TS-1 titanium silicalite molecular sieve, preparation method thereof and application of TS-1 titanium silicalite molecular sieve in catalyzing oxidation reaction of ethylene sulfite
By introducing a specific proportion of auxiliaries such as tetrapropylammonium hydroxide and alkylglucamide during the preparation process, the uniform dispersion of titanium source in TS-1 titanium-silicon molecular sieve is promoted, which solves the problems of high cost and difficult environmental treatment of precious metal catalysts in the existing technology. It realizes the efficient and environmentally friendly oxidation of vinyl sulfite to vinyl sulfate, which meets the high standard requirements of lithium battery electrolyte.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YUEYANG HANKANG TECHNOLOGY CO LTD
- Filing Date
- 2026-01-29
- Publication Date
- 2026-05-08
AI Technical Summary
Existing technologies for producing vinyl sulfate from vinyl sulfite oxidation suffer from problems such as high cost of precious metal catalysts, difficulty in environmental treatment, low product purity, long reaction time, and high safety risks, making it difficult to meet the high standards required for lithium battery electrolytes.
TS-1 titanium-silicon molecular sieves were prepared by mixing tetrapropylammonium hydroxide, alkylglucamide, tetraethyl silicate and titanium source in a specific ratio in the presence of an organic solvent, followed by crystallization and calcination. Fatty alcohol polyoxyethylene ether phosphate was used to promote uniform dispersion of the titanium source and inhibit hydrolysis, forming a uniform spatial network structure and improving catalytic performance.
It achieves high vinyl sulfite conversion rate and high vinyl sulfite selectivity, reduces production costs, avoids environmental problems, and provides a green industrial production path.
Smart Images
Figure CN121990582A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of molecular sieve synthesis, specifically to TS-1 titanium-silicon molecular sieve, its preparation method, and its application in the catalytic oxidation reaction of vinyl sulfite. Background Technology
[0002] The oxidation of vinyl sulfite to produce vinyl sulfate (DTD), a key process for lithium-ion battery electrolyte additives, still faces multiple technical bottlenecks. The traditional mainstream sodium hypochlorite oxidation method relies on expensive ruthenium trichloride catalysts, which are difficult and costly to recover. It also generates a large amount of high-salt wastewater, putting significant pressure on environmental treatment. Furthermore, residual sodium and chloride ions in the product can affect product purity, making it difficult to meet the high standards required for electrolytes.
[0003] Early hydrogen peroxide oxidation systems suffered from long reaction times and easy hydrolysis of the product, vinyl sulfate. Batch reactor reactions had low yields, and continuous processes were prone to product decomposition and excessive acid values due to high temperatures or long residence times. Furthermore, some in-situ hydrogen peroxide generation processes required the use of hydrogen and oxygen, posing extremely high explosion risks. The contradiction between the emissions of waste gas, wastewater, and solid waste, cost control, and product stability in traditional processes was difficult to reconcile.
[0004] The emergence of the TS-1 titanium silicate molecular sieve catalytic system provides a feasible solution for this process. TS-1 molecular sieve, with its unique Si-O-Ti bond structure and shape-selective catalytic properties, reacts mildly with hydrogen peroxide in an oxidation system, producing only water as a byproduct, thus avoiding the environmental challenges of traditional processes from the outset. This system requires no precious metals, and the oxidant hydrogen peroxide is readily available and environmentally friendly, reducing production costs and providing a reliable pathway for the green industrial production of vinyl sulfate. However, the synthesis of high-performance titanium silicate molecular sieves remains a pressing challenge. Summary of the Invention
[0005] The purpose of this invention is to provide a TS-1 titanium silicate molecular sieve with high vinyl sulfite conversion rate and high vinyl sulfite selectivity.
[0006] To achieve the above objectives, a first aspect of the present invention provides a method for preparing TS-1 titanium-silicon molecular sieves, the method comprising: (1) In the presence of water, tetrapropylammonium hydroxide and alkylglucamide are first mixed to obtain mixture I; Furthermore, in the presence of an organic solvent, tetraethyl silicate, titanium source, and fatty alcohol polyoxyethylene ether phosphate are mixed a second time to obtain mixture II; the mass ratio of tetraethyl silicate to fatty alcohol polyoxyethylene ether phosphate is 1:0.003-0.03. (2) Mix the mixture I and the mixture II in a third mixing process to obtain mixture III; (3) The mixture III is crystallized and the resulting solid product is calcined to obtain TS-1 titanium silicon molecular sieve; The molar ratio of the tetraethyl silicate, tetrapropylammonium hydroxide, titanium source, and alkyl glucamide is 1:0.02-0.5:0.02-0.3:0.01-0.05.
