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    • 专利摘要:
    Solvothermal synthesis process of molecular sieves A method is provided to synthesize frog molecular sieve by the solvothermal method and the catalyst prepared by it. the synthesis method comprises the following steps: a) mixing organic amine, aluminum source, silicon source, phosphorus source and water according to the molar ratio of 6 to 30: 1: 0.5 to 5: 0, 01 to 1.0: 0.1 to 15 to obtain an initial mixture to prepare the frog molecular sieve, in which the molar ratio of water and organic amine is less than 2.0; b) Aging the initial mixture obtained in step a) under agitation of 30 to 60ºc for no more than 24 hours to obtain an initial gel; c) crystallize the initial gel obtained in step b) from 150 to 250ºc for 0.5 to 15 days. after being calcined from 400 to 700ºc in air, the frog molecular sieve prepared in this way is used as a catalyst for reactions catalyzed by acid or for the conversion of reactions from compounds containing oxygen to olefins.
    公开号:BR112013016489B1
    申请号:R112013016489
    申请日:2011-06-24
    公开日:2020-04-07
    发明作者:Fan Dong；Tian Peng；Su Xiong；Zhang Ying；Liu Zhongmin
    申请人:Dalian Inst Chem & Physics Cas；
    IPC主号:
    专利说明:

    SOLVOTHERMAL SYNTHESIS PROCESS OF MOLECULAR SIEVES
    Technical Field [1] The present invention relates to a process for synthesizing SAPO molecular sieves.
    [2] The present invention also relates to the application of the catalyst of the material described above in conversion reactions of oxygen-containing compounds to low carbon olefins.
    Background of the Technique [3] Since a series of molecular sieves of aluminum phosphate and its derivatives were synthesized successively in 1982 by Union Carbide Corporation, US, in US Patent No. 4,310,440, aluminum phosphate molecular sieves and substituted derivatives in the heteroatom are continuously one of the hot spots of research in the field of material and catalyst field. These types of SAPO molecular sieve synthesis technologies are characterized in that a silicon source, an aluminum source, a phosphorus source, and various standard agents are used in the synthesis, and the structural unit is composed of PO 2+ tetrahedrons , AlO 2- , and SiO2. Among these types of molecular sieves, some molecular sieves having a microporous structure such as SAPO-34 have been successfully applied to MTG, MTO and so on, and show excellent catalytic performance.
    [4] The SAPO molecular sieve synthesis in general uses a hydrothermal process, in which water is used as the continuous phase and the main solvent, and the molar ratio of water to the standard organic amine agent is generally greater than 10 The synthesis results in a large amount of residual liquids that are difficult to use, increasing the loads of environmental treatment. However, the synthesis process has a low relative yield that is generally less than 80%.
    Petition 870190085817, of 9/2/2019, p. 8/57 / 21
    This is mainly due to the fact that the precursor formed by the synthetic raw materials has a relatively high solubility in the aqueous solution.
    [5] Taking SAPO-34 as an example, SAPO-34 is a chabasite-type molecular sieve (CHA), having eight-membered ellipsoidal ring cages formed by the six-packaged six-membered rings in the ABC way and a channel structure 1 in three dimensional, wherein the pore size is 0.38 x 0.38 nm, and the size of the cage is 1.0 x 0.67 nm, belonging to the microporous molecular sieve. Its spatial symmetry group is R3m, belonging to the trigonal system. SAPO-34 is composed of four elements of Si, Al, P, and O, with an alterable composition in a certain range, in general n (Si) <n (P) <n (Al). Its matrix is composed of SiO4, AlO4 - , and PO4 + tetrahedrons, in which three types of [Al-OP], [Si-O-Al] and [Si-O-Si] bonds are present, but do not exist no connection [Si-OP].
    [6] Traditionally, the SAPO-34 molecular sieve is generally produced by a hydrothermal synthesis process that uses water as the solvent and is conducted in a sealed autoclave. The components for the synthesis comprise an aluminum source, a silicon source, a phosphorus source, a standard agent, and deionized water. The silicon source can be chosen from silica sol, silica fume, and orthosilicate ester. The aluminum source can be active alumina, pseudo-bohemian, or aluminum alkoxy. The preferred silicon source and aluminum source are silica sol and pseudo-bohemian. The source of phosphorus is generally 85% phosphoric acid. The standard agent commonly used comprises tetraethyl ammonium hydroxide (TEAOH), morpholine (MOR), piperidine, isopropylamine (i-PrNH2), triethylamine (TEA), diethylamine (DEA), dipropylamine, and the like, and a mixture thereof.
    [7] In traditional hydrothermal synthesis of SAPO-34, the molar quantity of the standard organic amine agent used is significantly less
    Petition 870190085817, of 9/2/2019, p. 9/57 / 21 than the molar amount of water, and as the amount of the standard agent gradually increases, both product yield and crystallinity decrease to some degree, see Table 1 in Microporous and Mesoporous Materials, 2008, 114 ( 1-3): 4163.
