CN110721741A - Preparation method of gold catalyst for synthesizing propylene oxide - Google Patents

Preparation method of gold catalyst for synthesizing propylene oxide Download PDF

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Publication number
CN110721741A
CN110721741A CN201910931662.3A CN201910931662A CN110721741A CN 110721741 A CN110721741 A CN 110721741A CN 201910931662 A CN201910931662 A CN 201910931662A CN 110721741 A CN110721741 A CN 110721741A
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China
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cinnamomum camphora
solution
gold
propylene oxide
ionic liquid
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CN201910931662.3A
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李清彪
洪英灵
黄加乐
杜明明
孙道华
王海涛
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Xiamen University
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Xiamen University
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • C07D301/10—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 with catalysts containing silver or gold
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a preparation method of a gold catalyst for synthesizing propylene oxide, which comprises the steps of mixing a chloroauric acid solution with a cinnamomum camphora leaf extracting solution, reducing Au (III) ions into a gold simple substance in situ, adding a titanium-silicon molecular sieve and an ionic liquid, and adding the ionic liquid [ BMIM ]][BF4]The bonding strength between the gold simple substance and the titanium silicalite molecular sieve can be enhanced, the vegetable substance in the cinnamomum camphora leaf extracting solution can protect gold particles from agglomeration in the calcining process, and the prepared gold catalyst has good reaction activity, can obtain higher catalytic stability and has good application prospect.