[0007] A second aspect of the present invention provides TS-1 titanium-silicon molecular sieve prepared by the method described in the first aspect.
[0008] The third aspect of the present invention provides the application of the TS-1 titanium-silicon molecular sieve described in the second aspect in the catalytic oxidation reaction of vinyl sulfite.
[0009] A fourth aspect of the present invention provides a method for preparing vinyl sulfate, the method comprising: oxidizing vinyl sulfite with hydrogen peroxide in the presence of a catalyst to obtain vinyl sulfate; The catalyst is the TS-1 titanium-silicon molecular sieve described in the second aspect.
[0010] The method provided by this invention can achieve uniform dispersion of titanium and improve the catalytic performance of TS-1 titanium-silicon molecular sieve. The TS-1 titanium-silicon molecular sieve prepared by the method provided by this invention is a highly efficient catalyst for the oxidation of vinyl sulfite to vinyl sulfate, and has the characteristics of high conversion rate, good selectivity, few side reactions and stable performance. Attached Figure Description
[0011] Figure 1 This is the XRD pattern of the TS-1 titanium-silicon molecular sieve prepared in Example 1 of this invention; Figure 2 This is a SEM image of the TS-1 titanium-silicon molecular sieve prepared in Example 1 of this invention. Detailed Implementation
[0012] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0013] The C 12 -C 14 The alkyl group refers to a straight-chain alkyl or branched alkyl group with a total number of carbon atoms of 12-14 (e.g., 12, 13 or 14).
[0014] It should be noted that the terms "first," "second," and "third" are merely used to distinguish the reactions at different steps and have no substantive meaning.
[0015] The solvent I, solvent II, and mixture III are simply designated by the numbers "I", "II", and "III" to distinguish the mixtures used in different steps and to avoid confusion; they have no substantive meaning.
[0016] As previously described, a first aspect of the present invention provides a method for preparing TS-1 titanium-silicon molecular sieves, the method comprising: (1) In the presence of water, tetrapropylammonium hydroxide and alkylglucamide are first mixed to obtain mixture I; Furthermore, in the presence of an organic solvent, tetraethyl silicate, titanium source, and fatty alcohol polyoxyethylene ether phosphate are mixed a second time to obtain mixture II; the mass ratio of tetraethyl silicate to fatty alcohol polyoxyethylene ether phosphate is 1:0.003-0.03. (2) Mix the mixture I and the mixture II in a third mixing process to obtain mixture III; (3) The mixture III is crystallized and the resulting solid product is calcined to obtain TS-1 titanium silicon molecular sieve; The molar ratio of the tetraethyl silicate, tetrapropylammonium hydroxide, titanium source, and alkyl glucamide is 1:0.02-0.5:0.02-0.3:0.01-0.05.
[0017] The method provided by this invention uses tetraethyl silicate and a titanium source to be mixed with the assistance of an organic solvent. Fatty alcohol polyoxyethylene ether phosphate prevents premature hydrolysis of the titanium source. The interaction between ether bonds and phosphate bonds prevents the aggregation of the titanium source, promotes uniform mixing of tetraethyl silicate and titanium source, and inhibits premature hydrolysis of titanium source. It also promotes the formation of a spatial network structure between titanium source and tetraethyl silicate through hydrogen bonding, ensuring uniform hydrolysis of tetraethyl silicate and titanium source in subsequent processes.
[0018] Furthermore, alkyl glucamide can rapidly bond with titanium source and tetraethyl silicate via fatty alcohol polyoxyethylene ether phosphate, inhibiting the hydrolysis of tetraethyl silicate and titanium source in solution, coordinating their hydrolysis rates, and preventing the titanium source from hydrolyzing too quickly and thus failing to participate in crystallization.
[0019] Furthermore, the combination of alkyl glucamide and fatty alcohol polyoxyethylene ether phosphate can inhibit the rapid growth of crystals during the crystallization process of TS-1 titanium-silicon molecular sieve, ensuring the uniform growth of titanium and silicon during the crystallization process. The alkyl and fatty alcohol groups can also utilize their hydrophobic properties to ensure that the final TS-1 titanium-silicon molecular sieve crystals are smaller, thereby improving the catalytic performance of TS-1 titanium-silicon molecular sieve.
