CN1187118C - Catalyst for pressurized oxidative coupling of methane to prepare ethylene and its prepn. - Google Patents
Catalyst for pressurized oxidative coupling of methane to prepare ethylene and its prepn. Download PDFInfo
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- CN1187118C CN1187118C CNB021195676A CN02119567A CN1187118C CN 1187118 C CN1187118 C CN 1187118C CN B021195676 A CNB021195676 A CN B021195676A CN 02119567 A CN02119567 A CN 02119567A CN 1187118 C CN1187118 C CN 1187118C
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000005977 Ethylene Substances 0.000 title claims abstract description 7
- 238000005691 oxidative coupling reaction Methods 0.000 title abstract description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 12
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims 3
- 230000008878 coupling Effects 0.000 claims 2
- 238000010168 coupling process Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000003085 diluting agent Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种甲烷加压氧化偶联制乙烯催化剂及制备方法，该催化剂是以SiO2为担体，活性组分由Mn2O3、Na2WO4、SnO2组成，活性组分含量10wt%-20wt%。本发明提供的催化剂用于加压条件下的甲烷氧化偶联反应，在无稀释气、0.6MPa和高空速情况下，可获得33.0%的甲烷转化率和24.1%的C2 +烃收率。The invention discloses a catalyst for producing ethylene by pressurized oxidative coupling of methane and a preparation method thereof. The catalyst uses SiO 2 as a support, and the active components are composed of Mn 2 O 3 , Na 2 WO 4 , and SnO 2 . The content of the active components is 10wt%-20wt%. The catalyst provided by the invention is used for the oxidative coupling reaction of methane under pressurized conditions. Under the conditions of no diluent gas, 0.6 MPa and high space velocity, a methane conversion rate of 33.0% and a yield of C 2 + hydrocarbons of 24.1% can be obtained.
Description
技术领域technical field
本发明涉及一种用于加压条件下甲烷氧化偶联制乙烯反应的催化剂及其制备方法。The invention relates to a catalyst for ethylene oxidative coupling reaction under pressure and a preparation method thereof.
背景技术Background technique
甲烷氧化偶联制乙烯过程是天然气直接转化的最重要的方向之一，当前国内外研究非常活跃并受到普遍关注。涉及甲烷氧化偶联催化剂体系的文献和专利报道非常多，其催化剂多达千余种，多为常压条件下的催化剂体系。但是，用于加压条件下甲烷氧化偶联的催化剂却很少。Aika曾在Journal of Catalysis(J.Catal.1999，181，160)上发表文章报道过SnO2-Li/MgO甲烷氧化偶联催化剂。ZL 91104243.1公开了一种含碱金属如Na和变价金属氧化物如Mn和W的甲烷选择氧化制乙烯催化剂，其催化剂组成为1.9％Mn2O3和5％Na2WO4担载于SiO2，在常压与有稀释气条件下，可得到较高的甲烷转化率和C2 +烃选择性。Lunsford曾在Journal of Catalysis(1995，(154)：163)上发表文章报道过12％Na2WO4/CeO2催化剂可在加压条件下操作。但升高反应压力后，已有的催化剂体系催化活性和选择性下降，不利于在加压条件下操作。The process of oxidative coupling of methane to ethylene is one of the most important directions of direct conversion of natural gas. At present, the research at home and abroad is very active and has attracted widespread attention. There are many literatures and patent reports related to methane oxidative coupling catalyst systems, and there are more than a thousand kinds of catalysts, most of which are catalyst systems under normal pressure conditions. However, few catalysts have been developed for the oxidative coupling of methane under pressure. Aika once published an article in Journal of Catalysis (J. Catal. 1999, 181, 160) and reported SnO 2 -Li/MgO methane oxidative coupling catalyst. ZL 91104243.1 discloses a catalyst for the selective oxidation of ethylene from methane containing alkali metals such as Na and variable-valence metal oxides such as Mn and W. The catalyst composition is 1.9% Mn 2 O 3 and 5% Na 2 WO 4 supported on SiO 2 , under the conditions of normal pressure and diluent gas, higher methane conversion rate and C 2 + hydrocarbon selectivity can be obtained. Lunsford once published an article in Journal of Catalysis (1995, (154): 163) and reported that 12% Na 2 WO 4 /CeO 2 catalyst could be operated under pressure. However, when the reaction pressure is increased, the catalytic activity and selectivity of the existing catalyst system decrease, which is not conducive to operation under pressurized conditions.
