Rigaku company is used for measurement; CuKα radiation is adopted; the voltage is 40 kV; the current is 100 mA; the range of the scanning diffraction angle is 2θ=4-40°; the scanning speed is 2°/min; and the scanning stride is 0.08°. The relative crystallinity is obtained according to the ratio of the sum of the peak intensities of five MFI structural characteristic peaks at 2θ=7.8°, 8.8°, 23.2°, 23.8° and 24.3° in the XRD spectrogram and the sum of the intensities of five diffraction peaks (selected) of the reference sample.
X-ray fluorescence spectroscopy (XRF) composition analysis: a German Bruker S8 Tiger X-ray fluorescence spectrometer is used; 1.2 g of TS-1 sample is uniformly mixed with 4 g of boric acid to prepare tablets; and a standard-sample-free method is used for measurement.
Framework vibration characterization of FT-IR spectrum TS-1: characterization is carried out on the IS10 infrared spectrometer of Nicolet company; KBr is used for tableting; the range of the scanning wave number is 4000-400 cm -1 ; and the scanning frequency is 64.
Embodiment 1. The present embodiment is used to illustrate that the large-crystal micron-size TS-1 zeolite modified by the degree controlled hydrothermal treatment method of the alkali metal hydroxide solution containing a small amount of TPA+ ions provided by the present invention exhibits high activity and selectivity and utilization rate of hydrogen peroxide for the gas phase epoxidation of propylene and hydrogen peroxide.
At first step: synthesizing and preparing the large-crystal micron-sized TS-1 zeolite matrix according to the method introduced in the publication literature Appl. Catal. A, 185, (1999) 11-18.
The specific feed amount and synthesis steps are as follows:
220 ml of deionized water is added to 225 g of silica sol (26% wt); after stirring for 10 minutes, 18.4 g of tetrapropylammonium bromide is added to the diluted silica sol solution; after continuing stirring for 20 minutes, a silicon solution is obtained; tetrabutyl titanate and acetylacetone are mixed at a mass ratio of 1:0.8, and stirred for 15 minutes to prepare a titanium solution; 19.7 ml of the titanium solution is added to the silicon solution; after stirring for 30 minutes, 57 ml of n-butylamine is added and continuously stirred for 15 minutes to obtain uniform gel; then the obtained gel is added to a 21 stainless steel autoclave and the hydrothermal synthesis is carried out at 170° C. for 96 hours under agitation. After the crystallization time is reached, the hydrothermal crystallization autoclave is naturally cooled to room temperature at first, then the autoclave is opened, and the mother solution is separated by Buchner funnel suction filtration to obtain a zeolite filter cake. The filter cake is washed with deionized water for several times until the pH value of the washing solution is close to 7.0. Then, the filter cake is put into an electric oven and dried overnight at 110° C. The dried solid is then transferred into a muffle furnace for temperature-programmed calcination to remove the templating agent. The temperature-programmed calcination starts at room temperature, and the temperature is raised to 300° C. at a temperature rise rate of 10° C./min, and then the temperature is raised from 300° C. to 500° C. at a temperature rise rate of 1° C./min and kept constant until the sample is completely white, so as to obtain the large-crystal micron-sized TS-1 (2) matrix.
In order to use a reference sample to calculate the relative crystallinity of the large-crystal micron-sized TS-1 matrix, embodiment 1 in the Chinese invention patent (application number) 201110295555.x is used to prepare the reference sample. Specifically: 220 ml of deionized water is added to 225 g of silica sol (20% wt); after stirring for 10 minutes, 18.4 g of tetrapropylammonium bromide and 5.1 g of seed crystals are added to the diluted silica sol solution; after continuing stirring for 20 minutes, a silicon solution is obtained; tetrabutyl titanate and acetylacetone are mixed at a mass ratio of 1:0.8, and stirred for 15 minutes to prepare a titanium solution; 19.7 ml of the titanium solution is added to the silicon solution; after stirring for 30 minutes, 57 ml of n-butylamine is added and continuously stirred for 15 minutes to obtain uniform gel; then 6.0 g of Na2SO4 is added and stirred for 10 minutes; and then the obtained gel is added to a 21 stainless steel autoclave and crystallized at 170° C. for 24 hours under agitation. The post-treatment method of the reference sample is conducted by referring to the processing method of the large-crystal micron-sized TS-1 zeolite matrix.
SEM, XRF, FT-IR and XRD are used to characterize the crystal size of the large-crystal micron-size TS-1 zeolite matrix. Results show that the crystal size is 1×2×5 μm, the total Si/Ti molar ratio is about 34.5, and no sodium ion is measured. The index value I960 cm−1/I550 cm−1 of the framework titanium content is about 0.50 and the relative crystallinity is about 100%. The measurement results show that the synthesized large-crystal micron-size TS-1 matrix meets the requirements of the present invention.
