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    • 专利摘要:
    Molded catalyst for converting methanol into aromatic compounds and process for producing the same. The present invention relates to a catalyst for converting methanol into aromatic compounds and preparing them. the catalyst comprises 85 to 99 parts by weight of a zsm-5 zeolite, 0.1 to 15 parts by weight of element m1, which is at least one element selected from the group consisting of ag, zn and ga, and to 5 parts by weight of the m2 element, which is at least one element selected from the group consisting of mo, cu, la, p, c and c, where the total catalyst-specific surface area ranges from 350 to 500 m2 / g, and the specific surface area of the micropores ranges from 200 to 350 m2 / g. The catalyst has high total specific surface area, microporous specific surface area and microporous volume. A good catalytic activity can be shown from the results of the reaction of preparing aromatic compounds from methanol using the catalyst provided by the present invention.
    公开号:BR102013017946B1
    申请号:R102013017946-9
    申请日:2013-07-12
    公开日:2019-11-05
    发明作者:Xiqiang Chen；Zheming WANG；Jingxian Xiao；Feng Xu
    申请人:Shanghai Research Institute Of Petrochemical Technology Sinopec；China Petroleum & Chemical Corporation；
    IPC主号:
    专利说明:

    “PROCESSES TO PRODUCE A MOLDED CATALYST FOR THE CONVERSION OF METHANOL TO AROMATIC COMPOUNDS AND TO CONVERT METHANOL TO AROMATIC COMPOUNDS”
    Field of the Invention [001] The present invention relates to the field of the production of aromatic compounds from methanol. More specifically, the present invention relates to a molded catalyst for converting methanol into aromatic compounds and a process for producing it. In another aspect, the present invention relates to a process for converting methanol into aromatic compounds.
    Background of the Invention [002] Aromatic compounds, especially light aromatic compounds, such as BTX (benzene, toluene and xylenes), are important basic organic materials. With the continued development of the global industry and the economy in recent years, the demand for aromatic compounds is steadily increasing. Currently, aromatic compounds are mainly derived from the naphtha reform process and the pyrolysis gasoline hydrogenation process, which use oil as a raw material. According to statistics, aromatic compounds produced by the use of oil as a raw material account for more than 90% of the total aromatic compounds worldwide.
    [003] However, the cost of producing aromatic compounds from oil increases dramatically due to continuous consumption and the increase in the price of petroleum resources. Therefore, in the long run, the production of aromatic compounds through the naphtha reform process and the pyrolysis gasoline hydrogenation process may not satisfy the growing demand for aromatic compounds and the cost is higher.
    [004] Comparing with oil resources, the world's coal resources are more abundant, so they can supply raw materials
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    2/25 abundant for the coal chemical industry. So far, the process of producing methanol from coal as a raw material has been mature. At the same time, the excessive capacity to produce methanol on a global scale has become a serious problem. Therefore, the direct conversion of methanol to produce aromatic compounds can be considered as a very promising aromatic production line.
    [005] U.S. Document No. 4,686,312 relates to a catalyst and a process for converting C1-C4 oxygenated hydrocarbons to aromatic compounds. The process comprises a two-step reaction, where in the primary step, the raw material enriched in methanol is placed in contact with the HZSM-5 zeolite and is then converted into an intermediate product containing predominantly aliphatic hydrocarbons; and a secondary stage, where the intermediate product of the first stage is placed in contact with the metal modified ZSM-5 zeolite to generate a product rich in aromatic compounds.
    [006] U.S. document No. 2002/0099249 relates to a process for converting methanol into aromatic compounds and a hybrid catalyst system is used. In the process, the raw material containing methanol is converted into aromatic compounds through the sequential contact of the raw material with a first catalyst containing silicoaluminophosphate (SAPO) and then with a second catalyst containing metal modified ZSM-5 zeolite. Both catalysts contain a certain amount of binders.
    [007] US No. 2010/0234658 discloses an aromatization catalyst in the type of molecular sieve of zeolite loaded with various metals. The catalyst comprises La and a molecular sieve, a binder, and at least one element selected from Mo, Ce and Cs. In an example of the present invention, using methanol as a reagent, at 450 ° C, ambient pressure and a WHSV of 9 h -1 , the yield of aromatic compounds and BTX (based on weight
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    3/25 methanol) are above 18.8% and 13.7%, respectively, that is, 43.0% and 31.5%, respectively, based on carbon.
    [008] CN 1880288A discloses a process for converting methanol into aromatic compounds and a catalyst used. The catalyst is prepared by mixing a small particle size ZSM-5 zeolite auxiliary / support agent with a binder (pseudo-bohemite, gamma-alumina or diatomaceous earth) and then molding the mixture, followed by loading of Ga and La active components The binder content in the catalyst can vary from 14 ~ 34%, by weight. Under the conditions of 300 ~ 460 ° C, 0.1 ~ 5.0 MPa and 0.1 ~ 6.0 h -1 (WHSV of the liquid raw material), methanol is placed in contact with the above catalyst. The yield of aromatic compounds in the product formed is greater than 31% (based on the weight of methanol), that is, greater than 72% based on carbon. However, this process requires two steps to increase the total yield of aromatic compounds, in which the low carbon hydrocarbons, obtained from a first stage, are subjected to a second reactor to proceed with the aromatization. Thus, this is a very complex process, with many stages of separation.
    [009] CN 101244969A refers to equipment and a method for continuous aromatization and reactivation of the catalyst. Specifically, it refers to a fluidized bed equipment for the aromatization of C1 C2 hydrocarbons or methanol and the reactivation of the catalyst and their operational approach. The catalyst used in the present invention consists of three components, that is, a molecular sieve, a metal and a structure stability agent or reinforcing agent (which corresponds to a binder), where the content of the structure stability agent or the reinforcing agent is greater than 20%. It is stated in this invention that, when an aromatization using methanol as raw material is carried out, 97.5% methanol conversion is obtained, 72% yield of compounds
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    4/25 aromatics in a single pass (carbon based) and 55% BTX selectivity. Although a high yield of aromatic compounds is obtained, the conversion of methanol is low and, in addition, the selectivity of BTX, which is most valuable in aromatic compounds, is only 55% or less.
