CN1117941A - Ceramic-metal composite film reactor and its preparation and application - Google Patents
Ceramic-metal composite film reactor and its preparation and application Download PDFInfo
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- CN1117941A CN1117941A CN 94112487 CN94112487A CN1117941A CN 1117941 A CN1117941 A CN 1117941A CN 94112487 CN94112487 CN 94112487 CN 94112487 A CN94112487 A CN 94112487A CN 1117941 A CN1117941 A CN 1117941A
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- palladium
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- 239000002905 metal composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 18
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000007747 plating Methods 0.000 description 18
- 239000002131 composite material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017906 NH3H2O Inorganic materials 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention relates to a ceramic-metal composite film reactor hydrogen-producing method for methanol steam conversion hydrogen production. It is characterized by that the thickness of metal film of said reactor is 1-10 micrometers, its adoped reaction temp. is 250-300 deg.C, and a pressure operation mode is used to prepare pure hydrogen. Its hydrogen purity is up to 100%, methanol conversion efficiency is 80%, H2 recovery rate is 90%, and its film permeability is up to 60-150 ml/square cm.min. square root of atm.
Description
The invention belongs to the field of chemical industry, and particularly relates to a preparation of an inorganic membrane reactor and a hydrogen extraction process.
The reaction of preparing hydrogen by converting methanol steam into hydrogen-rich gas containing hydrogen, carbon monoxide, carbon dioxide and unreacted methanol and water, and separating out crude hydrogen and pure hydrogen, which is a common hydrogen preparing method in industry.
Japanese patent (sho 63-295402) proposes a method for producing hydrogen using a porous glass-Pd-Cu composite membrane reactor, which employs a membrane reactor to synchronize reaction-separation, breaks the chemical equilibrium limitation, and improves the conversion rate, but this method employs a high operating temperature to achieve a high hydrogen yield and prevent hydrogen embrittlement, and is high in energy consumption, and the process has a low gas production rate, and the direct product is a mixed gas of hydrogen and hydrogen, not pure hydrogen, and is difficult to separate.
The invention aims to overcome the defects and provide a metal composite membrane reactor capable of preparing pure hydrogen and a method for preparing hydrogen by using the reactor.
The invention uses the inner wall of a ceramic-ultrathin metal palladium (or palladium-silver alloy) membrane tube to form a permeation cavity, uses a concentric annular space between a stainless steel tube and the outer wall of the palladium membrane tube to form a reaction cavity, and fills a methanol decomposition hydrogen production catalyst in the reaction cavity to form an operable membrane reactor for producing pure hydrogen. The thickness of a palladium-silver metal film plated on a ceramic base pipe of the membrane reactor is 1-10 mu m, the metal film is Pd-Ag alloy, and the contents of the Pd-Ag (palladium-silver) alloy are respectively palladium (Pd): 70-100%, silver: 0 to 30 percent.
The preparation method of the composite membrane is to carry out surface treatment on a commercial ceramic base tube and then obtain the composite membrane by a method of chemically plating Pd or chemically plating Pd-Ag. Specifically, the ceramic base tube is subjected to surface treatment to form a ceramic matrix with the average pore diameter of 0.02-3 microns, preferably 0.07-1.0 microns, then a Pd core is impregnated to form an activation point on the surface and in the hole of the base film, the steps of calcining, chemical plating and direct vacuum heat treatment are carried out, the steps of impregnating the Pd core, calcining and chemical plating can be repeatedly carried out, and the chemical plating solution contains 0.01-1% (volume) of surfactant, so that the ceramic metal composite film is obtained. The palladium-silver activated points are not only formed on the surface of the base film, but also mainly formed in the pores, and a part of the prepared palladium-silver film enters the pores of the base film.
A strip-shaped ceramic metal composite membrane and a stainless steel sleeve form a membrane reactor, the inner cavity of the ceramic tube is a permeation cavity, a reaction cavity is formed between the ceramic tube and the stainless steel sleeve, a catalyst, namely a commercially available copper catalyst, is filled in the reaction cavity, methanol steam enters the reaction cavity and is decomposed to produce hydrogen under the action of the catalyst, and the reaction formula is as follows:
the total reaction is as follows:
the molar ratio of the raw material water to the methanol is 1.0-2.5, preferably: 1.0 to 1.3.
The reactiontemperature is 150-300 deg.C, preferably 250-300 deg.C
Reaction chamber pressure: 0 to 4MPa (gauge pressure), preferably: 0.2 to 1.5MPa (gauge pressure)
Osmotic chamber pressure: -0.2 to 0.5MPa (gauge pressure), preferably: 0 to 0.1MPa (gauge pressure)
The catalyst and the raw materials in the reaction cavity are replaced, so that the device can be suitable for other hydrogen production reactions, such as ammonia decomposition reaction, hydrazine decomposition reaction, hydrocarbon steam conversion hydrogen production reaction and the like.
