CN1696084A - A kind of method that catalyzes the oxidative coupling of methane to prepare carbon dihydrocarbons - Google Patents
A kind of method that catalyzes the oxidative coupling of methane to prepare carbon dihydrocarbons Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 6
- 238000005691 oxidative coupling reaction Methods 0.000 title abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- -1 AgNO 3 and silver Chemical class 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种甲烷氧化偶联制碳二烃的方法，具有在低温下甲烷氧化偶联的特点。发明选用活性组份为银，载体主要为二氧化硅、三氧化二铝、MCM－41、SBA－15、HZSM－5、HMCM－22的硅铝材料，催化剂采用超声浸渍法或化学牵引法制备。可以在较低的温度下进行甲烷氧化偶联反应。The invention relates to a method for producing carbon dihydrocarbons through oxidative coupling of methane, which has the characteristic of oxidative coupling of methane at low temperature. The active component of the invention is silver, the carrier is mainly silicon dioxide, aluminum oxide, MCM-41, SBA-15, HZSM-5, HMCM-22, and the catalyst is prepared by ultrasonic impregnation or chemical traction. . Methane oxidative coupling reactions can be performed at lower temperatures.
Description
技术领域technical field
本发明涉及一种甲烷氧化偶联制碳二烃的方法。The invention relates to a method for producing carbon dihydrocarbons through oxidative coupling of methane.
背景技术Background technique
随着石油资源的日渐减少，储量丰富的天然气和煤层气资源的有效利用越来越受到重视.甲烷是天然气和煤层气的主要成分(＞90％)，据预测我国可开采天然气储量为12-16万亿m3，煤层气储量约为100万亿m3(其中埋藏深度不超过2000米的有30-35万亿m3，占全球储量的13％)，折合成原油有1,200亿吨；与煤炭相比，天然气的氢碳比高，污染小，是一种清洁的能源。但是天然气(或甲烷)最具有吸引力的一个潜在应用途径是通过甲烷氧化偶联制碳二烃。With the decrease of petroleum resources, the effective utilization of abundant reserves of natural gas and coalbed methane resources has been paid more and more attention. Methane is the main component (>90%) of natural gas and coalbed methane, and it is predicted that China's recoverable natural gas reserves are 12- 16 trillion m 3 , and the reserves of coalbed methane are about 100 trillion m 3 (30-35 trillion m 3 of which are buried at a depth of no more than 2000 meters, accounting for 13% of the global reserves), equivalent to 120 billion tons of crude oil; Compared with coal, natural gas has a higher hydrogen-to-carbon ratio and less pollution, making it a clean energy source. However, one of the most attractive potential applications of natural gas (or methane) is through the oxidative coupling of methane to carbon dihydrocarbons.
研究在尽可能低的温度下，实现甲烷氧化偶联，有重要的科学意义和实用价值，也是一项很有挑战性的课题，传统的甲烷氧化偶联催化剂，AU-8654352和US-4777313专利公开了一种碱金属促进的单一或混合金属氧化物催化剂，AU-A-42806-89和EP418071专利公开了一种碱金属或碱土金属氯化物促进的金属氧化物催化剂；US4914252、AU8652925和EP418971等专利公开了一种金属卤化物负载在Al2O3、SiO2、浮石等惰性载体上的催化利，CN1100669A公开的BaF2/LaOF催化利以及CN1145824A公开的的Sm2O3-LiMgO催化剂，甲烷的转化率和C2烃的选择性较高，是目前报道中较好的催化利。但上述催化剂都存在反应温度高(高于750℃)，低温下无反应活性的弱点，Research on the realization of methane oxidative coupling at the lowest possible temperature has important scientific significance and practical value, and is also a very challenging subject. Traditional methane oxidative coupling catalysts, AU-8654352 and US-4777313 patents A single or mixed metal oxide catalyst promoted by an alkali metal is disclosed. AU-A-42806-89 and EP418071 patents disclose a metal oxide catalyst promoted by an alkali metal or alkaline earth metal chloride; US4914252, AU8652925 and EP418971, etc. The patent discloses a catalyst in which metal halides are supported on inert carriers such as Al 2 O 3 , SiO 2 , pumice, etc., the BaF 2 /LaOF catalyst disclosed in CN1100669A and the Sm 2 O 3 -LiMgO catalyst disclosed in CN1145824A, methane The conversion rate and the selectivity of C2 hydrocarbons are high, and it is a better catalytic benefit in the current reports. However, the above-mentioned catalysts all have the disadvantages of high reaction temperature (higher than 750°C) and no reactivity at low temperature.
