CN1046098C - Coupling catalyst for methane oxidation under steam dilution - Google Patents

Coupling catalyst for methane oxidation under steam dilution Download PDF

Info

Publication number
CN1046098C
CN1046098C CN93112016A CN93112016A CN1046098C CN 1046098 C CN1046098 C CN 1046098C CN 93112016 A CN93112016 A CN 93112016A CN 93112016 A CN93112016 A CN 93112016A CN 1046098 C CN1046098 C CN 1046098C
Authority
CN
China
Prior art keywords
catalyst
calcium
methane
alkaline earth
earth metal
Prior art date
Application number
CN93112016A
Other languages
Chinese (zh)
Other versions
CN1096469A (en
Inventor
徐竹生
林励吾
张涛
吴金荣
臧连发
王涛
刘增林
Original Assignee
中国科学院大连化学物理研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Priority to CN93112016A priority Critical patent/CN1046098C/en
Publication of CN1096469A publication Critical patent/CN1096469A/en
Application granted granted Critical
Publication of CN1046098C publication Critical patent/CN1046098C/en

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

一种甲烷氧化偶联催化剂,是在有水蒸汽稀释的反应条件下,即在甲烷、氧和水共进料的状态下使用的甲烷氧化偶联催化剂,其特征在于,催化剂以氧化钙为主活性物质,添加一定量的除钙以外的碱土金属氧化物作为助剂,其含量为(金属原子百分比)除钙以外的碱土金属1~40,钙余。 One of methane oxidative coupling catalysts, under reaction conditions, dilution steam, i.e., methane oxidative coupling catalyst used in the methane, oxygen and water co-feed state, characterized in that the calcium oxide-based catalyst active substance, adding an amount of alkaline earth metal oxides other than calcium as an adjuvant, in an amount of (metal atom percent) of alkaline earth metals other than calcium 1 to 40, than calcium. 本发明不含碱金属元件素是一种具有良好高温热稳定性的催化剂,并且在水蒸汽稀释的情况下又能保持优良的甲烷氧化偶联反应性能。 No alkali metal element of the present invention is a prime catalyst having good thermal stability, and can maintain an excellent methane oxidation coupling reaction performance in the case of dilution steam.

Description

水蒸汽稀释下甲烷氧化偶联催化剂 Methane oxidation coupling catalyst under steam dilution

本发明涉及甲烷氧化偶联生成C2烃以上碳氢化合物技术,特别是在水蒸汽稀释条件下所使用的催化剂。 The present invention relates to the oxidative coupling of methane to C2 hydrocarbons generate more hydrocarbon technology, especially in the catalyst is diluted with steam conditions used.

甲烷氧化偶联是一个高温强放热反应,因此,在放大过程中,为了控制反应温度,在固定床反应工艺中,通常采用分段进氧及中间冷却的多段式反应器,水蒸汽是最理想的中间冷却剂,在反应气中添加一定量的水蒸汽有利于控制反应温度,USP4,788,372提出了反应物中添加水对变价金属氧化物催化剂可提高其甲烷氧化偶联反应的选择性,其组成为(1)变价元素为Mn,Sn,In,Ge,Pb,Sb,Bi,Tb,Ce,Feand/or Ru,(2)碱金属元素,(3)硼元素,(4)除钙以外的碱土金属元素,典型的催化剂为0.5B∶1Na∶1Mn∶2.5Mg和0.6B∶0.5Li∶1Mn∶2.9Mg∶0.3Si。 Oxidative coupling of methane is a highly exothermic reaction temperature, therefore, the amplification process in order to control the reaction temperature, the reaction process in a fixed bed, multi-stage reactor is usually segmented into intermediate cooling and oxygen, water vapor is the most over the middle of the coolant, the reaction gas in an amount of water added to facilitate control of the reaction temperature steam, USP4,788,372 proposes selectively adding water to the reactants variable valence metal oxide catalyst can be improved oxidative coupling reaction of methane, consisting of (1) variable price elements Mn, Sn, In, Ge, Pb, Sb, Bi, Tb, Ce, Feand / or Ru, (2) an alkali metal element, and (3) boron, (4) addition of calcium alkaline earth metal element other than, and typically catalysts 0.5B:1Na:1Mn:2.5Mg 0.6B:0.5Li:1Mn:2.9Mg:0.3Si. USP4,801,762提出了反应物中添加水对不变价金属氧化物催化剂可提高其甲烷氧化偶联反应的选择性,其组成为碱金属和除钙以外的碱土金属氧化物,典型的催化剂为Li/MgO。 USP4,801,762 proposes selectively adding water to the reactants constant divalent metal oxide catalyst can be improved oxidative coupling reaction of methane, consisting of alkali metal and alkaline earth metal oxides other than calcium, the catalyst is typically Li / MgO. 上述加水的甲烷氧化偶联反应中,其催化剂都含有碱金属组分,而碱金属元素在高温下容易流失,如若在反应气中添加水,那就更加速碱金属组分的流失,使催化剂在反应中很快失活。 Reaction of the oxidative coupling of methane with water in which the catalyst contains an alkali metal component, an alkali metal element and at high temperatures easily lost, should the water is added in the reaction gas, that will accelerate the loss of the alkali metal component, the catalyst soon inactivation in the reaction.

