CN106732574B - A kind of alkane dehydrogenating catalyst and preparation method thereof of the Pt crystal containing mixing - Google Patents
A kind of alkane dehydrogenating catalyst and preparation method thereof of the Pt crystal containing mixing Download PDFInfo
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- CN106732574B CN106732574B CN201611029686.2A CN201611029686A CN106732574B CN 106732574 B CN106732574 B CN 106732574B CN 201611029686 A CN201611029686 A CN 201611029686A CN 106732574 B CN106732574 B CN 106732574B
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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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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- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- 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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Abstract
The invention discloses a kind of alkane dehydrogenating catalysts of Pt crystal containing mixing, the catalyst is made of active component, auxiliary agent and carrier three parts, active component is Pt, auxiliary agent is alkali metal and IV B race metal, wherein Pt-IVB Complex Crystal concentrates on carrier inside, and Pt- alkali metal octahedral crystal concentrates on carrier surface.The invention also discloses the preparation method of above-mentioned catalyst, this method first prepares acid concentration on the Pt-IVB metal impregnation liquid of 1-3M, incipient impregnation to carrier, is placed at room temperature for, is dried, roasting the carrier that the crystal containing Pt-Sn is made；Then the Pt- alkali metal maceration extract that acid concentration is 0.2-0.8M again, it is obtained after being placed at room temperature for, dry, roast on incipient impregnation to the carrier containing Pt-Sn.Compared to the catalyst containing only single crystal, the catalyst dehydrogenation activity that the present invention contains mixing Pt crystal is more preferable, inactivates slower, longer life expectancy.
Description
Technical field
The present invention relates to the catalyst and preparation method of a kind of corresponding alkene of dehydrogenating low-carbon alkane system, especially raising low-carbon
Dehydrating alkanes alkene catalyst activity and the catalyst in service life and preparation method thereof, belong to field of catalyst preparation.
Background technique
Propylene is important Organic Chemicals, and the byproduct of the conventional refinery process such as steam cracking and catalytic cracking is it
Main source, therefore propylene yield is limited by the production of major product ethylene and product oil.The propylene yield of current traditional handicraft cannot
Meets the needs of market is to propylene, the substitution production new technique of propylene, including dehydrogenating propane (PDH), methanol are gradually paid close attention in market
Five kinds of techniques such as alkene (MTO, MTP), deep catalytic cracking (DCC), olefin cracking and olefin(e) disproportionation processed.In comparison, third
Alkane De-hydrogen Technology advantage becomes apparent, and has the advantages that technology maturation, good product quality, high conversion rate, by-product are few.At present
Industrialized preparing propylene by dehydrogenating propane production technology is mainly the Oleflex technique of Uop Inc., the Oleflex technique of Uop Inc.
Used is precious metals pt catalyst.Propane catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, must high temperature, low pressure it is severe
It is carried out under the conditions of quarter.
Industrial dehydrogenating propane production propylene is carried out at a high temperature of 620 DEG C or so, in addition to dehydrogenation main reaction, also just like
Side reactions, these side reactions such as cracking, aromatisation and polymerization can accelerate catalyst surface carbon deposit, make rapid catalyst deactivation, urge
Agent needs repeated regeneration.Therefore, activity, anti-carbon and the regeneration rear stability for improving catalyst are that dehydrogenating low-carbon alkane is urged
The emphasis and hot spot of agent research.A kind of catalyst disclosed in Chinese patent CN 1069226C, bears respectively on the alumina support
Sn, Pt and K are carried, although improving the activity and selectivity of catalyst, catalyst preparation process is complicated, increases catalyst
Preparation cost, and without provide catalyst repeatedly regenerate after performance.One disclosed in 103055857 B of Chinese patent CN
Kind catalyst for dehydrogenation of low-carbon paraffin, various auxiliary agents are added in carrier molding, and active component Pt introduces carrier using infusion process,
The activity of catalyst and the stability after regeneration improve, but the patent does not provide in carrier molding preparation process and introduces various help
Influence of the agent to its mechanical strength.A kind of catalyst for dehydrogenation of low-carbon paraffin disclosed in Chinese patent CN 103055953B, use are small
The method of inorganic oxygen-containing and the object doping of partial size aluminium obtains mixed oxidization alumina supporter, enhances catalytic mechanical intensity, still
The stability of catalyst is poor, and iso-butane conversion ratio drops to 27.9% from the 44.3% of initial reaction stage after 72h.
