CN115487840A - Preparation method and application of catalyst containing lanthanum oxycarbonate - Google Patents
Preparation method and application of catalyst containing lanthanum oxycarbonate Download PDFInfo
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- lanthanum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 32
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000011343 solid material Substances 0.000 claims abstract description 13
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 8
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- MCYSFVUDODFQPV-UHFFFAOYSA-K lanthanum(3+) trichlorate Chemical compound [La+3].[O-][Cl](=O)=O.[O-][Cl](=O)=O.[O-][Cl](=O)=O MCYSFVUDODFQPV-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005470 impregnation 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
- 239000003345 natural gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- VYGHOXHBHAWHDO-UHFFFAOYSA-L lanthanum(3+) carbonate hydrate Chemical compound O.[La+3].[O-]C([O-])=O VYGHOXHBHAWHDO-UHFFFAOYSA-L 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical group [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material 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
-
- 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 the field of catalysts, in particular to a preparation method and application of a catalyst containing lanthanum oxycarbonate. The method comprises the following steps: (1) Adding alkali liquor into a solution containing water-soluble lanthanum salt to obtain a mixed material containing precipitate; wherein the alkali liquor is sodium hydroxide with the concentration of more than 15 weight percent; (2) Maintaining the mixture at a temperature of from room temperature to 100 ℃ under normal pressure; (3) And (3) separating the materials maintained in the step (2) to obtain solid materials, and then carrying out first drying and roasting on the solid materials to obtain the catalyst containing the lanthanum oxycarbonate. The method adopts the conventional strong alkali coprecipitation method to prepare the catalyst containing the lanthanum oxycarbonate, and does not carry out hydrothermal reaction, so the method can reduce the preparation cost, and can show satisfactory catalytic effect when being applied to methane oxidative coupling reaction.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method and application of a catalyst containing lanthanum oxycarbonate.
Background
Coal, petroleum, natural gas and the like are main pillars of world energy and modern chemical industry, along with the current increasingly depleted petroleum resources, natural gas resources play an increasingly important role as important alternative resources, the current utilization of natural gas is realized by directly burning, so that the great waste of methane resources is caused, at present, except for the preparation of synthesis gas, acetylene and hydrocyanic acid from methane, other utilization ways are in a laboratory research state, further promotion is urgently needed, and the effective conversion and utilization of methane are promoted, wherein the most remarkable purpose is that methane is oxidized and coupled to an ethylene ethane path, because ethylene is one of chemical products with the largest yield in the world, the ethylene industry is the core of the petrochemical industry, and ethylene products account for more than 75% of petrochemical products, and occupy an important position in national economy. Ethylene production has been regarded worldwide as one of the important indicators for the petrochemical development of a country.
However, the direct conversion of methane to produce ethylene is very difficult and challenging. The current high-temperature catalyst patent requires a high reaction temperature, generally greater than 750 ℃, and the reaction is an exothermic reaction, which brings a problem to engineering amplification, so that the research on the catalyst for the methane oxidative coupling reaction at a low temperature draws attention of researchers, in the medium-low temperature catalyst, the research on a catalyst system based on lanthanum oxide is more, and patent application US20120041246 reports a nanowire catalyst, which can activate methane at a lower temperature, but a biological template agent is required in the preparation process of the catalyst, so that the repeatability of the preparation process is poor, the preparation process is complex, and patent application CN109663587 adopts a hydrothermal method to prepare a nano lanthanum oxide catalyst, and the hydrothermal method is adopted to treat, so that the preparation process is complex, and the industrial amplification difficulty is high.
Disclosure of Invention
The invention aims to overcome the defect of complex catalyst preparation process in the prior art, and provides a preparation method and application of a catalyst containing lanthanum oxycarbonate.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a catalyst containing lanthanum oxycarbonate, the method comprising:
(1) Adding alkali liquor into a solution containing water-soluble lanthanum salt to obtain a mixed material containing precipitate; wherein the concentration of the alkali liquor is more than 15 wt%;
(2) Maintaining the mixture at a temperature of from room temperature to 100 ℃ at atmospheric pressure;
(3) And (3) separating the materials maintained in the step (2) to obtain solid materials, and then drying and roasting the solid materials to obtain the catalyst containing the lanthanum oxycarbonate.
In another aspect of the invention there is provided a catalyst comprising lanthanum oxycarbonate prepared by the process described above.
In a further aspect, the present invention provides a process for the preparation of carbo-hydrocarbons from methane, which process comprises: the catalyst is prepared as described above, and then methane is brought into contact with the resulting catalyst in the presence of oxygen and under the conditions of the oxidative coupling reaction of methane.
