CN1189483A - 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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- CN1189483A CN1189483A CN97105068A CN97105068A CN1189483A CN 1189483 A CN1189483 A CN 1189483A CN 97105068 A CN97105068 A CN 97105068A CN 97105068 A CN97105068 A CN 97105068A CN 1189483 A CN1189483 A CN 1189483A
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Abstract
The gas-phase catalytic dehydrogenation-hydrogenation couple reaction in Pd/ceramic compound membrane reactor features use of Pb/ceramic compound membrane which is prepared by chemical plating, that is, after surficial modification of basic ceramic membrane, metal Pd is deposited on the surface of said basic membrane to form ultra-thin (1-10 microns) compound membrane. During the catalytic dehydrogenation-hydrogenation reactor, catalyst is filled in the reaction cavities at both sides of membrane. Its advantages are unique reaction result, high productivity, simple process.
Description
The present invention relates to a chemical reaction process, specifically provide and utilize the Pd/ ceramic composite membrane reactor, carry out a class coupling reaction of vapor catalytic dehydrogenation and hydrogenation.
The film reaction process is the chemical reaction process of routine and a kind of new chemical process that film selective separation process gathers together and carries out, its purpose generally is to utilize the selection separation property of certain film to separate a kind of even several product of dereaction to improve the transformation efficiency or the selectivity of reaction in chemical reaction, especially for balanced reaction, the film reaction process can break through the restriction of chemical thermodynamics equilibrated and realize higher reaction conversion ratio.Most of reaction systems that present film reaction process is studied are gas phase catalytic reactions.Wherein, the coupling and catalyzing reaction in the membrane reactor is meant in this course simultaneously have two reactions to carry out in the both sides of separatory membrane, and the product of a reaction can be through the reactant that becomes another reaction behind the film.
The research of film reaction coupling process starts from the sixties, then the eighties initial stage Soviet Union Gryaznov and co-worker (English Patent 1,342,869 (1974) .) thereof a large amount of research has been done in the coupling of many reaction systems.Mostly its selected reaction system is dehydrogenation and hydrogenation reaction, used mould material all is pure metal palladium or palladium alloy membrane, though film itself is a selective diffusion barrier, it is again catalyzer, but it is very low as its saturating amount of separatory membrane, not high as its activity of catalyzer yet, so the achievement in research of this respect does not obtain effect preferably.Then, late nineteen eighties has a large amount of research to be directed to the film reaction process (German Patent 3 that porous-film or metallic membrane one side are filled with catalyzer, 003,993 (1981)), but, in order to improve reaction conversion ratio, opposite side employing at film vacuumizes, abundant with inert blowing gas or will see through methods such as hydrogen burning sub-fraction, to accelerate the selected infiltration rate that sees through reaction product, this makes industrial production in the future increase energy consumption and extra treatment measures undoubtedly, therefore, can obtain commercial applications to it, at present still among research.
The purpose of this invention is to provide the vapor catalytic dehydrogenation that a kind of Pd/ of utilization ceramic composite membrane reactor carries out, the hydrogenation coupled reaction process, this reaction process makes vapor catalytic dehydrogenation, and hydrogenation coupled reaction can be applied in the suitability for industrialized production.
Vapor catalytic dehydrogenation, hydrogenation coupled film reaction process is to carry out dehydrogenation and hydrogenation reaction respectively in the film both sides of membrane reactor, and the product hydrogen-permeable film that dehydrogenation reaction produces enters into the many reactants as hydrogenation reaction of hydrogenation reaction body, and the available reaction formula down of above-mentioned reaction is represented:
A in the following formula, B are the reactant of dehydrogenation reaction I, H
2And P
1Be its product, C and H
2Be the reactant of hydrogenation reaction II, P
2Be its product.As the coupled film reaction process, be with reaction I (producing the dehydrogenation reaction of hydrogen) and reaction II (consuming the hydrogenation reaction of hydrogen) and membrane sepn process integration one, realize that in a membrane reactor reaction I and reaction II are gas phase catalytic reaction.Under ideal conditions, reaction I produces hydrogen and product P
1, hydrogen can see through film immediately, participates in reaction II then and generates product P
2, whole process be can't see the generation of hydrogen, and like this, for reaction I, if irreversible reaction, because product hydrogen is in time separated, the carrying out that reacts accelerated in the influence that reactant concn is not increased by hydrogen concentration; If the balance reversible reaction because product hydrogen is in time separated, divides and impels molecular balance to move right, finally make reaction no longer be subjected to the restriction of thermodynamic(al)equilibrium, reach higher reaction conversion ratio.For reaction II, be not only and utilized sharp hydrogen in time, and this coupling process to be equivalent to axially parallel reinforced, especially to the strong exothermal reaction system, be easy to control its speed of reaction, avoid temperature runaway or runaway reaction.
