CN116212948A - Propylene gas-phase epoxidation forming catalyst and preparation method thereof - Google Patents

Propylene gas-phase epoxidation forming catalyst and preparation method thereof Download PDF

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CN116212948A
CN116212948A CN202310112277.2A CN202310112277A CN116212948A CN 116212948 A CN116212948 A CN 116212948A CN 202310112277 A CN202310112277 A CN 202310112277A CN 116212948 A CN116212948 A CN 116212948A
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catalyst
ivb
oxide
alkali metal
metal carbonate
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CN116212948B (en
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伏劲松
苏林
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Sichuan Jiutian Wuyang New Material Co ltd
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Sichuan Jiutian Wuyang New Material Co ltd
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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
    • 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
    • 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
    • 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
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a propylene gas-phase epoxidation forming catalyst and a preparation method thereof, belonging to the technical field of chemical catalytic materials. The propylene gas-phase epoxidation forming catalyst is a titanium silicon molecular sieve TS-1 loaded with Au and IVB oxides, and the mol ratio of the Au to the IVB oxides in the catalyst is 1: 8-12. The invention also discloses a corresponding preparation method thereof, and the IVB oxide is introduced into Au/TS-1, so that the catalyst product can be directly pressed into tablets for forming, the temperature for catalyzing and synthesizing propylene oxide is reduced, the hydrogen efficiency is improved, the selectivity of propylene oxide is improved, and the activity and stability of the catalyst are improved.

Description

Propylene gas-phase epoxidation forming catalyst and preparation method thereof
Technical Field
The invention relates to a propylene gas-phase epoxidation forming catalyst and a preparation method thereof, belonging to the technical field of chemical catalytic materials.
Background
Propylene Oxide (PO) is an important organic chemical raw material and is widely applied to various fields of daily life such as buildings, automobiles, cosmetics, foods and the like. At present, about 70% of propylene oxide products in China are still produced by adopting a chlorohydrin method with larger environmental hazard, and in the production method of the propylene oxide products, the co-oxidation method and the direct oxidation method of hydrogen peroxide are used for producing propylene oxide, so that the environmental hazard problem of the chlorohydrin method can be effectively solved, but the economical efficiency is limited by the market demand of the co-products, and meanwhile, the problems of high cost and high danger of hydrogen peroxide transportation exist.
The loading of Au on anatase TiO was found by Japanese scientist 1998 Haruta et al (Journal of Catalysis:1998,178 (2): 566-575) 2 Au/TiO prepared on a support 2 The catalyst can effectively catalyze H 2 、O 2 、C 3 H 6 The new process for preparing the propylene oxide by directly oxidizing the propylene with the hydrogen and the oxygen has the advantages of environmental protection, simple operation, low equipment investment and operation cost and the like and is widely paid attention to. Around the findings, systematic researches on the structure type, silicon-titanium atomic ratio, surface hydrophobicity, particle mass transfer performance regulation and control method, and electronic effect, spatial distribution, size effect and the like of Au are carried out by people, so that the activity and stability of the powder catalyst are improved to a certain extent. However, such catalysts still present the following problems: 1. the use temperature is high, the use temperature is generally 200 ℃, the lowest use temperature disclosed in the prior art is 164 ℃, and the higher use temperature is easy to cause the agglomeration growth of Au particles serving as a catalytic active component, so that the stability of a catalyst and the selectivity of propylene oxide are reduced; 2. hydrogen peroxide is ineffective and decomposed too much in the reaction, resulting in low catalytic activity and low hydrogen efficiency; 3. the powder catalyst is difficult to form by tabletting, if the catalyst is extruded to form by adopting a glue adding mode, the formed catalyst is easy to grow Au particles after glue removal at high temperature, and the activity of the catalyst is reduced; if the Au is loaded after the glue is added to squeeze strips or the ball is formed and treated at high temperature, the strength of the catalyst is reduced in the impregnation process, and the catalyst is seriously pulverized in the use process, so that the use of the catalyst in a fixed bed is affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a propylene gas-phase epoxidation forming catalyst and a preparation method thereof.
The first aspect of the invention provides a propylene gas-phase epoxidation forming catalyst, wherein the catalyst is a titanium silicalite molecular sieve TS-1 loaded with Au and IVB oxides, and the molar ratio of the Au to the IVB oxides in the catalyst is 1: 8-12.
