WO2013063894A1 - 一种钛硅分子筛的改性方法 - Google Patents

一种钛硅分子筛的改性方法 Download PDF

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WO2013063894A1
WO2013063894A1 PCT/CN2012/072500 CN2012072500W WO2013063894A1 WO 2013063894 A1 WO2013063894 A1 WO 2013063894A1 CN 2012072500 W CN2012072500 W CN 2012072500W WO 2013063894 A1 WO2013063894 A1 WO 2013063894A1
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selectivity
conversion
modification
modified
tpaoh
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French (fr)
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郭洪臣
刘光红
刘玲
苏际
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Dalian University of Technology
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Dalian University of Technology
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Priority claimed from CN201110338224XA external-priority patent/CN102502689A/zh
Priority claimed from CN2011103376094A external-priority patent/CN102502688A/zh
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Priority to US14/355,138 priority Critical patent/US20140356279A1/en
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • 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
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • 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
    • 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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment

Definitions

  • the invention belongs to the technical field of inorganic chemical synthesis and relates to a modification method of titanium silicon molecular sieve (TS-1).
  • Titanium silicon molecular sieve (TS-1) is a transition metal titanium introduced into MFI during synthesis
  • TS-1 The green catalytic system composed of low concentration hydrogen peroxide can be widely used in the selective oxidation reaction of organic substances such as alcohols, phenols, olefins and ethers, among which phenol hydroxylation, cyclohexanone amine oxidation and propylene epoxidation have been industrialized. .
  • TS-1 hydrothermal synthesis has formed two types of systems, one of which uses tetrapropylammonium hydroxide (TPAOH).
  • TPAOH tetrapropylammonium hydroxide
  • the templating agent synthesizes the TS-1 system (classical system).
  • TS-1 can also be synthesized by various methods such as isomorphous substitution. But because the Ti-O bond is better than Si-O The bond length is difficult for the titanium atoms to enter the silicon skeleton, so no matter which method is used to synthesize TS-1, the non-skeletal titanium species will inevitably be produced more or less. The production of non-skeletal titanium species will be TS-1 The product has two negative effects. First, these non-framework titanium species do not have oxidative catalytic activity but can cause a large amount of decomposition of the oxidant hydrogen peroxide, so its presence will cause TS-1. The catalytic performance is reduced; secondly, the non-framework titanium amount is difficult to control, which inevitably results in the performance of different batches of synthetic TS-1 not being repeated.
  • a method for silanization modification of zeolites of MFI structure is described in US Pat. No. 5,637,099, US Pat. No. 5,607,888, US Pat. No. 5,476, 682, US Pat. No. 5,365,003, CN 10,
  • a representative patent CN101602013A discloses a gas phase silanized TS-1 modification method. The technical feature is that a silylation reagent is introduced in a nitrogen atmosphere at a temperature of 50-300 o C for 0.5-10 h.
  • Patent CN1245090A, US 4794198, CN1657168A, CN101591024A, CN101417238A and the like introduce a modification method for pickling TS-1 molecular sieve.
  • One representative of the patent CN1657168A discloses a method for modifying uncalcined TS-1 molecular sieves with an acid. Which is a technique wherein the unfired TS-1 molecular sieve raw powder, an acidic compound mixed solution, at room temperature for pickling -200 o C, then the conventional filter, washed, dried, calcined for processing.
  • One representative of the patent CN1268400A discloses a method for modifying TS-1 using an aqueous solution of a metal salt or a mixture thereof. The basic principle is to use a salt cation to inhibit a stronger acid center in the TS-1 molecular sieve that can cause a side reaction.
  • TS-1 can be modified with organic or inorganic lye at TS-1.
  • the formation of holes is conducive to the diffusion of reactants and products.
  • the following patent describes a method for modifying TS-1 using an organic or inorganic lye.
  • a method for modifying TS-1 using an organic base is disclosed in conjunction with US Pat. No. 6,475,465 B2 and CN 1 301 599 A (Application No. 1999.12.24, Application No. 99126289.1).
  • the common technical feature is an organic base such as a fatty amine compound, an alcohol amine compound, a quaternary ammonium base compound or a mixture of these organic bases (mol): TS-1 molecular sieve (g): water (mol) according to (0.005- 0.5 ) :100 :( 5-200 ) ratio mixing, reacting at 150-180 o C autogenous pressure for 2 hours to 3 days.
  • the technical feature is also that the TS-1 molecular sieve used may be TS-1 raw powder or acid-modified TS-1.
  • Patent CN124090A (Application No. 1998.8.18, Application No. 98117503.1) discloses a method for further modifying an acid-modified TS-1 sample using an organic base.
  • the technical feature is that the synthesized TS-1 molecular sieve is uniformly mixed with the acidic compound solution, and reacted at 5-95 o C for 5 minutes to 6 hours, and then the obtained acid-modified TS-1 molecular sieve and organic base are further obtained.
  • the mixed solution was mixed and reacted under autogenous pressure at 120-200 o C for 2 hours to 8 days in a sealed reaction vessel.
  • the organic base is an organic base such as a fatty amine compound, an alcohol amine compound or a quaternary ammonium base compound or a mixture of these organic bases.
  • Patent CN101850985A (Application Date 2009.03.31, Application No. 200910131993.5) discloses a method for modifying TS-1 by using an alkali solution of a pore former.
  • the pore former is selected from the group consisting of sucrose, starch, furfural, phenolic, benzothiophene, dibenzothiophene, naphthalene, naphthothiophene, quinoline, carbazole, anthracene, polypropylene, polyethylene glycol, polystyrene. , one or a mixture of polyvinyl chloride and polyethylene and their derivatives.
  • the alkali source is divided into an organic base and an inorganic base, and the organic base is selected from the group consisting of urea, a quaternary ammonium base compound, a fatty amine compound, an alcohol amine compound or a mixture thereof; the inorganic base is selected from the group consisting of ammonia water, sodium hydroxide and hydrogen. Potassium oxide, barium hydroxide or a mixture thereof.
  • Patent CN101537372A, CN101618338A, CN101618339A, CN101623653A, 101658791A, CN101658798A, CN1016646696A, CN101665256A, CN101670298A et al. disclose a method for modifying TS-1 using an alkaline solution of a noble metal source. Its common technical feature is to be TS-1 The molecular sieve, the aqueous solution of silicon, the precious metal source, the protective agent, and the alkali source are uniformly mixed, and then the mixture is hydrothermally modified in a closed reaction vessel, and the product is recovered.
  • the precious metal source is selected from the group consisting of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag, and Au
  • the protective agent is a polymer or a surfactant, a polymer such as glucose, cyclodextrin, polybenzimidazole, and polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene, etc., and the surfactant includes a cation.
  • Surfactants, anionic surfactants and nonionic surfactants are examples of surfactants.
  • the alkali source is divided into an organic base and an inorganic base, and the organic base is selected from the group consisting of urea, a quaternary ammonium base compound, a fatty amine compound, an alcohol amine compound or a mixture thereof; the inorganic base is selected from the group consisting of ammonia water, sodium hydroxide and hydrogen. Potassium oxide, barium hydroxide or a mixture thereof.
  • Patent CN1260241 (Application No. 1998.4.10, Application No. 98101357.0) discloses a method for modifying TS-1 by using an alkaline titanium source hydrolysis solution.
  • the alkaline solution is provided by an organic amine such as a quaternary ammonium base compound, a fatty amine compound, an alcohol amine compound or a mixture thereof.
  • Patent CN1421389A (Application No. 2001.11.29, Application No. 01404182.6) discloses a method for modifying TS-1 using an alkali solution of silicon.
  • the alkaline solution is provided by an organic amine such as a quaternary ammonium base compound, a fatty amine compound, an alcohol amine compound or a mixture thereof.
  • Patent CN101850986A (Application Date 2009.03.31, Application No. 200910131992.0) discloses a method for modifying TS-1 by using a mixed alkali solution.
