CN110508290A - High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof - Google Patents
High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof Download PDFInfo
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- CN110508290A CN110508290A CN201910814713.4A CN201910814713A CN110508290A CN 110508290 A CN110508290 A CN 110508290A CN 201910814713 A CN201910814713 A CN 201910814713A CN 110508290 A CN110508290 A CN 110508290A
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- catalyst
- palladium
- dispersion
- carrier
- acetylene
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000006185 dispersion Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims description 4
- 229910003445 palladium oxide Inorganic materials 0.000 title description 2
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002803 maceration Methods 0.000 claims description 13
- 150000002941 palladium compounds Chemical class 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a high-dispersion Pd/Co (OH)2The invention firstly prepares Co (OH) with higher specific surface area by a simple method2Then calcining to make the surface of said carrier have more defect sites, then loading the palladium impregnating solution on Co (OH)2On the carrier, high dispersion Pd/Co (OH) with better performance is prepared2A catalyst; highly dispersed Pd/Co (OH) of the invention2The preparation of the catalyst is applied to the selective hydrogenation reaction of acetylene, and the catalyst not only has high catalytic activity and high BThe alkene selectivity also has the advantages of excellent stability, high atom utilization rate and the like.
Description
(1) technical field
The present invention relates to a kind of high-dispersion Pd/Co (OH)2Catalyst and preparation method thereof, and in selective hydrogenation of acetylene
Application in reaction.
(2) background technique
Ethylene is one of most important chemical products in world wide, is widely used in synthetic plastic, rubber, fibre
The every field such as dimension, medicine, pesticide and dyestuff.Industrial ethylene mainly passes through the cracking of the raw materials such as naphtha and diesel oil and is made,
But the acetylene of about 0.3%-3% is often generated during preparing ethylene gas；These trace acetylenes can poison downstream
The Ziegler-Natta catalyst of polyethylene process can not only reduce the activity and service life of catalyst, and also can be serious
Influence the product quality of polyethylene process.Therefore, removing trace acetylene in unstripped gas has important industrial significance.
The method of industrial common removing acetylene is selection hydrogenation method, with pollution-free, low energy consumption, technical process is simple
The advantages that and be widely used.However, although the palladium-based catalyst of industrial tradition possesses preferably catalytic activity, still
But there is poor ethylene selectivity, it may occur that excessive hydrogenation generates ethane and oligomerization generation green oil occurs either to shadow
Ring the service life of catalyst.Then ethylene selectivity of the palladium-based catalyst in acetylene hydrogenation reaction is for ethylene industry
It is vital, it is therefore desirable to catalyst is modified, prevent ethylene from excessive hydrogenation occurs and generate ethane, to further mention
The selectivity of high ethylene.
The carrier surface of synthesis has defect sites more abundant, so as to higher in conjunction with metal phase.And surface
- OH functional group abundant can effectively be anchored metallic atom, to make metallic atom high dispersive on the surface of the carrier.Synthesis
The acidity of the more typical aluminium oxide of carrier, defect sites is weaker, further improves the selectivity and stability of catalyst.
Based on background above, the invention proposes a kind of high-dispersion Pd/Co (OH)2The preparation of catalyst, to improve palladium base
Selectivity of the catalyst in acetylene hydrogenation reaction.
(3) summary of the invention
The present invention provides a kind of high-dispersion Pd/Co (OH)2Catalyst and preparation method thereof, and add in selective acetylene
Application in hydrogen reaction.Preparation method simple process of the present invention, catalyst obtained can largely improve selective acetylene
Ethylene selectivity in hydrogenation reaction.
