CN111484031A - Modified titanium silicalite molecular sieve, preparation method and application thereof, and thioether oxidation method - Google Patents
Modified titanium silicalite molecular sieve, preparation method and application thereof, and thioether oxidation method Download PDFInfo
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- CN111484031A CN111484031A CN201910081707.2A CN201910081707A CN111484031A CN 111484031 A CN111484031 A CN 111484031A CN 201910081707 A CN201910081707 A CN 201910081707A CN 111484031 A CN111484031 A CN 111484031A
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- Prior art keywords
- molecular sieve
- silicon
- titanium
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- titanium silicalite
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 168
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000000034 method Methods 0.000 title claims abstract description 83
- 150000003608 titanium Chemical class 0.000 title claims abstract description 52
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 74
- 239000010703 silicon Substances 0.000 claims abstract description 73
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 56
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010936 titanium Substances 0.000 claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003513 alkali Substances 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
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- 239000012265 solid product Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 46
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 39
- 238000009826 distribution Methods 0.000 claims description 31
- 230000002378 acidificating effect Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/643—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
Abstract
The invention relates to the field of molecular sieves, and discloses a modified titanium silicalite molecular sieve, a preparation method and application thereof, and a thioether oxidation method, wherein the molecular sieve comprises the following components: titanium element, aluminum element, silicon element and oxygen element, wherein the molecular sieve satisfies X1‑1.8/X0.4‑0.9＝C，0.1<C<0.5. The preparation method of the molecular sieve comprises the following steps: (1) carrying out acid steam modification on the titanium silicalite molecular sieve; (2) mixing and contacting the titanium-silicon molecular sieve modified in the step (1) with an aluminum source, an alkali source and water; (3) carrying out heat treatment on the solid product obtained in the step (2) in an alkaline steam atmosphere. The modified titanium silicalite molecular sieve provided by the invention is used for thioether oxidation, and the selectivity of sulfone can be effectively improved.
Description
Technical Field
The invention relates to the field of molecular sieves, in particular to a modified titanium silicalite molecular sieve, a preparation method and application thereof, and a thioether oxidation method.
Background
The titanium-silicon molecular sieve is a molecular sieve with a framework composed of silicon, titanium and oxygen elements, and has wide application prospect in petroleum refining and petrochemical industry. Wherein, the TS-1 molecular sieve is a novel titanium silicalite molecular sieve with excellent catalytic selective oxidation performance formed by introducing a transition metal element titanium into a molecular sieve framework with a ZSM-5 structure.
TS-1 not only has the catalytic oxidation effect of titanium, but also has the shape-selective effect and excellent stability of ZSM-5 molecular sieve. Although titanium silicalite molecular sieves have achieved industrial applications in certain catalytic oxidation fields (e.g., the process for preparing cyclohexanone oxime by catalytic ammoxidation of cyclohexanone), the titanium silicalite molecular sieves have poor catalytic performance, which makes them limited in other industrial applications.
Sulfones are important sulfur-containing compounds, such as dimethyl sulfone, which is a white crystalline powder, readily soluble in water, ethanol, benzene, methanol and acetone, and slightly soluble in ethers. Dimethyl sulfone is industrially used as a high-temperature solvent and raw material for organic synthesis, a gas chromatography stationary liquid, an analytical reagent, a food additive, and a drug. Dimethyl sulfone, as an organic sulfide, has the functions of enhancing the human body's ability to produce insulin, and promoting the metabolism of saccharides, and is an essential substance for the synthesis of human collagen.
At present, the sulfone can be prepared by a thioether oxidation method, and when the thioether is oxidized by an oxidizing agent (especially peroxide), the oxidation product is mainly a mixture of sulfoxide and sulfone. Therefore, modulating the selectivity of the target product (sulfone) according to the production needs is an important research content in the thioether oxidation process.
Disclosure of Invention
The invention aims to overcome the problem of low sulfone selectivity in the thioether oxidation process in the prior art, and provides a modified titanium silicalite molecular sieve, a preparation method and application thereof, and a thioether oxidation method. The modified titanium silicalite molecular sieve provided by the invention is used for thioether oxidation, and the selectivity of sulfone can be effectively improved.
In order to achieve the above object, a first aspect of the present invention provides a modified titanium silicalite molecular sieve comprising: titanium element, aluminum element, silicon element and oxygen element, wherein the molecular sieve satisfies X1-1.8/X0.4-0.9＝C，0.1<C<0.5，X0.4-0.9The ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter, X1-1.8Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 1-1.8nm in the distribution quantity of the pore diameter of the total micropores.
Preferably, the surface silicon-titanium ratio of the molecular sieve is not lower than the bulk silicon-titanium ratio, the silicon-titanium ratio refers to the molar ratio of silicon oxide to titanium oxide, and further preferably, the ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is 1.2-5.
In a second aspect, the present invention provides a method for preparing the above modified titanium silicalite molecular sieve, the method comprising:
(1) carrying out acid steam modification on the titanium silicalite molecular sieve;
(2) mixing and contacting the titanium-silicon molecular sieve modified in the step (1) with an aluminum source, an alkali source and water;
(3) and (3) carrying out heat treatment on the solid product obtained in the step (2) in an alkaline steam atmosphere.
Preferably, a silicon source is further added in the contacting process in the step (2), more preferably, the silicon source is an organic silicon source, and still more preferably, the hydrolysis rate of the organic silicon source is 40-60%.
In a third aspect, the invention provides the use of the modified titanium silicalite molecular sieve of the invention in the oxidation of thioethers.
According to a fourth aspect of the present invention, there is provided a thioether oxidation process comprising: under the condition of thioether oxidation, a liquid mixture is contacted with a catalyst, wherein the liquid mixture contains thioether, at least one oxidant and optionally at least one solvent, and the catalyst contains the modified titanium silicalite molecular sieve or the modified titanium silicalite molecular sieve prepared by the preparation method.
The modified titanium silicalite molecular sieve with the special physical and chemical characteristic structure is used for thioether oxidation reaction, and can obtain better catalytic effect. Namely, since the material of the present invention has a pore size distribution of micropores in the range of 1 to 1.8nm, and X1-1.8/X0.4-0.9＝C，0.1<C<0.5, the catalyst is beneficial to the diffusion of reactant and product molecules in the catalytic reaction, is beneficial to the oxidation reaction of thioether, and can effectively modulate the selectivity of the target product sulfone.
