CN107649114A - A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium - Google Patents
A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium Download PDFInfo
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- CN107649114A CN107649114A CN201710839653.2A CN201710839653A CN107649114A CN 107649114 A CN107649114 A CN 107649114A CN 201710839653 A CN201710839653 A CN 201710839653A CN 107649114 A CN107649114 A CN 107649114A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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
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- 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
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- 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
A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium, A positions ion precursor using lanthanum nitrate, praseodymium nitrate, samaric nitrate, yttrium nitrate etc. as pyrochlore, A, B position ion precursor are 1 in molar ratio as pyrochlore B positions ion precursor by cerous nitrate:1 is soluble in water, uses concentrated ammonia liquor（22%‑25%）PH value is adjusted to 2.The citric acids of 2 times of metal cation mole amount are added, is placed on water-bath to be evaporated pyrochlore Ln is made in gel, then aging 12h, roasting2Ce2O7(Ln=La, Pr, Sm, Y) catalyst.Catalyst shows good low-temp reaction performance and stability in the reaction of simulation Catalyst for Oxidative Coupling of Methane and ethane.The present invention prepares associated catalysts using cheap metal salt as raw material using sol-gel method.Catalyst has the advantages that production cost is low, and synthesis technique is simple, and course of reaction is easily controlled.
Description
Technical field
The invention belongs to energy catalysis technical field, is related to one kind and is used for oxidative coupling of methane, directly by cheap first
Alkane changes into the preparation method of the cerium base pyrochlore catalyst of ethene and ethane product with high economy and industrial value.
Background technology
Global Oil resource worsening shortages, the unclean environmental pollution for causing getting worse using the energy of the mankind, global fossil
Energy industry revolution has raised the curtain.What State Council printed and distributed in the recent period《" 13 " national strategy new industry development plan》It is bright
Really establish 21 Important Projects such as carbon cycle and development new energy.Using catalysis process, the low value such as natural gas chemicals is turned
High level chemicals and energy-rich chemical fuel are turned to, is an effective way for being expected to solve energy shortage and problem of environmental pollution simultaneously
Footpath.With reserves relative abundance and cheap substitute gas Petroleum Production liquid fuel and basic chemical, with shale
The breakthrough of gas production technique, in recent years as worldwide study hotspot.China's shale gas exploitation core technology in 2014
Important breakthrough is obtained, is turned into after America ＆ Canada, the 3rd carries out shale gas commercialization exploitation using proprietary technology equipment
Country；The same year China with Russia signature 30 years natural gas purchase agreements, illustrate China by development utilization natural gas resource
One of grand strategy as energy development.Methane is the main component of natural gas, compared to other petrochemical industry moneys such as coal and oil
Source is more cleaned and abundance.Raw material is utilized methane as, synthesizes high level chemicals, such as methanol, ethene, are always the world
The study hotspot of scientists from all over the world.Effective utilization of methane, is divided into direct method and indirect method.Direct method has oxidative coupling, chlorination
Coupling, direct dehydrogenation method；Indirect method is that methane first is converted into synthesis gas, then by synthesis gas alkene, including steam methane weight
The methods of whole, methane portion oxidation, methane dry gas are reformed, improvement Fischer-Tropsch methods, methanol decomposition alkene.Indirectly
High energy consumption, high water consume, high CO be present in method2The problems such as discharge and flow are more complicated.And direct method is used efficiently to be synthesized using methane
High level chemicals, reduces CO from source2Discharge, atmospheric environment, optimization using energy source structure can be improved, to chemicals industrial chain
Adjustment improvement is significant.Therefore, people always all make great efforts to explore natural gas straight connect the effective ways of trans-utilization with
Process.Methane oxidation coupling (OCM) technique either still economically considers there is its realistic meaning from thermodynamics of reactions, and
The technique is one of technique that natural gas ethene is most simple and direct so far, and one step of reaction is completed.
