CN101711987B - Dehydrogenation catalyst and preparation method thereof - Google Patents
Dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN101711987B CN101711987B CN2009101545461A CN200910154546A CN101711987B CN 101711987 B CN101711987 B CN 101711987B CN 2009101545461 A CN2009101545461 A CN 2009101545461A CN 200910154546 A CN200910154546 A CN 200910154546A CN 101711987 B CN101711987 B CN 101711987B
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- catalyst
- hydrogen
- carrier
- removing hydrogen
- metal promoter
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 238000003541 multi-stage reaction Methods 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 239000010970 precious metal Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 230000008030 elimination Effects 0.000 description 9
- 238000003379 elimination reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 210000000952 spleen Anatomy 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a dehydrogenation catalyst, which comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, wherein the carrier is Al2O3The active component is noble metal Pd, the assistant is a metal assistant, and the metal assistant is a mixture of any two or more than three of the following components: ni, Fe, Ba, Ce, La, Sm or Pr; the loading amount of the noble metal Pd is 0.25-1.0 wt%, and the ratio of the noble metal Pd to the total amount of all metals in the metal auxiliary agent is 0.3-1.5: 1. The invention also discloses a preparation method of the dehydrogenation catalyst and an oxyhydrogen composite reaction applied to a dehydrogenation process in a trace hydrogen environment. The invention has the beneficial effects that: by adopting a special preparation technology, the obtained dehydrogenation catalyst has the characteristics of high dispersity, high low-temperature activity, high toxicity resistance, high humidity resistance and the like, the heavy metal Pd loading is only 0.25-1.0 wt%, and high activity and low cost are realized.
Description
(1) technical field
The present invention relates to a kind of catalyst for removing hydrogen that is used to have the hydrogen environment and preparation method thereof, its action principle is to utilize the catalysis hydrogen-oxygen to be combined into water to eliminate the micro-hydrogen in the environment.
(2) background technology
Along with being widely used of organic hydrogenation synthesis technique, little hydrogen environment is more and more.Like all kinds of hydrogen laboratories of using; The charge and discharge process of lead-acid accumulator, the part water decomposition produces hydrogen; In the nuclear submarine, adopt the water electrolytic oxygen generating device to produce oxygen and supply submarine person to breathe, and be discharged to hydrogen outside the ship; In the nuclear power plant containment shell, because high-temperature metal and water reaction also can produce hydrogen.All these all exist hydrogen with hydrogen and the place that has micro-hydrogen to produce in the middle of its environment, the accumulation of hydrogen in the closed environment is easy to cause accident to take place, and therefore eliminates the necessary guarantee that this hydrogen-like is safety in production as far as possible.
The compound hydrogen-oxygen of employing catalysis is that the dehydrogenating process of water is the most easily; For guaranteeing its high efficiency, general most employing precious metals pt and Pd are the catalyst of main active, but efficient, long-life, low cost for guaranteeing catalyst; Still need from prior art and to address the problem: 1, because hydrogen oxygen composite reaction is the gas-solid heterogeneous catalytic reaction; Be to keep activity of such catalysts, catalyst surface can not moistening by aqueous water (promptly wet water problems), and the product of reaction is a water; Therefore temperature how to control reaction system is very crucial; Can not be too high, can not be low excessively, suitable reaction temperature is controlled effective operation that can make product water leave reaction system with gaseous form and guarantee catalyst.2, because little hydrogen environment of removing generally is a room temperature, so the compound initial temperature of hydrogen-oxygen is lower, desired catalyst should possess very high low temperature active.3, owing to used noble metal to be active component, how reducing its consumption with the control product cost, is that can catalyst business-like key point.4, consider that the sulfur-bearing that possibly contain in the environment etc. poisons gas, and want stable operation several years, so the poison resistance of this catalyst is had specific (special) requirements.
Existing patent report (the US4459270 of existing hydrogen-eliminating catalyst; CN1040156A etc.); But generally all use two kinds of noble metals of Pt and Pd to be host; And because its preparation method limit, all exist decentralization not high cause noble metal dosage (>=1wt%) than greatly and cost is higher, and fail to solve fully wet water problems.
(3) summary of the invention
To above-mentioned situation, the inventor thinks that the low temperature active that improves catalyst is the effective means that addresses the above problem, and key is how to improve the decentralization of noble metal in carrier surface.The raising of decentralization not only can strengthen the low temperature active of catalyst, and can also reduce the consumption of noble metal greatly and reduce cost.
