CN107537486A - The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane - Google Patents

The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane Download PDF

Info

Publication number
CN107537486A
CN107537486A CN201610498208.XA CN201610498208A CN107537486A CN 107537486 A CN107537486 A CN 107537486A CN 201610498208 A CN201610498208 A CN 201610498208A CN 107537486 A CN107537486 A CN 107537486A
Authority
CN
China
Prior art keywords
catalyst
low
carbon
dehydrogenating
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610498208.XA
Other languages
Chinese (zh)
Inventor
曾铁强
缪长喜
吴文海
姜冬宇
樊志贵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201610498208.XA priority Critical patent/CN107537486A/en
Publication of CN107537486A publication Critical patent/CN107537486A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Prepare the catalyst and its application method of low-carbon alkene for dehydrogenating low-carbon alkane the present invention relates to a kind of, mainly solves the problems, such as to be currently used for the catalyst of dehydrogenating low-carbon alkane producing light olefins olefine selective is low under the high temperature conditions, carbon deposit seriously, one way stability difference.The present invention passes through a kind of catalyst and its application method that low-carbon alkene is prepared for dehydrogenating low-carbon alkane, the catalyst is using Pt, Sn and IB race element as active component and auxiliary agent, the mass content of Ti elements is less than 900ppm in catalyst, the mass content of Mn elements is less than 900ppm, the mass content of Zr elements is less than 900ppm technical scheme, preferably solves the problem, efficiently, stably preparing low-carbon olefins, in the industrial production available for dehydrogenating low-carbon alkane producing light olefins.