The catalyst applied to oxidative coupling of methane mainly includes following four classes at present：Mn/Na2WO4/SiO2Class is urged
Agent；ABO3Perovskite composite oxide class catalyst；Li/MgO classes catalyst and RexO yClass catalyst.Chinese patent
CN105170138A discloses a kind of modified Mn/Na2WO4/SiO2Method for preparing catalyst, catalyst activity prepared by this method
Component particle size is small, is evenly distributed, and applied in oxidative coupling of methane, can improve the conversion ratio and C of methane simultaneously2Product
Selectivity.Chinese patent CN104759291A disclose one kind by step impregnation method by manganese-sodium-tungsten load in titanium silicon molecule
Sieve or pure silicon molecular sieve on and it is fired titaniferous or not manganese-sodium-tungsten-Si composite oxide catalyst of titaniferous is prepared, should
Catalyst is used for oxidative coupling of methane, has excellent catalytic activity and generation ethylene/propene selectivity and reaction steady
It is qualitative.But such modified Mn/Na2WO4/SiO2The reaction temperature of catalyst is higher, and the first of maximum need to be can be only achieved at 800 DEG C
Alkane conversion ratio and C2Selectivity of product.Chinese patent CN102471181A discloses a kind of including lanthanide series, Mg, Ca and week
The composite catalyst of phase table Group IVB element (Ti, Zr and Hf) is applied to methane oxidation coupling, catalyst activity component composition
Complexity, preparation section is cumbersome, and relatively low in 500 DEG C of -700 DEG C of methane conversions and selectivity.Chinese patent CN103350002A
Disclose a kind of N/M with nano bar-shape structurexOyO composite metallic oxide catalyst applies to oxidative coupling of methane, M
Can be able to be one kind in alkali metal for one kind in alkaline-earth metal or one kind in rare earth metal, N, can also
It is one kind of alkaline-earth metal.The catalyst structure is stable, and higher methane conversion is shown for oxidative coupling of methane,
But C2Selectivity of product is relatively low.Chinese patent CN103118777A disclose it is a kind of using biological template prepare include group ia
The element of any family, lanthanide series, actinides or one or more elements in combinations thereof into V Group IIB
Catalyst with nanometer linear structure is applied to oxidative coupling of methane, and the catalyst series preparation method is complicated, C2Production
Thing yield is relatively low.There is problems with for current methane oxidative coupling catalyst：Reaction temperature is high, 700 DEG C-
900 DEG C, the process is strong exothermal reaction and needs active oxygen species and basic center etc. to act synergistically；Existing reaction mechanism does not have
Standby epitaxy and universality.Researcher is directed to the research of oxidative coupling of methane always, but due to C2Product yield reaches
Industrialized less than more than 30% without realizing.Exploitation one kind is in cryogenic conditions oxidative coupling of methane superior performance, stability
Good, catalyst cheap and easy to get is current domestic and international researcher focus of attention.
A2B2O7Pyrochlore constitution opens, and A positions and B positions can form stable composite oxides by extensive substitution.
As described above, its A position be mostly ionic radius it is larger+trivalent cation, such as La3+、Pr3+、Y3+、Sm3+、Bi3+Etc. member
Element.And B positions are mostly smaller+4 valency cation of ionic radius, such as Zr4+、Ti4+、Sn4+、Ce4+Deng.
Correlative study shows, generally, as A positions and B positions ionic radius move closer to, rA/rBRatio from greatly to
It is small, A2B2O7The transfer ability enhancing of oxonium ion, the increase of oxonium ion randomness degree in structure.Therefore A positions or B positions can be passed through
Ion substitution, change rA/rBRatio, reach modulation A2B2O7The purpose of type composite oxides oxygen mobility.For many aerobic ginsengs
With reaction, catalyst oxygen mobility enhancing obviously can promote its reactivity worth.Therefore, pyrochlore composite oxides are tools
There is the catalysis material of potential using value.Worldwide generally acknowledged relatively good methane oxidative coupling catalyst is at present
Mn/Na2WO4/SiO2Class catalyst, the catalyst methane oxidative coupling activity of the type is high and stability is good, but reaction temperature compared with
It is high（725-950℃）, it is basic without activity below 700 DEG C.The type catalyst reported at present can reach more than 800 DEG C
Maximum C2Product yield is 20%-26%.Up to the present due to the C of all catalyst2Product yield do not reach more than 30% and
It is not carried out industrializing.The catalyst of gained of the invention shows good low temperature in oxidative coupling of methane is simulated and lived
Property and stability.