    [010] As mentioned above, molded catalysts for converting methanol into the reported aromatic compounds, currently generally consist of a zeolite molecular sieve, such as ZSM-5, ZSM-11 or MCM-22, a binder and an active component and a modified component for dehydrogenation. The binder is generally an amorphous oxide, such as aluminum oxide, silicon oxide, etc. Since there is a certain amount of binder in these molded catalysts, a portion of the pores of the zeolite molecular sieve is blocked, which inhibits the diffusion of reagents and products and ultimately results in a decrease in catalyst activity and selectivity the product in question. The active component and the modified component for dehydrogenation are normally loaded onto the catalyst by impregnation or mechanical mixing method. However, the active component and the modified component are not distributed homogeneously, remaining more on the surface of the catalyst, while only a small part enters the interior of the catalyst when they are loaded using these conventional methods.
    [011] In the current situation, where the process of producing methanol from coal as a raw material has been matured and the production capacity of methanol may be excessive, the way of promoting the properties of catalysts for converting methanol in aromatic compounds, for example, how to promote the activity of catalysts or to simplify the preparation process, can be a main direction of development in the field.
    Summary of the Invention [012] The purpose of the present invention is to provide a new catalyst
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    5/25 molded for the conversion of methanol into aromatic compounds, which has a high total specific surface area, specific surface area of the micropores and the volume of the micropores. The catalyst has a high reaction activity in the conversion of methanol into aromatic compounds, where a high yield of aromatic compounds and a high yield and selectivity of BTX can be obtained. It is yet another object of the present invention to provide a method for making the aforementioned catalyst.
    [013] In addition, a process for producing aromatic compounds from methanol using the aforementioned catalyst is provided in the present invention.
    [014] In accordance with the present invention, a molded catalyst, which can be used in converting methanol into aromatic compounds, is provided. This catalyst comprises 85 to 99 parts by weight of a ZSM-5 zeolite, 0.1 to 15 parts by weight of the element M1, which is at least one element selected from the group consisting of Ag, Zn and Ga, and 0 to 5 parts by weight of the M2 element, which is at least one element selected from the group consisting of Mo, Cu, La, P, Ce and Co, where the total specific catalyst surface area varies between 350 to 500 m 2 / g, preferably between 380 to 450 m 2 / g, the specific surface area of the micropore catalyst varies between 200 to 350 m 2 / g, preferably between 260 to 350 m 2 / g . In addition, the volume of micropores in the catalyst can vary between 0.08 to 0.20 cm 3 / g, preferably between 0.12 to 0.20 cm 3 / g.
    [015] The total specific surface area of a catalyst indicates the adsorption and diffusion properties of the catalyst. The greater the total specific surface area of the catalyst used, the greater the rate of adsorption of the reagents and the rate of desorption of the products, and the greater the activity of the reaction catalyst. As defined by the International Union of Pure and Applied Chemistry (IUPAC), a micropore refers to an orifice with a diameter less than 2 nm, a mesopore refers to an orifice with a diameter between 2 to 50 nm, and a macropore,
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    6/25 refers to an orifice that has a diameter greater than 50 nm. A zeolite molecular sieve generally has a diameter between 0.3 ~ 2 nm and therefore fits the characteristics of a micropore. Therefore, one of the important indices to indicate the content of zeolite molecular sieves in a zeolite catalyst is the specific surface area of the catalyst micropores. For the same type of zeolite catalyst, the larger the specific surface area of the micropore, the higher the zeolite content in the catalyst, and the more necessary acidic sites can be provided for the reaction, and the greater the activity of the catalyst reaction. . The volume of micropores refers to the volume of micropores per unit mass of a catalyst. Similar to the specific surface area of the micropores, the volume of the micropores can also indicate the zeolite content in a catalyst.
    [016] In general, the total specific surface area of a ZSM-5 zeolite varies from 300 to 400 m 2 / g and the specific surface area of micropores of the same varies between 250 to 350 m 2 / g. The total specific surface area of the molded catalyst, which is obtained by mixing a ZSM-5 zeolite with a binder and, subsequently, by molding the mixture, can be significantly less than that of the zeolite. This results mainly from two reasons: on the one hand, a part of the pores of the zeolite is blocked by the introduced binder, which results in a decrease in the specific surface area of the micropores and the total specific surface area; on the other hand, since the specific surface area of a binder, in relation to that of a zeolite, is very small and can be almost ignored, the total specific surface area of the catalyst will decrease approximately in corresponding proportion with the increase of the binder. Conventional molded catalysts used in the preparation of aromatic compounds from methanol have a total specific surface area of less than 300 m 2 / g and a specific surface area of the micropore less than 200 m 2 / g. However, the catalyst
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    7/25 provided by the present invention can also maintain a high total specific surface area of 350 to 500 m 2 / g, as well as a high specific microporous surface area of 200 to 350 m 2 / g. Thus, one can advantageously provide more active sites for the reaction and better diffusion properties, which are beneficial for improving the reaction activity.
    [017] In a catalyst, the M1 element mainly provides a dehydrocycling function, that is, a process for producing benzene rings from hydrocarbon chains. If the amount of the M1 element is lower, the dehydrogenation effects may be weaker, which results in a decrease in the selectivity of aromatic compounds in the product. Conversely, if the amount of the M1 element is too high, the decomposition of methanol will be impaired, which results in an increase in hydrogen and carbon oxides in the products and a decrease in the selectivity of aromatic compounds. In a preferred embodiment of the present invention, the amount of the M1 element in the catalyst provided by the present invention is 1 to 10 parts by weight. Considering that Zn is much cheaper than Ga or Ag, in the event that a similar activity reaction is required, Zn may be a preferable option as an M1 element.