[0020] Preferably, in step (1), the first mixing operation includes: S1: Tetrapropylammonium hydroxide is mixed with a portion of water to obtain a tetrapropylammonium hydroxide solution; S2: Mix the tetrapropylammonium hydroxide solution, alkylglucamide and the remaining water to obtain the mixture I.
[0021] In a preferred embodiment, in step (1), the molar ratio of the tetrapropylammonium hydroxide to the water is 1:500-3400; for example, it can be any ratio between 1:500, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3400 or 1:500-3400.
[0022] In this invention, the portion of water described in step S1 and the remaining portion of water described in step S2 together constitute the water described in the first aspect. That is, the molar amount of the portion of water and the remaining portion of water is the total molar amount of water in the method described in the first aspect.
[0023] More preferably, the mass concentration of the tetrapropylammonium hydroxide solution is 20-25%.
[0024] Preferably, in step (1), the molar ratio of the tetraethyl silicate to the organic solvent is 1:2-50, more preferably 1:5-30; for example, it can be any ratio between 1:5, 1:10, 1:20, 1:30 or 1:5-30.
[0025] In a preferred embodiment, in step (1), the alkyl glucamide is selected from at least one of octyl glucamide, lauryl glucamide, myristyl glucamide, and stearyl glucamide.
[0026] Preferably, in step (1), the fatty alcohol polyoxyethylene ether phosphate has the general structural formula RO(C2H4O). n PO(OH)2, R is C 12 -C 14 The alkyl group, n is selected from integers from 3 to 9.
[0027] Preferably, the fatty alcohol polyoxyethylene ether phosphate has the general structural formula RO(C2H4O).n PO(OH)2, R is C 12 The alkyl group, n, is selected from integers from 5 to 8. The inventors have discovered that, under these preferred conditions, titanium-silicon molecular sieves with higher vinyl sulfite conversion and higher vinyl sulfate selectivity can be prepared.
[0028] More preferably, the fatty alcohol polyoxyethylene ether phosphate is lauryl ether phosphate (AEO-7P).
[0029] In a preferred embodiment, in step (1), the titanium source is tetrabutyl titanate and / or tetraethyl titanate.
[0030] Preferably, in step (1), the organic solvent is methanol and / or ethanol.
[0031] This invention does not impose special requirements on the specific methods and conditions for the first and second mixing processes, as long as they achieve uniform mixing. Those skilled in the art can use methods known in the art to perform the mixing. This invention will not be described in detail here, and those skilled in the art should not construe this as a limitation of the invention.
[0032] In a preferred embodiment, the specific steps of the third mixing include: adding the mixture I dropwise to the mixture II under stirring conditions to obtain the mixture III.
[0033] This invention does not have specific requirements for the dropping rate, as long as sufficient reaction is achieved. This invention will not be described in detail here, and those skilled in the art should not interpret this as a limitation of the invention.
[0034] According to a preferred embodiment, in step (2), the conditions for the third mixing include: a temperature of 75-95°C and a time of 10-60 min; for example, it can be any value between 10 min, 20 min, 30 min, 40 min, 50 min, 60 min or 10-60 min.
[0035] According to another preferred embodiment, in step (3), the crystallization conditions include: a temperature of 180-240°C, preferably 190-240°C; for example, it can be any value between 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or 190-240°C; and a time of 140-340h, for example, it can be any value between 140h, 160h, 180h, 200h, 220h, 240h, 260h, 280h, 300h, 320h, 340h or 140-340h.
[0036] Preferably, the calcination conditions include: a temperature of 400-600℃ and a time of 4-10h.
[0037] The method described in step (4) of the present invention may further include subjecting the crystallized solid product to conventionally known post-processing methods in the art, such as cooling, filtering, and drying, before calcining to obtain the TS-1 titanium-silicon molecular sieve. For example, the crystallized solid product is sequentially cooled, filtered, dried at 100-150°C for 4-10 hours, and then calcined to obtain the TS-1 titanium-silicon molecular sieve.
[0038] As previously stated, a second aspect of the present invention provides TS-1 titanium-silicon molecular sieve prepared by the method described in the first aspect.