Through the technical scheme, the defect of complex catalyst preparation process in the prior art is overcome, the solid material is prepared by coprecipitation mainly through a strong alkali method, and then the solid material is maintained in situ at the temperature of not higher than 100 ℃ under normal pressure, and the step of carrying out hydrothermal reaction in a hydrothermal kettle is omitted, so that the preparation cost can be reduced, and the method can show satisfactory catalytic effect when being applied to methane oxidative coupling reaction.
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise stated, "room temperature" means a temperature of 20 to 40 ℃.
It will be appreciated that conventional hydrothermal reactions are carried out in tetrafluoro-lined reactors under sealed conditions, i.e., at a pressure (above atmospheric pressure). Therefore, although the holding temperature of the present invention and the hydrothermal reaction temperature intersect with each other, they cannot be understood as hydrothermal reactions.
In a first aspect, the present invention provides a method for preparing a catalyst containing lanthanum oxycarbonate, the method comprising:
(1) Adding alkali liquor into a solution containing water-soluble lanthanum salt to obtain a mixed material containing precipitate; wherein the concentration of the lye is more than 15 weight percent;
(2) Maintaining the mixture at a temperature of from room temperature to 100 ℃ under normal pressure;
(3) And (3) separating the materials maintained in the step (2) to obtain solid materials, and then carrying out first drying and roasting on the solid materials to obtain the catalyst containing the lanthanum oxycarbonate.
According to the present invention, the water soluble lanthanum salt may be a variety of water soluble lanthanum salts conventionally used, for example, may include, but are not limited to, lanthanum chloride, lanthanum chlorate and lanthanum nitrate.
The concentration of the lanthanum element in the solution can be selected from a wide range, and preferably, in order to obtain a catalyst with better performance, the concentration of the lanthanum element in the solution is 0.05 to 10 wt%, for example, 0.05 wt%, 0.1 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, preferably 0.1 to 5 wt%, and more preferably 0.7 to 1 wt%.
Although the inventors of the present invention found in their research that the step of performing the hydrothermal reaction in the reaction kettle can be omitted as long as the concentration of the alkali solution is more than 15 wt% (e.g., may be 15.5 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%), the concentration of the alkali solution is preferably 18 to 30 wt%, more preferably 20 to 30 wt%.
The lye is preferably a solution of a strong base, for example a sodium hydroxide solution and/or a potassium hydroxide solution, preferably a sodium hydroxide solution.
According to the invention, the form of adding the alkali liquor into the solution is not particularly limited, and the alkali liquor can be added intermittently or in a feeding manner, and feeding is preferred in the invention. Preferably, the feeding rate is 0.1-10g, preferably 0.15-8g, more preferably 1.6-8g, for example, 1.6g, 2g, 2.5g, 3g, 3.5g, 4g, 4.5g, 5g, 5.5g, 6g, 6.5g, 7g, 7.5g, 8g of the alkali liquor per minute in terms of sodium hydroxide per kilogram of the solution.
According to the invention, the lye is potassium hydroxide, provided that the rate of addition is such that the change in hydroxyl (pH) in the system is consistent with the change in the lye when sodium hydroxide is used.
According to the invention, the lye is preferably added to a pH of the resulting mixture of 10 to 14, which may be, for example, 11, 11.5, 12, 12.5, 13, 13.5, 14, more preferably 11 to 13, even more preferably 11.5 to 12.5.
According to the invention, the addition temperature of the lye is not particularly limited and may be in accordance with the temperature maintained.
According to the invention, the precipitate is lanthanum hydroxide.
According to the present invention, the temperature to be maintained may be 20 ℃, 30 ℃,40 ℃,50 ℃,60 ℃, 70 ℃,80 ℃, 90 ℃,100 ℃, more preferably from room temperature to 80 ℃, and still more preferably from 25 ℃ to 50 ℃.
According to the invention, the maintaining time can be equivalent to the time of the conventional hydrothermal reaction, and can be 12-60h, preferably 20-60h, and more preferably 40-60h.
According to the present invention, the method of separation may be filtration, centrifugation, or the like. According to a preferred embodiment of the invention, the solid material is obtained by means of centrifugation. The conditions of the centrifugation preferably include: the rotating speed is 5000rpm-10000rpm, preferably 8000rpm-10000rpm; the time is 20min-60min, preferably 20min-40min.