During research, the inventors of the present invention found that the modified titanium silicalite molecular sieve having a specific characteristic structure of the present invention, for example, having a pore size distribution of micropores in the range of 1 to 1.8nm, can be prepared by subjecting the titanium silicalite molecular sieve to acidic steam modification, then mixing and contacting with an aluminum source, an alkali source and water, and then performing heat treatment under an alkaline steam atmosphere.
Under the preferable condition of the invention, in the contacting process of the step (2), an optional silicon source is introduced simultaneously, so that the ratio of silicon to titanium on the surface of the modified titanium silicalite molecular sieve is not lower than the ratio of silicon to titanium on the bulk phase, and the obtained modified titanium silicalite molecular sieve is used for thioether oxidation reaction, thereby being more favorable for effectively modulating the selectivity of the target product sulfone.
The modified titanium silicalite molecular sieve provided by the invention has a special physicochemical characteristic structure, is used for thioether oxidation reaction, and is favorable for modulating the selectivity of a target product (sulfone).
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a modified titanium silicalite molecular sieve, which comprises the following components: element, aluminum element, silicon element and oxygen element, wherein the molecular sieve satisfies X1-1.8/X0.4-0.9＝C，0.1<C<0.5，X0.4-0.9The ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter, X1-1.8Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 1-1.8nm in the distribution quantity of the pore diameter of the total micropores.
According to a preferred embodiment of the present invention, 0.25<C<0.5. The molecular sieve provided by the invention has pore diameter distribution within the range of 0.4-0.9nm and also has distribution within the range of 1-1.8nm, the ratio of the proportion of the pore diameter of micropores within the range of 1-1.8nm to the total pore diameter distribution of micropores within the range of 0.4-0.9nm is C, and the ratio of the pore diameter of micropores within the range of 0.1 to the total pore diameter distribution of micropores is C<C<0.5, preferably, 0.25<C<0.5, further preferably 0.3<C<0.5. When the molecular sieve of the preferred technical scheme is used for thioether oxidation reaction, the molecular sieve is more beneficial to the diffusion of reactant and product molecules in the catalytic reaction, not only can the conversion rate of an oxidant (such as peroxide) be further improved, but also the selectivity of a target product (such as sulfone) can be more effectively modulated. In the present invention, the pore size of the micropores can be measured by a conventional method, and the method of the present invention has no particular requirement and is well known to those skilled in the art, for example, by using N2Static adsorption and the like. In the present invention, the pore size distribution was measured on an ASAP2405 static nitrogen adsorber from Micromeritics.
It is to be noted that, in particular, if the proportion of the pore size distribution of the micropores to the total pore size distribution of the micropores is in the range of 1 to 1.8nm<At 1%, the pore distribution of the micropores is negligible, i.e. no micropore distribution in the range of 1-1.8nm is considered, as known to the person skilled in the art. Thus, the invention is described in N2The pore diameter of the micropores in the range of 1-1.8nm in the static adsorption test refers to the proportion of the pore diameter distribution of the micropores in the range of 1-1.8nm to the total pore diameter distribution>1 percent. Conventional direct hydrothermal synthesisThe prepared microporous molecular sieve has the ratio of the pore size distribution of micropores to the total pore size distribution in the range of 1-1.8nm<1 percent of microporous molecular sieve which is treated and modified by a common treatment and modification method and has a lower proportion of the distribution of the pore diameters of the micropores in the range of 1-1.8nm in the distribution of the pore diameters of the total micropores, namely<10%, typically<1％。
The molecular sieve according to the invention, preferably said molecular sieve satisfies Tw/Tk＝D，0.2<D<0.5, further preferably 0.25<D<0.45, wherein, TwIs the micropore volume of the molecular sieve, TkIs the total pore volume of the molecular sieve. In the present invention, the pore volume can be measured by a conventional method, and the present invention is not particularly limited and is well known to those skilled in the art, for example, by using N2Static adsorption and the like.
According to the molecular sieve of the present invention, preferably, the molecular sieve has a silicon element: titanium element: the molar ratio of aluminum elements is 100: (0.1-10): (0.01-5), preferably 100: (0.2-5): (0.2-4), and more preferably silicon element: titanium element: the molar ratio of aluminum elements is 100: (0.5-4): (0.5-4), most preferably silicon: titanium element: the molar ratio of aluminum elements is 100: (1-4): (0.5-4).
In the invention, the contents of titanium element, silicon element and aluminum element in the molecular sieve are measured by adopting an X-ray fluorescence spectrum analysis method (XRF). The test methods are performed according to conventional methods without special requirements, which are well known to those skilled in the art and will not be described herein.
According to the modified titanium silicalite molecular sieve, the surface silicon-titanium ratio of the molecular sieve is preferably not lower than the bulk silicon-titanium ratio, wherein the silicon-titanium ratio refers to the molar ratio of silicon oxide to titanium oxide; further preferably, the ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is 1.2-5; more preferably, the ratio of the surface silicon to titanium ratio to the bulk silicon to titanium ratio is 1.5-4.5.
In the invention, the surface silicon-titanium ratio is measured by adopting an X-ray photoelectron spectroscopy, and the bulk silicon-titanium ratio is measured by adopting an X-ray fluorescence spectroscopy.
The modified titanium-silicon molecular sieve has the advantages of micropore size distribution in the range of 1-1.8nm, and preferably, the surface silicon-titanium ratio is not lower than the bulk silicon-titanium ratio. The invention has no special requirements on the preparation method of the modified titanium silicalite molecular sieve, and only needs to be capable of preparing the modified titanium silicalite molecular sieve with the structure.
The invention also provides a preparation method of the modified titanium silicalite molecular sieve, which comprises the following steps:
(1) carrying out acid steam modification on the titanium silicalite molecular sieve;
(2) mixing and contacting the titanium-silicon molecular sieve modified in the step (1) with an aluminum source, an alkali source and water;
(3) and (3) carrying out heat treatment on the solid product obtained in the step (2) in an alkaline steam atmosphere.
According to a specific embodiment of the present invention, the acidic vapor modification refers to contacting a titanium silicalite molecular sieve with acidic vapor. Preferably, the acid steam modification of step (1) comprises: and contacting the titanium-silicon molecular sieve with acid steam to modify the acid steam.
The source of the acid vapor in the present invention is not particularly limited, and any method for obtaining the acid vapor may be used. Specifically, the acid vapor may be formed by heating an aqueous acid solution, or may be formed by passing superheated steam through an aqueous acid solution. The present invention is exemplified by heating an aqueous acid solution to obtain an acid vapor.