本发明的目的在于提供一种不含碱金属元素具有良好高温热稳定性的催化剂,并且在水蒸汽稀释的情况下又能保持优良的甲烷氧化偶联反应性能。 Object of the present invention to provide a catalyst containing no alkali metal element having good thermal stability, and can maintain an excellent methane oxidation coupling reaction performance in the case of dilution steam.

本发明所提供的甲烷氧化偶联催化剂,是在有水蒸汽稀释的反应条件下,即在甲烷、氧和水共进料的状态下使用的甲烷氧化偶联催化剂,其特征在于,催化剂以氧化钙为主活性物质,添加一定量的第二元素除钙以外的碱土金属氧化物作为助剂形成二元体系催化剂,具体含量为(金属原子百分比)除钙以外的碱土金属 钙1~40 余除钙以外的碱土金属的含量最好在5~25。 Methane oxidation coupling catalyst provided by the present invention, under the reaction conditions of the dilution water vapor, methane oxidative coupling catalyst that is used in the methane, oxygen and water co-feed state, characterized in that the oxidation catalyst calcium-based active material, a certain amount of the second element of alkaline earth metal oxides other than calcium binary system is formed as an auxiliary catalyst, in particular an amount of (metal atom percent) calcium alkaline earth metal other than calcium in addition to 1 to 40 content of alkaline earth metal other than calcium is preferably 5 to 25. 本发明所提供的催化剂还可以再添加La系金属稀土元素化合物形成三元体系催化剂,具体含量为除钙以外的碱土金属 稀土元素 钙1~40 2~35 余除钙以外的碱土金属的含量最好在5~25%,稀土金属最好为2~30。 The catalyst provided by the present invention may also add a rare earth element La-based metal compound form a ternary catalyst system, particularly a calcium content of an alkaline earth metal rare earth elements other than calcium 1 to 40 2 to 35 other than the content of alkaline earth metal other than calcium most Fortunately, 5 to 25%, preferably from 2 to 30 rare earth metal.