According to the present invention, it is preferable that the solid material is washed before the first drying, and water and/or ethanol may be used for washing. According to a preferred embodiment of the invention, the washing is first carried out with water (distilled water) until neutral and then with ethanol for 1-2 times.
According to the present invention, the temperature of the primary drying may be varied within a wide range, and preferably, the temperature of the primary drying is 80 ℃ to 120 ℃, for example, 80 ℃, 90 ℃,100 ℃,110 ℃,120 ℃.
According to the invention, the time of the first drying can vary within wide limits, preferably the time of the first drying is 10h to 50h, for example 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h, 50h.
According to a preferred embodiment of the present invention, in order to further improve the performance of the prepared catalyst, the method further comprises: before roasting, the first dried material is put into a solution containing a zirconium compound for dipping, then secondary drying is carried out, and finally the second dried material is roasted.
According to the invention, the zirconium-containing compound may be a zirconium-containing compound soluble in water, and may be chosen, for example, from zirconium fluoride and potassium fluorozirconate.
The amount of the zirconium-containing compound used may vary within a wide range, and is preferably in a molar ratio of 1.
The concentration of the zirconium-containing compound in the solution of the zirconium-containing compound may be 1 to 10% by weight, more preferably 3 to 8% by weight, and still more preferably 5 to 6% by weight.
According to the present invention, the amount of the solution of the zirconium-containing compound used is not particularly limited as long as the first dried material can be immersed.
The impregnation conditions can be selected within a wide range, and preferably, the impregnation temperature is room temperature and the impregnation time is 0.5-6h.
Wherein the temperature of the second drying can be changed in a wide range, preferably, the temperature of the second drying is 80 ℃ to 120 ℃, for example, 80 ℃, 90 ℃,100 ℃,110 ℃,120 ℃.
According to the invention, the time of the second drying can vary within a wide range, preferably the time of the second drying is 10-50h, for example 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h, 50h.
According to a more preferred embodiment of the present invention, the second drying method comprises stirring at a temperature of 50-100 ℃, preferably 60-80 ℃ until the solvent is completely volatilized, and then drying the obtained solid material in an oven at a temperature of 80-120 ℃, for example, 80 ℃, 90 ℃,100 ℃,110 ℃,120 ℃ for 10h-30h, for example, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h.
According to the invention, the temperature of the calcination may vary within wide limits, preferably the calcination temperature is 450 to 650 ℃, for example 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃.
According to the invention, the time of the calcination can vary within wide limits, preferably the calcination time is between 1h and 6h, for example 1h, 2h, 3h, 4h, 5h, 6h.
According to the present invention, the atmosphere for the calcination is not particularly limited, and may be an air atmosphere or a carbon dioxide atmosphere, or may be a nitrogen atmosphere, and is preferably an air atmosphere or a carbon dioxide atmosphere.
According to a preferred embodiment of the present invention, a method for preparing a catalyst containing lanthanum oxycarbonate includes:
accurately weighing lanthanum acetate, dissolving the lanthanum acetate in deionized water (the concentration of lanthanum element is 0.85-0.9 wt%), stirring to completely dissolve the lanthanum acetate, slowly dropwise adding 18-22 wt% of sodium hydroxide solution into the solution (4-5 g of sodium hydroxide is added per minute per kilogram of the solution) at 40-50 ℃, adjusting the end point pH value to 11.5-12, keeping the temperature for 40-45h under the condition, separating the solid product by a centrifugal separator at 7500-8500rpm for 25-35min, washing the solid product with deionized water to be neutral, washing the solid product with ethanol for 1-3 times, drying the solid product in an oven at 90-110 ℃ for 18-22h, then soaking the material in a potassium fluozirconate solution (the molar ratio of zirconium element to lanthanum element is 1-15-18, the concentration of potassium fluozirconate is 5-6 wt%), stirring at 60-65 ℃ after 4-6h until the solvent is volatilized, placing the soaked solid in the oven, keeping the temperature for 110-120 h, then placing the material in the oven at 450-25 h, keeping the atmosphere of lanthanum in the oven at 450-500 ℃ to prepare the lanthanum carbonate catalyst, and keeping the oxygen atmosphere at 5-3 h.
In a second aspect, the present invention provides a catalyst comprising lanthanum oxycarbonate prepared by the method described above.
In a third aspect, a method for producing a carbo-carb-ydrocarbon from methane, the method comprising: the catalyst is prepared as described above, and then methane is brought into contact with the resulting catalyst in the presence of oxygen and under the conditions of the oxidative coupling reaction of methane.