The technical scheme that the present invention adopts is: a kind of catalyst for removing hydrogen, described catalyst comprise carrier and are carried on active component and the auxiliary agent on the carrier that described carrier is Al
2O
3, described active component is a precious metals pd, and described auxiliary agent is a metal promoter, and described metal promoter is following any mixing more than two or three: Ni, Fe, Ba, Ce, La, Sm or Pr; The load capacity of said precious metals pd is 0.25～1.0wt%, and the ratio of the total amount of substance of all metals is 0.3～1.5: 1 in said precious metals pd and the metal promoter.
Metal promoter of the present invention is preferably following any combination more than two or three: Ni, Fe, Sm or Ba.
The present invention also provides a kind of method for preparing described catalyst for removing hydrogen, and described method is: the Al that takes by weighing respective amount according to the load capacity of precious metals pd
2O
3, H
2PdCl
6, metal promoter nitrate, described H
2PdCl
6, metal promoter nitrate be made into the aqueous solution, with macromolecular compound, organic solvent under 25～50 ℃ of temperature, placing frequency is 20～60KHz ultrasonic oscillation, stirs 1～2 hour, adds described Al again
2O
3Carrier in the identical ultrasonic oscillation, flooded 2～5 hours, and said dipping requires the complete submergence Al of reaction solution
2O
3Carrier, the dipping finish after, with complete reaction mixture in 100～120 ℃ of oven dry; Complete reaction mixture described herein comprises all reaction solutions and impregnated in the carrier in the reaction solution, 300～600 ℃ of roastings 2～5 hours, obtains calcining matter then; Calcining matter is under 200～600 ℃ reduction temperature; (hydrogeneous 10～30%v/v) reduce, and the recovery time is 2～6 hours, and the control gas space velocity is 200～900h to feed pure hydrogen or hydrogen nitrogen mixed gas
-1, obtain said catalyst for removing hydrogen; Said macromolecular compound is enanthol, hexanol or octanol, and said organic solvent is an ethanol.
In the inventive method, said macromolecular compound is preferably enanthol, said macromolecular compound and carrier A l
2O
3Volume ratio be 0.1～0.3: 1.
In the inventive method, the volume ratio of the material of said organic solvent and macromolecular compound is 1.0～5.0: 1.
The condition of the said oven dry of the inventive method is: reactant mixture is dried to the former Al of mass ratio
2O
3Carrier weightening finish≤5%.
Beneficial effect of the present invention is:
1, said catalyst for removing hydrogen only uses Pd to be main catalytic active component for one kind, and because high degree of dispersion only needs very low content, load capacity is merely 0.25～1.0wt%, and is with low cost.
2, use two kinds of auxiliary agents at least, low-temperature catalytic activity is high, poison resistance is strong.
3, among the preparation method,, improve the decentralization of precious metals pd, the simple easy operating of method through macromolecular compound and hyperacoustic synergy.Wherein the selection of macromolecular compound is most important, and it not only plays the effect of modifying carrier, can also influence the particle size of active component simultaneously.Action of ultrasonic waves mainly is to help the dispersion of precious metals pd at carrier surface.
4, the present invention can make the hydrogen-oxygen combined temp controlled through selecting different macromolecular compounds to improve the decentralization of Pd.
In sum, dehydrogenation catalyst for removing hydrogen provided by the invention and preparation method thereof owing to adopted special technology of preparing, has obtained having high degree of dispersion, the catalyst of characteristics such as high low temperature active, high antitoxin high moisture-resistant, has realized high activity, low cost.
Catalyst of the present invention can be applicable to the hydrogen oxygen composite reaction of dehydrogenation process in the micro-hydrogen environment, carries out practical application on hydrogenation laboratory, lead-acid accumulator and other places, and the dehydrogenation effect is obvious.