发明内容Contents of the invention
本发明的目的在于提供一种适于加压操作的甲烷氧化偶联催化剂及其制备方法，将该催化剂用于加压甲烷氧化偶联反应时，在无稀释气条件下，获得较高的C2 +烃收率，具有较高的时空产率。The purpose of the present invention is to provide a methane oxidative coupling catalyst suitable for pressurized operation and a preparation method thereof. When the catalyst is used for pressurized methane oxidative coupling reaction, under the condition of no diluent gas, a higher C 2+ hydrocarbon yield with high space-time yield.
本发明叙述的催化剂以SiO2为担体，活性组分由Mn2O3、Na2WO4、SnO2组成，活性组分含量10wt％-20wt％，活性组分Mn2O3、Na2WO4、SnO2的摩尔比为1∶1.3∶x，其中x为0.5～10.5。The catalyst described in the present invention uses SiO 2 as a support, the active components are composed of Mn 2 O 3 , Na 2 WO 4 , SnO 2 , the active component content is 10wt%-20wt%, and the active components Mn 2 O 3 , Na 2 WO 4. The molar ratio of SnO 2 is 1:1.3:x, wherein x is 0.5-10.5.
本发明所述催化剂的制备过程如下：The preparation process of catalyst of the present invention is as follows:
本发明所述催化剂通过等体积浸渍法制备。具体方法为：按活性组分Mn2O3、Na2WO4、SnO2的摩尔比为1∶1.3∶x，其中x为0.6～10.8。称取Mn(NO3)2，Na2WO4·2H2O溶于适量的蒸馏水中，将其分别浸渍于SiO2担体上，在80℃-120℃下搅拌并烘干，将含Sn的化合物溶解于水或极性有机溶剂中浸渍于SiO2担体上，在80℃-120℃下烘干，分别在550℃和850℃焙烧制得催化剂。The catalyst of the present invention is prepared by an equal volume impregnation method. The specific method is: the molar ratio of the active components Mn 2 O 3 , Na 2 WO 4 , and SnO 2 is 1:1.3:x, wherein x is 0.6-10.8. Dissolve Mn(NO 3 ) 2 and Na 2 WO 4 ·2H 2 O in an appropriate amount of distilled water, respectively impregnate them on the SiO 2 support, stir and dry at 80°C-120°C, and put the Sn-containing The compound is dissolved in water or a polar organic solvent, impregnated on the SiO 2 carrier, dried at 80°C-120°C, and calcined at 550°C and 850°C respectively to obtain the catalyst.
本发明叙述的含Sn的化合物可以是无机化合物和有机化合物。本发明叙述的有机溶剂可以是甲苯，甲醇。The Sn-containing compound described in the present invention may be an inorganic compound or an organic compound. The organic solvent described in the present invention can be toluene, methyl alcohol.
本发明催化剂在不锈钢反应系统上于750℃、0.6±0.1MPa、100,000h-1、烷氧比为4条件下可以有效的实现甲烷氧化偶联反应，得到的最佳结果为：33.0％甲烷转化率和73.1％C2 +烃选择性。The catalyst of the present invention can effectively realize methane oxidative coupling reaction on a stainless steel reaction system at 750°C, 0.6±0.1MPa, 100,000h -1 , and an alkoxygen ratio of 4, and the best result obtained is: 33.0% methane conversion rate and 73.1% C 2 + hydrocarbon selectivity.
本发明叙述的催化剂与现有技术相比，有如下优点：Compared with the prior art, the catalyzer described in the present invention has the following advantages:
1、催化剂含有三种变价金属氧化物，活性组分含量高。1. The catalyst contains three kinds of metal oxides with variable valence, and the content of active components is high.
2、催化剂在甲烷氧化偶联反应过程中，反应原料气不需要稀释气，在加压(0.6MPa)和高空速下可获得较高的C2烃收率。2. In the process of methane oxidative coupling reaction, the reaction raw material gas does not need diluent gas, and a higher yield of C2 hydrocarbons can be obtained under pressurization (0.6MPa) and high space velocity.