担载银催化剂对乙烯环氧化制环氧乙烷的反应具有活性高，选择性好的特点、其中银上的次表层氧具有选择氧化的能力，而表层氧物种导致完全氧化。但文献报道银，氧化银以及担载银催化剂对甲烷氧化偶联反应没有活性，纳米金属粒子由于纳米尺寸效应具有一些独特的催化性能，减小银粒子的尺寸可以使表层氧物种向次表层的迁移变得容易，因此对担载纳米银用于甲烷氧化偶联尚缺乏最基本的了解。The supported silver catalyst has the characteristics of high activity and good selectivity for the reaction of ethylene epoxidation to ethylene oxide, wherein the subsurface oxygen on the silver has the ability of selective oxidation, while the surface oxygen species lead to complete oxidation. However, it has been reported in the literature that silver, silver oxide and supported silver catalysts are not active for the oxidative coupling reaction of methane. Nano-metal particles have some unique catalytic properties due to the nano-size effect. Reducing the size of silver particles can make the surface oxygen species migrate to the subsurface. Migration becomes easy, so the fundamental understanding of supporting nanosilver for methane oxidative coupling is still lacking.
发明内容Contents of the invention
本发明的目的在于提供一种甲烷氧化偶联的方法，所用的催化剂在低温下就具有较好的甲烷氧化偶联活性。The object of the present invention is to provide a method for oxidative coupling of methane, the catalyst used has better methane oxidative coupling activity at low temperature.
本发明的催化剂使用的活性组份为银，载体主要为二氧化硅、三氧化二铝、MCM-41、SBA-15、HZSM-5、HMCM-22的硅铝材料，银在催化剂上的担载量为0.5-20％。The active component that catalyst of the present invention uses is silver, and carrier is mainly the silicon-aluminum material of silica, aluminum oxide, MCM-41, SBA-15, HZSM-5, HMCM-22, and the support of silver on catalyst The loading is 0.5-20%.
本发明的催化剂载体可以来自市售或自行合成，合成方法参照文献。银可以来自盐类或金属，如：AgNO3和银等。The catalyst carrier of the present invention can be commercially available or self-synthesized, and the synthesis method refers to literature. Silver can come from salts or metals, such as: AgNO 3 and silver, etc.
本发明所用催化剂的制备方法可以是超声浸渍法。The preparation method of the catalyst used in the present invention may be an ultrasonic impregnation method.
本发明中浸渍时所用的银盐浓度为0.5×10-4-5×10-4molAg/ml，浸渍时间为5-10h，干燥温度为50-200℃，干燥时间5-24h，焙烧温度为200-600℃，焙烧时间为2-8h。The concentration of silver salt used during immersion in the present invention is 0.5×10 -4 -5×10 -4 molAg/ml, the immersion time is 5-10h, the drying temperature is 50-200°C, the drying time is 5-24h, and the roasting temperature is 200-600°C, the roasting time is 2-8h.
催化剂的浸渍制备过程是：将载体加入到适量的银盐溶液中，超声浸渍，干燥、焙烧、处理即可得到所需的催化剂。The impregnation preparation process of the catalyst is as follows: the carrier is added to an appropriate amount of silver salt solution, ultrasonically impregnated, dried, calcined and treated to obtain the required catalyst.
催化剂的评价在固定床反应器中，于常压下，使用CH4∶O2＝80∶1-2∶1的原料气，空速为10,000h-1的条件下进行的。反应温度为400-800℃。Catalyst evaluation was carried out in a fixed-bed reactor under normal pressure, using feed gas of CH 4 : O 2 =80:1-2:1, and a space velocity of 10,000 h -1 . The reaction temperature is 400-800°C.