本发明所提供的催化剂可以通过将助剂原料与氧化钙采用浸渍法或湿混法制备,烘干温度100~140℃,焙烧温度500~900℃,当催化剂为二元体系时,助剂原料为除钙以外的碱土金属的硝酸盐、氯化物、碳酸盐、草酸盐、氧化物或氢氧化物等;当催化剂为三元体系时,助剂原料为除钙以外的碱土金属和稀土金属的硝酸盐、氯化物、碳酸盐、草酸盐、氧化物或氢氧化物等。 The catalyst of the present invention may be provided with calcium oxide feed additives by a dipping method or a wet mixing prepared, drying temperature 100 ~ 140 ℃, firing temperature 500 ~ 900 ℃, when the catalyst is a binary system, the feed additives nitrates of alkaline earth metals other than calcium, chlorides, carbonates, oxalates, hydroxides, oxides, or the like; and when the catalyst is a ternary system, auxiliary raw materials other than calcium and rare earth metal metal nitrates, chlorides, carbonates, oxalates, hydroxides, oxides, or the like. 本发明所提供的催化剂在甲烷氧化偶联反应生成C2烃。 The catalyst of the present invention is provided in the oxidative coupling reaction of methane to C2 hydrocarbons. 以上的碳氢化合物中的应用,应采用甲烷、氧和水共同进料的方式,反应条件如下:H2O/CH4为0.5~3(摩尔比),CH4/O2为2~10(摩尔比),反应温度为700~1200℃,甲烷空速为1000~10000h-1,反应压力为0.01~1MPa。 Application of the above hydrocarbons, the mode should be methane, oxygen and water co-feed, the reaction conditions were as follows: H2O / CH4 0.5 to 3 (molar ratio), CH4 / O2 2 to 10 (molar ratio), The reaction temperature is 700 ~ 1200 ℃, methane space velocity of 1000 ~ 10000h-1, reaction pressure 0.01 ~ 1MPa. 本发明利用水蒸汽稀释的方法,以甲烷,氧和水共进料进行甲烷氧化偶联反应,大大的提高了甲烷氧化偶联反应性能,所用的催化剂,不含碱金属元素,在反应温度下,排除了催化剂活性组分的流失,增加了催化剂在高温下的稳定性,从而可极大的提高催化剂的使用寿命,由于利用水蒸汽作为反应的稀释气,增加了热传导性能,有利于工艺放大,因此,对于甲烷氧化偶联制乙烯的工业应用有较大的实用意义。 The present invention utilizes steam dilution method, methane, oxygen and water cofeed oxidative coupling reaction of methane, the methane coupling greatly improve performance of the oxidation reaction, the catalyst used, alkali metal elements, at a reaction temperature , excluding the loss of the catalyst active components, increased catalyst stability at high temperatures, which can greatly improve the service life of the catalyst, since the reaction of water vapor as the diluent gas, increasing the thermal conductivity, the process is conducive to enlarge Therefore, the industrial applications of ethylene coupling has great practical significance for methane oxidation. 下面通过实施例详述本发明。 The present invention is described in detail below by way of Examples.