3、本发明叙述的催化剂可在较温和的温度条件下实现加压甲烷氧化偶联反应。3. The catalyst described in the present invention can realize the oxidative coupling reaction of pressurized methane under relatively mild temperature conditions.
具体实施方式Detailed ways
实施例1：量取1ml Mn(NO3)2(50％wt)，用20ml蒸馏水稀释，加热至80℃搅拌中一次加入到已加热至80℃的10.5g SiO2，于110℃烘干；称取0.53g Na2WO4溶解于20ml蒸馏水中，加热至80℃搅拌中加入到已加热至80℃的SiO2并烘干；称取3.38g二丁基二月桂酸锡溶解于20ml甲醇中，搅拌加入到已加热至80℃的SiO2，在110℃烘箱中烘烤16小时，转移至550℃马富炉在空气中焙烧4小时，升温至850℃再焙烧8小时制得催化剂。催化剂的催化反应性能数据如下：Example 1: Measure 1ml of Mn(NO 3 ) 2 (50%wt), dilute with 20ml of distilled water, heat to 80°C and add 10.5g of SiO 2 heated to 80°C while stirring, and dry at 110°C; Weigh 0.53g Na 2 WO 4 and dissolve it in 20ml of distilled water, heat it to 80°C while stirring, add it to SiO 2 heated to 80°C and dry it; weigh 3.38g dibutyltin dilaurate and dissolve it in 20ml methanol , stirred and added to SiO 2 heated to 80°C, baked in an oven at 110°C for 16 hours, transferred to a muffle furnace at 550°C and baked in air for 4 hours, then heated to 850°C and baked for 8 hours to prepare the catalyst. The catalytic performance data of the catalyst are as follows:
催化剂 温度 压力 甲烷流 CH4/ CH4转 C2+选 C2+收Catalyst Temperature Pressure Methane flow CH 4 / CH 4 to C 2+ to C 2+
装量g ℃ MPa 速L/h O2 化率％ 择性％ 率％Loading g ℃ MPa Velocity L/h O 2 Yield% Selectivity% Rate%
0.4 700 0.6 0.78 4 25.5 60.8 15.50.4 700 0.6 0.78 4 25.5 60.8 15.5
0.4 750 0.6 0.78 4 31.6 71.0 20.40.4 750 0.6 0.78 4 31.6 71.0 20.4
0.4 780 0.6 1.11 4 30.2 61.3 18.50.4 780 0.6 1.11 4 30.2 61.3 18.5
0.4 780 0.6 1.51 4 29.1 62.4 18.20.4 780 0.6 1.51 4 29.1 62.4 18.2
0.4 780 0.6 0.78 4 33.0 73.1 24.10.4 780 0.6 0.78 4 33.0 73.1 24.1
0.4 780 1.0 0.78 4 26.2 60.0 15.60.4 780 1.0 0.78 4 26.2 60.0 15.6
0.4 780 1.5 0.78 4 23.2 46.7 10.80.4 780 1.5 0.78 4 23.2 46.7 10.8
实施例2：取3.0ml Mn(NO3)2(50％wt)，1.59g Na2WO4，用40ml蒸馏水稀释，浸渍于31.5g SiO2上，方法同例1。再用40ml含8.32g二丁基二月桂酸锡的甲苯溶液浸渍到SiO2上。催化剂的烘干于焙烧于例1相同。实施于甲烷氧化偶联结果如下：Example 2: Take 3.0ml of Mn(NO 3 ) 2 (50%wt), 1.59g of Na 2 WO 4 , dilute with 40ml of distilled water, and impregnate on 31.5g of SiO 2 , the method is the same as in example 1. The SiO2 was then impregnated with 40 ml of a toluene solution containing 8.32 g of dibutyltin dilaurate. The drying and roasting of the catalyst are the same as in Example 1. Implemented in methane oxidative coupling results are as follows:
催化剂装量 温度 压力 甲烷流 CH4 CH4 C2+选 C2+收Catalyst loading temperature pressure methane flow CH 4 CH 4 C 2+ or C 2+
g ℃ MPa 速L/h /O2 转化 择性 率％g ℃ MPa Speed L/h /O 2 Conversion Selectivity %
率％ ％ Rate% %
0.4 730 0.6 0.89 8 20.0 75.5 15.10.4 730 0.6 0.89 8 20.0 75.5 15.1
实施例3：取1.0ml Mn(NO3)2(50％wt)，0.53g Na2WO4，用20ml蒸馏水稀释，浸渍于10.5g SiO2上，方法同例1。在浸渍活性组分Sn时采用的是20ml含1.54g SnSO4的10％甲醇水溶液。催化剂的烘干于焙烧于例1相同。用于甲烷氧化偶联评价结果如下：Example 3: Take 1.0ml of Mn(NO 3 ) 2 (50%wt), 0.53g of Na 2 WO 4 , dilute with 20ml of distilled water, and impregnate on 10.5g of SiO 2 , the method is the same as Example 1. When impregnating the active component Sn, 20ml of 10% methanol aqueous solution containing 1.54g SnSO4 was used. The drying and roasting of the catalyst are the same as in Example 1. The evaluation results for methane oxidative coupling are as follows:
