CN109289833B - Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane - Google Patents

Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane Download PDF

Info

Publication number
CN109289833B
CN109289833B CN201811280546.1A CN201811280546A CN109289833B CN 109289833 B CN109289833 B CN 109289833B CN 201811280546 A CN201811280546 A CN 201811280546A CN 109289833 B CN109289833 B CN 109289833B
Authority
CN
China
Prior art keywords
solid acid
powder
tio
roasting
methane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811280546.1A
Other languages
Chinese (zh)
Other versions
CN109289833A (en
Inventor
丑凌军
程飞
杨建�
宋焕玲
赵军
赵华华
闫亮
牛建中
张兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN201811280546.1A priority Critical patent/CN109289833B/en
Publication of CN109289833A publication Critical patent/CN109289833A/en
Application granted granted Critical
Publication of CN109289833B publication Critical patent/CN109289833B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • 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

Abstract

The invention relates to a preparation method of a solid acid catalyst for preparing ethylene by oxidative coupling of methane, which comprises the following steps: making TiO into a composite material2Fully grinding to 6000-7000 meshes, adding the obtained product into a tungsten salt solution, carrying out ultrasonic impregnation and stirring in a water bath, and evaporating to dryness to obtain a tungsten-titanium solid acid precursor; roasting and grinding the tungsten-titanium solid acid precursor into powder to obtain WO3Solid acid WO with the content of 5-15 wt%3/TiO2A carrier; sequentially adding LiNO into ionized water3、Mn(NO3)2And allowing it to dissolve completely, and then impregnating the solid acid WO by an excess impregnation method3/TiO2Carrying to obtain an impregnated matter; and thirdly, stirring and evaporating the impregnated substance in a water bath, grinding the impregnated substance into powder and roasting the powder to obtain the solid acid catalyst. The preparation method is simple, the preparation conditions are mild, the industrial three wastes are less, and the obtained catalyst has the advantages of good performance, long service life and the like.

