CN1065852C - Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor - Google Patents
Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000007772 electroless plating Methods 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 210000004379 membrane Anatomy 0.000 claims 6
- 210000002469 basement membrane Anatomy 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 208000012839 conversion disease Diseases 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种Pd/陶瓷复合膜反应器中的气相催化脱氢和加氢耦合反应，其特征在于是采用的膜材料为Pd/陶瓷复合膜。该复合膜是用化学镀的方法，在陶瓷基膜经过表面改性修饰以后，将金属钯沉积在基膜的表面，形成厚度为1～10μm的Pd/陶瓷超薄钯复合膜。利用该膜反应器进行加、脱氢催化反应中还应分别在膜的两侧反应腔内装填催化剂。该反应过程不仅实现了传统的反应工艺不能得到的结果，也提高了工程上单位设备体积的生产效率，极大地简化了工艺过程，降低了设备投资，易于实现工业化。A gas-phase catalytic dehydrogenation and hydrogenation coupling reaction in a Pd/ceramic composite membrane reactor is characterized in that the membrane material used is a Pd/ceramic composite membrane. The composite film adopts the electroless plating method, and after the surface of the ceramic base film is modified, metal palladium is deposited on the surface of the base film to form a Pd/ceramic ultra-thin palladium composite film with a thickness of 1-10 μm. Catalysts should also be filled in the reaction chambers on both sides of the membrane when the membrane reactor is used for the catalytic reactions of addition and dehydrogenation. The reaction process not only achieves the results that cannot be obtained by the traditional reaction process, but also improves the production efficiency per unit equipment volume in the project, greatly simplifies the process, reduces equipment investment, and is easy to realize industrialization.
Description
本发明涉及一化学反应过程，具体地说是提供利用Pd／陶瓷复合膜反应器，进行气相催化脱氢和加氢的一类耦合反应。The invention relates to a chemical reaction process, in particular, it provides a kind of coupling reaction for gas-phase catalytic dehydrogenation and hydrogenation by using a Pd/ceramic composite membrane reactor.
膜反应过程是常规的化学反应过程与膜选择性分离过程集合在一起进行的一种新化工过程，其目的一般是利用某种膜的选择分离性在化学反应的同时分离去反应的一种甚至几种产物以提高反应的转化率或选择性，尤其对于平衡反应，膜反应过程能够突破化学热力学平衡的限制实现较高的反应转化率。目前膜反应过程所研究的大多数反应体系是气相催化反应。其中，膜反应器中的耦合催化反应是指在这一过程中同时于分离膜的两侧有两个反应进行，而且一个反应的产物可以透过膜后成为另一个反应的反应物。Membrane reaction process is a new chemical process that combines conventional chemical reaction process and membrane selective separation process. Several products can be used to improve the conversion rate or selectivity of the reaction, especially for the equilibrium reaction, the membrane reaction process can break through the limitation of chemical thermodynamic equilibrium to achieve a higher reaction conversion rate. Most of the reaction systems currently studied in the membrane reaction process are gas-phase catalytic reactions. Among them, the coupled catalytic reaction in the membrane reactor means that two reactions are carried out on both sides of the separation membrane at the same time in this process, and the product of one reaction can pass through the membrane and become the reactant of the other reaction.