    [018] The M2 element serves mainly to improve hydrothermal stability and inhibit carbon deposition and deactivation of a catalyst. At the same time, the proper addition of the M2 element can also improve the selectivity of BTX in the product. This is probably due to the effect of the modification in the pores of the zeolite by the M2 element, which decreases the production of heavy aromatic compounds. In an embodiment of the present invention, the amount of M2 element in the catalyst can preferably be from 0 to 2 parts by weight, and preferably from 0.5 to 2 parts by weight.
    [019] The catalyst provided by the present invention contains little or
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    8/25 no binder, that is, the binder content is 0 to 5% by weight. In a preferred embodiment of the present invention, the catalyst does not contain any binders. Many of the conventional catalysts for converting methanol into aromatic compounds contain a binder (the content of binders in a conventional catalyst is generally greater than 15% by mass). The binder is added mainly to improve the strength of the molded catalyst. However, many negative impacts can be brought about at the same time. For example, the pores of the molecular sieves can be blocked and the active sites can be covered. As a result, the diffusion of reagents and products can be inhibited and, finally, the catalytic activity of the catalyst and product selectivity can be affected. However, the catalyst provided by the present invention does not contain binders, or hardly any binders, due to the placement of a dry molded body on the upper dam-board and a mold and water agent on the bottom of a autoclave so that the gas phase crystallizes the molded body (for example, in step iii to be described below) in order to convert most or all of the precursor to amorphous silicon aluminum oxide and the binders used in a ZSM-5 zeolite. As a result, the aforementioned defects can be avoided and the good catalytic effect can be achieved.
    [020] The aromatization of methanol is a reaction of synergy between a Bronsted acid (B acid) and a Lewis acid (L acid). Therefore, more acid B and acid L can be advantageous for the reaction. The acid B of a catalyst is mainly supplied by a ZSM-5 zeolite. In addition, the amount of acid B will decrease as the Si / Al molar ratio of the ZSM-5 zeolite increases and the reaction activity will also decrease, which is indicated in the result of the Examples of the present invention. However, the hydrothermal stability of a ZSM-5 zeolite will gradually decrease as the molar ratio of Si / Al decreases. During the methanol aromatization process, a large amount of water will be produced. Under the
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    9/25 high temperature condition and a large amount of existing water, if the hydrothermal stability of the ZSM-5 zeolite decreases, the structure of the zeolite will collapse, which would result in an irreversible reduction of acid B and the catalyst would be deactivated permanently. Therefore, after making experimental models and carrying out a large number of experiments accordingly, it turns out that, in a preferred catalyst of the present invention, the molar ratio of Si / Al of the ZSM-5 zeolite is 10 to 200: 1 , preferably, it is from 10 to 100: 1, and even more, it is from 10 to 50: 1.
    [021] In the present invention, a method is provided for preparing the catalyst, mentioned above, for converting methanol into aromatic compounds. The method comprises: step i: mixing a molding agent I, an inorganic acid, a silicon source, an aluminum source, water, a soluble compound of the element M1 and, optionally, a soluble compound of the element M2 to produce a mixing, gelling the mixture, and then aging and drying the resulting gel to obtain an amorphous silicon aluminum oxide precursor; step ii: mixing the amorphous silicon aluminum oxide precursor obtained in step i with a crystal seed and a binder, mold, and dry the mixture to obtain a molded body; and step iii: crystallize and then calcine the molded body obtained in step ii to obtain said catalyst.
    [022] The soluble compounds of the elements M1 and M2 above are both preferably soluble acids and / or salts.
    [023] In step i, the molding agent is preferably at least one element selected from the group consisting of polyethylene glycol, polyethylene oxide, polyoxyethylene - polyoxypropylene - polyoxyethylene (P123) and hexadecyltrimethylammonium bromide (CTAB) .
    [024] The inorganic acid used in step i is preferably at least one element selected from the group consisting of hydrochloric acid, nitric acid
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    10/25 and sulfuric acid.
    [025] The silicon source used in step i is preferably at least one element selected from the group consisting of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane.
    [026] The aluminum source used in step i is preferably at least one element selected from the group consisting of aluminum nitrate, aluminum chloride and aluminum sulfate.
    [027] In the mixture from step i, the weight ratio of the molding agent I: the inorganic acid: the aluminum source: H2O: element M1: element M2: the silicon source is 0.2 ~ 1.8: 0.05 ~ 1.0: 0.005 ~ 0.085: 5 ~ 10: 0.005 ~ 0.3: 0 ~ 0.025: 1, where the weight of the aluminum source and the silicon source are calculated as the weight of ALO3 and SiO2, respectively.
    [028] In a specific embodiment of the present invention, in step i, all components are mixed at a temperature of 0 to 60 ° C to obtain a mixture. The mixture reacts for 0.1 to 10 h, under stirring, and then is transferred to a hermetically sealed container, where the mixture is gelled at 30 to 90 ° C. An amorphous silicon aluminum oxide precursor is obtained after aging and drying of the generated gel.
    [029] In step ii, the binder is preferably at least one element selected from the group consisting of silica sol, sol alumina, white silica such as smoked silica, and pseudo-bohemite. The crystal seed is preferably selected from HZSM-5 zeolites. Preferably, the molar ratio of Si / Al in the HZSM-5 zeolites is 10 ~ 200: 1.
    [030] In step ii, the weight ratio of the crystal seed: the binder: the amorphous silicon aluminum oxide precursor is 0.001 ~ 0.1: 0.1 ~ 1: 1.
    [031] In a preferred embodiment of the present invention, a pore-forming agent is subsequently added in step ii, and the pore-forming agent
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    11/25 pores are preferably selected from sesbania powders and / or starch. In the present invention, the added pore-forming agent will be converted to water and carbon dioxide after it has been calcined, and will not exist in the catalyst. When pseudo-boemite is used as a binder in step ii, diluted nitric acid is generally added to improve the adhesive property during the molding process.
    [032] In an embodiment of the present invention, crystallization in step iii is carried out at a temperature of 100 to 180 ° C, by adding the molding agent II and water to the bottom of an autoclave and adding the molded body obtained from step ii on the upper dam-board of the autoclave.