Further, the loading of the IVB-group oxide is 15-65% of the total mass of the catalyst.
Further, the IVB-group oxide is any one or more of titanium dioxide, zirconium dioxide and hafnium dioxide.
Further, the catalyst also comprises alkali metal carbonate, and the mol ratio of the alkali metal carbonate to the Au in the catalyst is 8-22: 1.
further, the alkali metal carbonate is one or more of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
In a second aspect, the present invention provides a method for preparing the propylene gas phase epoxidation forming catalyst, comprising the steps of:
au is loaded on TS-1 to obtain Au/TS-1, and IVB oxide and the TS-1 loaded with Au are mixed and mechanically stirred; or alternatively, the process may be performed,
TS-1 is mixed with IVB oxide and Au is then supported on the mixture of TS-1 and IVB oxide.
Preferably, the loading is to mix chloroauric acid with TS-1 powder and/or IVB oxide powder, add alkali carbonate solution, stir, deposit Au in chloroauric acid solution on carrier, collect solid part after centrifugal separation, wash with deionized water and dry to obtain the loaded product.
Further, the method also comprises the steps of dipping an alkali metal carbonate solution, dipping Au/TS-1 or Au/TS-1 loaded with IVB-group oxide into the alkali metal carbonate solution, and drying after dipping. Preferably, the molar ratio of alkali metal carbonate to supported Au in the alkali metal carbonate solution is 8-12: 1, dispersing the mixture by ultrasonic waves, soaking for 8-12 h, and drying to obtain the product.
In a third aspect, the present invention provides another method for preparing the propylene gas phase epoxidation forming catalyst, comprising the steps of:
preparation of Au/TS-1: au was supported on TS-1. Preferably, the load is that chloroauric acid and TS-1 powder are mixed, alkali metal carbonate solution is added and stirred, au in the chloroauric acid solution is deposited and precipitated on a carrier TS-1, solid parts are collected after centrifugal separation, and the solid parts are washed by deionized water and dried to obtain Au/TS-1.
Preparing Au/IVB oxide: au was supported on IVB-group oxide powder. Preferably, the load is to mix chloroauric acid solution with IVB oxide powder, add alkali carbonate solution and stir to deposit Au on IVB oxide powder, collect solid part after centrifugal separation, wash with deionized water and dry to obtain Au/IVB oxide.
Au/TS-1 was mixed with Au/IVB-group oxide and mechanically stirred.
Further, the method also comprises the steps of dipping alkali metal carbonate solution, respectively dipping Au/TS-1 and Au/IVB oxide or a mixture thereof after mixing and stirring into the alkali metal carbonate solution, and drying after dipping. Preferably, the molar ratio of alkali metal carbonate to supported Au in the alkali metal carbonate solution is 18-22: 1, dispersing the mixture by ultrasonic waves, soaking for 8-12 h, and drying to obtain the product.
A fourth aspect of the present invention provides the use of the above-described propylene gas phase epoxidation forming catalyst in a propylene epoxidation reaction. Preferably, each raw material component in the propylene epoxidation reaction is prepared according to H 2 :O 2 :C 3 H 6 :N 2 = (3-4): (3-4): (3-4): (24-25) mL/min, and the reaction temperature is 125-135 ℃.
The beneficial effects of the invention are as follows:
1) By adding IVB group oxide, on one hand, the forming performance of the powder catalyst can be effectively improved by utilizing the large specific gravity and viscosity of the oxide, so that the catalyst can be formed into solid catalysts with various shapes by adopting a direct tabletting mode of a tablet press, secondary treatment is reduced, various sol extrusion strips or rolling balls and the like are avoided, and further deactivation caused by cluster growth of Au particles in the catalyst which is easily caused by subsequent high-temperature sol treatment is avoided. On the other hand, the introduction of IVB oxide can coordinate with hydrogen peroxide generated in situ to form a metal-OOH intermediate, so that the ineffective decomposition of hydrogen peroxide is effectively reduced, the concentration of oxide in a reaction system is improved, the temperature for synthesizing propylene oxide is reduced, and the hydrogen efficiency is improved. In addition, the reduction of the reaction temperature further improves the selectivity of propylene oxide, reduces the risk of Au agglomeration and growth, reduces carbon deposition on the surface of the catalyst, effectively improves the activity and stability of the catalyst, effectively reduces the energy consumption in the catalytic reaction process, and improves the economy of the propylene oxide production process.