At second step: preparing 0.1 mol/L of sodium hydroxide modification solution containing 0.15 mol/L of TPA+.
The solution is prepared with analytically pure sodium hydroxide solid particles (96%), tetrapropylammonium bromide (TPABr) and deionized water.
Firstly, 4.17 g of solid sodium hydroxide particles is accurately weighed, and 40 g of solid TPABr particles which are accurately weighed are added into the volumetric flask. Then, the 1 l volumetric flask is used to prepare a 0.1 mol/L sodium hydroxide solution containing 0.15 mol/L of TPA+ (cooled to room temperature). For the sake of caution, a standard reagent potassium hydrogen phthalate and a phenolphthalein indicator are used to calibrate the prepared sodium hydroxide solution in accordance with conventional operation. A qualified solution has a relative deviation of the concentration value of less than 5%. Otherwise, the modification solution is prepared again.
At third step: using 0.1 mol/L sodium hydroxide solution containing 0.15 mol/L of TPA+ to conducted the degree controlled hydrothermal treatment on the large-crystal micron-size TS-1 zeolite matrix.
Specifically, 50 ml of the calibrated 0.1 mol/L sodium hydroxide solution containing 0.15 mol/L of TPA+ is accurately measured with a measuring cylinder and added to a plastic cup with magnetic stirrer. Then, 5 g of the large-crystal micron-size TS-1 zeolite matrix that is calcined in the first step and completely removed from the templating agent is weighed, and slowly added into the modification solution under agitation. After the large-crystal micron-size TS-1 zeolite matrix is completely added to the solution, the stirring speed is appropriately increased to make the slurry to a uniform state. The stirring is continued for 2 hours at room temperature, and then stopped; and the slurry is transferred into a 100 ml hydrothermal autoclave and sealed. The hydrothermal autoclave is heated into the oven of 170° C. for 16 hours at constant temperature.
At fourth step: conducting post-treatment on the hydrothermally modified TS-1 zeolite.
After the hydrothermal treatment is ended, the hydrothermal autoclave is taken out of the electric oven and quickly cooled to room temperature with tap water. Then the hydrothermal autoclave is carefully opened, and the modification solution is removed by Buchner funnel suction filtration to obtain a zeolite filter cake. The filter cake is washed with 0.01 mol/L of sodium hydroxide solution until no precipitate appears after the filtrate is neutralized with acid. Then, the filter cake is put into the electric oven and dried overnight at 110° C. to ensure that the dry basis content of the solid powder (solid content measured after calcining at 500° C. for 3 hours) is not less than 90%. Finally, the dried solid powder is calcined at a constant temperature of 540° C. for 6 hours to obtain about 4.46 g of modified TS-1 zeolite product of embodiment 1, with a product yield of 91 wt. %.
The sodium ion modified TS-1 zeolite prepared in the present embodiment is tested and evaluated below:
Firstly, infrared spectroscopy is used to characterize the absorption peak position of the framework titanium active site of the modified TS-1 zeolite.
An appropriate amount of the modified product in the fourth step is put into a small beaker; an appropriate amount of spectral purity KBr is put into another small beaker; and the two small beakers are simultaneously put into the oven at 110° C. for pre-drying for 4 hours. Then KBr and the modified TS-1 zeolite product are mixed and ground at a ratio of 200:1, and pressed into a wafer under a pressure of 6 MPa; the wafer is put into an infrared sample cell for testing to obtain an infrared spectra; and finally, the second derivative spectrum in the infrared software is used to accurately locate the infrared characteristic absorption peak position of the framework titanium active site modified by the alkali metal ions, which is at 978 cm−1 for the modified zeolite product of embodiment 1.
In addition, the X-ray fluorescence spectroscopy (XRF) method mentioned in the first step is used to obtain the silicon-titanium molar ratio and sodium-titanium molar ratio of the modified product of embodiment 1, which are 33.6 and 0.46, respectively.
The characterization results of the infrared spectroscopy and the X-ray fluorescence spectroscopy show that the hydrothermal treatment of the large-crystal micron-size TS-1 zeolite matrix with 0.1 mol/L sodium hydroxide solution containing 0.15 mol/L of TPA+ produces the partial dissolution-recrystallization effect, so that the silicon-titanium molar ratio of the modified catalyst is slightly lower than that of the matrix. At the same time, a large amount of sodium ions exist in the modified catalyst, which makes that the infrared characteristic absorption peak of the framework titanium active site shift from 962 cm−1 (matrix,
Then, a small fixed bed reactor is used to evaluate the gas phase epoxidation performance of the modified TS-1 zeolite catalyst.