Technical scheme is as follows:
A kind of high-dispersion Pd/Co (OH)2Catalyst is prepared as follows to obtain:
(1) it prepares palladium maceration extract: palladium compound is dissolved in solvent, palladium maceration extract is made；
In the palladium maceration extract, concentration of the palladium compound in terms of palladium is 0.001-0.01g/mL；
The palladium compound is palladium acetate, palladium acetylacetonate, dichloro diamino palladium, tetrachloro-palladium acid ammonium, chlorine palladium acid sodium or nitric acid
Four ammino palladiums, preferably palladium acetate；
The solvent can be water, hydrochloric acid, ethyl alcohol, acetone etc., the present invention does not have this depending on the type of palladium compound
There is particular/special requirement；
(2)Co(OH)2The synthesis of carrier: cobalt chloride hexahydrate, precipitating reagent are dissolved in deionized water, stir 0.5h, so
After be added propylene oxide, stir 0.5~5h under room temperature (20~30 DEG C), Precipitation, be placed at 80 DEG C dry 12h, Gu
Body product is washed with methanol and deionized water, and 8~12h is dried at 110 DEG C, is finally putting into Muffle furnace, at 350~700 DEG C
2-6h is roasted, Co (OH) is obtained2Carrier；
The ratio between amount of substance of the cobalt chloride hexahydrate, precipitating reagent, propylene oxide be 1:1~5:1~10, preferably 1:2:
10；
The precipitating reagent is lauryl sodium sulfate, hexa, ammonium nitrate, ammonium fluoride or ammonium chloride, preferably chlorine
Change ammonium；
(3) high-dispersion Pd/Co (OH)2The preparation of catalyst: by Co (OH)2Carrier is immersed in palladium maceration extract, and dispersion is equal
It is even, 9-12h is impregnated at room temperature, and the dry 9-12h at 110-130 DEG C, is subsequently placed into tube furnace, at 300-700 DEG C later
6-10h is calcined, high-dispersion Pd/Co (OH) is obtained2Catalyst；
In the present invention, after the cobalt hydroxide in step (3) is immersed in palladium maceration extract and impregnates 9-12h, system can be placed in
In microwave reactor, the microwave 20-80min at 110-130 DEG C can further promote dispersion of the metal component on carrier, so
Sample is put into 110~130 DEG C of baking ovens dry 9~12h again afterwards, calcining obtains final catalyst later.
In gained catalyst of the invention, the quality based on carrier, load capacity of the palladium compound in terms of palladium is 0.01-
0.5wt%, preferably 0.01-0.1wt%, more preferable 0.01-0.03wt%.
In the preparation method of catalyst of the present invention, palladium compound is regarded as whole loads, those skilled in the art
The additional amount of load capacity the selection palladium compound and carrier that can according to need.
High-dispersion Pd/Co (OH) of the present invention2Catalyst can be applied in acetylene hydrogenation reaction.Specifically, described answer
Method are as follows:
Before selective hydrogenation of acetylene reaction, need first to restore the catalyst with hydrogen, reduction temperature is
130-230 DEG C, time 1-4h；The catalyst after reduction is used for selective hydrogenation of acetylene reaction, reaction condition are as follows: temperature again
60-210 DEG C (preferably 60-150 DEG C), pressure 0.1-1MPa (preferably 0.1-0.3MPa, more preferable normal pressure), air speed 1000-
10000h-1(preferably 4000-8000h-1)；
In the selective hydrogenation of acetylene reaction, the gas composition for reacting initial is (volume fraction): 0.33%C2H2、
0.66%H2, 33.3%C2H4, surplus N2。
Compared with prior art, the beneficial effects of the present invention are:
(1) high-dispersion Pd/Co (OH) of the invention2The preparation of catalyst is to prepare by simple method first
The higher Co of specific surface area (OH)2Carrier, then by calcining etc. operations so that carrier surface has more defect sites.
Then palladium maceration extract is supported on Co (OH)2On carrier, performance preferably high-dispersion Pd/Co (OH) has been prepared2Catalyst.One
Aspect, palladium obtain higher dispersion degree on carrier, this is advantageous acetylene hydrogenation reaction；On the other hand, this carrier
The acidity on surface is lower compared with aluminium oxide, that is to say, that this carrier surface is substantially without middle strong acid site, in acetylene
Less green oil can be generated in hydrogenation reaction, so that the high-dispersion Pd/Co (OH) prepared2Catalyst has higher stabilization
Property；Finally, high-dispersion Pd/Co (OH)2Catalyst surface contains a large amount of hydroxyl group, and this hydroxyl group can more preferably be stablized
Anchoring palladium presence, so that the further high dispersive of palladium be made to be present on catalyst.In addition the anchoring between hydroxyl and palladium be with
Existing for chemical species, hydroxyl can provide electronics transfer to palladium active site, so that electron rich state is presented in palladium activated centre, from
And obtain high ethylene selectivity.
