CN114618568B - Application of Ti-beta molecular sieve in preparing methane oxidative coupling reaction catalyst, ytterbium-based catalyst and preparation method and application thereof - Google Patents
Application of Ti-beta molecular sieve in preparing methane oxidative coupling reaction catalyst, ytterbium-based catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of catalysts, and discloses application of a Ti-beta molecular sieve in preparing a methane oxidative coupling reaction catalyst, and a ytterbium-based catalyst, and a preparation method and application thereof. The ytterbium-based catalyst contains a molecular sieve carrier and an active component; wherein the molecular sieve carrier is Ti-beta molecular sieve; the active component contains an active metal component ytterbium and lanthanum oxide carbonate. The ytterbium-based catalyst provided by the invention has higher catalytic performance.
Description
Technical Field
The invention relates to the field of catalysts, in particular to application of a Ti-beta molecular sieve in preparing a methane oxidative coupling reaction catalyst, an ytterbium-based catalyst, and a preparation method and application thereof.
Background
The oxidative coupling of methane to ethylene and ethane is one of the most challenging and focused research subjects in the catalytic field at present because of its academic significance and potential great economic value. Since the papers of Keller and Bhasin in 1982, the papers have been focused on the fields of catalysis, chemical industry and petroleum and natural gas, and the research activity reaches a peak before and after 1992, and then the research heat is slightly reduced for a period of time. By 2010, along with the breakthrough of the united states in the shale gas field, a large amount of methane which is difficult to mine is mined, and chemical utilization of methane attracts great importance to the industry, wherein research on oxidative coupling of methane to prepare ethylene and ethane, which is considered to be the most promising, is a hot spot subject worldwide. However, the catalytic performance of the current methane oxidative coupling catalyst is still to be further improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide application of Ti-beta molecular sieve in preparing a methane oxidative coupling reaction catalyst, an ytterbium-based catalyst, and a preparation method and application thereof. The ytterbium-based catalyst provided by the invention has higher catalytic performance.
In order to achieve the above object, the first aspect of the present invention provides an application of a Ti-beta molecular sieve in preparing a catalyst for oxidative coupling reaction of methane.
In a second aspect of the present invention, there is provided an ytterbium-based catalyst comprising a molecular sieve support and an active component;
wherein the molecular sieve carrier is Ti-beta molecular sieve;
the active component contains an active metal component ytterbium and lanthanum oxide carbonate.
In a third aspect of the present invention, there is provided a method for preparing an ytterbium-based catalyst, the method comprising:
(1) Impregnating a Ti-beta molecular sieve by using a ytterbium precursor solution to obtain a Ti-beta molecular sieve sample loaded with ytterbium elements;
(2) Under alkaline condition, carrying out hydrothermal reaction on a mixed solution containing a lanthanum compound, water and optional alcohol to obtain a lanthanum oxide carbonate precursor;
(3) And uniformly mixing the Ti-beta molecular sieve sample loaded with ytterbium element and the lanthanum oxide carbonate precursor, and then sequentially drying and roasting to obtain the ytterbium-based catalyst.
In a fourth aspect of the present invention, there is provided an ytterbium-based catalyst prepared by the method as described above.
In a fifth aspect of the invention, there is provided the use of an ytterbium-based catalyst as described above in a methane oxidative coupling reaction.
In a sixth aspect of the present invention, there is provided a process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with the ytterbium-based catalyst as described above in the presence of oxygen and under the conditions of oxidative coupling reaction of methane;
alternatively, the ytterbium-based catalyst is prepared as described above, and then methane is contact-reacted with the resulting ytterbium-based catalyst in the presence of oxygen and under the conditions of oxidative coupling reaction of methane.
By the technical scheme of the invention, the following beneficial effects can be obtained:
1. the catalyst provided by the invention has a special structure and composition, and shows good catalytic activity for the oxidative coupling reaction of methane.
2. The catalyst provided by the invention has good catalytic stability due to low reaction temperature, and is beneficial to industrial production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the invention provides the use of a Ti-beta molecular sieve in the preparation of a catalyst for oxidative coupling of methane.
According to the present invention, the Ti-beta molecular sieve may be various Ti-beta molecular sieves conventionally used, which may be commercially available or may be prepared by itself.
According to a preferred embodiment of the present invention, the Ti-beta molecular sieve has a specific surface area of 500-520m 2 Per g, pore volume of 0.2-0.3cm 3 /g。
Wherein the specific surface area is calculated by the BET method.
The pore volume is calculated by the BJH method.
According to a preferred embodiment of the present invention, in order to improve the application effect of the Ti-beta molecular sieve in the catalyst for the oxidative coupling reaction of methane, the preparation method of the Ti-beta molecular sieve comprises:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve.
According to the present invention, the Al-beta zeolite may be various Al-beta zeolite existing, and preferably, the weight ratio of silica to alumina in the Al-beta zeolite is 20 to 60, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60.
According to the invention, the acid is preferably nitric acid, preferably in a concentration of 10-16mol/L.
According to the invention, it is preferred that the acid is used in an amount of 150 to 250ml relative to 10g of the Al-beta zeolite.
