CN112742472A - Preparation method of epoxidation catalyst with high activity and low byproduct - Google Patents
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Abstract
The invention discloses a preparation method of a propylene or chloropropene liquid-phase epoxidation catalyst. The S auxiliary agent is added in the preparation process of the catalyst to obtain the titanium-rich TS-1 molecular sieve catalyst, amorphous species on the catalyst are stabilized by the S auxiliary agent, the decomposition of hydrogen peroxide can be reduced, and meanwhile, the introduced alkali metal ions reduce the acidity of the catalyst and can reduce the occurrence of side reactions, so that the high-activity low-byproduct epoxidation catalyst can be obtained.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a preparation method of an epoxidation catalyst.
Background
Since 1983, the titanium silicalite TS-1 is reported by the US4410501 patent for the first time, and is concerned by researchers due to the catalytic oxidation characteristic. It has the same MFI topology as ZSM-5 molecular sieve due to Ti4+Ion substitution of Al in regular molecular sieve framework3+Ions, Ti having hexacoordinating ability on the surface of TS-14+Ions having the potential to accept an electron pair, pair H2O2Has unique adsorption activation performance and can selectively oxidize various organic compounds, wherein phenol hydroxylation, cyclohexanone ammoxidation and olefin epoxidation processes are all examples of industrial application.
The theoretical content of framework titanium in the titanium silicalite molecular sieve obtained by the traditional preparation method is 2.5 percent, so the quantity of active centers of the titanium silicalite molecular sieve is limited, and the activity of the catalyst is further limited. Therefore, how to obtain the TS-1 molecular sieve rich in framework titanium is a difficulty of a titanium silicalite molecular sieve, and a great deal of work is also done by the researchers. However, the obtained titanium-rich catalyst generates more non-framework titanium and amorphous titanium species, and therefore, the application of the TS-1 molecular sieve catalyst is influenced, so that the post-treatment is mostly needed to eliminate the adverse effects.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a preparation method of an epoxidation catalyst with high activity and low byproduct, wherein the chemical composition of the epoxidation catalyst is TS-1.
The invention is realized by the following technical scheme:
an epoxidation catalyst with high activity and low byproduct and a preparation method thereof are characterized in that: the preparation method of the catalyst specifically comprises the following steps:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a silicon source hydrolysate A;
(2) uniformly mixing a titanium source and a complexing agent, dropwise adding the mixture into the silicon source hydrolysate A, and uniformly stirring to obtain a silicon-titanium hydrolysate B;
(3) heating the silicon-titanium hydrolysate B to remove alcohol, supplementing corresponding water, and adding an S auxiliary agent to obtain silicon-titanium gel C;
(4) and (3) filling the silicon-titanium gel C into a crystallization kettle, crystallizing at the temperature of 150-210 ℃ for 20-120h to obtain a crystallized product, and filtering, separating, drying, washing and roasting to obtain the titanium-silicon molecular sieve TS-1.
Further, the S auxiliary agent in the step (3) is one or a mixture of more of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, rubidium sulfite, rubidium bisulfite, cesium sulfite and cesium bisulfite.
Further, the titanium-silicon ratio of the titanium-silicon molecular sieve is 31-33; the content of framework titanium is 3.0-3.2 wt%;
further, the composition of the substance molar ratio in the silicon-titanium gel C in the step (3) is SiO2：TiO2: template agent: and (2) S auxiliary agent: h2O is 1: (0.033-0.05): (0.25-0.4): (0.001-0.01): (25-30); the molar composition of the silicon-titanium gel C is preferably SiO2：TiO2: template agent: and (2) S auxiliary agent: h2O＝1：(0.035-0.05)：(0.25-0.4)：(0.002-0.008)：(25-30)。
Further, the drying temperature in the step (4) is preferably 80-120 ℃, and the roasting temperature is preferably 500-650 ℃.
Preferably, in the step (1), the silicon source is one or a mixture of more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate.
Further, the template agent in the step (1) is tetrapropylammonium hydroxide (TPAOH).
Preferably, in the step (2), the titanium source is one or a mixture of more of tetraethyl orthotitanate, tetrabutyl orthotitanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride, and more preferably tetrabutyl orthotitanate.
Further, in the step (2), the complexing agent is one of isopropanol, acetylacetone and ethanol.