2) The alkali metal carbonate is adopted for impregnation, so that residual chloride ions on the surface of the catalyst can be effectively covered, the agglomeration and growth cause of Au particles is further eliminated, the alkalinity of the surface of the catalyst is increased, conditions are provided for desorption of propylene oxide on the surface of the catalyst, and the catalyst deactivation caused by carbon deposition on the surface of the catalyst is reduced.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The first aspect of the invention provides a propylene gas-phase epoxidation forming catalyst, wherein the catalyst is a titanium silicalite molecular sieve TS-1 loaded with Au and IVB oxides, and the molar ratio of the Au to the IVB oxides in the catalyst is 1: 8-12. Wherein the loading of the IVB-group oxide is 15-65% of the total mass of the catalyst. The group IVB oxide is any one or a mixture of a plurality of titanium dioxide, zirconium dioxide and hafnium dioxide.
In one embodiment of the invention, the catalyst further comprises an alkali metal carbonate, the molar ratio of alkali metal carbonate to Au in the catalyst being from 8 to 22:1. the alkali metal carbonate is one or more of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
In a second aspect, the present invention provides a method for preparing the propylene gas phase epoxidation forming catalyst, comprising the steps of:
au is loaded on TS-1 to obtain Au/TS-1, and IVB oxide and the TS-1 loaded with Au are mixed and mechanically stirred; or alternatively, the process may be performed,
TS-1 is mixed with IVB oxide and Au is then supported on the mixture of TS-1 and IVB oxide.
The specific loading method comprises the following steps: mixing chloroauric acid with TS-1 powder and/or IVB oxide powder, adding alkali carbonate solution, stirring to deposit Au in the chloroauric acid solution on a carrier, centrifuging, collecting solid part, washing with deionized water, and drying to obtain the load product.
In one embodiment of the invention, the preparation method further comprises the step of impregnating an alkali metal carbonate solution, wherein Au/TS-1 or Au/TS-1 loaded with IVB-group oxide is impregnated in the alkali metal carbonate solution, and drying is carried out after the impregnation. That is, in one preparation method, the step of impregnating the alkali metal carbonate solution may occur before or after loading the group ivb oxide, the Au/TS-1 may be impregnated with the alkali metal carbonate solution before loading the group ivb oxide, or the alkali metal carbonate may be impregnated after loading the group ivb oxide. In another preparation method, the mixture of the TS-1 and IVB oxides loaded with Au is directly subjected to impregnation treatment. Preferably, the molar ratio of alkali metal carbonate to supported Au in the alkali metal carbonate solution is 8-12: 1, dispersing the mixture by ultrasonic waves, soaking for 8-12 h, and drying to obtain the product.
In a third aspect, the present invention provides another method for preparing the propylene gas phase epoxidation forming catalyst, comprising the steps of:
preparation of Au/TS-1: au was supported on TS-1. Preferably, the load is that chloroauric acid and TS-1 powder are mixed, alkali metal carbonate solution is added and stirred, au in the chloroauric acid solution is deposited and precipitated on a carrier TS-1, solid parts are collected after centrifugal separation, and the solid parts are washed by deionized water and dried to obtain Au/TS-1.
Preparing Au/IVB oxide: au was supported on IVB-group oxide powder. Preferably, the load is to mix chloroauric acid solution with IVB oxide powder, add alkali carbonate solution and stir, make Au deposit and deposit on IVB oxide powder, collect the solid part after centrifugal separation, wash with deionized water and dry, get Au/IVB oxide.
Au/TS-1 was mixed with Au/IVB-group oxide and mechanically stirred.
In one embodiment of the invention, the preparation method further comprises the steps of dipping an alkali metal carbonate solution, dipping the mixture of Au/TS-1 and Au/IVB oxide after mixing and stirring in the alkali metal carbonate solution, and drying after dipping. That is, the step of impregnating the alkali metal carbonate solution may occur before or after mixing the Au/ivb group oxides, the Au/TS-1 and Au/ivb group oxides may be impregnated with the alkali metal carbonate solution and then mixed, or the two may be mixed and mechanically stirred before impregnating the alkali metal carbonate together. Preferably, the molar ratio of alkali metal carbonate to supported Au in the alkali metal carbonate solution is 18-22: 1, dispersing the mixture by ultrasonic waves, soaking for 8-12 h, and drying to obtain the product.