[0039] As previously stated, a third aspect of the present invention provides the application of the TS-1 titanium-silicon molecular sieve described in the second aspect in the catalytic oxidation reaction of vinyl sulfite.
[0040] As mentioned above, a fourth aspect of the present invention provides a method for preparing vinyl sulfate, the method comprising: oxidizing vinyl sulfite with hydrogen peroxide in the presence of a catalyst to obtain vinyl sulfate; The catalyst is the TS-1 titanium-silicon molecular sieve described in the second aspect.
[0041] In a preferred embodiment, the method for preparing vinyl sulfate according to the present invention further includes: crushing the catalyst to a particle size of 5-40 mesh before carrying out the oxidation reaction.
[0042] The present invention does not have special requirements for the crushing method, as long as a catalyst with a particle size of 5-40 mesh is obtained. For example, the titanium-silicon molecular sieve is crushed by compression.
[0043] In this invention, "particle size of 5-40 mesh" refers to passing the material through a 5-mesh Chinese sieve to collect the undersize material and then through a 40-mesh Chinese sieve to collect the oversize material; the Chinese sieve refers to the sieve that complies with the national standards and specifications of China regarding sieves.
[0044] In a preferred embodiment, the molar ratio of the vinyl sulfite to the hydrogen peroxide is 1:1.2-1.4.
[0045] It should be noted that the molar amount of hydrogen peroxide is measured in terms of the molar amount of H2O2, excluding the water present in it.
[0046] Preferably, the hydrogen peroxide has a mass concentration of 25-50%.
[0047] According to a preferred embodiment, the conditions for the oxidation reaction include: a temperature of 20-70°C, a pressure of 0.1-1.0 MPa, and a liquid hourly space velocity of 0.1-20 h⁻¹. -1 Preferably 5-20h -1 For example, it could be 5h.-1 10h -1 15h -1 20h -1 or 5-20h -1 Any value between.
[0048] The present invention will be described in detail below through examples. Unless otherwise specified, specific experimental steps or conditions in the following examples can be performed according to known experimental steps or conditions described in the literature in this field. Unless otherwise specified, the raw materials or instruments used are commercially available. Unless otherwise specified, the reaction temperature in the following examples is at room temperature, which refers to 25±2℃.
[0049] Hydrogen peroxide: mass concentration of 30%.
[0050] Fatty alcohol polyoxyethylene ether phosphate I: AEO-7P, purchased from BASF.
[0051] Fatty alcohol polyoxyethylene ether phosphate II: AEO-15P, purchased from BASF.
[0052] Alkyl glucosamide: Octylglucamide: CAS No.: 23323-37-7; Lauryl glucoamide: CAS No.: 87246-72-8; Myristyl glucosamide: CAS No.: 18375-64-9; Stearyl glucosamide: CAS No.: 18375-66-1.
[0053] Preparation Example 1 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and octyl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, ethanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.006. (2) Add mixture II slowly to mixture I in a water bath at 90°C and stir continuously for 60 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 220°C for 240h, and the resulting solid was cooled, filtered, dried at 120°C for 10h, and calcined at 550°C for 4h to obtain TS-1 titanium silicon molecular sieve I. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, octyl glucosamide, water, and ethanol is 1:0.04:0.03:0.02:21.3:5.
[0054] Preparation Example 2 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and lauryl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, ethanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.012. (2) Add mixture II slowly dropwise to mixture I under a water bath at 80°C and stir continuously for 30 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 240℃ for 144h, and the resulting solid was cooled, filtered, dried at 100℃ for 4h, and calcined at 600℃ for 8h to obtain TS-1 titanium silicon molecular sieve II. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, lauryl glucamide, water, and ethanol is 1:0.03:0.1:0.03:101:20.9.
[0055] Preparation Example 3 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and myristyl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetraethyl titanate, methanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.013. (2) Add mixture II slowly dropwise to mixture I under a water bath at 95°C and stir continuously for 15 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 200℃ for 330h, and the resulting solid was cooled, filtered, dried at 150℃ for 6h, and calcined at 500℃ for 10h to obtain TS-1 titanium silicon molecular sieve III. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetraethyl titanate, myristyl glucamide, water, and methanol is 1:0.25:0.25:0.02:175:14.4.