(2) high-dispersion Pd/Co (OH) of the invention2The preparation method of catalyst, simple process.
(3) high-dispersion Pd/Co (OH) of the invention2The application and preparation of catalyst is in selective hydrogenation of acetylene reaction, no
Only there is high catalytic activity and high ethylene selectivity, while it is excellent also to have excellent stability and atom utilization height etc.
Point.
(4) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
In following embodiment, Co (OH)2Carrier synthesizes as follows:
The precipitating reagent ammonium chloride of the cobalt chloride hexahydrate of 0.01mol, 0.02mol are placed in small beaker, are added a certain amount of
Deionized water to dissolve, stir 0.5h, 0.1mol propylene oxide be then added, stirs 5h at room temperature, Precipitation, postposition
Dry 12h, solid product are washed 3-5 times with methanol and deionized water, dry overnight at 110 DEG C, be finally putting into horse at 80 DEG C
Not in furnace, 6h is roasted at 600 DEG C, obtains Co (OH)2Carrier.
Embodiment 1-5
It weighs a certain amount of palladium acetate to be dissolved in concentrated hydrochloric acid, be transferred in volumetric flask, a certain amount of deionized water is added
To corresponding scale, the mass concentration that palladium is made is the chlorine palladium acid solution of 0.001g/mL.According to load capacity listed by table 2 and its match
Than the chlorine palladium acid solution of metering and a certain amount of deionized water being mixed, after mixing evenly, equably by high dispersive Co (OH)2
(specific surface area is about 150-250m to carrier2/ g) it pours into maceration extract, ultrasound makes it be uniformly dispersed.By the Co (OH) of wetting2It carries
Body is in room temperature immersion 12h, and the dry 12h at 110 DEG C, and after taking out sample, sample is forged under the conditions of 350~700 DEG C
After burning calcining 6h, high-dispersion Pd/Co (OH) is obtained2Catalyst.
Co (OH) in embodiment 42Carrier texture Nature comparison before and after loading Pd is shown in Table 1:
Table 1 loads carrier texture Nature comparison before and after Pd
Embodiment 6
Referring to the operation of embodiment 5, it is 60m that difference, which is only that carrier changes specific surface area into,2The aluminium oxide of/g is made simple
Pd/Al2O3Catalyst.
Embodiment 7
Referring to the operation of embodiment 5, it is 420m that difference, which is only that carrier changes specific surface area into,2Letter is made in the aluminium oxide of/g
Single Pd/Al2O3Catalyst.
Embodiment 8
High-dispersion Pd/Co (OH) prepared by embodiment 22Catalyst in microwave reactor in 100 DEG C of reaction 80min,
Obtain finished catalyst.
Embodiment 9
High-dispersion Pd/Co (OH) prepared by embodiment 52Catalyst in microwave reactor in 120 DEG C of reaction 60min,
Obtain finished catalyst.
Catalyst obtained carries out catalyst activity and selective evaluation according to following method:
0.3g catalyst is placed in small-sized quartz tube reactor, quartz ampoule is placed in the heating mantle of controllable temperature, In
Before selective hydrogenation of acetylene reaction evaluating, catalyst is needed in pure H21h is restored in atmosphere at 180 DEG C, reduction gas velocity is
10mL/min；After reduction, by being reacted at temperature shown in table 2.Reaction gas group becomes (volume fraction): 0.33% acetylene,
The flow velocity of 33.3% ethylene, 0.66% hydrogen, surplus nitrogen, reaction gas is 50mL/min, and reaction pressure is normal pressure.Reaction gas goes out
Mouth connects gas-chromatography on-line checking, and the evaluation result of catalyst see the table below shown in 2.