Description

Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane
Technical Field
The invention relates to the technical field of chemical catalysts, in particular to a preparation method of a catalyst for preparing ethylene solid acid by oxidative coupling of methane.
Background
The preparation of the low-carbon olefin by methane oxidation coupling is an important development direction for realizing the petroleum cracking route by the comprehensive utilization of natural gas, the direct synthesis of ethylene from natural gas can be realized by the industrialization of the low-carbon olefin, a new ethylene raw material source can be provided in the future when petroleum resources are in short supply, and the method has great strategic significance and great industrial application value. There are a great many documents and patents relating to catalyst systems in this field, but with respect to the catalyst systems in this field at present, the catalyst for oxidative coupling of methane is present in C2The problems of low hydrocarbon yield, high temperature required by the reaction and the like make the industrialization of the reaction system difficult.
ZL 91104243.1 discloses the use of SiO2As carrier, active component is composed of 1.9% Mn2O3 And 5% Na2WO4The catalyst can obtain higher methane conversion rate and C in the oxidative coupling reaction of methane2Selectivity, but the reaction process needs to be carried out at high temperature (higher than 800 ℃). CN1389293A discloses a SiO2As a carrier, carrying Mn2O3、Na2WO4And SnO2The multi-component catalyst can obtain higher methane conversion rate and C under the condition of pressurization (0.6 MPa)2Selectivity, but the reaction process needs pressurization, so that potential safety hazards exist. CN1696084A discloses that an active component is Ag and a carrier is SiO2、Al2O3Catalysts such as SBA-15, which can perform the oxidative coupling of methane at a relatively low temperature, C2The yield is low. CN 102471181 a discloses a Ba modified MgO catalyst for ethylene production by selective methane oxidation, which can perform methane oxidative coupling reaction at a lower temperature, but has a lower methane conversion rate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a catalyst for preparing ethylene solid acid by methane oxidative coupling, which has the advantages of simple method, mild condition and less industrial three wastes.
In order to solve the problems, the preparation method of the solid acid catalyst for preparing ethylene by oxidative coupling of methane comprises the following steps:
making TiO into a composite material2Fully grinding to 6000-7000 meshes, adding the obtained product into a tungsten salt solution, carrying out ultrasonic impregnation and stirring in a water bath, and evaporating to dryness to obtain a tungsten-titanium solid acid precursor; roasting and grinding the tungsten-titanium solid acid precursor into powder to obtain WO3Solid acid WO with the content of 5-15 wt%3/TiO2A carrier;
the molar ratio of active components Li, Mn and Ti is 1-4: 1-4: 17.2 LiNO was added to the ionized water in order3、Mn(NO3)2And allowing it to dissolve completely, and then impregnating the solid acid WO by an excess impregnation method3/TiO2Carrying to obtain an impregnated matter;
and thirdly, stirring and evaporating the impregnated substance in a water bath, grinding the impregnated substance into powder, roasting the powder for 1-3 h at 400 ℃, and then raising the temperature to 700-900 ℃ for roasting for 2-4 h to obtain the solid acid catalyst.
TiO in the step of processing2Is any one of amorphous titanium dioxide, brookite titanium dioxide, anatase titanium dioxide or rutile titanium dioxide.
The tungsten salt solution in the step is ammonium tungstate solution or ammonium metatungstate solution with the concentration of 0.112 g/5 mL-0.375 g/5 mL.
The ultrasonic dipping conditions in the steps refer to that the ultrasonic frequency is 45-200 KHz, the temperature is 20-60 ℃, and the time is 20-60 min.
The roasting condition in the step refers to that the temperature is 120-900 ℃ and the time is 2-4 h.
The step I and the condition that the stirring and the drying in the water bath in the step III are carried out until the temperature is 80-120 ℃.
Compared with the prior art, the invention has the following advantages:
1. the solid acid catalyst obtained by the invention is solid acid WO3/TiO2The carrier is loaded with alkali metal Li and valence-variable metal Mn, which neutralizes the excessive alkalinity of the catalyst and inhibits deep oxidation, thereby improving the reaction result of methane oxidative coupling.
2. The invention firstly prepares the solid acid WO3/TiO2Method for recombining and impregnating carrier to anchor active components Li and Mn to solid acid WO uniformly3/TiO2On the carrier, the interaction of the active component and the carrier is enhanced, and the activity of the catalyst is enhanced.
3. The solid acid catalyst obtained by the invention can be used for preparing C by selective oxidation of methane at the lower temperature of 700-800 ℃ under the normal pressure condition2The catalytic performance of the hydrocarbon reaction is better.
The catalyst of the invention has the temperature of 750 ℃ and CH4:O2:N2The best results obtained under the condition of = 20:8:10 mL/min are as follows: methane conversion of 30.54% and C of 59.17%2Hydrocarbon selectivity, realizes a better reaction result at a lower temperature and normal pressure, and is more suitable for industrial application and popularization.
Compared with the catalysts disclosed in ZL 91104243.1 and CN1389293A and reaction results, the catalyst has relatively high catalytic performance at lower reaction temperature. Compared with the low-temperature catalyst disclosed in CN1696084A and CN 102471181A, the catalyst shows higher methane conversion rate and C in the reaction of preparing ethylene by oxidative coupling of methane2A hydrocarbon selectivity.
4. The preparation method is simple, the conditions are mild, the industrial three wastes are less, and the obtained catalyst has the advantages of long service life and the like.
Detailed Description
The catalyst activity evaluation is carried out on a fixed bed quartz reactor, and the analysis of reaction products is monitored on line by adopting gas chromatography. The methane conversion rate and the product selectivity are calculated by adopting a carbon atom normalization method, and are defined as follows:
conversion rate = [ 1-/(/) methane concentration in tail gas + CO in tail gas =2Concentration +2 × total concentration of ethylene and ethane in tail gas +3 × total concentration of propylene and propane in tail gas)]×100% ；
Selectivity = [ n x concentration of carbonaceous product in tail gas/(CO concentration in tail gas + CO in tail gas)2Concentration +2 × total concentration of ethylene and ethane in tail gas +3 × total concentration of propylene and propane in tail gasDegree)]X 100%, where n is the number of carbon atoms in the product.
Embodiment 1 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is in CH4:O2:N2The data of catalytic reaction performance at 20:8:10 mL/min are shown in Table 1.
TABLE 1
Figure 639081DEST_PATH_IMAGE001
