CN107308962A - A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method - Google Patents
A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method Download PDFInfo
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- CN107308962A CN107308962A CN201710440908.8A CN201710440908A CN107308962A CN 107308962 A CN107308962 A CN 107308962A CN 201710440908 A CN201710440908 A CN 201710440908A CN 107308962 A CN107308962 A CN 107308962A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
Abstract
The present invention relates to a kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method, the chemical representation of the catalyst is：Pd‑Cl/CeOCl.The present invention finely controls catalyst activity component and the In-situ reaction process of carrier, period CeO by the optimization of preparation method2The formation of Pd Cl Ce monomers is promoted to CeOCl conversion, the interaction between active component-carrier is also enhanced while Pd Cl keys are enhanced.Compared with existing dehydrogenation, the Ostwald that the catalyst that the present invention is prepared is induced CO cures effect, product H2O erosion all possesses good immunity, has higher stability, the life-span with more than 1000 hours under reaction atmosphere.
Description
Technical field
The present invention relates to the technology of preparing of catalyst, and in particular to a kind of preparation method of Pd-Cl/CeOCl catalyst, should
Dehydrogenation for CO unstripped gas purifies reaction.
Background technology
CO is the important source material of the organic chemicals such as synthesis of oxalate, carbonic ester.Generally changed by coal, methane, biomass etc.
Stone resource rearrangement obtains synthesis gas (CO+H2), then obtain CO unstripped gas by transformation (alternating temperature) adsorbing separation.These unstripped gas contain
There is 0.5~5% H2Impurity, has a strong impact on the efficiency of CO synthesis of oxalate or carbonic ester, it is necessary to be given by Selective Oxidation
To remove purification.The reaction is generally by carried noble metal (Pd, Pt, Rh) catalyst driven, and the stability of catalyst is restriction
The key point of dehydrogenation reaction.
Chinese patent 201410309019.4 once disclosed a kind of high-performance Pd-Cl/Al2O3Dehydrogenation, Chinese patent
201610520443.2 a kind of deficiency PdCl was once disclosedx/Al2O3Dehydrogenation, by the electronics knot for modifying Pd activated centres
Structure, the catalyst series possess very high dehydrogenation activity and selectivity.However, because CO your morals of Oswald induced cure effect
The sintering of active metal can be accelerated to assemble, reaction product H2O erosion can destroy the structure in activated centre, anti-by thousands of hours
Answering the performance of rear catalyst can inevitably decline.For problem above, the present invention prepares a kind of Pd- with high stability
Cl/CeOCl catalyst, strengthens strong between Pd active components and CeOCl carriers using the bridging effect of Cl in Pd-Cl-Ce monomers
Interaction.The catalyst is to CO and H2O erosion all has good immunity, and the stability under reaction environment is significantly carried
It is high.
The content of the invention
The present invention is intended to provide a kind of high stability Pd-Cl base catalyst and preparation method thereof, the catalyst is mainly applied
The H in high-purity CO unstripped gas in oxalate or carbonic acid Lipase absobed2The selective oxidation removing of impurity.
The chemical representation of catalyst provided by the present invention is：Simple substance Pd accounts for catalyst in Pd-Cl/CeOCl, catalyst
Mass percent be 0.5~2wt.%；Cl/Pd mol ratio is 3~2 in catalyst：1；Catalyst carrier is with four directions
The CeOCl of crystalline phase.
The catalyst is using chloride palladium salt as active component precursors, with CeO2As precursor carrier, pass through precise controlling
In-situ reaction process forms the Pd-Cl-Ce monomers with high stability on the interface of active component-carrier, in the process
CeO2Precursor is converted into CeOCl, while Pd-Cl bond energy and its being significantly increased with the interaction of CeOCl carriers.
The preparation method of above-mentioned catalyst, is comprised the following steps that：
A. chloride palladium salt is weighed to be dissolved in absolute ethyl alcohol, then by surfactant and Pd mol ratio be 1：10~20 add
Surfactant, 5~6h of ultrasound, compound concentration is 0.01~0.04mol/L active component solution A；The chloride palladium salt is
Palladium bichloride or ammonium chloropalladate, preferably palladium bichloride；The surfactant is that oleic acid, polyvinylpyrrolidone, the degree of polymerization are 200
One kind in~600 polyethylene glycol, preferably polyvinylpyrrolidone.
B. by CeO2Dry colloidal dispersion adds surfactant in absolute ethyl alcohol, and 0.5~1h of ultrasound obtains concentration and is
0.3~0.6mol/L solution B；Wherein the mol ratio of surfactant and Ce is 1：1~5；The surfactant is chlorination
One of ammonium, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, preferably cetyl trimethyl chlorine
Change ammonium.
C. under inert gas shielding, solution B is slowly added dropwise in solution A, wherein A, the addition of B solution are according to most
Pd accounts for the mass percent determination of catalyst in whole catalyst, and keeps 1000~3000rpm mixing speed, in 20~60 DEG C
React after 4~12h, be dried in vacuo 10~12h in 0.02-0.03MPa, obtain solid sample.
D. the obtained solid samples of step C are placed in crystal reaction tube, in 300~500 DEG C under inert gas shielding
Room temperature is down to after 4~8h of processing, then is passed through H2Concentration is 5~20% H2/ Ar gaseous mixtures are warming up to 1~3 DEG C/min speed
500~650 DEG C and stablize room temperature is down to after 6~8h, Pd- is obtained after 10~12h of inert gas Passivation Treatment is passed through at room temperature
Cl/CeOCl finished catalysts.
Fig. 1 is the high-resolution-ration transmission electric-lens photo of Pd-Cl/CeOCl catalyst in embodiment 1, and illustration is in CeOCl Fu
Leaf transformation diffraction pattern, the CeO in the preparation process of catalyst is proved by interplanar distance and diffraction spot arrangement2It is fully converted to
CeOCl。
Fig. 2 is the X-ray powder diffraction spectrogram of catalyst sample：(a) the Pd-Cl/CeOCl catalyst of embodiment 1 is represented,
(b) Pd-Cl/CeO of comparative example 1 is represented2Catalyst, the CeO in the preparation process of catalyst is proved by the position of diffraction maximum2
It is fully converted to CeOCl.
Beneficial effects of the present invention are embodied in：By the In-situ reaction mistake for finely controlling catalyst activity component and carrier
The technological parameters such as reduction rate, temperature, passivation time in journey, and last handling process, induction of carrier by CeO2To CeOCl
Conversion and promote the formation of Pd-Cl-Ce monomers, also enhance active component-carrier while Pd-Cl keys are enhanced
Between interaction.Compared with existing dehydrogenation, the oersted Wa Er that the catalyst that the present invention is prepared is induced CO
Moral curing effect, product H2O erosion all possesses good immunity, has higher stability under reaction atmosphere, has
Life-span more than 1000 hours.
Brief description of the drawings
Fig. 1 is the high-resolution-ration transmission electric-lens photo of Pd-Cl/CeOCl catalyst in embodiment 1, and illustration is in CeOCl Fu
Leaf transformation diffraction pattern.
Fig. 2 is the X-ray powder diffraction spectrogram of two catalyst samples：(a) it is catalyzed for the Pd-Cl/CeOCl of embodiment 1
Agent, (b) is the Pd-Cl/CeO of comparative example 12Catalyst.
Embodiment
Embodiment 1：
A. 0.089g palladium bichlorides are weighed to be dissolved in 50ml absolute ethyl alcohols, are added after polyvinylpyrrolidone, ultrasonically treated 5h
Prepare the active component solution for obtaining that concentration is 0.01mol/L.
B. 2.7g CeO are weighed2Dry colloidal dispersion adds hexadecyltrimethylammonium chloride in 25ml absolute ethyl alcohols, surpasses
Sonication 0.5h obtains the solution that concentration is 0.6mo/L.
C. step B is obtained into solution to be slowly added dropwise in the solution that step A is obtained, during which blanketing with inert gas all the time is simultaneously
Keep 3000rpm mixing speed.Reacted in 20 DEG C after 10h, be dried in vacuo 10h in 0.02MPa, obtain solid sample.
D. the obtained solid samples of step C are placed in crystal reaction tube, 8h is handled in 300 DEG C under inert gas shielding
After be down to room temperature, then be passed through H2Concentration is 20% H2/ Ar gaseous mixtures are warming up to after 650 DEG C and stable 6h with 1 DEG C/min speed
Room temperature is down to, is passed through at room temperature after inert gas treatment 10h and obtains catalyst Pd-Cl/CeOCl.Pass through plasma optical emission
Spectrum measures Pd in the catalyst and accounts for the mass percent of catalyst for 0.63wt.%；Measured by photoelectron spectroscopy in catalyst
Cl/Pd surface concentration ratio is 2.2：1.
Take 1g catalyst to carry out 1000h stability tests and investigate its application performance, specific test condition is：Reaction temperature
140 DEG C, reaction pressure 0.25MPa, unstripped gas air speed 2000h-1, pending unstripped gas proportioning is that CO accounts for 98.5%, H2Account for
1.5%, add O2With H2Flow-rate ratio be 2：1, catalyst performance evaluation the results are shown in Table 1.
The surface Pd decentralization of the catalyst after above-mentioned operation 1000h is analyzed using the static chemiadsorptions of CO, is penetrated using X
The Pd-Cl coordination structures in its activated centre of line fine-structure distribution, the results are shown in Table 2.
Embodiment 2：
The preparation process of be the same as Example 1, difference is that the addition of palladium bichloride in step A is 0.36g, active component solution
Concentration is 0.04mol/L.Measuring the mass percent that Pd accounts for catalyst in the catalyst by plasma emission spectrum is
1.99wt.%；The surface concentration ratio for measuring Cl/Pd in catalyst by photoelectron spectroscopy is 2.2：1.
The evaluating catalyst condition of be the same as Example 1, Evaluation results are shown in Table 1.Post catalyst reaction surface Pd species
Decentralization and Pd-Cl coordination structure analysis results are shown in Table 2.
Embodiment 3：
A. 0.089g palladium bichlorides are weighed to be dissolved in 50ml absolute ethyl alcohols, are added after polyvinylpyrrolidone, ultrasonically treated 5h
Prepare the active component solution for obtaining that concentration is 0.01mol/L.
B. 2.7g CeO are weighed2Dry colloidal dispersion adds ammonium chloride in 25ml absolute ethyl alcohols, and ultrasonically treated 0.5h is obtained
Concentration is 0.6mo/L solution.
C. step B is obtained into solution to be slowly added dropwise in the solution that step A is obtained, during which blanketing with inert gas all the time is simultaneously
Keep 1000rpm mixing speed.Reacted in 60 DEG C after 4h, be dried in vacuo 10h in 0.02MPa, obtain solid sample.
D. the obtained solid samples of step C are placed in crystal reaction tube, 8h is handled in 300 DEG C under inert gas shielding
After be down to room temperature, then be passed through H2Concentration is 5% H2/ Ar gaseous mixtures are warming up to after 500 DEG C and stable 6h with 3 DEG C/min speed
Room temperature is down to, is passed through at room temperature after inert gas treatment 10h and obtains catalyst Pd-Cl/CeOCl.Pass through plasma optical emission
Spectrum measures Pd in the catalyst and accounts for the mass percent of catalyst for 0.64wt.%；Measured by photoelectron spectroscopy in catalyst
Cl/Pd surface concentration ratio is 2.8：1.
The evaluating catalyst condition of be the same as Example 1, Evaluation results are shown in Table 1.Analytical reactions rear catalyst surface Pd things
The decentralization and Pd-Cl coordination structures planted, the results are shown in Table 2.
Embodiment 4：
The preparation process of be the same as Example 3, difference is that the palladium salt added in step A is 0.14g ammonium chloropalladates.By wait from
Sub- emission spectrum measures Pd in the catalyst and accounts for the mass percent of catalyst for 0.61wt.%；Measured by photoelectron spectroscopy
Cl/Pd surface concentration ratio is 3 in catalyst：1.
The evaluating catalyst condition of be the same as Example 1, Evaluation results are shown in Table 1.Analytical reactions rear catalyst surface Pd things
The decentralization and Pd-Cl coordination structures planted, the results are shown in Table 2.
Comparative example 1：
Pd-Cl/Al is obtained according to the preparation method in the disclosed embodiment 2 of Chinese patent 201410309019.42O3Catalysis
Agent, as comparative example.Appreciation condition with the embodiment of the present invention 1 carries out catalyst stability test, Evaluation results
It is shown in Table 1.The decentralization and Pd-Cl coordination structures of analytical reactions rear catalyst surface Pd species, the results are shown in Table 2.
Table 1：Evaluation results after catalyst 1000h
| H after dehydrogenation2Concentration (ppm) | H2Selectivity (%) | |
| Embodiment 1 | 65 | 81.4 |
| Embodiment 2 | 80 | 83.3 |
| Embodiment 3 | 101 | 78 |
| Embodiment 4 | 99 | 78.9 |
| Comparative example 1 | 717 | 57.1 |
The as shown by data of table 1, the dehydrogenation efficiency and Dehydrogenation Stability of catalyst prepared by the present invention are much better than comparative example 1
Pd-Cl/Al2O3Catalyst.
Table 2：React the decentralization and Pd-Cl coordination structures of Pd species in 1000h rear catalysts
The as shown by data of table 2：Good Pd divergences are still kept after catalyst result 1000h prepared by present invention operation and initial
Pd-Cl active sites, are much better than the Pd-Cl/Al of comparative example 12O3Catalyst.
Claims (3)
1. Pd-Cl/CeOCl catalyst is used in a kind of CO dehydrogenations purification, its chemical representation is：It is single in Pd-Cl/CeOCl, catalyst
The mass percent that matter Pd accounts for catalyst is 0.5~2wt.%；Cl/Pd mol ratio is 3~2：1；Catalyst carrier be with
The CeOCl of tetragonal phase.
2. a kind of method of the catalyst prepared described in claim 1, is comprised the following steps that：
A. chloride palladium salt is weighed to be dissolved in absolute ethyl alcohol, then by surfactant and Pd mol ratio be 1：10~20 add surface
Activating agent, 5~6h of ultrasound, compound concentration is 0.01~0.04mol/L active component solution A；The chloride palladium salt is chlorination
Palladium or ammonium chloropalladate；During the surfactant is the polyethylene glycol that oleic acid, polyvinylpyrrolidone, the degree of polymerization are 200~600
One kind；
B. by CeO2Dry colloidal dispersion adds surfactant in absolute ethyl alcohol, 0.5~1h of ultrasound obtain concentration for 0.3~
0.6mol/L solution B；Wherein the mol ratio of surfactant and Ce is 1：1~5；The surfactant is ammonium chloride, ten
One of tetraalkyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride；
C. under inert gas shielding, solution B is slowly added dropwise in solution A, wherein A, the addition of B solution are according to finally urging
Pd accounts for the mass percent determination of catalyst in agent, and keeps 1000~3000rpm mixing speed, in 20~60 DEG C of reactions
After 4~12h, 10~12h is dried in vacuo in 0.02-0.03MPa, solid sample is obtained；
D. the obtained solid samples of step C are placed in crystal reaction tube, 4 is handled in 300~500 DEG C under inert gas shielding
Room temperature is down to after~8h, then is passed through H2Concentration is 5~20% H2/ Ar gaseous mixtures are warming up to 500 with 1~3 DEG C/min speed~
650 DEG C and stablize room temperature is down to after 6~8h, Pd-Cl/ is obtained after 10~12h of inert gas Passivation Treatment is passed through at room temperature
CeOCl finished catalysts.
3. the preparation method of catalyst according to claim 2, it is characterized in that the chloride palladium salt described in step A is chlorination
Palladium；The surfactant is polyvinylpyrrolidone；Surfactant described in step B is cetyl trimethyl chlorination
Ammonium.
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Cited By (2)
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| CN109046398A (en) * | 2018-08-07 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenation purification Mn base non-precious metal catalyst and preparation method thereof |
| CN111762783A (en) * | 2020-07-22 | 2020-10-13 | 中国科学院福建物质结构研究所 | Method for removing hydrogen impurities in CO raw material gas by three-stage catalyst filling method |
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| CN111762783A (en) * | 2020-07-22 | 2020-10-13 | 中国科学院福建物质结构研究所 | Method for removing hydrogen impurities in CO raw material gas by three-stage catalyst filling method |
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