实例1:7.55g硝酸锶加入50ml蒸馏水至完全溶解,10g粉末氧化钙缓慢加入硝酸锶溶液中,充分搅拌,放置24小时后,在水浴上蒸干,然后在120℃烘4小时,置入马弗炉中,500℃焙烧5小时,900℃焙烧10小时,制成含量为22%Sr/CaO催化剂,在水蒸汽稀释的条件下其甲烷氧化偶联反应性能如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 700 5400 5.5 0.4 10.24 38.31 3.922 800 5400 5.5 0.4 21.34 58.96 12.582 860 5400 5.5 0.2 24.79 69.38 17.202 700 5400 4.0 0.4 7.56 39.75 3.002 800 5400 4.0 0.4 19.77 50.95 10.072 875 5400 4.0 0.2 30.64 60.54 18.55在2ml装量上较长时间甲烷 Example 1: 7.55g of strontium nitrate in 50ml distilled water until completely dissolved, 10g powder of calcium oxide, strontium nitrate solution was slowly added, stirred well, after 24 hours, evaporated to dryness on a water bath, and then baked at 120 deg.] C for 4 hours and placed horse Eph oven, 500 ℃ calcined 5 hours, 900 deg.] C calcined 10 hours to prepare an amount of 22% Sr / CaO catalyst at conditions which steam dilution performance of the oxidation reaction of methane coupling is as follows: reaction temperature of catalyst loading amount of methane empty speed CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 700 5400 5.5 0.4 10.24 38.31 21.34 5.5 0.4 3.922 8,005,400 8,605,400 5.5 0.2 58.96 12.582 69.38 17.202 24.79 4.0 0.4 7.56 7,005,400 8,005,400 4.0 0.4 3.002 39.75 19.77 50.95 10.072 8755400 60.54 18.55 4.0 0.2 30.64 2ml mounted on a longer amount of methane 氧化偶联反应性能的考察反应时间 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(hr) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)0 860 5400 5.5 0.2 24.49 69.27 16.9610 860 5400 5.5 0.2 25.07 69.10 17.3220 860 5400 5.5 0.2 25.12 68.87 17.3030 860 5400 5.5 0.2 24.80 67.63 16.7740 860 5400 5.5 0.2 23.95 69.25 16.5850 860 5400 5.5 0.2 24.70 68.33 16.8560 860 5400 5.5 0.2 24.94 67.83 16.9270 860 5400 5.5 0.2 24.65 68.13 16.7980 860 5400 5.5 0.2 25.01 67.10 16.7890 860 5400 5.5 0.2 24.45 66.96 16.37100 860 5400 5.5 0.2 24.80 66.86 16.58实例24.36gBaCl2.2H2O加入50 The influence of reaction time the performance of the reaction temperature of the methane oxidative coupling reaction space velocity CH4 / O2 CH4 conversion into the water C2 C2 selectivity Yield (hr) (℃) (h-1) (ml / min) (mol%) (mol %) (mol%) 0 860 5400 5.5 0.2 24.49 69.27 16.9610 860 5400 5.5 0.2 25.07 69.10 17.3220 860 5400 5.5 0.2 25.12 68.87 17.3030 860 5400 5.5 0.2 24.80 67.63 16.7740 860 5400 5.5 0.2 23.95 69.25 16.5850 860 5400 5.5 0.2 24.70 68.33 16.8560 860 5400 5.5 0.2 5.5 24.94 67.83 16.9270 8,605,400 8,605,400 0.2 5.5 24.65 68.13 0.2 16.7980 16.7890 25.01 67.10 24.45 66.96 0.2 5.5 8,605,400 8,605,400 5.5 0.2 16.37100 24.80 66.86 16.58 example 50 was added 24.36gBaCl2.2H2O ml蒸馏水至完全溶解,10g粉末氧化钙缓慢加入氯化钡溶液中,充分搅拌,放置24小时后,在水浴上蒸干,然后在120℃烘4小时,置入马弗炉中,500℃焙烧5小时,900℃焙烧10小时,制成含量为9.06%Ba/CaO催化剂,在水蒸汽稀释的条件下其甲烷氧化偶联反应性能如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 850 5400 5.5 0.4 25.61 66.38 17.002 850 5400 4.0 0.4 28.83 61.38 17.702 850 5400 3.0 0.4 33.02 53.98 17.82 ml distilled water until completely dissolved, 10g of calcium oxide powder was slowly added to a solution of barium chloride, thoroughly stirred, after 24 hours, evaporated to dryness on a water bath, and then baked at 120 deg.] C for 4 hours in a muffle furnace, 500 ℃ calcined 5 hours, 900 deg.] C calcined 10 hours to prepare an amount of 9.06% Ba / CaO catalyst performance oxidative coupling of methane as in the dilution steam conditions: temperature of the loading amount of the catalyst space velocity of methane CH4 / O2 CH4 into the water conversion C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 850 5400 5.5 0.4 25.61 66.38 17.002 850 5400 4.0 0.4 28.83 61.38 17.702 8505400 33.02 53.98 3.0 0.4 17.82