膜反应耦合过程的研究开始于六十年代，然后在八十年代初期苏联的Gryaznov及其合作者(英国专利1，342，869(1974)．)对许多反应体系的耦合做了大量的研究。其所选择的反应体系多是脱氢和加氢反应，所用的膜材料都是纯金属钯或者是钯合金膜，膜本身虽然既是选择性分离膜，又是催化剂，但是作为分离膜其透量很低，作为催化剂其活性也不高，所以，这方面的研究成果未获得较好的应用效果。接着，八十年代末有大量的研究针对于多孔膜或金属膜一侧装填有催化剂的膜反应过程(德国专利3，003，993(1981))，但是，为了提高反应转化率，在膜的另一侧采用抽真空，用惰性气体吹殷或者将透过的氢燃烧一小部分等方法，以加快被选择透过反应产物的渗透速率，这无疑使将来的工业生产增加能耗和额外的处理措施，因此，对其能否得到商业应用，目前尚在研究之中。The research on membrane reaction coupling process began in the 1960s, and then in the early 1980s, Gryaznov and his collaborators in the Soviet Union (British Patent 1,342,869 (1974).) did a lot of research on the coupling of many reaction systems. Most of the selected reaction systems are dehydrogenation and hydrogenation reactions, and the membrane materials used are pure metal palladium or palladium alloy membranes. Although the membrane itself is both a selective separation membrane and a catalyst, its permeability as a separation membrane It is very low, and its activity as a catalyst is not high, so the research results in this area have not obtained good application effects. Then, at the end of the 1980s, a large amount of research was directed at the membrane reaction process (German Patent 3,003,993 (1981)) that was loaded with a catalyst on one side of the porous membrane or the metal membrane. However, in order to improve the reaction conversion rate, the The other side adopts methods such as vacuuming, blowing with inert gas, or burning a small part of the permeated hydrogen to speed up the permeation rate of the selected permeated reaction product, which will undoubtedly increase energy consumption and additional costs for future industrial production. Therefore, its commercial application is still under study.
本发明的目的是提供一种利用Pd／陶瓷复合膜反应器进行的气相催化脱氢，加氢耦合反应过程，该反应过程使气相催化脱氢，加氢耦合反应可以应用到工业化生产中。The object of the present invention is to provide a gas-phase catalytic dehydrogenation and hydrogenation coupling reaction process carried out by using Pd/ceramic composite membrane reactor. The reaction process enables the gas-phase catalytic dehydrogenation and hydrogenation coupling reaction to be applied to industrial production.
气相催化脱氢，加氢耦合膜反应过程是在膜反应器的膜两侧分别进行脱氢和加氢反应，且脱氢反应产生的产物氢气可透过膜进入到加氢反应体多中作为加氢反应的反应物，上述反应可用下反应式表示：
上式中A，B为脱氢反应Ⅰ的反应物，H2和P1为其产物，C和H2为加氢反应Ⅱ的反应物，P2为其产物。作为耦合膜反应过程，是将反应Ⅰ(产生氢的脱氢反应)和反应Ⅱ(消耗氢的加氢反应)以及膜分离过程集成一体，在一个膜反应器中实现，反应Ⅰ和反应Ⅱ均为气相催化反应。在理想条件下，反应Ⅰ产生氢和产物P1，氢会立即透过膜，然后参与反应Ⅱ生成产物P2，整个过程看不到氢的生成，这样，对于反应Ⅰ，若是不可逆反应，由于产物氢的及时被分离，反应物浓度不受氢浓度增大的影响，加快了反应的进行；若是平衡可逆反应，由于产物氢的及时被分离，分促使反应平衡向右移动，最终使反应不再受热力学平衡的限制，达到较高的反应转化率。对于反应Ⅱ，不仅是及时地利用了利氢，而且这种耦合过程相当于轴向平行加料，尤其对强放热反应体系，易于控制其反应速率，避免飞温或反应失控。In the above formula, A and B are reactants of dehydrogenation reaction I, H2 and P1 are their products, C and H2 are reactants of hydrogenation reaction II, and P2 is their product. As a coupled membrane reaction process, the reaction I (dehydrogenation reaction that produces hydrogen) and reaction II (hydrogenation reaction that consumes hydrogen) and the membrane separation process are integrated into one membrane reactor. Reaction I and reaction II are both It is a gas-phase catalytic reaction. Under ideal conditions, reaction I produces hydrogen and product P 1 , hydrogen will permeate the membrane immediately, and then participate in reaction II to produce product P 2 , and no hydrogen can be seen in the whole process. Thus, for reaction I, if it is an irreversible reaction, due to The product hydrogen is separated in time, and the concentration of the reactant is not affected by the increase of the hydrogen concentration, which speeds up the reaction; if the equilibrium reversible reaction is due to the timely separation of the product hydrogen, the reaction balance is moved to the right, and finally the reaction is not stable. Restricted by the thermodynamic equilibrium, a higher reaction conversion rate is achieved. For reaction II, not only is the timely use of hydrogen, but this coupling process is equivalent to axial parallel feeding, especially for strong exothermic reaction systems, it is easy to control the reaction rate and avoid overheating or reaction runaway.