  • the technical feature is that TS-1 is added to a mixed alkaline aqueous solution containing an inorganic base and an organic base to obtain a composition of TS-1: inorganic base: organic base: water is 100: (0.005-5): (0.01-10 ): (200-10000) mixture, in which TS-1 and water are in grams, organic base and inorganic base are modified on a molar basis, and the mixture is modified at a temperature of 80-200 o C and self-lifting pressure for 2-360 hours. .
  • the organic base is selected from the group consisting of urea, a quaternary ammonium base compound, a fatty amine compound, an alcohol amine compound or a mixture thereof;
  • the inorganic base is selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, barium hydroxide or a mixture thereof.
  • the patent clearly indicates that the molar ratio of the organic base to the inorganic base is 1-50:1.
  • the following publication also describes a method for modifying TS-1 using an organic lye.
  • TS-1 catalyzes the optimization of H 2 O 2 epoxidized styrene
  • Yin Jianbo, master thesis reported a method for modifying TS-1 using organic and inorganic lye and alkaline salts. It is characterized in that TS-1 is placed in a solution of organic and inorganic lye and salt, and after modification at 175 °C for 24 hours, it is filtered, washed, dried at 100 ° C, and calcined in an air atmosphere at 540 ° C for 6 h.
  • the salts include sodium carbonate, sodium citrate, sodium acetate and sodium nitrate; the inorganic base is ammonia water; and the organic base includes tetrapropylammonium hydroxide, tetraethylammonium bromide (salt), triethanolamine, propylamine and urea. It is worth mentioning that the modification effect of the inorganic lye and the salt is greatly different from the modification by the organic base, and the salt modification only utilizes the action of the salt cation as the acidic inhibitor.
  • lye for TS-1 Modified method. It is characterized by the fact that the lye includes TMAOH, TEAOH, TPAOH, TBAOH, NaOH, NH 3 , Na 2 CO 3 , etc. and the TPAOH modification effect is optimal.
  • the modification of TS-1 by inorganic bases is mainly manifested in the alkaline medium causing the TS-1 skeleton to dissolve and etching TS-1. Holes are formed inside the crystal; general organic bases such as fatty amines, alcohol amines, etc. act similarly to inorganic bases; but in addition to the solubilization, quaternary ammonium bases can recrystallize dissolved silicon-titanium species, thereby allowing some Non-skeletal titanium re-enters the skeleton.
  • Public literature generally considers TPAOH modified TS-1 is superior to other quaternary ammonium bases.
  • TPAOH modification has a problem of applicability, ie this method is not for all TS-1 It has a modification effect and is only suitable for TS-1 which is synthesized by classical systems and individual inexpensive systems. This is mainly because of cheap TS-1 The grains are large and the pores contain more amorphous non-skeletal titanium species. These factors lead to a long outward diffusion path for the titanium species dissolved inside the modification process, and the diffusion resistance is large. Titanium species in solution are very easy to condense into titanium dioxide in the form of anatase, so most of them are cheap. The improvement of TS-1 by TPAOH modification activity is not obvious.
  • the technical problem to be solved by the present invention is to provide a method for modifying TS-1 by using a mixture of TPAOH and an inorganic salt, which can simultaneously improve the catalytic performance of the gas phase and liquid phase propylene epoxidation of the TS-1 molecular sieve.
  • the key to the present invention is the addition of an alkali metal salt when the TS-1 is modified with TPAOH.
  • Our study found that the modification of TS-1 with a mixture of TPAOH and an alkali metal salt can solve the applicability problem of TPAOH modified TS-1, that is, TPAOH and alkali metal salt mixture can be applied to modification.
  • the TS-1 synthesized by the classical system can also be applied to the TS-1 synthesized by the modified inexpensive system.
  • the alkali metal cation can form a monodisperse or oligomeric titanate ion pair with the titanate ion in the solution, avoiding the condensation of the titanate ion into the anatase form of the polytitanium dioxide.
  • This is important for the modification of the inexpensive system TS-1, because the cheap TS-1 grains are large, and when modified, the OH - attacks the skeleton, causing the Si and Ti species to fall off from the internal defects of the crystal.
  • the strong interaction of alkali metal cations with titanium species avoids the polymerization of titanium species, allowing more titanium species to migrate out of the inexpensive large-grain TS-1 crystals and re-enter the framework externally.
  • TS-1 modified with TPAOH and an alkali metal salt mixture produced a skeleton Ti-O-Ti structure (Raman characteristic peak 850 cm -1 ).
  • the skeleton Ti-O-Ti can become a highly active titanium species in the reaction, so it is more advantageous to modify TS-1 by using a mixture of TPAOH and an alkali metal salt to enhance the catalytic activity.
  • TS-1 Pretreatment refers to high temperature removal of the templating agent pretreatment, which can be carried out in an air atmosphere or a protective gas atmosphere.
  • the calcination temperature is generally 300-700 ° C, preferably 400-600 °C; calcination time is 30min-200h, preferably 3-24h.
  • the purpose of the calcination is to remove the organic templating agent deposited in the pores during the synthesis, and the templating agent blocked in the pores can hinder the lye pair TS-1.
  • TS-1 can be hydrothermally synthesized according to the patents and publications mentioned in the background of the patent. Any engineer familiar with the art can prepare the invention according to the literature. TS-1 molecular sieve.
  • the pretreated TS-1 is treated with a mixture containing TPAOH and an alkali metal salt.
  • the alkali metal salt refers to all lithium, sodium, potassium-containing salt compounds and mixtures thereof.
  • the ratio of TS-1, TPAOH, alkali metal salt and water can be set to TS-1 during the modification process.
  • TPAOH ( mol ): salt ( g ): water ( g ) 50 : 0.005-50 : 0.05-5 : 200-2000
  • the reaction is best after modification.
  • the modification is carried out in a reaction vessel with a modification temperature range of 50-250 ° C and a suitable time of 2 hours to 10 Day.
  • the modification can be carried out under stirring or in a static state. If stirring is used, the stirring speed is to ensure the solution concentration and temperature are uniform.
  • the third step is on the modified TS-1.
  • Post-processing The post-treatment described is meant to include solid-liquid separation, washing, drying, and calcination. Washing is carried out with deionized water and washed to a pH of 7-9; drying can be carried out in an air or protective atmosphere at a temperature 60-200 ° C, time is 1-100h, preferably 3-10h; roasting can be carried out in air or in a protective gas atmosphere, the roasting temperature can be selected from 200 °C -500 °C, time 30min-100h. When the washing is higher than 9, the residual alkali metal cation of TS-1 will affect the modification effect. Modified TS-1 does not roast or is not at 200 °C -500 Calcined in the °C range, TS-1 has poor stability and low activity.
  • the effect and benefit of the present invention is that the method for modifying TS-1 molecular sieve has universal applicability, and is suitable for TS-1 synthesized by various methods.
  • Molecular sieves especially TS-1 molecular sieves synthesized by inexpensive systems, can simultaneously improve the catalytic performance of the gas phase and liquid phase propylene epoxidation of TS-1 zeolite.
  • This comparative example illustrates the modification of TS-1 synthesized by the classical system using a mixture of TPAOH and an alkali metal salt.
  • the TS-1 synthesized by the classic system (patent USP4410501) was calcined at 540 °C in an air atmosphere. 6h to remove the templating agent.
  • the obtained TS-1 is suction filtered, deionized water is washed to pH ⁇ 7, dried, and finally calcined at 390 °C. Hours.
  • the TS-1 sample before and after the modification was subjected to a gas phase epoxidation reaction of propylene according to the reaction conditions described in the published literature (Journal of Catalysis, 31 (2010) 1195-1199).