Preferably, the acidic steam is obtained by heating an aqueous acid solution, wherein the concentration of the aqueous acid solution is more than 0.1 mol/L, more preferably more than or equal to 1 mol/L, and even more preferably 1-15 mol/L.
Preferably, the acid in the aqueous acid solution is an organic acid and/or an inorganic acid, more preferably an inorganic acid; wherein, the inorganic acid can be one or more of HCl, sulfuric acid, perchloric acid, nitric acid and phosphoric acid; the organic acid can be C1-C10 organic carboxylic acid, preferably one or more of formic acid, acetic acid, propionic acid, naphthenic acid, peroxyacetic acid and peroxypropionic acid.
According to a preferred embodiment of the invention, the temperature of the acid steam modification is in the range of 40 to 200 ℃, more preferably 60 to 180 ℃, even more preferably 80 to 150 ℃.
According to the method of the present invention, the time for the acid steam modification can be determined as required, and for the present invention, the time is preferably 0.5 to 360 hours, more preferably 1 to 240 hours, and still more preferably 2 to 120 hours.
According to the method of the present invention, preferably, the molar ratio of the titanium silicalite molecular sieve to the acid vapor is 100: (0.5-40), more preferably 100: (1-15), more preferably 100: (5-15), most preferably 100: (5-12), wherein the titanium silicalite is SiO2Acid steam is counted as H+And (6) counting.
According to the method of the present invention, preferably the method of the present invention further comprises: before the titanium silicalite molecular sieve is modified by acidic steam, the titanium silicalite molecular sieve is roasted. In the present invention, the optional range of the calcination conditions is wide, and for the present invention, the calcination conditions preferably include: the roasting temperature is 300-800 ℃, preferably 550-600 ℃; the roasting time is 2-12h, preferably 2-4h, and the roasting atmosphere comprises air atmosphere.
The process of the present invention, step (1), may be carried out in a fixed bed reactor.
In the invention, specifically, after the acidic steam passes through the titanium silicalite molecular sieve in the fixed bed reactor, the acidic steam can be returned to the process of forming the acidic steam for recycling, and the acidic steam passing through the titanium silicalite molecular sieve in the fixed bed reactor can be directly introduced into the fixed bed reactor again to carry out acidic steam modification on the titanium silicalite molecular sieve.
In the present invention, the aluminum source is a substance capable of providing aluminum, and preferably the aluminum source is one or more of aluminum sol, aluminum salt, aluminum hydroxide and alumina, and the aluminum sol is preferably contained in an amount of 10 to 50 wt% based on the alumina.
In the present invention, the aluminum salt may be an inorganic aluminum salt, which may be one or more of aluminum sulfate, sodium metaaluminate, aluminum chloride and aluminum nitrate, and/or an organic aluminum salt, which is preferably an organic aluminum salt having C1-C10.
According to a preferred embodiment of the present invention, in step (2), the modified titanium silicalite molecular sieve: an aluminum source: alkali source: the molar ratio of water is 100: (0-10): (0.5-50): (20-1000), further preferably the modified titanium silicalite molecular sieve: an aluminum source: alkali source: the molar ratio of water is 100: (0.2-5): (1-20): (100-800), the modified titanium silicalite molecular sieve is further preferred: an aluminum source: alkali source: the molar ratio of water is 100: (0.5-3): (5-15): (200-600), wherein the modified titanium-silicon molecular sieve is SiO2Calculated by Al as the aluminum source2O3The alkali source is N or OH-And (6) counting.
According to the method of the present invention, the variety of the alkali source is wide, and the alkali source can be an organic alkali source and/or an inorganic alkali source, wherein the inorganic alkali source can be ammonia, or alkali whose cation is alkali metal or alkaline earth metal, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, etc., and the organic alkali source can be one or more of urea, aliphatic amine compound, aliphatic alcohol amine compound, and quaternary ammonium base compound. Preferably, the alkali source is one or more of ammonia, an aliphatic amine, an aliphatic alcohol amine and a quaternary ammonium base.
In the invention, the quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH3In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), which may be a variety of NH3Wherein at least one hydrogen is substituted with a hydroxyl-containing aliphatic hydrocarbon group (preferably an alkyl group).
Specifically, the quaternary ammonium base may be a quaternary ammonium base represented by formula II, the aliphatic amine may be an aliphatic amine represented by formula III, and the aliphatic alcohol amine may be an aliphatic alcohol amine represented by formula IV:
in the formula II, R5、R6、R7And R8Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r5、R6、R7And R8Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R9(NH2)n(formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R9Is C1～C6Alkyl of (2) including C1～C6Straight chain alkyl of (2) and C3-C6Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R9Is C1-C6Alkylene of (2) including C1～C6Linear alkylene of (A) and (C)3～C6Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene. More preferably, the aliphatic amine compound is one or more of ethylamine, n-butylamine, butanediamine and hexamethylenediamine
(HOR10)mNH(3-m)(formula IV)
In the formula IV, m are R10Are the same or different and are each C1-C4Alkylene of (2) including C1-C4Linear alkylene of (A) and (C)3-C4Branched alkylene groups of (a), such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. More preferably, the aliphatic alcohol amine compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
According to a preferred embodiment of the present invention, in order to further improve the pore order of the synthesized modified titanium silicalite molecular sieve, the alkali source is preferably one or more of sodium hydroxide, ammonia water, ethylenediamine, n-butylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
Wherein, when the alkali source contains ammonia water, the mol ratio of the alkali source includes NH in molecular form3And NH in ionic form4 +The presence of ammonia.
In the present invention, the alkali source contains both N and OH-When, without particular reference, the alkali source is OH-And (6) counting.
According to the process of the present invention, preferably the alkali source is provided in the form of an alkali solution, more preferably an alkali solution having a pH > 9.
According to the method of the present invention, in the step (2), preferably, the titanium silicalite molecular sieve modified in the step (1) is mixed with an aluminum source, an alkali source and water for contacting for a period of time, and preferably, the contacting conditions include: the contact temperature is 20 to 80 ℃, more preferably 40 to 70 ℃, and the contact time is 0.5 to 12 hours, more preferably 1 to 8 hours.
According to the method of the present invention, in the step (3), the source of the alkaline steam atmosphere is not particularly limited. Specifically, the alkaline steam atmosphere may be provided by alkaline steam. In the present invention, the source of the alkaline steam is not particularly limited, and the alkaline steam may be formed by heating the alkaline aqueous solution to form the acidic steam, or may be formed by passing superheated steam through the alkaline aqueous solution. The present invention is exemplified by heating an aqueous alkaline solution to obtain an alkaline vapor.