In any film reaction process, the excellent property of mould material is the basis of technical study undoubtedly.The present invention's used mould material different from the past is the Pd/ ceramic composite membrane, and it is the method with electroless plating, after ceramic basement membrane is modified through surface modification, palladium metal is deposited on the surface of basement membrane, forms Pd/ ceramic ultra-thin palladium-based composite membrane.This kind mould material has the big advantage of the hydrogen permeate selectivity saturating amount of gas high and ceramic porous membrane of pure metal palladium or its alloy film concurrently, and has overcome both some defectives, and therefore, it is used in practice.
In dehydrogenation of the present invention, in the hydrogenation coupled film reaction process, its Pd/ ceramic composite membrane to be only as the film that sees through of hydrogen, add, loading catalyst in the reaction chamber of the both sides of film respectively also in the catalysis dehydrogenation reaction.For example in reacting the cavity of I, add the dehydrogenation reaction catalyzer, and in reacting the cavity of II, insert hydrogenation catalyst.
Can adopt the reactor of a shell-and-tube as a kind of membrane reactor of using among the present invention, with a Pd/ ceramic pipe type Membrane cover in a stainless steel body, the shell side filling dehydrogenation reaction catalyst series that the film pipe is outer, film tube cavity filling hydrogenation reaction catalyst series, and can be according to design, rationally regulate the ratio of catalyst levels and membrane area, come concerted reaction speed and seepage velocity.
The used ultra-thin Pd-ceramic composite membrane of the invention described above is meant that thickness is the ultra-thin Pd/ ceramic composite membrane of 1～10 μ m, and its preparation method is pressed following step:
1. will carry out surface treatment, cleaning and dried porous ceramic film at SnCl through conventional method
2Acidic solution in carry out sensitization, clean.
2. again in PdCl
2Acidic solution in activate, clean.
3. the porous ceramic film after sensitization, the activation is put into and contained the Pd solion and carry out the electroless plating first time;
4. the porous ceramic film after electroless plating is modified processing, as vacuumizing (vacuum tightness reach-0.1MPa is following) in the film pipe, the film pipe is immersed in outward in the alumina sol, and the macropore that the film surface is left over dwindles gradually, works as N
2Measure less than 5～10ml/mincm thoroughly
2During atm, again the film pipe is put into chemical plating fluid and carried out second time electroless plating, finish the preparation of metal-ceramic composite membrane of the present invention to desired thickness.The technology that detailed preparation process can be provided with reference to Chinese invention patent application number 96115291.5.
Below by example technology of the present invention is given to illustrate further.