According to the present invention, the conditions for the contact dealumination may be selected within a wide range as long as the Al-beta zeolite can be effectively removed from the Al. Preferably, the contact dealumination is carried out under the condition of stirring, the temperature of the contact dealumination is 80-150 ℃ and the time is 8-20h.
The solid-liquid separation method according to the present invention may be a conventional method of solid-liquid separation, such as filtration, centrifugation, etc. According to a preferred embodiment of the invention, the solid phase is obtained by centrifugation at 4000-5000 rpm.
The manner in which the solid phase is washed according to the present invention is not particularly limited, and it is preferable that the solid phase is washed to neutrality with deionized water.
According to the invention, the drying is preferably vacuum drying. The drying temperature can be 100-200 ℃ and the drying time is 8-20h.
According to the invention, the amounts of the solid phase and of the bis (cyclopentadienyl) titanium dichloride may be chosen within wide limits, preferably in amounts of 0.1 to 0.5g, for example 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, on a dry weight basis, relative to 1g of the solid phase.
According to the invention, the conditions of the calcination may be conventional in the art, preferably the calcination is carried out under an inert atmosphere (nitrogen), and the temperature of the calcination may be 500-600 ℃ for 8-20 hours.
Wherein the firing may be in Schlenk tubes.
According to a specific embodiment of the present invention, the preparation method of the Ti-beta molecular sieve comprises:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
wherein, in the Al-beta zeolite, the weight ratio of the silicon dioxide to the aluminum oxide is 20-60;
wherein the acid is nitric acid with the concentration of 10-16 mol/L;
wherein the acid is used in an amount of 150 to 250ml relative to 10g of the Al-beta zeolite;
wherein the contact dealumination is carried out under the condition of stirring, the temperature of the contact dealumination is 80-150 ℃ and the time is 8-20h;
(ii) Washing the solid phase to be neutral, drying at 100-200 ℃ for 8-20h, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride in a weight ratio of 1:0.1-0.5 in an inert atmosphere, and roasting at 500-600 ℃ for 8-20h in the inert atmosphere to obtain the Ti-beta molecular sieve. The specific surface area of the Ti-beta molecular sieve is 500-520m calculated by BET method 2 /g, calculating the Ti by BJH method-beta molecular sieve with pore volume of 0.2-0.3cm 3 /g。
In a second aspect, the present invention provides an ytterbium-based catalyst comprising a molecular sieve support and an active component;
wherein the molecular sieve carrier is Ti-beta molecular sieve;
the active component contains an active metal component ytterbium and lanthanum oxide carbonate.
According to the invention, the molecular sieve support may be present in the catalyst in an amount of from 40 to 80 wt%, preferably from 50 to 70 wt%, for example 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, based on the total weight of the catalyst.
According to the present invention, in the catalyst, the ytterbium element may be contained in an amount of 0.5 to 10 wt%, preferably 1 to 8 wt%, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, based on the total weight of the catalyst.
According to the invention, in the catalyst, the lanthanum oxycarbonate may be present in an amount of 10 to 50 wt.%, based on the total weight of the catalyst. Preferably 20-40 wt%, for example, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%.
The selection of the Ti-beta molecular sieve according to the present invention has been described in detail in the first aspect, and in order to avoid unnecessary repetition, a detailed description is not repeated here.
In a third aspect, the present invention provides a method for preparing an ytterbium-based catalyst, the method comprising:
(1) Impregnating a Ti-beta molecular sieve by using a ytterbium precursor solution to obtain a Ti-beta molecular sieve sample loaded with ytterbium elements;
(2) Under alkaline condition, carrying out hydrothermal reaction on a mixed solution containing a lanthanum compound, water and optional alcohol to obtain a lanthanum oxide carbonate precursor;
(3) And uniformly mixing the Ti-beta molecular sieve sample loaded with ytterbium element and the lanthanum oxide carbonate precursor, and then sequentially drying and roasting to obtain the ytterbium-based catalyst.
According to the present invention, in step (1), the ytterbium precursor may be selected conventionally, as long as it is soluble in water. Preferably, the ytterbium precursor is ytterbium nitrate and/or ytterbium chloride.
The concentration of the ytterbium precursor in the ytterbium precursor solution may be selected within a wide range, and is preferably 0.1 to 10 wt%, more preferably 0.3 to 0.5 wt%, for example, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, in terms of ytterbium element.
According to the present invention, the conditions of the impregnation may be selected within a wide range as long as it enables the ytterbium precursor to be supported on the ti—β molecular sieve. Preferably, the conditions of the impregnation include: the temperature is 25-80deg.C, preferably 50-80deg.C, and the time is 3-8 hr, preferably 8-12 hr.
The method for obtaining the impregnated solid material according to the present invention may be not particularly limited, for example, filtration, centrifugation or evaporation of water therein by conventional means.
According to a preferred embodiment of the invention, the method further comprises drying the impregnated solid material to obtain a sample of ytterbium element loaded Ti-beta molecular sieve.
Wherein the drying conditions may include: the temperature is 80-150 ℃ and the time is 8-20h.
