CN115463678A - Lanthanum oxycarbonate catalyst, preparation method and application thereof - Google Patents
Lanthanum oxycarbonate catalyst, preparation method and application thereof Download PDFInfo
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- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 67
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 23
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 17
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000005610 enamide group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/232—Carbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts, and particularly relates to a lanthanum oxycarbonate catalyst, and a preparation method and application thereof. The method comprises the following steps: (1) Adding a lanthanum-containing compound to a solution containing D-glucose and acrylamide to obtain a first mixture; (2) Adding ammonium hydroxide into the first mixture, and carrying out hydrothermal reaction; (3) And (3) sequentially cooling, carrying out solid-liquid separation, drying and roasting on the reacted materials to obtain the lanthanum oxycarbonate catalyst. The catalyst has better catalytic performance in the preparation of ethane and ethylene by low-temperature conversion in methane oxidative coupling, and improves the selectivity of ethylene and ethane and the conversion rate of methane.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a lanthanum oxycarbonate catalyst, and a preparation method and application thereof.
Background
The technology for preparing ethylene and ethane by natural gas comprises two routes of direct conversion and indirect conversion, and the indirect conversion process has multiple steps and wastes energy, and although the process is easy to realize, the process needs to be optimized and improved; the direct methane conversion process is known as a holy cup in the chemical field because of the atom economy, the attention of the industrial and academic circles is always paid to the direct methane conversion process since the emergence of 1982, wherein the anaerobic methane conversion of methane needs the temperature of more than 1000 ℃, the product is mainly aromatic hydrocarbon, carbon deposition is easy to occur in the process, the industrial implementation is difficult due to the high temperature, the reaction temperature for preparing ethylene by oxidative coupling of methane is relatively low, the reaction activation temperature can be reduced to 600 ℃ or below with the continuous progress of the material preparation level and means, and a path is further opened for industrial application.
At present, the development of a high-performance catalyst for preparing ethylene and ethane by oxidative coupling of medium-low temperature methane is a core problem related to whether the oxidative coupling technology of methane can realize industrial application, but the existing catalyst has generally low methane conversion rate under the low-temperature condition, and if the selectivity of the reaction products ethylene and ethane and the conversion rate of methane can be further improved at low temperature, the catalyst has a promotion effect on the application of the technology.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a lanthanum oxycarbonate catalyst, a preparation method and application thereof. The lanthanum oxycarbonate catalyst prepared by the invention has better catalytic performance in the preparation of ethane and ethylene by low-temperature conversion in methane oxidative coupling, and improves the selectivity of ethylene and ethane and the conversion rate of methane.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a lanthanum oxycarbonate catalyst, the method comprising:
(1) Adding a lanthanum-containing compound to a solution containing D-glucose and acrylamide to obtain a first mixture;
(2) Adding ammonium hydroxide into the first mixture, and carrying out hydrothermal reaction;
(3) And (3) cooling, carrying out solid-liquid separation, drying and roasting on the reacted materials in sequence to obtain the lanthanum oxycarbonate catalyst.
A second aspect of the invention provides a lanthanum oxycarbonate catalyst prepared by the method described above.
A third aspect of the invention provides the use of a lanthanum oxycarbonate catalyst as described above in an oxidative coupling reaction of methane.
In a fourth aspect, the invention provides a method for preparing ethane and ethylene from methane, which comprises the steps of contacting methane with the lanthanum oxycarbonate catalyst in the presence of oxygen-containing gas, and carrying out reaction under the condition of methane oxidative coupling reaction to obtain ethane and ethylene;
alternatively, the lanthanum oxycarbonate catalyst is prepared as described above, and then methane is subjected to a contact reaction with the obtained lanthanum oxycarbonate catalyst in the presence of oxygen and under the condition of methane oxidative coupling reaction to obtain ethane and ethylene.