2 high-dispersion Pds of table/Co (OH)2The selective hydrogenation of acetylene reaction evaluating result of catalyst
Embodiment 10-15
Referring to the preparation method of the catalyst of embodiment 1-5, the load capacity of palladium maceration extract is shown in Table 3, prepares high-dispersion Pd/Co
(OH)2Catalyst.
The evaluation method of catalyst activity and selectivity is same as above, and changes simultaneously the calcination temperature for preparing catalyst and acetylene adds
Reaction temperature in hydrogen reaction, the evaluation result of catalyst see the table below shown in 3.
3 high-dispersion Pds of table/Co (OH)2The selective hydrogenation of acetylene reaction evaluating result of catalyst
Claims (7)
1. a kind of high-dispersion Pd/Co (OH)2Catalyst, which is characterized in that be prepared as follows to obtain:
(1) it prepares palladium maceration extract: palladium compound is dissolved in solvent, palladium maceration extract is made；
The palladium compound is palladium acetate, palladium acetylacetonate, dichloro diamino palladium, four ammonia of tetrachloro-palladium acid ammonium, chlorine palladium acid sodium or nitric acid
Close palladium；
(2)Co(OH)2The synthesis of carrier: cobalt chloride hexahydrate, precipitating reagent are dissolved in deionized water, 0.5h is stirred, is then added
Propylene oxide, stirs 0.5~5h at room temperature, Precipitation, be placed at 80 DEG C dry 12h, solid product methanol and go
Ion water washing dries 8~12h at 110 DEG C, is finally putting into Muffle furnace, roasts 2-6h at 350~700 DEG C, obtain Co
(OH)2Carrier；
The ratio between amount of substance of the cobalt chloride hexahydrate, precipitating reagent, propylene oxide is 1:1~5:1~10；
The precipitating reagent is lauryl sodium sulfate, hexa, ammonium nitrate, ammonium fluoride or ammonium chloride；
(3) high-dispersion Pd/Co (OH)2The preparation of catalyst: by Co (OH)2Carrier is immersed in palladium maceration extract, is uniformly dispersed, room
Temperature is lower to impregnate 9-12h, and the dry 9-12h at 110-130 DEG C, is subsequently placed into tube furnace, calcines 6- at 300-700 DEG C later
10h obtains high-dispersion Pd/Co (OH)2Catalyst.
2. high-dispersion Pd/Co (OH) as described in claim 12Catalyst, which is characterized in that in step (1), the palladium maceration extract
In, concentration of the palladium compound in terms of palladium is 0.001-0.01g/mL.
3. high-dispersion Pd/Co (OH) as described in claim 12Catalyst, which is characterized in that in step (2), the six hydrations chlorine
Changing the ratio between amount of substance of cobalt, precipitating reagent, propylene oxide is 1:2:10.
4. high-dispersion Pd/Co (OH) as described in claim 12Catalyst, which is characterized in that the cobalt hydroxide submergence in step (3)
In palladium maceration extract and after impregnating 9-12h, system is placed in microwave reactor, the microwave 20-80min at 110-130 DEG C, then
Sample is put into 110~130 DEG C of baking ovens dry 9~12h again, calcining obtains final catalyst later.
5. high-dispersion Pd/Co (OH) as described in claim 12Catalyst, which is characterized in that in the catalyst, based on carrier
Quality, load capacity of the palladium compound in terms of palladium is 0.01-0.5wt%.
6. high-dispersion Pd/Co (OH) as described in claim 12Catalyst is applied in acetylene hydrogenation reaction.
7. application as claimed in claim 6, which is characterized in that the method for the application are as follows:
Selective hydrogenation of acetylene reaction before, first the catalyst is restored with hydrogen, reduction temperature be 130-230 DEG C,
Time is 1-4h；The catalyst after reduction is used for selective hydrogenation of acetylene reaction, reaction condition again are as follows: 60-210 DEG C of temperature,
Pressure 0.1-1MPa, air speed 1000-10000h-1；
In the selective hydrogenation of acetylene reaction, initial gas composition is reacted are as follows: 0.33%C2H2, 0.66%H2, 33.3%
C2H4, surplus N2。
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