The integrated reactor reported in Chin. J. Catal., 2010, 31: 1195-119 is used for a gas phase epoxidation experiment. The upper segment of the reactor is a self-cooling dielectric barrier discharge reactor for in-situ synthesis of gaseous hydrogen peroxide from hydrogen and oxygen plasma. The lower segment of the integrated reactor is a conventional fixed bed reactor which contains titanium silicalite zeolite particles (20-40 meshes) for the gas phase epoxidation of propylene and hydrogen peroxide. Specific operation steps are as follows: (1) the yield of the hydrogen peroxide is calibrated with the upper segment of plasma reactor: at this moment, the lower segment of reactor should be removed. Firstly, the self-cooling circulating water of the upper segment of reactor is opened. Then, a hydrogen cylinder and the mass flow controller are started to control the hydrogen flow to be 170 ml/min; and next, the oxygen cylinder and the mass flow controller are started to slowly increase the oxygen flow to be 8 ml/min. During the discharge reaction of the upper segment of reactor, the flows of the hydrogen and the oxygen should be accurately controlled and the hydrogen and the oxygen should be mixed uniformly before entering the upper segment of reactor. Then, dielectric barrier discharge is performed according to the discharge methods introduced in Chinese invention patents (application numbers) 200310105210.9, 200310105211.3 and 200310105212.8, so that the hydrogen-oxygen mixture entering the self-cooling dielectric barrier discharge reactor at the upper segment of the integrated reactor conducts a plasma reaction to produce gaseous hydrogen peroxide. Through calibration by conventional iodometry, the yield of the hydrogen peroxide is about 0.35 g/h. (2) The two segments of reactors are integrated for the gas phase epoxidation of propylene and hydrogen peroxide. After the calibration step, firstly the discharge is stopped, then the oxygen is stopped, and the hydrogen is stopped after 10 minutes. 0.5 g of modified large-crystal micron-size TS-1 zeolite catalyst (tableted, crushed, and sieved to obtain 20-40 meshes in advance according to conventional methods) is loaded into the lower segment of fixed bed epoxidation reactor, and the lower segment of reactor and the upper segment of reactor are connected together. The lower segment of reactor is inserted into an electric heating furnace. Next, the self-cooling circulating water of the upper segment of reactor is opened. Then, a hydrogen cylinder and the mass flow controller are started to control the hydrogen flow to be 170 ml/min; and next, the oxygen cylinder and the mass flow controller are started to slowly increase the oxygen flow to be 8 ml/min. The flows of the hydrogen and the oxygen are accurately controlled and the hydrogen and the oxygen shall be mixed uniformly before entering the upper segment of reactor. Then, the propylene feed of the lower segment of reactor is started, and the propylene flow is controlled as 18 ml/min by the mass flow controller. After the three gas flows are stable and the cooling water flow of the upper segment of reactor is also stable, a plasma power supply of the upper segment of reactor is turned on for dielectric barrier discharge. In this way, the hydrogen peroxide gas synthesized by the discharge of the upper segment is carried by excess hydrogen to enter the epoxidation reactor in the lower segment from a gas hole between the two segments of reactors, and is fully mixed with the propylene gas which enters the segment of reactor from a side line to jointly enter the TS-1 zeolite catalyst bed for conducting the epoxidation. The actual molar ratio of propylene and hydrogen peroxide is calculated to be about 5:1. The reaction temperature of the lower segment of reactor is controlled as 130° C. through the electric heating furnace. After the discharge is conducted for 30 minutes, through an online gas chromatography (analysis by DB-Wax chromatographic column (30 m×0.32 mm, PEG20M) (temperature programming to 50° C. for 5 minutes, at 10° C. to 180° C. per minute for 2 minutes, at 20° C. to 200° C. per minute for 5 minutes), the reaction product is analyzed, from the analysis data the propylene conversion rate is calculated as 14.8%, the PO selectivity is calculated as 94.3%, and the utilization rate of the hydrogen peroxide is calculated as 74.0%.
Reference embodiment 1. The reference embodiment 1 is used to illustrate that the unmodified large-crystal micron-size TS-1 zeolite has poor activity and selectivity for the gas phase epoxidation of propylene and hydrogen, and the utilization rate of the hydrogen peroxide is low.
The embodiment 1 is repeated, but the large-crystal micron-size TS-1 zeolite synthesized in the first step is directly used for the evaluation of the gas phase epoxidation of propylene and hydrogen peroxide without the subsequent hydrothermal modification using the sodium hydroxide solution containing TPA+. Then, the propylene conversion rate is 4.3%, the PO selectivity is 58.1%, and H2O2 utilization rate is 21.5%.