本发明的催化甲烷氧化偶联方法可以在较低的温度下实现甲烷氧化偶联制碳二烃，实现了低温下无甲烷氧化偶联活性的突破，不仅对应用研究而且对基础研究都有重要的指导意义。The catalytic methane oxidative coupling method of the present invention can realize the oxidative coupling of methane to produce carbon dihydrocarbons at a relatively low temperature, and realizes a breakthrough without methane oxidative coupling activity at low temperature, which is important not only for applied research but also for basic research guiding significance.
具体实施方式Detailed ways
下面由实施举例对本发明作进一步的说明。The present invention will be further described below by implementing examples.
实施例1：Example 1:
称取二氧化硅载体20克，投入45ml 0.2mol/l的室温硝酸银溶液中，超声浸渍10h，100℃干燥12h，500℃焙烧5h，得到所需催化剂。由TEM分析得，银粒子的平均直径为4-5nm。在原料气组成为CH4∶O2＝50∶1，He平衡(体积百分比)，气体体积空速为1.0×104h-1的情况下，在550℃时的碳二的时空产率为22mmol/kgh；在700℃时的时空产率为700mmol/kgh。Weigh 20 grams of silica carrier, put it into 45 ml of 0.2 mol/l silver nitrate solution at room temperature, ultrasonically impregnate for 10 hours, dry at 100°C for 12 hours, and calcinate at 500°C for 5 hours to obtain the desired catalyst. According to TEM analysis, the average diameter of the silver particles is 4-5 nm. Under the condition that the raw material gas composition is CH 4 : O 2 =50:1, He balance (volume percentage), and the gas volume space velocity is 1.0×10 4 h -1 , the space-time yield of C2 at 550°C is 22mmol/kgh; the space-time yield at 700°C is 700mmol/kgh.
实施例2：Example 2:
步骤同实施例1，但以SBA-15载体代替二氧化硅载体，其它不变，得到所需的催化剂。由TEM分析得，银粒子的平均直径为4-5nm。在原料气组成为CH4∶O2＝80∶1，He平衡(体积百分比)，气体体积空速为1.0×104h-1的情况下，在550℃时的碳二的时空产率为134mmol/kgh；在700℃时的碳二时空产率为1405mmol/kgh。The steps are the same as in Example 1, but the SBA-15 carrier is used instead of the silica carrier, and other changes are made to obtain the desired catalyst. According to TEM analysis, the average diameter of the silver particles is 4-5 nm. Under the condition that the feed gas composition is CH 4 : O 2 =80:1, He is balanced (volume percentage), and the gas volume space velocity is 1.0×10 4 h -1 , the space-time yield of C2 at 550°C is 134mmol/kgh; the space-time yield of C2 at 700°C was 1405mmol/kgh.
实施例3：Example 3:
步骤同实施例1，但以HZSM-5载体代替二氧化硅载体，其它不变，得到所需的催化剂。由TEM分析得，银粒子的平均直径为2-3nm。在原料气组成为CH4/O2＝50∶1，He平衡(体积百分比)，气体体积空速为1.0×104h-1的情况下，在400℃时的碳二的时空产率为5mmol/kgh。The steps are the same as in Example 1, but the HZSM-5 carrier is used instead of the silica carrier, and other changes are made to obtain the desired catalyst. According to TEM analysis, the average diameter of silver particles is 2-3nm. Under the condition that the feed gas composition is CH 4 /O 2 =50:1, He balance (volume percentage), and the gas volume space velocity is 1.0×10 4 h -1 , the space-time yield of carbon two at 400°C is 5mmol/kgh.
实施例4：Example 4:
步骤同实施例3，但以0.4mol/l的硝酸银溶液代替0.2mol/l的硝酸银溶液，其它不变，得到所需的催化剂。在原料气组成为CH4/O2＝50∶1，He平衡(体积百分比)，气体体积空速为1.0×104h-1的情况下，在400℃时的碳二的时空产率为40mmol/kgh。The steps are the same as in Example 3, but the silver nitrate solution of 0.4 mol/l is used instead of the silver nitrate solution of 0.2 mol/l, and the others remain unchanged to obtain the required catalyst. Under the condition that the feed gas composition is CH 4 /O 2 =50:1, He balance (volume percentage), and the gas volume space velocity is 1.0×10 4 h -1 , the space-time yield of carbon two at 400°C is 40mmol/kgh.
