CN104549307A - Methane oxychlorination reaction catalyst and preparation method and application thereof - Google Patents
Methane oxychlorination reaction catalyst and preparation method and application thereof Download PDFInfo
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- CN104549307A CN104549307A CN201310468154.9A CN201310468154A CN104549307A CN 104549307 A CN104549307 A CN 104549307A CN 201310468154 A CN201310468154 A CN 201310468154A CN 104549307 A CN104549307 A CN 104549307A
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Abstract
The invention discloses an oxychlorination reaction catalyst and a preparation method and an application thereof, wherein the method comprises the following steps: (1) mixing active components and a carrier to obtain a mixture; and (2) rising the temperature at a speed of 0.2-2 DEG C/min, and roasting the mixture obtained in the step (1), wherein the active components contain a copper component, an alkali metal component and a rare earth metal component. In the method, due to adopting of the relatively low temperature-rising speed, the catalytic activity of the obtained catalyst is high; therefore, under the same reaction conditions, the catalyst prepared by the method has the methane conversion rate, the monochloro methane selectivity and the monochloro methane yield slightly higher than those of catalysts prepared by conventional methods (such as an impregnation method); and the method has simple operation steps, saves energy consumption, and has no need of the use of a solvent in the preparation process.
Description
Technical field
The present invention relates to a kind of methane catalyst in oxychlorination reaction and its preparation method and application
Background technology
Methane is the main moiety of Sweet natural gas, coal-seam gas and shale gas, being the Chemicals such as raw material production methyl alcohol, acetic acid, aromatic hydrocarbons and stop bracket gasoline with methane, is that mankind's basic chemical reduces or breaks away from the most promising new way relied on petroleum resources.
The chemical property very torpescence of methane.The main path that current methane utilizes first is translated into synthetic gas, and then change into chemical products with high added-value, but this process need be carried out under high temperature (>800 DEG C), high pressure (>2MPa) condition, is the process of high energy consumption, high investment.Another activation method oxidative coupling of methane also needs to carry out under comparatively high temps (>650 DEG C).And by oxi-chlorination Methane Activation, whole reaction can be made to carry out at lesser temps (<500 DEG C), is a kind of potential methane activation mode.
The methane catalyst in oxychlorination reaction of current research is active ingredient mainly with Cu, and alkali doped, alkaline-earth metal, rare earth are as promotor.Conventional method for preparing catalyst has pickling process and the precipitator method, also has mechanical mixing in addition.
Pickling process is mixed with carrier by the solubility solution of active ingredient, and drying, roasting make catalyzer.For porous support, in solvent evaporation process, first liquid evaporate near the hole of outside surface, and liquid continues to move on to outside surface from endoporus.Catalyst component upon evaporation in liquid is just deposited, and thus near outside surface or it, is more easily condensed into larger crystal.In addition, adopt preparation catalyst, need to use solvent, need experience dissolving, dipping, dry, roasting four steps.Preparation high capacity amount catalyzer, in order to make Active components distribution comparatively even, repeatedly need flood, adding operation steps.
The precipitator method are mixed with carrier by the solubility solution of active ingredient, adds precipitation agent, make active ingredient be deposited on carrier surface, refilter, wash, dry, roasting obtains catalyzer.Or the solubility solution of active ingredient is mixed with the solubility solution of carrier, add precipitation agent, active ingredient and carrier are precipitated simultaneously, refilters, wash, dry, roasting obtains catalyzer, this method is also called coprecipitation method.In order to overcome the shortcoming of single copper component catalyst, basic metal, alkaline-earth metal, rare earth element usually can be added to improve stability and the selectivity of catalyzer.Because basic metal is as sylvite, not easily form precipitation, make potassium content in the catalyzer adopting the precipitator method or coprecipitation method to obtain very low, be unfavorable for that catalyst stability and selectivity are improved.