(4) specific embodiment
Below in conjunction with embodiment the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1
Take by weighing the Al after the oven dry
2O
3Carrier 10 grams (20mL is measured with graduated cylinder) are subsequent use.The concentration that in the 100ml there-necked flask, adds 2ml enanthol, 6ml ethanol, 5.0ml respectively is the H of 0.010gPd/ml
2PdCl
6The concentration of solution, 5.0ml is the Ni (NO of 0.0080gNi/ml
3)
2The concentration of solution, 5.0ml is the Sm (NO of 0.0080gSm/ml
3)
3Solution places under the 40kHz ultrasonic oscillation, under 30 ℃ of temperature, stirs to become mixed liquor in 1 hour, again with Al
2O
3Dipping is 3 hours in the carrier adding mixed liquor.Said process all carries out under the ultrasonic oscillation effect, after dipping finishes, with complete reaction mixture in 110 ℃ of oven dry (increase weight≤5%); Place 450 ℃ of roastings of Muffle furnace 4 hours again; Logical then hydrogen reducing, reduction temperature is controlled at 400 ℃, 4 hours time; Air speed 800/ hour (volume) obtains light grey catalyst finished product 20ml.
The above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures, hydrogen-argon-mixed with hydrogeneous 2v% measured the hydrogen activity that removes of catalyst in 2000/ hour air speed, and the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 90.1%.
Instance 2
Take by weighing the Al after the oven dry
2O
3Carrier 10 grams (20mL is measured with graduated cylinder) are subsequent use.The concentration that in the 100ml there-necked flask, adds 2ml enanthol, 6ml ethanol, 5.0ml respectively is the H of 0.010gPd/ml
2PdCl
6The concentration of solution, 5.0ml is the Ni (NO of 0.0080gNi/ml
3)
2The concentration of solution, 5.0ml is the La (NO of 0.0080gLa/ml
3)
3Solution places under the 50Hz ultrasonic oscillation, under 30 ℃ of temperature, stirs to become mixed liquor in 1 hour, again with Al
2O
3Dipping is 4 hours in the carrier adding mixed liquor.Said process all carries out under the ultrasonic oscillation effect, after dipping finishes, complete reaction mixture in 120 ℃ of oven dry, is placed 450 ℃ of roastings of Muffle furnace 4 hours again, logical then hydrogen reducing, and reduction temperature is controlled at 300 ℃, 5 hours time, air speed 800h
-1(volume) obtains the catalyst finished product 20ml of light ash.
The above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures, hydrogen-argon-mixed with hydrogeneous 2v% measured the hydrogen activity that removes of catalyst in 2000/ hour air speed, and the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 87.1%.
Instance 3
Take by weighing the Al after the oven dry
2O
3Carrier 10 grams (20mL is measured with graduated cylinder) are subsequent use.The concentration that in the 100ml there-necked flask, adds 2ml enanthol, 6ml ethanol, 5.0ml respectively is the H of 0.010gPd/ml
2PdCl
6The concentration of solution, 5.0ml is the Fe (NO of 0.0080gFe/ml
3)
2The concentration of solution, 5.0ml is the Sm (NO of 0.0080gSm/ml
3)
3Solution places under the 60Hz ultrasonic oscillation, under 50 ℃ of temperature, stirs to become mixed liquor in 1 hour, again with Al
2O
3Dipping is 4 hours in the carrier adding mixed liquor.Said process all carries out under the ultrasonic oscillation effect, after dipping finishes, complete reaction mixture in 100 ℃ of oven dry, is placed 450 ℃ of roastings of Muffle furnace 5 hours again, logical then hydrogen reducing, and reduction temperature is controlled at 300 ℃, 5 hours time, air speed 800h
-1(volume) obtains the catalyst finished product 20ml of light ash.
The above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures, with hydrogeneous 2% hydrogen-argon-mixed, measure the hydrogen activity that removes of catalyst in 2000/ hour air speed, the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 85.1%.
Instance 4
Take by weighing the Al after the oven dry
2O
3Carrier 10 grams (20mL is measured with graduated cylinder) are subsequent use.The concentration that in the 100ml there-necked flask, adds 2ml enanthol, 6ml ethanol, 5.0ml respectively is the H of 0.010gPd/ml
2PdCl
6The concentration of solution, 5.0ml is the Fe (NO of 0.0080gFe/ml
3)
2The concentration of solution, 5.0ml is the La (NO of 0.0080gLa/ml
3)
3Solution places under the 40Hz ultrasonic oscillation, under 30 ℃ of temperature, stirs to become mixed liquor in 1 hour, again with Al
2O
3Dipping is 4 hours in the carrier adding mixed liquor.Said process all carries out under the ultrasonic oscillation effect, the dipping finish after, with complete reaction mixture in 110 ℃ of oven dry; Place 600 ℃ of roastings of Muffle furnace 5 hours again, logical then hydrogen nitrogen mixed gas (hydrogeneous 30%v/v)) reduction, reduction temperature is controlled at 400 ℃; 6 hours time, air speed 900h
-1(volume) obtains the catalyst finished product 20ml of light ash.