The content of the invention
The purpose of the present invention is to propose to a kind of preparation method of the cerium base pyrochlore catalyst for methane oxidation coupling, with
And application of the cerium base pyrochlore catalyst in methane-oxidizing and-coupling reaction, can be direct by oxidative coupling of methane
Cheap methane is changed into the ethane with high economy and industrial value, ethene cerium base pyrochlore catalyst.
The catalyst series are prepared using Citrate Sol-gel Process.At ambient pressure, reaction gas 10%O2+40%CH4,
50%Ar Balance Airs, under the conditions of gas velocity is 30mL/min~60mL/min, the catalyst has high catalytic activity.
A kind of preparation method of cerium base pyrochlore catalyst for methane oxidation coupling of the present invention, its feature exist
In comprising the following steps.
（1）It is A positions ion precursor salt to weigh La, Pr, Sm or Y nitrate, with B positions ion presoma cerous nitrate by mole
Than for 1:1, which is dissolved in distilled water, is made into the aqueous solution.
（2）The citric acid that load weighted mole is twice of A, B position total ion concentration is added to step（1）The aqueous solution
In, use ammoniacal liquor（22%-25%）PH to 2 is adjusted, stirs 2-3h at room temperature.
（3）The water bath method at 80-90 DEG C, gained gel is in 110-120 DEG C of aging 12h.
（4）Xerogel obtained by aging is ground, then with 5 DEG C/min heating rates in Muffle furnace, at 800 DEG C
Under the conditions of be calcined 4h, be made a series of B positions be cerium pyrochlore catalyst Ln2Ce2O7(Ln=La,Pr,Sm,Y)。
A kind of cerium base pyrochlore catalyst of the present invention is applied in methane-oxidizing and-coupling reaction, and its feature exists
In at ambient pressure, reaction gas 10%O2+40%CH4, 50%Ar Balance Airs, gas velocity is 30mL/min~60mL/min, and cerium base burns green
Stone is directly used in methane-oxidizing and-coupling reaction.
Compared with prior art, the catalyst that prepared by the present invention has the following advantages that：
（1）Low raw-material cost of the present invention, preparation process is simple and easy, equipment requirement is low, nontoxic solvent is harmless, to environment without two
Secondary pollution.
（2）The present invention prepares method using traditional citric acid sol-gel method and prepares serial cerium base catalyst, preparation technology letter
Single, course of reaction is easily controlled.
（3）Use the cerium base pyrochlore La of A positions ion prepared by the inventive method for La2Ce2O7Catalyst in methane oxygen
Change in coupling reaction and show excellent low temperature active and stability.
Brief description of the drawings
Fig. 1 is Ln prepared by the inventive method2Ce2O7The XRD material phase analysis results of pyrochlore catalyst.Synthesized
Ln2Ce2O7Series compound is pyrochlore constitution.
Fig. 2 is La prepared by the inventive method2Ce2O7The oxidative coupling of methane stability test of pyrochlore catalyst
As a result.
Embodiment
For the clearer explanation present invention, following examples are enumerated, but it is without any restrictions to the scope of the present invention.
Embodiment 1.
Weigh 4.3g lanthanum nitrates（Hexahydrate）With 4.3g cerous nitrates（Hexahydrate）In 200mL beakers, 50mL is added
Deionized water dissolving, 4.2g citric acids stirring 0.5h is added, concentrated ammonia liquor is added dropwise dropwise（Mass fraction 25%-28%）Regulation pH=
2, continue to stir 1-2h.Mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C of dry aging 12h, then
800 DEG C of roasting 4h are heated to 5 DEG C/min heating rate in Muffle furnace, catalyst La is made2Ce2O7。
Embodiment 2.
Weigh 4.3g praseodymium nitrates（Hexahydrate）With 4.3g cerous nitrates（Hexahydrate）In 200mL beakers, 50mL is added
Deionized water dissolving, 4.2g citric acids stirring 0.5h is added, concentrated ammonia liquor is added dropwise dropwise（Mass fraction 25%-28%）Regulation pH=
2, continue to stir 1-2h.Mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C of dry aging 12h, then
800 DEG C of roasting 4h are heated to 5 DEG C/min heating rate in Muffle furnace, catalyst Pr is made2Ce2O7-δ。
Embodiment 3.