Mechanically mixing is one of method for preparing catalyst, is normally having under regimen condition, by the method for simple mechanically mixing, catalyst component and carrier is all being mixed under insoluble state.US6174834B1 discloses a kind of preparation method of oxychlorination catalyst, wet carrier, cupric chloride and Repone K Homogeneous phase mixing pulp, roasting after evaporating water.This method and pickling process are very similar, need equally to add aqueous solvent, need evaporating water before roasting equally, and just the quantity of solvent of this method is little, is about the 50-60% of soup compound weight.
US4755497 discloses a kind of preparation method of copper aluminium borate catalyzer, by CuO, Al
2o
3and B
2o
3after fully mixing in proportion, there is solid state reaction and generate copper aluminium borate catalyzer in high-temperature roasting between each component.Compared with the catalyzer adopting pickling process to prepare, owing to not adding aqueous solvent, do not need consuming time dewatering, and gained catalyst activity component is more evenly distributed, this method gained catalyzer be used for p-ethyltoluene Oxidative Dehydrogenation p-vinyl toluene, initial activity and selectivity higher, catalyst life is longer.
US4130595A discloses a kind of oxychlorination process being prepared trieline and zellon by vinyl trichloride, FeCl
3, KCl, CuCl and CuCl
2mechanically mixing is even, and at the reaction temperatures in molten state, gas reactant and molten state catalyst exposure generate chloroethylenes.Gas reactant and molten state catalyst exposure degree are the key factors affecting reaction effect, adopt loaded catalyst that exposure level can be avoided the impact of transformation efficiency.
US5939351 discloses a kind of preparation method of loaded catalyst, by Fe
2(MoO
4)
3and MoO
3with carrier A l
2o
3mixing rear mould and be pressed into definite shape, then roasting, in order to make form not too large change before and after catalyzer roasting, the liquid-containing binder such as the solid binder such as stearic acid, Palmiticacid or glycerine, paraffin oil, PFPE need be added.
Appl.Catal.B:Environ.2005,61,212-218 is by CuCl and γ-Al
2o
3(specific surface area 340m
2/ g) 380 DEG C of roasting 4h are obtained after mechanically mixing catalyzer is used for aviation kerosene and diesel fuel desulfurization.Studies in Surface Science and Catalysis, 1998,118,441-449 and Journal of Catalysis, 1998,176,474-487 describes by the method Kaolinite Preparation of Catalyst of solid chemical compound spontaneous Monolayer Dispersion to carrier surface, this method requires that solid chemical compound fusing point is suitable, and carrier has comparatively bigger serface, and the aperture of carrier is greater than the kinetic diameter of solid chemical compound.The catalyzer prepared in this way, its active catalyzer with adopting pickling process to prepare is suitable, but operation steps is simple, does not need to use solvent, save energy.
But above-mentioned document relates to is all preparations of single component catalyst.Adopt when preparing multicomponent catalyst in this way, may occur that the order sprawled along with intensification post liquefaction individual layer is different, and cause active ingredient dispersiveness low, the problems such as catalyst activity is low.
Summary of the invention
The object of the invention is the operation steps complexity (being generally more than 4 steps) in order to overcome methane catalyst in oxychlorination reaction preparation method in prior art, and the defect that the catalyst activity of preparation is lower, provide a kind of method that two-step approach prepares the higher methane catalyst in oxychlorination reaction of a kind of activity.
The invention provides a kind of preparation method of methane catalyst in oxychlorination reaction, the method comprises the following steps:
(1) active ingredient and carrier are mixed to get mixture;
(2) mixture obtained in calcination steps (1) is carried out with the ramp of 0.2-2 DEG C/min;
Wherein, described active ingredient contains copper component, alkaline components and rare earth component.
The methane catalyst in oxychlorination reaction that the present invention also provides above-mentioned preparation method to prepare.
The present invention also provides the application of the methane catalyst in oxychlorination reaction prepared by above-mentioned preparation method in the reaction of methane oxychlorination.