The ceramic metal composite membrane of the invention has the advantages that the metal layer is firmly combined with the matrix, the metal layer is an ultrathin layer, the internal stress is small, so that pure hydrogen is separated at the temperature of 150-300 ℃ lower than the hydrogen embrittlement temperature, and the permeation quantity reaches 60-150 ml/cm2·min·atm1/2The method has the advantages of no hydrogen embrittlement or breakage after continuous use for more than 1000 hours, 80% hydrogen yield, 90% hydrogen recovery rate, reduced reaction temperature, low energy consumption, synchronous reaction and separation, convenient operation and less equipment investment. The invention breaks through the convention that the hydrogen production of the ceramic metal composite membrane can only be carried out at the temperature of more than 300 ℃, the purity of the hydrogen produced in the reaction reaches 100 percent, and the scale of the produced gas is 11-1 m3/h。
FIG. 1 is a membrane reactor configuration;
FIG. 2 is a hydrogen production flow diagram;
FIG. 3 is a 1000 hour reaction diagram;
FIG. 4 shows hydrogen conversion at various feed rates and pressures.1. Raw materials (methanol + water); 2. pure H2(ii) a 3. A seal ring; 4. a catalyst; 5. a thermocouple; 6. a ceramic metal composite membrane; mixed gas of N2 + H2 (reduction catalyst); 8, N2; 9. methanol + water mixed raw material; 10. a rotameter; 11. a metering pump; 12. a preheater; 13. a heater; 14. a membrane reactor; 15. a wet flow meter; 16. a cooler; 17. a pressure gauge; GC: a gas column chromatograph; t: hours; p: pressure (unit 0.1 MPa); r: conversion rate; d: the purity of hydrogen.
The following is further described in conjunction with the examples and the figures:
EXAMPLE 1 preparation of ceramic-Pd composite membranes
A commercially available cylindrical ceramic tube with a thickness of 1mm, an inner diameter of 18mm and a length of 400mm and a closed end is taken, washed with dilute alkali solution (KOH, 0.1N), boiled in boiling distilled water for 30 minutes and dried at 100 ℃ for 6 hours. Preparing 0.2N PdCl2Adding 10ml of 1N HCl solution into the solution, and placing the treated ceramic substrate tube on the PdCl2Soaking in solution at room temperature for 15 hr, taking out, calcining at 650 deg.C for 5 hr, drying, cooling, chemically plating Pd in prepared plating solution at 30 deg.C for 2b, vacuum-pumping at 200 deg.C, and placing in PdCl2Soaking in the solution for 10 hours, roasting at 650 ℃ for 5 hours, drying, cooling, chemically plating Pd3 hours, and processing at 200 ℃ under vacuum to obtain the ceramic-Pd composite membrane with the Pd membrane thickness of 3 microns.
The plating solution comprises the following components: PdCl26g/l，EDTA67g/L，NH3·H2O350ml/L，N2NNH20.5ml/L, surfactant: 1% by volume of sodium + ethanesulfonate.
The prepared ceramic-Pd composite membrane has an effective area of 70cm2At 300 ℃ H2The permeation volume is 80ml/cm2·min·atm1/2Separation of H at 150 ℃2No hydrogen embrittlement occurs because the Pd membrane is firmly combined with the pore matrix, the mechanical strength is increased, the metal layer is thin, and the internal stress is small.
EXAMPLE 2 preparation of ceramic-Pd-Ag composite film
Taking a commercially available cylindrical ceramic tube with the thickness of 1mm, the inner diameter of 18mm and the length of 350mm and one end sealed, carrying out surface treatment on a base film, dipping Pd particles, calcining, chemically plating and the like under the same conditions as in example 1, wherein the composition of a Pd plating solution is the same, after chemically plating Pd, chemically plating Ag by using an Ag plating solution at the temperature of 30 ℃ for 5 hours, then placing the tube in the Pd plating solution for chemically plating Pd2 hours, and carrying out vacuum heat treatment for 8 hours at the temperature of 850 ℃ to obtain the ceramic-Pd-Ag composite film.
The Ag plating solution comprises the following components:
[Pd(NH3)4]Cl2·H2O0.5g/l
AgNO35g/l
EDTA 36g/l
NH3H2O 400ml/l
H2NNH20.5ml/l was determined by a change in the composition of the plating solution whether the desired Pd-Ag ratio was achieved.
The ceramic-Pd-Ag membrane obtained by the method has an effective membrane area of 60cm2The film thickness is 10 μm, and the permeability to H is at 300 DEG C2The amount is: 65ml/cm2·min·atm1/2No hydrogen embrittlement occurred at 250 ℃.
Example 3 Membrane reactor
As shown in figure 1, the inner pipe of the ceramic metal composite membrane pipe 6 forms a permeation cavity, a stainless steel pipe 7 concentric with the composite membrane pipe is used as the wall of the reactor, the stainless steel pipe and the composite membrane pipe are sealed by an O-shaped ring 3 to form a reaction cavity, and a commercially available copper catalyst 4 is filled in the reaction cavity to form the membrane reactor, which is shown in figure 2.