  • the main parameters for the evaluation of the performance of propylene gas solid phase epoxidation are: C 3 H 6 conversion and PO (propylene oxide) selectivity. The results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.6% and 91.2%, respectively, and the modified C 3 H 6 conversion and PO selectivity of the modified samples were 7.9% and 94.2. %.
  • Comparative Example 1 was repeated, but the modified sample was a large-grain inexpensive TS-1 synthesized according to the publication Appl. Catal. A, 185, (1999) 11.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively, and the modified C 3 H 6 conversion and PO selectivity of the sample were 5.2. % and 82.2%.
  • the conversion of TS-1 hydrogen peroxide before modification was 76.3%, and the selectivity of propylene oxide was 78.8%, the effective utilization rate of hydrogen peroxide is 78.2%; the converted TS-1 hydrogen peroxide is 87.2%, the propylene oxide selectivity is 91.3%, and the effective utilization rate of hydrogen peroxide is 89.5%.
  • the first step will be in accordance with the open literature Appl.Catal. A, 185, (1999) 11
  • the synthesized large-grain inexpensive TS-1 was calcined at 540 ° C for 6 hours to remove the templating agent.
  • the TS-1 sample before and after the modification was subjected to a gas phase epoxidation reaction of propylene according to the reaction conditions described in the published literature (Journal of Catalysis, 31 (2010) 1195-1199).
  • the main parameters for the performance evaluation of propylene gas solid phase epoxidation are: C 3 H 6 conversion and PO selectivity. The results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively, and the modified C 3 H 6 conversion and PO selectivity of the modified samples were 8.8% and 99.2. %.
  • Example 1 was repeated, but the modified sample was TS-1 synthesized by the classical system (Patent USP 4410501).
  • the epoxidation results showed that the TS-1C 3 H 6 conversion and PO selectivity were 4.6% and 91.2%, respectively, and the C 3 H 6 conversion and PO selectivity of TS-1 after modification were 9.5%. And 99.4%.
  • Example 1 to carry out propylene liquid phase epoxidation under the following reaction conditions: 400 ml stainless steel high pressure batch reactor, add 0.2g catalyst A, 30ml methanol, 2ml 30% hydrogen peroxide, propylene is fed under stirring, propylene pressure 0.4MPa, reaction temperature 50 °C, reaction time 60 Samples were taken at minute and the conversion of hydrogen peroxide was measured by iodometric method. The selectivity of propylene oxide and the effective utilization of hydrogen peroxide were analyzed by gas chromatography.
  • the conversion of TS-1 hydrogen peroxide before reformation was 72.7%, and the selectivity of propylene oxide was 73.4%, the effective utilization rate of hydrogen peroxide is 68.8%; the converted TS-1 hydrogen peroxide is 89.2%, the propylene oxide selectivity is 91.5%, and the effective utilization rate of hydrogen peroxide is 93.4%.
  • Example 1 was repeated, but with equal amounts of lithium bromide, potassium bromide, lithium chloride, sodium chloride, potassium chloride, lithium carbonate, sodium carbonate, potassium carbonate, lithium sulfite, potassium sulfite, lithium sulfate, sulfuric acid, respectively.
  • Sodium, potassium sulphate, lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, lithium sulfide, sodium sulfide, potassium sulfide, and the like are substituted for sodium bromide.
  • the epoxidation reaction showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the conversion of C 3 H 6 and PO selectivity of lithium bromide modified sample were 8.1% and 99.1%; the potassium bromide modified sample C 3 H 6 conversion and PO selectivity were 8.1% and 98.9%; the lithium chloride modified sample C 3 H 6 conversion and PO selectivity were 8.0% and 99.0%; C 3 H 6 conversion and PO selectivity of sodium chloride modified samples were 8.1% and 99.1%; potassium chloride modified sample C 3 H 6 conversion and PO selectivity 8.2% and 99.0%; the conversion of C 3 H 6 and the selectivity of PO of 8.1% and 99.1% of the sample modified by lithium carbonate; the conversion of C 3 H 6 and the selectivity of PO of 8.2 after sodium carbonate modification are 8.2 % and 98.5%; potassium carbonate modified sample C 3 H 6 conversion and PO selectivity were 7.8% and 99.0%; lithium sulfite modified sample C 3 H 6 conversion and PO selectivity
  • the conversion of C 3 H 6 and the selectivity of PO of the samples modified by sodium hydrogen sulfite were 8.6% and 99.5% ;
  • the conversion of C 3 H 6 and the selectivity of PO of the sample modified by potassium bisulfite were 8.6% and 99.2%;
  • the conversion of C 3 H 6 and the selectivity of PO of the sample modified by lithium hydrogen sulfate were 8.5% and 99.3%.
  • the sample modified by sodium bisulfate had a C 3 H 6 conversion and PO selectivity of 8.4% and 99.5%;
  • the potassium sulphate modified sample had a C 3 H 6 conversion and PO selectivity of 8.5% and 99.1%.
  • the lithium sulfide modified sample had a C 3 H 6 conversion and PO selectivity of 8.3% and 99.3%; the sodium sulfide modified sample had a C 3 H 6 conversion and PO selectivity of 8.4% and 99.3%;
  • the potassium modified sample had a C 3 H 6 conversion and PO selectivity of 8.4% and 99.2%.
  • Example 1 was repeated, but with a mixture of equal amounts of lithium bromide and potassium bromide (mixing ratio 1:1), a mixture of sodium chloride and potassium chloride (mixing ratio 1:4), a mixture of lithium carbonate and sodium carbonate, respectively.
  • a mixture (mixing ratio 1:2), a mixture of lithium hydrogen sulfate and sodium hydrogensulfate (mixing ratio 1:3), a mixture of lithium sulfide and sodium sulfide, and potassium sulfide (mixing ratio 1:1:1) was substituted for sodium bromide.
  • the epoxidation reaction showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; after modification with a mixture of lithium bromide and potassium bromide (mixing ratio 1:1)
  • the sample C 3 H 6 conversion and PO selectivity were 7.9% and 99.2%
  • the properties were 7.8% and 98.8%
  • the mixture of lithium carbonate and sodium carbonate (mixing ratio 1:2) modified C 3 H 6 conversion and PO selectivity were 7.6% and 99.3%
  • the C 3 H 6 conversion and PO selectivity of the modified potassium mixture were 8.7% and 98.5%
  • Sample C 3 H 6 conversion and PO selectivity were 8.4% and 98.3%; mixture of lithium bisulfite and sodium bisulfite
  • Example 1 was repeated, but the amount of water to be adjusted was adjusted according to the ratio of TS-1, TPAOH, sodium bromide and water, respectively.
  • g): water (g) 50 : 0.035 : 1.4 : 200 and 50 : 0.035 : 1.4 : 2000 Mix.
  • Example 1 was repeated, but the modification was carried out under stirring.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the C 3 H 6 conversion and PO selectivity of the modified sample after stirring were 8.7% and 99.1%.
  • Example 1 was repeated, but the pretreatment temperatures were changed to 300 ° C, 400 ° C, 600 ° C, and 700 ° C, respectively.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the C 3 H 6 conversion and PO selectivity of the sample pretreated at 300 °C were 6.4% and 91.3%; under 400 deg.] C sample pretreatment C 3 H 6 conversion rate and PO selectivity of 94.5% and 7.7%; pretreated sample 600 °C C 3 H 6 conversion rate and PO selectivity 7.6% And 93.7%; samples pretreated at 700 °C C 3 H 6 conversion and PO selectivity were 6.2% and 91.4%.
  • Example 1 was repeated, but the pretreatment times were changed to 30 min, 3 h, 24 h, and 200 h, respectively.
  • the epoxidation reaction showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively.
  • the conversion of C 3 H 6 and PO selectivity after pretreatment for 30 min were 5.4% and 89.7%; C 3 H 6 conversion and PO selectivity were 7.2% and 94.5% after 3h modification; C 3 H 6 conversion and PO selectivity were 8.2% and 95.5 after 24h modification.