[0056] Preparation Example 4 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and stearyl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, ethanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.019. (2) Add mixture II slowly dropwise to mixture I under a water bath at 90°C and stir continuously for 25 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 220°C for 240h, and the resulting solid was cooled, filtered, dried at 120°C for 10h, and calcined at 450°C for 8h to obtain TS-1 titanium silicon molecular sieve IV. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, stearyl glucamide, water, and ethanol is 1:0.04:0.02:0.02:21.3:26.1.
[0057] Preparation Example 5 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and myristyl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, ethanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.017. (2) Add mixture II slowly dropwise to mixture I under a water bath at 75°C and stir continuously for 40 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 190°C for 272 h, and the resulting solid was cooled, filtered, dried at 120°C for 10 h, and calcined at 400°C for 10 h to obtain TS-1 titanium silicon molecular sieve V. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, myristyl glucamide, water, and ethanol is 1:0.04:0.07:0.03:84.6:9.8.
[0058] Preparation Example 6 Using a method similar to that used in Preparation Example 1, except that AEO-7P in step (1) was replaced with an equal mass of AEO-15P, TS-1 titanium silicon molecular sieve VI was obtained.
[0059] Comparative Preparation Example 1 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and dissolve it in deionized water (the remaining water). After complete dissolution, a clear mixed solution I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, ethanol, and AEO-7P were weighed and mixed evenly to obtain mixture II; the mass ratio of tetraethyl silicate to AEO-7P was 1:0.006. (2) Add mixture II slowly dropwise to mixture I under a water bath at 90°C and stir continuously for 60 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 220°C for 240h, and the resulting solid was cooled, filtered, dried at 120°C for 10h, and calcined at 550°C for 4h to obtain TS-1 titanium silicon molecular sieve DI. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, water, and ethanol is 1:0.04:0.03:21.3:5.
[0060] Comparative Preparation Example 2 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and octyl glucamide and dissolve them in deionized water (the remaining water). After complete dissolution, a clear mixture I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, and ethanol were weighed and mixed evenly to obtain mixture II; (2) Add mixture II slowly dropwise to mixture I under a water bath at 90°C and stir continuously for 60 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 220°C for 240h, and the resulting solid was cooled, filtered, dried at 120°C for 10h, and calcined at 550°C for 4h to obtain TS-1 titanium silicon molecular sieve DII. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, octyl glucosamide, water, and ethanol is 1:0.04:0.03:0.02:21.3:5.
[0061] Comparative preparation example 3 (1) Mix tetrapropylammonium hydroxide with some water to obtain a tetrapropylammonium hydroxide solution with a mass concentration of 25%. Weigh the tetrapropylammonium hydroxide solution and dissolve it in deionized water (the remaining water). After complete dissolution, a clear mixed solution I is obtained. Additionally, 208g of tetraethyl silicate, tetrabutyl titanate, and ethanol were weighed and mixed evenly to obtain mixture II; (2) Add mixture II slowly dropwise to mixture I under a water bath at 90°C and stir continuously for 60 min to obtain mixture III (gel liquid). (3) The mixture III was crystallized at 220°C for 240h, and the resulting solid was cooled, filtered, dried at 120°C for 10h, and calcined at 550°C for 4h to obtain TS-1 titanium silicon molecular sieve DIII. The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, tetrabutyl titanate, water, and ethanol is 1:0.04:0.03:21.3:5.
[0062] Comparative preparation example 4 Using a method similar to that used in Preparation Example 1, except that octyl glucosamide in step (1) was replaced with an equimolar amount of acetamide, TS-1 titanium silicate molecular sieve DIV was obtained.
[0063] Comparative preparation example 5 Using a method similar to that used in Preparation Example 1, except that AEO-7P in step (1) was replaced with an equal mass of polyoxyethylene ether, TS-1 titanium silicon molecular sieve DV was obtained.
[0064] Example 1 TS-1 titanium-silicon molecular sieve I was crushed into tablets to obtain TS-1 titanium-silicon molecular sieve I with a particle size of 5-40 mesh; then 1.0 g of TS-1 titanium-silicon molecular sieve I was placed in a fixed bed, and a mixed solution of vinyl sulfite and hydrogen peroxide with a molar ratio of 1:1.2 was used as raw material. The raw material was fed into the fixed bed reactor through a micro pump to carry out the oxidation reaction to obtain vinyl sulfate. The oxidation reaction conditions were: temperature 60℃, pressure 0.5 MPa, and liquid hourly space velocity (LISH) 5.0 h⁻¹. -1 .
