CN105646153B - A kind of support type Au/C3N4The method of the nanocatalyst catalytic oxidation of cyclohexane of@SBA 15 - Google Patents
A kind of support type Au/C3N4The method of the nanocatalyst catalytic oxidation of cyclohexane of@SBA 15 Download PDFInfo
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- CN105646153B CN105646153B CN201510972006.XA CN201510972006A CN105646153B CN 105646153 B CN105646153 B CN 105646153B CN 201510972006 A CN201510972006 A CN 201510972006A CN 105646153 B CN105646153 B CN 105646153B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J29/03—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
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0354—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
The invention discloses a kind of support type Au/C3N4The method of the nanocatalyst catalytic oxidation of cyclohexane of@SBA 15, belongs to technical field of chemistry and chemical engineering.Dicyanodiamine is supported on SBA 15 to be calcined through certain temperature by above-mentioned catalyst using infusion process is made C3N4The carriers of@SBA 15, the pay(useful) load of gold is then carried out using anion exchange method, by filtering, washing, drying, being calcined and be prepared.The catalyst prepared is placed in reactor by the present invention, adds a certain amount of hexamethylene, reactor is risen into certain temperature, is passed through oxygen and is risen to certain pressure and kept for a period of time, finally collects product and carry out gas chromatographic analysis.Using catalyst progress cyclohexane oxidation, the selectivity of product cyclohexanol and cyclohexanone is more than 90%, and conversion ratio is more than 13%, hence it is evident that better than the catalyst of Au/SBA 15.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to a kind of support type Au/C3N4@SBA-15 nanocatalysts
The method of catalytic oxidation of cyclohexane.
Background technology
Cyclohexane selectivity oxidation is an important industrial processes, and its target product is cyclohexanone, actually past
It is past to obtain the mixture (being commonly called as KA oil) of cyclohexanone and cyclohexanol.Cyclohexanone is mainly for the production of adipic acid and caprolactam, and two
Person is important Organic Chemicals, is widely used in the industry such as medicine, paint, spices, is production nylon66 fiber and Buddhist nun respectively
The monomer of dragon 6.Traditional cyclohexane oxidation technique exist conversion ratio low (4%), poor selectivity (80%), severe reaction conditions (>
160 DEG C), the problems such as environmental pollution is serious, these shortcomings are always to restrict the bottleneck of nylon fiber industry development.
Nano catalyst has excellent low-temperature catalytic oxidation activity, is not easy to be poisoned and suitable for polytype anti-
Should, and higher catalytic activity is shown in many reactions.In recent years, Au catalyst table in liquid phase selective oxidation reaction
Reveal higher commercial application potentiality, such as alkene epoxidation, oxidation of alkanes, reducing sugar oxidation.Au catalyst is with molecule
Oxygen for oxidant paraffin selectivity oxidation in show activate C-H keys excellent properties, but the catalyst still show it is relatively low
Conversion ratio (9%), how by suitably it is modified further improve catalyst catalytic activity be still current research key.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of support type Au/C3N4@SBA-15 nano-catalytics
The method of agent catalytic oxidation of cyclohexane, support type Au/C3N4@SBA-15 nanocatalysts have good catalytic activity and choosing
Selecting property.
The technical solution adopted for the present invention to solve the technical problems is as follows.
By support type Au/C3N4@SBA-15 nanocatalysts are placed in reactor, add hexamethylene, reactor is risen to
130~150 DEG C, it is passed through oxygen pressure and rises to 1.3~1.6MPa, react 3~6h, obtain product cyclohexanone and cyclohexanol；
The support type Au/C3N4@SBA-15 nanocatalysts include Au, C3N4, SBA-15, wherein：Au is derived from
HAuCl4, C3N4Presoma be dicyanodiamine, Au and SBA-15 mass ratio are 0.001~0.01:1, dicyanodiamine and
SBA-15 mass ratio is 0.1~0.8:1；
The support type Au/C3N4The preparation of@SBA-15 nanocatalysts comprises the following steps：
(1) matched according to above-mentioned catalytic component, weigh dicyanodiamine and be dissolved in distilled water, added SBA-15, ultrasound, steam
Solid carbon dioxide point, dry, nitrogen atmosphere temperature-programmed calcination, prepare C3N4@SBA-15,
(2) C for preparing step (1)3N4@SBA-15 carriers are placed in container, are added chlorauric acid solution, are heated to 60 DEG C,
NaOH solution regulation pH=6 is added, and stirs 2h；
(3) after the solution filtering obtained step (2), then by washing, Muffle kiln roasting is transferred to, that is, is loaded
Type Au/C3N4@SBA-15 nanocatalysts.