Embodiment 2 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.185 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 200KHz and the temperature is 60 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; the tungsten-titanium solid acid precursor is in a muffle furnaceHeating to 800 deg.C at a heating rate of 4 deg.C/min, calcining for 3 hr, and grinding into powder to obtain WO3Solid acid WO with a content of 8 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.493 g of solid acid WO were added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The data of the catalytic reaction performance of the catalyst at 750 ℃ are shown in Table 2.
TABLE 2
Figure 307959DEST_PATH_IMAGE002
Embodiment 3a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 2h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 840 ℃ for roasting the powder for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in table 3.
TABLE 3
Figure 488274DEST_PATH_IMAGE003
Embodiment 4a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 150KHz and the temperature is 50 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 900 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 4.
TABLE 4
Figure 242603DEST_PATH_IMAGE004
Embodiment 5 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.375 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 80KHz and the temperature is 30 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 15 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.619 g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 3h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in table 5.
TABLE 5
Figure 917298DEST_PATH_IMAGE005
Embodiment 6 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 120KHz and the temperature is 50 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.276 g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 6.
TABLE 6
Figure 440683DEST_PATH_IMAGE006
Embodiment 7 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium tungstate solution, ultrasonically dipping for 60min under the conditions that the ultrasonic frequency is 100KHz and the temperature is 40 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.069 g of LiNO into 10 mL of ionized water3、1.432 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
CH4:O2:N2The data on the catalytic performance at 20:8:10 mL/min are shown in table 7.
TABLE 7
Figure 870528DEST_PATH_IMAGE007
Embodiment 8 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 2h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.069 g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic performance at 20:8:10 mL/min are shown in table 8.
TABLE 8
Figure 800569DEST_PATH_IMAGE008
Embodiment 9 a method for preparing a solid acid catalyst for ethylene production by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 2h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.276 g of LiNO into 10 mL of ionized water3、1.432 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 9.
TABLE 9
Figure 75692DEST_PATH_IMAGE009
Embodiment 10 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
making 2g of amorphous TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 160KHz and the temperature is 45 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 10.
Watch 10
Figure 656846DEST_PATH_IMAGE010
Embodiment 11 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
firstly, 2g rutile type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 3h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the steeped substance to dryness in a water bath at 80 ℃, grinding the steeped substance into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 700 ℃ for 2h to obtain the solid acid catalyst.
CH4:O2:N2The data on the catalytic performance at 20:8:10 mL/min are shown in Table 11.
TABLE 11
Figure 992013DEST_PATH_IMAGE011
Embodiment 12 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
preparation method of titanium dioxide (2 g) anatase type TiO2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium metatungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 130KHz and the temperature is 35 ℃, and then stirring and evaporating in a water bath at 80 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 120 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 4h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the impregnated material to dryness in a water bath at 80 ℃, grinding the impregnated material into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 1h, and then heating the powder to 800 ℃ for roasting for 2h to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in table 12.
TABLE 12
Figure 907885DEST_PATH_IMAGE012
Embodiment 13 a method for preparing a solid acid catalyst for the oxidative coupling of methane to ethylene, comprising the steps of:
firstly, 2g of titanium-based TiO plate2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.112 g/5 mL ammonium tungstate solution, ultrasonically dipping for 20min under the conditions that the ultrasonic frequency is 45KHz and the temperature is 20 ℃, and then stirring and evaporating in a 120 ℃ water bath to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 800 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 2h, and grinding into powder to obtain WO3Solid acid WO with a content of 5 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.448g of solid acid WO was added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the steeped substance to dryness in a water bath at 120 ℃, grinding the steeped substance into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 3 hours, and then heating the powder to 800 ℃ for roasting for 4 hours to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 13.
Watch 13
Figure 986699DEST_PATH_IMAGE013
Embodiment 14 a method for preparing an ethylene solid acid catalyst by oxidative coupling of methane, comprising the steps of:
firstly, 2g of titanium-based TiO plate2Fully grinding to 6000-7000 meshes, adding the ground particles into 0.185 g/5 mL ammonium tungstate solution, ultrasonically dipping for 40min under the conditions that the ultrasonic frequency is 130KHz and the temperature is 35 ℃, and then stirring and evaporating in a water bath at 100 ℃ to dryness to obtain a tungsten-titanium solid acid precursor; heating the tungsten-titanium solid acid precursor to 900 ℃ at the heating rate of 4 ℃/min in a muffle furnace, roasting for 2h, and grinding into powder to obtain WO3Solid acid WO with a content of 8 wt.%3/TiO2And (3) a carrier.
Sequentially adding 0.138g of LiNO into 10 mL of ionized water3、0.358 g Mn(NO3)2(50%) and allowed to dissolve completely, then 1.493 g of solid acid WO were added3/TiO2The carrier is impregnated by adopting an excessive impregnation method to obtain an impregnated matter;
thirdly, stirring and evaporating the steeped substance to dryness in a water bath at 100 ℃, grinding the steeped substance into powder, heating the powder to 400 ℃ in a muffle furnace at the heating rate of 4 ℃/min, roasting the powder for 2 hours, and then heating the powder to 800 ℃ for roasting the powder for 3 hours to obtain the solid acid catalyst.
The catalyst is at 750 ℃ and CH4:O2:N2The data on the catalytic reaction performance at 20:8:10 mL/min are shown in Table 14.
TABLE 14
Figure 422360DEST_PATH_IMAGE014