实例3实例1催化剂中,Sr含量改为10%,并添加20%La,以硝酸锶、硝酸镧与氧化钙共浸、烘干、焙烧制成20%La-10%Sr/CaO催化剂,在水蒸汽稀释的条件下其甲烷氧化偶联反应性能如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 850 5400 4.0 0.2 29.54 55.74 16.46实例4实例2催化剂中,Ba含量改为5%,并添加20%La,以氯化钡、硝酸镧与氧化钙共浸、干燥、焙烧制成20%La-5%Ba/CaO催化剂,在水蒸汽稀释的条件下其甲烷氧化偶联反应性能如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 850 5400 4.0 0.2 29.29 57.75 16.91实例5实例1催化剂中,Sr含量 Example 3 Example 1 catalyst, Sr content to 10%, and adding 20% ​​La, strontium nitrate, lanthanum nitrate and calcium oxide were dipped, dried, calcined made 20% La-10% Sr / CaO catalyst, diluted with water vapor conditions which OCM properties as follows: reaction temperature loading amount of catalyst space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 850 5400 4.0 0.2 29.54 55.74 16.46 example 4 example 2 catalyst, Ba content was changed to 5%, and adding 20% ​​La, to barium, lanthanum nitrate calcium oxide were dipped, dried, calcined made 20% La-5% Ba / CaO catalyst at conditions which steam dilution OCM properties are as follows: reaction temperature loading amount of catalyst space velocity of methane CH4 / O2 feed water CH4 conversion C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 850 5400 4.0 0.2 29.29 57.75 16.91 example 5 example 1 catalyst, Sr content 为10%,并添加25%La,以硝酸锶、硝酸镧与氧化钙共浸、烘干、焙烧制成25%La-10%Sr/CaO催化剂,在水蒸汽稀释的条件下其甲烷氧化偶联反应性能如下:反应时间 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(hr) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)0 860 7200 4.0 0.2 34.25 63.61 21.8010 860 7200 4.0 0.2 33.66 61.46 20.6920 860 7200 4.0 0.2 34.07 60.42 20.5830 860 7200 4.0 0.2 33.15 61.54 20.4040 860 7200 4.0 0.2 31.85 60.32 18.6650 860 7200 4.0 0.2 32.44 60.32 19.6760 860 7200 4.0 0.2 32.20 59.86 19.2770 860 7200 4.0 0.2 31.88 59.61 19.0080 860 7200 4.0 0.2 32.83 58.92 19.3490 10%, and adding 25% La, strontium nitrate, lanthanum nitrate and calcium oxide were dipped, dried, calcined made 25% La-10% Sr / CaO catalyst in the oxidative coupling of methane steam dilution conditions The reaction with the following properties: The reaction time of the reaction temperature space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (hr) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 0 860 7200 4.0 0.2 34.25 63.61 21.8010 860 7200 4.0 0.2 33.66 61.46 20.6920 860 7200 4.0 0.2 34.07 60.42 20.5830 860 7200 4.0 0.2 33.15 61.54 20.4040 860 7200 4.0 0.2 31.85 60.32 18.6650 860 7200 4.0 0.2 32.44 60.32 19.6760 860 7200 4.0 0.2 4.0 32.20 59.86 19.2770 8,607,200 8,607,200 0.2 4.0 31.88 59.61 0.2 32.83 19.0080 58.92 19.3490 860 7200 4.0 0.2 32.05 59.05 18.97100 860 7200 4.0 0.2 32.66 59.30 19.37催化剂装置1.5ml。 4.0 8,607,200 8,607,200 0.2 4.0 32.05 59.05 0.2 32.66 18.97100 59.30 19.37 catalyst device 1.5ml.

实例6实例1催化剂,在有水和无水的反应条件下,甲烷氧化偶联反应性能比较如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 900 5400 5.5 0 23.63 53.16 12.562 900 5400 5.5 0.4 26.12 65.94 17.222 900 5400 4.0 0 27.39 50.06 13.712 900 5400 4.0 0.4 29.69 60.67 18.01实例7实例2催化剂,在有水和无水的反应条件下,甲烷氧化偶联反应性能比较如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 850 5400 5.5 0 24.00 51.30 12.312 850 5400 4.0 0.4 25.61 66.38 17.00 Example 6 Example 1 catalyst in water and anhydrous reaction conditions, the coupling reaction of methane oxidation performance compared as follows: the reaction temperature means the amount of catalyst space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity Yield (ml ) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 900 5400 5.5 0 23.63 53.16 12.562 900 5400 5.5 0.4 26.12 65.94 17.222 900 5400 4.0 0 27.39 50.06 13.712 900 5400 29.69 60.67 18.01 4.0 0.4 example 7 example 2 catalyst, water and anhydrous reaction conditions, the coupling reaction of methane oxidation performance compared as follows: the reaction temperature means the amount of catalyst space velocity of methane CH4 / O2 selectivity of the conversion into the water CH4 C2 C2 yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 850 5400 5.5 0 24.00 51.30 12.312 850 5400 4.0 0.4 25.61 66.38 17.00