催化剂装量 温度 压力 甲烷流 CH4 CH4 C2+选 C2+收Catalyst loading temperature pressure methane flow CH 4 CH 4 C 2+ or C 2+
g ℃ MPa 速L/h /O2 转化 择性 率％g ℃ MPa Speed L/h /O 2 Conversion Selectivity %
率％ ％ Rate% %
0.4 720 0.6 1.11 4 30.2 61.3 18.50.4 720 0.6 1.11 4 30.2 61.3 18.5
实施例4：取2.5ml Mn(NO3)2(50％wt)，1.32g Na2WO4，用20ml蒸馏水稀释，浸渍于25.0g SiO2上，方法同例1。在浸渍活性组分Sn时采用的是40ml含3.30gSnCl2的5％甲醇水溶液。催化剂的烘干于焙烧于例1相同。实施于甲烷氧化偶联结果如下：Example 4: Take 2.5ml of Mn(NO 3 ) 2 (50%wt), 1.32g of Na 2 WO 4 , dilute with 20ml of distilled water, and impregnate on 25.0g of SiO 2 , the method is the same as Example 1. What adopted when impregnating active component Sn is 40ml containing 3.30gSnCl 5% methanol aqueous solution. The drying and roasting of the catalyst are the same as in Example 1. Implemented in methane oxidative coupling results are as follows:
催化剂装量 温度 压力 甲烷流 CH4 CH4 C2+选 C2+收Catalyst loading temperature pressure methane flow CH 4 CH 4 C 2+ or C 2+
g ℃ MPa 速L/h /O2 转化 择性 率％g ℃ MPa Speed L/h /O 2 Conversion Selectivity %
率％ ％ Rate% %
0.4 710 0.6 0.78 4 27.1 67.0 18.10.4 710 0.6 0.78 4 27.1 67.0 18.1
从以上详细实施例看，本发明提供的由多种变价金属氧化物组成的催化剂，在加压甲烷氧化偶联反应中表现出良好的催化活性。From the above detailed examples, the catalyst provided by the present invention composed of various metal oxides with variable valences exhibits good catalytic activity in the pressurized methane oxidative coupling reaction.
Claims (5)
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| US11298684B2 (en) | 2017-03-13 | 2022-04-12 | East China Normal University | Catalyst for oxidative coupling of methane, preparation method thereof and application thereof |
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| CN112934216A (en) * | 2019-12-10 | 2021-06-11 | 中国石油化工股份有限公司 | Methane oxidative coupling catalyst, preparation method thereof and method for preparing carbon-dioxide hydrocarbon by methane oxidative coupling |
| CN113244909B (en) * | 2021-05-07 | 2023-02-28 | 中国科学院山西煤炭化学研究所 | Catalyst for producing C2 hydrocarbons through oxidative coupling of methane, preparation method and application thereof |
| WO2024157807A1 (en) * | 2023-01-27 | 2024-08-02 | 三菱重工業株式会社 | Oxidative coupling catalyst, method for producing oxidative coupling catalyst, and method for producing hydrocarbons |
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2002
- 2002-05-25 CN CNB021195676A patent/CN1187118C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11298684B2 (en) | 2017-03-13 | 2022-04-12 | East China Normal University | Catalyst for oxidative coupling of methane, preparation method thereof and application thereof |
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