Claims (4)

1. A preparation method of a solid acid catalyst for preparing ethylene by methane oxidative coupling comprises the following steps:
making TiO into a composite material2Fully grinding to 6000-7000 meshes, adding the obtained product into a tungsten salt solution, carrying out ultrasonic impregnation and stirring in a water bath, and evaporating to dryness to obtain a tungsten-titanium solid acid precursor; roasting and grinding the tungsten-titanium solid acid precursor into powder to obtain WO3Solid acid WO with the content of 5-15 wt%3/TiO2A carrier; the TiO is2Is any one of amorphous titanium dioxide, brookite titanium dioxide, anatase titanium dioxide or rutile titanium dioxide; the tungsten salt solution is an ammonium tungstate solution or an ammonium metatungstate solution with the concentration of 0.112 g/5 mL-0.375 g/5 mL;
the molar ratio of active components Li, Mn and Ti is 1-4: 1-4: 17.2 LiNO was added to the ionized water in order3、Mn(NO3)2And allowing it to dissolve completely, and then impregnating the solid acid WO by an excess impregnation method3/TiO2Carrying to obtain an impregnated matter;
and thirdly, stirring and evaporating the impregnated substance in a water bath, grinding the impregnated substance into powder, roasting the powder for 1-3 h at 400 ℃, and then raising the temperature to 700-900 ℃ for roasting for 2-4 h to obtain the solid acid catalyst.
2. The method for preparing the ethylene solid acid catalyst by oxidative coupling of methane as claimed in claim 1, wherein: the ultrasonic dipping conditions in the steps refer to that the ultrasonic frequency is 45-200 KHz, the temperature is 20-60 ℃, and the time is 20-60 min.
3. The method for preparing the ethylene solid acid catalyst by oxidative coupling of methane as claimed in claim 1, wherein: the roasting condition in the step refers to that the temperature is 120-900 ℃ and the time is 2-4 h.
4. The method for preparing the ethylene solid acid catalyst by oxidative coupling of methane as claimed in claim 1, wherein: the step I and the condition that the stirring and the drying in the water bath in the step III are carried out until the temperature is 80-120 ℃.
CN201811280546.1A 2018-10-30 2018-10-30 Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane Active CN109289833B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811280546.1A CN109289833B (en) 2018-10-30 2018-10-30 Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811280546.1A CN109289833B (en) 2018-10-30 2018-10-30 Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane

Publications (2)

Publication Number Publication Date
CN109289833A CN109289833A (en) 2019-02-01
CN109289833B true CN109289833B (en) 2021-08-03

Family

ID=65146096

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811280546.1A Active CN109289833B (en) 2018-10-30 2018-10-30 Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane

Country Status (1)

Country Link
CN (1) CN109289833B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115254087A (en) * 2021-04-30 2022-11-01 中国石油天然气股份有限公司 Supported catalyst and preparation method and application thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208669A (en) * 1997-08-20 1999-02-24 中国石油化工总公司 Catalyst for prodn. of ethylene by oxidating mixture of methane and ethane as raw material
CN1389293A (en) * 2002-05-25 2003-01-08 中国科学院兰州化学物理研究所 Catalyst for pressurized oxidative coupling of methane to prepare ethylene and its prepn.
CN102093157A (en) * 2009-12-09 2011-06-15 中国科学院兰州化学物理研究所 Joint process for preparing ethylene and synthesis gas by direct conversion of methane
CN103118777A (en) * 2010-05-24 2013-05-22 希路瑞亚技术公司 Nanowire catalysts
WO2012106453A3 (en) * 2011-02-01 2014-04-24 The Regents Of The University Of Colorado, A Body Corporate Materials and methods for improving selectivity in heterogeneous catalysts and products thereof
CN105170138A (en) * 2014-05-29 2015-12-23 中国石油化工股份有限公司 Methane oxidative coupling reaction catalyst and preparation method thereof
CN107108401A (en) * 2014-12-09 2017-08-29 沙特基础工业全球技术公司 By the way that methane oxidation coupling is reacted into the method for combining and producing ethene and synthesis gas with methane dry reforming
CN107406349A (en) * 2014-10-31 2017-11-28 沙特基础全球技术有限公司 Methane and ethane to synthesis gas and ethene conversion
WO2018048629A1 (en) * 2016-09-06 2018-03-15 Sabic Global Technologies, B.V. Multi-stage adiabatic oxidative coupling of methane
CN108273525A (en) * 2018-01-23 2018-07-13 吕晓东 A kind of method that magnetic nano solid acid catalysis prepares chemical intermediate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321740C (en) * 2004-03-03 2007-06-20 四川大学 Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method
CN104759291B (en) * 2014-01-02 2018-01-26 易高环保能源研究院有限公司 A kind of methane oxidative coupling catalyst and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208669A (en) * 1997-08-20 1999-02-24 中国石油化工总公司 Catalyst for prodn. of ethylene by oxidating mixture of methane and ethane as raw material
CN1389293A (en) * 2002-05-25 2003-01-08 中国科学院兰州化学物理研究所 Catalyst for pressurized oxidative coupling of methane to prepare ethylene and its prepn.
CN102093157A (en) * 2009-12-09 2011-06-15 中国科学院兰州化学物理研究所 Joint process for preparing ethylene and synthesis gas by direct conversion of methane
CN103118777A (en) * 2010-05-24 2013-05-22 希路瑞亚技术公司 Nanowire catalysts
WO2012106453A3 (en) * 2011-02-01 2014-04-24 The Regents Of The University Of Colorado, A Body Corporate Materials and methods for improving selectivity in heterogeneous catalysts and products thereof
CN105170138A (en) * 2014-05-29 2015-12-23 中国石油化工股份有限公司 Methane oxidative coupling reaction catalyst and preparation method thereof
CN107406349A (en) * 2014-10-31 2017-11-28 沙特基础全球技术有限公司 Methane and ethane to synthesis gas and ethene conversion
CN107108401A (en) * 2014-12-09 2017-08-29 沙特基础工业全球技术公司 By the way that methane oxidation coupling is reacted into the method for combining and producing ethene and synthesis gas with methane dry reforming
WO2018048629A1 (en) * 2016-09-06 2018-03-15 Sabic Global Technologies, B.V. Multi-stage adiabatic oxidative coupling of methane
CN108273525A (en) * 2018-01-23 2018-07-13 吕晓东 A kind of method that magnetic nano solid acid catalysis prepares chemical intermediate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A study on the monolayer dispersion of tungsten oxide on anatase;Xiao-Feng Yu et al.;《J. Mater. Chem.》;20011108;第11卷(第12期);第3337-3342页 *
载体对Li-Mn氧化物催化甲烷氧化偶联反应作用;刘玉兰等;《工业催化》;20160630;第24卷(第6期);第46-52页 *