2 850 5400 4.0 0 27.64 48.41 13.382 850 5400 3.0 0.4 28.83 61.38 17.702 850 5400 3.0 0 30.60 36.72 11.242 850 5400 3.0 0.4 33.02 53.98 17.82实例8实例3催化剂,在有水和无水的反应条件下,甲烷氧化偶联反应性能比较如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 850 5400 4.0 0 29.44 52.37 15.422 850 5400 4.0 0.2 29.86 54.86 16.38实例9实例4催化剂,在有水和无水的反应条件下,甲烷氧化偶联反应性能比较如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min)(mol%) (mol%) (mol%)2 850 28505400 0 27.64 48.41 13.382 4.0 3.0 8,505,400 8,505,400 0.4 3.0 28.83 61.38 17.702 36.72 11.242 30.60 0 8,505,400 3.0 0.4 33.02 53.98 17.82 Example 8 The catalyst of Example 3, in water and anhydrous reaction conditions, oxidative coupling of methane The reaction performance comparison are as follows: reaction temperature means the amount of catalyst space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol% ) (mol%) 2 850 5400 4.0 0 29.44 52.37 15.422 850 5400 4.0 0.2 29.86 54.86 16.38 example 9 the catalyst of example 4, in anhydrous and water under the reaction conditions, the coupling reaction of methane oxidation performance compared as follows: the amount of catalyst loading temperature space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 850 5400 4.0 0 28.40 55.70 15.822 850 5400 4.0 0.2 29.29 57.73 16.91实例10实例5催化剂,在有水和无水的反应条件下,甲烷氧化偶联反应性能比较如下:催化剂装量 反应温度 甲烷空速 CH4/O2进水量 CH4转化率 C2选择性 C2产率(ml) (℃) (h-1) (ml/min) (mol%) (mol%) (mol%)2 800 5400 5.5 0 22.51 53.11 11.96 5400 4.0 0 28.40 55.70 29.29 15.822 8505400 57.73 16.91 4.0 Example 10 0.2 Example 5 catalyst in water and anhydrous reaction conditions, the coupling reaction of methane oxidation performance compared as follows: the reaction temperature means the amount of catalyst space velocity of methane CH4 / O2 CH4 conversion into the water C2 C2 selectivity yield (ml) (℃) (h-1) (ml / min) (mol%) (mol%) (mol%) 2 800 5400 5.5 0 22.51 53.11 11.96

2 900 5400 5.5 0 23.75 46.95 11.152 850 5400 5.5 0.2 29.12 63.27 18.43上述结果表明对于双元除钙以外的碱土金属氧化物催化剂,在水蒸汽存在的条件下,无论其甲烷氧化偶联反应活性和C2选择性能都有较大幅度的提高;同样,对于除钙以外的碱土金属和稀土元素的三元金属氧化物催化剂,在有水蒸汽存在的情况下,其甲烷氧化偶联反应性能也有较大的改善。 29005400 11.152 46.95 23.75 0 5.5 5.5 0.2 8505400 29.12 63.27 18.43 The above results show for the binary alkaline earth metal other than calcium oxide catalyst in the presence of steam under the condition, whether reactive oxidative coupling of methane and C2 selection have a more substantial increase performance; Similarly, ternary metal oxide catalyst for the alkaline earth metals and rare earth elements other than calcium, in the presence of water vapor, the coupling reaction of methane oxidation performance has greatly improved .

