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    • 专利摘要:
    scm-10 molecular sieve, process for its production and use. the present invention relates to an scm-10 molecular sieve, a process for its production and its use. the molecular sieve has an empirical chemical composition as illustrated by the formula "the first oxide · the second oxide", wherein the molar ratio of the first oxide to the second oxide is less than 40, the first oxide is at least one selected from the group consisting of silica and germanium dioxide, the second oxide is at least one selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, titanium oxide, rare earth oxides, indium oxide and oxide of vanadium. the molecular sieve has a specific xrd pattern, and can be used as an adsorbent or a catalyst to convert an organic compound.
    公开号:BR102016026121B1
    申请号:R102016026121-0
    申请日:2016-11-08
    公开日:2021-09-14
    发明作者:Weimin Yang；Zhendong Wang；Hongmin Sun；Bin Zhang；Yi Luo
    申请人:China Petroleum & Chemical Corporation；Shanghai Research Institute Of Petrochemical Technology, Sinopec；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to a molecular sieve SCM-10, a process for its production and its use. Background technique
    [0002] In industry, porous inorganic materials have been widely used as catalysts and catalyst carriers. These porous materials generally include amorphous porous materials, crystalline molecular sieves and modified layered materials. The difference in minutes in the structure between either of the two materials can indicate a significant difference in properties such as catalytic performance and adsorption capacity between them and also a difference in the available parameters used to characterize them, such as morphology, specific surface area or size of pore.
    [0003] The structure of a molecular sieve is specifically confirmed by the X-ray diffraction pattern (XRD), while the X-ray diffraction pattern (XRD) is determined by X-ray powder diffraction with an α-ray source of Cu-K and a Ni filter. Different molecular sieves have different XRD characterization patterns. Known molecular sieves like A-type zeolite, Y-type zeolite, MCM-22 molecular sieve and so on have their XRD characterization patterns, respectively.
    [0004] At the same time, two molecular sieves, if they share the same characteristic XRD pattern, but comprising a different combination of structural elements, will be identified as different molecular sieves. For example, the TS-1 molecular sieve (US 4410501) and the ZSM-5 molecular sieve (US3702886), share the same characteristic XRD pattern, but comprise a different combination of structural elements. Specifically, the TS-1 molecular sieve comprises Si and Ti as structural elements, which have a catalytic oxidation capacity, while the ZSM-5 molecular sieve comprises Si and Al as the structural elements, showing an acidic catalytic capacity.
    [0005] Furthermore, two molecular sieves, if they share the same characteristic XRD pattern and the same combination of structural elements, but with different relative amounts of structural elements, will also be identified as different molecular sieves. For example, zeolite X (US2882244) and zeolite Y (US3130007), share the same characteristic XRD pattern and the same combination of structural elements (Si and Al), but with different relative amounts of Si and Al. zeolite X has an Si/Al molar ratio of less than 1.5, while zeolite Y has an Si/Al molar ratio of greater than 1.5. Invention Summary
    [0006] The present inventors, based on the prior art, found a new molecular sieve having the SFE structure, and further identified its beneficial properties.
    [0007] Specifically, this invention relates to the following aspects. 1. An SCM-10 molecular sieve having an empirical chemical composition as illustrated by the Formula "the first oxide • the second oxide", wherein the molar ratio of the first oxide to the second oxide is less than 40, preferably in the range of 3 to less than 40, more preferably from 5 to 30, the first oxide is at least one selected from the group consisting of silica and germanium dioxide, preferably silica, the second oxide is at least one selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, titanium oxide, rare earth oxides, indium oxide and vanadium oxide, preferably boron oxide or a combination of boron oxide and at least one selected from the group consisting of alumina, iron oxide, gallium oxide, titanium oxide, rare earth oxides, indium oxide and vanadium oxide, more preferably boron oxide or a combination of boron oxide and alumina, most preferably boron oxide , and the molecular sieve on the f Calcined form has an X-ray diffraction pattern as substantially illustrated in the following table,

    a:±0.3°, b: changed with 2θ. 2. The SCM-10 molecular sieve according to any of the foregoing aspects, wherein the X-ray diffraction pattern further includes X-ray diffraction peaks as substantially illustrated in the following table,
    a:±0.3°, b: changed with 2θ. 3. A process for producing an SCM-10 molecular sieve, including a step of crystallizing a mixture comprising a first oxide source, a second oxide source, an organic template and water to obtain the molecular sieve and optionally , a calcination step of the molecular sieve obtained, in which the organic model is selected from a compound represented by the following Formula (A), a quaternary ammonium salt thereof and its quaternary ammonium hydroxide, preferably 4-dimethylamino pyridine,