    [8] Like another type of SAPO molecular sieve, the RHO-SAPO molecular sieve having an RHO matrix structure is formed by connecting α cages through eight double-membered rings, belonging to the cubic crystalline system, and the main channel is composed of eight double-membered rings, having an aperture size of 0.36 nm x 0.36 nm. In 1973, Robson, HE et al. firstly, they reported that a molecular sieve of silicon aluminum zeolite with an RHO structure was synthesized using Na + and Cs + as structure directing agents (Adv. Chem. Ser., 121, 106-115). In 1987, Rouse, RC et al. reported the discovery of a type of natural ore having an RHO structure (N. Jb. Miner. Mh., 1987, 433-440). Henceforth, molecular sieves BePO (Stud. Surf. Sci. Catal., 1989, 49, 411-420), AlGeO (Microporous Mesoporous Mat., 1999, 28, 139-154), BeAsO (1991, Nature, 349, 508- 510), and GaSiO (J. Phys. Chem., 1995, 99, 9924-9932) having RHO structure were synthesized successively using Na + and Cs + as the structure directing agents. In 1998, Feng, PY et al. reported that the molecular sieves CoAPO-RHO, MgAPO-RHO and MnAPO-RHO were synthesized using N, N'-diisopropyl-
    1,3-propanediamine as the standard agent (Microporous Mesoporous Mat., 23, 315-322).
    [9] RHO-SAPO molecular sieve synthesis processes mainly include a hydrothermal synthesis of RHO-SAPO with the participation of surfactant and a dry gel synthesis process without the participation of surfactant (see Chinese patent application No. 200910169329 .X). For the hydrothermal synthesis process with the participation of surfactant, in one aspect, because the synthesis process
    Petition 870190085817, of 9/2/2019, p. 10/57 / 21 uses water as the continuous phase and as the main solvent of the synthesis system, a large amount of residual liquid difficult to be used will be produced after synthesis, increasing the loads of environmental treatment; on the other hand, the synthesis process uses the relatively expensive surfactant, increasing the cost of synthesis. In the dry gel synthesis process without the participation of surfactant, it requires firstly formulating a dry silicon-phosphorus-aluminum gel, which involves a complicated process; the crystallinity of the RHO-SAPO molecular sieve obtained by this synthesis process is not high, and the RHO-SAPO molecular sieve obtained is generally difficult to be separated through the washing method and so on from the dry silicon-phosphor gel - non-crystallized aluminum.
    [10] To solve the problems in the SAPO synthesis processes described above, the present inventors tried to synthesize SAPO by a solvothermal synthesis process, that is, synthesize SAPO molecular sieves by using a non-aqueous medium as the main solvent, and it was surprisingly discovered that, various types of SAPO molecular sieves can be successfully synthesized in the case where an organic amine is used both as the main solvent and as the standard agent of the synthesis system, in the presence of only a small amount of water. Description of the Invention [11] An objective of the present invention is to provide a process for synthesizing SAPO molecular sieves in solvothermal systems.
    [12] In order to achieve the objective described above, the present invention uses organic amines as the organic solvent and the standard agents of the solvothermal synthesis systems, to synthesize SAPO molecular sieves in the presence of a small amount of water.
    [13] Specifically, the present invention provides a process for solvothermal synthesis of SAPO molecular sieves, which comprises the following synthesis steps:
    Petition 870190085817, of 9/2/2019, p. 11/57 / 21
    a) an organic amine, an aluminum source, a phosphorus source, a silicon source, and water are mixed in a molar ratio of 6 to 30: 1: 0.5 to 5: 0.01 to 1.0: 0.1 to 15, to obtain an initial mixture to prepare the SAPO molecular sieves, in which the molar ratio of water to the organic amine is less than 2.0;
    b) the initial mixture obtained in step a) is maintained at 30 to 60 ° C, and aged with mixture for no more than 24 hours, to obtain an initial gel;
    c) the initial gel obtained in step b) is crystallized from 150 to 250 ° C for 0.5 to 15 days.
    [14] In the synthesis process of the present invention, the initial mixture in the preparation of SAPO molecular sieves can further comprise an organic alcohol, and the molar ratio of the organic amine, the aluminum source, the phosphorus source, the silicon source, organic alcohol and water in the initial mixture is 6 to 30: 1: 0.5 to 5: 0.01 to 1.0: 0.01 to 0.50: 0.1 to 15.
    [15] In the synthesis process of the present invention, the molar ratio of the organic amine to water is greater than 0.51, preferably greater than 1.0, more preferably greater than 1.5, most preferably greater than 3.0, and less than 300; the aging time is from 0 to 24 h, preferably from 0.5 to 15 h; and the crystallization time is 0.5 to 15 days, preferably 1 to 7 days.
    [16] The process of the present invention further comprises a step of separating, washing, and drying the crystallized product from step c), to obtain SAPO molecular sieves as synthesized.