A fourth aspect of the present invention provides the use of the above-described propylene gas phase epoxidation forming catalyst in a propylene epoxidation reaction. The raw material components in the epoxidation of propylene are in accordance with H 2 :O 2 :C 3 H 6 :N 2 = (3-4): (3-4): (3-4): (24-25) mL/min, and the reaction temperature is 125-135 ℃.
Example 1
The embodiment provides a preparation method of a propylene gas-phase epoxidation forming catalyst, which comprises the following steps:
step 1) preparation of Au/TS-1:
to 20g of deionized water, 5mL of 20mg/mL HAuCl was added at room temperature 4 The solution and commercially available TS-1 powder 1g, a mixture was obtained. The resulting mixture was stirred for 30 minutes and allowed to mix thoroughly. Adding 10% K by mass into the above mixture dropwise 2 CO 3 Stirring the solution to make the pH value of the mixed solution reach 7-8, and continuously stirring for 5 hours to make HAuCl 4 Au charge in solutionThe precipitate was separated and deposited onto the support TS-1. Subsequently, the liquid was centrifuged, the solid was collected, and the solid was washed three times with 200g of deionized water in total, and the washed solid was then put into a vacuum oven and dried to constant weight at 30℃to obtain an Au/TS-1 sample.
Step 2) impregnating an alkali carbonate solution to prepare K 2 CO 3 -Au/TS-1：
1g of Au/TS-1 solid powder was added to K at a concentration of 10% by weight 2 CO 3 In the aqueous solution, K is adopted 2 CO 3 The ratio of the amount of Au-loaded substance was 10:1, and deionized water was continued to just flood the solids, with the total mass of the mixture being about 1.5g. After 30 minutes of ultrasonic dispersion, the mixture was immersed in an equal volume for 10 hours. Vacuum drying at room temperature to constant weight to obtain K 2 CO 3 -Au/TS-1。
Step 3) supporting IVB group oxide to prepare K 2 CO 3 -Au/TS-1-TiO 2 ：
Will K 2 CO 3 -Au/TS-1 powder and TiO 2 (Au and TiO) 2 The ratio of the amounts of substances 1:10 Mechanically stirred in a round bottom flask for 30 minutes to allow for thorough mixing. Then transferring to a tablet press for tablet forming to obtain the target product K 2 CO 3 -Au/TS-1-TiO 2 。
Step 4) catalyst K 2 CO 3 -Au/TS-1-TiO 2 Activation treatment
0.3g of K 2 CO 3 -Au/TS-1-TiO 2 The whole particle catalyst is filled into a fixed bed reactor and is prepared according to H 2 :O 2 :C 3 H 6 :N 2 The flow rate ratio was 3.5:3.5:3.5: and (3) introducing air at a speed of 24.5mL/min, controlling the total flow rate of the mixed gas at 35mL/min, heating the reaction temperature from room temperature to 130 ℃ at a speed of 1 ℃/min, and performing activation treatment for 2 hours.
Example two
The difference between this embodiment and the first embodiment is mainly that: the group IVB oxide used in this example was ZrO 2 。
Example III
Example 1The differences are mainly as follows: the group IVB oxide employed in this example is HfO 2 。
Example IV
The preparation method of the embodiment comprises the following steps:
step 1) preparation of Au/TS-1:
to 20g of deionized water, 5mL of 20mg/mL HAuCl was added at room temperature 4 The solution and commercially available TS-1 powder 1g, a mixture was obtained. The resulting mixture was stirred for 30 minutes and allowed to mix thoroughly. Adding 10% K by mass into the above mixture dropwise 2 CO 3 Stirring the solution to make the pH value of the mixed solution reach 7-8, and continuously stirring for 5 hours to make HAuCl 4 Au in the solution is fully deposited and precipitated on the carrier TS-1. Subsequently, the liquid was centrifuged, the solid was collected, and the solid was washed three times with 200g of deionized water in total, and the washed solid was then put into a vacuum oven and dried to constant weight at 20℃to obtain an Au/TS-1 sample.