According to a preferred embodiment of the invention, the concentration of the alkaline aqueous solution is more than 0.1 mol/L, preferably more than or equal to 1 mol/L, and further preferably 1 to 10 mol/L. in the invention, the main solvent of the alkaline aqueous solution is water, and other solvent auxiliaries can be added according to the needs.
The alkali in the alkaline aqueous solution of the present invention may be selected from the same range as the alkali source in the step (2), and the alkali may be the same as or different from the alkali source in the step (2).
According to a preferred embodiment of the present invention, the concentration of the alkaline gas in the alkaline vapor (which can be formed by heating an alkaline aqueous solution) is 0.02 to 50% by volume, preferably 0.1 to 25% by volume, more preferably 3 to 10% by volume.
Step (3) of the present invention may be carried out in a fixed bed reactor or a reaction vessel. The specific implementation manner of performing the heat treatment on the solid product (which can be obtained by filtering and separating) obtained in the step (2) in the alkaline steam atmosphere in the step (3) may be to obtain alkaline steam by heating an alkaline aqueous solution, and introduce the alkaline steam into the reaction kettle to provide an alkaline steam atmosphere.
According to a preferred embodiment of the present invention, in the step (3), the heat treatment conditions include: the temperature is 100-200 ℃, more preferably 120-180 ℃, and still more preferably 140-170 ℃.
According to the method of the present invention, the time of the heat treatment is preferably determined as required, and for the present invention, the time of the heat treatment is preferably 0.5 to 96 hours, preferably 2 to 48 hours, and more preferably 6 to 24 hours.
According to the process of the present invention, it is preferred that the pressure of the heat treatment is 0 to 5MPa, more preferably 0.2 to 2MPa, still more preferably 1 to 1.5MPa, the pressure being in gauge pressure.
According to the method of the present invention, preferably the method of the present invention further comprises: and (4) roasting the molecular sieve obtained in the step (3). The conditions for the calcination can be selected widely, and for the present invention, preferred conditions for the calcination include: the roasting temperature is 300-800 ℃, preferably 350-600 ℃; the roasting time is 2-12h, preferably 2-4h, and the roasting atmosphere comprises an air atmosphere; more preferably, the firing conditions include: firstly, roasting at the temperature of 450-600 ℃ in a nitrogen atmosphere for 0.5-6h, and then roasting at the temperature of 450-600 ℃ in an air atmosphere for 0.5-12 h.
According to a preferred embodiment of the present invention, a silicon source is further added during the contacting in step (2), the silicon source is not particularly limited in the present invention, and may be any substance capable of providing silicon element in the art, for example, the silicon source may be an organic silicon source and/or an inorganic silicon source, and is further preferably an organic silicon source.
Specifically, the organic silicon source may be, for example, one or more selected from silicon-containing compounds represented by formula I,
in the formula I, R1、R2、R3And R4Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r1、R2、R3And R4Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Specifically, the organic silicon source may be one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, and tetra-n-butyl orthosilicate. Tetraethyl orthosilicate or methyl orthosilicate are used as examples in the specific embodiments of the invention, but do not limit the scope of the invention accordingly.
According to the method of the present invention, the optional range of the types of the inorganic silicon source is wide, and for the present invention, the inorganic silicon source is preferably silica sol and/or silica gel, and the silica gel or silica sol in the present invention may be silica gel or silica sol obtained by various production methods in various forms.
According to a preferred embodiment of the present invention, the hydrolysis rate of the organic silicon source is 40 to 60%. In the prior art, in the process of synthesizing the molecular sieve by using the organic silicon source, the organic silicon source needs to be hydrolyzed, and the hydrolysis rate of the organic silicon source is usually more than 70 wt%, and most of the hydrolysis rate is more than 90 wt%. In the preferred case of the invention, the hydrolysis rate of the organic silicon source is controlled to be 40-60 wt%, preferably 40-50 wt%, which is more favorable for regulating and controlling the pore size distribution of the modified titanium-silicon molecular sieve and is more favorable for improving the catalytic performance of the molecular sieve.
In the present invention, the hydrolysis ratio of the organic silicon source refers to the weight percentage of the hydrolyzed organic silicon source in the mixture obtained by mixing in step (2) with respect to the weight percentage of the organic silicon source charged at the time of mixing. By a hydrolyzable organosilicon source is meant an organosilicon source in which at least one of the hydrolyzable groups attached to the silicon atom in the organosilicon source is hydrolyzed to form a hydroxyl group. In the present invention, the hydrolysis rate can be calculated by measuring the amount of the hydrolyzed organic silicon source in the mixture by a conventional quantitative analysis method such as gas chromatography.
According to a preferred embodiment of the invention, SiO is used2The molar ratio of the modified titanium-silicon molecular sieve to the silicon source is 100: (0.1 to 10), more preferably 100: (0.5-5), most preferably 100: (1-5). By adopting the preferred embodiment of the invention, the surface silicon-titanium ratio of the obtained molecular sieve material is not lower than that of bulk silicon-titanium ratio, and in addition, the molecular sieve material obtained by the preferred embodiment has more micropore size distribution in the range of 1-1.8nm, and is particularly beneficial to thioether oxidation reaction. The time of the contacting in step (2) may be selected according to the contacting temperature and the desired hydrolysis rate.
The invention also provides the modified titanium silicalite molecular sieve and the application of the modified titanium silicalite molecular sieve prepared by the method in thioether oxidation. In the thioether oxidation reaction, the modified titanium silicalite molecular sieve and the modified titanium silicalite molecular sieve obtained by the method can effectively adjust the selectivity of a target product.
According to a fourth aspect of the present invention, there is provided a thioether oxidation process comprising: under the condition of thioether oxidation, a liquid mixture is contacted with a catalyst, wherein the liquid mixture contains thioether, at least one oxidant and optionally at least one solvent, and the catalyst contains the modified titanium silicalite molecular sieve or the modified titanium silicalite molecular sieve prepared by the preparation method.