The catalyst prepared by the invention can be applied to propylene liquid-phase epoxidation reaction or chloropropene liquid-phase epoxidation reaction.
The propylene liquid phase epoxidation reaction processComprises the following steps: adding the catalyst into a reaction kettle, and adding 1.5-5.0mol/L H2O2The reaction temperature of the methanol solution is maintained at 30-50 ℃, the propylene pressure is 1.8-4.0Mpa, and the reaction time is 0.5-3 h; the mass concentration of the titanium silicalite TS-1 in the catalytic system is 0.2-1%.
Specifically, the liquid phase propylene epoxidation reaction is carried out in a batch tank reactor. 0.4g of titanium silicalite TS-1 is added into a stainless steel batch reactor as a catalyst, and 3.5mol/L H is added2O270g of methanol solution, keeping the reaction temperature at 35 ℃, and filling 35-55g of propylene into a reactor under the propylene pressure of 3Mpa for reaction time of 1 h; then cooling, taking the feed liquid to analyze the product composition, and titrating the residual H by adopting a potentiometric titration method2O2The molar concentration of (c).
The chloropropene liquid-phase epoxidation reaction process comprises the following steps: adding the catalyst into a reaction kettle, and adding 3.1-3.4mol/L H2O2Methanol solution and 60-75g chloropropene, the reaction temperature is maintained at 35-50 ℃, the reaction pressure is 0.25-0.5Mpa, the reaction time is 1.5-3H, then the temperature is reduced, the feed liquid is taken out to analyze the product composition, and the residual H is analyzed by adopting potentiometric titration2O2The molar concentration of (c).
Specifically, the chloropropene epoxidation reaction is carried out in a batch kettle reaction apparatus. 0.5g of titanium silicalite TS-1 is added into a metal batch reaction kettle as a catalyst, and 3.2mol/L H is added2O280g of methanol solution, the reaction temperature is maintained at 40 ℃, the system pressure is 0.3Mpa, the reaction time is 2 hours, then the temperature is reduced, the feed liquid is taken out to analyze the product composition, and the residual H is analyzed by adopting potentiometric titration2O2The molar concentration of (c).
The invention has the beneficial effects that: adding an S auxiliary agent in the preparation process of the titanium silicalite TS-1, wherein the S auxiliary agent can greatly reduce the pH value of a synthetic glue solution, so that the crystallization process is slowed down, the crystallization process is matched with the speed of Ti entering a framework and the growth of crystals, and the TS-1 molecular sieve rich in framework titanium is obtained, wherein the content of the framework titanium is 3.1%; and S in the auxiliary agent can also stabilize amorphous framework titanium generated in the synthesis process to form Ti-S-O bond, lowering its pair H2O2The decomposition of the titanium silicalite molecular sieve can obtain the TS-1 with high framework titanium content which can not be obtained by the traditional preparation method, and the alkali metal ions are introduced together with the auxiliary agent, so that the acidity of the catalyst can be reduced, and the etherification side reaction on the catalyst can be inhibited.
Detailed Description
Comparative example 1
Mixing 45g of SiO2Adding 30% silica sol into a jacketed three-neck flask, adding 18g of TPABr and 90g of water, and stirring at normal temperature for 0.5h to obtain a silicon source hydrolysis mixture; dissolving 3.8g of tetrabutyl titanate in 5.0g of acetylacetone, stirring for 15min to obtain a titanium source hydrolysis mixture, dropwise adding the titanium source hydrolysis mixture into the silicon source hydrolysis mixture, and stirring for 0.5 h; finally adding 29g of n-butylamine, stirring for 1h, filling the obtained solution into a crystallization kettle, crystallizing for 3d at 170 ℃, washing and drying the crystallized product, and then washing with 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and drying the sample with Si/Ti ratio of 51.1 by XRF test to obtain TS-1-A.
Comparative example 2
Adding 46.2g of tetraethyl orthosilicate into a beaker, stirring, adding 44g of 25 wt% TPAOH aqueous solution and 38g of water, and hydrolyzing at 30 ℃ for 2 hours to obtain a silicon source hydrolysis mixture; dissolving 3.8g of tetrabutyl titanate in 18.7g of isopropanol, and then stirring for 30min to obtain a titanium source hydrolysis mixture; mixing a hydrolysis mixture of a titanium source and a silicon source, removing alcohol at 80 ℃ for 0.5h, supplementing water for 50.2g, stirring for 30min, filling the obtained transparent glue solution into a crystallization kettle for crystallization, crystallizing at 170 ℃ for 36h, washing and drying the obtained crystallized product, and washing with 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and testing by XRF to obtain TS-1-B with the Si/Ti ratio of 50.9.