According to the present invention, the conditions for the oxidative coupling reaction of methane are not particularly limited, and may be conventionally selected in the art, and the conditions for the oxidative coupling reaction of methane may include a reaction temperature of 450 ℃ to 700 ℃ (e.g., 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃) and a space velocity of methane of 5000 mL/(g.h) to 150000 mL/(g.h). Preferably, the molar ratio of the amounts of methane and oxygen is from 2 to 10:1, more preferably 3-8.
The present invention will be described in detail below by way of examples.
The drying box is produced by Shanghai-Hengheng scientific instruments Co., ltd, and has the model of DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A.
The methane conversion was calculated as follows:
methane conversion = amount of methane consumed by the reaction/initial amount of methane x 100%.
The ethylene selectivity was calculated as follows:
ethylene selectivity = amount of methane consumed by ethylene produced/total consumption of methane × 100%.
Ethane selectivity was calculated as follows:
ethane selectivity = amount of methane consumed by ethane produced/total consumption of methane × 100%.
The yield of carbo-diimides is calculated as follows:
carbo-carb yield = methane conversion x (ethane selectivity + ethylene selectivity).
Example 1
Lanthanum nitrate hexahydrate is accurately weighed and dissolved in deionized water (the concentration of lanthanum element is 0.74 wt%), the lanthanum nitrate hexahydrate is stirred to be completely dissolved, 25 ℃ of room temperature is carried out, 25 wt% of sodium hydroxide solution is slowly dripped into the solution (0.15 g of sodium hydroxide is added into each kilogram of the solution per minute), the end point pH value is adjusted to 12, the solution is kept for 60 hours under the condition, then a solid product is separated through a centrifugal separator, the rotation speed is 10000rpm, the time is 20 minutes, the solution is washed for 3 times by deionized water and is washed for 2 times by ethanol, then the solid is dried in an oven at 80 ℃ for 24 hours, and then the material is kept for 4 hours in an air atmosphere in a muffle furnace at 500 ℃ to prepare the lanthanum oxycarbonate catalyst A1.XRD showed the material to be La 2 O 2 CO 3 。
Example 2
Accurately weighing lanthanum acetate, dissolving the lanthanum acetate in deionized water (the concentration of lanthanum element is 1.0 wt%), stirring the lanthanum acetate to be completely dissolved, slowly dropwise adding a 30 wt% sodium hydroxide solution into the solution at 50 ℃ (2 g of sodium hydroxide is added into each kilogram of the solution per minute), adjusting the end point pH value to be 12.5, keeping the temperature for 50h under the condition, separating a solid product through a centrifugal separator at a rotating speed of 9000rpm for 25min, washing the solid product with the deionized water for 3 times, washing the solid product with ethanol for 2 times, drying the solid product in an oven at 120 ℃ for 15h, then keeping the material in an air atmosphere in a muffle furnace at 550 ℃ for 2h to prepare an oxygen carbonate catalyst A2, and XRD shows that the material is La 2 O 2 CO 3 。
Example 3
Preparation of catalyst A3 was carried out in accordance with the procedure of example 2, except that the dried material obtained after drying was immersed in a zirconium tetrafluoride solution (molar ratio of zirconium element to lanthanum element was 1 2 O 2 CO 3 And is doped with zirconium element.
Example 4
Accurately weighing lanthanum acetate, dissolving the lanthanum acetate in deionized water (the concentration of lanthanum element is 0.88 weight percent), stirring the lanthanum acetate to be completely dissolved, slowly dropwise adding 20 weight percent sodium hydroxide solution into the solution (5 g of sodium hydroxide is added into each kilogram of solution per minute) at the temperature of 45 ℃, adjusting the end point pH value to be 11.6, keeping the temperature for 40 hours under the condition, separating a solid product through a centrifugal separator, rotating the speed to be 8000rpm, keeping the time for 30 minutes, washing the solid product for 3 times by using deionized water, washing the solid product for 2 times by using ethanol, drying the solid product in an oven at the temperature of 100 ℃ for 20 hours, then keeping the material in an air atmosphere in a muffle furnace at the temperature of 450 ℃ for 4 hours to prepare an oxygen carbonate lanthanum catalyst A4, wherein XRD shows that the material is La 2 O 2 CO 3 。
Example 5
Catalyst A5 was prepared by following the procedure of example 4, except that the dried material obtained after drying was immersed in a potassium fluorozirconate solution (molar ratio of zirconium element to lanthanum element was 1 2 O 2 CO 3 And is doped with zirconium element.
