CN113457734A - Titanium-silicon molecular sieve and modification method and application thereof - Google Patents
Titanium-silicon molecular sieve and modification method and application thereof Download PDFInfo
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- CN113457734A CN113457734A CN202110853029.4A CN202110853029A CN113457734A CN 113457734 A CN113457734 A CN 113457734A CN 202110853029 A CN202110853029 A CN 202110853029A CN 113457734 A CN113457734 A CN 113457734A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a titanium-silicon molecular sieve and a modification method and application thereof, belonging to the technical field of petrochemical industry, and comprising the following steps: step 1, pretreating a titanium silicalite molecular sieve, mixing the pretreated titanium silicalite molecular sieve with silane and alkali metal hydroxide, and then carrying out ball milling treatment to obtain the ball-milled titanium silicalite molecular sieve; step 2, uniformly dispersing the titanium silicalite molecular sieve subjected to ball milling treatment in an alkali solution, and then reacting at the temperature of 80-160 ℃ for 3-18 h to obtain a primarily modified titanium silicalite molecular sieve; and 3, under the atmosphere of inert gas, preserving the temperature of the preliminarily modified titanium silicalite molecular sieve at 500-800 ℃ for 4-36 h, and finishing the modification of the titanium silicalite molecular sieve. The modification method is simple to operate, and the prepared titanium silicalite molecular sieve has strong hydrophobicity, good stability and good catalytic performance in the phase epoxidation reaction of propylene and hydrogen peroxide, and titanium species are not easy to lose.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a titanium silicalite molecular sieve (TS-1) and a modification method and application thereof.
Background
Titanium silicalite is a silicate zeolite with a titanium heteroatom in the crystal framework. Among them, TS-1 is an extremely important member of the titanium silicalite family. The method for preparing the TS-1 molecular sieve by adopting a hydrothermal synthesis method is firstly reported in 1983 by Taramasso and has an MFI topological structure, and a TS-1 molecular sieve channel is a three-dimensional ten-membered ring channel system formed by intersecting Z-shaped ten-membered ring channels and straight ten-membered ring channels.
Research shows that isolated four-coordination framework titanium in the TS-1 molecular sieve is an active center for catalytic oxidation, and most of the framework titanium species are positioned in the pore channels of the molecular sieve, so that the TS-1 is usually used as a catalyst and H in the prior art2O2The new process (HPPO process) for preparing PO by catalyzing propylene epoxidation by using an oxidant, however, the TS-1 molecular sieve prepared by the traditional method such as the classical method has low hydrophobicity, titanium species are easy to lose and the stability is poor, so that the performance of the molecular sieve in the HPPO process is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a titanium silicalite molecular sieve, a modification method and application thereof, so that the modified titanium silicalite molecular sieve has strong hydrophobicity, is difficult to lose titanium species, has good stability and has good catalytic performance in a new process for preparing PO by catalyzing propylene epoxidation.
The modification method of the titanium silicalite molecular sieve is realized by the following technical scheme:
the first purpose of the invention is to provide a method for modifying a titanium silicalite molecular sieve, which comprises the following steps:
step 1, pretreating a titanium silicalite molecular sieve to remove a template agent possibly remaining in a pore channel of the titanium silicalite molecular sieve; then mixing the pretreated titanium silicalite molecular sieve with silane and alkali metal hydroxide, and carrying out ball milling treatment to obtain a ball-milled titanium silicalite molecular sieve;
step 2, uniformly dispersing the titanium silicalite molecular sieve subjected to ball milling treatment in an alkaline solution, and then reacting at the temperature of 80-160 ℃ for 3-18 h to obtain a primarily modified titanium silicalite molecular sieve;
and 3, under the atmosphere of inert gas, preserving the temperature of the preliminarily modified titanium silicalite molecular sieve at 500-800 ℃ for 4-36 h, and finishing the modification of the titanium silicalite molecular sieve.
Further, the ball milling treatment is carried out for 1-12 h at the rotating speed of 300-600 r/min by using a grinding ball with the diameter of 3-10 mm at the temperature of 30-80 ℃ in an inert gas atmosphere.
Further, in the step 1, the mass ratio of the alkali metal hydroxide to the pretreated titanium silicalite molecular sieve is 0.01-0.05: 1.
Further, in the step 1, the mass ratio of the silane to the pretreated titanium silicalite molecular sieve is 0.05-0.1: 1;
the silane is monosilane SiH4Or disilane Si2H6。
Further, the dosage ratio of the alkaline solution to the titanium silicalite molecular sieve subjected to ball milling treatment is 5-15 mL/g.