Example 4
A reaction device is constructed as shown in figure 1, the membrane reactor of the embodiment 3 is adopted, the ceramic Ag composite membrane of the embodiment 2 is adopted, a group of heaters are arranged outside the reactor, the reaction temperature is 300 ℃, the pressure of a reaction cavity is 0.8MPa, the methanol feeding is 45g/h, the water-methanol molar ratio is 1: 1, the conversion rate of the methanol is 80%, the hydrogen recovery rate is 90%, and the purity of the product hydrogen reaches 100%.
The calculation formula is as follows:
example 5 Life test
Taking the ceramic-Pd composite membrane tube in example 1, the tube length is 450mm, and the effective membrane area is 65cm2The membrane permeation amount is 67ml/cm2·min·atm1/2A membrane reactor was assembled as in example 3, the apparatus was set up as in example 4, the amount of catalyst was 50g, the methanol feed amount was 30g/H, the molar ratio of water to methanol was 1: 1, the pressure in the reaction chamber was 0.4MPa, and the pressure in the permeation chamber was 0, and the reaction was carried out at 300 ℃ for 1000 hours, as a result, as shown below, in the permeation chamber H2Purity is plotted against time, see FIG. 3.
Example 6 examination of conditions
A membrane reactor was constructed in the same manner as in example 5, and the influence of different reaction pressures and methanol feed amounts on the conversion rate was examined, wherein the methanol feed amounts were 54g/h, 70g/h, and 100g/h, respectively, the reaction pressure was in the range of 0 to 1.5MPa (gauge pressure), the methanol conversion rate gap pressure increased and increased, and the methanol conversion rate decreased with the increase in the feed amount under the same pressure, as shown in FIG. 4.
Example 7
The device was constructed in the same manner as in example 5, and the low temperature performance of the membrane at 250 ℃ was examined, the methanol feed rate was 65g/h and 100g/h, and after 100 hours of stable operation, the membrane tube was removed, and no hydrogen embrittlement or rupture was observed.
Claims (3)
1. The utility model provides a reactor of ceramic metal complex film for hydrogen production is changeed to methanol steam, its characterized in that palladium silver metallic film thickness that the used ceramic substrate tube of reactor plated is 1 ~ 10 mu m, and the palladium silver content of constituteing the metallic film is palladium 70 ~ 100%, silver respectively: 0 to 30 percent.
2. The production of a reactor according to claim 1, wherein the palladium-silver active sites are formed not only on the surface of the base film but also mainly in the pores, and a part of the produced palladium-silver film is taken into the pores of the base film.
3. An application method for producing hydrogen by using the ceramic-metal composite membrane reactor of claim 1, wherein a methanol decomposition hydrogen production reaction catalyst is filled in the reactor, and is characterized in that the reaction temperature is 250-300 ℃, the pressure of a reaction cavity is 0.1-2.0 MPa, and the pressure of a permeation cavity is 0-0.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112487A CN1046251C (en) | 1994-09-02 | 1994-09-02 | Ceramic-metal composite film reactor and its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112487A CN1046251C (en) | 1994-09-02 | 1994-09-02 | Ceramic-metal composite film reactor and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117941A true CN1117941A (en) | 1996-03-06 |
| CN1046251C CN1046251C (en) | 1999-11-10 |
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| CN94112487A Expired - Fee Related CN1046251C (en) | 1994-09-02 | 1994-09-02 | Ceramic-metal composite film reactor and its preparation and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785956B (en) * | 2009-01-24 | 2012-02-29 | 碧氢科技开发股份有限公司 | Membrane-tube complex and high-purity hydrogen generator using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7252692B2 (en) * | 2004-01-21 | 2007-08-07 | Min-Hon Rei | Process and reactor module for quick start hydrogen production |
| CN101721919B (en) * | 2008-10-30 | 2012-09-26 | 中国石油化工股份有限公司 | Method for preparing tubular support dense oxide film |
| CN103446893B (en) * | 2013-09-06 | 2015-09-02 | 南京工业大学 | Method for preparing metal organic framework membrane on inner wall of tubular ceramic support |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1197998A1 (en) * | 1983-07-15 | 1985-12-15 | Институт нефтехимического синтеза им.А.В.Топчиева | Method of isolating hydrogen |
| JPS63295402A (en) * | 1987-05-27 | 1988-12-01 | Ise Kagaku Kogyo Kk | Hydrogen production method |
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1994
- 1994-09-02 CN CN94112487A patent/CN1046251C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785956B (en) * | 2009-01-24 | 2012-02-29 | 碧氢科技开发股份有限公司 | Membrane-tube complex and high-purity hydrogen generator using the same |
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| CN1046251C (en) | 1999-11-10 |
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