    [033] In step iii, the weight ratio of molding agent II: water: the molded body is 0.01 ~ 1: 0.5 ~ 20: 1.
    [034] Molding agent II is at least one element selected from the group consisting of tetrapropylammonium bromide, tetrapropylammonium hydroxide, ethylenediamine, triethylamine, n-propylamine, n-butylamine and hexamethylenediamine.
    [035] Generally, the crystallization time in step iii is 0.5 to 8 days. Then, the crystallization product is washed, dried at 60 ° C to 130 ° C for 2 to 24 h, and then calcined at 450 to 650 ° C for 1 to 8 h.
    [036] In another aspect, the present invention also provides a process for converting methanol into aromatic compounds, which comprises the step of contacting methanol, which is fed at an hourly space velocity by weight (WHSV) of 0.1 to 5.0 h -1 , with the catalyst as mentioned above, to generate aromatic products, at a temperature of 350 to 550 ° C and a gauge pressure of 0 to 0.5 MPa.
    [037] As for the aromatization reaction, although there is no unified conclusion about the reaction mechanism at the moment, many research results indicate that aromatization of hydrocarbons in a sieve catalyst
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    12/25 molecular metal requires a synergistic action between acid B, provided by the molecular sieve, and acid L, provided by the metal species, to achieve a better reaction result. Therefore, the distance between the B-acid sites and the metal species is particularly important. When a metal species is loaded into a molecular sieve using a conventional method, for example, impregnation or the mechanical mixing method, most metal species remain on the surface of the molecular sieve, while only a small part enters the molecular sieve. As a result, the synergistic action is limited and thus the activity of the reaction is less.
    [038] However, in the preparation of the catalyst of the present invention, an amorphous silicon aluminum oxide precursor with a high specific surface area is made first and the elements of the active components (M1 and M2) are introduced during this process for the aromatization of methanol. Then, the amorphous silicon aluminum oxide precursor and the binder added later are converted to a ZSM-5 zeolite by means of gas phase crystallization, generating a catalyst substantially without binders and with a high total specific surface area, surface area specificity of micropores and volume of micropores. This method of preparation has some excellent effects. On the one hand, the diffusion of reagents and products is improved and the activity of the reaction is increased. On the other hand, the dispersibility of the active components in the molecular sieve is also improved so that the active components are evenly distributed in the ZSM-5 zeolite, which not only facilitates the synergistic action between acid B and acid L, therefore, it increases the reaction activity, as well as promoting the stability of the M1 and M2 elements in the catalyst in order to reduce the loss of the M1 and M2 elements during the reaction and the catalyst regeneration processes. In addition, some steps are eliminated in the catalyst preparation process, including the exchange of ammonia ions and the loading of M1 and M2 elements after
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    Crystallization. The drying and calcination steps are also reduced. Consequently, the process of the present invention, decreases the energy consumption of the preparation of the catalyst.
    [039] Generally speaking, the catalyst for converting methanol to aromatic compounds provided by the present invention has a high total specific surface area, specific surface area of the micropores and volume of the micropores, and a uniform dispersion of the active components and thus, it has good catalytic activity. In the process of converting methanol into aromatic compounds using the catalyst provided by the present invention, a high conversion of methanol, high yield of aromatic compounds and high yield and selectivity of BTX can be obtained. For example, with the same Si / Al ratio of the molecular sieve and the same charge as the M1 element, the catalyst provided by the present invention demonstrates a better activity than the reaction of a common binder type catalyst, that is, the yield of aromatic compounds and that of BTX in the product increase by more than 8%, respectively.
    Detailed Description of Embodiments [040] The following examples are provided to further illustrate this invention and should not be unduly considered to limit the scope of the present invention.
    Example 1 (1) Preparation and characterization of the catalyst [041] 1) 4.0 g of polyethylene glycol, 8.0 grams of P123, 32.0 grams of hydrochloric acid with a concentration of 1.0 mol / L, 4 , 0 g of aluminum nitrate (with an Al content of 13.6% by weight, calculated as the weight of Al2O3), 56.0 g of tetraethoxysilane (with a Si content of 28.4% by weight, calculated as the weight of SiO2), 8.0 g of zinc nitrate (with a zinc content of 21.9% by weight) are uniformly mixed with 50 grams of water and then vigorously stirred at
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    14/25 room temperature for 2 h. The formed mixture is then transferred to an airtight container, in which the mixture is gelled at 65 ° C. Sample A1 is obtained after aging the resulting gel for 24 h followed by the drying process.
    [042] 2) 10.0 grams of sample A1.0.5 grams of an HZSM-5 zeolite (with a molar ratio of Si / Al of 30), 10.0 grams of silica sol (with a Si content 40.0% by weight, calculated as the weight of SiO2) are mixed and then molded. Sample B1 is obtained after drying the formed product.
    [043] 3) 10.0 grams of sample B1 are placed on the upper dam plate of an autoclave, while 10.0 grams of water and 2.0 grams of triethylamine are added to the bottom of the autoclave. Sample B1 is crystallized at 150 ° C and the pressure is self-generated for 70 h in the autoclave. The resulting product is washed, dried at 120 ° C for 12 h, and then calcined at 550 ° C for 5 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-1, is obtained.
    [044] 4) The contents of elements M1 and M2 in MTA-1 are tested by the plasma emission spectrum (ICP). The molar ratio of Si / Al in the structure of the ZSM-5 zeolite is tested by solid-state nuclear magnetic resonance (NMR). The total specific surface area, specific surface area of the micropores and volume of the micropores of MTA-1 are measured by the adsorption method - nitrogen desorption. All results are summarized in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [045] 1) 10 grams of MTA-1 are added to a reactor. Methanol is introduced into the reactor with a WHSV of 1 h -1 when the temperature is raised to 430 ° C at ambient pressure. The results are listed in Table 2.