According to the invention, in step (2), the pH of the alkaline conditions may be selected within a wide range, preferably the pH of the alkaline conditions is 9-12, for example, 9, 9.5, 10, 10.5, 11, 11.5, 12, more preferably 9.5-11.5.
Wherein the alkaline conditions can be obtained by conventional methods, for example, by supplying an alkaline substance, for example, an alkaline solution, to the system. The alkaline substance may be sodium hydroxide, sodium carbonate, etc., preferably sodium hydroxide. According to a preferred embodiment of the invention, the alkaline conditions are obtained by providing the system with sodium hydroxide solution, the concentration of which is preferably 10-15% by weight.
According to the invention, the lanthanum compound is preferably a water soluble salt of lanthanum, for example, which may include, but is not limited to, lanthanum chloride, lanthanum chlorate and lanthanum nitrate, preferably lanthanum nitrate.
Wherein the concentration of lanthanum element in the mixed solution can be selected within a wider range, and preferably, in order to obtain a lanthanum oxide carbonate catalyst with better performance, the proportion of lanthanum element in the mixed solution relative to the mixed solution is 1:100-500 by weight, for example, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450 and 1:500; preferably 1:100-350.
According to the present invention, the kind of the alcohol may be selected in a wide range, preferably monohydric and/or polyhydric alcohols, and the polyhydric alcohols may be dihydric and/or trihydric alcohols; more preferably, the alcohol is a monohydric alcohol and/or a dihydric alcohol, preferably a monohydric alcohol of C1-C4, preferably a dihydric alcohol of C2-C5, and even more preferably, the alcohol is ethanol and/or ethylene glycol.
Wherein, the volume ratio of water to alcohol in the mixed solution can be selected in a wider range, preferably is 1:0.01-1, for example, can be 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, more preferably is 1:0.1-1.
According to a preferred embodiment of the present invention, the method for preparing the mixed liquor comprises: under the condition of stirring, dissolving a lanthanum compound in an alcohol aqueous solution, then adding an alkaline substance into the solution to provide the alkaline condition, and continuously stirring until a solid is separated out, thereby obtaining the mixed solution.
According to the present invention, in order to further improve the structural uniformity of the obtained lanthanum oxycarbonate, it is preferable that the mixed solution is further subjected to ultrasonic treatment before the hydrothermal synthesis reaction. Wherein the condition of the ultrasound can be selected in a wide range, preferably, the condition of the ultrasound includes: the frequency is 35-120kHz, for example, 35kHz, 40kHz, 45kHz, 50kHz, 55kHz, 60kHz, 65kHz, 70kHz, 75kHz, 80kHz, 85kHz, 90kHz, 95kHz, 100kHz, 110kHz, 120kHz, preferably 45-100kHz; the time is 20-100min, for example, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, preferably 30-90min; the temperature is 25-100deg.C, for example, 25 deg.C, 40 deg.C, 55 deg.C, 70 deg.C, 85 deg.C, 100 deg.C, preferably 30-80deg.C.
According to the present invention, in order to further improve the structural and catalytic properties of the prepared catalyst, it is preferable that the ultrasound includes one-stage ultrasound and two-stage ultrasound performed sequentially, wherein the conditions of the one-stage ultrasound include: the frequency is 45-80kHz, and the time is 20-60min; the conditions of the two-stage ultrasound include: the frequency is 80-100kHz, and the time is 10-30min.
Wherein the frequency of the two-stage ultrasound is greater than the frequency of the one-stage ultrasound.
According to the present invention, in order to further enhance the structural properties and catalytic properties of the prepared catalyst, it is preferable that the one-stage ultrasound includes a first ultrasound and a second ultrasound which are sequentially performed, wherein the conditions of the first ultrasound include: the frequency is 45-60kHz, and the time is 10-30min; the conditions of the second ultrasound include: the frequency is 60-80kHz, and the time is 10-30min.
Wherein the frequency of the second ultrasound is greater than the frequency of the first ultrasound.
According to the present invention, the hydrothermal reaction conditions may be conventional hydrothermal reaction conditions, but preferably, in order to more effectively enhance the performance of the prepared lanthanum oxycarbonate catalyst, the hydrothermal reaction conditions include: the temperature is 100-200deg.C (e.g., may be 100deg.C, 110deg.C, 120deg.C, 130deg.C, 150deg.C, 160deg.C, 170deg.C, 180deg.C, 200deg.C), preferably 120-160deg.C, and the time is 10-72h (e.g., may be 10h, 20h, 30h, 40h, 50h, 60h, 70h, 72 h), preferably 12-48h.
According to the invention, the solid material after the hydrothermal reaction can be obtained by adopting the technical means conventional in the art, for example, the solid material is obtained by carrying out solid-liquid separation on the material after the hydrothermal reaction, and the solid-liquid separation method can be filtration, centrifugation and the like. According to a preferred embodiment of the invention, the solid material is obtained by means of centrifugation. The centrifugation conditions preferably include: the rotation speed is 5000-10000rpm, preferably 7000-8000rpm; the time is 20-60min, preferably 30-50min.
According to the invention, preferably, the method further comprises: and (3) sequentially washing the solid materials subjected to the hydrothermal reaction with water and alcohol. According to a preferred embodiment of the invention, the washing is carried out with water (distilled water) 3-5 times and then with ethanol 1-2 times.