Description

The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane
Technical field
The present invention relates to a kind of catalyst and its application method that low-carbon alkene is prepared for dehydrogenating low-carbon alkane.
Background technology
Low-carbon alkene is important Organic Chemicals, has extensive industrial use, and low-carbon alkene is widely used in moulding The production of material, synthetic rubber, medicine, gasoline additive, ion exchange resin, detergent, spices and various chemical intermediates.With The development of chemical industry, the demand growth to low-carbon alkene quickly, is developed and takes low-carbon alkene by the low carbon alkane preparation of added value Hydrocarbon process is for making full use of low-carbon alkanes resource, to open up new alkene source significant.Propylene/isobutene mainly comes It is only top at present from coproduction or the by-product of the steam cracking and refinery factory fluid catalytic cracking process of naphtha and liquefied petroleum gas State method and be difficult to meet the needs of China's chemical industry is fast-developing.Propane/dehydrogenation of isobutane technology has become after steam Important propylene/isobutene source after cracking and the coproduction of fluid catalytic cracking process or by-product.Propane/dehydrogenation of isobutane skill Art has realized industrialization, the main Oleflex techniques including Uop Inc., the Star techniques of Phillips companies, Air The Catofin techniques of Product＆Chemical companies, FDB-4 the and Linde companies of Snamprogetti SPA companies The techniques such as Linde.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, is developed high living Property, the catalyst of high selectivity and high stability turn into the key of the technology.Current industrialized catalyst mainly has two classes, One kind is using metal oxide as active component, as Chinese patent (CN200910012450.1, CN200610126812.6) discloses The catalyst using chromium as main active component, it is active high, cost is relatively low the advantages that, but inactivate it is fast and poisonous, be difficult to Meet environmental requirement.Another kind of is loaded noble metal catalyst, if the catalyst of United States Patent (USP) (US4438288) report is with Pt For active component, using Sn as auxiliary agent, platinum, tin are carried on γ-Al using infusion process2O3、SiO2Or on the carrier such as MgO, and impregnate Adding alkali metal or alkaline-earth metal, be that activity and selectivity is relatively low the shortcomings that the catalyst, iso-butane conversion ratio is 39%~ 44%.Catalyst disclosed in Chinese patent (CN 96117222.3), Pt is loaded to by MgAl (O) combined oxidation using infusion process Thing carrier, the initial iso-butane conversion ratio of the catalyst are 59%, and selective isobutene is 97%~98%, but catalyst inactivation Comparatively fast, iso-butane conversion ratio is down to 45.6% after reacting 5 hours.Chinese patent (CN200710020064.8) and (CN200710133324.2) disclose infusion process preparation platinum and tin-rare earth catalyst be used for dehydrogenating propane react, carrier for containing Na X-type, Y types or ZSM-5 molecular sieve, there is higher Propylene Selectivity, but conversion of propane is maintained at about 30%, the patent The stability data of multiple coke-burning regeneration process is not provided.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but is still in the case of higher alkane conversion Olefine selective is relatively low, and the easy coking deactivation of catalyst, after frequent regeneration the problems such as activity decrease.Catalytic component, or Micro (or a small amount of) influence of the element to catalyst performance is introduced in catalyst preparation process not furtherd investigate by document yet.
The content of the invention
The technical problems to be solved by the invention are to be currently used for dehydrogenating low-carbon alkane and prepare the catalyst of low-carbon alkene existing The problem of olefine selective is low under hot conditions, carbon deposit is serious, one way stability difference, there is provided a kind of new takes off for low-carbon alkanes Hydrogen prepares the catalyst of low-carbon alkene, and the method for preparing catalyst is easy, and units activity component effective rate of utilization is high, has in height In use, the advantages of catalyst olefine selective is high, coking deactivation speed is slow, catalyst stability is high under the conditions of temperature.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane system The catalyst of standby low-carbon alkene, is auxiliary agent by active component, Sn of Pt, it is characterised in that the mass content of Ti elements in catalyst Less than 900ppm；The mass content of Mn elements is less than 900ppm.
In above-mentioned technical proposal, it is preferred that the mass content of Ti elements is less than 900ppm more than 0 in catalyst.
In above-mentioned technical proposal, it is preferred that the mass content of Mn elements is less than 900ppm more than 0 in catalyst.
In above-mentioned technical proposal, the low-carbon alkanes are propane and/or iso-butane.
In above-mentioned technical proposal, the MO-Al2O3M is the metal with+divalent in the composite oxides of structure, composite oxygen Compound is selected from MgAl2O4、ZnAl2O4、FeAl2O4、CoAl2O4、CaAl2O4Or BaAl2O4In one kind, preferably MgAl2O4、 ZnAl2O4Or CaAl2O4In one kind.
In above-mentioned technical proposal, Pt is the 0.01~1.0% of catalyst weight, and content preferred scope is 0.1~0.8%； Sn is the 0.05~2.0% of catalyst weight, and content preferred scope is 0.2~1.0%.
In above-mentioned technical proposal, it is preferable that also comprising at least one of IB races element, preferred scheme Cu in catalyst Or at least one of Ag；IB races element is the 0.05~1.0% of catalyst weight, and preferred scheme is 0.1~5%.
In above-mentioned technical proposal, the preferred scheme of the mass content of Ti elements is less than 800ppm, more preferably in catalyst Scheme is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, the preferred scheme of the mass content of Mn elements is less than 800ppm, more preferably in catalyst Scheme is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, the mass content of Zr elements is less than 900ppm in catalyst, preferred scheme be less than 800ppm, more preferably scheme are that most preferably scheme is less than 400ppm less than 600ppm.
A kind of preparation method of catalyst that low-carbon alkene is prepared for dehydrogenating low-carbon alkane involved in the present invention, can be adopted Use following steps：
By the solution containing the adjuvant component and the carrier incipient impregnation, dipping temperature is 10 DEG C~80 DEG C, dipping Time is 1~24 hour, is dried, is calcined after dipping, and drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 small When, sintering temperature is 400 DEG C~650 DEG C, and roasting time is 1~24 hour, then through hydrogen in 400 DEG C~650 DEG C reduction treatments 1 ~10 hours.
In above-mentioned technical proposal, immersion solvent is using one kind in water or ethanol.To improve the activity of catalyst, catalyst After hydrogen reducing, also water vapour can use to be handled, 400 DEG C~650 DEG C for the treatment of temperature, 1~10 hour time.
The application of catalyst involved in the present invention in preparation of olefin through light alkane dehydrogenation, it can use and include following technique Step：
1) catalytic dehydrogenation：With low-carbon alkanes and H2Or the gaseous mixture of vapor is raw material, reaction temperature is 400 DEG C~600 DEG C, reaction pressure is 0.08MPa~0.12MPa, and alkane mass space velocity is 3.0~8.0h-1, in the reactor raw material urged with described Agent carries out catalytic dehydrogenating reaction and obtains low-carbon alkene；
2) catalyst regenerates：Reacted decaying catalyst carries out coke-burning regeneration, can use in-situ regeneration or ex-situ regeneration, Regeneration temperature is 400 DEG C~650 DEG C, and the recovery time is 1~10 hour, and regeneration atmosphere includes oxygen, air, carbon dioxide or water At least one of steam.
Compared with prior art, the present invention has the advantages of notable and high-lighting effect, has selected composite oxides to carry Body, vector stabilisation is high, and catalyst surface has suitable acid-base property, and catalyst performance is significantly improved；Sn oxides rise To catalyst activity and stability is improved, the effect of active component decentralization is improved, Sn has the electricity of filling Pt element 5d tracks Sub- effect, it can play reduction carbon deposit, suppress the effect of hydrogenolysis；Appropriate IB races element is easily rich in catalyst surface Collection, inhibits hydrogenolysis activity of the catalyst to Product olefins, so as to improve olefin yields to a certain extent.Catalytic component In, or some micro or oligo-element is introduced in catalyst preparation process can change the surface acidic-basic property of catalyst and electro Matter, influence performance so as to significantly affect catalyst.Understand fully which micro or oligo-element has catalyst performance to significantly affect, It is obviously significant to the industrial applications of dehydrogenating low-carbon alkane producing light olefins catalyst.Experiment confirms Ti, Mn, Zr etc. A small amount of presence of element can make catalyst inactivation serious.The catalyst it is active it is higher, olefine selective is high, coking deactivation The advantages of speed is slow, catalyst stability is high, reduce catalytic dehydrogenation processes cost.
Dehydrogenating low-carbon alkane reaction is continuously being carried out on the flowing miniature catalyst reaction device of quartz tube reactor.Product analysis Using HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis takes off Alkane, olefin(e) centent in hydrogen product simultaneously calculate conversion ratio, selectivity and the yield of reaction.Use method provided by the invention The catalyst of preparation reacts for dehydrogenating low-carbon alkane, and propane/iso-butane conversion ratio is higher than up to 45%/55%, olefine selective 92%；By 50 coke-burning regenerations, iso-butane conversion ratio is maintained at 54%, and olefine selective is higher than 92%, catalyst performance compared with Good and stability is high, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Raw materials used is high-purity.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then at 500 DEG C It is lower through hydrogen reducing 2 hours.Prepared sample is before for catalytic dehydrogenating reaction, then to handle at 500 DEG C with vapor 2 small When, catalyst A is obtained, 40~60 mesh particles is ground into and is used for evaluating catalyst.Pt load capacity is catalyst weight in catalyst A 0.3%, Sn of amount load capacity is the 0.4% of catalyst weight, in catalyst in terms of mass fraction also 200ppm containing Ti, Mn 200ppm、Zr 100ppm。
【Embodiment 2】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) ethanol solution in 60 DEG C of incipient impregnations 2 hours, then by the 110 DEG C of dryings 4 in an oven of the sample after dipping Hour.Raw materials used is high-purity.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then at 500 DEG C Through hydrogen reducing 2 hours.Prepared sample is before for catalytic dehydrogenating reaction, then to handle at 500 DEG C with vapor 2 small When, catalyst B is obtained, 40~60 mesh particles is ground into and is used for evaluating catalyst.Pt load capacity is catalyst weight in catalyst B 0.1%, Sn of amount load capacity is the 0.2% of catalyst weight, in catalyst in terms of mass fraction also 100ppm containing Ti, Mn 120ppm、Zr 60ppm。
【Embodiment 3】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 10 DEG C of incipient impregnations 24 hours, then by the sample after dipping in an oven 90 DEG C it is dry Dry 24 hours.Raw materials used is high-purity.Dried sample is calcined 24 hours in Muffle furnace at 400 DEG C again, then 400 Through hydrogen reducing 10 hours at DEG C.Prepared sample is handled before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C 2 hours, catalyst C is obtained, 40~60 mesh particles is ground into and is used for evaluating catalyst.Pt load capacity is catalysis in catalyst C 0.8%, Sn of agent weight load capacity is the 1.0% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 260ppm、Mn 240ppm、Zr 150ppm。
【Embodiment 4】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 80 DEG C of incipient impregnations 1 hour, then by the sample after dipping in an oven 150 DEG C it is dry Dry 1 hour.Raw materials used is high-purity.Dried sample is calcined 1 hour in Muffle furnace at 650 DEG C again, then at 650 DEG C It is lower through hydrogen reducing 1 hour.Prepared sample is before for catalytic dehydrogenating reaction, then to handle at 500 DEG C with vapor 2 small When, catalyst D is obtained, 40~60 mesh particles is ground into and is used for evaluating catalyst.Pt load capacity is catalyst weight in catalyst D 0.02%, Sn of amount load capacity is the 0.05% of catalyst weight, in catalyst in terms of mass fraction also 20ppm containing Ti, Mn 20ppm、Zr 10ppm。
【Embodiment 5】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Raw materials used is high-purity.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then at 500 DEG C It is lower through hydrogen reducing 2 hours.Prepared sample is before for catalytic dehydrogenating reaction, then to handle at 500 DEG C with vapor 2 small When, catalyst E is obtained, 40~60 mesh particles is ground into and is used for evaluating catalyst.Pt load capacity is catalyst weight in catalyst E 1.0%, Sn of amount load capacity is the 2.0% of catalyst weight, in catalyst in terms of mass fraction also 320ppm containing Ti, Mn 300ppm、Zr 180ppm。
【Embodiment 6】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) and the mixed aqueous solution of copper nitrate in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in baking oven In 110 DEG C of dryings 4 hours.Raw materials used is high-purity.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, Again through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Lower processing 2 hours, obtains catalyst F, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity in catalyst F The load capacity that load capacity for 0.3%, Sn of catalyst weight is 0.4%, Cu of catalyst weight is catalyst weight 0.2%, in catalyst in terms of mass fraction also 240ppm containing Ti, Mn 220ppm, Zr120ppm.
【Embodiment 7】
Weigh appropriate ZnAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) and the mixed aqueous solution of silver nitrate in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in baking oven In 110 DEG C of dryings 4 hours.Raw materials used is high-purity.Roasting 4 is small at 600 DEG C in Muffle furnace again for dried sample When, then through hydrogen reducing 2 hours at 500 DEG C.Prepared sample exists before for catalytic dehydrogenating reaction, then with vapor Handled 2 hours at 500 DEG C, obtain catalyst G, be ground into 40~60 mesh particles and be used for evaluating catalyst.Pt's is negative in catalyst G Carrying capacity is that the load capacity that 0.3%, Sn of catalyst weight load capacity is 0.4%, Ag of catalyst weight is catalyst weight 0.05%, in catalyst in terms of mass fraction also 220ppm containing Ti, Mn 220ppm, Zr100ppm.
【Embodiment 8】
Weigh appropriate FeAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) and the mixed aqueous solution of copper nitrate and silver nitrate in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping Product 110 DEG C of dryings 4 hours in an oven.Raw materials used is high-purity.Dried sample roasts in Muffle furnace at 600 DEG C again Burn 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.Prepared sample steams before for catalytic dehydrogenating reaction, then with water Gas is handled 2 hours at 500 DEG C, obtains catalyst H, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt in catalyst H Load capacity be that 0.3%, the Sn load capacity of catalyst weight is that 0.4%, the Cu load capacity of catalyst weight is catalyst 0.5%, Ag of weight load capacity is the 0.5% of catalyst weight, the also 300ppm containing Ti in terms of mass fraction in catalyst, Mn 280ppm、Zr 125ppm。
【Embodiment 9】
Weigh appropriate CoAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used raw material is higher degree.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst I, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst I 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 550ppm、Mn 500ppm、Zr 420ppm。
【Embodiment 10】
Weigh appropriate CaAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used raw material is higher degree.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst J, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst J 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 760ppm、Mn 700ppm、Zr 650ppm。
【Embodiment 11】
Weigh appropriate BaAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used raw material is higher degree.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst K, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst K 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 880ppm、Mn 850ppm、Zr 805ppm。
【Embodiment 12】
Weigh appropriate ZnAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used raw material is higher degree.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst L, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst L 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 800ppm、Mn 600ppm、Zr 1000ppm。
【Comparative example 1】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used material purity is relatively low.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst M, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst M 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 3000ppm、Mn 2000ppm、Zr 1600ppm。
【Comparative example 2】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry Dry 4 hours.Used material purity is relatively low.Dried sample is calcined 4 hours in Muffle furnace at 600 DEG C again, then Through hydrogen reducing 2 hours at 500 DEG C.Prepared sample is located before for catalytic dehydrogenating reaction, then with vapor at 500 DEG C Reason 2 hours, obtains catalyst n, is ground into 40~60 mesh particles and is used for evaluating catalyst.Pt load capacity is to urge in catalyst n 0.3%, Sn of agent weight load capacity is the 0.4% of catalyst weight, also contains Ti in terms of mass fraction in catalyst 1800ppm、Mn 1600ppm、Zr 1500ppm。
【Comparative example 3】
Weigh appropriate MgAl2O4Carrier, it is added to containing appropriate chloroplatinic acid (H2PtCl6·6H2O), anhydrous stannic chloride (SnCl4) and the mixed aqueous solution of copper nitrate in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in baking oven In 110 DEG C of dryings 4 hours.Used material purity is relatively low.Dried sample is calcined 4 in Muffle furnace at 600 DEG C again Hour, then through hydrogen reducing 2 hours at 500 DEG C.Prepared sample exists before for catalytic dehydrogenating reaction, then with vapor Handled 2 hours at 500 DEG C, obtain catalyst M, be ground into 40~60 mesh particles and be used for evaluating catalyst.Pt's is negative in catalyst M Carrying capacity is that the load capacity that 0.3%, Sn of catalyst weight load capacity is 0.4%, Cu of catalyst weight is catalyst weight 0.2%, in catalyst in terms of mass fraction also 1500ppm containing Ti, Mn 1400ppm, Zr 1200ppm.
【Embodiment 13】
Weigh 0.5g catalyst A and carry out dehydrogenating propane evaluation.Feeding gas are propane/H2O=5/3 (vol/vol)；Temperature 550℃；Reaction pressure is normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out activity rating, test result is listed in table 1.
Table 1*
Reaction time (h) Conversion of propane (%) Propylene Selectivity (%)
6 41.5(29.6) 93.6(82.5)
10 41.2(28.7) 93.5(80.6)
40 40.0(26.2) 93.2(75.2)
* it is catalyst M data in bracket
【Embodiment 14】
Weigh 0.5g catalyst A~O and carry out dehydrogenation of isobutane evaluation.Feeding gas are iso-butane/H2=5/2 (vol/vol)； 560 DEG C of temperature；Reaction pressure is normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out activity rating, test result is listed in table 2。
Table 2*
* the iso-butane conversion ratio and selective isobutene of 6 hours is reacted
【Comparative example 6】
Catalyst regenerating stability contrasts
0.5g catalyst A, 0.5g catalyst M is weighed respectively carries out dehydrogenation of isobutane evaluation.Feeding gas are iso-butane/H2= 5/2(vol/vol)；560 DEG C of temperature；Reaction pressure is normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out catalytic dehydrogenation work Property evaluation, after charging 40 hours, regenerated 5 hours under air atmosphere at 560 DEG C, the catalyst after circular response/regeneration 50 times Reactivity worth is listed in table 3.
Table 3*
* the iso-butane conversion ratio and selective isobutene of 6 hours is reacted.