在任何膜反应过程中，无疑膜材料的性能优良是技术研究的基础。本发明不同于以往所用的膜材料为Pd／陶瓷复合膜，其是用化学镀的方法，在陶瓷基膜经过表面改性修饰以后，将金属钯沉积在基膜的表面，形成Pd／陶瓷超薄钯复合膜。此种膜材料兼有纯金属钯或其合金膜的氢气渗透选择性高和陶瓷多孔膜的气体透量大的优点，而克服了两者的一些缺陷，因此，其得以在实际中应用。In any membrane reaction process, there is no doubt that the excellent performance of membrane materials is the basis of technical research. The present invention is different from the Pd/ceramic composite membrane used in the past as a membrane material. It uses electroless plating to deposit metal palladium on the surface of the base membrane after the surface of the ceramic base membrane is modified to form a Pd/ceramic composite membrane. Thin palladium composite film. This kind of membrane material has the advantages of high hydrogen permeation selectivity of pure metal palladium or its alloy membrane and large gas permeability of ceramic porous membrane, and overcomes some defects of both, so it can be used in practice.
在本发明的脱氢，加氢耦合膜反应过程中，其Pd／陶瓷复合膜仅作为氢的透过膜，在加、脱氢催化反应中还应分别在膜的两侧反应腔内装填催化剂。例如在进行反应Ⅰ的空腔内加脱氢反应催化剂，而在进行反应Ⅱ的空腔内填入加氢催化剂。In the process of dehydrogenation and hydrogenation coupled membrane reaction of the present invention, its Pd/ceramic composite membrane is only used as a permeable membrane for hydrogen, and catalysts should also be filled in the reaction chambers on both sides of the membrane in the catalytic reactions of hydrogenation and dehydrogenation. . For example, the dehydrogenation reaction catalyst is added in the cavity for reaction I, and the hydrogenation catalyst is filled in the cavity for reaction II.
作为本发明中应用的一种膜反应器可采用一管壳式的反应器，将一根Pd／陶瓷管式膜套在一不锈钢管体内，膜管外的壳程装填脱氢反应系列催化剂，膜管内腔装填加氢反应系列催化剂，并可以根据设计，合理调节催化剂用量与膜面积的比值，来协调反应速度和渗透速度。As a kind of membrane reactor used in the present invention, a shell-and-tube reactor can be used, and a Pd/ceramic tubular membrane is enclosed in a stainless steel tube body, and the shell side outside the membrane tube is filled with a series of catalysts for dehydrogenation reaction. The inner cavity of the membrane tube is filled with a series of hydrogenation reaction catalysts, and the ratio of catalyst dosage to membrane area can be adjusted reasonably according to the design to coordinate the reaction speed and permeation speed.
上述本发明所用的超薄Pd-陶瓷复合膜是指厚度为1～10μm的超薄Pd／陶瓷复合膜，其制备方法按下述步骤：The above-mentioned ultra-thin Pd-ceramic composite film used in the present invention refers to an ultra-thin Pd/ceramic composite film with a thickness of 1～10 μm, and its preparation method is as follows:
1．将经常规方法进行表面处理、清洗和干燥后的多孔陶瓷膜在SnCl2的酸性溶液中进行敏化，清洗。1. The porous ceramic membrane after surface treatment, cleaning and drying by conventional methods is sensitized and cleaned in an acidic solution of SnCl 2 .
2．再于PdCl2的酸性溶液中进行活化，清洗。2. Then activate and clean in the acidic solution of PdCl2 .
3．将敏化、活化后的多孔陶瓷膜放入含Pd离子溶液中进行第一次化学镀；3. Put the sensitized and activated porous ceramic membrane into the solution containing Pd ions for the first electroless plating;
4．将一次化学镀后的多孔陶瓷膜进行修饰处理，如将膜管内抽真空(真空度达-0．1MPa以下)，膜管外浸在氧化铝溶胶中，使膜表面遗留的大孔逐渐缩小，当N2透量小于5～10ml／min·cm2·atm时，再将膜管放入化学镀液中进行第二次化学镀至所需厚度，完成本发明的金属-陶瓷复合膜的制备。详细的制备过程可参照中国发明专利申请号96115291．5所提供的技术。4. The porous ceramic membrane after one chemical plating is modified, such as vacuuming the inside of the membrane tube (vacuum degree below -0.1MPa), and immersing the membrane tube in alumina sol, so that the remaining macropores on the membrane surface are gradually reduced. When the N 2 permeability is less than 5-10ml/min cm 2 atm, put the membrane tube into the chemical plating solution for the second chemical plating to the required thickness, and complete the preparation of the metal-ceramic composite membrane of the present invention . The detailed preparation process can refer to the technology provided by the Chinese invention patent application number 96115291.5.