Comparative example 1
Catalyst D1 was prepared according to the method of example 1, except that the concentration of the sodium hydroxide solution was 8% by weight, and 0.05g of sodium hydroxide per kg of solution per minute was added.
Comparative example 2
Lanthanum nitrate hexahydrate is accurately weighed, dissolved in deionized water (the concentration of lanthanum element is 0.74 wt%), stirred to be completely dissolved, 8 wt% of sodium hydroxide solution is slowly dripped into the solution (0.2 g of sodium hydroxide is added into each kilogram of the solution per minute) at room temperature (-25 ℃), the end point pH value is adjusted to 12, stirring is continued until solid is separated out, the mixed material is transferred into a stainless steel hot kettle lined with polytetrafluoroethylene, the temperature is kept at 120 ℃ for 48 hours, then a solid product is separated through a centrifugal separator, the rotating speed is 10000rpm, the time is 20 minutes, the mixed material is washed 3 times with deionized water, the mixed material is washed 2 times with ethanol, the solid is dried in an oven at 80 ℃ for 24 hours, and then the material is kept in a muffle furnace at 500 ℃ for 4 hours in the air atmosphere to prepare the lanthanum oxycarbonate catalyst D2.
Test example
0.1g of the catalyst prepared in the above examples and comparative examples was charged in a fixed bed quartz tube reactor under normal pressure conditions at a methane to oxygen molar ratio of 8:1, a methane space velocity of 100000ml/gh, a reaction temperature of 550 ℃ and methane conversion and ethylene ethane selectivity and yield as shown in Table 1.
TABLE 1
The results in table 1 show that the conventional hydrothermal method for preparing the catalyst is avoided, so that the method provided by the invention is simpler and lower in cost, and the catalytic effect of the catalyst can be ensured.
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 (11)
1. A method for preparing a catalyst containing lanthanum oxycarbonate, the method comprising:
(1) Adding alkali liquor into a solution containing water-soluble lanthanum salt to obtain a mixed material containing precipitate; wherein the concentration of the lye is more than 15 weight percent;
(2) Maintaining the mixture at a temperature of from room temperature to 100 ℃ under normal pressure;
(3) Separating the materials maintained in the step (2) to obtain solid materials, and then carrying out first drying and roasting on the solid materials to obtain the catalyst containing the lanthanum oxycarbonate.
2. The method according to claim 1, wherein the water soluble lanthanum salt is selected from lanthanum chloride, lanthanum chlorate, and lanthanum nitrate;
and/or, in the solution, the concentration of the lanthanum element is between 0.05 and 10% by weight, preferably between 0.1 and 5% by weight;
and/or the alkali liquor is sodium hydroxide solution and/or potassium hydroxide solution, preferably sodium hydroxide solution.
3. The method according to claim 1 or 2, wherein the lye is sodium hydroxide with a concentration of 18-30% by weight;
preferably, the lye is added in an amount of 0.1-10g, preferably 0.15-8g, most preferably 1.6-8g per minute in terms of sodium hydroxide per kg of said solution.
4. A method according to any one of claims 1 to 3, wherein the endpoint has a pH of from 11 to 14, preferably from 11.5 to 12.5.
5. The method of any of claims 1-4, wherein the method further comprises: before roasting, putting the first dried material into a solution containing a zirconium compound for dipping, then carrying out second drying, and finally roasting the second dried material;
preferably, the zirconium-containing compound is selected from zirconium fluoride and potassium fluorozirconate;
and/or the molar ratio of the zirconium element to the lanthanum element is 1.
6. The method of any one of claims 1-5, wherein the maintained temperature of the mixed mass is from room temperature to 80 ℃.
7. The method according to any one of claims 1-6, wherein the maintaining time is 12-60h, preferably 20-60h.
8. The method of any of claims 1-7, wherein the conditions of the first and second drying each independently comprise: the temperature is 80-120 ℃, and the time is 10-50h;
and/or the roasting conditions comprise: the temperature is 450-650 ℃, and the time is 1-6h.
9. A catalyst comprising lanthanum oxycarbonate prepared according to the process of any one of claims 1-8.
10. A method for producing a carbo-carb-ohydrocarbon from methane, the method comprising: the catalyst prepared by the process according to any one of claims 1 to 8, and then the methane is contacted with the resulting catalyst in the presence of oxygen and under the conditions of oxidative coupling of methane.
11. The process according to claim 10, wherein the molar ratio of the quantities of methane and oxygen used is between 2 and 10:1;
and/or the temperature of the contact reaction is 450-700 ℃; the space velocity of the methane is 5000-150000 mL/(g.h).
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