    wherein R1 and R2 may be identical or different from each other, each independently representing a C1-8 alkyl, preferably a C1-4 alkyl, more preferably a C12 alkyl. 4. The process according to any of the foregoing aspects, wherein the mixture does not contain an alkaline source. 5. The process according to any of the foregoing aspects, wherein the mixture does not contain a source of fluorine. 6. The process according to any of the foregoing aspects, wherein the mixture has a pH = 6 to 14, preferably pH = 7 to 14, more preferably 8 to 14, more preferably 8.5 to 13.5 , more preferably from 9 to 12, more preferably from 9 to 11. 7. The process according to any of the preceding aspects, wherein the first oxide source is at least that selected from the group consisting of a source of silicon and a source of germanium, preferably a source of silicon, the second source of oxide is at least one selected from the group consisting of a source of aluminum, a source of boron, a source of iron, a source of gallium, a source of titanium, a source of rare earths, a source of indium and a source of vanadium, preferably a source of boron or a combination of a source of boron and at least one selected from the group consisting of a source of aluminum, a source of iron, a source of gallium, a source of titanium, a source of rare earths, an indium source and a vanadium source, more preferably a boron source or a combination of a boron source and an aluminum source, more preferably a boron source, the molar ratio between the first oxide source (as the first oxide), the second oxide source (as the second oxide), the organic model and the water is 1:(0.025-1/3):(0.01-1.0):(4-50), preferably 1 :(1/30-1/3):(0.02-0.9):(4-40), more preferably 1:(1/30-1/5):(0.04-0.8) :(4-30), with the proviso that the molar ratio of the first oxide source (as the first oxide) to the second oxide source (as the second oxide) is less than 40, preferably less than 30 8. An SCM-10 molecular sieve composition, comprising the SCM-10 molecular sieve according to any one of the preceding aspects or an SCM-10 molecular sieve produced according to the process according to any one of the preceding aspects and a binder. 9. Use of the SCM-10 molecular sieve according to any one of the preceding aspects, an SCM-10 molecular sieve produced according to the process according to any one of the preceding aspects or the SCM-10 molecular sieve composition according to any of the foregoing aspects as an adsorbent or catalyst for the conversion of an organic compound. 10. Use according to any of the foregoing aspects, wherein the catalyst for converting an organic compound is at least one selected from the group consisting of an alkane isomerization catalyst, a catalyst for the alkylation between olefins and aromatics, a catalyst olefin isomerization catalyst, a naphtha cracking catalyst, a catalyst for the alkylation between alcohols and aromatics, an olefin hydration catalyst and an aromatic disproportionate catalyst. technical effects
    [0008] According to the present invention, the molecular sieve SCM-10 has the SFE structure, but with a chemical composition that has never been obtained in this field before. Description of Figures
    [0009] Fig. 1 illustrates the X-ray diffraction (XRD) pattern of the molecular sieve produced in Example 1. Specific Way to Carry Out this Invention
    [0010] This invention will be described in detail below with reference to the following specific embodiments. However, it should be noted that the scope of protection of this invention is not to be construed as limited to these specific embodiments, but rather as determined by the appended claims.
    [0011] All documents cited herein, including any contradicted by reference or related patent, are hereby incorporated by reference in their entirety unless expressly excluded or otherwise limited. Citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention.
    [0012] In addition, to the extent that any meaning or definition of a term herein conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition ascribed to that term in this document shall govern.
    [0013] In the context of this descriptive report, a molecular sieve, before any material (eg organic models) other than water and metal ions that was introduced into its pores during its production is removed from the pores, is referred to as " precursor".
    [0014] In the context of this descriptive report, the molecular sieve XRD data, w, m, s, vs indicates the intensity of a diffraction peak, with w referring to weak, medium ma, strong sa, vs very strong, which are well known in this field. In general, w represents a value of less than 20; m represents a value from 20 to 40; s represents a value from 40 to 70; vs represents a value greater than 70.
    [0015] In the context of this descriptive report, the structure of the molecular sieve is confirmed by X-ray diffraction pattern (XRD), while X-ray diffraction pattern (XRD) is determined by X-ray powder diffraction with a α-ray source of Cu-K and a Ni filter. Before determination, the crystalline state of the test sample is observed under a scanning electron microscope (SEM), to confirm that there is only one type of crystal there, which indicates that the molecular sieve as the test sample appears as a phase pure, and then the XRD determination is conducted on that, so as to ensure that there is no interference peak from another crystal in the XRD pattern.
    [0016] In the context of this specification, by specific surface area refers to the total area per unit mass of a sample, including the inner surface area and the outer surface area. A non-porous material has only an outer surface area, such as Portland cement or some clay mineral powder, while a porous material has an outer surface area and an inner surface area, such as asbestos fiber, diatomite, or molecular sieves. In a porous material, the surface area of pores having a diameter of less than 2 nm is referred to as the inner surface area, while the surface area obtained by subtracting the inner surface area from the total surface area is referred to as outer surface area. The outer surface area per unit mass of a sample is referred to as the specific outer surface area.