The above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures, with hydrogeneous 2% hydrogen-argon-mixed, measure the hydrogen activity that removes of catalyst in 2000/ hour air speed, the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 83.2%.
Instance 5
Operate according to embodiment 1, different is that the concentration that adds 5.0ml is the H of 0.010gPd/ml
2PdCl
6Solution changes into and adds 10.0ml, and the hydrogen reducing temperature changes 380 ℃ into, and other operations and condition are with embodiment 1; Obtain light grey catalyst finished product 20ml, the above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures; Hydrogen-argon-mixed with hydrogeneous 2v%; Measure the hydrogen activity that removes of catalyst in 2000/ hour air speed, the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 99.1%.
Instance 6
Operate according to embodiment 1, different is that the concentration that has increased 2.0ml is the Ba (NO of 0.010gBa/ml
3)
2Solution, hydrogen reducing temperature change 380 ℃ into, and the recovery time changes 6 hours into; Other operations and condition obtain light grey catalyst finished product 20ml with embodiment 1, and above-mentioned catalyst 3ml packs in the catalyst activity evaluation system; At normal temperatures and pressures, hydrogen-argon-mixed with hydrogeneous 2v% measured the hydrogen activity that removes of catalyst in 2000/ hour air speed; The detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen is 90.8%.
Instance 7
Operate according to embodiment 1, different is that the concentration that adds 5.0ml is the H of 0.010gPd/ml
2PdCl
6Solution changes into and adds 2.5ml, and the hydrogen reducing temperature changes 350 ℃ into, and other operations and condition are with embodiment 1; Obtain light grey catalyst finished product 20ml, the above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures; Hydrogen-argon-mixed with hydrogeneous 2v%; Measure the hydrogen activity that removes of catalyst in 2000/ hour air speed, the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 80.1%.
Instance 8
Operate according to embodiment 1, different is that the concentration that adds 5.0ml is the Ni (NO of 0.0080gNi/ml
3)
2The concentration of solution, 5.0ml is the Sm (NO of 0.0080gSm/ml
3)
3Solution all changes into and adds 2.5ml, and the hydrogen reducing temperature changes 350 ℃ into, and other operations and condition are with embodiment 1; Obtain light grey catalyst finished product 20ml, the above-mentioned catalyst 3ml that in the catalyst activity evaluation system, packs into, at normal temperatures and pressures; Hydrogen-argon-mixed with hydrogeneous 2v%; Measure the hydrogen activity that removes of catalyst in 2000/ hour air speed, the detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen are 88.1%.
Instance 9
Operate according to embodiment 1, different is to add the 2.0ml enanthol and change adding 6ml into; He the operation and condition with embodiment 1, obtain the about 20ml of light grey catalyst finished product, above-mentioned catalyst 3ml packs in the catalyst activity evaluation system; At normal temperatures and pressures, hydrogen-argon-mixed with hydrogeneous 2v% measured the hydrogen activity that removes of catalyst in 2000/ hour air speed; The detection residual hydrogen of working off one's feeling vent one's spleen, the elimination factor of hydrogen is 83.1%.
Instance 10
Place two solid fixed GF-200 lead-acid accumulators to disappear the catalyst 5ml of instance 1 preparation and carry out the dehydrogenation test in the hydrogen valve, in discharge current 10 peaces down, generation hydrogen is eliminated basically.
Claims (6)
1. a catalyst for removing hydrogen is characterized in that described catalyst comprises carrier and is carried on active component and the auxiliary agent on the carrier, and described carrier is Al
2O
3, described active component is a precious metals pd, and described auxiliary agent is a metal promoter, and described metal promoter is following any mixing more than two or three: Ni, Fe, Ba, Ce, La, Sm or Pr; The load capacity of said precious metals pd is 0.25～1.0wt%, and the ratio of the total amount of substance of all metals is 0.3～1.5: 1 in said precious metals pd and the metal promoter;
Said catalyst for removing hydrogen prepares by following method: the Al that takes by weighing respective amount according to the load capacity of precious metals pd
2O
3, H
2PdCl
6, metal promoter nitrate, described H
2PdCl
6, metal promoter nitrate be made into the aqueous solution, with macromolecular compound, organic solvent under 25～50 ℃ of temperature, place ultrasonic oscillation, stirred 1～2 hour, add described Al again
2O
3, in the ultrasonic oscillation, flooded 2～5 hours; The dipping finish after, with complete reaction mixture in 100～120 ℃ of oven dry, then 300～600 ℃ of roastings 2～5 hours; Obtain calcining matter, calcining matter is under 200～600 ℃ reduction temperature, and the hydrogen nitrogen mixed gas that feeds pure hydrogen or hydrogeneous 10～30%v/v reduces; Recovery time is 2～6 hours, and the control gas space velocity is 200～900h
-1, obtain said catalyst for removing hydrogen; Said macromolecular compound is enanthol, hexanol or octanol, and said organic solvent is an ethanol.