Further, the alkali solution is TPAOH, or TPAOH and NH3·H2And (3) mixed solution of O.
Further, the concentration of the TPAOH is 0.05-0.15 mol/L.
Further, the TPAOH and NH3·H2In a mixed solution of O, TPAOH and NH3·H2The molar ratio of O is 0.5-1.5: 1.
Further, in the step 1, the pretreatment is to bake the titanium silicalite molecular sieve at 400-600 ℃ for 3-20 h.
Further, the inert gas is one or more of argon and nitrogen.
The second purpose of the invention is to provide a modified titanium silicalite molecular sieve prepared according to the modification method.
The third purpose of the invention is to provide the application of the modified titanium silicalite molecular sieve in catalyzing the propylene and hydrogen peroxide gas phase epoxidation reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly carries out roasting pretreatment on the titanium silicalite molecular sieve to remove the template agent possibly remained in the pore channel of the titanium silicalite molecular sieve and simultaneously realizes the activation of the titanium silicalite molecular sieve so as to be convenient for the subsequent treatment.
The pretreated titanium-silicon molecular sieve, silane and alkali metal hydroxide are mixed and then are subjected to ball milling treatment, and the ball milling titanium-silicon molecular sieve is uniformly crushed, so that the pore channel of the titanium-silicon molecular sieve is fully exposed on the outer surface, and the alkali metal hydroxide and the silane can better enter the pore channel and are combined with the surface of the pore channel and the defect position of the pore channel, so that framework titanium is protected, and the condition that the activity of the titanium-silicon molecular sieve is influenced after the framework titanium is etched during subsequent alkali treatment is avoided; meanwhile, sintering and agglomeration of active sites of the titanium silicalite molecular sieve in the later heat treatment process can be avoided.
The titanium silicalite molecular sieve after ball milling is uniformly dispersed in an alkali solution, the titanium silicalite molecular sieve is etched through alkali, silicon, titanium and unstable silane combined with part of pore channels on the surface of the titanium silicalite molecular sieve can be etched, so that the titanium silicalite molecular sieve has more pores, the titanium silicalite molecular sieve has multi-stage pores, the specific surface area of the titanium silicalite molecular sieve is increased, and the catalytic performance of the titanium silicalite molecular sieve is improved.
The alkali metal hydroxide distributed on the surface of the titanium-silicon molecular sieve can convert alkali metal ions and hydroxyl ions under the action of water molecules, and meanwhile, silicon hydroxyl on the surface of the titanium-silicon molecular sieve loses protons in the alkali solution to form silicon-oxygen anions, so that the surface of the titanium-silicon molecular sieve is charged with negative charges, and then a part of the alkali metal ions and TPA in the alkali solution+The titanium-silicon molecular sieve can be adsorbed on the surface of the titanium-silicon molecular sieve under the interaction of positive and negative charges, so that the etching of the surface of the titanium-silicon molecular sieve is inhibited, the framework titanium in the titanium-silicon molecular sieve is further protected, the framework titanium is prevented from being etched, and the activity of the titanium-silicon molecular sieve is ensured. In addition, titanium and silicon species etched from the titanium-silicon molecular sieve and OH in the channels of the titanium-silicon molecular sieve, which is poorly bonded by silane, in the alkaline solution-Under the action of (3), the TPA can diffuse to the surface of the titanium silicalite molecular sieve and is adsorbed on the surface of the titanium silicalite molecular sieve+Under the action of the catalyst, secondary crystallization is carried out to form hollow zeolite, so that the titanium-silicon molecular sieve not only forms hierarchical pores, but also the surface of the molecular sieve is modified, and the titanium-silicon molecular sieve is extractedThe surface hydrophobicity of the macromolecular sieve leads the activity and the stability of the treated TS-1 to be obviously improved compared with the activity and the stability of the conventional TS-1 molecular sieve for catalyzing propylene epoxidation.
The invention uses TPAOH and NH3·H2The mixed use of O enhances the dissolution and recrystallization of silicon and titanium species of the molecular sieve in the alkali solution, shortens the alkali treatment time and improves the treatment efficiency of the invention.
According to the invention, the titanium silicalite molecular sieve subjected to alkali treatment is roasted under a specific temperature condition, so that water and redundant hydroxyl groups adsorbed on the surface and in a pore channel of the titanium silicalite molecular sieve and redundant groups introduced in the ball-milling treatment process can be removed to the maximum extent, more binding sites are provided for alkali metal ions, the alkali metal ions are dispersed on the surface and in the pore channel of the molecular sieve more uniformly, and the catalytic effect of the molecular sieve for catalyzing propylene epoxidation is further ensured.