Weigh 4.4g samaric nitrates（Hexahydrate）With 4.3g cerous nitrates（Hexahydrate）In 200mL beakers, 50mL is added
Deionized water dissolving, 4.2g citric acids stirring 0.5h is added, concentrated ammonia liquor is added dropwise dropwise（Mass fraction 25%-28%）Regulation pH=
2, continue to stir 1-2h.Mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C of dry aging 12h, then
800 DEG C of roasting 4h are heated to 5 DEG C/min heating rate in Muffle furnace, catalyst Sm is made2Ce2O7。
Embodiment 4.
Weigh 3.8g yttrium nitrates（Hexahydrate）With 4.3g cerous nitrates（Hexahydrate）In 200mL beakers, 50mL is added
Deionized water dissolving, 4.2g citric acids stirring 0.5h is added, concentrated ammonia liquor is added dropwise dropwise（Mass fraction 25%-28%）Regulation pH=
2, continue to stir 1-2h.Mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C of dry aging 12h, then
800 DEG C of roasting 4h are heated to 5 DEG C/min heating rate in Muffle furnace, catalyst Y is made2Ce2O7。
Test result indicates that La2Ce2O7Catalyst is best for Performance for Oxidative Coupling of Methane Over, and table 1 is represented in case study on implementation
La2Ce2O7Pyrochlore catalyst and the Mn/Na of universally acknowledged better performances2WO4/SiO 2Class catalyst methane oxidative coupling reaction
Cryogenic property comparing result, the results showed that catalyst shows superior property in the range of 650 DEG C -700 DEG C of low temperature in the present invention
Energy；Fig. 1 represents La in case study on implementation2Ce2O7Pyrochlore catalyst reaction stability test result curve figure.As a result show
Good reactivity worth, and highest C are remained in 100h stability test2Yield is 16.6%.
Table 1
Claims (2)
1. a kind of B positions for methane oxidation coupling for cerium pyrochlore catalyst preparation method, it is characterised in that including with
Lower step：
（1）It is A positions ion precursor salt to weigh La, Pr, Sm or Y nitrate, is in molar ratio with B positions ion presoma cerous nitrate
1:1, which is dissolved in distilled water, is made into the aqueous solution；
（2）Load weighted mole is added to step for the citric acid of 2 times of A, B position total ion concentration（1）The aqueous solution in, use ammonia
Water adjusts pH to 2, stirs 2-3h at room temperature；
（3）The water bath method at 80-90 DEG C, gained gel is in 110-120 DEG C of aging 12h；
（4）Xerogel obtained by aging is ground, then with 5 DEG C/min heating rates in Muffle furnace, under conditions of 800 DEG C
4h is calcined, a series of pyrochlore catalyst that B positions are cerium is made.
2. the B positions described in claim 1 are application of the pyrochlore catalyst of cerium in methane-oxidizing and-coupling reaction, it is special
Sign is that catalytic condition is：At ambient pressure, reaction gas 10%O2+40%CH4, 50%Ar Balance Airs, gas velocity is 30mL/min~60mL/
min。
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Cited By (5)
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| CN109364907A (en) * | 2018-11-29 | 2019-02-22 | 南昌大学 | A kind of Ca for methane oxidation coupling2+The preparation method and application of ion improved catalysts |
| CN109569565A (en) * | 2018-11-29 | 2019-04-05 | 南昌大学 | One kind being used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst and application |
| CN112473703A (en) * | 2020-11-28 | 2021-03-12 | 南昌大学 | Preparation method and application of high-ethylene-selectivity methane oxidation coupling catalyst |
| CN112547039A (en) * | 2021-01-19 | 2021-03-26 | 中国科学院山西煤炭化学研究所 | Preparation method and application of catalyst for preparing low-carbon hydrocarbon through oxidative coupling of methane |
| CN113289629A (en) * | 2021-04-27 | 2021-08-24 | 中汽研（天津）汽车工程研究院有限公司 | Three-dimensional composite pyrochlore ammoxidation catalyst for diesel vehicle exhaust purification |
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