    [0017] In the context of this specification, by pore volume refers to the pore volume per unit mass of a porous material (eg, a molecular sieve). By total pore volume, it refers to the volume of all pores (generally involving only pores having a pore diameter of less than 50 nm) per unit mass of a molecular sieve. By micropore volume, it refers to the volume of all micropores (generally referred to as pores having a pore diameter of less than 2 nm) per unit mass of a molecular sieve.
    [0018] The present invention relates to an SCM-10 molecular sieve. The SCM-10 molecular sieve has the SFE structure, but with a chemical composition that has never been obtained in this field before.
    [0019] According to the present invention, the SCM-10 molecular sieve has an empirical chemical composition as illustrated by the Formula "the first oxide • the second oxide". It is known that a molecular sieve will sometimes (especially immediately after its production) contain a certain amount of water, however, this invention does not specify or identify how much this amount can be, as the presence or absence of water will not substantially alter the XRD pattern of the present molecular sieve. In this context, the empirical chemical composition currently represents an anhydrous chemical composition of this molecular sieve. Furthermore, it is obvious that the empirical chemical composition represents the structural chemical composition of the molecular sieve.
    [0020] According to the present invention, in the SCM-10 molecular sieve, the molar ratio of the first oxide to the second oxide is generally less than 40, preferably in the range of 3 to less than 40, more preferably of 5 to 30.
    [0021] According to the present invention, in the SCM-10 molecular sieve, the first oxide is at least one selected from the group consisting of silica and germanium dioxide, preferably silica.
    [0022] According to the present invention, in the SCM-10 molecular sieve, the second oxide is at least one selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, titanium oxide, oxides of rare earths, indium oxide and vanadium oxide, preferably boron oxide or a combination of boron oxide and at least one selected from the group consisting of alumina, iron oxide, gallium oxide, titanium oxide, rare earth oxides , indium oxide and vanadium oxide, more preferably boron oxide or a combination of boron oxide and alumina, most preferably boron oxide.
    [0023] According to an embodiment of the present invention, the first oxide is silica, and the second oxide is boron oxide.
    [0024] According to another embodiment of the present invention, the first oxide is at least one selected from the group consisting of silica and germanium dioxide, and the second oxide is boron oxide.
    [0025] According to another embodiment of the present invention, the first oxide is silica, and the second oxide is at least one selected from the group consisting of boron oxide and alumina.
    [0026] According to an embodiment of the present invention, if multiple oxides are used in combination, the molar ratio of having each of two oxides is generally from 1 to 99.6:99 to 0.4, preferably from 33 to 99 .5:67 to 0.5, more preferably from 50 to 99:50 to 1, more preferably from 60 to 99:40 to 1, more preferably from 66 to 98:34 to 2, most preferably from 66 to 97:34 to 3.
    [0027] According to the present invention, the molecular sieve in calcined form has an X-ray pattern by diffraction as substantially illustrated in the following table,
    a: ±0.3°.
    [0028] In addition, the X-ray diffraction pattern still includes X-ray diffraction peaks as substantially illustrated in the following table,
    a: ±0.3°.
    [0029] According to the present invention, the SCM-10 molecular sieve has a specific surface area (by the BET method) from 250 to 600 m2/g, preferably from 280 to 450 m2/g.
    [0030] According to the present invention, the SCM-10 molecular sieve has a micropore volume (by the t-plot method) from 0.05 to 0.25 cm3/g, preferably from 0.08 to 0.18 cm3/g.
    [0031] According to the present invention, the SCM-10 molecular sieve has a pore size (by the Argon adsorption method) from 0.6 to 0.73 nm, preferably from 0.62 to 0.68 nm .
    [0032] According to the present invention, the SCM-10 molecular sieve can be produced according to the following process. In view of this, the present invention further relates to a process for the production of the SCM-10 molecular sieve, including a step of crystallizing a mixture comprising a first oxide source, a second oxide source, an organic model and water (referred to as the mixture) under crystallization conditions to obtain the molecular sieve (hereinafter referred to as the crystallization step).
    [0033] According to the present invention, in the process for the production of the molecular sieve, the organic model can be a compound represented by the following Formula (A), a quaternary ammonium salt thereof or its quaternary ammonium hydroxide, preferably 4 -dimethylamino pyridine.

    [0034] According to the present invention, in Formula (A), R1 and R2 may be identical or different from each other, each independently represents a C1-8 alkyl, preferably a C1-4 alkyl, more preferably a C1 alkyl -2, most preferable both methyl.