Comparative example 3
46.2g tetraethyl orthosilicate was added to a beaker and stirred, followed by 44gHydrolyzing 25 wt% TPAOH aqueous solution and 38g water at 30 ℃ for 2h to obtain a silicon source hydrolysis mixture; dissolving 3.8g of tetrabutyl titanate in 18.7g of isopropanol, and then stirring for 30min to obtain a titanium source hydrolysis mixture; mixing a hydrolysis mixture of a titanium source and a silicon source, removing alcohol at 80 ℃ for 0.5h, supplementing an aqueous solution containing 0.05g of ammonium sulfite and 50.2g of water, stirring for 30min, putting the obtained transparent glue liquid into a crystallization kettle for crystallization, crystallizing at 170 ℃ for 36h, washing and drying the obtained crystallized product, and washing with a 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and obtaining TS-1-C with the Si/Ti ratio of 31.2 through XRF test.
Example 1
Adding 46.2g of tetraethyl orthosilicate into a beaker, stirring, adding 44g of 25 wt% TPAOH aqueous solution and 38g of water, hydrolyzing at 30 ℃ for 2 hours to obtain a silicon source hydrolysis mixture, dissolving 3.8g of tetrabutyl titanate in 18.7g of isopropanol, and then stirring for 30min to obtain a titanium source hydrolysis mixture; mixing titanium source and silicon source hydrolyzed mixture, removing alcohol at 80 deg.C for 0.5h, supplementing water solution containing 0.05g sodium sulfite 50.2g water, stirring for 30min, crystallizing the obtained transparent glue solution in crystallization kettle, crystallizing at 170 deg.C for 36h, washing the obtained crystallized product, oven drying, and washing with 1M HCl water solution (liquid-solid ratio of 50ml g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and obtaining TS-1-D with the Si/Ti ratio of 31.8 through XRF test.
Example 2
Example 1 was repeated, the amounts of tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate in the preparation of TS-1 were changed to the amounts of tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate in the preparation of TS-1, and after crystallization, washing and drying were carried out, and then washing was carried out with 1M aqueous HCl (liquid-solid ratio: 50ml g/g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and XRF testing to obtain TS-1 samples with Si/Ti ratios of 31.9, 32.1 and 31.8 respectively, wherein the TS-1 samples have the following serial numbers: TS-1-E, TS-1-F, TS-1-G.
Example 3
Example 1 was repeated, replacing tetrabutyl titanate in the preparation of TS-1 with tetramethyltitanateEster, tetraethyl titanate and tetrapropyl titanate, the amount of the component substances is kept unchanged, and after crystallization, washing and drying are carried out, and then 1M HCl aqueous solution is adopted for washing (the liquid-solid ratio is 50ml g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and XRF testing to obtain TS-1 samples with Si/Ti ratios of 32.0, 32.0 and 31.9 respectively, wherein the TS-1 samples have the following serial numbers: TS-1-H, TS-1-I, TS-1-J.
Example 4
Example 1 was repeated, the complexing agent in the preparation of TS-1 was replaced with isopropanol and ethanol, the amounts of the component substances were kept constant, and after crystallization, washing and drying were carried out, followed by washing with 1M HCl aqueous solution (liquid-to-solid ratio 50ml g/g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, and XRF testing to obtain TS-1 samples with Si/Ti ratios of 31.9 and 32.1 respectively, wherein the serial numbers are as follows: TS-1-K, TS-1-L.
Example 5
Example 1 was repeated, wherein the S auxiliary agent in the preparation of TS-1 was replaced with sodium bisulfite, potassium sulfite, potassium bisulfite, rubidium sulfite, rubidium bisulfite, cesium sulfite, and cesium bisulfite, the amounts of the component substances were kept constant, and after crystallization, washing and drying were carried out, and then washing with 1M HCl aqueous solution (liquid-solid ratio: 50ml g/g)-1) And roasting in air at 550 ℃ for 6 hours to obtain a TS-1 sample, wherein the TS-1 samples with Si/Ti ratios of 31.8, 32.0, 32.2, 31.9, 31.8, 31.7 and 32.1 are obtained by XRF test and have the numbers as follows: TS-1-M, TS-1-N, TS-1-O, TS-1-P, TS-1-Q, TS-1-R, TS-1-S.