In preparation method according to a kind of methane catalyst in oxychlorination reaction provided by the invention, because temperature rise rate is low, be only 0.2-2 DEG C/min, with methane oxi-chlorination custom catalysts CuCl
2-KCl-LaCl
3for example, CuCl
2fusing point minimum, LaCl
3fusing point the highest, if temperature rise rate is too fast, then CuCl
2, KCl, LaCl
3being close to and liquefying simultaneously, sprawling simultaneously from being sent to carrier hole road, prepared catalyzer is similar to the catalyzer adopting pickling process to prepare, and catalyst activity is not high; And in the present invention, owing to adopting lower temperature rise rate, like this, only have CuCl at first
2liquefaction is sprawled, along with maturing temperature slowly raises, and KCl, LaCl
3liquefaction is sprawled successively, and thus, the catalyst activity obtained is high; Thus adopt catalyzer prepared by method of the present invention, under the same reaction conditions, methane conversion, monochloro methane selectivity and monochloro methane yield are a little more than the catalyzer adopting ordinary method (as pickling process) to prepare, and method operation steps of the present invention is simple, save power consumption, and without the need to using solvent in preparation process.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the graph of relation that methane conversion changes with roasting time under different maturing temperature;
Fig. 2 is maturing temperature and the graph of a relation reaching roasting time needed for stable state.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of methane catalyst in oxychlorination reaction, the method comprises the following steps:
(1) active ingredient and carrier are mixed to get mixture;
(2) mixture obtained in calcination steps (1) is carried out with the ramp of 0.2-2 DEG C/min;
Wherein, described active ingredient contains copper component, alkaline components and rare earth component.
In the present invention, described temperature rise rate can be 0.2-2 DEG C/min, preferred 0.5-1.5 DEG C/min.Main points of the present invention control temperature rise rate, because temperature rise rate speed does not affect substantially on Active components distribution during single component catalyst roasting, usually adopts higher temperature rise rate (5 DEG C/min-10 DEG C/min); And temperature rise rate speed can affect Active components distribution during multicomponent catalyst roasting, temperature rise rate affects the activity of active ingredient.Such as, with methane oxi-chlorination custom catalysts CuCl
2-KCl-LaCl
3for example, CuCl
2fusing point minimum, LaCl
3fusing point the highest, temperature rise rate is too fast, CuCl
2, KCl, LaCl
3being close to and liquefying simultaneously, sprawling simultaneously from being sent to carrier hole road, gained catalyzer is similar to the catalyzer adopting pickling process to prepare, and catalyst activity is not high; If adopt low temperature rise rate, due to CuCl
2fusing point minimum, only have CuCl at first
2liquefaction is sprawled, along with maturing temperature slowly raises, and KCl, LaCl
3liquefaction is sprawled successively, makes the Catalysts Cu Cl obtained
2dispersiveness is better than the catalyzer that high temperature rise rate obtains.Therefore, within the scope of above-mentioned temperature rise rate of the present invention roasting active ingredient and carrier mixture and the catalytic activity of the catalyzer prepared is high.
In the present invention, described maturing temperature and described roasting time interrelated, as depicted in figs. 1 and 2.Fig. 1 is the activity of catalyzer and the graph of relation of roasting time under different maturing temperature, and Fig. 2 is the graph of a relation that maturing temperature and catalyst activity reach stable state required time.As can be seen from Fig. 1 and Fig. 2, maturing temperature is low, and active ingredient stickiness is large, low at catalyst surface spreading rate, and it is just long that catalyst activity reaches stable state required time, and namely low maturing temperature needs long-time roasting; Maturing temperature is high, and active ingredient mobility strengthens, and reach stable state required time in carrier surface distribution short, namely high maturing temperature short period of time roasting just can reach stable state.
In the present invention, described maturing temperature can be 300-600 DEG C, is preferably 400-450 DEG C.Described roasting time can be 6-48h, is preferably 12-24h.The present inventor finds, maturing temperature and roasting time control in above-mentioned scope, and the activity of the catalyzer prepared is good.