The introducing of active component Pt is complexed using the independent dip loading of Pt or Pt-Sn in above-mentioned catalyst preparation process
On co-impregnation to carrier, catalyst can be only formed single Pt crystal, lead to the mechanical strength, activity, stabilization of catalyst in this way
Property and anti-carbon performance are poor.The dipping method preparation combined using substep with co-impregnation, first step dipping make Pt and transition
The crystal that the complex compound that metal Sn is formed is formed concentrates on carrier inside, the octahedron that second step dipping forms Pt and alkali metal
The document that crystal concentrates on carrier surface has not been reported.
Summary of the invention
It is single crystal form the technical problem to be solved by the present invention is to the active component Pt of catalyst in existing technology of preparing,
Lead to catalyst easy coking and deactivation in use at high temperature, provides a kind of system of the alkane dehydrogenating catalyst of Pt crystal containing mixing
Slowly, activation recovering is normal after regeneration for inactivation when the catalyst of Preparation Method, this method preparation uses at high temperature.
A kind of alkane dehydrogenating catalyst of the Pt crystal containing mixing, is made of, activity active component, auxiliary agent and carrier three parts
Group is divided into Pt, and auxiliary agent is one of alkali metal and IV A race metal or a variety of, remaining is carrier, carrier Al2O3；Wherein Pt-
IVA crystal concentrates on carrier inside, and Pt- crystalline alkali metal concentrates on carrier surface.
Catalyst of the present invention, on the basis of the weight of prepared catalyst, the content of Pt is 0.1%~
0.5%, auxiliary element content is 0.1~2.0wt%, remaining is carrier.
Catalyst of the present invention, wherein alkali metal is preferably at least one of K and Rb, and IV A race metal is preferably
Sn.The atomic ratio of alkali metal and Pt are that the atomic ratio of 5~20, Sn and Pt is 0.5~2.
The present invention also provides a kind of preparation methods of abovementioned alkyl dehydrogenation, comprising:
1) platiniferous presoma and IVA metal salt solution are uniformly mixed and obtain Pt-IVA metal impregnation liquid, then add salt
The acid concentration of acid solution to maceration extract is 1-3M, then on incipient impregnation to carrier, is placed at room temperature for, dries, roasts, and is made and contains
The carrier of Pt-IVA crystal；
2) platiniferous presoma and alkali metal salt soln are uniformly mixed, the acid concentration for adding hydrochloric acid solution to maceration extract is
0.2-0.8M on incipient impregnation to the carrier containing Pt-IVA, is made after being placed at room temperature for, dry, roasting.
Catalyst of the present invention is used for dehydrogenating low-carbon alkane, especially propane or dehydrogenation of isobutane, is used for low-carbon alkanes
The reaction condition of dehydrogenation is as follows: 500 DEG C -650 DEG C of reaction temperature, pressure is normal pressure, H2/ hydrocarbon (mol ratio)=0.2-2, gas are total
Air speed 500-5000h-1.Catalyst needs to carry out reduction treatment before the reaction, and treatment conditions are 500 DEG C -600 DEG C, restores 1-5h.
The alkane dehydrogenating catalyst of present invention Pt crystal containing mixing has good effect to low-carbon alkanes catalytic dehydrogenation, should
The dehydrogenation reaction activity of catalyst propane is very high, significantly improves the conversion per pass of propane, and at 600 DEG C of reaction temperature, pressure is
Normal pressure, the volume space velocity of propane are 1000h-1, H2The conversion ratio of the lower propane of/hydrocarbon (mol ratio)=0.6 is greater than 33%, and selectivity is big
In 90%, and there is good regenerating stability, extends catalyst service life.The preparation method of catalyst of the present invention has good
Good operability,
Specific embodiment
Embodiment below is for being specifically described technical principle of the invention, implementation method and effect, but this hair
Bright method and core concept is not limited except as.
Comparative example 1
Catalyst A: Pt, Sn and K are prepared using co-impregnation in catalyst A, and the preparation method is containing only a kind of Pt crystal, Pt:
0.3w%, Sn:0.6w% and K:0.9w%.
(1) prepared by carrier.A certain amount of alumina powder is mixed with the sesbania powder that mixed powder mass fraction is 5% is accounted for
Uniformly, it adding citric acid that mass concentration is 5% and mass concentration is that 15% dust technology carries out kneading, the kneading time is 1h,
The finally extrusion on banded extruder again, the carrier after extrusion is after room temperature dries in the air 8h, and then at 120 DEG C of drying 4h, the carrier of drying is last
900 DEG C of roasting 6h in Muffle furnace, obtain final carrier, water absorption rate 83%, and intensity is 80N/.
It (2) is that 0.18M stannous chloride water acid solution mixes by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration
Even, according to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the dipping being finally configured to
The concentration of the hydrochloric acid of liquid is 1.5M.The potassium nitrate of 0.58g is dissolved in above-mentioned maceration extract, adding deionized water makes maceration extract volume
For 22ml, on the carrier for shaking up and being impregnated into 26.66g, 12 hours are placed at room temperature for, is roasted at being dried 5 hours, 550 DEG C at 120 DEG C
4 hours, obtain finished catalyst A.
Comparative example 2
Catalyst B: Pt, Sn and Rb are prepared using co-impregnation in catalyst B, and the preparation method is containing only a kind of Pt crystal, Pt:
0.3w%, Sn:0.6w% and Rb:0.9w%.
(1) carrier preparation is the same as support preparation method in (1) of comparative example 1.
It (2) is that 0.18M stannous chloride water acid solution mixes by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration
Even, according to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the dipping being finally configured to
The concentration of the hydrochloric acid of liquid is 1.5M.The rubidium nitrate of 0.35g is dissolved in above-mentioned maceration extract, adding deionized water makes maceration extract volume
For 22ml, on the carrier for shaking up and being impregnated into 26.66g, 12 hours are placed at room temperature for, is roasted at being dried 5 hours, 550 DEG C at 120 DEG C
4 hours, obtain finished catalyst B.
Embodiment 1
Catalyst C: catalyst C is Pt and Sn elder generation co-impregnation to carrier inside, and co-impregnation is prepared to carrier surface again by Pt and K
, which makes two kinds of crystal containing Pt-Sn and Pt-K in catalyst, Pt:0.3w%, Sn:0.6w% and K:0.9w%.
(1) carrier preparation is the same as support preparation method in (1) of comparative example 1.
(2) 1.5ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are mixed for 0.18M stannous chloride water acid solution
Uniformly, according to the saturated water adsorptive value of used carrier, adding hydrochloric acid and water in Xiang Shangshu Pt-Sn maceration extract makes the leaching being finally configured to
The concentration of the hydrochloric acid of stain liquid is 1.5M, and maceration extract volume is 22ml, on the carrier for shaking up and being impregnated into 26.66g, is placed at room temperature for 12
Hour, it is roasted 4 hours at being dried 5 hours, 550 DEG C at 120 DEG C, the carrier containing Pt-Sn is made.
The potassium nitrate of 0.5ml concentration 0.2M chloroplatinic acid aqueous solution and 0.58g is uniformly mixed, according to the saturation of used carrier
Water absorption, add hydrochloric acid in Xiang Shangshu Pt-K maceration extract and water make the maceration extract being finally configured to hydrochloric acid concentration 0.5M,
Maceration extract volume is 22ml, shakes up and impregnates on the carrier containing Pt-Sn, is placed at room temperature for 12 hours, is dried 5 hours at 120 DEG C,
It is roasted 4 hours at 550 DEG C, obtains finished catalyst C.
Embodiment 2
Catalyst D: catalyst D is Pt and Sn elder generation co-impregnation to carrier inside, Pt and Rb again co-impregnation to carrier surface system
Standby, which makes two kinds of crystal containing Pt-Sn and Pt-Rb in catalyst, Pt:0.3w%, Sn:0.6w% and Rb:
0.9w%.
(1) carrier preparation is the same as support preparation method in (1) of comparative example 1.
(2) 1.5ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are mixed for 0.18M stannous chloride water acid solution
Uniformly, according to the saturated water adsorptive value of used carrier, adding hydrochloric acid and water in Xiang Shangshu Pt-Sn maceration extract makes the leaching being finally configured to
The concentration of the hydrochloric acid of stain liquid is 1.5M, and maceration extract volume is 22ml, on the carrier for shaking up and being impregnated into 26.66g, is placed at room temperature for 12
Hour, it is roasted 4 hours at being dried 5 hours, 550 DEG C at 120 DEG C, the carrier containing Pt-Sn is made.
The rubidium nitrate of 0.5ml concentration 0.2M chloroplatinic acid aqueous solution and 0.35g is uniformly mixed, according to the saturation of used carrier
Water absorption, add hydrochloric acid in Xiang Shangshu Pt-Rb maceration extract and water make the maceration extract being finally configured to hydrochloric acid concentration 0.5M,
Maceration extract volume is 22ml, shakes up and impregnates on the carrier containing Pt-Rb, is placed at room temperature for 12 hours, is dried 5 hours at 120 DEG C,
It is roasted 4 hours at 550 DEG C, obtains finished catalyst D.
Reaction evaluating is carried out to catalyst A, B, C and D, evaluation condition: 600 DEG C of reaction temperature, pressure is normal pressure, propane
Volume space velocity is 1000h-1, H2/ hydrocarbon (mol ratio)=0.6.Catalyst needs to carry out hydrogen reducing processing, treatment conditions before the reaction
It is 500 DEG C, restores 4h.Evaluation result such as table 1.
The dehydrogenation reaction performance of 1 catalyst of table
Find out from the reaction evaluating data of table 1, the reactivity worth for having the catalyst C and D of mixed-crystal structure is better than
Only have the catalyst A and B of single crystal structure.
Circular response-regeneration condition: catalyst A, B, C and D are subjected to the survey of circular response-regeneration catalyzing dehydrogenation activity
It is fixed.Reaction evaluating condition is constant.Catalyst regeneration conditions: catalyst H react 5 hours after, 500 DEG C with oxygen content be 5%
Nitrogen and oxygen mixture burn-up catalyst on carbon distribution, the burn soot time is 3h, then small in 480 DEG C of reductase 12s with hydrogen
When, it has restored rear catalyst and has then carried out reaction evaluating experiment.Circular response-regenerated outcome is listed in table 2, and each data are reaction 5h
Interior average value.
Circular response-regenerability of 2 catalyst of table
It can be seen that from circular response-regeneration data of table 2 and have single crystalline substance after repetitious reaction-regeneration
The catalyst A and B dehydrogenation activity decline of body structure is obvious, and catalyst C and the D dehydrogenation for having mixed-crystal structure is stablized.
Claims (4)
1. a kind of alkane dehydrogenating catalyst of the Pt crystal containing mixing, is made of, feature active component, auxiliary agent and carrier three parts
It is, active component Pt, auxiliary agent is one of alkali metal and IV A race metal or a variety of, remaining is carrier, and carrier is
Al2O3；Wherein Pt-IVA Complex Crystal concentrates on carrier inside, and Pt- alkali metal octahedral crystal concentrates on carrier surface；Its
In, the atomic ratio of the alkali metal and Pt are 5~20, and the atomic ratio of IV A race metal and Pt are 0.5~2.
2. catalyst according to claim 1, it is characterised in that on the basis of the weight of institute's catalyst, the content of Pt is
0.1%~0.5%, auxiliary element content is 0.1~2.0wt%, remaining is carrier.
3. catalyst according to claim 1 or 2, which is characterized in that the alkali metal is at least one in K and Rb
Kind, IV A race's metal is Sn.
4. the preparation method of catalyst according to claim 1 to 3, which is characterized in that
1) platiniferous presoma and IVA metal salt solution are uniformly mixed and obtain Pt-IVA metal impregnation liquid, it is molten then to add hydrochloric acid
The acid concentration of liquid to maceration extract is 1-3M, then on incipient impregnation to carrier, is placed at room temperature for, dries, roasts, and is made and contains Pt-
The carrier of IVA crystal；
2) platiniferous presoma and alkali metal salt soln are uniformly mixed, the acid concentration for adding hydrochloric acid solution to maceration extract is 0.2-
0.8M on incipient impregnation to the carrier containing Pt-IVA, is made after being placed at room temperature for, dry, roasting.
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| CN108325523B (en) * | 2018-02-02 | 2021-01-08 | 华东理工大学 | Propane dehydrogenation catalyst and preparation method thereof |
| US10981149B2 (en) | 2019-03-18 | 2021-04-20 | Uop Llc | Dehydrogenation catalyst with optimum modifier profile index |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872300B1 (en) * | 2002-03-29 | 2005-03-29 | Uop Llc | Reforming catalyst with chelated promotor |
| CN104588011A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN105582979A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for light alkanes and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6872300B1 (en) * | 2002-03-29 | 2005-03-29 | Uop Llc | Reforming catalyst with chelated promotor |
| CN104588011A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN105582979A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for light alkanes and preparation method thereof |
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