    [17] The aluminum source used in the present invention is any one of pseudo-bohemian, aluminum isopropoxide, alumina, aluminum hydroxide, aluminum chloride, and aluminum sulfate or a mixture thereof; the source of phosphorus used is any one of orthophosphoric acid, metaphosphoric acid, a phosphate, and a phosphite or a mixture thereof; The
    Petition 870190085817, of 9/2/2019, p. 12/57 / 21 source of silicon used is any one of silica sol, ethyl orthosilicate, white carbon black, and silica or a mixture thereof; the organic amine used is any of a primary, secondary, and tertiary organic amine or a mixture thereof, comprising any of morpholine, piperidine, isopropylamine, triethylamine, diethylamine, di-n-propylamine, diisopropylamine, hexamethyleneimine, N ' , N ', N, N-tetramethyl-1,6hexanediamine, and N, N-diisopropylethylamine or a mixture thereof, and preferably any of diethylamine, triethylamine, morpholine, hexamethyleneimine, and N, N-diisopropylethylamine or a mixture of them.
    [18] The organic alcohol used in the initial blend is either methanol, ethanol, n-propanol, and i-propanol or a mixture thereof. In the synthesis of molecular sieves SAPO, especially in the synthesis of molecular sieves SAPO-34, SAPO-18, SAPO-35, or SAPO-56, the addition of organic alcohol is mainly for the purpose of suppressing the formation of impure crystalline phase, ensuring thus the reproducibility of the synthesis process and the high purity.
    [19] In the present invention, the prepared SAPO molecular sieve is any one of SAPO-5, SAPO-34, SAPO-11, SAPO-17, SAPO-18, SAPO31, SAPO-35, SAPO-40, SAPO-41, SAPO-43, SAPO-56, and RHO-SAPO or a mixture of them.
    [20] In the present invention, the synthesis mixture initially prepared is aged with a mixture of 30 to 60 ° C for a period of time, and the main effect of this process is to efficiently increase the crystallinity of the product, while improving the yield.
    [21] The synthesized SAPO molecular sieves, after being calcined from 400 to 700 ° C in air, can be used as catalysts for acid catalyzed reactions.
    [22] The synthesized SAPO molecular sieves, after being calcined from 400 to 700 ° C in the air, can also be used as
    Petition 870190085817, of 9/2/2019, p. 13/57 / 21 catalysts for conversion reactions of compounds containing oxygen to olefins.
    [23] The present invention can realize the advantages as follows:
    (1) The yield of the synthesis is high, which is generally greater than 90% (calculation method: dry mass of the product / total dry mass of the oxides fed x 100%);
    (2) Because the amount of water used is relatively small in synthesis and the respective inorganic raw materials and synthesis precursors are difficult to be dissolved in the organic amine, the organic amine can be easily separated from the gel product, recovered and reused after synthesis, and the amount of residual liquid produced is low.
    (3) The prepared SAPO shows excellent catalytic performance in the reaction of conversion of methanol to olefin. For example, with the SAPO-34 prepared here, when compared to the SAPO-34 molecular sieve prepared by a general hydrothermal synthesis process, the reaction life is longer, and the selectivity for ethylene and propylene is improved in one a certain degree.
    Brief Description of the Drawings [24] Figure 1 is a scanning electron microscope (SEM) image of the product synthesized in Example 10 of the present invention.
    [25] Figure 2 is a scanning electron microscope (SEM) image of the product synthesized in Example 12 of the present invention. Specific Embodiments of the Invention [26] The present invention will be described in detail by the Examples, but the present invention is not limited to these Examples.
    Example 1 [27] 7.03 g of active alumina (mass percentage of Al <l · 72.5%) were mixed homogeneously with 60 ml of triethylamine by
    Petition 870190085817, of 9/2/2019, p. 14/57 / 21 stirring, in which 10.30 g of orthophosphoric acid (mass percentage of H3PO4 85%), 5.69 g of silica sol (mass percentage of SiO2 28.2%), 0.50 g of ethanol, and 0.3 g of deionized water were added sequentially with stirring, then the mixture was vigorously stirred until homogeneously mixed. After stirring at 40 ° C for 10 h, the gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 180 ° C for 60 hours. After crystallization, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 14.1 g of product as synthesized (weight loss on calcination of 15%). The sample was submitted to XRD analysis. The XRD data were shown in Table 1, and the results indicated that the synthesized product was the SAPO-34 molecular sieve.
    Comparative Example 1 [28] The formulation ratio and crystallization process were the same as in Example 1, but the addition of ethanol was omitted. After the crystallized product was washed and dried, XRD analysis was conducted, and the results indicated that the sample was SAPO-34 containing a small amount of SAPO-5, where a peak height ratio of the first strongest peaks of the two products was: SAPO-5 / SAPO-34 = 1/9.
    Comparative Example 2 [29] SAPO-34 was synthesized by a conventional hydrothermal synthesis process, see Microporous and Mesoporous Materials 53 (2002) 97-108.