In the present invention, with the gross weight of described catalyzer for benchmark, the consumption of described active ingredient can be 3-45 % by weight, is preferably 7-32%; The consumption of described carrier can be 55-97 % by weight, is preferably 68-93%.
In the present invention, described copper component can be cupric chloride and/or cuprous chloride; Described alkaline components can be selected from one or more of lithium salts, sodium salt, sylvite, rubidium salt and cesium salt, is preferably sylvite, is more preferably Repone K; Described rare earth component can be selected from lanthanum component, cerium component, neodymium component, praseodymium component and yttrium component one or more, be preferably lanthanum component, be more preferably Lanthanum trichloride.
In the present invention, described carrier can be selected from silicon-dioxide, aluminum oxide and Si-Al molecular sieve one or more, be preferably silicon-dioxide.
In the present invention, described carrier specific surface area can be 20-1000m
2/ g, is preferably 200-700m
2/ g; Aperture can be 0.5-50nm, is preferably 1-30nm, is more preferably 3-15nm.
In the present invention, in order to make the performance of the catalyzer of preparation better, under preferable case, described active ingredient contains Cu, K and La, and be also that the alkaline components in described active ingredient is sylvite, the rare earth component in described active ingredient is lanthanum component.More preferably, the consumption of described active ingredient and carrier makes in prepared catalyzer, with the gross weight of this catalyzer for benchmark, in the Cu consumption of Cu element for 1-15 % by weight, in the K consumption of K element for 1-15 % by weight, in the La consumption of La element for 1-15 % by weight, all metals are all deposited on carrier.Further in preferred situation, the consumption of described active ingredient and carrier to make in prepared catalyzer in the Cu consumption of Cu element for 4-10 % by weight, in the K consumption of K element for 2-12 % by weight, in the La consumption of La element for 1-10 % by weight.
Another object of the present invention is to provide the methane catalyst in oxychlorination reaction adopting method of the present invention to prepare.
Another object of the present invention is to provide the application of catalyzer in methane oxi-chlorination adopting method of the present invention to prepare.
In the present invention, the reaction conditions in methane oxi-chlorination is not particularly limited, the reaction conditions that can be well known to those skilled in the art, under preferable case, reaction conditions in methane oxi-chlorination can be: temperature of reaction is 400-500 DEG C, normal pressure, CH
4: HCl:O
2=2-3:1.5-2.5:1, all the other are nitrogen, and air speed can be 4500-5500mlh
-1g
-1.More preferably in situation, the reaction conditions in methane oxi-chlorination can be: temperature of reaction is 450 DEG C, normal pressure, CH
4: HCl:O
2=5:4:2, all the other are nitrogen, and air speed is 5000mlh
-1g
-1.
Compared with the catalyzer that catalyzer prepared by the present invention is obtained with ordinary method (as pickling process), under the same reaction conditions, methane conversion, monochloro methane selectivity and monochloro methane yield are higher.Meanwhile, catalyst preparation process of the present invention is simple, saves power consumption, and without the need to using solvent in preparation process.
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
Usedly in not specified embodiment and comparative example be commercially available product.
Embodiment 1
Take 0.93g CuCl
22H
2o, 1.14g KCl, 0.13g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 700m
2/ g, aperture is 3nm, is warming up to 400 DEG C in atmosphere with the temperature rise rate of 0.5 DEG C/min, roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverizes, sieve, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C1.
Embodiment 2
Take 1.40g CuCl
22H
2o, 0.23g KCl, 1.40g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 200m
2/ g, aperture is 15nm, is warming up to 430 DEG C in atmosphere with the temperature rise rate of 1 DEG C/min, and roasting is cooled to room temperature after 18 hours, compressing tablet at such a temperature, pulverizes, sieves, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C2.