Reference embodiment 2. The reference embodiment 2 is used to illustrate that if the large-crystal micron-size TS-1 is treated according to the sodium exchange method provided in the publication literature J. Catal., 1995,151, 77-86, the obtained modified zeolite has no improvement effect on the gas phase epoxidation of propylene and hydrogen peroxide.
The embodiment 1 is repeated, but the large-crystal micron-size TS-1 zeolite synthesized in the first step is not modified by the hydrothermal modification method of the sodium hydroxide solution provided by the present invention, but is modified in accordance with the sodium exchange method provided by J. Catal., 1995,151, 77-86. The specific method is as follows: 1 mol/L NaOH solution is prepared, and then 1 g of zeolite matrix is added to 100 mL of 1 mol/L NaOH solution, and stirred at 25° C. for 24 hours. Then the solution is subjected to suction filtration, dried at 110° C. for 12 hours, and calcined at 540° C. for 6 hours.
Then, the silicon-titanium molar ratio of the sodium exchange catalyst measured by XFR is reduced to 29.5, and the sodium-titanium molar ratio is 1.39. The infrared characteristic absorption peak of the framework titanium measured by the infrared spectroscopy appears near 985 cm−1 (
The evaluation results of the gas phase epoxidation show that the modified zeolite prepared by the sodium exchange method reported in the literature in the reference embodiment 2 has a propylene conversion rate of only 3.0%, a PO selectivity of 83.2%, and a H2O2 utilization rate of only 15.0%. In other words, the catalytic performance of the catalyst modified by the sodium exchange method in the gas phase epoxidation of propylene and hydrogen peroxide (except for selectivity) is not better than that of the matrix, and the catalyst has high activity for the self-decomposition reaction of the hydrogen peroxide, so that the utilization rate of the hydrogen peroxide is only 15.0%.
Reference embodiment 3. The reference embodiment 3 is used to illustrate the opposite side that when the large-crystal micron-size TS-1 is modified according to the degree controlled hydrothermal treatment method provided by the present invention, it is important that sodium ions are retained in the modified zeolite.
The embodiment 1 is repeated, but after the operation of the fourth step is completed, the modified titanium silicalite zeolite is subjected to conventional ammonium exchange treatment twice with 0.4 M ammonium nitrate at room temperature, each for 2 hours. The engineers familiar with the field can complete the ammonium exchange work according to the method described for preparing hydrogen type catalysts through ammonium exchange of silica-alumina zeolite reported by any publication literature. After the ammonium exchange, the solution is removed by Buchner funnel suction filtration to obtain a zeolite filter cake. Then, the filter cake is put into the electric oven and dried overnight at 110° C. to ensure that the dry basis content of the solid powder (solid content measured after calcining at 500° C. for 3 hours) is not less than 90%. Finally, the dried solid powder is calcined at a constant temperature of 540° C. for 6 hours to obtain an ammonium exchanged zeolite product. Then, the ammonium exchanged zeolite product is used for test characterization and the gas phase epoxidation of the propylene. The silicon-titanium ratio of the ammonium exchanged zeolite product measured by XRF is 32.1, and the sodium-titanium ratio is 0.12. The infrared spectroscopy characterization shows that the vibration characteristic absorption peaks of the framework titanium of the ammonium exchanged zeolite product are located at 963 cm−1 (
The reference embodiment 3 illustrates that after the modified TS-1 zeolite obtained in embodiment 1 is subjected to the conventional ammonium exchange, the sodium-titanium molar ratio of the modified zeolite is reduced to about 0.12, and at this moment, the infrared vibration characteristic absorption peak of the framework titanium also moves from 978 cm−1 (the high sodium state of embodiment 1) back to near 960 cm−1. It can be found from comparison of the reference embodiment 3 and embodiment 1 that the removal of the sodium ions also leads to the significant decrease of the conversion rate of the gas phase epoxidation and the utilization rate of the hydrogen peroxide. This fully demonstrates that the presence of sufficient sodium ions in the modified TS-1 zeolite is the key to obtain a good modification effect in the present invention. It can also be seen from the comparison of the selectivity of the propylene oxide that the degree controlled inorganic base hydrothermal treatment method provided by the present invention may produce some acidic sites in the zeolite due to the effect of silicon dissolution. The presence of the sodium ions neutralizes the acid sites at the same time, so that the modified zeolite of embodiment 1 reaches high selectivity close to 94.3%. However, in the reference embodiment, because most of the sodium ions are removed through the ammonium exchange, the acid sites produced by the modification is released, thereby causing very low selectivity of the ammonium exchanged zeolite, which is even lower than the selectivity of the propylene oxide of the matrix.