    Examples 2 to 9 (1) Preparation and characterization of catalysts
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    15/25 [046] The same process as in step 1) of Example 1, except that the zinc nitrate of Example 1 is replaced by the source of elements M1 and M2, as shown in Table 1, the catalysts of Examples 2 to 9, referred to as MTA-2, MTA-3, 4-MTA, MTA-5, MTA-6-7 MTA, MTA-8, MTA-9, respectively, are prepared. Their physical and chemical properties are also listed in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [051] The same process as in step 2) of Example 1, except that MTA-1 is replaced by MTA-2, 3-MTA, MTA- 4, MTA-5, 6-MTA, MTA-7, 8-MTA, MTA-9, respectively, to assess their reactivity. Refer to Table 2.
    Example 10 (1) Preparation and characterization of the catalyst [052] 1) 120.0 grams of polyethylene oxide, 50.0 g of P123, 550.0 grams of hydrochloric acid with a concentration of 1.0 mol / L, 52 , 0 grams of aluminum sulphate (with an Al content of 15.0% by weight, calculated as the weight of Al2O3), 250.0 grams of tetramethoxysilane (with a Si content of 39.0% by weight, calculated as the weight of SiO2), 70.0 grams of zinc nitrate are mixed with 400.0 grams of water, stirred evenly and then treated with ultrasound for 20 minutes. The formed mixture is then transferred to a hermetically sealed container, in which the mixture is gelled at 60 ° C. Sample A10 is obtained after aging the resulting gel for 40 h followed by the drying process.
    [053] 2) 100.0 grams of sample A10, 10.0 grams of an HZSM-5 zeolite (with a Si / Al molar ratio of 10), 30.0 grams of smoked silica, 4.0 grams of pseudo -bohemite, 28.0 grams of silica sol and an adequate amount of diluted nitric acid are mixed and then molded. Sample B10 is obtained after
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    16/25 drying of the formed product.
    [054] 3) 100.0 grams of sample B10 are placed on the upper dam plate of an autoclave, while 60.0 grams of water and 20.0 grams of hexanediamine are added to the bottom of the autoclave. The B10 sample is crystallized at 170 ° C and the pressure self-generated for 60 h in the autoclave. The resulting product is washed, dried for 8 h at 130 ° C, and then calcined at 600 ° C for 3 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-10, is obtained.
    [055] 4) The physical and chemical properties of MTA-10 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [056] The same processes as in step 2) of Example 1, except for the fact that MTA-1 is replaced by MTA-10, to evaluate its reactivity. Refer to Table 2.
    Example 11 (1) Preparation and characterization of the catalyst [060] 1) 8.0 g of P123, 48.0 grams of sulfuric acid with a concentration of 1.0 mol / L, 2.0 grams of aluminum chloride (with an Al content of 23.1% by weight, calculated as the weight of Al2O3), 100.0 grams of tetrapropoxosilane (with a Si content of 22.0% by weight, calculated as the weight of SiO2), 10, 0 grams of zinc nitrate are mixed with 50 grams of water, stirred for 6 h in the ice-water bath. The formed mixture is then transferred to an airtight container, in which the mixture is gelled at 80 ° C. Sample A11 is obtained after aging the resulting gel for 8 h followed by the drying process.
    [061] 2) 20.0 grams of sample A11, 0.4 grams of an HZSM-5 zeolite (with a molar ratio of Si / Al of 50), 20.0 grams of silica sol and a
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    17/25 adequate amount of water is mixed together and then molded. Sample B11 is obtained after drying the formed product.
    [062] 3) 10.0 grams of sample B11 are placed on the upper dam plate of an autoclave, while 10.0 grams of water and 3.0 g of nbutilamine are added to the bottom of the autoclave. Sample B11 is crystallized at 130 ° C and pressure autogenerated for 96 h in the autoclave. The resulting product is washed, dried for 18 h at 110 ° C, and then calcined at 550 ° C for 4 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-11, is obtained.
    [063] 4) The physical and chemical properties of MTA-11 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [064] The same process as in step 2) of Example 1, except that MTA-1 is replaced by MTA-11, to evaluate its reactivity. Refer to Table 2.
    Example 12 (1) Preparation and characterization of the catalyst [065] 1) 4.0 g of CTAB, 4.0 grams of P123, 40.0 grams of tetramethoxysilane, 0.8 g of aluminum nitrate, 5.0 g of zinc nitrate, 32.0 g of hydrochloric acid with a concentration of 1.0 mol / L are mixed with 70.0 grams of water, stirred for 4 h at room temperature. The formed mixture is then transferred to an airtight container, in which the mixture is gelled at a temperature of 70 ° C. Sample A12 is obtained after aging the resulting gel for 24 h followed by the drying process.
    [066] 2) 10.0 grams of sample A12, 0.5 grams of an HZSM-5 zeolite (with a molar ratio of Si / Al of 175), 8.0 grams of silica sol and a
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    18/25 adequate amount of water are mixed together and then molded. Sample B12 is obtained after drying the formed product.
    [067] 3) 10.0 grams of sample B12 are placed on the upper dam plate of an autoclave, while 6.0 grams of water and 1.5 grams of tetrapropylammonium hydroxide are added to the bottom of the autoclave. The B12 sample is crystallized at 150 ° C and the pressure is self-generated for 36 h in the autoclave. The resulting product is washed, dried for 24 h at 80 ° C and then calcined at 500 ° C for 6 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-12, is obtained.
    [070] 4) The physical and chemical properties of MTA-12 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [071] The same process as in step 2) of Example 1, except for the fact that MTA-1 is replaced by MTA-12, to evaluate its reactivity. Refer to Table 2.
    Example 13 (1) Preparation and characterization of the catalyst [072] 1) 8.0 grams of polyethylene glycol, 20.0 grams of P123, 60.0 grams of nitric acid with a concentration of 1 mol / L, 2.5 g of aluminum nitrate, 100.0 g of tetraethoxysilane, 30.0 grams of zinc nitrate are mixed with 100.0 grams of water and then stirred vigorously for 4 h at room temperature. The formed mixture is then transferred to an airtight container, in which the mixture is gelled at a temperature of 70 ° C. Sample A13 is obtained after aging the resulting gel for 30 h followed by the drying process.