In the preparation process of the lanthanum oxycarbonate catalyst, D-glucose, acrylamide and ammonium hydroxide are introduced, and the lanthanum oxycarbonate catalyst is prepared by combining a hydrothermal method, so that the lanthanum oxycarbonate catalyst is obtained, has a nano structure, has excellent catalytic performance in the preparation of ethane and ethylene by low-temperature conversion in methane oxidative coupling, and can effectively improve the selectivity of the ethane and the conversion rate of the methane.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing a lanthanum oxycarbonate catalyst, the method comprising:
(1) Adding a lanthanum-containing compound to a solution containing D-glucose and acrylamide to obtain a first mixture;
(2) Adding ammonium hydroxide into the first mixture, and carrying out hydrothermal reaction;
(3) And (3) sequentially cooling, carrying out solid-liquid separation, drying and roasting on the reacted materials to obtain the lanthanum oxycarbonate catalyst.
According to a preferred embodiment of the present invention, in the step (1), the preparation method of the first mixture comprises: at room temperature, D-glucose was dissolved in water, and then acrylamide was added to the resulting solution, followed by the addition of a lanthanum containing compound, to give the first mixture after the solution was clarified.
According to the present invention, the room temperature herein refers to a temperature of 20 to 40 ℃ unless otherwise stated.
The water may be conventional water, for example, deionized water, purified water, and the like, and preferably deionized water.
According to the present invention, the lanthanum-containing compound may be any compound containing lanthanum element, preferably a water-soluble lanthanum-containing compound, for example, but not limited to lanthanum acetate, lanthanum chloride and lanthanum nitrate, preferably selected from lanthanum nitrate and lanthanum acetate.
According to the invention, the amounts of the D-glucose, acrylamide and lanthanum compounds can be selected within a wide range, and in order to further improve the performance of the prepared catalyst, the amount ratio of the D-glucose, acrylamide and lanthanum elements is preferably 1-10.
According to the present invention, the amount of water to be used is not particularly limited, and preferably, the concentration of D-glucose in water is 1 to 5% by weight, more preferably 2 to 3% by weight.
According to the present invention, in the step (2), in order to further improve the performance of the catalyst prepared, it is preferable that the ammonium hydroxide is continuously added to the first mixture in the form of a solution, and the addition is stopped when the mixed system becomes milky white.
Further preferably, the ammonium hydroxide solution is added with stirring.
Preferably, the ammonium hydroxide has a solubility of 5 to 35wt%.
Wherein the adding speed of the ammonium hydroxide solution is not particularly limited, and preferably, the ammonium hydroxide solution with the concentration of 10-30wt% is added at the speed of 1-5ml/min, more preferably 2-4ml/min, relative to the 100-300ml system.
According to the invention, after the end of the ammonium hydroxide addition, in order to further improve the properties of the catalyst prepared, it is preferred that the milky white mass obtained is continuously stirred at room temperature. Wherein, the rotating speed of the stirring can be 500-1000rpm, preferably 800-900rpm, and the stirring time can be 2-10h, preferably 5-8h.
According to the present invention, the hydrothermal reaction conditions may be conventional hydrothermal reaction conditions, but preferably, in order to more effectively improve the performance of the prepared catalyst, the hydrothermal reaction conditions include: the temperature is 100-220 deg.C, preferably 120-180 deg.C, and the time is 24-100h, preferably 60-100h.
Wherein, the hydrothermal reaction can be carried out in a tetrafluoro-lined hydrothermal kettle.
Among them, the hydrothermal reaction is preferably completed under static conditions.
According to the present invention, the temperature after cooling may be room temperature.
According to the present invention, the solid-liquid separation may be any of various conventional solid-liquid separation methods, for example, centrifugation, filtration, and the like. According to a preferred embodiment of the invention, the cooled material is centrifuged at a centrifugation speed of 3000-8000rpm for 10-20min to obtain a solid phase.
According to the present invention, the method preferably further comprises washing the solid phase obtained after the solid-liquid separation, wherein the washing can be performed according to the conventional operation in the field, and preferably, the washing comprises water washing and alcohol washing which are sequentially performed.