    [30] 7.03 g of active alumina (mass percentage of 72.5% AlAE), 10.3 g of orthophosphoric acid (mass percentage of H3PO4 85%), 5.69 g of silica sol (percentage in mass of SiO2 28.2%), and 35 ml of deionized water were homogeneously mixed by stirring, and 21 ml of triethylamine were added under stirring. After the mixture was vigorously stirred until homogeneously mixed, the gel was
    Petition 870190085817, of 9/2/2019, p. 15/57 / 21 transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 200 ° C for 48 hours. After the crystallization was finished, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 11.0 g of product as synthesized (weight loss on calcination of 15.5%). The sample was subjected to XRD analysis, and the results indicated that the synthesized product was the SAPO-34 molecular sieve.
    Example 2 [31] 7.03 g of active alumina (mass percentage of AlTl · 72.5%) were homogeneously mixed with 50 ml of diethylamine and 15 ml of triethylamine by stirring, in which 9.5 g of orthophosphoric acid ( percentage by mass of H3PO4 85%), 4.55 g of silica sol (percentage by mass of SiO2 28.2%), and 0.38 g of methanol were added at once with stirring, and then vigorously stirred until homogeneously mixed. After the mixture was stirred at 55 ° C for 12 h, the gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 180 ° C for 100 hours. After the crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 13.0 g of product as synthesized (weight loss on calcination of 14.1%). The sample was submitted to XRD analysis. The XRD data were shown in Table 2. The results indicated that the synthesized product was the SAPO-34 molecular sieve.
    Comparative Example 3 [32] The formulation ratio and crystallization process were the same as in Example 2, but the addition of methanol was omitted. After the crystallized product was washed and dried, it was subjected to XRD analysis. The results indicated that the sample was SAPO-34 containing a small amount of SAPO-5. The peak height ratio of
    Petition 870190085817, of 9/2/2019, p. 16/57 / 21 first strongest peaks of the two products was: SAPO-5 / SAPO-34 = 1/11. Example 3 [33] 7.03 g of active alumina (mass percentage of AHE 72.5%) were homogeneously mixed with 23.13 ml of triethylamine and 60 ml of morpholine by stirring, in which 10.30 g of orthophosphoric acid (percentage by mass of H3PO4 85%), 4.55 g of silica sol (percentage by mass of SiO2 28.2%), 1.0 g of ethanol, and 2.04 g of deionized water were added at once under stirring, and then vigorously stirred until homogeneously mixed. After stirring at 35 ° C for 12 h, the gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 210 ° C for 24 hours. The solid product was centrifuged, washed with deionized water until neutral pH, and after drying at 100 ° C in air, 13.6 g of product as synthesized (weight loss on calcination of 14.5%) were obtained. The sample was subjected to XRD analysis, and the data were shown in Table 3. The XRD data showed that the synthesized product was the SAPO-34 molecular sieve.
    Comparative Example 4 [34] The formulation ratio and crystallization process were the same as in Example 3, but the aging process at low temperature was omitted. After the crystallized product was washed and dried, 11.5 g of product as synthesized (weight loss on calcination of 16.1%) was obtained. It was submitted to XRD analysis. The results indicated that the sample was pure SAPO-34, having a relative crystallinity of 80% (the relative crystallinity of FDZ-38-3 was defined as 100%).
    Example 4 [35] The same as in Example 3, except that 1.0 g of ethanol was changed to 1.0 g of n-propanol, the other components and the conditions of
    Petition 870190085817, of 9/2/2019, p. 17/57 / 21 crystallization have not been changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 5 [36] The same as in Example 3, except that 7.03 g of active alumina were changed to 20.65 g of aluminum isopropoxide and the amount of deionized water was changed to 1.0 g, the other components and crystallization conditions have not been changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 6 [37] The same as in Example 1, except that 7.03 g of active alumina were exchanged for 20.65 g of aluminum isopropoxide, 5.69 g of silica sol (mass percentage of SiO2 28.2 %) were changed to 1.6 g of fumigated silica, and the amount of deionized water was changed to 1.0 g, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 7 [38] The same as in Example 1, except that 7.03 g of active alumina were exchanged for 5.2 g of γ-alumina, 5.69 g of silica sol (mass percentage of SiO2 28.2 %) were changed to 1.6 g of fumigated silica, and the amount of deionized water was changed to 0.1 g, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 8 [39] The same as in Example 1, except that 7.03 g of active alumina
    Petition 870190085817, of 9/2/2019, p. 18/57 / 21 calcined at a high temperature of 600 ° C (the water content was removed there) were used as the aluminum source, 5.69 g of silica sol (percentage by mass of SiO2 28.2%) they were changed to 1.6 g of fumigated silica, and the amount of deionized water was changed to 0.1 g, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis, and the results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 9 [40] The samples obtained in Example 1, Comparative Example 2, and
    Example 7 were aerated with air and calcined at 600 ° C for 4 hours. Then they were pressed into tablets, and crushed to 20 to 40 meshes. 1.0 g of sample was weighed, loaded into a fixed bed reactor, and subjected to MTO reaction evaluation. Nitrogen gas was introduced and the sample was activated at 550 ° C for 1 hour, after which the temperature was lowered to 450 ° C to conduct the reaction. Methanol was charged by nitrogen gas at a flow rate of 40 ml / min, and the weighted spatial velocity of methanol was 2.0 h -1 . The reaction product was analyzed by line gas chromatography. The results were shown in Table 4.