下面通过实例对本发明的技术给予进一步地说明。The technology of the present invention is further illustrated below by examples.
实施例1 Pd／陶瓷复合膜的制备Example 1 Preparation of Pd/ceramic composite membrane
将孔径分布为0．5～2μm的、氧化铝含量为85％、外径为2cm、膜面积为250cm2的多孔陶瓷管HX7的内外表面洗净，再用乙醇超声波洗涤后，干燥、然后将上下管口用胶塞塞上，在SnCl2·3H2O(10g／1)和HCl(40ml／1)的溶液中敏化、清洗，再在PdCl2(0．1g／1)和HCl(1ml／1)的溶液中活化、清洗，反复交替进行4次，再放入Pd(NH3)4Cl2·H2O(4g／1)，EDTA(60g／1)，NH3·H2O(610ml／1)，NH2H2N·H2O(0．3ml／1)，PH为12的pd2+溶液中，当形成厚1．5μm的Pd表面镀层时，将膜管取出，清洗，真空干燥热处理，再堵孔修饰，即将膜管内抽真空，氧化铝溶胶用铝箔和AlCl3溶液于80～90℃下处理20小时制得，膜管外浸在氧化铝胶体中15秒，取出，再抽空10秒，缓慢放空，干燥，600℃焙烧，重复进行抽空溶胶堵孔修饰，当膜N2透量达到10ml／min·cm2·atm时，将膜管重新放入上述组成的pd2+溶液中进行反应6小时，制得膜厚4．6μm，清洗，真空干燥。这样即制得了总厚度为6．1μm的Pd膜。Clean the inner and outer surfaces of the porous ceramic tube HX7 with a pore size distribution of 0.5-2 μm, an alumina content of 85%, an outer diameter of 2 cm, and a membrane area of 250 cm 2 , then ultrasonically wash with ethanol, dry, and then The upper and lower nozzles are plugged with rubber stoppers, sensitized and cleaned in a solution of SnCl 2 3H 2 O (10g/1) and HCl (40ml/1), and then in PdCl 2 (0.1g/1) and HCl ( 1ml/1) solution for activation and cleaning, repeated alternately for 4 times, then put in Pd(NH 3 ) 4 Cl 2 ·H 2 O (4g/1), EDTA (60g/1), NH 3 ·H 2 O (610ml/1), NH 2 H 2 N·H 2 O (0.3ml/1), pH 12 pd 2+ solution, when a 1.5μm thick Pd surface coating is formed, take out the membrane tube , cleaning, vacuum drying and heat treatment, and then plugging and modifying, that is, the membrane tube is evacuated, and the alumina sol is prepared by treating aluminum foil and AlCl 3 solution at 80-90°C for 20 hours, and the membrane tube is immersed in alumina colloid for 15 seconds , take it out, and then evacuate for 10 seconds, slowly evacuate, dry, bake at 600°C, repeat the evacuation sol plugging modification, when the membrane N 2 permeability reaches 10ml/min·cm 2 ·atm, put the membrane tube back into the above composition The pd 2+ solution was reacted for 6 hours to obtain a film thickness of 4.6 μm, washed and dried in vacuum. Thus, a Pd film having a total thickness of 6.1 µm was obtained.