Embodiment 3
Take 0.46g CuCl
22H
2o, 0.61g KCl, 0.85g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 450m
2/ g, aperture is 8nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 1.5 DEG C/min, roasting is cooled to room temperature after 12 hours, compressing tablet at such a temperature, pulverizes, sieve, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C3.
Embodiment 4
Take 0.67g CuCl
22H
2o, 0.57g NaCl, 0.68g LaCl
37H
2o and 5g alumina supporter is mixed to get mixture, and wherein, the specific surface area of alumina supporter is 240.5m
2/ g, aperture is between 1.5-9.3nm, mix, be warming up to 450 DEG C with the temperature rise rate of 0.2 DEG C/min in atmosphere, roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverize, sieve, get the part between 0.45-0.90mm, prepare Cu-Na-La/ SiO 2 catalyst C4.
Embodiment 5
Take 0.67g CuCl
22H
2o, 0.57g LiCl, 0.68g LaCl
37H
2o and 5g H-ZSM-5 carrier is mixed to get mixture, and wherein, the specific surface area of H-ZSM-5 carrier is 368m
2/ g, aperture is 0.5nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 2 DEG C/min, roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverizes, sieve, get the part between 0.45-0.90mm, prepare Cu-Li-La/ SiO 2 catalyst C5.
Embodiment 6
Take 0.23g CuCl, 0.34g KCl, 0.40g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 89m
2/ g, aperture is 50nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 1 DEG C/min, and roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverizes, sieves, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C6.
Embodiment 7
Take 0.38g CuCl
2, 0.16g KCl, 0.39g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 650m
2/ g, aperture is 8nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 1 DEG C/min, and roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverizes, sieves, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C7.
Embodiment 8
Take 0.40g CuCl
2, 0.52g KCl, 0.10g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 650m
2/ g, aperture is 8nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 1 DEG C/min, and roasting is cooled to room temperature after 24 hours, compressing tablet at such a temperature, pulverizes, sieves, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C8.
Embodiment 9
Take 0.46g CuCl
2, 0.61g KCl, 0.85g LaCl
37H
2o and 3g silica supports is mixed to get mixture, and wherein, the specific surface area of silica supports is 650m
2/ g, aperture is 8nm, is warming up to 450 DEG C in atmosphere with the temperature rise rate of 1 DEG C/min, after roasting was cooled to room temperature after 24 hours at such a temperature, compressing tablet, pulverizes, sieve, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst C9.
Comparative example 1
This comparative example prepares methane catalyst in oxychlorination reaction for illustration of employing pickling process
Take 0.40g CuCl
22H
2o, 0.34g KCl, 0.41g LaCl
37H
2o is dissolved in 25mL water, adds 3g alumina supporter, and wherein, the specific surface area of alumina supporter is 240.5m
2/ g, aperture is that between 1.5-9.3nm, stirring is spent the night, water bath method at 80 DEG C, dry at 120 DEG C, be warming up to 450 DEG C with the temperature rise rate of 5 DEG C/min in atmosphere, roasting is cooled to room temperature after 5 hours, compressing tablet at such a temperature, pulverize, sieve, get the part between 0.45-0.90mm, prepare Cu-K-La/ SiO 2 catalyst DC1.
Comparative example 2
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1, institute's difference is, heats up, prepare Cu-K-La/ SiO 2 catalyst DC2 with the temperature rise rate of 10 DEG C/min.
Test case
Catalyzer prepared by embodiment 1-9 and comparative example 1-3 is used for methane oxi-chlorination, and reaction conditions is following but be not limited only to this condition: 450 DEG C, normal pressure, CH
4: HCl:O
2=5:4:2, all the other are nitrogen, and air speed is 5000ml h
-1g
-1.The results are shown in Table shown in 1 of the methane conversion tested, monochloro methane selectivity and monochloro methane yield.