The preparation of embodiment 1 Pd/ ceramic composite membrane
With pore size distribution be 0.5～2 μ m, alumina content is 85%, external diameter is that 2cm, membrane area are 250cm
2The surfaces externally and internally of porous ceramic pipe HX7 clean, use the ethanol ultrasonic washing again after, dry, will go up lower nozzle beyond the Great Wall then, at SnCl with plug
23H
2Sensitization in the solution of O (10g/l) and HCl (40ml/l), cleaning are again at PdCl
2(0.1g/l) and in the solution of HCl (1ml/l) activate, clean, hocket repeatedly 4 times, put into Pd (NH again
3)
4Cl
2H
2O (4g/l), EDTA (60g/l, NH
3H
2O (610ml/l), NH
2H
2NH
2O (0.3ml/l), PH are 12 Pd
2+In the solution, when forming the Pd overlay coating of thick 1.5 μ m, the film pipe is taken out, clean, vacuum-drying thermal treatment, plug-hole is modified again, is about to vacuumize in the film pipe, and alumina sol is with aluminium foil and AlCl
3Solution is handled down in 80～90 ℃ and was made in 20 hours, and the film pipe was immersed in outward in the alumina gel 15 seconds, took out, found time again 10 seconds, and slowly emptying, drying, 600 ℃ of roastings, the colloidal sol plug-hole that repeats to find time is modified, as film N
2Saturating amount reaches 10ml/min.cm
2During atm, the film pipe is reentered into the Pd of above-mentioned composition
2+Reacted in the solution 6 hours, and made thickness 4.6 μ m, clean vacuum-drying.So promptly having made total thickness is the Pd film of 6.1 μ m.
In the embodiment 2 Pd/ ceramic composite membrane reactors gas phase catalysis take off, hydrogenation coupled reaction
Use 1
Utilize the ultra-thin Pd/ ceramic compound film tube of example 1 preparation to make tubular membrane reactor (be contained in a stainless steel tube in make a Pd/ ceramic pipe type film), be used for the reaction that CO is converted into methane gas, wherein CO adds H
2O is the dehydrogenation transformationreation, and CO adds H
2Be the hydrogenation methanation reaction, the shell side filling CO transformationreation Fe outside the film pipe
2O
3-Cr
2O
3Catalyzer, film tube cavity filling methanation reaction Ni/Al
2O
3Catalyzer.The saturating amount of the hydrogen of used Pd/ ceramic composite membrane is 0.008ml/cm
2SKPs
0.5, experiment condition is: the dry gas air speed 175hr of transformationreation side
-1, steam and carbon monoxide mol ratio are H
2O/CO=1.5, pressure are 390KPa, and the unstripped gas of methanation reaction side is a pure carbon monoxide, and air speed is 80hr
-1, pressure is normal pressure, the temperature of reaction in the reactor is 350～450 ℃, and two chamber adverse current feedings, the typical consequence that obtains is listed in table 1.
Table 1
| Temperature of reaction (℃) | Methane concentration (v%) in the methanation reaction outlet dry gas | Corresponding dry gas calorific value (MJ/Nm 3) | Calorific value (the MJ/Nm of pure carbon monoxide gas 3) |
| ????373 | ????27.3 | ????16 | ????12.6 |
| ????400 | ????39.3 | ????18.1 | |
| ????426 | ????44.2 | ????19.6 |
In the embodiment 3 Pd/ ceramic composite membrane reactors gas phase catalysis take off, the application 2 of hydrogenation coupled reaction
The saturating amount of hydrogen of pressing the used Pd/ ceramic composite membrane of the identical conversion unit of example 2 is 0.0445ml/cm
2SKPa
0.5, experiment condition is: the air speed 640hr of transformationreation side
-1, steam and carbon monoxide mol ratio are H
2O/CO=3, pressure are 120KPa, and the unstripped gas of methanation reaction side is a carbonic acid gas, and air speed is 270～490hr
-1, pressure is normal pressure, the reaction temperature in the reactor is 345 ℃, two chamber adverse current feedings, the typical consequence that obtains is that the transformation efficiency of transformationreation is 98%, surpasses corresponding thermodynamic(al)equilibrium transformation efficiency 97/5%, and the methanation reaction of film opposite side the results are shown in table 2 simultaneously.
Table 2 methanation reaction transformation efficiency and methane concentration
| CO2 air speed (hr-1) | Outlet dry gas methane concentration (V%) | Reaction conversion ratio (%) |
| ????490 ????270 ????210 | ????32 ????34 ????37 | ????66 ????72 ????75 |
From experimental result as can be seen, in the unit membrane reactor, because the effect of membrane sepn, the carrying out of transformationreation is thorough, has surpassed equilibrium conversion, and at reactor outlet, obtained the dry gas methane concentration up to 44%, this is in a traditional unitary reactor, with the carbon monoxide of any mixed, when carbonic acid gas and water vapor react as unstripped gas, all be the result that can not obtain.