Reference embodiment 4. The reference embodiment 4 is used to further illustrate that when the large-crystal micron-size TS-1 zeolite is modified according to the controlled hydrothermal treatment method provided by the present invention, it is important that enough sodium ions are retained in the modified zeolite.
The reference embodiment 3 is repeated, but after the ammonium exchange catalyst is obtained, the ammonium exchange catalyst is subjected to reverse exchange treatment of the sodium nitrate solution at room temperature for 2 hours. The reverse exchange of the sodium nitrate solution is a conventional ion exchange treatment, and the practice is roughly the same as the ammonium exchange in the reference embodiment 3, except that the ammonium salt solution is changed to a sodium nitrate solution. The engineers familiar with the field can complete the work according to the zeolite ion exchange method recorded in any publication literature. After the ion exchange of the sodium nitrate solution (0.15 M) is completed, post treatments including the separation, drying and calcining are repeated. The obtained sodium nitrate exchange catalyst is subjected to characterization and the gas phase epoxidation of the propylene.
The sodium-titanium ratio of the sodium nitrate exchange zeolite product measured by XRF is increased to 0.25. The reaction results show that the conversion rate of the propylene of the sodium nitrate exchange zeolite product is 8.7%, the PO selectivity is 85.7% and the utilization rate of the hydrogen peroxide is 43.5%.
The above results further indicate that when the TS-1 zeolite is modified according to the degree controlled hydrothermal treatment method of the alkali metal hydroxide solution provided by the present invention, it is important that enough sodium ions are retained in the modified catalyst. Meanwhile, the reference embodiment 4 can also illustrate that for the ammonium exchange alkali metal ion modified zeolite, the lost alkali metal ions can be recovered to a certain extent through the alkali metal ion reverse exchange, thereby recovering the gas phase epoxidation activity and selectivity of the zeolite and the utilization rate of the hydrogen peroxide to a certain extent.
Reference embodiment 5. The reference embodiment 5 is used to illustrate that if the TS-1 zeolite is subjected to degree controlled hydrothermal modification with an alkali metal hydroxide solution that does not contain TPA+, the similar effect of improving the gas phase epoxidation performance of the TS-1 zeolite can also be achieved. However, the yield of the modified zeolite is low, and the soluble silicate species contained in the separation mother solution has high concentration, and is difficult for treatment to meet up-to-standard discharge.
The embodiment 1 is repeated, but in the operation of the second step, a 0.1 mol/L sodium hydroxide solution that does not contain TPA+ is directly prepared for subsequent modification. Then, the sodium-titanium molar ratio measured by XRF in the modified zeolite is 0.85; the infrared characteristic absorption peak positions of the framework titanium active site measured by the infrared spectroscopy method are at 968 cm−1; and the gas phase epoxidation results of propylene and hydrogen peroxide are: the conversion rate of the propylene is 15.0; the PO selectivity is 96.8%; and the utilization rate of the hydrogen peroxide is 75.0%.
It is impressive that in the present reference embodiment, the yield of the modified zeolite (the percent of the dry basis weight of the modified zeolite in the dry basis weight of the TS-1 matrix) is only 85%. Meanwhile, the inorganic ash (silicate) in the hydrothermally modified separation mother solution is measured as 654.4 mg/mL by a burning weight reduction method. In contrast, if the modification is conducted completely in accordance with the embodiment 1, the yield of the modified zeolite is increased to 91%. Correspondingly, the inorganic ash (silicate) in the hydrothermally modified separation mother solution measured by the burning weight reduction method is decreased to 211.7 mg/mL.
The above measurement results indicate that in the present invention, the use of a small amount of TPA+ ions reduces the modification loss of the titanium silicalite zeolite, and greatly reduces the content of the silicate solutes in the alkali metal hydroxide waste solution produced after modification, so that the discharged wastewater is easier to treat and discharge after meeting the standards, and the modification method of the present invention is relatively easy to implement.
Embodiment 2. The present embodiment is used to illustrate that the introduction of a small amount of TPA+ quaternary ammonium cations into the aqueous alkali metal hydroxide solution in the present invention allows the hydrothermal modification method to be applicable to the nano TS-1 zeolite matrix synthesized by the classical method.