实施例5：Example 5:
催化剂制备同实施例2，得到所需的催化剂。在原料气组成为CH4/O2＝3∶1，He平衡(体积百分比)，气体体积空速为1.0×104h-1的情况下，在550℃时的碳二的时空产率为84mmol/kgh；在700℃时的碳二时空产率为2032mmol/kgh。Catalyst preparation is the same as in Example 2 to obtain the desired catalyst. Under the condition that the feed gas composition is CH 4 /O 2 =3:1, He balance (volume percentage), and the gas volume space velocity is 1.0×10 4 h -1 , the space-time yield of carbon two at 550°C is 84mmol/kgh; the space-time yield of carbon two at 700°C is 2032mmol/kgh.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385982B (en) * | 2007-09-14 | 2010-11-24 | 北京化工大学 | A mesoporous molecular sieve catalyst for oxidative coupling of methane to ethylene and preparation method thereof |
| CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
| CN105330501A (en) * | 2015-11-13 | 2016-02-17 | 厦门中科易工化学科技有限公司 | Method for chlorinating and coupling methanol |
| CN105451874A (en) * | 2013-08-23 | 2016-03-30 | 沙特基础工业公司 | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105658605A (en) * | 2013-11-11 | 2016-06-08 | 沙特基础工业公司 | Process for converting methane to C2+ hydrocarbons |
| CN108136370A (en) * | 2015-07-15 | 2018-06-08 | 沙特基础工业全球技术公司 | Promote catalyst for the silver of methane oxidation coupling |
| CN111203285A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane |
| CN111790369A (en) * | 2020-07-14 | 2020-10-20 | 福州大学 | A silver-supported black indium-based composite photothermal catalytic material for methane coupling and its preparation method and application |
| CN115487853A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxycarbonate and silver loaded molecular sieve and preparation method and application thereof |
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2004
- 2004-05-10 CN CN 200410042178 patent/CN1696084A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385982B (en) * | 2007-09-14 | 2010-11-24 | 北京化工大学 | A mesoporous molecular sieve catalyst for oxidative coupling of methane to ethylene and preparation method thereof |
| US9770700B2 (en) * | 2013-08-23 | 2017-09-26 | Saudi Basic Industries Corporation | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105451874A (en) * | 2013-08-23 | 2016-03-30 | 沙特基础工业公司 | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| US20160199806A1 (en) * | 2013-08-23 | 2016-07-14 | Saudi Basic Industries Corporation | Reactor comprising a plasma source and a catalyst comprising a mesoporous support material for the preparation of ethene from methane |
| CN105658605A (en) * | 2013-11-11 | 2016-06-08 | 沙特基础工业公司 | Process for converting methane to C2+ hydrocarbons |
| CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
| CN108136370A (en) * | 2015-07-15 | 2018-06-08 | 沙特基础工业全球技术公司 | Promote catalyst for the silver of methane oxidation coupling |
| CN105330501A (en) * | 2015-11-13 | 2016-02-17 | 厦门中科易工化学科技有限公司 | Method for chlorinating and coupling methanol |
| CN111203285A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane |
| CN111790369A (en) * | 2020-07-14 | 2020-10-20 | 福州大学 | A silver-supported black indium-based composite photothermal catalytic material for methane coupling and its preparation method and application |
| CN111790369B (en) * | 2020-07-14 | 2021-07-13 | 福州大学 | A silver-supported black indium-based composite photothermal catalytic material for methane coupling and its preparation method and application |
| CN115487853A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxycarbonate and silver loaded molecular sieve and preparation method and application thereof |
| CN115487853B (en) * | 2021-06-18 | 2023-11-10 | 中国石油化工股份有限公司 | Mixed catalyst containing lanthanum oxide carbonate and silver loaded molecular sieve, and preparation method and application thereof |
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