Wherein, the number of times of the water washing can be 2-5.
Wherein, the alcohol for alcohol washing is preferably ethanol, and the washing times can be 1-3.
According to the present invention, preferably, the drying conditions include: the temperature is 60-100 deg.C, preferably 70-90 deg.C, and the time is 12-60 hr, preferably 12-48 hr.
According to the present invention, preferably, the firing conditions include: the temperature is 550-650 deg.C, preferably 580-620 deg.C, and the time is 2-10h, preferably 3-4h.
According to the invention, preferably, the calcination is carried out in an air and/or carbon dioxide atmosphere.
According to the present invention, in order to further improve the performance of the prepared catalyst, preferably, the method of the present invention further comprises: a cerium-containing compound and a lanthanum-containing compound are added together to a solution containing D-glucose and acrylamide, thereby preparing a catalyst containing a lanthanum element and a cerium element.
The cerium-containing compound may be any conventional soluble compound containing cerium, and may include, for example, but not limited to, cerium nitrate, cerium chloride, and hydrates thereof.
According to the present invention, it is preferred that the molar ratio of the cerium element to the lanthanum element is 1.
According to a more preferred embodiment of the present invention, the preparation method of the lanthanum oxycarbonate catalyst comprises: accurately weighing D-glucose, dissolving the D-glucose into 280-320g of deionized water (the concentration of the D-glucose is 2.8-3 wt%), adding acrylamide into the solution, continuously stirring, then weighing lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, dissolving into the mixed solution (the adding amount is that the mass ratio of the D-glucose, the enamide and the lanthanum element is 1.5-2.5.
In a second aspect, the present invention provides a lanthanum oxycarbonate catalyst prepared by the method described above.
In a third aspect, the present invention provides the use of a lanthanum oxycarbonate catalyst as described above in the oxidative coupling of methane reaction.
In a fourth aspect, the present invention provides a process for the production of ethane and ethylene from methane, which process comprises contacting methane with a lanthanum oxycarbonate catalyst as described above in the presence of an oxygen-containing gas, and reacting under the conditions of an oxidative coupling reaction of methane to obtain ethane and ethylene;
alternatively, the lanthanum oxycarbonate catalyst is prepared as described above, and then methane is subjected to a contact reaction with the obtained lanthanum oxycarbonate catalyst in the presence of oxygen and under the condition of methane oxidative coupling reaction to obtain ethane and ethylene.
Preferably, the reaction temperature is from 501 to 650 ℃, preferably from 520 to 650 ℃.
Preferably, the molar ratio of methane to oxygen in the reaction feed is from 2 to 10, preferably from 4 to 6.
Preferably, the space velocity of the reaction raw material methane is 5000-100000ml/gh.
Preferably, the reaction time is 10 to 200 hours.
The present invention will be described in detail below by way of examples.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents and apparatus used are those which are not specified by the manufacturer and are conventional products commercially available.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., ltd, and has the model of DHG-9030A.
The muffle furnace is manufactured by CARBOLITE, inc. under the model number CWF1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A. Methane conversion and ethylene ethane selectivity were calculated based on the composition of the product.