Step 2) loading IVB group oxide to prepare Au/TS-1-TiO 2 ：
1g of Au/TS-1 solid powder and TiO are mixed 2 (ratio of Au to group IVB oxide mass 1:10) in a round bottom flask was mechanically stirred for 30 minutes to allow for thorough mixing. Obtaining the target product Au/TS-1-TiO 2 。
Step 3) impregnating an alkali carbonate solution to prepare K 2 CO 3 -Au/TS-1-TiO 2 ：
1g Au/TS-1-TiO 2 Adding K with concentration of 10wt% into solid powder 2 CO 3 In the aqueous solution, K is adopted 2 CO 3 The ratio of the amount of Au-loaded substance was 10:1, and deionized water was continued to just flood the solids, with the total mass of the mixture being about 1.5g. After 30 minutes of ultrasonic dispersion, the mixture was immersed in an equal volume for 10 hours. Vacuum drying at room temperature to constant weight, and tabletting to obtain K 2 CO 3 -Au/TS-1-TiO 2 。
Step 4) catalyst K 2 CO 3 -Au/TS-1-TiO 2 Activation treatment
0.3g of K 2 CO 3 -Au/TS-1-TiO 2 The whole particle catalyst is filled into a fixed bed reactor and is prepared according to H 2 :O 2 :C 3 H 6 :N 2 The flow rate ratio was 3.5:3.5:3.5: and (3) introducing air at a speed of 24.5mL/min, controlling the total flow rate of the mixed gas at 35mL/min, heating the reaction temperature from room temperature to 130 ℃ at a speed of 1 ℃/min, and performing activation treatment for 2 hours.
Example five
The difference between this embodiment and the fourth embodiment is mainly that: the group IVB oxide used in this example was ZrO 2 The alkali metal carbonate is Na 2 CO 3 。
Example six
The difference between this embodiment and the fourth embodiment is mainly that: the group IVB oxide employed in this example is HfO 2 The alkali metal carbonate is Rb 2 CO 3 And Cs CO 3 I.e. the alkali metal carbonate solution used in step 3) is Rb 2 CO 3 And Cs CO 3 Is a mixed solution of (a) and (b).
Example seven
The preparation method of the embodiment comprises the following steps:
step 1) preparation of Au/TS-1:
5mL of 20mg/mL HAuCl was added to 20g deionized water at 35 ℃ 4 The solution and commercially available TS-1 powder 1g, a mixture was obtained. The resulting mixture was stirred for 30 minutes and allowed to mix thoroughly. Adding 10% K by mass into the above mixture dropwise 2 CO 3 Stirring the solution to make the pH value of the mixed solution reach 7-8, and continuously stirring for 5 hours to make HAuCl 4 Au in the solution is fully deposited and precipitated on the carrier TS-1. Subsequently, the liquid was centrifuged, the solid was collected, and the solid was washed three times with 200g of deionized water in total, and the washed solid was then put into a vacuum oven and dried to constant weight at 30℃to obtain an Au/TS-1 sample.
Step 2) preparing Au/IVB oxide:
2.5mL of 20mg/mL HAuCl was added to 20g of deionized water at 35 ℃ 4 Solutions and commercially available TiO 2 1g of powder to give a mixture. The resulting mixture was stirred for 30 minutes and allowed to mix thoroughly. Adding 10% K by mass into the above mixture dropwise 2 CO 3 Stirring the solution to make the pH value of the mixed solution reach 7-8, and continuously stirring for 5 hours to make HAuCl 4 Au in the solution is fully deposited and precipitated to a carrier TiO 2 On the powder. Subsequently, the liquid was centrifuged, the solid was collected, and a total of 200g of deionized water was used to wash the solid three times, and the washed solid was then put into a vacuum oven and dried to constant weight at 30℃to obtain Au/TiO 2 And (3) a sample.