    [073] 2) 10.0 grams of sample A13, 1.0 grams of an HZSM-5 zeolite (with a molar ratio of Si / Al of 100), 8.0 grams of silica sol and an amount
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    19/25 adequate water are mixed and then molded. Sample B13 is obtained after drying the formed product.
    [074] 3) 10.0 grams of sample B13 are placed on the upper dam plate of an autoclave, while 8.0 grams of water and 2.0 grams of n-propylamine are added to the bottom of the autoclave. Sample B13 is crystallized at 150 ° C and the pressure self-generated for 65 h in the autoclave. The resulting product is washed, dried at 100 ° C for 16 h and then calcined at 550 ° C for 4 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-13, is obtained.
    [075] 4) The physical and chemical properties of MTA-13 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [076] The same process as in step 2) of Example 1, except that MTA-1 is replaced by MTA-13, to assess its reactivity. Refer to Table 2.
    Example 14 (1) Preparation and characterization of catalyst [081] 1) 10.0 grams of sample A13 obtained from Example 13, 0.5 grams of an HZSM-5 zeolite (with a Si / Al molar ratio of 100 ), 8.0 grams of silica sol and an adequate amount of water are mixed and then molded. Sample B14 is obtained after drying the formed product.
    [082] 2) 10.0 grams of sample B14 are placed and placed on the upper dam plate of an autoclave, while 10.0 grams of water and 2.0 grams of tetrapropylammonium hydroxide are added to the bottom of the autoclave. Sample B14 is crystallized at 170 ° C and the pressure self-generated for 48 h in the autoclave. The resulting product is washed, dried at 110 ° C for 20 h, and then calcined
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    20/25 at 560 ° C for 3 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-14, is obtained.
    [083] 3) The physical and chemical properties of MTA-14 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [084] The same process as in step 2) of Example 1, except that MTA-1 is replaced by MTA-14, to evaluate its reactivity. Refer to Table 2.
    Comparative Example 1 (1) Preparation and characterization of the catalyst [085] 1) 7.0 g of ethanediamine, 90.0 grams of silica sol, 2.0 grams of sodium meta aluminate, 6.0 grams of sodium hydroxide are mixed evenly with 250.0 grams of water. The formed mixture is then transferred to a stainless autoclave, where the mixture is crystallized at 150 ° C and the pressure is self-generated for 70 h. Sample A15 is obtained after washing and drying the resulting product.
    [086] 2) 20.0 grams of sample A15, 7.0 grams of pseudo-bohemite and an adequate amount of diluted nitric acid are mixed and then molded. Sample B15 is obtained after drying and calcining the formed product.
    [087] 3) 20.0 grams of sample B15 are added to 100.0 grams of the ammonium nitrate solution with a concentration of 5.0% by weight and the mixture is subjected to a treatment with reflux heating at 90 ° C for 2 h. The sample is washed with water and the previous step is repeated three times. The sample is dried and calcined to obtain the C15 sample.
    [090] 4) 10.0 grams of sample C15 are mixed with 8.0 grams of the zinc nitrate solution (with a zinc content of 4.0% by weight) and then the
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    The mixture is dried at 130 ° C for 8 h, followed by calcination at 600 ° C for 3 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-15, is obtained.
    [091] 5) The physical and chemical properties of MTA-15 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [092] The same process as in step 2) of Example 1, except for the fact that MTA-1 is replaced by MTA-15, to evaluate its reactivity. Refer to Table 2.
    Comparative Example 2 (1) Preparation and characterization of the catalyst [093] 1) 6.0 g of tetrapropylammonium bromide, 100.0 grams of silica sol, 2.0 grams of aluminum sulphate, 6.0 grams of hydroxide sodium and 6.0 grams of sodium chloride, are uniformly mixed with 240.0 grams of water. The formed mixture is then transferred to a stainless autoclave, where the mixture is crystallized at 170 ° C and the pressure self-generated for 48 h. Sample A16 is obtained after washing and drying the formed product.
    [094] 2) 20.0 grams of sample A16, 20.0 grams of silica sol and an adequate amount of water are mixed and then molded. Sample B16 is obtained after drying and calcining the formed product.
    [095] 3) 20.0 grams of sample B16 are added to 60.0 grams of ammonium chloride solution with a concentration of 8.0% by weight The mixture is then subjected to a treatment with reflux heating at 90 ° C for 3 h. The sample is washed with water and the previous steps are repeated 3 times. The sample is dried and calcined to obtain the C16 sample.
    [096] 4) 10.0 grams of the C16 sample are mixed with 8.0 grams of the
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    22/25 zinc nitrate solution (with a zinc content of 4.0% by weight) and then the mixture is dried at 120 ° C for 12 h, followed by calcination at 550 ° C for 5 h. A catalyst for converting methanol into said aromatic compounds, such as MTA-16, is obtained.
    [097] 5) The physical and chemical properties of MTA-16 are tested by the same methods as in Example 1. The results are also shown in Table 1.
    (2) Reaction for the production of aromatic compounds from methanol [101] The same process as in step 2) of Example 1, except that MTA-1 is replaced by MTA-16, to evaluate its reactivity. Refer to Table
    2.
    Examples 15 to 25 [102] The reactivity of the MTA-10 catalyst is evaluated under different reaction conditions (see Table 3) and the results are shown in Table 3.