Description

Preparation method of gold catalyst for synthesizing propylene oxide
Technical Field
The invention belongs to the technical field of gold catalysts, and particularly relates to a preparation method of a gold catalyst for synthesizing propylene oxide.
Background
Propylene Oxide (PO) is an important basic chemical raw material, and the yield of the propylene derivative in the actual production is second to that of polypropylene and acrylonitrile. The propylene oxide is mainly used for producing polyether, propylene glycol ether and the like, and is also used for producing surfactants, oil field demulsifiers, pesticide emulsifiers and the like. The methods currently used industrially for the production of PO are mainly chlorohydrin process, co-oxidation process and H2O2Direct oxidation, and the like. The chlorohydrin method has a large amount of waste water and waste residue which are difficult to treat in the production process, and the generated hypochlorous acid seriously corrodes equipment. The co-oxidation method has high equipment cost and higher requirement on the purity of the propylene, and a large amount of co-products are easily influenced by the market price of the co-products in the production process. H2O2H required for direct oxidation2O2The freight cost is high and the TS-1 carrier is expensive, so the production cost is overhigh.
Preparation of Au/TiO by Haruta in 1998 using deposition precipitation2The catalyst is applied to propylene gas phase epoxidation reaction with hydrogen and oxygen as oxygen sources, and provides a new way for preparing propylene oxide. However, the catalyst prepared by the deposition precipitation method has the disadvantages of low gold loading amount in the loading process, low effective utilization rate of gold, low stability of the catalyst prepared by the method, and low stability of various catalysts in the subsequent documents.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a gold catalyst for synthesizing propylene oxide.
The technical scheme of the invention is as follows:
a preparation method of a gold catalyst for synthesizing propylene oxide comprises the following steps:
(1) washing, drying and crushing the cinnamomum camphora leaves to obtain dry cinnamomum camphora leaves powder, mixing the dry cinnamomum camphora leaves powder with water, and placing the mixture in a constant-temperature water bath shaking table to shake for 20-25h at 29-31 ℃ and 180r/min with 170-;
(2) adding chloroauric acid solution with the concentration of 48-49mmol/L into the cinnamomum camphora leaf extracting solution to obtain a first solution;
(3) mixing titanium-silicon molecular sieve and ionic liquid BMIM][BF4]Sequentially adding the first solution to obtain a second solution;
(4) and sequentially carrying out suction filtration, deionized water washing, vacuum drying, calcination, deionized water washing and vacuum drying on the second solution to obtain the gold catalyst (according to mass percentage (m)) for synthesizing the propylene oxide, wherein the gold loading is 0.05-2.5 wt%Au/mCatalyst and process for preparing same) The calcining atmosphere is air atmosphere, the temperature is 300-400 ℃, and the time is 3-6 h.
In a preferred embodiment of the present invention, in the step (1), the ratio of the dry powder of cinnamomum camphora leaves to water is 8-12 g: 1L.
Further preferably, in the step (1), the ratio of the dry powder of cinnamomum camphora leaves to water is 10 g: 1L.
In a preferred embodiment of the invention, the cinnamomum camphora leaf extract, chloroauric acid solution, titanium silicalite and ionic liquid [ BMIM][BF4]The ratio of the components is 20-26mL, 25-520 mu L, 0.4-0.6g and 90-110 mu L.
In a preferred embodiment of the present invention, in the step (1), after the dry powder of cinnamomum camphora leaves is mixed with water, the mixture is placed in a constant temperature water bath shaking table and shaken for 24 hours at 30 ℃ and 175r/min, and an cinnamomum camphora leaf extract is obtained.
In a preferred embodiment of the invention, the concentration of the chloroauric acid solution is 48.56 mmol/L.
Further preferably, the cinnamomum camphora leaf extract, the chloroauric acid solution, the titanium silicalite molecular sieve and the ionic liquid [ BMIM ]][BF4]The ratio of (A) to (B) is 25mL to 25-520 μ L to 0.5g to 100 μ L.
In a preferred embodiment of the invention, the temperature of the vacuum drying is 48-52 ℃ and the time is 12-24 h.
The invention has the beneficial effects that: the method comprises the steps of mixing a chloroauric acid solution with a cinnamomum camphora leaf extracting solution, reducing Au (III) ions into a gold simple substance in situ, adding a titanium-silicon molecular sieve and an ionic liquid, and adding the ionic liquid [ BMIM ]][BF4]The bonding strength between the gold simple substance and the titanium silicalite molecular sieve can be enhanced, the vegetable substance in the cinnamomum camphora leaf extracting solution can protect gold particles from agglomeration in the calcining process, and the prepared gold catalyst has good reaction activity, higher catalytic stability, low cost and good application prospect.
Drawings
FIG. 1 is a TEM image of a transmission electron microscope of a gold catalyst for synthesizing propylene oxide according to example 1 of the present invention, wherein the scale is 20 nm.
FIG. 2 is a TEM image of a transmission electron microscope of the gold catalyst after 850h of reaction for the synthesis of propylene oxide according to example 1 of the present invention, with the scale of 20 nm.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Washing, drying and crushing cinnamomum camphora leaves to obtain dry cinnamomum camphora leaf powder, mixing 1g of dry cinnamomum camphora leaf powder with 100mL of deionized water, and placing the mixture in a constant-temperature water bath shaking table to shake for 24 hours at the temperature of 30 ℃ and at the speed of 175r/min to obtain 10g/L cinnamomum camphora leaf extracting solution;
(2) adding 260 μ L chloroauric acid solution with concentration of 48.56mmol/L into the above folium Cinnamomi Camphorae extractive solution to obtain first solution, and stirring for 40 min;
(3) mixing 0.5g titanium-silicon molecular sieve and 100 microliter of ionic liquid [ BMIM ]][BF4]Sequentially adding the mixture into the first solution, and continuously stirring for 1h to obtain a second solution;
(4) and sequentially carrying out suction filtration, washing with 150mL of deionized water, vacuum drying at 50 ℃ for 12h, calcining at 375 ℃ in an air atmosphere for 6h, washing with 150mL of deionized water and vacuum drying at 50 ℃ for 24h on the second solution to obtain the gold catalyst for synthesizing propylene oxide shown in figure 1.
(5) 0.15g of the gold catalyst is added into a self-made normal-pressure fixed bed reaction device, and the reaction raw material gas is C3H6∶H2∶O2∶N21: 7 (molar ratio) and the space velocity of 7000mL gcat -1h-1(ii) a The reaction temperature was 305 ℃ and the results of the catalytic reaction are shown in Table 1; after 850h of reaction, a transmission electron microscopy TEM image of the above gold catalyst (labeled example 1) is shown in fig. 2. The results of the catalytic reaction are shown in Table 1.
Example 2
The amount of the chloroauric acid solution added in step (2) was 26. mu.L, the rest was the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 3
The amount of the chloroauric acid solution added in step (2) was 520. mu.L, the rest was the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 4
The calcination temperature in step (1) was 300 ℃ and the results of the catalytic reaction were shown in Table 1, except that the same conditions as in example 1 were used.
Example 5
The calcination temperature in step (1) was 400 ℃ as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 6
The reaction temperature in step (3) was 240 ℃ and the other steps were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
Example 7
The reaction temperature in step (3) was 320 ℃ and the other steps were the same as in example 1, and the results of the catalytic reaction are shown in Table 1.
TABLE 1
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (8)