  • the C 3 H 6 conversion and PO selectivity of the sample after modification for 100 h were 6.2% and 93.5%.
  • Example 1 was repeated, but the modification temperatures were changed to 50 and 250 °C, respectively.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the conversion of C 3 H 6 and PO selection after modification at 50 °C The sex was 6.6% and 91.7%.
  • the C 3 H 6 conversion and PO selectivity of the modified samples were 6.0% and 92.1% at 250 °C.
  • Example 1 was repeated, but the modification time was changed to 2 h and 10 days, respectively.
  • the results of the epoxidation reaction showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively.
  • the conversion of C 3 H 6 and PO selectivity after modification for 2 h were 5.0% and 89.7%.
  • the C 3 H 6 conversion and PO selectivity of the samples were 8.2% and 95.5%.
  • Example 1 was repeated, but the pH was 9 when the sample was was washed in the third step.
  • the results of the epoxidation reaction showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively, and the modified C 3 H 6 conversion and PO selectivity of the modified sample were 5.3% and 98.7%.
  • Example 1 was repeated, but the third step of drying the samples was 60 and 500 °C, respectively.
  • the results of the epoxidation reaction were as follows: the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the dried sample at 60 °C had a conversion of C 3 H 6 and a selectivity of PO of 8.4%. And 96.7%; 500 °C dried samples C 3 H 6 conversion and PO selectivity were 4.9% and 95.3%.
  • Example 1 was repeated, but the third step of drying the samples was 1 h and 100 h, respectively.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the C 3 H 6 conversion and PO selectivity of the sample dried after 1 h were 8.1. % and 93.6%; the C 3 H 6 conversion and PO selectivity of the samples dried over 100 h were 8.3% and 96.3%.
  • Example 1 was repeated, but the third step of calcining the samples was at temperatures of 200 and 500 °C, respectively.
  • the epoxidation results showed that the C 3 H 6 conversion and PO selectivity of TS-1 before modification were 4.5% and 78.4%, respectively; the C 3 H 6 conversion and PO selectivity of the sample calcined at 200 °C were 9.2. % and 99.5%; samples at 500 °C calcined C 3 H 6 conversion and PO selectivity were 5.0% and 97.3%.
  • Example 1 was repeated, but the third step of calcining the samples was 30 min and 100 h, respectively.

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Abstract

本发明属于无机化学品合成技术领域，涉及到一种钛硅分子筛的改性方法。其特征是首先对TS-1进行预处理；然后用含TPAOH和金属盐的混合液对预处理过的TS-1进行改性，最后对改性后的TS-1进行后处理。本发明所述的钛硅分子筛的改性方法具有普遍适用性，适合各种方法合成的TS-1分子筛，尤其是廉价体系合成的TS-1分子筛，且能同时提高TS-1分子筛的气相和液相丙烯环氧化反应的催化性能。

Description

一种钛硅分子筛的改性方法
技术领域
本发明属于无机化学品合成技术领域，涉及到一种钛硅分子筛（ TS-1 ）的改性方法。
背景技术
钛硅分子筛（ TS-1 ）是合成过程中将过渡金属钛引入到具有 MFI 结构的分子筛骨架中得到的，它具有优良的选择氧化性能和特定的择形性能。 TS-1 与低浓度双氧水组成的绿色催化体系可广泛应用于醇类，苯酚，烯烃，醚类等有机物的选择氧化反应中，其中苯酚羟基化、环己酮胺氧化和丙烯环氧化等已经实现工业化生产。
Macro Taramasso 等人于 1981 年首次公开了 TS-1 的合成方法（ GB2071071A 、 USP4410501 ）。三十年来，经过不断发展和丰富， TS-1 水热合成已形成两类体系，一类是采用四丙基氢氧化铵（ TPAOH ）做模板剂合成 TS-1 的体系（经典体系）。以下专利和公开文献属于经典体系： US5656252 、 WO2009077086 、 CN1167082A 、 CN 1260241A 、 CN 1169952A 、 CN 1239016A 、 CN1217232A 、 CN 1239015A 、 CN1245089A 、 CN 1247771A 、 CN1275530A 、 CN1275529A 、 CN1294030A 、 CN1328878A 、 CN1327947A 、 CN1418813A 、 CN1216801C 、 CN 1488438A 、 CN 1482062A 、 CN1634765A 、 CN 1843626A 、 CN 1830564A 、 CN 101134575A 、 CN101291877A 、 CN1935651A 、 CN101190792A 、 CN101190793A 、 CN 101434399A 、 CN101434400A 、 CN101327934A 、 CN101696019A 等和 Zeolites ， 1992 ， Vol 12 ， P943-950 、 Zeolites 16(1996)184-195 、 Zeolites 19(1997)238-245 、 Microporous and mesoporous materials 22(1998)23-31 、 Microporous and mesoporous material 66(2003)143-156 、 Chemical engineering journal 147(2009)316-322 等。另外一类是采用价格相对较低的四丙基溴化铵或者其他廉价模板剂合成 TS-1 的体系（廉价体系）。以下专利和公开文献属于廉价体系： US5688484 、 CN1167010A 、 CN 1513760A 、 CN1806918A 、 CN 101428814A 、 CN101767036A 等和 Material chemistry and pHysics 47(1997)225-230 、 Zeolites 19(1997)246-252 、 Microporous materials 12(1997)141-148 、 Catalysis today 74(2002)65-75 、 Appl. Catal. A, 185 ，（ 1999 ） 11 、催化学报 17 （ 1996 ） 173-176 等。