Optimize as one kind, the support type Au/C3N4In the preparation process (1) of@SBA-15 nanocatalysts：Nitrogen gas
Atmosphere temperature-programmed calcination refers to that heating rate is 2~4 DEG C/min, and keeping temperature is 500~700 DEG C, and the residence time is 4~6h；
In preparation process (3)：Sintering temperature is 180~230 DEG C in described Muffle furnace, and drying time is 2~4h.
Compared with prior art, the present invention has following technique effect：
The present invention uses infusion process, and catalyst preparation uses C3N4@SBA-15 are carrier, prepare support type Au/C3N4@
SBA-15 nanocatalysts, the catalyst not only have the duct characteristic of mesoporous SBA-15, while also have C3N4The electronics on surface
Omission, gold nano grain can be stablized well, improve its catalytic activity.The hexamethylene of wherein simple Au/SBA-15 catalyst turns
Rate is only 9%, and selectivity is 85.2%.Cyclohexane oxidation, product cyclohexanol and cyclohexanone are carried out using the catalyst
Selectivity be more than 90%, conversion ratio be more than 13%.The activity and selectivity of the catalyst is substantially better than Au/SBA-15 and urged
Agent.
Embodiment
The present invention is described in further details below by embodiment.But the example does not form the limit to the present invention
System.
Embodiment 1
Prepare catalyst process
Weigh 0.1g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 2 DEG C/min speed rise to 550 DEG C, stop 6h.
Modified SBA-15 carriers 0.5g is placed in container, adds 10.5ml 2.42*10-3Mol/L gold chloride is molten
Liquid, 60 DEG C are heated to, add certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 1%Au/
0.1C3N4@SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 130 DEG C, is passed through oxygen liter
To 1.6MPa, after reacting 3h, it is 13.4% to take out product analysis and measure conversion ratio, and selectivity is 91.1%.
Embodiment 2
Prepare catalyst process
Weigh 0.8g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 4 DEG C/min speed rise to 700 DEG C, stop 4h.
Modified SBA-15 carriers 0.5g is placed in container, adds 5.2ml 2.42*10-3Mol/L gold chloride is molten
Liquid, 60 DEG C are heated to, add certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 0.5%Au/
0.8C3N4@SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 150 DEG C, is passed through oxygen liter
To 1.6MPa, after reaction 36, it is 13.5% to take out product analysis and measure conversion ratio, and selectivity is 90.2%.
Embodiment 3
Prepare catalyst process
Weigh 0.6g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 3 DEG C/min speed rise to 600 DEG C, stop 5h.
Modified SBA-15 carriers 0.5g is placed in container, adds 1.1ml 2.42*10-3Mol/L chlorauric acid solutions,
60 DEG C are heated to, adds certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 0.1%Au/0.6C3N4@
SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 140 DEG C, is passed through oxygen liter
To 1.5MPa, after reacting 4h, it is 14.1% to take out product analysis and measure conversion ratio, and selectivity is 91.4%.
Embodiment 4
Prepare catalyst process
Weigh 0.4g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 3.5 DEG C/min speed rise to 600 DEG C, stop 5h.
Modified SBA-15 carriers 0.5g is placed in container, adds 3.1ml 2.42*10-3Mol/L gold chloride is molten
Liquid, 60 DEG C are heated to, add certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 0.3%Au/
0.4C3N4@SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 150 DEG C, is passed through oxygen liter
To 1.4MPa, after reacting 5h, it is 14.2% to take out product analysis and measure conversion ratio, and selectivity is 90.9%.
Embodiment 5
Prepare catalyst process
Weigh 0.2g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 2 DEG C/min speed rise to 600 DEG C, stop 4h.
Modified SBA-15 carriers 0.5g is placed in container, adds 6.3ml 2.42*10-3Mol/L gold chloride is molten
Liquid, 60 DEG C are heated to, add certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 0.6%Au/
0.2C3N4@SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 150 DEG C, is passed through oxygen liter
To 1.6MPa, after reacting 3h, it is 13.3% to take out product analysis and measure conversion ratio, and selectivity is 90.3%.
Embodiment 6
Prepare catalyst process
Weigh 0.5g dicyanodiamines to be dissolved in 70ml distilled water, add 1g SBA-15, ultrasonic 2h, 70 DEG C of evaporating waters, do
It is dry.Nitrogen atmosphere temperature-programmed calcination, 2.5 DEG C/min speed rise to 600 DEG C, stop 5h.