    Table 1: XRD results from the sample of Example 1
    At the. 2θ gives) 100x I / I0 1 9.4838 9.32578 100 2 12.8384 6.89556 13.12 3 13.9703 6.33933 2.59 4 16.0023 5.53863 36.38 5 16.9215 5.23976 2.91 6 19.0086 4.66891 0.95 7 20.5561 4.32079 41.4 8 21.2911 4.17326 2.84 9 23.0914 3.8518 2.39 10 24,099 3,69299 0.76 11 25.0766 3.5512 1.05 12 25.8444 3.44741 7.99 13 27.5828 3.23396 1.17 14 28,1603 3.166895 0.81 15 29.5158 3.02642 1.81 16 30.5066 2.93035 2.61 17 31,048 2.88048 5.06 18 36,1308 2.48607 0.77 19 43.238 2.09248 0.71 20 49.0196 1.85836 3.63 21 50.9873 1.79117 0.45 22 53.1682 1.7213 1.17
    Petition 870190085817, of 9/2/2019, p. 19/57 / 21
    Table 2: XRD results from the sample of Example 2
    At the. 2θ gives) 100X I / Iq 1 9.4545 9.35457 100 2 12.8344 6.8977 20.88 3 13.9189 6.3626 3.38 4 15.9622 5.55246 40.27 5 17.6853 5.01515 25.06 6 18.5142 4.79245 3.12 7 18.9682 4.67876 4.28 8 20.5336 4.32546 93.44 9 21.9097 4.05682 14.49 10 22.3181 3.98348 5.92 11 22.9725 3.87147 15.98 12 24.8162 3.58786 54.74 13 25.8284 3.44951 20.2 14 26.2107 3.40006 1.71 15 27.5669 3.23579 8.67 16 28.0275 3.18365 6.6 17 29.4615 3.03188 3.28 18 30,5062 2.92796 38.81 19 30.6299 2.92367 23.27 20 30.9433 2.88759 24.57 21 31.4801 2.83956 3.43 22 32.2688 2.77194 1.71 23 33.3591 2.68379 3.55 24 34,4001 2.60492 7.23 25 34.8399 2.57304 1.75 26 35.8666 2.50171 5.66 27 38.3234 2.34679 1.02 28 39.5752 2.27539 3.71 29 42.6257 2.11935 3.96 30 43,2903 2.08834 4 31 47.5413 1.91105 4.05 32 48.6651 1.86951 5.82 33 49.0438 1.85596 3.29 Table 3: XRD results from the sample of Example 3 At the. 2θ gives) 100X I / Iq 1 9.4514 9.35767 100 2 12.8291 6,90055 21.49 3 13.9125 6.3655 3.09 4 14.3377 6.17767 0.89 5 15.9594 5.5534 40.06 6 17.6902 5.01377 25.47 7 18.5204 4.79087 2.74 8 18.9616 4.68036 4.21 9 20.5265 4.32694 99.51 10 21.9084 4.05705 14.3 11 22.3198 3.98319 5.43 12 22.9648 3.87275 15.44 13 24.8165 3.58782 55.86 14 25.8241 3.45008 19.99 15 27.5629 3.23626 7.53 16 28,038 3.18249 5.87 17 29.4517 3.03286 4.03 18 30.4977 2.92876 39.05 19 30,633 2.92338 21.65 20 30.9388 2,888 25.98 21 31.4775 2.8398 3.24 22 32.2567 2.77296 1.81
    Petition 870190085817, of 9/2/2019, p. 20/57 / 21
    At the. 2θ gives) 100x I / I0 23 33.3489 2.68459 3.5 24 34.3856 2.60599 7.75 25 34.8176 2.57463 2.19 26 35.8657 2.50177 6.32 27 38.1446 2,35738 0.91 28 39.1675 2.29814 0.95 29 39.5678 2.2758 3.48 30 42.6337 2.11897 4.78 31 43,2908 2.08832 3.63 32 44.9355 2.01563 0.64 33 47.5282 1.91155 3.84 34 48.6704 1.86932 5.17 35 49.0618 1.85532 2.93
    Table 4 Sample results for the methanol to olefin conversion reaction
    Sample T in p o d e __________________________Selectivity (% by mass) * __________________________ life (min) CH4 C2H4 C2H6 C3H6 C3H8 C4 + C5 + C2H4 + C3H6 Example 1 160 2.2 45.9 0.8 39.5 1.2 8.5 1.9 85.4 ExampleComparative 2Example 7 140 2.7 44.3 0.8 38.1 1.9 10.1 2.1 82.4160 2.3 44.8 0.7 39.9 1.6 9.0 1.7 84.7
    * The highest selectivity (ethylene + propylene) in the case of 100% methanol conversion
    Example 10 [41] 10.37 g of orthophosphoric acid (percentage by mass of
    H3PO4 85%) were added in 60 ml of diethylamine under the condition of an ice water bath. 8.34 g of active alumina (mass percentage of Al2O3 72.5%), 5.69 g of silica sol (mass percentage of SiO2 28.2%), and 0.2 g of deionized water were added sequentially at this point under agitation condition, and vigorously stirred so as to be homogeneously mixed. The gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 200 ° C for 48 hours. After crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, and the sample was then subjected to XRD analysis. The XRD data was shown in Table 5. The results indicated that the synthesized product had an RHO structure. The sample composition was Al0.489P0.306 810.205 according to the XRF analysis, indicating that the sample obtained was the RHO-SAPO molecular sieve. the sample obtained was characterized by the scanning electron microscope, and the resulting electron microscope photograph was
    Petition 870190085817, of 9/2/2019, p. 21/57 / 21 shown in Figure 1.