Example 6
The liquid phase propylene epoxidation reaction is carried out in a batch kettle reactor. 0.4g of titanium silicalite TS-1 is added into a stainless steel batch reactor as a catalyst, and 3.5mol/L H is added2O270g of methanol solution, wherein the reaction temperature is maintained at 35 ℃, the propylene pressure is 3Mpa, and the reaction time is 1 h; then cooling, taking the feed liquid to analyze the product composition, titrating the residual H by adopting a potentiometric titration method2O2The molar concentration of (c).
The results are shown in Table 1. Wherein, UH2O2Showing the effective utilization rate of hydrogen peroxide and the calculation modeThe amount of material generated per the amount of hydrogen peroxide consumed per PO ═ 100%.
TABLE 1 Performance data for the TS-1 sample for the catalysis of propylene to propylene oxide
The results in the table show that due to the addition of the S auxiliary agent and the effect of the simultaneously introduced alkali metal ions, the catalyst shows excellent catalytic activity, and the propylene selectivity and the effective utilization rate of hydrogen peroxide are improved.
The chloropropene epoxidation reaction is carried out in a batch kettle reactor. 0.5g of titanium silicalite TS-1 is added into a metal batch reaction kettle as a catalyst, and 3.2mol/L H is added2O280g of methanol solution, and 65g of chloropropene is added; maintaining the reaction temperature at 40 deg.C, the system pressure at 0.3Mpa, and the reaction time at 2H, cooling, collecting the material liquid, analyzing the product composition, and analyzing the residual H by potentiometric titration2O2The molar concentration of (c).
The results are shown in Table 2. Wherein, UH2O2The effective utilization rate of hydrogen peroxide is shown, and the calculation mode is 100% of the amount of the substance generated by PO/the amount of the substance consumed by hydrogen peroxide.
TABLE 2 TS-1 Performance data of samples for catalyzing chloropropene to prepare epichlorohydrin
| Samples | XH2O2/％ | SPO/％ | UH2O2％ |
| TS-1-A | 44.8 | 80.1 | 70.5 |
| TS-1-B | 74.0 | 85.8 | 80.6 |
| TS-1-C | 91.3 | 95.3 | 86.5 |
| TS-1-D | 91.6 | 98.3 | 89.5 |
| TS-1-E | 91.5 | 98.5 | 89.1 |
| TS-1-F | 91.4 | 98.2 | 89.3 |
| TS-1-H | 91.6 | 98.4 | 89.1 |
| TS-1-I | 91.7 | 98.3 | 89.5 |
| TS-1-J | 91.5 | 98.5 | 89.2 |
| TS-1-K | 91.5 | 98.4 | 89.0 |
| TS-1-L | 91.6 | 98.1 | 89.1 |
| TS-1-M | 91.5 | 98.3 | 89.3 |
| TS-1-N | 91.5 | 98.5 | 89.2 |
| TS-1-O | 91.4 | 98.6 | 89.3 |
| TS-1-P | 91.5 | 98.4 | 89.4 |
| TS-1-Q | 91.3 | 98.6 | 89.2 |
| TS-1-R | 91.5 | 98.7 | 89.3 |
| TS-1-S | 91.4 | 98.6 | 89.2 |
The results in the table show that due to the addition of the S auxiliary agent and the effect of the simultaneously introduced alkali metal ions, the activity of the TS-1 molecular sieve catalyst is greatly improved, the selectivity of the epichlorohydrin and the effective rate of the hydrogen peroxide are both increased, which cannot be realized by the catalyst without the introduction of the S auxiliary agent and the alkali metal.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A process for the preparation of a catalyst for the liquid phase epoxidation of propene or chloropropene, which process comprises the steps of:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a silicon source hydrolysate A;
(2) uniformly mixing a titanium source and a complexing agent, dropwise adding the mixture into the silicon source hydrolysate A, and uniformly stirring to obtain a silicon-titanium hydrolysate B;
(3) heating the silicon-titanium hydrolysate B to remove alcohol, supplementing water and adding an S auxiliary agent to obtain silicon-titanium gel C;
(4) the silicon-titanium gel C is put into the container and crystallized for 20 to 120 hours at the temperature of 150-210 ℃ to obtain a crystallized product, and the titanium-silicon molecular sieve TS-1 is obtained after filtration, separation, drying, washing and roasting;
the S auxiliary agent is one or a mixture of more of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, rubidium sulfite, rubidium bisulfite, cesium sulfite and cesium bisulfite.