除以上两类水热合成方法外， TS-1 还可用同晶取代法等多种方法合成。但是由于 Ti-O 键较 Si-O 键长，钛原子进入硅骨架困难，因此无论采用哪种方法合成 TS-1 都必然会或多或少地产生非骨架钛物种。非骨架钛物种的产生会对 TS-1 产品产生两个负面影响，首先是这些非骨架钛物种不具有氧化催化活性但却能引起氧化剂过氧化氢的大量分解，因此其存在会造成 TS-1 催化性能降低；其次是非骨架钛量难控制，这必然会造成不同批次合成 TS-1 的性能不重复。
为了去除非骨架钛物种的不利影响，以下专利或公开文献介绍了 TS-1 的改性方法。
专利 US5367099 、 US5607888 、 US5476823 、 US5365003 、 CN101602013A 、 CN1844321A 等介绍了一种对 MFI 结构沸石进行硅烷化改性的方法。其中代表性专利 CN101602013A 披露的是一种气相硅烷化的 TS-1 改性方法。其技术特征是，在 50-300oC 温度条件下，在氮气气氛中通入硅烷化试剂反应 0.5-10h 。
专利 CN1245090A 、 US 4794198 、 CN1657168A 、 CN101591024A 、 CN101417238A 等介绍了一种对 TS-1 分子筛进行酸洗的改性方法。其中代表性专利 CN1657168A 披露的是一种利用酸对未焙烧 TS-1 分子筛进行改性的方法。其技术特征是将未焙烧的 TS-1 分子筛原粉、酸性化合物溶液混合均匀，室温 -200oC 下进行酸洗，然后用常规的过滤、洗涤、干燥、焙烧进行加工。
专利 CN1555923A 、 CN1268400A 、 CN101659599A 、 EP0958861 A1 及公开文献 Catal. Today,93-95(2004),p353 -357 ；化学工程， Vol39 ， No1 ， P53-57 等介绍了一种对 TS-1 分子筛进行盐改性的方法。其中代表性专利 CN1268400A 披露的是一种利用金属盐或者其混合物的水溶液对 TS-1 进行改性的方法。其基本原理是利用盐类的阳离子抑制 TS-1 分子筛中能够引起副反应发生的较强酸中心。其技术特征是将金属盐的水溶液与已合成的 TS-1 分子筛按照金属盐：水：分子筛 =0.01-10g ： 10-100ml ： 1g 的比例，将 TS-1 加到金属盐水溶液中，静止 6-100h ，在 30-100oC 水浴中蒸干，在 110-200oC 烘箱中干燥 1-20h ，以程序升温的方式，从室温用 1-12h 升至 200-800oC ，并在此温度下焙烧 2-20h 。
以上三种改性方法都能一定程度提高 TS-1 分子筛的催化性能。其中酸改性和盐改性可抑制非骨架钛物种在反应过程中的负面影响，但是这些方法都不能从根本上将其消除。
据报道以有机碱液或者无机碱液改性 TS-1 能在 TS-1 中产生孔穴，有利于反应物和产物的扩散。
以下专利介绍了利用有机或者无机碱液对 TS-1 进行改性的方法。
专利 US6475465B2 和 CN1301599A （申请日 1999.12.24, 申请号 99126289.1 ）共同披露了一种利用有机碱对 TS-1 进行改性的方法。其共同技术特征是将脂肪胺类化合物、醇胺类化合物、季铵碱类化合物等有机碱或者这些有机碱的混合物（ mol ）： TS-1 分子筛（ g ）：水（ mol ）按照（ 0.005-0.5 ） :100 ：（ 5-200 ）的比例混合，在 150-180oC 自生压力条件下反应 2 小时到 3 天。其技术特征还在于其采用的 TS-1 分子筛可以是 TS-1 原粉也可以是经过酸改性的 TS-1 。
专利 CN124090A （申请日 1998.8.18 ，申请号 98117503.1 ）披露了一种利用有机碱对酸改性过的 TS-1 样品进行进一步改性的方法。其技术特征是将合成的 TS-1 分子筛与酸性化合物溶液混合均匀，在 5-95oC 条件下反应 5 分钟到 6 小时，然后再将得到的酸改性后的 TS-1 分子筛与有机碱混合溶液混合，并在密封反应釜中于 120-200oC 条件下自生压力下反应 2 小时到 8 天。其中有机碱为脂肪胺类化合物、醇胺类化合物、季铵碱类化合物等有机碱或者这些有机碱的混合物。
专利 CN101850985A （申请日 2009.03.31 ，申请号 200910131993.5 ）披露了一种利用制孔剂的碱溶液对 TS-1 进行改性的方法。其技术特征是将 TS-1 加入到制孔剂的碱性溶液中，得到组成为 TS-1 ：制孔剂：碱源：水 =100 ：（ 0.001-5 ）：（ 0.005-5 ）：（ 200-10000 ）的混合物，再将混合物在温度 80-200oC 及自升压力下改性 2-360 小时。其中制孔剂为选自蔗糖、淀粉、糠醛、酚醛、苯并噻吩、二苯并噻吩、萘、萘并噻吩、喹啉、咔唑、吲哚、聚丙烯、聚乙二醇、聚苯乙烯、聚氯乙烯和聚乙烯以及他们衍生物种的一种或者它们的混合物。其中碱源分为有机碱和无机碱，有机碱选自尿素、季铵碱类化合物、脂肪胺类化合物、醇胺类化合物或者有它们组成的混合物；无机碱选自氨水、氢氧化钠、氢氧化钾、氢氧化钡或者它们的混合物。
专利 CN101537372A 、 CN101618338A 、 CN101618339A 、 CN101623653A 、 101658791A 、 CN101658798A 、 CN1016646696A 、 CN101665256A 、 CN101670298A 等都披露了一种利用贵金属源的碱性溶液对 TS-1 进行改性的方法。其共同技术特征是将 TS-1 分子筛、硅的水溶液、贵金属源、保护剂、碱源混合均匀，然后混合物在密闭反应釜内水热改性，并回收产物。其中贵金属源选自 Ru 、 Rh 、 Pd 、 Re 、 Os 、 Ir 、 Pt 、 Ag 和 Au 中的一种或几种贵金属的氧化物、卤化物、碳酸盐、硝酸盐、硝酸铵盐、氯化铵盐、氢氧化物或贵金属的其它络合物。其中保护剂为聚合物或表面活性剂，聚合物如葡萄糖、环糊精、聚苯并咪唑以及聚丙烯、聚乙二醇、聚苯乙烯、聚氯乙烯、聚乙烯等，表面活性剂包括阳离子表面活性剂、阴离子表面活性剂和非离子表面活性剂。其中碱源分为有机碱和无机碱，有机碱选自尿素、季铵碱类化合物、脂肪胺类化合物、醇胺类化合物或者有它们组成的混合物；无机碱选自氨水、氢氧化钠、氢氧化钾、氢氧化钡或者它们的混合物。
专利 CN1260241 （申请日 1998.4.10 ，申请号 98101357.0 ）披露了一种利用碱性钛源水解溶液对 TS-1 进行改性的方法。其技术特征是将钛源水解溶液与 TS-1 分子筛按照 TS-1 ：钛 =200-1500:1 的比例混合然后在反应釜中 120-180oC 温度下晶化 1-8 天，过滤、洗涤并干燥得到加钛 TS-1 。其中碱性溶液由季铵碱类化合物、脂肪胺类化合物、醇胺类化合物或者有它们组成的混合物等有机胺类提供。
专利 CN1421389A( 申请日 2001.11.29 ，申请号 01140182.6) 披露了一种利用硅的碱溶液对 TS-1 进行改性的方法。其技术特征是将硅的水溶液、 TS-1 分子筛按照 TS-1 ：硅 =70-1500:1 的比例混合然后在反应釜中 120-180oC 温度下 0.1-150h ，过滤、洗涤并干燥得到硅改性 TS-1 。其中碱性溶液由季铵碱类化合物、脂肪胺类化合物、醇胺类化合物或者有它们组成的混合物等有机胺类提供。
专利 CN101850986A （申请日 2009.03.31 ，申请号 200910131992.0 ）披露了一种利用混合碱液对 TS-1 进行改性的方法。其技术特征是将 TS-1 加入到含有无机碱和有机碱的混合碱性水溶液中，得到组成为 TS-1 ：无机碱：有机碱：水为 100 ：（ 0.005-5 ）：（ 0.01-10 ）：（ 200-10000 ）的混合物，其中 TS-1 和水以克计，有机碱和无机碱以摩尔计，在将混合物在温度 80-200oC 及自升压力下改性 2-360 小时。其中有机碱选自尿素、季铵碱类化合物、脂肪胺类化合物、醇胺类化合物或者有它们组成的混合物；无机碱选自氨水、氢氧化钠、氢氧化钾、氢氧化钡或者它们的混合物。同时专利中明确指出有机碱和无机碱的摩尔比为 1-50:1 。