    Comparative Example 5 [42] 8.34 g of active alumina (mass percentage of AI2O3 72.5%) were homogeneously mixed with 60 ml of diethylamine, and in which 10.37 g of orthophosphoric acid (mass percentage of H3PO4 85 %), 5.69 g of silica sol (28.2% SiO2 mass percentage), and 0.2 g of deionized water were added sequentially with stirring. after shaking vigorously to make the mixture homogeneously mixed, the gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 200 ° C for 48 hours. After crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, and the sample was then subjected to XRD analysis. The XRD results indicated that the synthesized product was the mixed crystal of the molecular sieves RHO-SAPO and SAPO-34.
    Comparative Example 6 [43] 8.34 g of active alumina (percentage by mass of AEO3
    72.5%), 10.37 g of orthophosphoric acid (mass percentage of H3PO4 85%), 5.69 g of silica sol (mass percentage of SiO2 28.2%), and 45 ml of deionized water were homogeneously mixed, to which 10 ml of diethylamine were added with stirring. after shaking vigorously to make the mixture homogeneously mixed, the gel was transferred into a stainless steel reaction pan, and dynamically synthesized at a crystallization temperature of 200 ° C for 48 hours. After crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air. The sample was subjected to XRD analysis, and the results indicated that the synthesized product was the SAPO-34 molecular sieve.
    Example 11 [44] The same as in Example 10, except that 8.34 g of
    Petition 870190085817, of 9/2/2019, p. 22/57 / 21 active alumina was changed to 24.5 g of aluminum isopropoxide, and the amount of deionized water was changed to 1.0 g, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the RHO-SAPO molecular sieve.
    Comparative Example 7 [45] The same as in Example 10, except that 8.34 g of active alumina was changed to 24.5 g of aluminum isopropoxide, and the amount of deionized water was changed to 10 g, the other components and crystallization conditions have not been changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the SAPO-34 molecular sieve.
    Example 12 [46] 11.52 g of orthophosphoric acid (mass percentage of H3PO4 85%) were added into a mixed solution of 60 ml of diethylamine and 15 ml of triethylamine under the condition of an ice water bath, and in what 7.03 g of active alumina (percentage by mass of AUOs
    72.5%), 4.55 g of silica sol (percentage by mass of SiO2 28.2%), and 0.1 g of deionized water were added sequentially with stirring. After shaking vigorously to make the mixture homogeneously mixed, the gel was transferred into a stainless steel reaction pan, and was dynamically synthesized at a crystallization temperature of 190 ° C for 48 hours. After crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, and the sample was then subjected to XRD analysis. The XRD data was shown in Table 6. The results indicated that the synthesized product had an RHO structure. The sample obtained was characterized by the scanning electron microscope, and the resulting electron microscope photograph
    Petition 870190085817, of 9/2/2019, p. 23/57 / 21 was shown in Figure 2.
    Example 13 [47] The same as in Example 10, except that 8.34 g of active alumina were exchanged for 24.5 g of aluminum isopropoxide, 5.69 g of silica sol (mass percentage of SiO2 28.2 %) were changed to 1.6 g of fumigated silica, and the amount of deionized water was changed to 1.2 g, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the RHOSAPO molecular sieve.
    Example 14 [48] The same as in Example 10, except that 8.34 g of active alumina were exchanged for 6.1 g of γ-alumina, and 5.69 g of silica sol (mass percentage of SiO2 28, 2%) were changed to 1.6 g of fumigated silica, the other components and the crystallization conditions were not changed. The crystallized product was subjected to XRD diffraction analysis. The results indicated that the synthesized sample was the RHO-SAPO molecular sieve.