Modified SBA-15 carriers 0.5g is placed in container, adds 8.3ml 2.42*10-3Mol/L gold chloride is molten
Liquid, 60 DEG C are heated to, add certain density NaOH solution regulation pH=6, and stir 2h.Catalyst is designated as 0.8%Au/
0.5C3N4@SBA-15, closed preservation.
Oxidation reaction process
The above-mentioned catalyst of 30mg is filled in reactor, hexamethylene is added, reactor is risen to 150 DEG C, is passed through oxygen liter
To 1.5MPa, after reacting 6h, it is 15.1% to take out product analysis and measure conversion ratio, and selectivity is 92.4%.
Claims (2)
- A kind of 1. support type Au/C3N4The method of@SBA-15 nanocatalyst catalytic oxidation of cyclohexane, it is characterised in that will load Type Au/C3N4@SBA-15 nanocatalysts are placed in reactor, add hexamethylene, reactor is risen into 130~150 DEG C, is passed through Oxygen pressure rises to 1.3~1.6MPa, reacts 3~6h, obtains product cyclohexanone and cyclohexanol；The support type Au/C3N4@SBA-15 nanocatalysts include Au, C3N4, SBA-15, wherein：Au derives from HAuCl4, C3N4Presoma be dicyanodiamine, Au and SBA-15 mass ratio are 0.001~0.01:1, dicyanodiamine and SBA-15 matter Amount is than being 0.1~0.8:1；The support type Au/C3N4The preparation of@SBA-15 nanocatalysts comprises the following steps：(1) matched according to above-mentioned catalytic component, weigh dicyanodiamine and be dissolved in distilled water, added SBA-15, ultrasound, be evaporated water Divide, dry, nitrogen atmosphere temperature-programmed calcination, prepare C3N4@SBA-15；(2) C for preparing step (1)3N4@SBA-15 carriers are placed in container, add chlorauric acid solution, are heated to 60 DEG C, then add Enter NaOH solution regulation PH=6, and stir 2h；(3) after the solution filtering obtained step (2), then by washing, Muffle kiln roasting is transferred to, that is, obtains support type Au/C3N4@SBA-15 nanocatalysts.
- A kind of 2. support type Au/C as claimed in claim 13N4The method of@SBA-15 nanocatalyst catalytic oxidation of cyclohexane, Characterized in that, the support type Au/C3N4In the preparation process (1) of@SBA-15 nanocatalysts：Nitrogen atmosphere temperature programming Roasting refers to that heating rate is 2~4 DEG C/min, and keeping temperature is 500~700 DEG C, and the residence time is 4~6h；Preparation process (3) In：Sintering temperature is 180~230 DEG C in described Muffle furnace, and drying time is 2~4h.
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| CN107362820A (en) * | 2017-08-16 | 2017-11-21 | 杭州更蓝生物科技有限公司 | It is a kind of to be used to be catalyzed catalyst of chlorinated organics burning and preparation method thereof |
| CN109806863A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of Au catalyst and its application in oxidative dehydrogenation of cyclonexane reaction |
| CN110577200B (en) * | 2019-09-17 | 2021-02-12 | 合肥工业大学 | Gold-doped mesoporous graphite phase carbon nitride material, and preparation method and detection method thereof |
| CN112973727B (en) * | 2019-12-16 | 2023-07-25 | 中国石油天然气股份有限公司 | Catalyst for cyclohexane oxidation, preparation method and application thereof |
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| US20040110995A1 (en) * | 2001-01-05 | 2004-06-10 | Fujio Mizukami | Reaction method utilizing diaphram type catalyst and apparatus therefor |
| CN1772723A (en) * | 2004-11-12 | 2006-05-17 | 中国科学院兰州化学物理研究所 | Selective oxidation process of cyclohexane to prepare cyclohexanone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040110995A1 (en) * | 2001-01-05 | 2004-06-10 | Fujio Mizukami | Reaction method utilizing diaphram type catalyst and apparatus therefor |
| CN1772723A (en) * | 2004-11-12 | 2006-05-17 | 中国科学院兰州化学物理研究所 | Selective oxidation process of cyclohexane to prepare cyclohexanone |
Non-Patent Citations (2)
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| SBA -15 在环己烷选择性氧化中的催化研究;张晓彤等;《石油化工高等学校学报》;20110430;第24卷(第2期);第1-2 * |
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