Also Published As

Publication number Publication date
CN109289833A (en) 2019-02-01

Similar Documents

Publication Publication Date Title
Li et al. Mechanism of the Mn promoter via CoMn spinel for morphology control: formation of Co2C nanoprisms for Fischer–Tropsch to olefins reaction
Li et al. Defective TiO2 for propane dehydrogenation
Feng et al. Photothermal synergistic effect of Pt1/CuO-CeO2 single-atom catalysts significantly improving toluene removal
Bagheri et al. Titanium dioxide as a catalyst support in heterogeneous catalysis
Li et al. Strong metal-support interaction and catalytic properties of anatase and rutile supported palladium catalyst Pd/TiO2
JP5920750B2 (en) Gold catalyst for ethanol oxidation and method for producing acetaldehyde and acetic acid using the same
Chernyak et al. Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook
Wang et al. Supported Au nanoparticles as efficient catalysts for aerobic homocoupling of phenylboronic acid
Lin et al. Methane conversion over artificial photocatalysts
Rao et al. Photocatalytic reduction of nitrogen over (Fe, Ru or Os)/TiO2 catalysts
Scotti et al. Dispersed copper oxide: A multifaceted tool in catalysis
Li et al. Support and promoter effects in the selective oxidation of ethane to acetic acid catalyzed by Mo-V-Nb oxides
Wang et al. Oxidative dehydrogenation of propane to propylene in the presence of CO2 over gallium nitride supported on NaZSM-5
CN105080576B (en) A kind of method that utilization plasma gas solid method activates MoVNbTeOx pure phase M1 catalyst
CN109289833B (en) Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane
Ren et al. Dual-component sodium and cesium promoters for Au/TS-1: enhancement of propene epoxidation with hydrogen and oxygen
CN113797947A (en) C-modified platinum-based catalyst and preparation method and application thereof
Wang et al. Main-group catalysts with atomically dispersed in sites for highly efficient oxidative dehydrogenation
US20160199819A1 (en) Bimetallic Mercaptan Conversion Catalyst for Sweetening Liquefied Petroleum Gas at Low Temperature
Ito et al. CO hydrogenation over RhVO4/SiO2, Rh/V2O3 and Rh/SiO2 catalysts: reduction and regeneration of RhVO4
KR102170320B1 (en) Low temperature oxidative coupling method of methane using oxidized palladium catalyst supported on cerium oxide
Jian et al. Engineering oxygen vacancy and crystal surfaces for TiO2-based photocatalysts for enhanced photocatalytic hydrogenation of bio-based carbonyls to biofuels
CN112275283A (en) Metal supported catalyst system for preparing ethylene by photocatalytic oxidation ethane dehydrogenation and ethane direct dehydrogenation
JP2020525278A (en) Composition capable of reducing CO and NOx emissions, production method and use thereof, and fluid catalytic cracking method
Uphade et al. Vapor-phase epoxidation of propene using H2 and O2 over Au/Ti-MCM-41 and Au/Ti-MCM-48

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant