CN1559683A - Preparing aromatics loading catalyst by methane at non oxidation catalyzing aromatization - Google Patents
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Abstract
A carried W/MCM-22-base catalyst for preparing ary/hydrocarbon by the non-oxidizing catalytic dehydroaromatization of methane in the condition of no oxygen gas has the chemical formula: Wox/MCM-22 or WOx-AOy/MCM-22, where MCM-22 is the zeolite molecular sieve and A is chosen from Zn, Mo, Ga and Co. It is prepared by isochoric dipping method. Its advantages are high stability, selectivity and conversion rate of methane.
Description
Technical Field
The invention relates to a catalyst for preparing aromatic hydrocarbon by non-oxidative catalytic dehydrogenation and aromatization of methane.
Background
The non-oxidative catalytic dehydroaromatization (marked as DHAM, the same below) of methane to prepare aromatic hydrocarbon under the condition of no gas-phase oxygen is one of the new research and development directions for optimizing and utilizing methane. The process isThe process is technically less complex, the main product being aromatics and unconverted CH4And by-product H2Easy to separate, byproduct H2Can also be used as a large amount of H for oil finish machining2The source of (a).
Most of the DHAM catalysts reported so far are oxides of supported transition metals (such as Pt, Re, Cr, Mo, W, etc.). Bragin et al (IZV, Akad., Nauk SSSR, Ser. Khim., 1989, 750) were first reported with Pt-CrO3The methane conversion and benzene selectivity of the/HZSM-5 catalyst were 18% and 78%, respectively, at a temperature of 1023K in the pulse reactor. The Wang et al (Catal. Lett.1993, 21: 35) of the institute of Dali-Fuji, China firstly reported that aromatic hydrocarbons are prepared by using Mo/HZSM-5 catalyst in a fixed bed continuous flow reactor. Chen Yuan et al (Natural gas chemical, 1994, 19: 1) and Liu Jitian et al (catalytic science, 1995, 16: 102) reported methane conversion of 7.2% and 5.6%, respectively, with corresponding benzene selectivities of 88% and 90%, respectively, at 973K over Mo/HZSM-5 catalyst. The improved Mo-based catalysts reported successively in recent years are mainly: Mo-Ni/HZSM-5 (Wang Dongjie et al, proceedings of higherschool chemistry, 1996, 17: 1776), Mo-Pt/HZSM-5(Chen et al, Catal. Lett., 1996, 39: 169), Mo-Ru/HZSM-5(Shu et al, J.Catal., 1997, 170: 11) and Mo-Co (or-Fe)/HZSM-5(Ohnishi et al, J.Catal., 1999, 182: 92), among others.
In the initial studies on the DHAM reaction, the analysis and calculation of heavy aromatics (naphthalene, etc.) and carbon deposition in the product were omitted, so that the yield of each carbon-containing product, which was originally calculated by the gas-phase product carbon-based normalization method, was significantly higher. Later on Lunsford et al (Topics Catal., 1997, 3: 289) used an internal standard method to analyze and calculate methane conversion and product distribution, thereby more accurately evaluating the activity of the Mo/HZSM-5 catalyst. They may contain 10% N2(as internal standard) CH4As raw material gas, at normal pressure, 973K, GHSV ═ 800h-1Evaluation of 2% Mo/HZSM-5 at reaction conditions over a period of 12 hours showed methane conversion and benzene selectivity of about 8% and 60% to 65%, respectively, naphthalene selectivity up to 15% at the beginning of the reaction, and about 15% conversion of methane to carbon deposits. Ichikawa et al (chem. Commun., 1997, 15: 1455) reported in the same year using Ar gas as an internal standard at 0.1MPa, 973K, B,1500mL-h-1-g-catal.-1The results of a 30 hour evaluation of the 3% Mo/HZSM-5 catalyst under the conditions were: the conversion rate of methane is 10% -6%, the selectivity of benzene is about 50%, the selectivity of naphthalene is gradually reduced from 20% in the initial stage of reaction to 5% in the later stage, and the selectivity of carbon deposition is as high as 32%. These results clarify the deviation in the analysis calculations of the previous experimental data,making it more practical to evaluate the process reactivity and product selectivity.
The DHAM reaction is an endothermic process. According to stoichiometric formula Thermodynamic calculations were performed to calculate CH at 873, 973, 1023, 1073, 1123K4The equilibrium conversion of (a) is, in order, 5.1%, 11.3%, 15.8%, 21.1%, 27.2% (see: Zeng et al, Catal. Lett., 1998, 53: 119). It follows that high operating temperatures favor methane conversion and aromatics yield enhancement. However, the selection of the actual operating temperature is often limited by factors such as catalyst performance. Since the Mo component is easy to sublimate and run off at the reaction temperature of 973K, the catalyst is inevitably deactivated and difficult to regenerate, so that the practical application of the Mo-based catalyst is greatly limited. The applicant provides a load type WO 97113358.1 in the invention patent ZL 97113358.1x-AOy-H2SO4catalyst/HZSM-5 (in the formula AO)yIs a metal oxide auxiliary agent, and A is selected from Zn, Nb, Mo, La and the like). The catalyst has higher thermal stability, allows the catalyst to be operated at the temperature of 1073K without sublimation loss of W-components, and is beneficial to improving the conversion rate of methane and the yield of benzene; but the content of heavy aromatics such as naphthalene in the product is higher, and the one-way operation period of the catalyst is shorter.
Disclosure of Invention
The invention aims to provide a methane non-oxidative catalytic dehydrogenation aromatization catalyst which has good heat resistance, longer one-way operation period of the catalyst and high methane conversion rate and benzene yield.
The present invention relates to a non-oxidative catalytic dehydrogenation aromatization of methane under the condition of no gas-phase oxygen to prepare aromatichydrocarbonA supported W/MCM-22-based catalyst having the formula: WOx/MCM-22 (non-promoted) or WOx-AOy/MCM-22 (promoted type). The catalyst is MCM-22 zeolite molecular sieve (commercially available, the Si/Al molar ratio of the catalyst is 20-35, and the specific surface area is more than or equal to 500m2The/g) is a carrier; WOxWherein x is 1/2 of the valence of W, said WOxThe content of (A) is 3-15% (mass percent, the same below) by corresponding W, preferably 6-12%; AOyIs a metal oxide auxiliary, AOyA in the formula (I) is one or two metal elements selected from Zn, Mo, Ga and Co, AOyY in (A) 1/2, AOyThe content of (A) is 0.1-2.0%, preferably 0.1-1.0% by corresponding A reduced scale; the balance is MCM-22 molecular sieve.
The catalyst of the invention is prepared by adopting an isochoric impregnation method, and is non-promoted WOxThe preparation method of the/MCM-22 catalyst comprises the following steps: firstly, drying a measured MCM-22 zeolite molecular sieve carrier at 373-393K, and then drying the dried MCM-22 zeolite molecular sieve carrier by H2SO4Acidified (NH) containing a measured amount of W4)2WO4Soaking an aqueous solution (pH value is 1.5) on the support, drying the soaked sample at 373-393K, and roasting at 673-873K for 4-8 hours to obtain the supported non-promoted WOxA/MCM-22 catalyst.
Promoted type of WOx-AOyThe preparation method of the/MCM-22 catalyst comprises the following steps: first of all, measured W in (NH)4)2WO4And A (NO) with the amount A3)2yMixing, dissolving in water and passing through H2SO4Acidifying to prepare a water solution with the pH value of 1.5, soaking the water solution on a measured MCM-22 molecular sieve carrier subjected to 373-393K drying treatment in advance, drying a soaked sample at the temperature of 373-393K, and roasting at the temperature of 673-873K for 4-8 hours to obtain the supported promoted WOx-AOyA/MCM-22 catalyst.
The activity evaluation test of the catalyst for the DHAM reaction was performed on an atmospheric fixed bed gas continuous flow reactor-GC combined system. The catalyst dosage for each experiment was 0.5g, based on 10% N2(internal standard, purity 99.99%) + CH4(purity 99.9%) as raw material gas, and its correspondent space velocity GHSV is 1500mL (STP) -h-1(-g-catal.)-1The pressure of the reaction system is 120kPa, and the reaction temperature is 1073K.
The invention uses MCM-22 zeolite molecular sieve to replace the HZSM-5 molecular sieve used previously as the catalyst carrier, the carrier has large aperture and high loading capacity, and some novel auxiliary agents are introduced to prepare single-promoted or double-promoted WOx-AOy(-A′Oy′) A/MCM-22 catalyst. The experimental results show that: in the first 4 hours of the reaction, the methane conversion (calculated by the internal standard method) reaches 20% -15%, and the selectivity of the carbon-containing product is as follows: 72-60% of benzene, 5-5% of toluene, 4-4% of ethylene and 1% of ethane, wherein the naphthalene content in reaction tail gas is below the TCD detection limit of a gas chromatograph; the total soot amount after 7.5 hours of reaction was 13.5% by weight of the catalyst (corresponding to an average soot selectivity of 20%). Therefore, the catalyst provided by the invention has high thermal stability and CH4High conversion rate and benzene selectivity, low selectivity of heavy aromatics such as naphthalene, slow carbon deposition and the like, and has good industrial application prospect.
Detailed Description
The invention is further illustrated by the following examples.
Example 1:
the converted W content is respectively 0.24g, 0.32g and 0.48g and is subjected to H2SO4Acidified to pH 1.5 (NH)4)2WO4Respectively soaking the aqueous solution on 4.0g MCM-22 molecular sieve carrier dried for 2 hours at 383K, drying the loaded material for 2 hours at the temperature of 383K, and roasting at 773K for 4 hours to obtain three loaded WO with different W contentsxthe/MCM-22 catalyst samples were scored as 6% W/MCM-22, 8% W/MCM-22, and 12% W/MCM-22.
The methane non-oxidative catalytic dehydrogenation aromatization test was performed on a constant pressure fixed bed gas continuous flow reactor-GC combined system. The amount of catalyst used in each test was 0.5g, so as to contain 10% N2(internal standard, purity 99.99%) of CH4(purity is 99.9%) as raw material gas, space velocity GHSV ═ space velocity1500mL(STP)-h-1(-g-catal.)-1The pressure of the reaction system was 120kPa, and the reaction temperature was 1073K. During the temperature rise, the catalyst is at N2(purity: 99.99%) under the protection of atmosphere, 10% N was directly introduced when the temperature reached 1073K2+CH4The raw material gas is reacted. The reactants and products are analyzed in situ by the combination of two thermal conductivity detectors of an online gas chromatograph (102 GD type and GC-950 type respectively); the former is a single column and a single gas path, the chromatographic column is filled with 5A molecular sieve, the column length is 2m, and H is used2As carrier gas for analyzing N2、CH4And CO; the latter is double-column double-gas path, the chromatographic column packing is Porapak-Qs and DNP respectively, the column length is 2m, and H is used2As carrier gas, CH was analyzed separately4、N2、C2H4、C2H6、CO2Etc. and CH4(containing N)2) Two groups of products such as benzene, toluene and xylene. The activity data of the catalyst is obtained from the beginning of the reaction to 45min after the reaction system reaches a steady state, and the conversion rate of methane and the selectivity of each carbon-containing product are calculated by an internal standard method. The evaluation results are shown in Table 1.
TABLE 1
| Catalyst sample | CH4Conversion (%) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 6％W/MCM-22 | 20～13 | 42.5 | 2.6 | 3.4 | 1.0 |
| 8％W/MCM-22 | 20～13 | 52.8 | 3.2 | 4.4 | 1.0 |
| 12％W/MCM-22 | 20～10 | 52.3 | 3.2 | 4.2 | 1.0 |
Example 2:
converting the converted mixture to contain 0.32gW +0.004gGa and H2SO4Acidified to pH 1.5 (NH)4)2WO4And Ga (NO)3)3The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier dried for 2 hours by 383K, the material is dried for 2 hours at the temperature of 383K, 773K is roasted for 5 hours, and the load type WO is obtainedx-GaOythe/MCM-22 single promoted W-based catalyst was reported as 8% W-0.1% Ga/MCM-22.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 2.
TABLE 2
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.1％Ga/MCM-22 | 14.3 | 51.1 | 4.9 | 4.8 | 1.0 |
Example 3:
converting the converted mixture to H, the mixture containing 0.32gW +0.024gZn2SO4Acidified to pH 1.5 (NH)4)2WO4And Zn (NO)3)2The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier which is dried by 383K for 2 hours; the converted mixture contains 0.32gW +0.020gMo and H2SO4Acidified to pH 1.5 (NH)4)2WO4And (NH)4)2MoO4The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier which is dried by 383K for 2 hours; the two samples obtained after the impregnation were at 383KDrying for 2 hours at the temperature, and roasting for 5 hours at 773K to respectively obtain the loaded WOx-ZnOy/MCM-22 and WOx-MoOy′the/MCM-22 single promoted W-based catalyst was reported as 8% W-0.6% Zn/MCM-22and 8% W-0.5% Mo/MCM-22, respectively.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 3.
TABLE 3
| Catalyst sample | CH4Conversion (%) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.6％Zn/MCM-22 | 14.0 | 61.2 | 3.4 | 3.7 | 0.9 |
| 8％W-0.5％Mo/MCM-22 | 15.4 | 60.9 | 3.4 | 4.3 | 0.9 |
Example 4:
converting the mixture to H, the mixture contains 0.32gW +0.004gCo +0.016gMo2SO4Acidified to pH 1.5 (NH)4)2WO4、Co(NO3)3And (NH)4)2MoO4The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier which is dried by 383K for 2 hours; drying the impregnated material at 383K for 2 hours, and roasting at 773K for 5 hours to obtain the loaded WOx-CoOy-MoOy′A/MCM-22 dual promoted W-based catalyst, reported as 8% W-0.1% Co-0.4% Mo/MCM-22.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 4.
TABLE 4
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.1％Co-0.4％Mo/ MCM-22 | 15.0 | 72.2 | 5.0 | 4.2 | 0.5 |
Example 5:
converting the converted mixture to H, wherein the H content of the H is 0.32gW +0.004gGa +0.024gZn2SO4Acidified to pH 1.5 (NH)4)2WO4、Ga(NO3)3And Zn (NO)3)2The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier which is dried by 383K for 2 hours; the converted warp yarn contains 0.32gW +0.004gGa +0.016gMo warp yarn H2SO4Acidified to pH 1.5 (NH)4)2WO4、Ga(NO3)3And (NH)4)2MoO4The mixture aqueous solution is dipped on 4.0g MCM-22 molecular sieve carrier which is dried by 383K for 2 hours; drying the two samples obtained after impregnation at 383K for 2 hours, and roasting at 773K for 5 hours to respectively obtain the loaded WOx-GaOy-ZnOy′/MCM-22 and WOx-GaOy-MoOy′A/MCM-22 dual promoted W-based catalyst was reported as 8% W-0.1% Ga-0.6% Zn/MCM-22 and 8% W-0.1% Ga-0.4% Mo/MCM-22, respectively.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 5.
TABLE 5
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.1％Ga-0.6％Zn/ MCM-22 | 15.3 | 71.1 | 5.9 | 4.1 | 1.0 |
| 8％W-0.1％Ga-0.4％Mo/ MCM-22 | 15.4 | 65.3 | 5.1 | 4.0 | 1.1 |
Example 6:
the procedure for the preparation of the catalyst of example 4 was followed, maintaining (NH)4)2WO4And the feeding amount of the carrier MCM-22 molecular sieve is unchanged, (NH)4)2MoO4The material charging amount is changed to 0.020g by corresponding Mo reduced amount, and Co (NO) is changed3)3Are added in amounts of (A) to prepare a mixture containingFour supported dual promoted W-based catalysts with different amounts of Co, namely: 8% W-0.05% Co-0.5% Mo/MCM-22, 8% W-0.1% Co-0.5% Mo/MCM-22, 8% W-0.2% Co-0.5% Mo/MCM-22 and 8% W-0.5% Co-0.5% Mo/MCM-22.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 6.
TABLE 6
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.05％Co-0.5％Mo/ MCM-22 | 15.5 | 63.4 | 4.1 | 4.3 | 1.0 |
| 8％W-0.1％Co-0.5％Mo/ MCM-22 | 15.8 | 66.6 | 5.0 | 5.0 | 0.5 |
| 8％W-0.2％Co-0.5％Mo/ MCM-22 | 15.4 | 65.4 | 7.0 | 5.8 | 1.0 |
| 8％W-0.5％Co-0.5％Mo/ MCM-22 | 15.4 | 60.3 | 4.6 | 3.6 | 0.9 |
Example 7:
the procedure for the preparation of the catalyst of example 4 was followed, maintaining (NH)4)2WO4、Co(NO3)3And the input amount of the carrier MCM-22 molecular sieve is unchanged and changed (NH)4)2MoO4The four supported double-promoted W-based catalysts with different Mo contents are respectively prepared, namely: 8% W-0.1% Co-0.1% Mo/MCM-22, 8% W-0.1% Co-0.3% Mo/MCM-22, 8% W-0.1% Co-0.7% Mo/MCM-22 and 8% W-0.1% Co-0.9% Mo/MCM-22.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalyticdehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 7.
TABLE 7
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.1％Co-0.1％Mo/ MCM-22 | 13.2 | 58.2 | 4.1 | 4.2 | 1.0 |
| 8％W-0.1％Co-0.3％Mo/ MCM-22 | 15.8 | 66.0 | 4.5 | 3.3 | 0.8 |
| 8％W-0.1％Co-0.7％Mo/ MCM-22 | 15.3 | 62.6 | 4.3 | 3.4 | 0.8 |
| 8％W-0.1％Co-0.9％Mo/ MCM-22 | 15.8 | 60.7 | 4.6 | 3.7 | 1.0 |
Example 8:
according to WO of example 5x-GaOy-ZnOy′Procedure for preparation of/MCM-22 catalyst, maintenance of (NH)4)2WO4、Ga(NO3)3Andthe material input of the carrier MCM-22 molecular sieve is unchanged, and Zn (NO) is changed3)2The four supported double-promoted W-based catalysts with different Zn contents are respectively prepared, namely: 8% W-0.1% Ga-0.1% Zn/MCM-22, 8% W-0.1% Ga-0.3% Zn/MCM-22, 8% W-0.1% Ga-0.5% Zn/MCM-22 and 8% W-0.1% Ga-0.9% Zn/MCM-22.
The experiment for preparing aromatic hydrocarbon by methane non-oxidative catalytic dehydrogenation and aromatization is the same as that of example 1. The evaluation results are shown in Table 8.
TABLE 8
| Catalyst sample | CH4Conversion rate (％) | Selectivity to C-containing product (C%) | |||
| C6H6(Ben.) | C7H8(Tol.) | C2H4 | C2H6 | ||
| 8％W-0.1％Ga-0.1％Zn/ MCM-22 | 13.9 | 52.2 | 7.5 | 5.4 | 1.3 |
| 8％W-0.1％Ga-0.3％Zn/ MCM-22 | 14.4 | 62.3 | 5.1 | 5.9 | 1.2 |
| 8％W-0.1％Ga-0.5％Zn/ MCM-22 | 14.9 | 68.8 | 7.6 | 6.3 | 1.2 |
| 8％W-0.1％Ga-0.9％Zn/ MCM-22 | 14.2 | 63.3 | 5.2 | 8.1 | 1.2 |
Claims (6)
1. The non-oxidative catalytic dehydrogenation and aromatization of methane toprepare aromatic hydrocarbon supported catalyst is characterized by that the chemical formula of said catalyst is: non-promoted type WOx/MCM-22 or promoted formWOx-AOyThe catalyst takes MCM-22 zeolite molecular sieve as a carrier; WOxIn which x is 1/2 of the valence of W, WOxThe mass percentage content of (A) is 3-15% in terms of corresponding W reduced scale, AOyIs a metal oxide auxiliary, AOyA in the formula (I) is one or two metal elements selected from Zn, Mo, Ga and Co, AOyY in (A) 1/2, AOyThe content of the component A is 0.1 to 2.0 percent by corresponding A reduced scale, and the balance is MCM-22 molecular sieve;
2. the supported catalyst for producing aromatic hydrocarbons by non-oxidative catalytic dehydroaromatization of methane according to claim 1 wherein the non-promoted form of WO isxThe preparation steps of the/MCM-22 catalyst are as follows: firstly, drying a measured MCM-22 zeolite molecular sieve carrier at 373-393K, and then drying the dried MCM-22 zeolite molecular sieve carrier by H2SO4Acidified to pH 1.5 with a measured amount of W (NH)4)2WO4Soaking the water solution on the support, drying the soaked sample at 373-393K, and roasting the sample at 673-873K for 4-8 hours to obtain the supported non-promoted WOxA/MCM-22 catalyst.
3. The supported catalyst for producing aromatic hydrocarbons by non-oxidative catalytic dehydroaromatization of methane according to claim 1 wherein the promoted form of WO isx-AOyThe preparation steps of the/MCM-22 catalyst are as follows: first of all, measured W in (NH)4)2WO4And A (NO) with the amount A3)2yMixing, dissolving in water and passing throughH2SO4Acidifying to prepare a water solution with the pH value of 1.5, soaking the water solution on a measured MCM-22 molecular sieve carrier subjected to 373-393K drying treatment in advance, drying a soaked sample at the temperature of 373-393K, and roasting at the temperature of 673-873K for 4-8 hours to obtain the supported WOx-AOyA/MCM-22 catalyst.
4. The catalyst as claimed in claim 1, wherein the MCM-22 zeolite molecular sieve has Si/Al molar ratio of 20-35, specific surface area of 20-35≥500m2/g。
5. The supported catalyst for preparing aromatic hydrocarbons by non-oxidative catalytic dehydrogenation and aromatization of methane according to claim 1, wherein the catalyst is WOxThe content of (b) is 6-12% by corresponding W reduced amount.
6. The supported catalyst for preparing aromatic hydrocarbons by non-oxidative catalytic dehydrogenation and aromatization of methane according to claim 1, wherein AO isyThe content of (A) is 0.1-1.0% by corresponding A reduced scale.
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| CN104909975A (en) * | 2014-03-10 | 2015-09-16 | 中国科学院大连化学物理研究所 | Method for oxygen-free and direct preparation of ethylene through shape selection on methane with microporous molecular sieve, and catalyst |
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| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
| CN104909975A (en) * | 2014-03-10 | 2015-09-16 | 中国科学院大连化学物理研究所 | Method for oxygen-free and direct preparation of ethylene through shape selection on methane with microporous molecular sieve, and catalyst |
| CN111468170A (en) * | 2020-04-07 | 2020-07-31 | 浙江恒澜科技有限公司 | Molybdenum-tungsten supported catalyst, preparation method and application thereof, and method for preparing anthraquinone from anthracene |
| CN111468170B (en) * | 2020-04-07 | 2022-05-17 | 浙江恒逸石化研究院有限公司 | Molybdenum-tungsten supported catalyst, preparation method and application thereof, and method for preparing anthraquinone from anthracene |
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