    [0035] According to the present invention, as the quaternary ammonium salt of the compound represented by Formula (A), a quaternary nitrogen (N+) structure obtained by the additional bonding of a C1-8 alkyl (preferably an alkyl) can be exemplified. C1-4, more preferably a C1-2 alkyl or methyl) to the N atom in addition to the R1 and R2 groups. As a quaternary nitrogen counterion, a halo ion such as Br- can be exemplified, but not limiting.
    [0036] According to the present invention, as the quaternary ammonium hydroxide of the compound represented by Formula (A), a quaternary nitrogen (N+) structure can be exemplified by the additional bonding of a C1-8 alkyl (preferably a C1-4 alkyl, more preferably a C1-2 alkyl or methyl) to the N atom in addition to the R1 and R2 groups. As a quaternary nitrogen counterion, a hydroxyl ion (OH-) is required.
    [0037] According to the present invention, in the process for the production of the molecular sieve, the crystallization step can be conducted in any manner known in this field, a mode can be exemplified in which the first oxide source, the second oxide source, organic model and water are mixed in predetermined ratios, and then the obtained mixture is allowed to crystallize hydrothermally under the crystallization conditions.
    [0038] According to the present invention, in the process for producing the molecular sieve, the crystallization conditions include: a crystallization temperature from 140 to 210 degrees Celsius, preferably from 150 to 190 degrees Celsius, more preferably from 160 to 180 degrees Celsius, a crystallization duration from 10 to 10 days, preferably from 1 to 7 days, more preferably from 1 to 5 days, most preferably from 1 to 3 days.
    [0039] According to the present invention, in the process for the production of the molecular sieve, the first oxide source is at least that selected from the group consisting of a silicon source and a germanium source, preferably a silicon source .
    [0040] According to the present invention, in the process for producing the molecular sieve, the second oxide source is at least that selected from the group consisting of a source of aluminum, a source of boron, a source of iron, a source of gallium, a titanium source, a rare earth source, an indium source and a vanadium source, preferably a boron source or a combination of a boron source and at least one selected from the group consisting of a source of aluminum, an iron source, a gallium source, a titanium source, a rare earth source, an indium source and a vanadium source, most preferably a boron source, a combination of a boron source and a aluminum source, more preferably a boron source.
    [0041] According to the present invention, in the process for producing the molecular sieve as the first oxide source, any corresponding oxide source known in this field for this purpose can be used. For example, if the first oxide is silica, as the first oxide source (silicon source), silicic acid, silica gel, silica sol, sodium silicate or tetraalkoxysilane can be exemplified. If the first oxide is germanium dioxide, as the first oxide source (germanium source), then germanium tetraalkoxy, germanium dioxide, germanium nitrate can be exemplified. As the first source of oxide, a type or a mixture of two or more types in any relationship to each other can be used.
    [0042] According to the present invention, in the process for producing the molecular sieve as the second oxide source, any corresponding oxide source known in this field for this purpose can be used, including, but not limited to, oxides , alkoxides, oxometalates, acetates, oxalates, ammonium salts, sulfates and nitrates of the corresponding metal in the second oxide. For example, if the second oxide is alumina, as the second oxide source (aluminum source), aluminum hydroxide, sodium aluminate, aluminum salts, aluminum alkoxides, kaolin or montmorillonite can be exemplified. As aluminum salts, aluminum sulfate, aluminum nitrate, aluminum carbonate, aluminum phosphate, aluminum chloride or alum can be exemplified. As aluminum alkoxides, aluminum isopropoxide, aluminum ethoxide, aluminum butoxide can be exemplified. If the second oxide is boron oxide, as the second oxide source (boron source), boric acid, borate salt, borax, diboron trioxide can be exemplified. If the second oxide is iron oxide, as the second oxide source (iron source), ferric nitrate, ferric chloride, iron oxide can be exemplified. If the second oxide is gallium oxide, as the second oxide source (gallium source), gallium nitrate, gallium sulfate, gallium oxide can be exemplified. If the second oxide is titanium oxide, as the second oxide source (titanium source), titanium tetra alkoxide, titania, titanium nitrate can be exemplified. If the second oxide is rare earth oxides, as the second oxide source (rare earth source), lanthanum oxide, neodymium oxide, yttrium oxide, cerium oxide, lanthanum nitrate, neodymium nitrate can be exemplified, yttrium nitrate, ceric ammonium sulfate. If the second oxide is indium oxide, as the second oxide source (indium source), indium chloride, indium nitrate, indium oxide can be exemplified. If the second oxide is vanadium oxide, as the second oxide source (vanadium source), vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate can be exemplified. As the second source of oxide, one type or a mixture of two or more types in any relationship to each other can be used.