    Table 1
    Examples Catalyst Molar proportion of Si / Al of zeolite ZSM-5 ElementM1 (% by weight) Element M2 (% by weight) Total specific surface area (m 2 / g) Microporous specific surface area (m2 / g) Micropore volume (cm 3 / g) Example 1 MTA-1 30 Zn, 3.0 / 429 299 0.139 Example 2 MTA-2 28 Ag, 1.0 / 433 302 0.139 Example 3 MTA-3 31 Ga, 2.0 / 430 297 0.139 Example 4 MTA-4 31 Zn, 3.0 Mo, 1.0 413 289 0.138 Example 5 MTA-5 33 Zn, 3.0 Cu, 2.0 406 286 0.138 Example 6 MTA-6 29 Zn, 3.0 La, 1.0 414 289 0.138 Example 7 MTA-7 29 Zn, 3.0 P, 1.0 407 280 0.136 Example 8 MTA-8 30 Zn, 3.0 Ce, 1.0 420 291 0.137 Example 9 MTA-9 29 Ag, 1.0 Co, 1.0 420 294 0.138 Example 10 MTA-10 10 Zn, 3.0 / 445 305 0.142 Example 11 MTA-11 50 Zn, 3.0 / 388 271 0.128 Example 12 MTA-12 175 Zn, 3.0 / 447 326 0.157 Example 13 MTA-13 100 Zn, 10.0 / 419 291 0.137 Example 14 MTA-14 100 Zn, 10.0 / 428 315 0.143
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    23/25
    Examples Catalyst Molar proportion of Si / Al of zeolite ZSM-5 ElementM1 (% by weight) ElementM2 (% by weight) Total specific surface area (m 2 / g) Microporous specific surface area (m2 / g) Micropore volume (cm 3 / g) Comparative Example 1 MTA-15 10 Zn, 3.0 / 225 168 0.074 Comparative Example 2 MTA-16 50 Zn, 3.0 / 207 149 0.068
    Table 2
    Examples Catalyst Methanol conversion (%) Yield of aromatic compounds (based on% carbon) BTX yield (based on% carbon) BTX selectivity (%) Example 1 MTA-1 99.9 62.4 51.2 82.0 Example 2 MTA-2 99.9 63.7 52.6 82.6 Example 3 MTA-3 99.9 58.3 47.6 81.6 Example 4 MTA-4 99.9 55.6 46.1 82.9 Example 5 MTA-5 99.9 57.9 47.8 82.6 Example 6 MTA-6 99.9 61.0 50.8 83.3 Example 7 MTA-7 99.9 60.8 51.3 84.4 Example 8 MTA-8 99.9 59.7 49.0 82.1 Example 9 MTA-9 99.9 63.2 52.8 83.5 Example 10 MTA-10 99.9 65.9 54.4 82.5 Example 11 MTA-11 99.9 55.7 45.0 80.8 Example 12 MTA-12 99.8 51.7 41.4 80.1 Example 13 MTA-13 99.9 53.7 42.9 79.9 Example 14 MTA-14 99.9 58.4 46.0 78.8 Comparative Example 1 MTA-15 99.9 51.2 39.5 77.1 Comparative Example 2 MTA-16 99.9 46.3 35.4 76.5
    Table 3
    Examples Temperatures (° C) Pressure gauge (MPa) WHSV (h- 1 ) Conversion of methanol(%) Yield of aromatic compounds (based on% carbon) BTX yield (based on% carbon) Example 15 370 0 1.0 99.9 58.0 49.8 Example 16 420 0 1.0 99.9 64.7 53.2
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    Examples Temperatures (° C) Pressure gauge (MPa) WHSV (h -1 ) Conversion of methanol(%) Yield of aromatic compounds (based on% carbon) BTX yield (based on% carbon) Example 17 470 0 1.0 99.9 66.2 55.8 Example 18 520 0 1.0 99.9 67.4 54.2 Example 19 420 0.1 1.0 99.9 62.4 51.2 Example 20 420 0.3 1.0 99.9 60.1 48.6 Example 21 420 0.5 1.0 99.9 56.4 45.1 Example 22 420 0 0.1 99.9 67.8 56.2 Example 23 420 0 0.5 99.9 65.3 54.7 Example 24 420 0 2.0 99.8 61.2 49.8 Example 25 420 0 4.0 99.7 56.3 45.2
    [103] The catalysts in the examples above and the comparative examples are all cast catalysts. From Table 1, it can be seen that the catalysts provided by the present invention have a greater total specific surface area, specific surface area of the micropores and volume of the micropores. For example, catalysts MTA-1 to MTA-10 have a total specific surface area greater than 350 m 2 / g, and most of them are greater than 400 m 2 / g. On the other hand, the total specific surface areas of the catalysts of Comparative Example 1 and Comparative Example 2 are only 225 m 2 / g and 207 m 2 / g, respectively. The specific surface areas of the micropores of the catalysts MTA-1 to MTA-10 are always greater than 270 m 2 / g. On the other hand, the specific surface areas of the micropores of the catalysts of Comparative Example 1 and Comparative Example 2 are, respectively, 168 m 2 / g and 149 m 2 / g, only. In addition, the volume of the micropores of the catalysts in the examples is also significantly greater than that of the catalysts in the comparative examples.
    [104] Comparing Example 10 with Comparative Example 1, in the case where the type and content of the M1 element and the molar ratio of Si / Al of the ZSM-5 zeolite molecular sieve are the same, the yield of aromatic compounds, and the BTX yield and BTX selectivity of Example 10 are 65.9%, 54.4% and 82.5%, respectively, which are higher than those of Example
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    25/25
    Comparative 1. The comparison between Example 11 and Comparative Example 2 indicates a similar conclusion. In conclusion, the catalysts produced by the process of the present invention have a better reaction activity. The reaction for the production of aromatic compounds from methanol, using the catalysts provided by this invention, achieves better results, for example, as higher yield of aromatic compounds and higher yield and selectivity of BTX.
    [105] Table 3 lists the results of the reaction of converting methanol into aromatic compounds using the MTA-10 catalyst under different conditions of the reaction process. It can be seen that, although the yield of aromatic compounds decreases to a certain extent with decreasing temperature, increasing pressure or increasing WHSV, the conversion of methanol is still greater than 99%. This also demonstrates a high activity of the catalyst of the present invention.
    [106] In addition, from the original raw materials to the catalyst finally obtained, there are three drying steps and a calcination step in the process of the present invention, while there are four drying steps and three calcination steps in the process of one method conventional. This means that the present invention has a significant advantage in terms of energy saving and cost reduction.