Claims (6)

1.一种甲烷、氧和水共进料下使用的甲烷氧化偶联催化剂,其特征在于催化剂以氧化钙为主活性物质,添加除钙以外的碱土金属氧化物作为助剂,催化剂的组成为(金属原子百分比)除钙以外的碱土金属 钙1~40 余 A methane, oxidative coupling catalyst and the oxygen co-feed water, characterized in that the catalyst is calcium oxide as a main active material, adding an alkaline earth metal other than calcium oxide as an auxiliary agent, the composition of the catalyst was (metal atom percent) of alkaline earth metal other than calcium Ca 1 to 40
2.一种甲烷、氧和水共进料下使用的甲烷氧化偶联催化剂,其特征在于催化剂以氧化钙为主活性物质,添加除钙以外的碱土金属氧化物和La系金属稀土元素化合物作为助剂,催化剂的组成为(金属原子百分比)除钙以外的碱土金属 稀土元素 钙1~40 2~35 余 A catalyst under oxidative coupling of methane methane, oxygen and water co-feed, wherein the catalyst is calcium oxide as a main active material, adding an alkaline earth metal oxides and rare earth element La-based metal compound other than calcium as adjuvant composition, catalyst (metal atomic%) 1 40 2 ~ 35 ~ I alkaline earth metal rare-earth element other than calcium Ca
3.按权利要求1所述催化剂,其特征在于除钙以外的碱土金属的含量在5~25%。 3. The catalyst according to claim 1, wherein the content of alkaline earth metals other than calcium is in the 5 to 25%.
4.按权利要求2所述催化剂,其特征在于除钙以外的碱土金属的含量在5~25%,稀土金属为2~30%。 4. A catalyst according to claim 2, wherein the content of alkaline earth metals other than calcium is in the 5 to 25%, 2 to 30% of a rare earth metal.
5.权利要求1,2所述催化剂在甲烷氧化偶联反应生成C2烃以上的碳氢化合物中的应用,其特征在于应采用甲烷、氧和水共同进料的方式,反应条件如下:H2O/CH4为0.5~3(摩尔比),CH4/O2为2~10(摩尔比),反应温度为700~1200℃,甲烷空速为1000~10000h-1,反应压力为0.01~1MPa。 The catalyst according to claim 1, 2 generated in Oxidative Coupling of Methane over the application of hydrocarbons to C2 hydrocarbons, characterized in that the mode should be methane, oxygen and water co-feed, the reaction conditions were as follows: H2O / CH4 0.5 to 3 (molar ratio), CH4 / O2 2 to 10 (molar ratio), the reaction temperature is 700 ~ 1200 ℃, methane space velocity of 1000 ~ 10000h-1, reaction pressure 0.01 ~ 1MPa.
6.权利要求1,2,3,4所述催化剂的制备方法,将助剂原料与氧化钙采用浸渍法或湿混法制备,其特征在于烘干温度100~140℃,焙烧温度500~900℃;当催化剂为二元体系时,助剂原料为除钙以外的碱土金属的硝酸盐、氯化物、碳酸盐、草酸盐、氧化物或氢氧化物;当催化剂为三元体系时,助剂原料为除钙以外的碱土金属和稀土金属的硝酸盐、氯化物、碳酸盐、草酸盐、氧化物或氢氧化物。 The method for preparing 1,2,3,4 catalyst of claim 1, the auxiliary material with calcium oxide by impregnation or wet mixing prepared, wherein the drying temperature is 100 ~ 140 ℃, calcination temperature of 500 to 900 ℃; when the catalyst is a binary system, auxiliary raw materials other than the alkaline earth metal nitrate, calcium chloride, carbonate, oxalate, oxide or hydroxide; when the catalyst is a ternary system, the aid material is an alkaline earth metal and rare earth metals other than calcium nitrate, chloride, carbonate, oxalate, oxide or hydroxide.
CN93112016A 1993-06-18 1993-06-18 Coupling catalyst for methane oxidation under steam dilution CN1046098C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN93112016A CN1046098C (en) 1993-06-18 1993-06-18 Coupling catalyst for methane oxidation under steam dilution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN93112016A CN1046098C (en) 1993-06-18 1993-06-18 Coupling catalyst for methane oxidation under steam dilution