以下公开文献也介绍了利用有机碱液对 TS-1 进行改性的方法。
公开文献 Microporous and Mesoporous Materials 102 (2007) 80-85 报道了一种利用四丙基氢氧化铵的水溶液对 TS-1 进行改性的方法。其特点是将 1gTS-1 分子筛置于 4.17ml TPAOH （ 1M ）和 3.32ml 水混合溶液中，在静止釜中 170oC 条件下晶化 24h ，然后抽滤、洗涤、干燥最后在 520 oC 条件下焙烧 16 小时得到改性后的 TS-1 。
公开文献钛硅沸石 TS-l 的合成 - 有机碱改性 - 挤条成型及其催化氧化环己烷的研究（张宝吉，博士论文）报道了一种利用有机碱液对 TS-1 进行改性的方法。其特点是有机碱液包括 TPAOH 、乙醇胺、氨水、六亚甲基四胺、四乙基氢氧化铵、氨水和四丙基溴化铵混合物、四乙基氢氧化铵和四丙基溴化铵混合物等。其中值得一提的是，以 TPAOH 改性效果最佳，活性提高两倍以上。同时以氨水和四丙基溴化铵混合物、四乙基氢氧化铵和四丙基溴化铵混合物改性后活性提高近一倍。
公开文献 TS-1 催化 H2O2 环氧化苯乙烯的优化（尹建波，硕士论文）报道了一种利用有机和无机碱液以及偏碱性的盐类对 TS-1 进行改性的方法。其特点是将 TS-1 置于有机和无机碱液以及盐类的溶液之中，在 175 ℃改性 24h 后，过滤，洗涤， 100 ℃下烘干，于 540 ℃空气气氛中焙烧 6h 。其中盐类包括，碳酸钠、柠檬酸钠、乙酸钠和硝酸钠；无机碱为氨水；有机碱包括四丙基氢氧化铵、四乙基溴化铵（盐）、三乙醇胺、丙胺和尿素。其中值得一提的是，利用无机碱液和盐类的改性效果与利用有机碱改性差距较大，而利用盐类改性仅仅是利用了盐类阳离子为酸性抑制剂的作用。
公开文献钛硅分子筛 TS 一 1 的合成、改性及其甲乙酮氨氧化反应性能的研究（夏丽珍， 硕士论文 ）；有机碱改性 TS-1 的表征及其甲乙酮氨氧化性能的研究（李鹏， 硕士论文 ）；钛硅分子筛催化氧化脱除硫化物的研究（赵丽霞， 硕士论文 ）；微米 TS-1 的改性、表征及催化性能（毛 璟 博，硕士论文 ）； TS-1 分子筛合成过程中影响因素的研究（刘阳，硕士论文）；改性对 TS-1 及其丙烯气相环氧化性能的影响（刘光红，硕士论文）； TS-1 催化剂制备及其丙烯环氧化性能研究（刘欣旭，硕士论文）；石油学报（石油化工）， 2008, 24(1):57-62 ；燃料化学学报， 2008,36 （ 4 ）： 484-488 等报道了一种利用有机碱液对 TS-1 进行改性的方法。其特点是碱液包括 TMAOH 、 TEAOH 、 TPAOH 、 TBAOH 、 NaOH 、 NH3 、 Na2CO3 等并且 TPAOH 改性效果最优。
综上所述，无机碱对 TS-1 的改性作用主要体现在碱性介质导致 TS-1 骨架溶解从而刻蚀 TS-1 晶体内部产生孔穴；一般的有机碱如脂肪胺、醇胺等的作用与无机碱相似；但季铵碱除具有所说的溶解作用外还能够使溶解的硅钛物种重新晶化，从而使一些非骨架钛重新进入骨架。公开文献一般认为 TPAOH 改性 TS-1 效果优于其他季铵碱。但 TPAOH 改性存在适用性问题，即此方法并不对所有的 TS-1 都有改性效果，仅适合经典体系和个别廉价体系合成的 TS-1 。这主要是因为廉价 TS-1 晶粒较大，且孔道中含有较多无定形非骨架钛物种。这些因素导致改性过程中内部溶解下来的钛物种向外扩散路径较长，扩散阻力较大。溶液中钛物种又十分容易缩合成锐钛矿形式的二氧化钛，所以大多数廉价 TS-1 经过 TPAOH 改性活性提高并不明显。
发明内容
本发明要解决的技术问题是提供一种利用 TPAOH 和无机盐混合液改性 TS-1 的方法 ， 用此方法能同时提高 TS-1 分子筛的气相和液相丙烯环氧化反应的催化性能。本发明的关键是在用 TPAOH 对 TS-1 进行改性时 加入 碱金属盐类。我们研究发现，利用 TPAOH 和碱金属盐类的混合液改性 TS-1 能够解决 TPAOH 改性 TS-1 存在的适用性问题，也就是说 TPAOH 和碱金属盐类混合液既可适用于改性经典体系合成的 TS-1 ，也可适用于改性廉价体系合成的 TS-1 。这主要是因为碱金属阳离子能够和溶液中的钛酸根离子形成单分散或者低聚态的钛酸根离子对，避免了钛酸根离子缩合成锐钛矿形式的聚二氧化钛。这对于廉价体系 TS-1 的改性十分重要，因为廉价 TS-1 晶粒大，在进行改性时， OH- 进攻骨架，使 Si 和 Ti 物种从晶体内部缺陷位置脱落。碱金属阳离子与钛物种的强相互作用避免了钛物种的聚合，从而使更多的钛物种能够从廉价大晶粒 TS-1 晶体中迁移出来，在外部重新进入骨架。我们研究还发现，利用 TPAOH 和碱金属盐类混合液改性后的 TS-1 产生了骨架 Ti-O-Ti 结构（拉曼特征峰 850 cm-1 ）。骨架 Ti-O-Ti 在反应中可以变成高活性的钛物种，因此利用 TPAOH 和碱金属盐类的混合液改性 TS-1 对其催化活性提升更有利。
本发明采用的技术方案如下：
第一步， TS-1 的预处理。预处理是指进行高温脱除模板剂预处理，可以在空气气氛或保护气体气氛中进行。预处理时，焙烧温度一般为 300-700 ℃，优选 400-600 ℃；焙烧时间为 30min-200h ，优选 3-24h 。焙烧的目的是脱除合成过程中寄存在孔道中的有机模板剂，堵塞在孔道中的模板剂能够阻碍碱液对 TS-1 的溶解和重结晶过程。 TS-1 可以根据本专利技术背景中提及的专利和公开文献进行水热合成。任何熟悉本领域的工程师都可以根据所述文献来制备出本发明采用的 TS-1 分子筛。
第二步，用含 TPAOH 和碱金属盐的混合液对预处理过的 TS-1 进行改性。所述的碱金属盐是指所有含锂、钠、钾的盐类化合物及其混合物。改性过程中可以将 TS-1 、 TPAOH 、碱金属盐和水的比例关系设定为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.005-50 ： 0.05-5 ： 200-2000 ，改性后反应效果最佳。改性在反应釜中进行，改性温度范围为 50-250 ℃，适宜时间为 2 小时至 10 天。改性可以在搅拌下进行，也可以在静止状态进行。如采用搅拌改性，搅拌速度以保证溶液浓度和温度均匀为宜。
第三步，对改性后的 TS-1 进行后处理。所述的后处理是指包括固液分离、洗涤、干燥和焙烧。洗涤用去离子水进行，洗涤至 pH 值为 7-9 ；干燥可以在空气气氛或保护气气氛中进行，温度 60-200 ℃，时间为 1-100h ，优选 3-10h ；焙烧可以在空气中进行或在保护气体气氛中进行，焙烧温度可以选择 200 ℃ -500 ℃，时间 30min-100h 。洗涤时高于 9 时， TS-1 残存的碱金属阳离子会影响改性效果。改性后的 TS-1 不焙烧或不在 200 ℃ -500 ℃范围内焙烧， TS-1 的稳定性差、活性低。
本发明的效果和益处是对 TS-1 分子筛进行改性的方法具有普遍适用性，适合各种方法合成的 TS-1 分子筛，尤其是廉价体系合成的 TS-1 分子筛，且能同时提高 TS-1 分子筛的气相和液相丙烯环氧化反应的催化性能。
具体实施方式
下面通过实施例对本发明进行进一步的说明，但是本发明不受这些实施例的限制。
对比例 1 ：
本对比例说明利用 TPAOH 和碱金属盐混合碱液对经典体系合成的 TS-1 的改性过程。
第一步，将经典体系（专利 USP4410501 ）合成的 TS-1 在 540 ℃空气气氛条件下焙烧 6h 以脱除模板剂。
第二步，将经典 TS-1 、 TPAOH 和水的比例关系为 TS-1 （ g ）： TPAOH （ mol ）：水（ g ） =50 ： 0.035 ： 500 的比例均匀混合。在静止釜中 170 ℃条件下改性 24h 。
第三步，将所得 TS-1 抽滤、去离子水洗涤至 pH ≈ 7 、干燥，最后在 390 ℃条件下焙烧 6 小时。
将改性前后的 TS-1 样品按照公开文献（催化学报 ,31(2010)1195-1199 ）中描述的反应条件进行丙烯气相环氧化反应。反应条件为：氢气、氧气、丙烯气速分别为 170ml/min, 8ml/min and 18ml/min (H2/O2/C3 = 170/8/18) ，催化剂添加量 0.8g (WHSVC3=2.53h-1) ，环氧化反应为 110 oC 。 丙烯气固相环氧化反应性能评价的主要参数是： C3H6 转化率和 PO （环氧丙烷）选择性。反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.6% 和 91.2% ；改性后的样品 C3H6 转化率和 PO 选择性为 7.9% 和 94.2% 。
对比例 2 ：