    权利要求:
    Claims (15)
    [1]
    1. Process for producing a molded catalyst for converting methanol into aromatic compounds, the molded catalyst for converting methanol into aromatic compounds comprising from 85 to 99 parts by weight of a ZSM-5 zeolite, 0.1 to 15 parts in weight of element M1, which is at least one selected from the group consisting of Ag, Zn and Ga, and from 0 to 5 parts by weight of element M2, which is at least one selected from the group consisting of Mo, Cu, La, P , Ce and Co, where the total specific surface area of the catalyst ranges from 350 to 500 m 2 / g, and the specific surface area of the micropore ranges from 200 to 350 m 2 / g, the catalyst contains from 0 to 5 % by weight of a binder;
    the process being CHARACTERIZED by the fact that it comprises:
    step i: mixing molding agent I, an inorganic acid, a silicon source, an aluminum source, water, a soluble compound of the element M1 and, optionally, a soluble compound of the element M2 to produce a mixture, gel the mixture, and then aging and drying the resulting gel to obtain an amorphous silicon aluminum oxide precursor;
    step ii: mix the amorphous silicon aluminum oxide precursor obtained in step i with a crystal seed and a binder, mold, and dry the mixture to obtain a molded body; and step iii: crystallize and then calcine the molded body obtained in step ii to obtain said catalyst.
    [2]
    2. Process, according to claim 1, CHARACTERIZED by the fact that the specific surface area of the catalyst varies from 380 to 450 m 2 / g.
    [3]
    3. Process, according to claim 1, CHARACTERIZED by the fact that the specific surface area of the micropore ranges from 260 to 350 m 2 / g.
    [4]
    4. Process according to claim 1, CHARACTERIZED by the fact that the volume of microporous of the catalyst varies from 0.08 to 0.20 cm 3 / g.
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    2/3
    [5]
    5. Process, according to claim 4, CHARACTERIZED by the fact that the catalyst micropore volume varies from 0.12 to 0.20 cm 3 / g.
    [6]
    6. Process according to any one of claims 1 to 4, CHARACTERIZED by the fact that the amount of element M1 varies from 1 to 10 parts by weight and the amount of element M2 varies from 0 to 2 parts by weight.
    [7]
    7. Process according to any one of claims 1 to 4, CHARACTERIZED by the fact that the catalyst does not contain any binder.
    [8]
    8. Process according to any one of claims 1 to 4, CHARACTERIZED by the fact that the molar ratio of Si to Al in the ZSM5 zeolite is in the range 10 to 200: 1.
    [9]
    9. Process according to claim 8, CHARACTERIZED by the fact that the molar ratio of Si to Al in the ZSM-5 zeolite is in the range of 10 to 100: 1.
    [10]
    10. Process according to claim 1, CHARACTERIZED by the fact that the molding agent I used in step i is at least one selected from the group consisting of polyethylene glycol, polyethylene oxide, polyoxyethylene-polyoxypropylene polyoxyethylene and hexadecyltrimethylammonium bromide;
    the inorganic acid used in step i is at least one selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid;
    the source of silicon used in step i is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane;
    the aluminum source used in step i is at least one selected from the group consisting of aluminum nitrate, aluminum chloride and aluminum sulfate;
    in the mixture from step i, the weight ratio of the molding agent I: the inorganic acid: the aluminum source: H2O: element M1: element M2: the silicon source is 0.2 ~ 1.8: 0.05 ~ 1.0: 0.005 ~ 0.085: 5 ~ 10: 0.005 ~ 0.3: 0 ~ 0.025: 1, where the weight of the aluminum source and the silicon source are calculated as the weight of Al2O3 and SiO2,
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    3/3 respectively.
    [11]
    11. Process according to claim 1 or 10, CHARACTERIZED by the fact that in step ii, the binder is at least one selected from the group consisting of silica sol, alumina sol, white silica and pseudo-bohemite.
    [12]
    12. Process according to claim 11, CHARACTERIZED by the fact that in step ii, the crystal seed is an HZSM-5 zeolite and the weight ratio of the crystal seed: the binder: the silicon aluminum oxide precursor amorphous is 0.001 ~ 0.1: 0.1 ~ 1: 1.
    [13]
    13. Process according to claim 1 or 10, CHARACTERIZED by the fact that a pore-forming agent is added in step ii, and the pore-forming agent is selected from sesbania and / or starch powders.
    [14]
    14. Process according to claim 1 or 10, CHARACTERIZED by the fact that the crystallization in step iii is carried out at a temperature of 100 to 180 ° C, by adding the molding agent II and water to the bottom of an autoclave and addition of the molded body obtained in step ii in the upper dam-board of the autoclave;
    in step iii, the weight ratio of molding agent II: water: molded body is 0.01 ~ 1: 0.5 ~ 20: 1;
    molding agent II is at least one selected from the group consisting of tetrapropylammonium bromide, tetrapropylammonium hydroxide, ethylenediamine, triethylamine, n-propylamine, n-butylamine and hexamethylenediamine.
    [15]
    15. Process for converting methanol into aromatic compounds, CHARACTERIZED by the fact that it comprises the step of contacting methanol, which is fed at an hourly spatial speed in weight of 0.1 to 5.0 h -1 , with the catalyst prepared by process, as defined in any one of claims 1 to 14, for generating the aromatic products, at a temperature of 350 to 550 ° C and a gauge pressure of 0 to 0.5 MPa.
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    同族专利:
    公开号 | 公开日
    CN103537315B|2015-11-25|
    RU2607633C2|2017-01-10|
    RU2013132371A|2015-01-20|
    SA113340714B1|2015-10-05|
    BR102013017946A2|2015-09-01|
    CN103537315A|2014-01-29|
    AU2013206818B2|2017-02-23|
    US20140018592A1|2014-01-16|
    US9339801B2|2016-05-17|
    ZA201305248B|2014-03-26|
    AU2013206818A1|2014-01-30|
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    法律状态:
    2015-09-01| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201210240007.1A|CN103537315B|2012-07-12|2012-07-12|Methanol arenes catalytic agent and preparation method thereof|
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