1. A preparation method of a gold catalyst for synthesizing propylene oxide is characterized by comprising the following steps: the method comprises the following steps:
(1) washing, drying and crushing the cinnamomum camphora leaves to obtain dry cinnamomum camphora leaves powder, mixing the dry cinnamomum camphora leaves powder with water, and placing the mixture in a constant-temperature water bath shaking table to shake for 20-25h at 29-31 ℃ and 180r/min with 170-;
(2) adding chloroauric acid solution with the concentration of 48-49mmol/L into the cinnamomum camphora leaf extracting solution to obtain a first solution;
(3) mixing titanium-silicon molecular sieve and ionic liquid BMIM][BF4]Sequentially adding the first solution to obtain a second solution;
(4) and sequentially carrying out suction filtration, deionized water washing, vacuum drying, calcining, deionized water washing and vacuum drying on the second solution to obtain the gold catalyst for synthesizing the propylene oxide, wherein the gold load is 0.05-2.5 wt%, the calcining atmosphere is air atmosphere, the temperature is 300-400 ℃, and the time is 3-6 hours.
2. The method of claim 1, wherein: in the step (1), the ratio of the dry powder of the cinnamomum camphora leaves to water is 8-12 g: 1L.
3. The method of claim 2, wherein: in the step (1), the ratio of the dry powder of the cinnamomum camphora leaves to water is 10 g: 1L.
4. The method of claim 1, wherein: the cinnamomum camphora leaf extracting solution, the chloroauric acid solution, the titanium silicalite molecular sieve and the ionic liquid [ BMIM ]][BF4]The ratio of the components is 20-26mL, 25-520 mu L, 0.4-0.6g and 90-110 mu L.
5. The method of claim 1, wherein: in the step (1), the dry powder of the cinnamomum camphora leaves is mixed with water and then placed in a constant-temperature water bath shaking table to shake for 24 hours at the temperature of 30 ℃ and the speed of 175r/min, so as to obtain the cinnamomum camphora leaf extracting solution.
6. The method of claim 1, wherein: the concentration of the chloroauric acid solution is 48.56 mmol/L.
7. The method of claim 6, wherein: the cinnamomum camphora leaf extracting solution, the chloroauric acid solution, the titanium silicalite molecular sieve and the ionic liquid [ BMIM ]][BF4]The ratio of (A) to (B) is 25mL to 25-520 μ L to 0.5g to 100 μ L.
8. The method of claim 1, wherein: the temperature of the vacuum drying is 48-52 ℃, and the time is 12-24 h.
CN201910931662.3A 2019-09-27 2019-09-27 Preparation method of gold catalyst for synthesizing propylene oxide Pending CN110721741A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940946A (en) * 2010-08-24 2011-01-12 厦门大学 Preparation method for propylene epoxidation catalyst
CN101961663A (en) * 2010-09-10 2011-02-02 厦门大学 Biological in-situ reduction preparation method of catalyst for synthesizing epoxy-propane
CN103894227A (en) * 2014-04-21 2014-07-02 厦门大学 Preparation method of gold catalyst for preparing epoxypropane by virtue of propylene epoxidation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940946A (en) * 2010-08-24 2011-01-12 厦门大学 Preparation method for propylene epoxidation catalyst
CN101961663A (en) * 2010-09-10 2011-02-02 厦门大学 Biological in-situ reduction preparation method of catalyst for synthesizing epoxy-propane
CN103894227A (en) * 2014-04-21 2014-07-02 厦门大学 Preparation method of gold catalyst for preparing epoxypropane by virtue of propylene epoxidation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
廉婷: "芳樟提取液中的活性成分对丙烯环氧化Au/TS-1催化剂催化性能的作用分析", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *
黄加乐: "银纳米材料和金纳米材料的植物生物质还原制备及应用初探", 《中国博士学位论文全文数据库 工程科技I辑》 *

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Application publication date: 20200124