Examples 1 to 3
This example illustrates a lanthanum oxycarbonate catalyst and a method for preparing the same
As shown in table 1, D-glucose was accurately weighed and dissolved in deionized water, acrylamide was then added to the solution, stirring was continued, lanthanum nitrate hexahydrate was then weighed and dissolved in the mixed solution, after the solution was stirred until clear, ammonium hydroxide solution was added under stirring, the mixed solution turned into a milky gel, which was continuously stirred at room temperature, finally the mixture was transferred to a teflon-lined hydrothermal kettle, static aging was carried out for hydrothermal reaction, after the hydrothermal kettle was cooled to room temperature, the solid material was separated by centrifugation at 5000rpm for 20min with a centrifuge, washed three times with deionized water, then washed twice with ethanol, the resulting solid was dried in a drying oven, and then calcined in air in a muffle furnace to prepare the lanthanum oxycarbonate catalyst.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| D-glucose concentration (wt.%)/deionized water mass (g) | 2.5/130 | 2/250 | 3/300 |
| D-glucose: an enamide: lanthanum element (mass ratio) | 4:2.5:1 | 5:3:1 | 1.8:1:1 |
| Ammonium hydroxide solution concentration (wt.%) | 25 | 30 | 10 |
| Ammonium hydroxide solution addition rate (ml/min) | 3 | 2 | 4 |
| Continuous stirring speed (rpm) | 850 | 800 | 900 |
| Continuous stirring time (h) | 5 | 6 | 8 |
| Hydrothermal reaction temperature (. Degree.C.) | 180 | 120 | 160 |
| Hydrothermal reaction time (h) | 60 | 70 | 65 |
| Drying temperature (. Degree.C.) | 80 | 70 | 90 |
| Drying time (h) | 12 | 48 | 24 |
| Calcination temperature (. Degree.C.) | 600 | 580 | 620 |
| Calcination time (h) | 3 | 4 | 3.5 |
Example 4
This example illustrates a lanthanum oxycarbonate catalyst and a method for preparing the same
A lanthanum oxycarbonate catalyst was prepared as described in example 1, except that cerium nitrate hexahydrate was added in an amount such that the molar ratio of cerium to lanthanum was 1.
Example 5
This example illustrates a lanthanum oxycarbonate catalyst and a method for preparing the same
The preparation of a lanthanum oxycarbonate catalyst was carried out as described in example 1, except that the lanthanum containing compound was dissolved in water and then acrylamide was added to the resulting solution, followed by addition of D-glucose.
Example 6
This example illustrates a lanthanum oxycarbonate catalyst and a method for preparing the same
The lanthanum oxycarbonate catalyst was prepared as described in example 1, except that after the mixed solution turned to a milky white gel, it was stirred uniformly at room temperature, i.e., without continuous stirring.
Comparative example 1
Comparative example to illustrate a reference lanthanum oxycarbonate catalyst and method of making the same
The preparation of lanthanum oxycarbonate catalyst was carried out as described in example 1, except that no D-glucose was used.
Comparative example 2
Comparative example to illustrate a reference lanthanum oxycarbonate catalyst and method of making the same
The preparation of a lanthanum oxycarbonate catalyst was carried out as described in example 1, except that acrylamide was not used.
Comparative example 3
Comparative example to illustrate a reference lanthanum oxycarbonate catalyst and method of making the same
Lanthanum oxycarbonate catalyst was prepared as described in example 1, except that instead of using D-glucose and acrylamide, lanthanum nitrate hexahydrate was directly dissolved in deionized water and adjusted to pH 10.5, stirring was continued at room temperature until a solid precipitated, after which the procedure of example 3 was followed.
Test example
The catalysts prepared in the above examples and comparative examples were tableted, sieved, and loaded into a fixed bed quartz tube reactor, and methane and oxygen were introduced under atmospheric pressure at a molar ratio of 4. The conversion of methane, selectivity to ethylene ethane and yield are shown in table 2.
TABLE 2
| Numbering | Methane conversion (%) | Ethylene ethane selectivity (%) | Ethylene ethane yield (%) |
| Example 1 | 25.1 | 53.2 | 13.35 |
| Example 2 | 24.9 | 54.5 | 13.57 |
| Example 3 | 24.3 | 52.6 | 12.78 |
| Example 4 | 26.9 | 50.6 | 13.61 |
| Example 5 | 26.3 | 48.9 | 12.86 |
| Example 6 | 26.7 | 49.1 | 13.11 |
| Comparison ofExample 1 | 26.8 | 46.2 | 12.38 |
| Comparative example 2 | 26.7 | 43.9 | 11.72 |
| Comparative example 3 | 26.4 | 44.2 | 11.67 |
The results in table 1 show that the lanthanum oxycarbonate catalyst prepared by the method has excellent catalytic performance in the preparation of ethane and ethylene by low-temperature conversion in methane oxidative coupling, and can effectively improve the selectivity of ethylene and ethane and the conversion rate of methane.