The embodiment 1 is repeated, but in the first step of hydrothermal synthesis of the TS-1 zeolite matrix, the TS-1 zeolite matrix is synthesized according to the formula of the classical method introduced by the Chinese invention patent (application number) 200910131993.5. The silicon-titanium molar ratio, the framework titanium index data, and the relative crystallinity index of the matrix meet the requirements of the present invention, but the crystal size is 200-300 nanometers. Thus, the matrix belongs to a nano TS-1. The sodium content of the nano TS-1 zeolite matrix measured by XRF is lower than a measurement limit, and the sodium-titanium molar ratio of the modified product is 0.49. The infrared spectroscopy characterization shows that the vibration characteristic absorption peaks of the framework titanium of the nano TS-1 zeolite matrix are located at 960 cm−1, and the vibration characteristic absorption peaks of the framework titanium of the modified zeolite product are located at 975 cm−1. Then, the following results of the gas phase epoxidation experiment of propylene and hydrogen peroxide are obtained: the conversion rate of the propylene of the nano TS-1 matrix is 7.3%, the PO selectivity is 76.7% and the utilization rate of the hydrogen peroxide is 36.5%; and the conversion rate of the propylene of the modified nano TS-1 catalyst is 12.3%, the PO selectivity is 94.6% and the utilization rate of the hydrogen peroxide is 61.5%.
Reference embodiment 6. The reference embodiment 6 is used to illustrate that if the aqueous alkali metal hydroxide solution does not contain TPA+ quaternary ammonium cations, the purpose of improving the gas phase epoxidation performance of the nano TS-1 zeolite cannot be achieved when the nano TS-1 zeolite matrix is hydrothermally modified with a pure aqueous alkali metal hydroxide solution.
The embodiment 2 is repeated, but the modification solution prepared in the second step only contains 0.1 mol/L sodium hydroxide and 0.01 mol/L sodium hydroxide. Then, the following results of the gas phase epoxidation experiment of propylene and hydrogen peroxide are obtained: the modified catalyst obtained through hydrothermal treatment of the nano TS-1 zeolite matrix with 0.1 mol/L sodium hydroxide solution shows 0.50% propylene conversion rate, 87.3% PO selectivity and 2.5% utilization rate of the hydrogen peroxide; the modified nano TS-1 catalyst obtained through hydrothermal treatment of the nano TS-1 matrix with 0.01 mol/L sodium hydroxide solution shows 6.9% propylene conversion, 96.6% PO selectivity and 34.5% utilization rate of the hydrogen peroxide.
It can be seen from the reference embodiment 6 and embodiment 2 that if the modification solution does not contain a small amount of TPA+ quaternary ammonium cations, even if a particularly low concentration alkali metal hydroxide solution is used, the conversion rate of propylene and hydrogen peroxide selectivity in the modified zeolite product do not exceed the matrix (at this time, the selectivity of the modified catalyst is better than that of the matrix, as mentioned above, due to the effect of acidity neutralization.). Obviously, the introduction of a small amount of TPA+ quaternary ammonium cations into the alkali metal hydroxide modification solution in the present invention widens the applicability of the modification method for the zeolite matrix.
Embodiment 3. The present embodiment is used to illustrate that the yield of the modified catalyst can be adjusted by changing the content of TPA+ in the modification solution. However, TPA+ cannot improve the catalytic performance of the TS-1 zeolite.
The embodiment 1 is repeated, but in the operation of the second step, the TPA+ concentrations in the modification solution are changed to 0.08 mol/L and 0.23 mol/L respectively. The yields of the modified catalysts are 90.6% and 91.1% respectively; the results of the gas phase epoxidation of the propylene over the obtained catalysts are as follows: the conversion rates of the propylene are 14.2% and 14.0% respectively; the PO selectivities are 95.4% and 94.6% respectively; and the utilization rates of the hydrogen peroxide are 71.0% and 70.0% respectively.
It can be seen from comparison of the results of this embodiment with those of the embodiment 1 that, the main effect of the TPA+ quaternary ammonium cations is not the modification of catalysis but the influence of recrystallization and catalyst recovery rate.
Embodiment 4. The present embodiment is used to illustrate that by changing a modification time parameter, the degree of hydrothermal modification of the alkali metal hydroxide can be adjusted, and the catalytic performance of the modified zeolite for the gas phase epoxidation of propylene and hydrogen peroxide is changed accordingly.
The embodiment 1 is repeated, but in the operation of the third step, the duration of hydrothermal treatment modification is sequentially changed to 2, 4, 8 and 24 hours. Then, the relative crystallinity data (
However, from the comparison with the reaction result of the matrix (reference embodiment 1), it can be seen that the modification effectiveness of the modification method provided by the present invention for the modification of the TS-1 matrix can be reflected in a wide time range.