    Example 15 [49] The same as in Example 10, except that 60 ml of diethylamine was switched to a mixed solution of 60 ml of diethylamine and 18 ml of morpholine, the amount of phosphoric acid (85% by weight) was changed to 12 , 35 g, and the amount of deionized water was changed to 0.5 g, the other components and the crystallization conditions were not changed. The product obtained was marketed as FDZ-31-2. The results of the XRD diffraction analysis were shown in Table 7. The results indicated that the synthesized product was the RHOSAPO molecular sieve.
    Petition 870190085817, of 9/2/2019, p. 24/57 / 21
    Table 5: Sample XRD results from Example 10
    At the. 2θ gives) 100x I / I0 1 8.2149 10,76318 100 2 11.6288 7.60998 6.49 3 14.2579 6.21209 54.61 4 16.4743 5.381 22.21 5 18.4368 4.81239 21.81 6 20.2103 4.39393 6.4 7 21.8497 4.06781 35.21 8 23.3771 3.80537 9.48 9 24.8198 3.58735 46.77 10 26.1863 3.40317 62.07 11 28.7405 3.10628 17.34 12 29.94 2.9845 29.97 13 32.2224 2,77812 23.32 14 35.3993 2.53575 15.54 15 41.9817 2.15214 2.79 16 43.7264 2.06852 6.33 17 47.0375 1.93194 7.7 18 47.8344 1.90159 7.46 19 48.6516 1.87155 3.14 20 49,424 1.84409 1.44 21 50.9384 1.79277 7.34 22 54.7545 1.67067 4.44 23 56.8143 1.62052 1.23 24 57.4795 1.60201 5.14
    Table 6: XRD results from the sample of Example 12
    At the. 2θ gives) 100x I / I0 1 8.2168 10,76076 100 2 11.6307 7.60871 5.72 3 14.2605 6.21094 54.77 4 16.48 5.37915 18.84 5 18,437 4.81235 19.03 6 20.2168 4.39252 5.09 7 21.8576 4.06636 32.43 8 23.3892 3.80343 8.85 9 24.8322 3.58559 44.47 10 26.1985 3.40161 54.73 11 28.7666 3.10351 14.45 12 29.9569 2.98286 28.75 13 32.2382 2.7768 21.63 14 35.4144 2.5347 15.12 15 41.9265 2.10811 2.63 16 43.7355 2.06982 5.39 17 47.0589 1.92951 6.95 18 47.8646 1.89889 6.73 19 48.6834 1.8704 2.66 20 49.4289 1.84391 1.63 21 50.9569 1,79216 6.91 22 54.7386 1.67368 2.34 23 56.0994 1.63811 4.6 24 57.4955 1.60161 4.53
    Petition 870190085817, of 9/2/2019, p. 25/57 / 21
    Table 7: Sample XRD results from Example 15
    At the. 2θ gives) 100x I / I0 1 8.2217 10.75434 100 2 11,637 7.60463 5.86 3 14.2673 6.20799 55.11 4 16.4873 5.37676 19.21 5 18,449 4.80923 19.66 6 20.2242 4.39094 4.98 7 21.8654 4.06493 29.95 8 23.3978 3.80206 9.34 9 24.8392 3.5846 42.88 10 26.2065 3,40059 56.1 11 28.7624 3.10396 14.92 12 29.9631 2.98226 28.28 13 32.2449 2,77624 20.67 14 35.4242 2.53402 13.81 15 42.0138 2.15057 2.4 16 43.7605 2.0687 5.52 17 47.0754 1.93047 6.4 18 47.8707 1,90024 6.25 19 48.6616 1.86964 3.63 20 49.4318 1.84382 1.81 21 50.9796 1.79142 6.18 22 54.7219 1.67743 1.28 23 56,1134 1.63773 4.05 24 57.5244 1.60087 4.37
    Example 16 [50] The same as in Example 1, except that the crystallization temperature was changed to 210 ° C, the crystallization time was changed to 48 h, and the silicon source was changed to 1.6 g of fumigated silica . After the crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 12.2 g of product as synthesized (14% weight loss on calcination). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-18 molecular sieve.
    Example 17 [51] The same as in Example 1, except that the organic amine was changed to 65 ml of N ', N-diisopropylethylamine, and the silicon source was changed to 1.6 g of fumigated silica. After the crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining
    Petition 870190085817, of 9/2/2019, p. 26/57 / 21
    12.6 g of product as synthesized (weight loss on calcination of 15.2%). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-18 molecular sieve.
    Example 18 [52] The same as in Example 1, except that the organic amine was changed to 65 ml of N ', N', N, N-tetramethyl-1,6-hexanediamine. After the crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 13.6 g of product as synthesized (weight loss on calcination of 16.8%). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-56 molecular sieve.
    Example 19 [53] The same as in Example 1, except that the organic amine was changed to 60 ml of hexamethyleneimine. After the crystallization ended, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 12.1 g of product as synthesized (weight loss on calcination of 13.8%). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-35 molecular sieve.
    Example 20 [54] The same as in Example 1, except that the organic amine was changed to 65 ml of hexamethyleneimine, the crystallization temperature was changed to 205 ° C, and the crystallization time was changed to 48 h, the other conditions have not been changed. After the crystallization was finished, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 13.3 g of product as synthesized (weight loss on calcination of 14%). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-34 molecular sieve.