重复对比例 1 ，但是改性的样品为按照公开文献 Appl.Catal. A, 185 ，（ 1999 ） 11 合成的大晶粒廉价 TS-1 。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；改性后的样品 C3H6 转化率和 PO 选择性为 5.2% 和 82.2% 。
对比例 3 ：
重复对比例 1 ，在如下反应条件下 进行丙烯液相环氧化反应： 400ml 不锈钢高压间歇反应釜中，加入 0.2g 催化剂 A,30ml 甲醇， 2ml30% 的双氧水，搅拌下通入丙烯，丙烯压力 0.4MPa ，反应温度 50 ℃ ，反应时间为 60 分钟时取样，碘量法测双氧水的转化率。气相色谱分析环氧丙烷的选择性和过氧化氢的有效利用率。改性前 TS-1 过氧化氢转化率为 76.3% ，环氧丙烷选择性为 78.8% ，过氧化氢有效利用率为 78.2% ；改性后 TS-1 过氧化氢转化率为 87.2% ，环氧丙烷选择性为 91.3% ，过氧化氢有效利用率为 89.5% 。
实施例 1
第一步，将 按照公开文献 Appl.Catal. A, 185 ，（ 1999 ） 11 合成的大晶粒廉价 TS-1 在 540 ℃空气气氛条件下焙烧 6h 以脱除模板剂。
第二步，将廉价 TS-1 、 TPAOH 、溴化钠和水的比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） = 50 ： 0.035 ： 1.4 ： 500 的比例均匀混合。在静止釜中 170 ℃条件下改性 24h 。
第三步，将所得 TS-1 抽滤、洗涤至 pH = 7 ， 110 ℃下干燥 12h ，最后在 390 ℃条件下焙烧 6h 。
将改性前后的 TS-1 样品按照公开文献（催化学报 ,31(2010)1195-1199 ）中描述的反应条件进行丙烯气相环氧化反应。反应条件为：氢气、氧气、丙烯气速分别为 170ml/min, 8ml/min and 18ml/min (H2/O2/C3 = 170/8/18) ，催化剂添加量 0.8g (WHSVC3=2.53h-1) ，环氧化反应为 110 oC 。 丙烯气固相环氧化反应性能评价的主要参数是： C3H6 转化率和 PO 选择性。反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；改性后的样品 C3H6 转化率和 PO 选择性为 8.8% 和 99.2% 。
实施例 2
重复实施例 1 ，但是改性的样品为 经典体系（专利 USP4410501 ）合成的 TS-1 。环氧化 反应结果为：改性前 TS-1C3H6 转化率和 PO 选择性分别为 4.6% 和 91.2% ；改性后 TS-1 的 C3H6 转化率和 PO 选择性为 9.5% 和 99.4% 。
实施例 3
重复实施例 1 ，在如下反应条件下 进行丙烯液相环氧化反应： 400ml 不锈钢高压间歇反应釜中，加入 0.2g 催化剂 A,30ml 甲醇， 2ml30% 的双氧水，搅拌下通入丙烯，丙烯压力 0.4MPa ，反应温度 50 ℃ ，反应时间为 60 分钟时取样，碘量法测双氧水的转化率。气相色谱分析环氧丙烷的选择性和过氧化氢的有效利用率。改性前 TS-1 过氧化氢转化率为 72.7% ，环氧丙烷选择性为 73.4% ，过氧化氢有效利用率为 68.8% ；改性后 TS-1 过氧化氢转化率为 89.2% ，环氧丙烷选择性为 91.5% ，过氧化氢有效利用率为 93.4% 。
实施例 4
重复实施例 1 ， 但 是分别用等量的溴化锂、溴化钾、氯化锂、氯化钠、氯化钾、碳酸锂、碳酸钠、碳酸钾、亚硫酸锂、亚硫酸钾、硫酸锂、硫酸钠、硫酸钾、亚硫酸氢锂、亚硫酸氢钠、亚硫酸氢钾、硫酸氢锂、硫酸氢钠、硫酸氢钾、硫化锂、硫化钠、硫化钾等替代溴化钠。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 溴化锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.1% 和 99.1% ； 溴化钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.1% 和 98.9% ； 氯化锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.0% 和 99.0% ； 氯化钠 改性后的样品的 C3H6 转化率和 PO 选择性为 8.1% 和 99.1% ；氯 化钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.2% 和 99.0% ； 碳酸锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.1% 和 99.1% ； 碳酸钠 改性后的样品 C3H6 转化率和 PO 选择性为 8.2% 和 98.5% ； 碳酸钾 改性后的样品 C3H6 转化率和 PO 选择性为 7.8% 和 99.0% ； 亚硫酸锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.7% 和 99.2% ； 亚硫酸钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.8% 和 99.3% ； 硫酸锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.5% 和 99.5% ； 硫酸钠 改性后的样品的 C3H6 转化率和 PO 选择性为 8.5% 和 99.5% ； 硫酸钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.4% 和 99.3% ； 亚硫酸氢锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.5% 和 99.4% ； 亚硫酸氢钠 改性后的样品 C3H6 转化率和 PO 选择性为 8.6% 和 99.5% ； 亚硫酸氢钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.6% 和 99.2% ； 硫酸氢锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.5% 和 99.3% ； 硫酸氢钠 改性后的样品 C3H6 转化率和 PO 选择性为 8.4% 和 99.5% ； 硫酸氢钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.5% 和 99.1% ； 硫化锂 改性后的样品 C3H6 转化率和 PO 选择性为 8.3% 和 99.3% ； 硫化钠 改性后的样品 C3H6 转化率和 PO 选择性为 8.4% 和 99.3% ； 硫化钾 改性后的样品 C3H6 转化率和 PO 选择性为 8.4% 和 99.2% 。
实施例 5
重复实施例 1 ， 但 是分别用等量的溴化锂和溴化钾的混合物（混合比例 1:1 ）、氯化钠和氯化钾的混合物（混合比例 1:4 ）、碳酸锂和碳酸钠的混合物（混合比例 1:2 ）、亚硫酸锂和亚硫酸钾的混合物（混合比例 1:1 ）、硫酸钠和硫酸钾的混合物（混合比例 1:4 ）、亚硫酸氢锂和亚硫酸氢钠的混合物（混合比例 1:2 ）、硫酸氢锂和硫酸氢钠混合物（混合比例 1:3 ）、硫化锂和硫化钠以及硫化钾的混合物（混合比例 1:1:1 ）替代溴化钠。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 用溴化锂和溴化钾混合物（混合比例 1:1 ）改性后的样品 C3H6 转化率和 PO 选择性为 7.9% 和 99.2% ；用 氯化钠和氯化钾的混合物（混合比例 1:4 ）改性后的样品 C3H6 转化率和 PO 选择性为 7.8% 和 98.8% ； 碳酸锂和碳酸钠的混合物（混合比例 1:2 ）改性后的样品 C3H6 转化率和 PO 选择性为 7.6% 和 99.3% ； 亚硫酸锂和亚硫酸钾混合物（混合比例 1:1 ）改性后的样品 C3H6 转化率和 PO 选择性为 8.7% 和 98.5% ；用 硫酸钠和硫酸钾的混合物（混合比例 1:4 ）改性后的样品 C3H6 转化率和 PO 选择性为 8.4% 和 98.3% ； 亚硫酸氢锂和亚硫酸氢钠的混合物（混合比例 1:2 ）改性后的样品 C3H6 转化率和 PO 选择性为 8.6% 和 99.2% ； 硫酸氢锂和硫酸氢钠混合物（混合比例 1:3 ）改性后的样品 C3H6 转化率和 PO 选择性为 8.2% 和 98.9% ； 硫化锂和硫化钠以及硫化钾的混合物（混合比例 1:1:1 ）改性后的样品 C3H6 转化率和 PO 选择性为 8.0% 和 98.6% 。
实施例 6