According to the invention, the method further comprises: the alcohol-washed material is dried, the temperature of which may vary within a wide range, preferably 80-180 c, for example 80 c, 90 c, 100 c, 110 c, 120 c, 130 c, 140 c, 150 c, 160 c, 170 c, 180 c, preferably 80-100 c.
The drying time may vary within wide limits, preferably is from 10 to 30 hours, for example from 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, preferably from 12 to 15 hours.
According to a preferred embodiment of the present invention, in step (3), the ytterbium element-loaded ti—β molecular sieve sample and lanthanum oxycarbonate precursor are uniformly mixed in the presence of an organic solvent.
Preferably, the organic solvent is an alcohol, the type of the alcohol can be selected within a wide range, preferably monohydric alcohol and/or polyhydric alcohol, and the polyhydric alcohol can be dihydric alcohol and/or trihydric alcohol; more preferably, the alcohol is a monohydric alcohol and/or a dihydric alcohol, preferably a monohydric alcohol of C1-C4, preferably a dihydric alcohol of C2-C5, and even more preferably, the alcohol is ethanol and/or ethylene glycol.
According to the invention, the organic solvent is used in such an amount that the total concentration of lanthanum oxycarbonate precursor and ytterbium element loaded Ti-beta molecular sieve sample is 0.5-2g/10ml, preferably 1.2-1.7g/10ml.
Preferably, the mixing is ultrasonic mixing; the ultrasonic mixing frequency is 20-120kHz, the time is 20-100min, and the temperature is 25-80 ℃.
Preferably, in order to further improve the performance of the prepared catalyst, the method further comprises contacting the uniformly mixed materials at a temperature of 25-80 ℃ for 3-8 hours before drying and roasting.
Preferably, the method further comprises removing the organic solvent from the mixed and contacted material, followed by drying and calcination. The removal may be by rotary evaporation.
According to the invention, the amounts of the materials are such that the ytterbium-based catalyst obtained has a molecular sieve support content of 40 to 80 wt.%, preferably 50 to 70 wt.% (for example, 50 wt.%, 52 wt.%, 54 wt.%, 56 wt.%, 58 wt.%, 60 wt.%, 62 wt.%, 64 wt.%, 66 wt.%, 68 wt.%, 70 wt.%) based on the total weight of the catalyst; the content of ytterbium element is 0.5 to 10 wt%, preferably 1 to 8 wt% (for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%); the lanthanum oxycarbonate content is 10-50 wt%. Preferably 20-40 wt% (e.g., 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%).
According to the invention, the drying temperature may be 100-200 ℃ for 8-20 hours.
According to the present invention, the conditions of the calcination may be conventional in the art, preferably, the temperature of the calcination is 500 to 600 ℃ for 1 to 6 hours.
According to the present invention, in order to further improve the catalytic performance of the prepared catalyst, it is preferable that the calcination process is raised to the calcination end temperature at a temperature raising rate of 1 to 10 c/min, preferably 1 to 5 c/min, and then the calcination is performed for a predetermined time.
According to the present invention, the baking atmosphere is not particularly limited, and may be an air atmosphere, a carbon dioxide atmosphere, or a nitrogen atmosphere, and is preferably an air atmosphere or a carbon dioxide atmosphere.
In a fourth aspect, the present invention provides an ytterbium-based catalyst prepared by the method described above.
In a fifth aspect, the present invention provides the use of the ytterbium-based catalyst obtained as described above in the oxidative coupling of methane.
According to the present invention, the catalyst of the present invention may be used in a continuous flow reactor to produce c2+ hydrocarbons from methane (e.g., natural gas). The continuous flow reactor may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or an ebullated bed reactor. The catalyst may be arranged in layers in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullated bed).
In a sixth aspect, the present invention provides a process for producing carbon two or more hydrocarbons from methane, the process comprising: contacting methane with the ytterbium-based catalyst as described above in the presence of oxygen and under the conditions of oxidative coupling reaction of methane;
alternatively, a supported catalyst is prepared as described above, and then methane is contact-reacted with the resulting ytterbium-based catalyst in the presence of oxygen and under the conditions of oxidative coupling of methane.
According to the present invention, the conditions for the oxidative coupling reaction of methane are not particularly limited and may be selected conventionally in the art, and the conditions for the oxidative coupling reaction of methane may include a reaction temperature of 500 to 600℃C (e.g., 500 ℃, 550 ℃, 600 ℃) and a reaction pressure of 0.03 to 0.1MPa, e.g., normal pressure, and a space velocity of methane of 10000 to 200000 ml/(g.h). In order to increase the methane conversion, the molar ratio of methane to oxygen is preferably from 2 to 10:1, preferably 4-8:1.
the lanthanum oxide carbonate catalyst provided by the invention has good catalytic performance in the reaction of preparing C2+ hydrocarbon by oxidative coupling of methane.
The present invention will be described in detail by examples. In the following examples of the present invention,
the drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the 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%.
Ethylene and ethane selectivity = ethylene selectivity + ethane selectivity;
the ethylene selectivity was calculated as follows:
ethylene selectivity = amount of methane consumed by ethylene produced/total amount of methane consumed x 100%;
the ethane selectivity was calculated as follows:
ethane selectivity = amount of methane consumed by ethane produced/total consumption of methane x 100%.
The yields of ethylene and ethane were calculated as follows:
ethylene and ethane yields = methane conversion x (ethane selectivity + ethylene selectivity)
Preparation example 1
This preparation example is used to illustrate the preparation of Ti-beta molecular sieves
The Al-beta zeolite (SiO 2 /Al 2 O 3 =33) at 13mol/L HNO 3 200ml of solution, stirring for 12h at 100℃for dealumination, then centrifuging at 4500rpm, washing with deionized water to neutral pH, vacuum drying at 150℃for 12h, transferring the sample into a glove box, and reacting with bis (cyclopentadienyl) titanium (IV) dichloride (Cp 2 TiCl) under nitrogen protection 2 97%) was mixed (mass ratio 4: 1) Post-milling was carried out uniformly, the mixture was transferred to a Schlenk tube and kept at N prior to calcination 2 Roasting in a muffle furnace at 550 ℃ for 12h, preparing the Ti-beta molecular sieve.
PREPARATION EXAMPLE 2-1
This preparation example is used to illustrate the preparation of lanthanum oxycarbonate precursor
Weighing lanthanum nitrate hexahydrate, dissolving in deionized water (lanthanum element is counted, the concentration is 0.4 g/ml), regulating the pH value to 12 by using sodium hydroxide solution, continuously stirring until solid is separated out, transferring to a hydrothermal kettle reactor with a polytetrafluoroethylene lining after ultrasonic treatment for 1h (80 kHz), maintaining at 160 ℃ for 12h, then washing with water for five times until the solution is neutral, washing with ethanol once, and then placing in an oven for drying at 80 ℃ for 12h to obtain a lanthanum oxide carbonate precursor.
PREPARATION EXAMPLE 2-2
This preparation example is used to illustrate the preparation of lanthanum oxycarbonate precursor
The preparation of lanthanum oxycarbonate precursor was performed as in preparation example 2-1, except that the ultrasound was three-frequency ultrasound: that is, firstly, the ultrasonic is performed for 30min at the frequency of 45kHz, then the ultrasonic frequency is adjusted to be 80kHz, the ultrasonic is performed for 10min, finally the ultrasonic frequency is adjusted to be 100KHz, the ultrasonic is performed for 10min, and the ultrasonic is finished.
PREPARATION EXAMPLES 2-3
This preparation example is used to illustrate the preparation of lanthanum oxycarbonate precursor
Lanthanum oxycarbonate precursor was prepared as in preparation example 2-1, except that the ultrasound was two-frequency ultrasound, i.e., ultrasound was first performed at a frequency of 45kHz for 40min, then adjusted to an ultrasound frequency of 80kHz for 10min.
PREPARATION EXAMPLES 2 to 4
This preparation example is used to illustrate the preparation of lanthanum oxycarbonate precursor
Lanthanum oxycarbonate precursor was prepared as in preparation example 2-1, except that the deionized water was replaced with a water and ethanol mixture (weight ratio of water to ethanol 1:0.1).
PREPARATION EXAMPLES 2 to 5
This preparation example is used to illustrate the preparation of lanthanum oxycarbonate precursor
Lanthanum oxycarbonate precursor was prepared as in preparation example 2-1, except that no ultrasound-assisted treatment was used during the preparation,
example 1
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
(1) Ytterbium nitrate pentahydrate is dissolved in deionized water (the concentration of ytterbium element is 0.38 weight percent), after stirring and dissolution, the Ti-beta molecular sieve prepared in preparation example 1 is added into the solution for soaking, stirring is uniform, the mixture is kept at 80 ℃ for 8 hours, a solid phase is obtained by centrifugation, and then the solid phase is transferred to an oven and dried at 120 ℃ for 12 hours. And obtaining a Ti-beta molecular sieve sample impregnated with ytterbium.
(2) Adding lanthanum oxide precursor of preparation example 2-1 and a Ti-beta molecular sieve sample impregnated with ytterbium into ethanol (total solid content 1.5g/10 ml), placing in an ultrasonic device, performing ultrasonic treatment at 80kHz for 60min, completely evaporating the ethanol in a rotary evaporator, transferring to an oven at 80 ℃ for drying for 12h, placing in a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min under carbon dioxide atmosphere, and maintaining for 2h to obtain the catalyst CAT-1.
Wherein, the usage amount of each component is that the content of the molecular sieve carrier is 60 weight percent based on the total weight of the catalyst in the catalyst CAT-1; the content of ytterbium element was 2% by weight; the lanthanum oxycarbonate content was 30 wt.%.
XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 2
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
(1) Ytterbium nitrate pentahydrate is dissolved in deionized water (the concentration of ytterbium element is 0.3 weight percent), after stirring and dissolution, the Ti-beta molecular sieve prepared in preparation example 1 is added into the solution for soaking, stirring is uniform, the temperature is kept at 80 ℃ for 8 hours, the solid phase is obtained by centrifugation, and then the solid phase is transferred to an oven and dried at 120 ℃ for 12 hours. And obtaining a Ti-beta molecular sieve sample impregnated with ytterbium.
(2) Adding lanthanum oxide precursor of preparation example 2-1 and a Ti-beta molecular sieve sample impregnated with ytterbium into ethanol (total solid content 1.2g/10 ml), placing in an ultrasonic device, performing ultrasonic treatment at 70kHz for 50min, completely evaporating the ethanol in a rotary evaporator, transferring to an oven at 80 ℃ for drying for 12h, placing in a muffle furnace, heating to 550 ℃ at a heating rate of 1 ℃/min under carbon dioxide atmosphere, and maintaining for 1.5h to obtain the catalyst CAT-2.
Wherein, the usage amount of each component is that the content of the molecular sieve carrier in the catalyst CAT-2 is 55 weight percent based on the total weight of the catalyst; the content of ytterbium element was 1% by weight; the lanthanum oxycarbonate content was 25 wt.%.
XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 3
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
(1) Ytterbium nitrate pentahydrate is dissolved in deionized water (the concentration of ytterbium element is 0.5 weight percent), after stirring and dissolution, the Ti-beta molecular sieve prepared in preparation example 1 is added into the solution for soaking, stirring is uniform, the temperature is kept at 80 ℃ for 8 hours, the solid phase is obtained by centrifugation, and then the solid phase is transferred to an oven and dried at 120 ℃ for 12 hours. And obtaining a Ti-beta molecular sieve sample impregnated with ytterbium.
(2) Adding lanthanum oxide precursor of preparation example 2-1 and a Ti-beta molecular sieve sample impregnated with ytterbium into ethanol (total solid content 1.7g/10 ml), placing in an ultrasonic device, performing ultrasonic treatment at 90kHz for 70min, completely evaporating the ethanol in a rotary evaporator, transferring to an oven at 80 ℃ for drying for 12h, placing in a muffle furnace, heating to 600 ℃ at a heating rate of 3 ℃/min under carbon dioxide atmosphere, and maintaining for 1h to obtain the catalyst CAT-3.
Wherein, the usage amount of each component is that the content of the molecular sieve carrier is 65 percent by weight based on the total weight of the catalyst in the catalyst CAT-3; the content of ytterbium element was 3% by weight; the lanthanum oxycarbonate content was 35 wt.%.
XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 4
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Ytterbium-based catalyst CAT-4 was prepared as in example 1, except that Ti-beta molecular sieves were prepared as disclosed in Tang, B.A procedure for the preparation of Ti-Beta zeolites for catalytic epoxidation with hydrogen peroxi. Green Chemistry 2014,16 (4), 2281-2291. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 5
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-5 was carried out as in example 1, except that lanthanum oxycarbonate precursor was lanthanum oxycarbonate precursor prepared in preparation example 2-2. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 6
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-6 was carried out as in example 1, except that lanthanum oxycarbonate precursor was lanthanum oxycarbonate precursor prepared in preparation examples 2-3. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 7
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-7 was carried out as in example 1, except that lanthanum oxycarbonate precursor was lanthanum oxycarbonate precursor prepared in preparation examples 2 to 4. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 8
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-8 was carried out as in example 1, except that lanthanum oxycarbonate precursor was lanthanum oxycarbonate precursor prepared in preparation examples 2 to 5. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 9
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-9 was carried out as in example 1, except that ytterbium nitrate pentahydrate was replaced with ytterbium chloride hexahydrate, and the ytterbium element concentration was 0.5% by weight. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Example 10
This example is for explaining the ytterbium-based catalyst of the present invention and the method of preparing the same
Preparation of ytterbium-based catalyst CAT-10 was carried out as in example 1, except that in step (2), lanthanum oxycarbonate precursor of preparation 2-1 and ytterbium-impregnated Ti-. Beta.molecular sieve sample were added to deionized water. XRD detection shows that the material mainly contains La by comparing the spectrogram with PXRD database (Bruker diffrac. Eva, version 4.2.1) 2 O 2 CO 3 。
Comparative example 1
Ytterbium-based catalyst for reference and method for producing the same
Preparation of ytterbium-based catalyst CAT-D1 was carried out as in example 1, except that the Ti-. Beta.molecular sieve prepared in preparation example 1 was replaced with a silica support.
Comparative example 2
Ytterbium-based catalyst for reference and method for producing the same
The ytterbium-based catalyst CAT-D2 was prepared as in comparative example 1, except that lanthanum oxycarbonate was not doped.
Comparative example 3
This example illustrates a reference catalyst and method of making the same
Preparation of ytterbium-based catalyst CAT-D3 was carried out in accordance with the method of comparative example 1, except that ytterbium was not supported.
Test case
This test example is used to illustrate the method for preparing ethylene ethane by oxidative coupling of methane
0.1g of the catalyst was charged into a fixed bed Inconel reactor, the molar ratio of methane to oxygen was 8:1, the space velocity of methane was 60000ml/gh, the reaction temperature was 550 ℃, and the methane conversion, ethylene ethane selectivity and ethylene and ethane yields were as shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalyst for preparing ethylene ethane by oxidative coupling of methane prepared by the invention is used for oxidative coupling reaction of methane, higher methane conversion rate, selectivity and yield of carbon dioxide can be maintained, which indicates that the catalyst for oxidative coupling of methane has excellent catalytic performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (27)
1. An ytterbium-based catalyst, characterized in that the ytterbium-based catalyst comprises a molecular sieve carrier and an active component;
wherein the molecular sieve carrier is Ti-beta molecular sieve;
the active component contains an active metal component ytterbium and lanthanum oxide carbonate.