The modification method of the invention is simple to operate and convenient to popularize and use.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be noted that the titanium silicalite molecular sieves used in the following examples are prepared by the classical method, and those skilled in the art should know how to prepare them, so the present invention is not described herein.
Example 1
The embodiment provides a modification method of a titanium silicalite molecular sieve, which comprises the following steps:
roasting the titanium silicalite TS-1 prepared by a classical method at 500 ℃ for 8h, cooling, mixing 1000g of the roasted TS-1 with 10g of sodium hydroxide and 50g of silane, putting the mixture into a ball mill, and treating for 6h at 60 ℃ by using grinding balls with the diameter of 5mm in a nitrogen atmosphere at the rotating speed of 500r/min to obtain the ball-milled titanium silicalite.
Uniformly dispersing the ball-milled titanium silicalite molecular sieve in an alkali solution, then reacting for 10h at the temperature of 120 ℃, filtering, washing filter residue with deionized water until the pH value of a washing solution is neutral, and drying for 3h in a drying oven at the temperature of 60 ℃ to obtain the primarily modified titanium silicalite molecular sieve.
And (3) placing the preliminarily modified titanium silicalite molecular sieve in a muffle furnace under argon atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, and preserving heat at the temperature of 600 ℃ for 4h to finish the modification of the titanium silicalite molecular sieve.
The aqueous alkali is TPAOH and NH3·H2Mixed solution of O, TPAOH concentration of 0.15mol/L, NH3·H2The concentration of O was 0.15 mol/L.
The dosage ratio of the alkali solution to the titanium silicalite molecular sieve after ball milling treatment is 10 mL/g;
the flow rate of argon was 50 mL/min.
Example 2
The embodiment provides a modification method of a titanium silicalite molecular sieve, which comprises the following steps:
roasting the titanium silicalite TS-1 prepared by a classical method at 400 ℃ for 20h, cooling, mixing 1000g of the roasted TS-1 with 30g of sodium hydroxide and 70g of silane, putting the mixture into a ball mill, and treating for 12h at the rotation speed of 600r/min by using a grinding ball with the diameter of 3mm at the temperature of 30 ℃ in the nitrogen atmosphere to obtain the ball-milled titanium silicalite.
Uniformly dispersing the ball-milled titanium silicalite molecular sieve in an alkali solution, then reacting for 18h at the temperature of 80 ℃, filtering, washing filter residue with deionized water until the pH value of a washing solution is neutral, and drying for 3h in a drying oven at the temperature of 60 ℃ to obtain the primarily modified titanium silicalite molecular sieve.
And (3) placing the preliminarily modified titanium silicalite molecular sieve in a muffle furnace under argon atmosphere, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat at 500 ℃ for 20h to finish the modification of the titanium silicalite molecular sieve.
The aqueous alkali is TPAOH and NH3·H2Mixed solution of O, TPAOH concentration of 0.08mol/L, NH3·H2The concentration of O was 0.16 mol/L.
The dosage ratio of the alkali solution to the titanium silicalite molecular sieve after ball milling treatment is 5 mL/g;
the flow rate of argon was 50 mL/min.
Example 3
The embodiment provides a modification method of a titanium silicalite molecular sieve, which comprises the following steps:
roasting the titanium silicalite TS-1 prepared by a classical method at 600 ℃ for 3h, cooling, mixing 1000g of the roasted TS-1 with 50g of sodium hydroxide and 100g of silane, putting the mixture into a ball mill, and treating the mixture for 1h at 80 ℃ by using a grinding ball with the diameter of 3mm in a nitrogen atmosphere at the rotating speed of 300r/min to obtain the ball-milled titanium silicalite.
Uniformly dispersing the ball-milled titanium silicalite molecular sieve in an alkali solution, then reacting for 3h at 160 ℃, filtering, washing filter residue with deionized water until the pH value of a washing solution is neutral, and drying for 3h in a 60 ℃ oven to obtain the primarily modified titanium silicalite molecular sieve.
And (3) placing the preliminarily modified titanium silicalite molecular sieve in a muffle furnace under argon atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving heat at the temperature of 800 ℃ for 3h to finish the modification of the titanium silicalite molecular sieve.
The aqueous alkali is TPAOH and NH3·H2Mixed solution of O, TPAOH concentration of 0.15mol/L, NH3·H2The concentration of O was 0.1 mol/L.
The dosage ratio of the alkali solution to the titanium silicalite molecular sieve after ball milling treatment is 15 mL/g;
the flow rate of argon was 50 mL/min.