[0065] Example 2 TS-1 titanium-silicon molecular sieve II was crushed into tablets to obtain TS-1 titanium-silicon molecular sieve II with a particle size of 5-40 mesh; then 1.0 g of TS-1 titanium-silicon molecular sieve II was placed in a fixed bed, and a mixed solution of vinyl sulfite and hydrogen peroxide with a molar ratio of 1:1.3 was used as raw material. The raw material was fed into the fixed bed reactor through a micro pump to carry out the oxidation reaction to obtain vinyl sulfate. The oxidation reaction conditions were: temperature 40℃, pressure 0.5 MPa, and liquid hourly space velocity (LISH) 10.0 h⁻¹. -1 .
[0066] Example 3 TS-1 titanium-silicon molecular sieve III was crushed into tablets to obtain TS-1 titanium-silicon molecular sieve III with a particle size of 5-40 mesh; then 1.0 g of TS-1 titanium-silicon molecular sieve III was placed in a fixed bed, and a mixed solution of vinyl sulfite and hydrogen peroxide with a molar ratio of 1:1.4 was used as raw material. The raw material was fed into the fixed bed reactor through a micro pump to carry out the oxidation reaction to obtain vinyl sulfate. The conditions for the oxidation reaction were: temperature 60℃, pressure 0.8 MPa, and liquid hourly space velocity (LISH) 15.0 h⁻¹. -1 .
[0067] Example 4 TS-1 titanium-silicon molecular sieve IV was crushed into tablets to obtain TS-1 titanium-silicon molecular sieve IV with a particle size of 5-40 mesh; then 1.0 g of TS-1 titanium-silicon molecular sieve IV was placed in a fixed bed, and a mixed solution of vinyl sulfite and hydrogen peroxide with a molar ratio of 1:1.2 was used as raw material. The raw material was fed into the fixed bed reactor through a micro pump to carry out the oxidation reaction to obtain vinyl sulfate. The conditions for the oxidation reaction were: temperature 20℃, pressure 1.0 MPa, and liquid hourly space velocity (LISH) 5.0 h⁻¹. -1 .
[0068] Example 5 TS-1 titanium-silicon molecular sieve V was crushed into tablets to obtain TS-1 titanium-silicon molecular sieve V with a particle size of 5-40 mesh; then 1.0 g of TS-1 titanium-silicon molecular sieve V was placed in a fixed bed, and a mixed solution of vinyl sulfite and hydrogen peroxide with a molar ratio of 1:1.2 was used as raw material. The raw material was fed into the fixed bed reactor through a micro pump to carry out the oxidation reaction to obtain vinyl sulfate. The conditions for the oxidation reaction were: temperature 40℃, pressure 0.8MPa, and liquid hourly space velocity (LISH) 8.0 h⁻¹. -1 .
[0069] Example 6 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium silicon molecular sieve I was replaced with an equal mass of TS-1 titanium silicon molecular sieve VI to obtain vinyl sulfate.
[0070] Comparative Example 1 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium silicon molecular sieve I was replaced with an equal mass of TS-1 titanium silicon molecular sieve DI to obtain vinyl sulfate.
[0071] Comparative Example 2 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium silicon molecular sieve I was replaced with an equal mass of TS-1 titanium silicon molecular sieve DII to obtain vinyl sulfate.
[0072] Comparative Example 3 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium silicon molecular sieve I was replaced with an equal mass of TS-1 titanium silicon molecular sieve DIII to obtain vinyl sulfate.
[0073] Comparative Example 4 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium-silicon molecular sieve I was replaced with an equal mass of TS-1 titanium-silicon molecular sieve DIV to obtain vinyl sulfate.
[0074] Comparative Example 5 The procedure was carried out using a method similar to that in Example 1, except that TS-1 titanium-silicon molecular sieve I was replaced with an equal mass of TS-1 titanium-silicon molecular sieve DV to obtain vinyl sulfate.
[0075] Test Example 1 The TS-1 titanium-silicon molecular sieve prepared in this invention was subjected to the following characterization tests: 1. The present invention provides, by way of example, the XRD pattern of the TS-1 titanium-silicon molecular sieve prepared in Example 1, as shown below. Figure 1 As shown in the figure, the TS-1 titanium-silicon molecular sieve prepared in Example 1 has regular diffraction peaks with good peak symmetry and sharp main crystal plane peaks, indicating that the synthesized sample has a typical MFI type topology.