重复实施例 1 ， 但 是调变 TPAOH 添加量，将 TS-1 、 TPAOH 、溴化钠和水分别按照比例关系 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.005 ： 1.4 ： 500 和 50 ： 50 ： 1.4 ： 500 混合。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.005 ： 1.4 ： 500 方案改性后的样品 C3H6 转化率和 PO 选择性为 6.2% 和 83.1% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 50 ： 1.4 ： 500 方案改性后的样品 C3H6 转化率和 PO 选择性为 5.6% 和 82.3% 。
实施例 7
重复实施例 1 ， 但 是调变溴化钠的添加量，将 TS-1 、四丙基溴化铵、氢氧化钠和水分别按照比例关系 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 0.05 ： 500 和 50 ： 0.035 ： 5 ： 500 混合。环氧化 反应结果为：改性前 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 0.05 ： 500 方案改性后的样品 C3H6 转化率和 PO 选择性为 6.0% 和 87.1% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 5 ： 500 方案改性后的样品 C3H6 转化率和 PO 选择性为 7.8% 和 96.4% 。
实施例 8
重复实施例 1 ， 但 是调变水的添加量，将 TS-1 、 TPAOH 、溴化钠和水分别按照比例关系 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 1.4 ： 200 和 50 ： 0.035 ： 1.4 ： 2000 混合。环氧化 反应结果为：改性前 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 1.4 ： 200 方案改性后样品的 C3H6 转化率和 PO 选择性为 7.5% 和 96.5% ；按照比例关系为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.035 ： 1.4 ： 2000 方案改性后的样品 C3H6 转化率和 PO 选择性为 6.6% 和 91.4% 。
实施例 9
重复实施例 1 ， 但 是改性在搅拌状态下进行。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；搅拌状态改性后 样品 C3H6 转化率和 PO 选择性为 8.7% 和 99.1% 。
实施例 10
重复实施例 1 ， 但 是分别改变预处理温度为 300 ℃、 400 ℃、 600 ℃和 700 ℃。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 300 ℃预处理的样品 C3H6 转化率和 PO 选择性为 6.4% 和 91.3% ； 400 ℃条件下 预处理后 样品 C3H6 转化率和 PO 选择性为 7.7% 和 94.5% ； 600 ℃预处理的样品 C3H6 转化率和 PO 选择性为 7.6% 和 93.7% ； 700 ℃预处理的样品 C3H6 转化率和 PO 选择性为 6.2% 和 91.4% 。
实施例 11
重复实施例 1 ， 但 是分别改变预处理时间为 30min 、 3h 、 24h 和 200h 。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 经 30min 预处理后 样品 C3H6 转化率和 PO 选择性为 5.4% 和 89.7% ； 经 3h 改性 后 样品 C3H6 转化率和 PO 选择性为 7.2% 和 94.5% ； 经 24h 改性 后 样品 C3H6 转化率和 PO 选择性为 8.2% 和 95.5% ； 经 100h 改性 后 样品 C3H6 转化率和 PO 选择性为 6.2% 和 93.5% 。
实施例 12
重复实施例 1 ， 但 是分别改变改性温度为 50 和 250 ℃。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 50 ℃条件下 改性后 样品 C3H6 转化率和 PO 选择性为 6.6% 和 91.7% 。 250 ℃条件下 改性后 样品 C3H6 转化率和 PO 选择性为 6.0% 和 92.1% 。
实施例 13
重复实施例 1 ， 但 是分别改变改性时间为 2h 和 10 天。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 经 2h 改性后 样品 C3H6 转化率和 PO 选择性为 5.0% 和 89.7% 。 经 10 天改性 后 样品 C3H6 转化率和 PO 选择性为 8.2% 和 95.5% 。
实施例 14
重复实施例 1 ， 但 是第三步洗涤样品时 pH 为 9 。环氧化 反应结果为：改性前 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；改性后 样品 C3H6 转化率和 PO 选择性为 5.3% 和 98.7% 。
实施例 15
重复实施例 1 ， 但 是第三步干燥样品是温度分别为 60 和 500 ℃。环氧化 反应结果为：改性前 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 60 ℃ 干燥的样品 C3H6 转化率和 PO 选择性为 8.4% 和 96.7% ； 500 ℃ 干燥的样品 C3H6 转化率和 PO 选择性为 4.9% 和 95.3% 。
实施例 16
重复实施例 1 ， 但 是第三步干燥样品时间分别为 1h 和 100h 。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；经 1h 干燥的样品 C3H6 转化率和 PO 选择性为 8.1% 和 93.6% ；经 100h 干燥的样品 C3H6 转化率和 PO 选择性为 8.3% 和 96.3% 。
实施例 17
重复实施例 1 ， 但 是第三步焙烧样品是温度分别为 200 和 500 ℃。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ； 200 ℃焙烧的样品 C3H6 转化率和 PO 选择性为 9.2% 和 99.5% ； 500 ℃ 焙烧的样品 C3H6 转化率和 PO 选择性为 5.0% 和 97.3% 。
实施例 18
重复实施例 1 ， 但 是第三步焙烧样品时间分别为 30min 和 100h 。环氧化 反应结果为：改性前的 TS-1 的 C3H6 转化率和 PO 选择性分别为 4.5% 和 78.4% ；经 30min 焙烧 的样品 C3H6 转化率和 PO 选择性为 8.5% 和 96.8% ；经 100h 焙烧的样品 C3H6 转化率和 PO 选择性为 7.8% 和 97.5% 。

Claims (1)

1 、 一种钛硅分子筛改性方法，其特征在于如下步骤，
第一步， TS-1 的预处理：在空气或保护气体气氛中进行，焙烧温度为 300-700 ℃，优选 400-600 ℃，焙烧时间为 30min-200h ，优选 3h-24h ；
第二步，用含 TPAOH 和碱金属盐的混合液对预处理过的 TS-1 进行改性：所述的碱金属盐是指所有含锂、钠、钾的盐类化合物及其混合物；改性温度为 50-250 ℃，时间为 2h-10 天；
第三步，对改性后的 TS-1 进行后处理：所述的后处理是指包括固液分离、洗涤、干燥和焙烧。洗涤用去离子水进行，干燥在空气或保护气体气氛中进行，温度为 60-200 ℃，时间为 1-100 h ，干燥后，选择焙烧或不焙烧。
2 、根据权利要求 1 所述的方法，其特征还在于， TS-1 的预处理时，焙烧温度为 400-600 ℃，焙烧时间为 3h-24h 。
3 、根据权利要求 1 所述的方法，其特征还在于，进行改性时， TS-1 、 TPAOH 、碱金属盐和水的比例关系设定为 TS-1 （ g ）： TPAOH （ mol ）：盐（ g ）：水（ g ） =50 ： 0.005-50 ： 0.05-5 ： 200-2000 。
4 、根据权利要求 1 所述的方法，其特征还在于，改性后进行后处理时，洗涤至 pH 为 7-9 。
5 、根据权利要求 1 或 4 所述的方法，其特征还在于，进行后处理时焙烧，焙烧在空气或保护气体气氛中进行，焙烧温度 200 ℃ -500 ℃，时间 30 min-100h 。
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