Experimental part
The invention uses the titanium silicalite molecular sieve obtained by the classical method without modification, the modified titanium silicalite molecular sieve obtained by the comparative example 1, the example 2 and the example 3 as the catalyst, H2O2As the oxidizing agent, the vapor phase epoxidation of propylene was carried out according to the reaction conditions described in the publication (catalytic bulletin, 31(2010) 1195-1199).
The reaction conditions are as follows: the gas velocities of hydrogen, oxygen and propylene were 170mL/min, 8mL/min and 18mL/min (H), respectively2/O2/C3170/8/18), catalysisThe additive amount of the agent is 0.5g (WHSVC)3＝2.53h-1) The epoxidation reaction temperature was 110 ℃.
The main parameters for the evaluation of the performance of the gas phase epoxidation of propylene are: propylene conversion, PO selectivity and hydrogen peroxide availability. Wherein, the conversion rate of hydrogen peroxide is measured by an iodometry method, the selectivity of propylene oxide and the effective utilization rate of hydrogen peroxide are analyzed by gas chromatography, and the evaluation results are shown in table 1.
TABLE 1
| Catalyst and process for preparing same | Oxidizing agent | Conversion of propylene% | PO selectivity% | Effective utilization rate of hydrogen peroxide% |
| Comparative example | H2O2 | 7.3 | 76.7 | 36.5 |
| Example 1 | H2O2 | 14.8 | 96.1 | 72.2 |
| Example 2 | H2O2 | 14.1 | 94.9 | 70.6 |
| Example 3 | H2O2 | 14.5 | 95.7 | 71.9 |
As can be seen from Table 1, the modified titanium silicalite molecular sieve obtained by the modification method of the invention has greatly improved catalytic performance in the reaction of preparing PO by catalyzing the epoxidation of propylene.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A modification method of a titanium silicalite molecular sieve is characterized by comprising the following steps:
step 1, pretreating a titanium silicalite molecular sieve, mixing the pretreated titanium silicalite molecular sieve with silane and alkali metal hydroxide, and then carrying out ball milling treatment to obtain the ball-milled titanium silicalite molecular sieve;
step 2, uniformly dispersing the titanium silicalite molecular sieve subjected to ball milling treatment in an alkali solution, and then reacting at the temperature of 80-160 ℃ for 3-18 h to obtain a primarily modified titanium silicalite molecular sieve;
and 3, under the atmosphere of inert gas, preserving the temperature of the preliminarily modified titanium silicalite molecular sieve at 500-800 ℃ for 4-36 h, and finishing the modification of the titanium silicalite molecular sieve.
2. The modification method according to claim 1, wherein in the step 1, the mass ratio of the alkali metal hydroxide to the pretreated titanium silicalite molecular sieve is 0.01-0.05: 1;
the alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
3. The modification method according to claim 1, wherein in the step 1, the mass ratio of the silane to the pretreated titanium silicalite molecular sieve is 0.05-0.1: 1;
the silane is monosilane SiH4Or disilane Si2H6。
4. The modification method according to claim 1, wherein the ball milling treatment is carried out at a temperature of 30 to 80 ℃ in an inert gas atmosphere with a rotating speed of 300 to 600r/min for 1 to 12 hours by using a grinding ball having a diameter of 3 to 10 mm.
5. The modification method of claim 1, wherein the dosage ratio of the alkali solution to the ball-milled titanium silicalite molecular sieve is 5-15 mL/g;
the alkali solution is TPAOH or TPAOH and NH3·H2And (3) mixed solution of O.
6. The modification method according to claim 5, wherein the concentration of TPAOH is 0.05 to 0.15 mol/L.
7. The modification method according to claim 6, wherein the TPAOH is reacted with NH3·H2In a mixed solution of O, TPAOH and NH3·H2The molar ratio of O is 0.5-1.5: 1.
8. The modification method according to claim 1, wherein in the step 1, the pretreatment is to calcine the titanium silicalite molecular sieve at 400-600 ℃ for 3-20 h.
9. A modified titanium silicalite molecular sieve prepared according to the modification method of any one of claims 1 to 8.
10. Use of the modified titanium silicalite molecular sieve of claim 9 in catalyzing the hydrogen peroxide vapor phase epoxidation of propylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118681593A (en) * | 2024-08-26 | 2024-09-24 | 天津渤化化工发展有限公司 | High-activity titanium-silicon molecular sieve microsphere catalyst, preparation method and application thereof |
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| CN118681593A (en) * | 2024-08-26 | 2024-09-24 | 天津渤化化工发展有限公司 | High-activity titanium-silicon molecular sieve microsphere catalyst, preparation method and application thereof |
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