Claims (3)
1. vapor catalytic dehydrogenation and the hydrogenation coupled reaction in the Pd/ ceramic composite membrane reactor is characterized in that it being that the mould material that adopts is the Pd/ ceramic composite membrane.
2. according to described vapor catalytic dehydrogenation of claim 1 and hydrogenation coupled reaction, it is characterized in that the Pd/ ceramic composite membrane is the method with electroless plating, after ceramic basement membrane is modified through surface modification, palladium metal is deposited on the surface of basement membrane, and forming thickness is the Pd/ ceramic ultra-thin palladium-based composite membrane of 1～10 μ m.
3. according to described vapor catalytic dehydrogenation of claim 1 and hydrogenation coupled reaction, it is characterized in that the Pd/ ceramic composite membrane only as the film that sees through of hydrogen, add, loading catalyst in the reaction chamber of the both sides of film respectively also in the catalysis dehydrogenation reaction.
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| CN97105068A CN1065852C (en) | 1997-01-31 | 1997-01-31 | Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor |
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| CN97105068A CN1065852C (en) | 1997-01-31 | 1997-01-31 | Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor |
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| CN1065852C CN1065852C (en) | 2001-05-16 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334254C (en) * | 2004-12-16 | 2007-08-29 | 四川材料与工艺研究所 | Surface treating method for improving lanthanum alloy vapour impurity poisoning performance |
| CN100569361C (en) * | 2007-07-18 | 2009-12-16 | 中山大学 | Pd carried iolite honeycomb ceramic catalyze material and preparation method thereof |
| CN101439267B (en) * | 2008-12-09 | 2011-04-06 | 南京工业大学 | Method for preparing palladium-based composite membranes |
| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst supported on ceramic membrane |
| CN106365936A (en) * | 2016-08-27 | 2017-02-01 | 福州大学 | Tubular reactor for liquid-phase alcohol dehydrogenation, and method for liquid-phase alcohol dehydrogenation |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327942C (en) * | 2004-01-09 | 2007-07-25 | 中国科学院大连化学物理研究所 | Composite metal palladium membrane or alloy palladium membrane and its preparing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60183025A (en) * | 1984-03-02 | 1985-09-18 | Mitsubishi Chem Ind Ltd | Steam separation method |
| FR2655873B1 (en) * | 1989-12-20 | 1992-04-10 | Medal Lp | PROCESS AND DEVICE FOR THE PERIMATION REMOVAL OF CARBON MONOXIDE IN A GAS MIXTURE BASED ON HYDROGEN. |
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1997
- 1997-01-31 CN CN97105068A patent/CN1065852C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334254C (en) * | 2004-12-16 | 2007-08-29 | 四川材料与工艺研究所 | Surface treating method for improving lanthanum alloy vapour impurity poisoning performance |
| CN100569361C (en) * | 2007-07-18 | 2009-12-16 | 中山大学 | Pd carried iolite honeycomb ceramic catalyze material and preparation method thereof |
| CN101439267B (en) * | 2008-12-09 | 2011-04-06 | 南京工业大学 | Method for preparing palladium-based composite membranes |
| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst supported on ceramic membrane |
| CN106365936A (en) * | 2016-08-27 | 2017-02-01 | 福州大学 | Tubular reactor for liquid-phase alcohol dehydrogenation, and method for liquid-phase alcohol dehydrogenation |
| CN106365936B (en) * | 2016-08-27 | 2019-01-15 | 福州大学 | The method of the shell and tube reactor and liquid phase alcohol dehydrogenase of liquid phase alcohol dehydrogenase |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
| CN109954500B (en) * | 2017-12-25 | 2023-05-05 | 沈阳三聚凯特催化剂有限公司 | Copper-based skeleton composite membrane type hydrogenation catalyst, and preparation method and application thereof |
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