Comparing example 1 with example 4, it can be seen that the introduction of cerium element can further improve the performance of the catalyst.
Comparing example 1 with examples 5-6, it can be seen that the catalyst performance can be further improved with the further preferred process of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a lanthanum oxycarbonate catalyst is characterized by comprising the following steps:
(1) Adding a lanthanum-containing compound to a solution containing D-glucose and acrylamide to obtain a first mixture;
(2) Adding ammonium hydroxide into the first mixture, and carrying out hydrothermal reaction;
(3) And (3) cooling, carrying out solid-liquid separation, drying and roasting on the reacted materials in sequence to obtain the lanthanum oxycarbonate catalyst.
2. The method of claim 1, wherein in step (1), the first mixture is prepared by a method comprising: at room temperature, D-glucose was dissolved in water, and then acrylamide was added to the resulting solution, followed by the addition of a lanthanum containing compound, to give the first mixture after the solution was clarified.
3. The method according to claim 1 or 2, wherein in step (1), the lanthanum-containing compound is selected from lanthanum nitrate, lanthanum chloride and lanthanum acetate, preferably lanthanum nitrate and/or lanthanum acetate; and/or
The dosage ratio of the D-glucose, the acrylamide and the lanthanum elements is 1-10 by dry weight.
4. The method according to any one of claims 1 to 3, wherein in the step (2), ammonium hydroxide is continuously added into the first mixture in the form of solution under the condition of stirring, the ammonium hydroxide is stopped when the system becomes milky white, then the obtained materials are continuously stirred at room temperature, and the hydrothermal reaction is carried out after the stirring is finished;
preferably, the solubility of ammonium hydroxide is 5 to 35wt%; and/or
The obtained material is continuously stirred for 2-10h at room temperature.
5. The method according to any one of claims 1 to 4, wherein in step (3), the hydrothermal reaction conditions include: the temperature is 100-220 ℃, and the time is 24-100h; and/or
The drying conditions include: the temperature is 60-100 ℃, and the time is 12-60h; and/or
The roasting conditions comprise: the temperature is 550-650 ℃, and the time is 2-10h; and/or
The calcination is carried out in an air and/or carbon dioxide atmosphere.
6. The method of any of claims 1-5, wherein the method further comprises: adding a cerium-containing compound and a lanthanum-containing compound together to a solution containing D-glucose and acrylamide;
preferably, the cerium-containing compound is selected from the group consisting of cerium nitrate, cerium chloride and hydrates thereof;
preferably, the molar ratio of cerium to lanthanum is 1.
7. An oxolanthanum carbonate catalyst prepared by the method of any of claims 1-6.
8. Use of the lanthanum oxycarbonate catalyst of claim 7 in oxidative coupling of methane reactions.
9. A process for producing ethane and ethylene from methane, comprising contacting methane with the lanthanum oxycarbonate catalyst of claim 7 in the presence of an oxygen-containing gas, and reacting the mixture under methane oxidative coupling conditions to produce ethane and ethylene;
alternatively, a lanthanum oxycarbonate catalyst is prepared according to the method of any one of claims 1 to 6, and then methane is subjected to a contact reaction with the obtained lanthanum oxycarbonate catalyst in the presence of oxygen and under the condition of methane oxidative coupling reaction to obtain ethane and ethylene.