    [0043] According to an embodiment of the present invention, for the first oxide source, if multiple oxide sources are used in combination, the molar ratio between each of the two oxide sources is generally 1-99.6:99- 0.4, preferably 3399.5:67-0.5, more preferably 50-99:50-1, more preferably 6099:40-1, more preferably 66-98:34-2, most preferably 6697:34-3 .
    [0044] According to an embodiment of the present invention, for the second oxide source, if multiple oxide sources are used in combination, the molar ratio between each of the two oxide sources is generally 1-99.6:99- 0.4, preferably 3399.5:67-0.5, more preferably 50-99:50-1, more preferably 6099:40-1, more preferably 66-98:34-2, most preferably 6697:34-3 .
    [0045] According to an embodiment of the present invention, in the process for the production of the molecular sieve, from the point of facilitating the obtainment of the molecular sieve of the present invention, the mixture does not contain an alkaline source. As the alkaline source, alkaline substances can be exemplified except for the first oxide source, the second oxide source and the organic model, specifically any alkaline source conventionally used in this field to alkalinize the reaction system can be exemplified, more specifically it can be exemplified alkali metal containing inorganic alkali or alkaline earth metal as the cation, especially NaOH and KOH. In this document, by “does not contain an alkaline source” means unintentionally or purposefully introducing an alkaline source into the mixture.
    [0046] According to an embodiment of the present invention, in the process for the production of a molecular sieve, from the point of facilitating the obtainment of the molecular sieve of the present invention, the mixture does not contain a source of fluorine. As the fluorine source, fluoride or an aqueous solution thereof, especially HF, can be exemplified. In this article, by “does not contain a source of fluorine”, we do not intentionally or purposefully introduce a source of fluorine into the mixture.
    [0047] According to an embodiment of the present invention, in the process for the production of a molecular sieve, from the point of facilitating the obtainment of the molecular sieve of the present invention, at least at the beginning of the crystallization step, preferably throughout the In the crystallization step, mixing is controlled at pH = 6 to 14, preferably pH = 7 to 14, more preferably from 8 to 14, more preferably from 8.5 to 13.5, most preferably from 9 to 12.
    [0048] According to the present invention, in the process for the production of the molecular sieve, the molar ratio between the first oxide source (as the first oxide), the second oxide source (as the second oxide), the organic model and water is 1:(0.025-1/3):(0.01-1.0):(4-50), preferably 1:(1/30-1/3):(0.02-0.9 ):(4-40), more preferably 1:(1/30-1/5):(0.04-0.8):(4-30), with the proviso that the molar ratio of the first source of oxide (as the first oxide) to the second oxide source (as the second oxide) is less than 40, preferably less than 30.
    [0049] According to this invention, in the process, after completion of the crystallization step, any separation method conventionally known in this field can be used to isolate a molecular sieve from the reaction mixture obtained as the final product, whereby the molecular sieve of the present invention is obtained. As the separation method, a method can be exemplified in which the obtained reaction mixture is filtered, washed and dried. Here, filtration, washing and drying can be carried out in any manner conventionally known in this field. Specifically, like filtration, a simple suction method that filters the obtained reaction mixture can be exemplified. As for washing, a method of washing with deionized water can be exemplified. As for the drying temperature, a temperature of 40 to 250 degrees Celsius can be exemplified, preferably a temperature of 60 to 150 degrees Celsius, as for the duration of drying, a duration of 8 to 30 h can be exemplified, preferably a duration of 10 to 20 h. Drying can be carried out under normal pressure or a reduced pressure.
    [0050] According to this invention, in the process, if necessary, the obtained molecular sieve can be calcined in order to remove the organic model and any water therefrom, through which a calcined molecular sieve is obtained (i.e., the molecular sieve in calcined form), which also corresponds to the molecular sieve of the present invention. The calcination can be carried out in any manner conventionally known in the field, for example the calcination temperature is generally 300 to 800 degrees Celsius, preferably 400 to 650 degrees Celsius, while the calcination duration is generally 1 to 10 h , preferably from 3 to 6 h. Furthermore, calcination is generally conducted under an oxygen-containing atmosphere, for example under the air atmosphere or under the oxygen atmosphere.
    [0051] According to the present invention, the obtained molecular sieves can be used in any physical form, for example, powder, particulate or a molded product (for example, strip, clover). These physical forms can be obtained in any manner conventionally known in the field, without any specific limitation.
    [0052] The molecular sieve according to this invention can be combined with another material, through which a molecular sieve composition is obtained. Like these other materials, an active material and a non-active material can be exemplified. As active material, synthesized zeolites can be exemplified and natural zeolites, as non-active material (generally referred to as binder), clay, white earth, silica gel and alumina can be exemplified. As with these other materials, a grade or a mixture of two or more grades in any relationship to each other may be used. As for the quantity of these other materials, any conventional quantity used in this field can be used, without any specific limitation.
    [0053] The molecular sieve or molecular sieve composition of the present invention can be used as an adsorbent, for example, which is to be used in a gaseous or liquid phase to isolate at least one component of a mixture made up of multiple components. In this way, a part or substantially all of the at least one component can be isolated from the mixture. Specifically, a way can be exemplified in which the molecular sieve or molecular sieve composition is produced to come into contact with the mixture, whereby it selectively adsorbs this component.
    [0054] The molecular sieve or molecular sieve composition of the present invention can be directly or after treated or converted (for example, after ion exchange) in a manner conventionally used in this field with respect to a molecular sieve used as a catalyst to convert an organic compound (or as an active catalyst component thereof). Specifically, in accordance with the present invention, for example, reactants can be made to conduct a predetermined reaction in the presence of the catalyst to convert an organic compound to obtain the intended product. As the predetermined reaction, normal paraffin isomerization, liquid phase alkylation between benzene and ethylene to produce ethyl benzene, liquid phase alkylation between benzene and propene to produce iso-propyl benzene, butene isomerization, reaction of naphtha cracking, benzene alkylation with ethanol, hydration with cyclohexene, toluene disproportion to produce p-xylene, toluene alkylation with methanol to produce p-xylene or iso-propyl naphthalene disproportion to produce 2,6-di(isolatedly -propyl) naphthalene. In view of this, as the catalyst for the conversion of an organic compound, an alkane isomerization catalyst, a catalyst for the alkylation between olefins and aromatics, an olefin isomerization catalyst, a naphtha cracking catalyst, a catalyst for the alkylation between alcohols and aromatics, an olefin hydration catalyst or an aromatic disproportionate catalyst. EXAMPLE
    [0055] The following examples illustrate rather than limit the invention. Example 1
    [0056] 10.995 g of the organic model 4-dimethylamino pyridine, 54.0 g of water, 1.879 g of boric acid, 22.5 g of silica sol (containing 40% by weight SiO2) were mixed until homogeneous, to obtain obtain a mixture with a ratio (molar ratio) of: SiO2/B2O3= 10 4-dimethylamino pyridine /SiO2 = 0.6 H2O/SiO2 = 25 and then loaded into a stainless steel reactor, under stirring at 175 degrees Celsius crystallized during 3 days, after completion of crystallization, filtered, washed, dried to obtain a molecular sieve precursor, and then the precursor was at 650 degrees Celsius with calcined air for 6 hours to obtain a molecular sieve.
    [0057] The XRD data of the resulting molecular sieve were listed in table 1, and the XRD pattern was as illustrated in Fig.1.
    [0058] The resulting molecular sieve has a specific surface area of 297 m2/g, a micropore volume of 0.11 cm3/g.
    [0059] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 16.2. Table 1

    Example 2
    [0060] 36.651 g of the organic template 4-dimethylamino pyridine, 45 g of water, 3.488 g of germanium dioxide, 3.34 g of boric acid, 75 g of silica sol (containing 40% by weight SiO2) were mixed until than homogeneous, to obtain a mixture with a ratio (molar ratio) of: (SiO2+GeO2)/B2O3 = 20 4-dimethylamino pyridine /SiO2 = 0.6 H2O/SiO2= 10 and then loaded into a stainless steel reactor , under stirring at 180 degrees Celsius, crystallized for 2 days, after completion of the crystallization, filtered, washed, dried, to obtain a molecular sieve in the synthesized form.
    [0061] The XRD data of the resulting molecular sieve were listed in table 2 while the XRD pattern is similar to Fig.1.
    [0062] The resulting molecular sieve has a specific surface area of 342 m2/g, a micropore volume of 0.12 cm3/g.
    [0063] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 25.2. Table 2

    Example 3
    [0064] 109.95 g of the organic model 4-dimethylamino pyridine, 540 g of water, 9.394 g of boric acid, 3.939 g of aluminum hydroxide, 225.0 g of silica sol (containing 40% by weight SiO2) were mixed until homogeneous, to obtain a mixture with a ratio (molar ratio) of: SiO2/(B2O3+Al2O3) = 15 4-dimethylamino pyridine /SiO2 = 0.6 H2O/SiO2 = 25 and then charged into a reactor stainless steel, under stirring at 170 degrees Celsius crystallized for 3 days, after completion of crystallization, filtered, washed, dried, and then the precursor was at 650 degrees Celsius with calcined air for 6 hours to obtain a molecular sieve.
    [0065] The XRD data of the resulting molecular sieve were listed in table 3 while the XRD pattern is similar to Fig.1.
    [0066] The resulting molecular sieve has a specific surface area of 321 m2/g, a micropore volume of 0.13 cm3/g.
    [0067] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3= 25.2, SiO2/Al2O3 = 63.0. Table 3

    Example 4
    [0068] Similar to Example 2, except that SiO2/GeO2 = 19.2,(SiO2+GeO2)/B2O3 = 35.2, 4-dimethylamino pyridine /SiO2 = 0.8, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 70 hours.
    [0069] The XRD data of the resulting molecular sieve were listed in table 4 while the XRD pattern is similar to Fig.1.
    [0070] The resulting molecular sieve has a specific surface area of 297 m2/g, a micropore volume of 0.11 cm3/g.
    [0071] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 35.2. Table 4

    Example 5
    Similar to Example 1, except that SiO2/B2O3 = 27, 4-dimethylamino pyridine /SiO2 = 0.3, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 3 days.
    [0073] The XRD data of the resulting molecular sieve were listed in table 5 while the XRD pattern is similar to Fig.1.
    [0074] The resulting molecular sieve has a specific surface area of 343 m2/g, a micropore volume of 0.13 cm3/g.
    [0075] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 31.5. Table 5
    Example 6
    Similar to Example 1, except that SiO2/B2O3 = 20.4, 4-dimethylamino pyridine /SiO2 = 0.2, H2O/SiO2 = 30, at 170 degrees Celsius crystallized for 80 hours.
    [0077] The XRD data of the resulting molecular sieve were listed in table 6 while the XRD pattern is similar to Fig.1.
    [0078] The resulting molecular sieve has a specific surface area of 347 m2/g, a micropore volume of 0.12 cm3/g.
    [0079] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 28.0. Table 6

    Example 7
    Similar to Example 1, except that SiO2/B2O3 = 10, 4-dimethylamino pyridine /SiO2 = 0.4, H2O/SiO2 =17.5, at 170 degrees Celsius crystallized for 2 days.
    [0081] The XRD data of the resulting molecular sieve were listed in table 7 while the XRD pattern is similar to Fig.1.
    [0082] The resulting molecular sieve has a specific surface area of 357 m2/g, a micropore volume of 0.13 cm3/g.
    [0083] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 14.2. Table 7

    Example 8
    Similar to Example 1, except that SiO2/B2O3 = 5,4-dimethylamino pyridine /SiO2 = 0.5, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 66 hours.
    [0085] The XRD data of the resulting molecular sieve were listed in table 8 while the XRD pattern is similar to Fig.1.
    [0086] The resulting molecular sieve has a specific surface area of 342 m2/g, a micropore volume of 0.12 cm3/g.
    [0087] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcination has SiO2/B2O3 = 12.1. Table 8

    Example 9
    Similar to Example 1, except that SiO2/B2O3 = 35.4-dimethylamino pyridine /SiO2 = 0.36, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 3 days.
    [0089] The XRD data of the resulting molecular sieve were listed in table 9 while the XRD pattern is similar to Fig.1.
    [0090] The resulting molecular sieve has a specific surface area of 331 m2/g, a micropore volume of 0.12 cm3/g.
    [0091] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 39.5. Table 9

    Example 10
    [0092] Similar to Example 3, except that aluminum sulfate was used as the source of aluminum, SiO2/(Al2O3+B2O3) = 20, 4-dimethylamino pyridine /SiO2 = 0.4, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 3 days.
    [0093] The XRD data of the resulting molecular sieve were listed in table 10 while the XRD pattern is similar to Fig.1.
    [0094] The resulting molecular sieve has a specific surface area of 288 m2/g, a micropore volume of 0.09 cm3/g.
    [0095] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3= 35.2, SiO2/Al2O3 = 63.3. Table 10
    Example 11
    [0096] Similar to Example 1, except that HF was added as the fluorine source, SiO2/B2O3 = 15, 4-dimethylamino pyridine /SiO2 = 0.5, F/SiO2 = 0.4, H2O/SiO2 = 25, at 170 degrees Celsius crystallized for 60 hours.
    [0097] The XRD data of the resulting molecular sieve were listed in table 11 while the XRD pattern is similar to Fig.1.
    [0098] The resulting molecular sieve has a specific surface area of 318 m2/g, a micropore volume of 0.10 cm3/g.
    [0099] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcining has SiO2/B2O3 = 21.2. Table 11
    Example 12
    [00100] Similar to Example 1, except that tetra-n-butyl titanate was added as the titanium source, SiO2/B2O3 = 10, SiO2/TiO2 = 30, 4-dimethylamino pyridine /SiO2 = 0.8, H2O/ SiO2 = 25, at 170 degrees Celsius crystallized for 3 days.
    [00101] The XRD data of the resulting molecular sieve has been listed in table 12 while the XRD pattern is similar to Fig.1.
    [00102] The resulting molecular sieve has a specific surface area of 335 m2/g, a micropore volume of 0.10 cm3/g.
    [00103] If determined by inductively coupled plasma atomic emission spectroscopy (ICP), the sample after calcination has SiO2/B2O3 = 16.2, SiO2/TiO2 = 39.1. Table 12

    Example 13
    [00104] 30 g of the molecular sieve produced in Example 3 in powder form were ionically exchanged for an aqueous solution of ammonium nitrate (with a concentration of 1 mol/L) for 4 times, filtered and dried at 110 degrees Celsius, calcined at 500 degrees Celsius with air for 6 hours. Then, 1.5 g of the calcined molecular sieve was loaded into a 100 ml stainless steel reactor, still introducing 35 g of iso-propyl naphthalene and the reactor was closed. At 250 °C, under stirring at 200 rpm, the reaction was carried out for 48 hours. After completion of the reaction, the system was cooled to room temperature, after centrifugal isolation of the molecular sieve powder, the reaction product was analyzed on an Agilent 19091N-236 gas chromatograph, indicating a conversion of iso-propyl naphthalene to 26.82% and a total selectivity for the planned product 2,6-di(isopropyl) naphthalene and 2,7-di(isopropyl) naphthalene of 74.88%.
    权利要求:
    Claims (10)
    [0001]
    1. SCM-10 molecular sieve, characterized by the fact that it has an empirical chemical composition as illustrated by the Formula "the first oxide • the second oxide", in which the molar ratio of the first oxide to the second oxide is less than 40, preferably in the range from 3 to less than 40, more preferably from 5 to 30, the first oxide is silica, the second oxide is boron oxide or a combination of boron oxide and at least one selected from the group consisting of alumina and titanium oxide, more preferably boron oxide or a combination of boron oxide and alumina, most preferably boron oxide, and the molecular sieve in calcined form has an X-ray diffraction pattern as substantially illustrated in the following table,
    [0002]
    2. SCM-10 molecular sieve according to claim 1, characterized in that the X-ray diffraction pattern further includes X-ray diffraction peaks as substantially illustrated in the following table,
    [0003]
    3. Process for the production of an SCM-10 molecular sieve, as defined in claim 1, characterized in that it includes a step of crystallizing a mixture comprising a first oxide source, a second oxide source, an organic model and water to obtain the molecular sieve and, optionally, a calcination step of the obtained molecular sieve, in which the organic model is selected from a compound represented by the following Formula (A), a quaternary ammonium salt thereof and its quaternary ammonium hydroxide , preferably 4-dimethylamino pyridine,
    [0004]
    4. Process according to claim 3, characterized in that the mixture does not contain an alkaline source.
    [0005]
    5. Process according to claim 3, characterized in that the mixture does not contain a source of fluorine.
    [0006]
    6. Process according to claim 3, characterized in that the mixture has a pH = 6 to 14, preferably pH = 7 to 14, more preferably from 8 to 14, more preferably from 8.5 to 13.5 , more preferably from 9 to 12, more preferably from 9 to 11.
    [0007]
    7. Process according to claim 3, characterized in that the molar ratio between the first oxide source (as the first oxide), the second oxide source (as the second oxide), the organic model and the water is 1:(1/30-1/3):(0.02-0.9):(4-40), more preferably 1:(1/30-1/5): (0.04-0.8 ):(4-30).
    [0008]
    8. SCM-10 molecular sieve composition, characterized in that it comprises the SCM-10 molecular sieve as defined in claim 1 or an SCM-10 molecular sieve produced according to the process as defined in claim 3, and a binder.
    [0009]
    Use of the SCM-10 molecular sieve as defined in claim 1, of an SCM-10 molecular sieve produced according to the process as defined in claim 3, or of the SCM-10 molecular sieve composition as defined in claim 8, characterized because it is like an adsorbent or a catalyst for the conversion of an organic compound.
    [0010]
    10. Use according to claim 9, characterized in that the catalyst for converting an organic compound is at least one selected from the group consisting of an alkane isomerization catalyst, a catalyst for the alkylation between olefins and aromatics, a olefin isomerization catalyst, a naphtha cracking catalyst, a catalyst for the alkylation between alcohols and aromatics, an olefin hydration catalyst and an aromatic disproportionate catalyst.
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    同族专利:
    公开号 | 公开日
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    EP3165282A1|2017-05-10|
    SG10201609391UA|2017-06-29|
    ES2711549T3|2019-05-06|
    JP6669633B2|2020-03-18|
    BR102016026121A2|2017-07-11|
    US20170128923A1|2017-05-11|
    KR20170058287A|2017-05-26|
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    法律状态:
    2017-07-11| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2020-01-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-23| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-07-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-14| 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 08/11/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201510755226.7|2015-11-09|
    CN201510755226|2015-11-09|
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