Publications (2)

Publication Number Publication Date
CN1096469A CN1096469A (en) 1994-12-21
CN1046098C true CN1046098C (en) 1999-11-03

Family

ID=4989761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN93112016A CN1046098C (en) 1993-06-18 1993-06-18 Coupling catalyst for methane oxidation under steam dilution

Country Status (1)

Country Link
CN (1) CN1046098C (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0196541A1 (en) * 1985-03-19 1986-10-08 Phillips Petroleum Company Methane conversion
WO1991004240A1 (en) * 1989-09-19 1991-04-04 Union Carbide Chemicals And Plastics Company Inc. Perovskite catalysts for oxidative coupling
CN1050864A (en) * 1989-09-19 1991-04-24 联合碳化化学品及塑料有限公司 Low temperature catalysts fer oxidative coupling processes
CN1050862A (en) * 1989-09-19 1991-04-24 联合碳化化学品及塑料有限公司 High ethylene to ethane process for oxidative coupling

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0196541A1 (en) * 1985-03-19 1986-10-08 Phillips Petroleum Company Methane conversion
WO1991004240A1 (en) * 1989-09-19 1991-04-04 Union Carbide Chemicals And Plastics Company Inc. Perovskite catalysts for oxidative coupling
CN1050864A (en) * 1989-09-19 1991-04-24 联合碳化化学品及塑料有限公司 Low temperature catalysts fer oxidative coupling processes
CN1050862A (en) * 1989-09-19 1991-04-24 联合碳化化学品及塑料有限公司 High ethylene to ethane process for oxidative coupling

Also Published As

Publication number Publication date
CN1096469A (en) 1994-12-21

Similar Documents

Publication Publication Date Title
Chen et al. Promoted Fe/ZSM-5 catalysts prepared by sublimation: de-NOx activity and durability in H 2 O-rich streams
Bettahar et al. On the partial oxidation of propane and propylene on mixed metal oxide catalysts
KR100622851B1 (en) Catalyst for the oxidative dehydrogenation of hydrocarbons and preparation thereof
JP3609456B2 (en) Catalyst and method for alkane dehydrogenation
JP4231374B2 (en) Hydrothermally synthesized MO-V-M-NB-X oxide catalyst for selective oxidation of hydrocarbons
CA1070659A (en) Process for the preparation of a palladium catalyst
US6777371B2 (en) Ni catalysts and methods for alkane dehydrogenation
US3975300A (en) One step method of preparation of vanadium-phosphorus complex in the absence of hydrogen halide
CA1265537A (en) Conversion of a lower alkane
US5093299A (en) Catalyst for process for the manufacture of acrylonitrile and methacrylonitrile
EP0179856B1 (en) Methane conversion process
EP0705136B1 (en) New catalyst, and process for dehydrogenating dehydrogenatable hydrocarbons
RU1836140C (en) Catalyst for hydrocarbons dehydration
US6087545A (en) Process for oxidative conversion
US6414209B1 (en) Catalyst for converting paraffinic hydrocarbon into corresponding olefin
US4115518A (en) Gas desulphurization
US5041405A (en) Lithium/magnesium oxide catalyst and method of making
US3258432A (en) Method of preparing catalyst compositions consisting of the oxides of antimony and tin
US2414585A (en) Catalytic dehydrogenation
CA1234842A (en) Methane conversion
US5173468A (en) Compositions of the formula MO12 Pa Vb X1c X2d X3e Sbf Reg Sh On
US4658077A (en) Composition of matter and method of oxidative conversion of organic compounds therewith
US3285882A (en) Catalysts for polyphenylene sulfide type resins
US5055282A (en) Method of decomposing ammonia using a ruthenium catalyst
EP0206044B1 (en) Method of oxidative conversion of organic compounds

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
CF01 Termination of patent right due to non-payment of annual fee
C19 Lapse of patent right due to non-payment of the annual fee