Table 1
Can be found out by the data of embodiment 1-9 and comparative example 1, the catalyst application adopting method provided by the invention to prepare is in methane oxi-chlorination, under identical reaction conditions, methane conversion, monochloro methane selectivity and monochloro methane yield are all better than catalyzer prepared by employing pickling process; Can be found out by the data of embodiment 1 and comparative example 2, the too high raising being unfavorable for catalyst activity of temperature rise rate; In addition, adopt method provided by the invention operation steps in Kaolinite Preparation of Catalyst process simple, save power consumption, and without the need to using solvent in preparation process.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a preparation method for methane catalyst in oxychlorination reaction, the method comprises the following steps:
(1) active ingredient and carrier are mixed to get mixture;
(2) mixture obtained in calcination steps (1) is carried out with the ramp of 0.2-2 DEG C/min;
Wherein, described active ingredient contains copper component, alkaline components and rare earth component.
2. method according to claim 1, wherein, in step (2), carrys out the mixture obtained in calcination steps (1) with the ramp of 0.5-1.5 DEG C/min.
3. method according to claim 1 and 2, wherein, the temperature of described roasting is 300-600 DEG C, is preferably 400-450 DEG C; The time of described roasting is 6-48h, is preferably 12-24h.
4. method according to claim 1, wherein, with the gross weight of described catalyzer for benchmark, the consumption of described active ingredient is 3-45 % by weight, is preferably 7-32%; The consumption of described carrier is 55-97 % by weight, is preferably 68-93%.
5. method according to claim 1, wherein, described copper component is cupric chloride and/or cuprous chloride; Described alkaline components be selected from lithium salts, sodium salt, sylvite, rubidium salt and cesium salt one or more, be preferably sylvite, be more preferably Repone K; Described rare earth component be selected from lanthanum component, cerium component, neodymium component, praseodymium component and yttrium component one or more, be preferably lanthanum component, be more preferably Lanthanum trichloride.
6. the method according to claim 1 or 4, wherein, one or more in described carriers selected from silica, aluminum oxide and Si-Al molecular sieve, are preferably silicon-dioxide.
7. according to the method in claim 1,4 and 6 described in any one, wherein, the specific surface area of described carrier is 20-1000m
2/ g, is preferably 200-700m
2/ g; The aperture of described carrier is 0.5-50nm, is preferably 1-30nm, is more preferably 3-15nm.
8. the method according to claim 1 or 4, wherein, described active ingredient contains Cu, K and La.
9. method according to claim 8, wherein, the consumption of described active ingredient and described carrier makes in prepared catalyzer, with the gross weight of this catalyzer for benchmark, in the Cu consumption of Cu element for 1-15 % by weight, in the K consumption of K element for 1-15 % by weight, in the La consumption of La element for 1-15 % by weight, under preferable case, in the Cu consumption of Cu element for 4-10 % by weight, in the K consumption of K element for 2-12 % by weight, in the La consumption of La element for 1-10 % by weight.
10. according to methane oxychlorination catalysts prepared by the preparation method in claim 1-9 described in any one.
The application of 11. methane oxychlorination catalysts according to claim 10 in the reaction of methane oxychlorination.
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| CN108144632A (en) * | 2018-01-22 | 2018-06-12 | 西安元创化工科技股份有限公司 | A kind of ruthenic oxide catalyst of methane oxychlorination and preparation method thereof |
| CN108144632B (en) * | 2018-01-22 | 2020-11-03 | 西安元创化工科技股份有限公司 | Ruthenium dioxide catalyst for methane oxychlorination and preparation method thereof |
| CN114729277A (en) * | 2019-06-27 | 2022-07-08 | 道格拉斯·约翰·弗雷德里克·哈雷特 | Method for reducing organic material to produce methane and/or hydrogen |
| CN114729277B (en) * | 2019-06-27 | 2024-08-06 | 道格拉斯·约翰·弗雷德里克·哈雷特 | Process for the reduction of organic material to produce methane and/or hydrogen |
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