[0076] 2. The present invention provides, by way of example, SEM images of the TS-1 titanium-silicon molecular sieve prepared in Example 1, as shown below. Figure 2 As shown in the figure, the sample prepared in Example 1 has an ellipsoidal shape formed by the assembly of nanosheets, with small grain size and a relatively concentrated grain size distribution, which is beneficial to mass transfer during the reaction process.
[0077] Test Example 2 The formula for calculating the conversion rate of vinyl sulfite is: (Molar flow rate of vinyl sulfite in raw material - Molar flow rate of vinyl sulfite in product) / Molar flow rate of vinyl sulfite in raw material × 100%.
[0078] The formula for calculating the selectivity of vinyl sulfate is: (Molar flow rate of vinyl sulfate in the product / (Molar flow rate of vinyl sulfite in the feed - Molar flow rate of vinyl sulfite in the product)) × 100%.
[0079] The conversion rate of vinyl sulfite and the selectivity of vinyl sulfate were calculated after 5 hours and 50 hours of reaction, respectively.
[0080] The results are shown in Table 1.
[0081] Table 1
[0082] As can be seen from the results in Table 1, the TS-1 titanium-silicon molecular sieve prepared by the method provided in this invention has a significantly higher conversion rate of vinyl sulfite and selectivity for vinyl sulfate.
[0083] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A method for preparing TS-1 titanium-silicon molecular sieves, characterized in that, The method includes: (1) In the presence of water, tetrapropylammonium hydroxide and alkylglucamide are first mixed to obtain mixture I; Furthermore, in the presence of an organic solvent, tetraethyl silicate, titanium source, and fatty alcohol polyoxyethylene ether phosphate are mixed a second time to obtain mixture II; the mass ratio of tetraethyl silicate to fatty alcohol polyoxyethylene ether phosphate is 1:0.003-0.
03. (2) Mix the mixture I and the mixture II in a third mixing process to obtain mixture III; (3) Crystallize the mixture III and calcine the resulting solid product to obtain TS-1 titanium silicon molecular sieve; The molar ratio of the tetraethyl silicate, tetrapropylammonium hydroxide, titanium source, and alkyl glucamide is 1:0.02-0.5:0.02-0.3:0.01-0.
05.
2. The method according to claim 1, characterized in that, In step (1), the alkyl glucamide is selected from at least one of octyl glucamide, lauryl glucamide, myristyl glucamide, and stearyl glucamide.
3. The method according to claim 1 or 2, characterized in that, In step (1), the general structural formula of the fatty alcohol polyoxyethylene ether phosphate is RO(C2H4O). n PO(OH)2, R is C 12 -C 14 The alkyl group, n is selected from integers from 3 to 9.
4. The method according to claim 1 or 2, characterized in that, In step (1), the titanium source is tetrabutyl titanate and / or tetraethyl titanate; And / or, the organic solvent is methanol and / or ethanol.
5. The method according to claim 1 or 2, characterized in that, In step (2), the conditions for the third mixing include: a temperature of 75-95°C and a time of 10-60 min.
6. The method according to claim 1 or 2, characterized in that, In step (3), the crystallization conditions include: a temperature of 180-240℃ and a time of 140-340h; And / or, the calcination conditions include: a temperature of 400-600℃ and a time of 4-10h.
7. The TS-1 titanium-silicon molecular sieve prepared by the method according to any one of claims 1-6.
8. The application of the TS-1 titanium-silicon molecular sieve according to claim 7 in the catalytic oxidation reaction of vinyl sulfite.
9. A method for preparing vinyl sulfate, characterized in that, The method includes: oxidizing vinyl sulfite with hydrogen peroxide in the presence of a catalyst to obtain vinyl sulfate; The catalyst is the TS-1 titanium-silicon molecular sieve as described in claim 7.
10. The method according to claim 9, characterized in that, The molar ratio of the vinyl sulfite to the hydrogen peroxide is 1:1.2-1.4; And / or, the conditions for the oxidation reaction include: a temperature of 20-70°C, a pressure of 0.1-1.0 MPa, and a liquid hourly space velocity of 0.1-20 h⁻¹. -1 .