    Example 21 [55] The same as in Example 1, except that the organic amine
    Petition 870190085817, of 9/2/2019, p. 27/57 / 21 was changed to 60 ml of di-n-propylamine, the other conditions were not changed. After the crystallization was finished, the solid product was centrifuged, washed, and dried at 100 ° C in air, obtaining 12.8 g of product as synthesized (weight loss on calcination of 14.2%). The sample was submitted to XRD analysis. The results indicated that the synthesized product was the SAPO-43 molecular sieve.
    权利要求:
    Claims (11)
    [1]
    1. Solvothermal synthesis process for SAPO molecular sieves, characterized by the fact that the main steps are as follows:
    a) an organic amine, an aluminum source, a phosphorus source, a silicon source, and water are mixed in a molar ratio of 6 to 30: 1: 0.5 to 5: 0.01 to 1.0: 0.1 to 15, to obtain an initial mixture to prepare the SAPO molecular sieves, in which the organic amine is an organic amine having function as the main solvent for the synthesis system and as a standard agent, the organic amine being any among morpholine, piperidine, isopropylamine, triethylamine, diethylamine, dipropylamine, diisopropylamine, hexamethyleneimine, N ', N', N, N-tetramethyl1,6-hexanediamine, and N, N-diisopropylethylamine and the molar ratio of the organic amine for water being 3.0 to 300;
    b) the initial mixture obtained in step a) is maintained at 30 to 60 ° C and aged with agitation for no more than 24 hours, to obtain an initial gel;
    c) the initial gel obtained in step b) is crystallized from 150 to 250 ° C for 0.5 to 15 days.
    [2]
    2. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the initial mixture to prepare SAPO molecular sieves further comprises an organic alcohol in it.
    [3]
    3. Solvothermal synthesis process of SAPO molecular sieves according to claim 2, characterized by the fact that organic alcohol is any one of methanol, ethanol, n-propanol, and ipropanol or a mixture thereof.
    [4]
    4. Solvothermal synthesis process of SAPO molecular sieves according to claim 2, characterized by the fact that the molar ratio of the organic amine, the source of aluminum, the source of phosphorus, the source of
    Petition 870190085817, of 9/2/2019, p. 29/57
    2/3 silicon, organic alcohol and water in the initial mixture are 6 to 30: 1: 0.5 to 5: 0.01 to 1.0: 0.01 to 0.50: 0.1 to 15.
    [5]
    5. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the aluminum source is any one of aluminum isopropoxide, alumina, aluminum hydroxide, aluminum chloride, and aluminum sulfate or mixture of them.
    [6]
    6. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the phosphorus source is any one of orthophosphoric acid, metaphosphoric acid, a phosphate, and a phosphite or a mixture thereof.
    [7]
    7. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the silicon source is any one of silica sol, ethyl orthosilicate, and silica or a mixture thereof; and the organic amine is any one of a primary, secondary, and tertiary organic amine or a mixture thereof.
    [8]
    8. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the SAPO molecular sieve is any one of SAPO-5, SAPO-34, SAPO-11, SAPO-17, SAPO-18, SAPO-35, SAPO-40, SAPO-41, SAPO-43, SAPO-56, and RHO-SAPO or a mixture of them.
    [9]
    9. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the aging time in step b) is 0.5 to 15 h.
    [10]
    10. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the crystallization time in step c) is from 1 to 7 days.
    [11]
    11. Solvothermal synthesis process of SAPO molecular sieves according to claim 1, characterized by the fact that the
    Petition 870190085817, of 9/2/2019, p. 30/57
    The process further comprises a step of separating, washing, and drying the crystallized product from step c).
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    同族专利:
    公开号 | 公开日
    DK2660203T3|2018-11-26|
    CN102530987A|2012-07-04|
    JP2014506227A|2014-03-13|
    EP2660203B1|2018-08-22|
    AU2011349908B2|2014-11-27|
    KR101461541B1|2014-12-02|
    JP5667311B2|2015-02-12|
    US9168516B2|2015-10-27|
    EP2660203A1|2013-11-06|
    SG191421A1|2013-07-31|
    US20130280161A1|2013-10-24|
    ZA201305421B|2014-10-29|
    EP2660203A4|2017-04-12|
    WO2012088854A1|2012-07-05|
    BR112013016489A2|2016-09-27|
    CN105110348A|2015-12-02|
    KR20130108653A|2013-10-04|
    MY157590A|2016-06-30|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-02| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-03-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN2010106105155A|CN102530987A|2010-12-29|2010-12-29|Solvent thermal synthesis method of SAPOmolecular sieve and catalyst prepared by SAPO molecular sieve|
    PCT/CN2011/076332|WO2012088854A1|2010-12-29|2011-06-24|Method for synthesizing sapo molecular sieve by solvothermal method and catalyst prepared thereby|
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