According to the method of the present invention, the catalyst may be used in an amount of a catalyst capable of performing a catalytic function. In particular, the liquid hourly weight hourly space velocity of the thioether can be 0.01-20h-1Preferably 0.1 to 10h-1E.g. 1-5h-1。
The oxidizing agent may be any of various substances commonly used in the art that are capable of oxidizing a thioether to form a sulfone. The method is particularly suitable for occasions of oxidizing thioether by using peroxide as an oxidizing agent so as to prepare sulfone, so that the effective utilization rate of the peroxide can be obviously improved, and the thioether oxidation cost can be reduced. The peroxide is a compound containing an-O-O-bond in the molecular structure, and can be selected from hydrogen peroxide, hydroperoxide and peracid. The hydroperoxide is a substance obtained by substituting one hydrogen atom in a hydrogen peroxide molecule with an organic group. The peracid refers to an organic oxyacid having an-O-O-bond in the molecular structure. Specific examples of the peroxide may include, but are not limited to: hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid and propionic acid. Preferably, the oxidizing agent is hydrogen peroxide, which further reduces the separation cost. The hydrogen peroxide may be hydrogen peroxide in various forms commonly used in the art.
From the viewpoint of further improving the safety of the method of the present invention, it is preferable to use hydrogen peroxide in the form of an aqueous solution. According to the process of the invention, when the hydrogen peroxide is provided in the form of an aqueous solution, the concentration of the aqueous hydrogen peroxide solution may be a concentration conventional in the art, for example: 20-80 wt%. Aqueous solutions of hydrogen peroxide at concentrations meeting the above requirements may be prepared by conventional methods or may be obtained commercially, for example: can be 30 percent by weight of hydrogen peroxide, 50 percent by weight of hydrogen peroxide or 70 percent by weight of hydrogen peroxide which can be obtained commercially.
According to the process of the present invention, the thioether may be any of various compounds having an-S-bond, preferably the thioether is selected from the group consisting of thioethers having 2 to 18 carbon atoms, more preferably dimethyl sulfide or dimethyl sulfide. In the examples of the present invention, dimethyl sulfide is taken as an example for illustration, but the present invention is not limited thereto.
According to the process of the invention, preferably, the molar ratio of thioether to oxidant is 1: (0.1-10), and more preferably 1: (0.2-5), more preferably 1: (0.2-3).
According to the process of the present invention, the liquid mixture may or may not contain a solvent, preferably a solvent. Preferably, the contacting is in at least one solventIn the presence of oxygen. Thus, by adjusting the content of the solvent in the liquid mixture, the reaction speed can be adjusted, and the reaction is more stable. The solvent may be a variety of liquid substances that are capable of dissolving the thioether and the oxidizing agent, or facilitating mixing of the two, as well as dissolving the target oxidation product. In general, the solvent may be selected from water, C1-C6Alcohol of (1), C3-C8Ketone and C2-C6A nitrile of (a). Specific examples of the solvent may include, but are not limited to: water, methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile. Preferably, the solvent is selected from water and C1-C6The alcohol of (1). More preferably, the solvent is at least one of acetone, methanol and water. By adopting the preferred embodiment, the mixing degree of reactants in the reaction system can be improved, the diffusion can be enhanced, and the intensity of the reaction can be adjusted more conveniently.
The amount of the solvent to be used may be appropriately selected depending on the amounts of the thioether and the oxidizing agent to be used. Generally, the molar ratio of solvent to thioether may be from 0.1 to 100: 1, preferably 2 to 80: 1.
according to the method of the present invention, the oxidation reaction conditions are dependent on the target oxidation product. In general, the thioether oxidation reaction can be carried out at a temperature of from 0 to 120 ℃ and preferably at a temperature of from 20 to 80 ℃; the pressure in the reactor may be in the range of 0 to 5MPa, preferably 0.1 to 3MPa, in terms of gauge pressure.
The thioether oxidation method provided by the invention can be carried out in a fixed bed reactor.
The method according to the present invention may further comprise separating the reaction mixture output from the fixed-bed reactor to obtain the target oxidation product as well as unreacted reactants. The method for separating the reaction mixture may be a method conventionally selected in the art, and is not particularly limited. The separated unreacted reactant can be recycled.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the reagents used were all commercially available analytical grade reagents, and the pressures were measured as gauge pressures.
The pore volume and pore size distribution of the sample were measured on a Micromeritics ASAP2405 static nitrogen adsorption apparatus, and the specific data are shown in Table 1.
The elemental compositions of titanium, silicon and aluminum of the samples were measured on a 3271E model X-ray fluorescence spectrometer, manufactured by Nippon chemical and mechanical Co., Ltd., and the data are shown in Table 1.
In the present invention, the surface Si/Ti ratio was measured by an ESCA L ab250 model X-ray photoelectron spectrometer manufactured by Thermo Scientific, and the bulk Si/Ti ratio was measured by a 3271E model X-ray fluorescence spectrometer manufactured by Nippon geometry electric Co., Ltd., and the surface Si/Ti ratio/bulk Si/Ti ratio is shown in Table 1.
In the following examples, the amount of hydrolysis of the organosilicon source was measured by gas chromatography, which was Agilent6890N, a capillary column (30m 320 μm 25 μm) equipped with thermal conductivity detector TCD and HP-5, wherein the inlet temperature was 180 ℃, the column temperature was 150 ℃, nitrogen was used as a carrier gas, and the flow rate of the carrier gas was 25m L/min.
XOrganic silicon source％＝[(mo Organic silicon source－mOrganic silicon source)/mo Organic silicon source]×100％
In the formula, XOrganic silicon sourceThe hydrolysis rate of the organic silicon source is shown; m iso Organic silicon sourceRepresents the mass of the added organic silicon source; m isOrganic silicon sourceThe mass of the unhydrolyzed organic silicon source is indicated.
In the following examples, titanium silicalite molecular sieves were prepared using the method described in Zeolite, 1992, Vol.12, pp 943-950.
The acid vapors in the following examples and comparative examples were obtained by heating an aqueous solution of hydrochloric acid having a concentration of 2 mol/L.
The alkaline vapors in the following examples and comparative examples were obtained by heating an aqueous tetrapropylammonium hydroxide solution, wherein the concentration of alkaline gas formed was 5% by volume.
In the following examples, the pressure is in gauge pressure unless otherwise specified.
Example 1
This example illustrates the method and product provided by the present invention.
(1) Filling 10g of titanium silicalite molecular sieve in a fixed bed reactor, introducing acidic steam into the fixed bed reactor, and contacting the titanium silicalite molecular sieve with the acidic steam to modify the acidic steam, wherein the temperature of the modification of the acidic steam is 100 ℃, the time is 8h, and the molar ratio of the titanium silicalite molecular sieve to the acidic steam is 100: 10, titanium silicalite molecular sieve with SiO2Acid steam is counted as H+And (6) counting.