10. The process of claim 9, wherein the reaction temperature is 501-650 ℃; and/or
The molar ratio of methane to oxygen in the reaction raw materials is 2-10; and/or
The space velocity of the reaction raw material methane is 5000-100000ml/gh; and/or
The reaction time is 10-200h.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061670A (en) * | 1988-06-29 | 1991-10-29 | 501 Societe Nationale Elf Aquitaine | Process for the preparation of a catalyst capable of promoting the oxidative conversion of methane into higher hydrocarbons and use of catalyst |
| CN1087291A (en) * | 1992-11-20 | 1994-06-01 | 中国石油化工总公司 | The methane oxidative coupling low temperature catalyst |
| CN1899966A (en) * | 2005-07-22 | 2007-01-24 | 中国科学院物理研究所 | Flower structure nano cerium oxide base composite material and its preparing method and use |
| CN101822976A (en) * | 2010-03-31 | 2010-09-08 | 辽宁石油化工大学 | A kind of with combustion synthesis nanometer La 2O 3/ La 2O 2CO 3The method of composite |
| CN105418071A (en) * | 2015-07-28 | 2016-03-23 | 山东合创明业精细陶瓷有限公司 | Synthetic method of high-purity ultrafine ZrC-SiC composite powders |
| CN106501448A (en) * | 2016-10-17 | 2017-03-15 | 中国石油大学(华东) | A kind of carbonic acid gas lanthanum nano-particular film sensitive to carbon dioxide |
| US20180353940A1 (en) * | 2015-06-08 | 2018-12-13 | Sabic Global Technoligies B.V. | Methane oxidative coupling with la-ce catalysts |
| CN109663587A (en) * | 2018-11-30 | 2019-04-23 | 中国科学院山西煤炭化学研究所 | A kind of nanometer of methane oxidative coupling catalyst and its preparation method and application |
| CN109999871A (en) * | 2019-04-15 | 2019-07-12 | 常州大学 | A kind of La2O2CO3The preparation method and applications of nanometer triangular plate Pt-supported catalyst |
-
2021
- 2021-06-11 CN CN202110652790.1A patent/CN115463678A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061670A (en) * | 1988-06-29 | 1991-10-29 | 501 Societe Nationale Elf Aquitaine | Process for the preparation of a catalyst capable of promoting the oxidative conversion of methane into higher hydrocarbons and use of catalyst |
| CN1087291A (en) * | 1992-11-20 | 1994-06-01 | 中国石油化工总公司 | The methane oxidative coupling low temperature catalyst |
| CN1899966A (en) * | 2005-07-22 | 2007-01-24 | 中国科学院物理研究所 | Flower structure nano cerium oxide base composite material and its preparing method and use |
| CN101822976A (en) * | 2010-03-31 | 2010-09-08 | 辽宁石油化工大学 | A kind of with combustion synthesis nanometer La 2O 3/ La 2O 2CO 3The method of composite |
| US20180353940A1 (en) * | 2015-06-08 | 2018-12-13 | Sabic Global Technoligies B.V. | Methane oxidative coupling with la-ce catalysts |
| CN105418071A (en) * | 2015-07-28 | 2016-03-23 | 山东合创明业精细陶瓷有限公司 | Synthetic method of high-purity ultrafine ZrC-SiC composite powders |
| CN106501448A (en) * | 2016-10-17 | 2017-03-15 | 中国石油大学(华东) | A kind of carbonic acid gas lanthanum nano-particular film sensitive to carbon dioxide |
| CN109663587A (en) * | 2018-11-30 | 2019-04-23 | 中国科学院山西煤炭化学研究所 | A kind of nanometer of methane oxidative coupling catalyst and its preparation method and application |
| CN109999871A (en) * | 2019-04-15 | 2019-07-12 | 常州大学 | A kind of La2O2CO3The preparation method and applications of nanometer triangular plate Pt-supported catalyst |
Non-Patent Citations (3)
| Title |
|---|
| CHUNWEN SUN ET AL.: "Mesoscale Organization of Flower-Like La2O2CO3 and La2O3 Microspheres", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》, vol. 90, no. 8, pages 2576 - 2581 * |
| HOU, YH等: "封面 Structure sensitivity of La2O2CO3 catalysts in the oxidative coupling of methane(Article)", 《ACS CATALYSIS》, vol. 5, no. 3, pages 1663 - 1674 * |
| 昝逸凡;张彦飞;赵新鹏;孔令照;: "原生生物质水热炭化制备碳材料及其应用", 辽宁石油化工大学学报, no. 04, pages 73 - 82 * |
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