Embodiment 5. The present embodiment is used to illustrate that by changing a concentration parameter of the alkali metal hydroxide of the modification solution, the degree of hydrothermal modification can also be adjusted, and the catalytic performance of the modified zeolite for the gas phase epoxidation of propylene and hydrogen peroxide is changed accordingly.
The embodiment 1 is repeated, but in the operation of the second step, the concentrations of the sodium hydroxide in the prepared modification solutions are sequentially changed to 0.05, 0.15 and 0.20 mol/L. Then, the infrared characteristic absorption peak positions of the framework titanium active site measured by the infrared spectroscopy method (
Similarly, the present invention is intended to state that from the comparison with the reaction result of the matrix (reference embodiment 1), it can be seen that the modification effectiveness of the modification method provided by the present invention for the modification of the TS-1 zeolite matrix can be reflected in a wide concentration range of the alkali metal hydroxide.
Embodiment 6. The present embodiment is used to illustrate that by changing a temperature parameter, the degree of hydrothermal modification of the alkali metal hydroxide can be adjusted, and the catalytic performance of the modified zeolite for the gas phase epoxidation of propylene and hydrogen peroxide is changed accordingly.
The embodiment 1 is repeated, but in the operation of the third step, the temperatures of hydrothermal treatment modification are sequentially changed to 25° C., 80° C., 110° C., 150° C., 190° C. and 210° C. Then, the results of the gas phase epoxidation of propylene and hydrogen peroxide over the obtained catalysts are as follows: the conversion rates of the propylene are 3.9%, 6.0%, 10.4%, 12.8%, 11.9% and 7.1% in sequence; the PO selectivities are 92.0%, 92.3%, 93.2%, 92.4% and 92.3% in sequence; and the utilization rates of the hydrogen peroxide are 19.5%, 30.0%, 52%, 64.0%, 59.5% and 35.5% in sequence. Considering that the hydrothermal treatment temperature adopted in embodiment 1 is 170° C., the conversion rate of the propylene, the PO selectivity, and the utilization rate of the hydrogen peroxide of the obtained modified zeolite are 14.8%, 94.3% and 74.0% respectively. It can be seen that the hydrothermal treatment temperature also has a suitable region. Therefore, the present invention provides a preferred range of 100-200° C., and a more preferred range of 150-190° C.
Herein, the present invention is intended to state that from the comparison with the reaction result of the matrix (reference embodiment 1), it can be seen that the modification effectiveness of the modification method provided by the present invention for the modification of the TS-1 matrix can be reflected in a wide range of the hydrothermal treatment temperature.
Embodiment 7. The present embodiment is used to illustrate that by regulating a liquid-solid ratio parameter, the degree of hydrothermal modification of the alkali metal hydroxide can be adjusted, and the catalytic performance of the modified zeolite for the gas phase epoxidation of propylene and hydrogen peroxide is changed accordingly.
The embodiment 1 is repeated, but in the operation of the third step, the liquid-solid ratios of hydrothermal treatment modification are sequentially changed to 4, 5, 7 and 15. The results of the gas phase epoxidation of propylene and hydrogen peroxide over the obtained modified zeolites are as follows: the conversion rates of the propylene are 9.4%, 11.8%, 13.7% and 9.8% in sequence; the PO selectivities are 93.0%, 94.5%, 93.7% and in sequence; and the utilization rates of the hydrogen peroxide are 47.0%, 59.0%, 68.5% and 49.0% in sequence. Similarly, considering that the liquid-solid ratio adopted in embodiment 1 is 10, the conversion rate of the propylene, the PO selectivity, and the utilization rate of the hydrogen peroxide of the obtained catalyst are 14.8%, 94.3% and 74.0% respectively. Obviously, the liquid-solid ratio also has a suitable region. Therefore, the present invention provides a preferred range of 5-15, and a more preferred range of 8-12.
Therefore, from the comparison with the reaction result of the matrix (reference embodiment 1), it can be seen that the modification effectiveness of the modification method provided by the present invention for the modification of the TS-1 matrix can be reflected in a wide range of the liquid-solid ratio.
Embodiment 8. The present embodiment is used to illustrate that in the washing step after the hydrothermal treatment, the use of a suitable low-concentration alkali metal hydroxide solution as the washing solution is beneficial to achieve the modification effect.
The embodiment 1 is repeated, but in the post-treatment washing step of the fourth step, deionized water, and 0.001, 0.005 and 0.05 mol/L sodium hydroxide solutions are successively used to wash the filter cake. When no precipitation appears after the filtrate is neutralized, the sodium-titanium molar ratio data of the obtained catalyst are 0.20, 0.45, 0.46 and 0.48 in sequence. The results of the gas phase epoxidation of propylene and hydrogen peroxide over the above catalysts are as follows: the conversion rates of the propylene are 8.8%, 14.2%, 14.8% and 14.6% in sequence; the PO selectivities are 85.1%, 93.9%, 94.2% and 94.5% in sequence; and the utilization rates of the hydrogen peroxide are 44.0%, 71.0%, 74.0% and 73.0% in sequence.
Embodiment 9. The present embodiment is used to illustrate that potassium hydroxide is also effective according to the degree controlled hydrothermal treatment method provided by the present invention.
The embodiment 1 is repeated, but in the second step of preparing the hydrothermal modification solution, the potassium hydroxide is used to replace the sodium hydroxide. Then, after the obtained modified sample is analyzed by XRF, the silicon-titanium molar ratio is 33.4 and a potassium-titanium molar ratio is 0.38. The results of the gas phase epoxidation of propylene and hydrogen peroxide over the potassium ion modified TS-1 zeolite are: the conversion rate of the propylene is 13.8%, the PO selectivity is 94.6% and the utilization rate of the hydrogen peroxide is 69.0%.
Embodiment 10. The present embodiment is used to illustrate that lithium hydroxide is also effective according to the modification by the degree controlled alkali metal hydroxide hydrothermal treatment method provided by the present invention.
The embodiment 1 is repeated, but in the second step of preparing the hydrothermal modification solution, the lithium hydroxide is used to replace the sodium hydroxide. Then, the results of the gas phase epoxidation of propylene and hydrogen peroxide in the lithium ion modified TS-1 zeolite are: the conversion rate of the propylene is 13.5%, the PO selectivity is 94.2% and the utilization rate of the hydrogen peroxide is 67.5%.
Reference embodiment 7. The reference embodiment 7 is used to illustrate that the modified TS-1 zeolite obtained according to the method of the present invention has improvement effects on the gas phase epoxidation of propylene and hydrogen peroxide, but has no obvious improvement effect on the liquid phase epoxidation of propylene and hydrogen peroxide.
The liquid phase epoxidation can be conducted according to the method introduced by any publication literature. Specifically, in the reference embodiment, the liquid phase epoxidation is conducted in a 450 ml stainless steel reactor under water bath temperature control and magnetic stirring. Experimental conditions are as follows: the reaction temperature is 40° C., the propylene pressure is 0.6 MPa, and the reaction time is 1 h. The ingredients are as follows: 0.2 g of catalyst, 30 ml of methanol and 2 ml of H2O2 (30%). Before the experiment, the reactor is pressurized with propylene gas, and then gas is vented. The replacement is repeated for 5-6 times in this way for the purpose of replacing the air in the reactor. The concentration of H2O2 in the product solution is measured by iodometry, and the composition of organic matter is analyzed by chromatography.
In the embodiment, the modified zeolite samples of embodiment 1 and embodiment 4 are respectively used for the liquid phase epoxidation. See Table 1 for the results. It can be seen from Table 1 that if the modified zeolite prepared by the method of the present invention is used in the liquid phase epoxidation, the conversion rate of the raw material hydrogen peroxide is reduced, and the utilization rate of the hydrogen peroxide is also reduced. The selectivity improvement effect of the modified zeolite in the liquid phase epoxidation is actually the result of neutralizing a small amount of weakly acidic side reaction sites on the surface of the catalyst by the sodium ions. These are consistent with the rules of the results obtained on the sodium exchange TS-1 zeolite by J. Catal., 1995,151, 77-86. The important information to be emphasized in the embodiment is: the alkali metal ion modified framework titanium active site obtained by the method of the present invention, i.e., the degree controlled hydrothermal modification method of the alkali metal hydroxide solution containing a small amount of TPA+ quaternary ammonium cations, is also not conducive to the liquid phase oxidation reaction. The presence of the sodium ions on the silicon hydroxyls near the framework titanium hinders the liquid phase oxidation reaction (reduces the conversion rate), but is relatively conducive to the self-decomposition reaction of the hydrogen peroxide (reduces the utilization rate). The experimental results confirm that the framework titanium active site modified by the alkali metal ions is conducive to the gas phase epoxidation, which is an important discovery.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201910515501.6 | Jun 2019 | CN | national |
This application is a Divisional application Ser. No. 17/296,204, filed on May 21, 2021, which is a National Stage Application of International Application No. PCT/CN2020/084656 filed on Apr. 14, 2020, for which priority is claimed under 35 U.S.C. § 120, and this application claims priority of Application No. 201910515501.6 filed in China on Jun. 14, 20219 under 35 U.S.C. § 119, the entire contents of all of which are hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17296204 | May 2021 | US |
| Child | 18543520 | US |