2. The production method according to claim 1,
the titanium-silicon ratio of the titanium-silicon molecular sieve is 31-33; the content of framework titanium is 3.0-3.2 wt%;
the silicon-titanium gel C in the step (3) has the composition of SiO in the molar ratio2：TiO2: template agent: and (2) S auxiliary agent: h2O＝1：(0.033-0.05)：(0.25-0.4)：(0.001-0.01)：(25-30)；
In the step (4), the drying temperature is 80-120 ℃, and the roasting temperature is 500-650 ℃.
3. The method according to claim 2, wherein the molar ratio of the substances in the silicon-titanium gel C in the step (3) is SiO2：TiO2: template agent: and (2) S auxiliary agent: h2O＝1：(0.035-0.05)：(0.25-0.4)：(0.002-0.008)：(25-30)。
4. The preparation method according to claim 1, wherein in the step (1), the silicon source is one or a mixture of more of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate; the template agent is tetrapropylammonium hydroxide.
5. The preparation method according to claim 1, wherein in the step (2), the titanium source is one or a mixture of more of tetraethyl orthotitanate, tetrabutyl orthotitanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride, and the complexing agent is one of isopropanol, acetylacetone and ethanol.
6. The production method according to claim 5, wherein the titanium source is tetrabutyl orthotitanate.
7. A catalyst prepared by the method of any one of claims 1 to 6.
8. Use of the catalyst of claim 7 in liquid phase epoxidation of propene or liquid phase epoxidation of chloropropene.
9. The use according to claim 8, wherein in the liquid phase epoxidation of propylene, the catalyst is added into a reaction kettle, and 1.5-5.0mol/L of H is added2O2The reaction temperature of the methanol solution is maintained at 30-50 ℃, the propylene pressure is 1.8-4.0Mpa, the propylene addition amount is 35-55g, and the reaction time is 0.5-3 h; the mass concentration of the catalyst in the catalytic system is 0.2-1%.
10. The use of claim 8, wherein the catalyst is added into a reaction kettle in the liquid phase epoxidation reaction of chloropropene, and 3.1-3.4mol/L of H is added2O2Methanol solution and 60-75g chloropropene, the reaction temperature is maintained at 35-50 ℃, the reaction pressure is 0.25-0.5Mpa, the reaction time is 1.5-3H, then the temperature is reduced, the feed liquid is taken out to analyze the product composition, and the residual H is analyzed by adopting potentiometric titration2O2The molar concentration of (c).
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| CN101279958A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane by epoxidation of propylene chloride |
| WO2011119217A1 (en) * | 2010-03-25 | 2011-09-29 | Dow Global Technologies Llc | Process for producing propylene oxide using a pretreated epoxidation catalyst |
| CN102320619A (en) * | 2011-10-06 | 2012-01-18 | 大连理工大学 | Synthesis method of titanium silicalite TS-1 |
| CN102502688A (en) * | 2011-10-31 | 2012-06-20 | 大连理工大学 | Titanium silicon molecular sieve modifying method based on mixed solution of TPAOH (tetrapropylammonium hydroxide) with sulfur-contained metal salts |
| CN110180586A (en) * | 2019-06-14 | 2019-08-30 | 大连理工大学 | The alkali metal ion modifying titanium-silicon molecular sieve TS-1 and preparation method thereof reacted for propylene and hydrogen peroxide gas-phase epoxidation |
| CN111036290A (en) * | 2019-12-25 | 2020-04-21 | 中国科学院大连化学物理研究所 | Preparation method of titanium silicalite molecular sieve for inhibiting byproduct generation in propylene epoxidation process |
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| CN114054084A (en) * | 2021-12-14 | 2022-02-18 | 红宝丽集团股份有限公司 | Preparation method of epoxidation catalyst |
| CN114054084B (en) * | 2021-12-14 | 2023-09-01 | 红宝丽集团股份有限公司 | Preparation method of epoxidation catalyst |
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