Step 3) preparation of Au/TS-1-TiO 2
Au/TS-1 powder and Au/TiO 2 (TS-1 and TiO) 2 5:1), and mechanically stirred for 30 minutes to allow for thorough and uniform mixing. Tabletting and molding the uniformly mixed powder catalyst to obtain a target product Au/TS-1-TiO 2 。
Step 4) catalyst Au/TS-1-TiO 2 Activation treatment
0.3g Au/TS-1-TiO 2 The whole particle catalyst is filled into a fixed bed reactor and is prepared according to H 2 :O 2 :C 3 H 6 :N 2 The flow rate ratio was 3.5:3.5:3.5: and (3) introducing air at a speed of 24.5mL/min, controlling the total flow rate of the mixed gas at 35mL/min, heating the reaction temperature from room temperature to 130 ℃ at a speed of 1 ℃/min, and performing activation treatment for 2 hours.
Example eight
The difference between this embodiment and the seventh embodiment is mainly that: the group IVB oxide used in this example was ZrO 2 。
Example nine
The difference between this embodiment and the seventh embodiment is mainly that: the group IVB oxide employed in this example is HfO 2 。
Examples ten
The difference between this embodiment and the seventh embodiment is mainly that: step 3) in this example is the preparation of K 2 CO 3 -Au/TS-1-TiO 2 The preparation process also comprises the steps of mixing Au/TS-1 powder with Au/TiO 2 After mixing and mechanical stirring, K with a concentration of 10% by weight is added 2 CO 3 In the aqueous solution, K is adopted 2 CO 3 The ratio of the mass of the mixture to the mass of the Au-loaded substance was 20:1, and deionized water was continuously added until the total mass of the mixture reached 2g. After 30 minutes of ultrasonic dispersion, the mixture was immersed in an equal volume for 10 hours. Then vacuum drying to constant weight at room temperature, tabletting and molding the dried powder catalyst to obtain K 2 CO 3 -Au/TS-1-TiO 2 A catalyst.
Example eleven
The difference between this embodiment and the tenth embodiment is mainly that: the group IVB oxide used in this example was ZrO 2 。
Example twelve
The difference between this embodiment and the tenth embodiment is mainly that: the group IVB oxide employed in this example is HfO 2 。
Example thirteen
The difference between this embodiment and the seventh embodiment is mainly that: step 3) in this example is the preparation of K 2 CO 3 -Au/TS-1-TiO 2 The preparation process also comprises the steps of using K first 2 CO 3 For Au/TS-1 and Au/TiO respectively 2 Dipping treatment is carried out to obtain K 2 CO 3 -Au/TS-1 and K 2 CO 3 -Au/TiO 2 Then mixing the two materials, mechanically stirring and tabletting to obtain the formed catalyst, wherein the impregnation treatment process comprises the following steps: au/TS-1 and Au/TiO respectively 2 Adding K with concentration of 10wt% into solid powder 2 CO 3 In the aqueous solution, K is adopted 2 CO 3 The ratio of the mass of the Au-loaded substance to the mass of the Au-loaded substance is 10:1, deionized water is continuously added until the solid is just submerged, and after ultrasonic dispersion is carried out for 30 minutes, the mixture is immersed for 10 hours in an equal volume. Then vacuum drying at room temperature to obtain K 2 CO 3 -Au/TS-1 and K 2 CO 3 -Au/TiO 2 。
Examples fourteen
The preparation method of the embodiment comprises the following steps:
step 1) preparation of TS-1-TiO 2 ：
TS-1 powderTiO 2 (TS-1 and TiO) 2 The ratio of the amounts of the substances is 5: 1) Mixing, mechanically stirring for 30 min to obtain TS-1-TiO 2 。
Step 2) preparation of Au/TS-1-TiO 2 ：
5mL of 20mg/mL HAuCl was added to 20g deionized water at 35 ℃ 4 Solution and TS-1-TiO prepared in step 1) 2 1g of powder to give a mixture. The resulting mixture was stirred for 30 minutes and allowed to mix thoroughly. Adding 10% K by mass into the above mixture dropwise 2 CO 3 Stirring the solution to make the pH value of the mixed solution reach 7-8, and continuously stirring for 5 hours to make HAuCl 4 The Au in the solution is fully deposited and precipitated on the carrier TS-1-TiO 2 On the powder. Subsequently, centrifugally separating, pouring the liquid, collecting the solid, washing the solid three times with 200g of deionized water in total, and drying the washed solid to constant weight at 30 ℃ in a vacuum oven to obtain Au/TS-1-TiO 2 And (3) a sample.