2. The ytterbium-based catalyst according to claim 1, wherein, in the catalyst, the content of the molecular sieve carrier is 40 to 80% by weight based on the total weight of the catalyst; the content of ytterbium element is 0.5-10 wt%; the lanthanum oxycarbonate content is 10-50 wt%.
3. The ytterbium-based catalyst according to claim 2, wherein, in the catalyst, the content of the molecular sieve carrier is 50 to 70% by weight based on the total weight of the catalyst; the content of ytterbium element is 1-8 wt%; the lanthanum oxycarbonate content is 20-40 wt%.
4. The ytterbium-based catalyst according to any one of claims 1 to 3, wherein the preparation method of the Ti- β molecular sieve comprises:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the conditions for contact dealumination include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
5. The preparation method of the ytterbium-based catalyst is characterized by comprising the following steps:
(1) Impregnating a Ti-beta molecular sieve by using a ytterbium precursor solution to obtain a Ti-beta molecular sieve sample loaded with ytterbium elements;
(2) Under alkaline condition, carrying out hydrothermal reaction on a mixed solution containing a lanthanum compound, water and optional alcohol to obtain a lanthanum oxide carbonate precursor;
(3) And uniformly mixing the Ti-beta molecular sieve sample loaded with ytterbium element and the lanthanum oxide carbonate precursor, and then sequentially drying and roasting to obtain the ytterbium-based catalyst.
6. The method of claim 5, wherein in step (1), the method further comprises drying the impregnated solid material to obtain a Ti-beta molecular sieve sample loaded with ytterbium element;
the ytterbium precursor is ytterbium nitrate and/or ytterbium chloride;
the conditions of the impregnation include: the temperature is 25-80 ℃ and the time is 3-12h.
7. The method according to claim 5 or 6, wherein in step (2), the alkaline condition has a pH of 9-12;
the method further comprises the steps of: carrying out ultrasonic treatment on the mixed solution before the hydrothermal reaction;
the conditions of the ultrasonic treatment include: the frequency is 20-120kHz, the time is 20-100min, and the temperature is 25-100 ℃;
the ultrasonic treatment comprises a one-stage ultrasonic treatment and a two-stage ultrasonic treatment which are sequentially carried out, wherein the conditions of the one-stage ultrasonic treatment comprise: the frequency is 45-80kHz, and the time is 20-60min; the conditions of the two-stage ultrasonic treatment include: the frequency is 80-100kHz, and the time is 10-30min;
the one-stage ultrasonic treatment comprises a first ultrasonic treatment and a second ultrasonic treatment which are sequentially carried out, wherein the conditions of the first ultrasonic treatment comprise: the frequency is 45-60kHz, and the time is 10-30min; the conditions of the second sonication include: the frequency is 60-80kHz, and the time is 10-30min;
the lanthanum compound is a water soluble salt of lanthanum;
the alcohol is selected from monohydric alcohol and/or polyhydric alcohol;
in the mixed solution, the volume ratio of water to alcohol is 1:0.01-1;
in the mixed solution, the proportion of lanthanum element relative to the mixed solution is 1:100-500 by weight;
the conditions of the hydrothermal reaction include: the temperature is 100-200 ℃ and the time is 10-72h;
the method further comprises the steps of: and sequentially washing the solid material subjected to the hydrothermal reaction with water, washing with alcohol and drying to obtain the lanthanum oxycarbonate precursor.
8. The method of claim 7, wherein the lanthanum compound is selected from lanthanum chloride, lanthanum chlorate, and lanthanum nitrate;
in the mixed solution, the volume ratio of water to alcohol is 1:0.1-1;
in the mixed solution, the proportion of lanthanum element relative to the mixed solution is 1:100-350 by weight;
the conditions of the hydrothermal reaction include: the temperature is 120-160 ℃ and the time is 12-48h;
the method further comprises the steps of: and sequentially washing the solid material subjected to the hydrothermal reaction with water, washing with alcohol and drying to obtain the lanthanum oxycarbonate precursor.
9. The method of claim 8, wherein the lanthanum compound is lanthanum nitrate.
10. The method according to any one of claims 5, 6, 8, 9, wherein in step (3), the ytterbium element-loaded Ti-beta molecular sieve sample and lanthanum oxycarbonate precursor are mixed uniformly in the presence of an organic solvent;
the organic solvent is alcohol, and the alcohol is selected from monohydric alcohol and/or polyhydric alcohol;
the mixing is ultrasonic mixing; the ultrasonic mixing frequency is 20-120kHz, the time is 20-100min, and the temperature is 25-80 ℃;
the method further comprises contacting the uniformly mixed materials for 3-8 hours at a temperature of 25-80 ℃ before drying and roasting.