2. catalyst for removing hydrogen as claimed in claim 1 is characterized in that described metal promoter is following any combination more than two or three: Ni, Fe, Sm or Ba.
3. catalyst for removing hydrogen as claimed in claim 1 is characterized in that said frequency of ultrasonic is 20～60KHz.
4. catalyst for removing hydrogen as claimed in claim 1 is characterized in that said macromolecular compound and carrier A l
2O
3Volume ratio be 0.1～0.3: 1.
5. catalyst for removing hydrogen as claimed in claim 1, the volume ratio that it is characterized in that said organic solvent and macromolecular compound is 1.0～5.0: 1.
6. catalyst for removing hydrogen as claimed in claim 1 is applied to the hydrogen oxygen composite reaction of dehydrogenation process in the micro-hydrogen environment.
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|---|---|---|---|
| CN2009101545461A CN101711987B (en) | 2009-11-11 | 2009-11-11 | Dehydrogenation catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101545461A CN101711987B (en) | 2009-11-11 | 2009-11-11 | Dehydrogenation catalyst and preparation method thereof |
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| CN101711987B true CN101711987B (en) | 2012-05-30 |
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Citations (7)
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|---|---|---|---|---|
| US4459270A (en) * | 1982-03-12 | 1984-07-10 | Cjb Developments Limited | Process for the removal of hydrogen from gases |
| CN1040156A (en) * | 1988-10-18 | 1990-03-07 | 中国科学院兰州化学物理研究所 | Hydrogen-eliminating catalyst |
| EP0398446A1 (en) * | 1989-05-18 | 1990-11-22 | Engelhard De Meern B.V. | Catalyst for hydrogenation and/or dehydrogenation |
| CN1249964A (en) * | 1999-10-26 | 2000-04-12 | 湖北省化学研究所 | Dehydrogenation catalyst for urea synthesizing CO2 gas and its preparation |
| CN1334140A (en) * | 2001-07-27 | 2002-02-06 | 湖北省化学研究所 | Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea |
| US20040129135A1 (en) * | 2002-03-05 | 2004-07-08 | Roark Shane E. | Dense, layered membranes for hydrogen separation |
| CN1736590A (en) * | 2005-07-27 | 2006-02-22 | 中国船舶重工集团公司第七一八研究所 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
-
2009
- 2009-11-11 CN CN2009101545461A patent/CN101711987B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459270A (en) * | 1982-03-12 | 1984-07-10 | Cjb Developments Limited | Process for the removal of hydrogen from gases |
| CN1040156A (en) * | 1988-10-18 | 1990-03-07 | 中国科学院兰州化学物理研究所 | Hydrogen-eliminating catalyst |
| EP0398446A1 (en) * | 1989-05-18 | 1990-11-22 | Engelhard De Meern B.V. | Catalyst for hydrogenation and/or dehydrogenation |
| US5482616A (en) * | 1989-05-18 | 1996-01-09 | Engelhard De Meern B. V. | Process for hydrogenation and/or dehydrogenation |
| CN1249964A (en) * | 1999-10-26 | 2000-04-12 | 湖北省化学研究所 | Dehydrogenation catalyst for urea synthesizing CO2 gas and its preparation |
| CN1334140A (en) * | 2001-07-27 | 2002-02-06 | 湖北省化学研究所 | Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea |
| US20040129135A1 (en) * | 2002-03-05 | 2004-07-08 | Roark Shane E. | Dense, layered membranes for hydrogen separation |
| CN1736590A (en) * | 2005-07-27 | 2006-02-22 | 中国船舶重工集团公司第七一八研究所 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101711987A (en) | 2010-05-26 |
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