(2) Mixing the titanium-silicon molecular sieve modified in the step (1), aluminum source aluminum sulfate, organic silicon source tetraethyl orthosilicate, a sodium hydroxide aqueous solution (pH is 10) and water at 40 ℃, and filtering and separating the obtained mixture after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate of the organic silicon source is 50%) to obtain a solid product, wherein the modified titanium-silicon molecular sieve: an aluminum source: silicon source: alkali source: the molar ratio of water is 100: 3: 5: 10: 600, the modified titanium-silicon molecular sieve and the silicon source are SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
(3) Putting the solid product obtained in the step (2) into a reaction kettle, introducing alkaline steam into the reaction kettle until the pressure in the reaction kettle is 1.3MPa, sealing the reaction kettle, and carrying out heat treatment at 140 ℃ for 12 hours; and roasting the molecular sieve subjected to heat treatment at 450 ℃ for 2h in a nitrogen atmosphere, and then roasting at 550 ℃ for 2h in an air atmosphere to obtain the modified titanium-silicon molecular sieve S-1.
Example 2
This example illustrates the method and product provided by the present invention.
(1) Filling 10g of a titanium silicalite molecular sieve in a fixed bed reactor, introducing acidic steam into the fixed bed reactor, and contacting the titanium silicalite molecular sieve with the acidic steam to modify the acidic steam, wherein the temperature of the modification of the acidic steam is 150 ℃, the time is 2 hours, and the molar ratio of the titanium silicalite molecular sieve to the acidic steam is 100: 12, titanium silicalite molecular sieve with SiO2Metering acid steamWith H+And (6) counting.
(2) Mixing the titanium-silicon molecular sieve modified in the step (1), aluminum source aluminum sol (content is 20 weight percent), organic silicon source methyl orthosilicate, tetrapropyl ammonium hydroxide aqueous solution (pH is 14) and water at 50 ℃, and filtering and separating the obtained mixture after the methyl orthosilicate is hydrolyzed (hydrolysis rate of the organic silicon source is 60 percent) to obtain a solid product, wherein the modified titanium-silicon molecular sieve: an aluminum source: silicon source: alkali source: the molar ratio of water is 100: 1: 2: 15: 400, the modified titanium-silicon molecular sieve and the silicon source are SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
(3) Putting the solid product obtained in the step (2) into a reaction kettle, introducing alkaline steam into the reaction kettle until the pressure in the reaction kettle is 1MPa, sealing the reaction kettle, and carrying out heat treatment at 170 ℃ for 6 hours; and roasting the molecular sieve subjected to heat treatment at 500 ℃ for 2h in a nitrogen atmosphere, and then roasting at 500 ℃ for 2h in an air atmosphere to obtain the modified titanium-silicon molecular sieve S-2.
Example 3
This example illustrates the method and product provided by the present invention.
(1) Filling 10g of titanium silicalite molecular sieve in a fixed bed reactor, introducing acidic steam into the fixed bed reactor, and contacting the titanium silicalite molecular sieve with the acidic steam to modify the acidic steam, wherein the temperature of the modification of the acidic steam is 80 ℃, the time is 15h, and the molar ratio of the titanium silicalite molecular sieve to the acidic steam is 100: 5, titanium-silicon molecular sieve is made of SiO2Acid steam is counted as H+And (6) counting.
(2) Mixing the titanium-silicon molecular sieve modified in the step (1), aluminum source aluminum hydroxide, organic silicon source methyl orthosilicate, sodium hydroxide aqueous solution (pH is 12) and water at 60 ℃, and filtering and separating the obtained mixture after the methyl orthosilicate is hydrolyzed (the hydrolysis rate of the organic silicon source is 55%) to obtain a solid product, wherein the modified titanium-silicon molecular sieve: an aluminum source: silicon source: alkali source: the molar ratio of water is 100: 0.5: 1: 5: 300, the modified titanium-silicon molecular sieve and the silicon source are SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
(3) Putting the solid product obtained in the step (2) into a reaction kettle, introducing alkaline steam into the reaction kettle until the pressure in the reaction kettle is 1.5MPa, sealing the reaction kettle, and carrying out heat treatment at 150 ℃ for 18 hours; and roasting the molecular sieve subjected to heat treatment at 450 ℃ for 2h in a nitrogen atmosphere, and then roasting at 500 ℃ for 2h in an air atmosphere to obtain the modified titanium-silicon molecular sieve S-3.
Example 4
This example illustrates the method and product provided by the present invention.
The process of example 1 is followed except that in step (1), the molar ratio of titanium silicalite molecular sieve to acid steam is 100: 2, obtaining the modified titanium silicalite molecular sieve S-4.
Example 5
This example illustrates the method and product provided by the present invention.
The process of example 1 is followed except that in step (1), the molar ratio of titanium silicalite molecular sieve to acid steam is 100: 30 to obtain the modified titanium silicalite molecular sieve S-5.
Example 6
This example illustrates the method and product provided by the present invention.
The procedure of example 2 was followed except that the temperature for the acidic steam modification was 200 ℃ to obtain modified titanium silicalite molecular sieve S-6.
Example 7
This example illustrates the method and product provided by the present invention.
The procedure of example 3 was followed except that the temperature for the acid steam modification was 50 ℃ to obtain modified titanium silicalite molecular sieve S-7.
Example 8
This example illustrates the method and product provided by the present invention.
The procedure of example 1 was followed except that after hydrolysis of tetraethyl orthosilicate (hydrolysis of the source of organosilicon to 100%), the resulting mixture was filtered. Obtaining the modified titanium-silicon molecular sieve S-8.
Example 9
This example illustrates the method and product provided by the present invention.
The procedure of example 1 was followed, except that no silicon source tetraethyl orthosilicate was added in step (2). Obtaining the modified titanium-silicon molecular sieve S-9.
Example 10
This example illustrates the method and product provided by the present invention.
The process of example 1 was followed except that the temperature of the heat treatment of step (3) was 100 ℃. Obtaining the modified titanium-silicon molecular sieve S-10.
Example 11
This example illustrates the method and product provided by the present invention.
The process of example 1 was followed except that the temperature of the heat treatment of step (3) was 200 ℃. Obtaining the modified titanium silicalite molecular sieve S-11.
Example 12
This example illustrates the method and product provided by the present invention.
The process of example 1 is followed except that step (3) does not include calcining the heat-treated molecular sieve. Obtaining the modified titanium-silicon molecular sieve S-12.
Example 13
This example illustrates the method and product provided by the present invention.
The process of example 1 was followed except that in step (3), the heat-treated molecular sieve was calcined at 550 ℃ for 4 hours in an air atmosphere. Obtaining the modified titanium-silicon molecular sieve S-13.
Comparative example 1
The process of example 1 was followed except that the acid steam modification of step (1) was not included. Obtaining the modified titanium silicalite molecular sieve D-1.
Comparative example 2
The process of example 1 was followed except that the mixing contact process of step (2) was not included. Obtaining the modified titanium silicalite molecular sieve D-2.
Comparative example 3
The process of example 1 was followed except that the basic steam modification process of step (3) was not included. Obtaining the modified titanium silicalite molecular sieve D-3.
TABLE 1
In table 1:
C＝X1-1.8/X0.4-0.9，X0.4-0.9the ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter, X1-1.8The proportion of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution amount is adopted;
D＝Tw/Tk，Twis the micropore volume of the molecular sieve, TkIs the total pore volume of the molecular sieve;
silicon: titanium: aluminum refers to the element silicon: titanium element: molar ratio of aluminum element.
As can be seen from the results of table 1:
the molecular sieve prepared by the preferred method of the invention has the following pore size distribution, the proportion of the pore volume of micropores in the total pore volume: titanium element: the molar ratio of aluminum element, the ratio of surface silicon-titanium ratio to bulk silicon-titanium ratio and other data completely satisfy all the characteristics of the product of the invention. In contrast, the titanium-silicon materials obtained in comparative examples 1 to 3 had a pore size distribution, a ratio of micropore volume to total pore volume, and a ratio of silicon element: titanium element: the molar ratio of the aluminum element and the like cannot satisfy all the characteristics of the product of the present invention.
Test example
The catalyst (the molecular sieve prepared in the catalyst in the embodiment and the comparative example is pressed into tablets, the particle size is 10-20 meshes) is filled in a fixed bed reactor to form a catalyst bed layer, and the height-diameter ratio of the catalyst bed layer is 10.
Dimethyl sulfide, hydrogen peroxide (provided as 30 wt.% hydrogen peroxide) as an oxidant and acetone as a solvent were mixed to form a liquid mixture, which was fed from the bottom of the fixed bed reactor and passed through the catalyst bed. Wherein the molar ratio of dimethyl sulfide to hydrogen peroxide is 1:1, and the molar ratio of dimethyl sulfide to acetone isThe molar ratio is 1: 8, the weight hourly space velocity of the dimethyl sulfide is 1.5h-1The reaction temperature is 60 ℃, water is used as a heat exchange medium to exchange heat with the catalyst bed layer in the reaction process so as to remove reaction heat, and the pressure in the fixed bed reactor is controlled to be 1MPa in the reaction process.
The composition of the reaction mixture output from the reactor during the continuous reaction was monitored and the relative amounts of dimethyl sulfide conversion and sulfone selectivity increase in the product were calculated and the results obtained at 0.5 hour of reaction are listed in table 2.
Conversion (%) of dimethyl sulfide [ (molar amount of dimethyl sulfide charged-molar amount of unreacted dimethyl sulfide)/molar amount of dimethyl sulfide charged ] × 100%;
the relative increase in sulfone selectivity in the product (%) — (moles of sulfone in the reaction mixture from the test example-moles of sulfone in the reaction mixture from the test reference)/moles of sulfone in the reaction mixture from the test reference × 100% was calculated.
The invention is based on the titanium silicalite molecular sieves described above.
TABLE 2
As can be seen from the data in Table 2, the titanium silicalite molecular sieve with the special physicochemical characteristic structure is used for the reaction of thioether oxidation, which is beneficial to adjusting the selectivity of a target product (sulfone) and can obtain better catalytic effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. A modified titanium silicalite molecular sieve, comprising: titanium element, aluminum element, silicon element and oxygen element, wherein the molecular sieve satisfies X1-1.8/X0.4-0.9＝C，0.1<C<0.5, preferably 0.25<C<0.5，X0.4-0.9The ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter, X1-1.8Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 1-1.8nm in the distribution quantity of the pore diameter of the total micropores.
2. The modified titanium silicalite molecular sieve of claim 1, wherein the molecular sieve satisfies Tw/Tk＝D，0.2<D<0.5，TwIs the micropore volume of the molecular sieve, TkIs the total pore volume of the molecular sieve, preferably, 0.25<D<0.45。
3. The modified titanium silicalite molecular sieve of claim 1 or 2, wherein the molar ratio of elemental silicon: titanium element: the molar ratio of aluminum elements is 100: (0.1-10): (0.01-5), preferably 100: (0.2-5): (0.2-4).
4. The modified titanium silicalite molecular sieve of any one of claims 1 to 3, wherein the molecular sieve has a surface silicon to titanium ratio of not less than a bulk silicon to titanium ratio, the silicon to titanium ratio being the molar ratio of silicon oxide to titanium oxide;
preferably, the ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is 1.2-5;
further preferably, the ratio of the surface silicon-titanium ratio to the bulk silicon-titanium ratio is 1.5-4.5.
5. A method of preparing the modified titanium silicalite molecular sieve of any one of claims 1 to 4, comprising:
(1) carrying out acid steam modification on the titanium silicalite molecular sieve;
(2) mixing and contacting the titanium-silicon molecular sieve modified in the step (1) with an aluminum source, an alkali source and water;
(3) and (3) carrying out heat treatment on the solid product obtained in the step (2) in an alkaline steam atmosphere.
6. The method of claim 5, wherein the acid steam modification of step (1) comprises: contacting a titanium silicalite molecular sieve with acid steam to modify the acid steam; the temperature of the acid steam modification is 40-200 ℃, preferably 60-180 ℃, and further preferably 80-150 ℃;
preferably, the time for the acid steam modification is 0.5 to 360h, more preferably 1 to 240h, and even more preferably 2 to 120 h.
7. The production process according to claim 6, wherein the acidic steam is obtained by heating an aqueous acid solution having a concentration >0.1 mol/L, preferably ≥ 1 mol/L, further preferably 1-15 mol/L;
preferably, the acid in the aqueous acid solution is an organic acid and/or an inorganic acid.
8. The preparation method according to any one of claims 5 to 7, wherein the molar ratio of the titanium silicalite molecular sieve to the acid vapor is 100: (0.5-40), preferably 100: (1-15), more preferably 100: (5-15), wherein the titanium silicalite is SiO2Acid steam is counted as H+And (6) counting.
9. The preparation method according to any one of claims 5 to 8, wherein in the step (2), the modified titanium silicalite molecular sieve: an aluminum source: alkali source: the molar ratio of water is 100: (0-10): (0.5-50): (20-1000), wherein the modified titanium silicalite molecular sieve is SiO2Calculated by Al as the aluminum source2O3The alkali source is N or OH-Counting;
preferably, the modified titanium silicalite molecular sieve: the molar ratio of the aluminum source is 100: (0.2-5), more preferably 100: (0.5-3);
preferably, the temperature of the contacting of the step (2) is 20-80 ℃;
preferably, the alkali source is one or more of ammonia, an aliphatic amine, an aliphatic alcohol amine and a quaternary ammonium base; the aluminum source is one or more of aluminum sol, aluminum salt, aluminum hydroxide and aluminum oxide.
10. The production method according to any one of claims 5 to 9, wherein the alkaline steam atmosphere is provided by alkaline steam obtained by heating an alkaline aqueous solution;
preferably, the concentration of the alkaline gas in the alkaline vapor is 0.02 to 50% by volume, preferably 0.1 to 25% by volume, more preferably 3 to 10% by volume.
11. The production method according to any one of claims 5 to 10, wherein in step (3), the conditions of the heat treatment include: the temperature is 100-200 ℃, preferably 120-180 ℃, and more preferably 140-170 ℃; the time is 0.5 to 96 hours, preferably 2 to 48 hours, and further preferably 6 to 24 hours; the pressure is 0 to 5MPa, preferably 0.2 to 2MPa, in terms of gauge pressure.
12. The production method according to any one of claims 5 to 11, wherein the method further comprises: roasting the molecular sieve obtained in the step (3), wherein roasting conditions comprise: the roasting temperature is 300-800 ℃, preferably 350-600 ℃, the roasting time is 2-12h, preferably 2-4h, and the roasting atmosphere comprises air atmosphere;
preferably, the conditions of the calcination include: roasting at the temperature of 450-600 ℃ in a nitrogen atmosphere for 0.5-6h, and then roasting at the temperature of 450-600 ℃ in an air atmosphere for 0.5-12 h.
13. The preparation method according to any one of claims 5 to 12, wherein a silicon source is further added during the contacting in step (2), wherein the silicon source is an organic silicon source and/or an inorganic silicon source, preferably an organic silicon source, and further preferably one or more selected from the silicon-containing compounds represented by formula I,
in the formula I, R1、R2、R3And R4Each independently is C1-C4Alkyl groups of (a);
preferably in SiO2The molar ratio of the modified titanium-silicon molecular sieve to the silicon source is 100: (0.1-10);
preferably, the hydrolysis rate of the organic silicon source is 40-60%.
14. Use of the modified titanium silicalite molecular sieve of any one of claims 1 to 4 and the modified titanium silicalite molecular sieve prepared by the preparation method of any one of claims 5 to 13 in the oxidation of thioethers.
15. A method of oxidizing a thioether, the method comprising: contacting a liquid mixture with a catalyst under thioether oxidation conditions, wherein the liquid mixture contains thioether, at least one oxidant and optionally at least one solvent, and the catalyst contains the modified titanium silicalite molecular sieve as defined in any one of claims 1 to 4 or the modified titanium silicalite molecular sieve as prepared by the preparation method as defined in any one of claims 5 to 13;
preferably, the thioether is dimethyl sulfide and/or benzyl sulfide; the oxidant is peroxide, and the molar ratio of the thioether to the oxidant is 1: (0.1-10), the thioether oxidation conditions comprising: the temperature is 0-120 ℃, and the pressure is 0-5MPa in gauge pressure.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2140863A1 (en) * | 1992-07-24 | 1994-02-03 | Diane Renata Cornelia Huybrechts | Catalysts and their use in oxidation of saturated hydrocarbons |
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| FR2784672A1 (en) * | 1998-10-19 | 2000-04-21 | Rhodia Chimie Sa | New process for the preparation of a titanium silicalite of type MEL by impregnation with structuring agents and a mobility agent, useful as a transformation catalyst particularly for the hydroxylation of phenols |
| CN104291352A (en) * | 2014-09-30 | 2015-01-21 | 浙江大学 | Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation |
| CN105017103A (en) * | 2014-04-29 | 2015-11-04 | 中国石油化工股份有限公司 | Dimethyl sulfone preparation method |
| CN106032279A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve, preparation method and applications thereof, and cyclic ketone conversion method |
| CN106032277A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Titanium-silicon-aluminum molecular sieve, preparation method and applications thereof, and a cyclic ketone oxidation method |
| CN107556220A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method and method that is a kind of while producing sulfoxide and sulfone |
| CN108658727A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Propylene method for oxidation |
-
2019
- 2019-01-28 CN CN201910081707.2A patent/CN111484031B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2140863A1 (en) * | 1992-07-24 | 1994-02-03 | Diane Renata Cornelia Huybrechts | Catalysts and their use in oxidation of saturated hydrocarbons |
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| FR2784672A1 (en) * | 1998-10-19 | 2000-04-21 | Rhodia Chimie Sa | New process for the preparation of a titanium silicalite of type MEL by impregnation with structuring agents and a mobility agent, useful as a transformation catalyst particularly for the hydroxylation of phenols |
| CN105017103A (en) * | 2014-04-29 | 2015-11-04 | 中国石油化工股份有限公司 | Dimethyl sulfone preparation method |
| CN104291352A (en) * | 2014-09-30 | 2015-01-21 | 浙江大学 | Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation |
| CN106032279A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve, preparation method and applications thereof, and cyclic ketone conversion method |
| CN106032277A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Titanium-silicon-aluminum molecular sieve, preparation method and applications thereof, and a cyclic ketone oxidation method |
| CN107556220A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method and method that is a kind of while producing sulfoxide and sulfone |
| CN108658727A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Propylene method for oxidation |
Non-Patent Citations (3)
| Title |
|---|
| TEKLA, J ET AL.: "Effective hierarchization of TS-1 and its catalytic performance in cyclohexene epoxidation", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| XU, H ET AL.: "Postsynthesis of mesoporous MOR-type titanosilicate and its unique catalytic properties in liquid-phase oxidations", 《JOURNAL OF CATALYSIS》 * |
| 徐保明等: "TS-1分子筛催化剂的修饰改性方法研究进展", 《河南大学学报(自然科学版)》 * |
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