实施例2 Pd／陶瓷复合膜反应器中气相催化脱、加氢耦合反应的应用1Example 2 Application of gas-phase catalytic de-hydrogenation coupling reaction in Pd/ceramic composite membrane reactor 1
利用实例1制备的超薄Pd／陶瓷复合膜管作成管式膜反应器(将一根Pd／陶瓷管式膜装在一不锈钢管内制成)，用于CO转化为甲烷气体的反应，其中CO加H2O为脱氢变换反应，CO加H2为加氢甲烷化反应，在膜管外的壳程装填CO变换反应用Fe2O3-Cr2O3催化剂，膜管内腔装填甲烷化反应用Ni／Al2O3催化剂。所用的Pd／陶瓷复合膜的氢气透量为0．008ml／cm2·s·KPs0．5，实验条件为：变换反应侧的干气空速175hr-1，水汽和一氧化碳摩尔比是H2O／CO=1．5，压力为390KPa，甲烷化反应侧的原料气为纯一氧化碳，空速为80hr-1，压力为常压，反应器中的反应温度为350～450℃，两腔逆流进料，得到的典型结果列于表1。The ultra-thin Pd/ceramic composite membrane tube prepared in Example 1 is used to make a tubular membrane reactor (a Pd/ceramic tubular membrane is installed in a stainless steel tube), which is used for the reaction of CO into methane gas, wherein CO Adding H 2 O is a dehydrogenation shift reaction, and CO adding H 2 is a hydromethanation reaction. The shell side outside the membrane tube is filled with Fe 2 O 3 -Cr 2 O 3 catalyst for CO shift reaction, and the inner cavity of the membrane tube is filled with methanation Ni/Al 2 O 3 catalyst was used for the reaction. The hydrogen permeation rate of the Pd/ceramic composite membrane used is 0.008ml/cm 2 ·s·KPs 0.5 , the experimental conditions are: the dry gas space velocity on the shift reaction side is 175hr -1 , the molar ratio of water vapor and carbon monoxide is H 2 O/CO=1.5, the pressure is 390KPa, the raw material gas on the methanation reaction side is pure carbon monoxide, the space velocity is 80hr -1 , the pressure is normal pressure, the reaction temperature in the reactor is 350-450℃, and the two chambers are countercurrent The typical results obtained are listed in Table 1.
表1
实施例3 Pd／陶瓷复合膜反应器中气相催化脱、加氢耦合反应的应用2Example 3 Application of gas-phase catalytic de-hydrogenation coupling reaction in Pd/ceramic composite membrane reactor 2
按实例2相同的反应设备所用的Pd／陶瓷复合膜的氢气透量为0．0445ml／cm2·s·KPa0．5，实验条件为：变换反应侧的空速640hr-1，水汽和一氧化碳摩尔比是H2O／CO=3，压力为120KPa，甲烷化反应侧的原料气为二氧化碳，空速为270～490hr-1，压力为常压，反应器中的反应入口温度为345℃，两腔逆流进料，得到的典型结果为变换反应的转化率为98％，超过相应的热力学平衡转化率97／5％，同时膜另一侧的甲烷化反应结果列于表2。The hydrogen permeability of the Pd/ceramic composite membrane used in the same reaction equipment as in Example 2 is 0.0445ml/cm 2 ·s·KPa 0.5 . The molar ratio is H 2 O/CO=3, the pressure is 120KPa, the raw material gas on the methanation reaction side is carbon dioxide, the space velocity is 270-490hr -1 , the pressure is normal pressure, and the reaction inlet temperature in the reactor is 345°C. Two chambers are fed in countercurrent, and the typical result obtained is that the conversion rate of the shift reaction is 98%, which exceeds the corresponding thermodynamic equilibrium conversion rate of 97/5%, and the results of the methanation reaction on the other side of the membrane are listed in Table 2.
表2 甲烷化反应转化率和甲烷浓度
从实验结果可以看出，在单元膜反应器中，由于膜分离的怍用，变换反应的进行彻底，已超过平衡转化率，而且在反应器出口，得到了高达44％的干气甲烷浓度，这在传统的一个单元反应器中，以任何比例混合的一氧化碳，二氧化碳和水蒸汽作为原料气反应时，都是不能得到的结果。As can be seen from the experimental results, in the unit membrane reactor, due to the exhaustion of the membrane separation, the conversion reaction is carried out thoroughly, exceeding the equilibrium conversion rate, and at the outlet of the reactor, a dry gas methane concentration of up to 44% is obtained. This is a result that cannot be obtained when reacting carbon monoxide, carbon dioxide and water vapor mixed in any proportion as raw material gas in a traditional unit reactor.
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