11. The method of claim 10, wherein the organic solvent is an alcohol selected from the group consisting of monohydric alcohols, dihydric alcohols, and trihydric alcohols.
12. The method of claim 11, wherein the organic solvent is an alcohol selected from ethanol and/or ethylene glycol.
13. The method of claim 7, wherein in step (3), the ytterbium element-loaded Ti-beta molecular sieve sample and lanthanum oxycarbonate precursor are mixed uniformly in the presence of an organic solvent;
the mixing is ultrasonic mixing; the ultrasonic mixing frequency is 20-120kHz, the time is 20-100min, and the temperature is 25-80 ℃;
the method further comprises contacting the uniformly mixed materials for 3-8 hours at a temperature of 25-80 ℃ before drying and roasting.
14. The method of claim 13, wherein the organic solvent is an alcohol selected from the group consisting of monohydric alcohols, dihydric alcohols, and trihydric alcohols.
15. The method of claim 14, wherein the organic solvent is an alcohol selected from ethanol and/or ethylene glycol.
16. The method according to any one of claims 5, 6, 8, 9, wherein the amount of each material is such that the molecular sieve carrier content in the resulting ytterbium-based catalyst is 40-80% by weight, based on the total weight of the catalyst; the content of ytterbium element is 0.5-10 wt%; the lanthanum oxycarbonate content is 10-50 wt%.
17. The method according to claim 7, wherein the amount of each material is such that the molecular sieve carrier is 40-80 wt% based on the total weight of the catalyst in the resulting ytterbium-based catalyst; the content of ytterbium element is 0.5-10 wt%; the lanthanum oxycarbonate content is 10-50 wt%.
18. The process according to claim 16 or 17, wherein the amount of each material is such that the molecular sieve carrier is present in the resulting ytterbium-based catalyst in an amount of 50-70% by weight, based on the total weight of the catalyst; the content of ytterbium element is 1-8 wt%; the lanthanum oxycarbonate content is 20-40 wt%.
19. The method of any one of claims 5, 6, 8, 9, 11-15, 17, wherein the Ti-beta molecular sieve is prepared by a process comprising:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the contacting conditions include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
20. The method of claim 7, wherein the Ti-beta molecular sieve is prepared by a process comprising:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the contacting conditions include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
21. The method of claim 10, wherein the Ti-beta molecular sieve is prepared by a process comprising:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the contacting conditions include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
22. The method of claim 16, wherein the Ti-beta molecular sieve is prepared by a process comprising:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the contacting conditions include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
23. The method of claim 18, wherein the Ti-beta molecular sieve is prepared by a process comprising:
(i) The Al-beta zeolite is subjected to acid contact dealumination, and the dealuminated material is subjected to solid-liquid separation to obtain a solid phase;
(ii) Washing and drying the solid phase, mixing and grinding the solid phase with bis (cyclopentadienyl) titanium dichloride under an inert atmosphere, and roasting the solid phase under the inert atmosphere to obtain the Ti-beta molecular sieve;
in step (i), the contacting conditions include: the temperature is 80-150 ℃ and the time is 8-20 hours;
in step (ii), the amount of bis (cyclopentadienyl) titanium dichloride used is 0.1 to 0.5g relative to 1g of the solid phase.
24. Ytterbium-based catalyst prepared by the method of any one of claims 5 to 23.
25. Use of the ytterbium-based catalyst of any of claims 1-4 and 24 in a methane oxidative coupling reaction.
26. A process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with the ytterbium-based catalyst of any of claims 1-4 and 24 in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, the ytterbium-based catalyst is prepared according to the method of any one of claims 5 to 23, and then methane is contacted with the obtained ytterbium-based catalyst in the presence of oxygen and under the conditions of oxidative coupling reaction of methane;
the molar ratio of the methane to the oxygen is 2-10:1, a step of;
the temperature of the contact reaction is 500-600 ℃; the space velocity of methane is 10000-200000 mL/(g.h).
27. The method of claim 26, wherein the molar ratio of methane to oxygen is 4-8:1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101353169A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Synthetic method of Ti-beta molecular sieve |
| CN101534941A (en) * | 2006-11-17 | 2009-09-16 | 陶氏环球技术公司 | Hydro-oxidation process using a catalyst prepared from a gold cluster complex |
| CN102371179A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst for preparing low carbon olefin and preparation method thereof |
| CN103420392A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Rare earth-containing titanium silicalite and preparation method and applications thereof |
| CN104759291A (en) * | 2014-01-02 | 2015-07-08 | 易高环保能源研究院有限公司 | Methane oxidation coupling catalyst and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101534941A (en) * | 2006-11-17 | 2009-09-16 | 陶氏环球技术公司 | Hydro-oxidation process using a catalyst prepared from a gold cluster complex |
| CN101353169A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Synthetic method of Ti-beta molecular sieve |
| CN102371179A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Catalyst for preparing low carbon olefin and preparation method thereof |
| CN103420392A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Rare earth-containing titanium silicalite and preparation method and applications thereof |
| CN104759291A (en) * | 2014-01-02 | 2015-07-08 | 易高环保能源研究院有限公司 | Methane oxidation coupling catalyst and preparation method thereof |
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