Step 3) catalyst Au/TS-1-TiO 2 Activation treatment
0.3g Au/TS-1-TiO 2 The whole particle catalyst is filled into a fixed bed reactor and is prepared according to H 2 :O 2 :C 3 H 6 :N 2 The flow rate ratio was 3.5:3.5:3.5: and (3) introducing air at a speed of 24.5mL/min, controlling the total flow rate of the mixed gas at 35mL/min, heating the reaction temperature from room temperature to 130 ℃ at a speed of 1 ℃/min, and performing activation treatment for 2 hours.
Catalyst activity evaluation:
the catalyst subjected to the activation treatment prepared in each example was subjected to in-situ activity evaluation, that is, the catalyst after the activation treatment was subjected to the continuous reaction at 130 ℃ for 2 hours until the catalyst performance was stable. The activity evaluation measured at 130℃was carried out using Au/TS-1 as a powder catalyst as a comparative example; the activity evaluation measured by continuing to raise the temperature to 200℃at a rate of 1℃per minute after activation and continuing the reaction at this temperature until the catalyst performance was stable was taken as a comparative example II. The propylene vapor phase epoxidation reaction was carried out under the action of a catalyst, and the catalyst activities of each of examples and comparative examples are shown in table 1.
Table 1 catalyst activity performance for each of the examples and comparative examples
Figure BDA0004077221340000131
As can be seen from Table 1, the catalyst containing IVB-group oxide prepared by the method of the present invention is easy to be tableted and formed, and can catalyze the reaction for synthesizing propylene oxide at a relatively low temperature, the selectivity and space-time yield of propylene oxide are both obviously improved, the propylene conversion rate and hydrogen efficiency are also improved, and especially ZrO is adopted 2 The prepared catalyst has excellent catalytic activity and stability.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.

Claims (10)

1. A propylene gas-phase epoxidation forming catalyst is characterized in that: the catalyst is a titanium silicalite molecular sieve TS-1 loaded with Au and IVB oxides, and the molar ratio of the Au to the IVB oxides in the catalyst is 1: 8-12.
2. The propylene gas phase epoxidation forming catalyst of claim 1, wherein: the loading of the IVB-group oxide is 15-65% of the total mass of the catalyst.
3. The propylene gas phase epoxidation forming catalyst of claim 1, wherein: the IVB oxide is any one or more of titanium dioxide, zirconium dioxide and hafnium dioxide.
4. The propylene gas phase epoxidation forming catalyst of claim 1, wherein: the catalyst also comprises alkali metal carbonate, and the mol ratio of the alkali metal carbonate to Au in the catalyst is 8-22: 1.
5. the catalyst for the vapor phase epoxidation of propylene according to claim 4, wherein: the alkali metal carbonate is one or more of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
6. A process for preparing a shaped catalyst for the vapor phase epoxidation of propylene according to any of claims 1 to 5, characterized in that: the method comprises the following steps:
au is loaded on TS-1 to obtain Au/TS-1, and IVB oxide and the TS-1 loaded with Au are mixed and mechanically stirred; or alternatively, the process may be performed,
TS-1 is mixed with IVB oxide and Au is then supported on the mixture of TS-1 and IVB oxide.
7. The method of manufacturing according to claim 6, wherein: also comprises dipping alkali metal carbonate solution, dipping Au/TS-1 or Au/TS-1 loaded with IVB oxide into alkali metal carbonate solution, drying after dipping.
8. A process for preparing a shaped catalyst for the vapor phase epoxidation of propylene according to any of claims 1 to 5, characterized in that: the method comprises the following steps:
preparation of Au/TS-1: au is loaded on TS-1;
preparing Au/IVB oxide: loading Au on IVB oxide powder;
Au/TS-1 was mixed with Au/IVB-group oxide and mechanically stirred.
9. The method of manufacturing according to claim 8, wherein: the method also comprises the steps of dipping alkali metal carbonate solution, respectively dipping Au/TS-1 and Au/IVB oxide or a mixture thereof after mixing and stirring into the alkali metal carbonate solution, and drying after dipping.
10. Use of the catalyst according to any one of claims 1 to 5 for the epoxidation of propene in the gas phase.
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