Claims (10)

1. a kind of catalyst that low-carbon alkene is prepared for dehydrogenating low-carbon alkane, is auxiliary agent by active component, Sn of Pt, its feature 900ppm is less than in the mass content of the Ti elements in catalyst；The mass content of Mn elements is less than 900ppm.
2. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 1, it is characterised in that the Ti The mass content of element is less than 800ppm；The mass content of Mn elements is less than 800ppm.
3. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 2, it is characterised in that the Ti The mass content of element is less than 600ppm；The mass content of Mn elements is less than 600ppm.
4. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 3, it is characterised in that the Ti The mass content of element is less than 400ppm；The mass content of Mn elements is less than 400ppm.
5. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 1, it is characterised in that catalyst The mass content of middle Zr elements is less than 900ppm.
6. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 5, it is characterised in that catalyst The mass content of middle Zr elements is less than 400ppm.
7. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 1, it is characterised in that described low Carbon alkane includes propane and/or iso-butane.
8. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 1, it is characterised in that its feature It is catalyst with MO-Al2O3The composite oxides of structure are carrier, and wherein M is the metal with+divalent, composite oxides choosing From MgAl2O4、ZnAl2O4、FeAl2O4、CoAl2O4、CaAl2O4Or BaAl2O4In one kind.
9. it is used for the catalyst that dehydrogenating low-carbon alkane prepares low-carbon alkene according to claim 1, it is characterised in that catalyst Also comprising at least one of IB races element, IB races element is selected from least one of Cu or Ag, and IB races element is catalyst weight The 0.05~1.0% of amount.
10. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, with low-carbon alkanes and H2Or the gaseous mixture of vapor is original Material, reaction temperature are 400 DEG C~600 DEG C, and reaction pressure is 0.08MPa~0.12MPa, and alkane mass space velocity is 3.0~8.0h-1, raw material after the catalyst haptoreaction described in any one of claim 1~9 with obtaining low-carbon alkene.
CN201610498208.XA 2016-06-29 2016-06-29 The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane Pending CN107537486A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610498208.XA CN107537486A (en) 2016-06-29 2016-06-29 The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610498208.XA CN107537486A (en) 2016-06-29 2016-06-29 The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane

Publications (1)

Publication Number Publication Date
CN107537486A true CN107537486A (en) 2018-01-05

Family

ID=60966456

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610498208.XA Pending CN107537486A (en) 2016-06-29 2016-06-29 The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane

Country Status (1)

Country Link
CN (1) CN107537486A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112536035A (en) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 Cobalt aluminate-containing catalyst, preparation method and application thereof, and low-carbon alkane dehydrogenation method
WO2024008169A1 (en) * 2022-07-07 2024-01-11 润和科华催化剂(上海)有限公司 Low-carbon alkane dehydrogenation catalyst, preparation method therefor and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DONG WEN-SHENG ET AL.,: "Effects of promoters on catalytic performance of Pt-Sn/MgAl2O4 catalyst for propane dehydrogenation in the presence of steam", 《JOURNAL OF NATURAL GAS CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112536035A (en) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 Cobalt aluminate-containing catalyst, preparation method and application thereof, and low-carbon alkane dehydrogenation method
CN112536035B (en) * 2019-09-20 2023-05-02 中国石油化工股份有限公司 Cobalt aluminate-containing catalyst, preparation method and application thereof, and method for dehydrogenating low-carbon alkane
WO2024008169A1 (en) * 2022-07-07 2024-01-11 润和科华催化剂(上海)有限公司 Low-carbon alkane dehydrogenation catalyst, preparation method therefor and application thereof

Similar Documents

Publication Publication Date Title
CN105363443B (en) Catalyst and application thereof for dehydrogenating low-carbon alkane producing light olefins
CN105363447B (en) The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane
CN101884922B (en) Method for preparing propylene catalyst by propane dehydrogenation process
CN104107704B (en) The renovation process of platiniferous catalyst for dehydrogenation of low-carbon paraffin
CN102049267B (en) Catalyst for preparing propylene by dehydrogenating propane as well as preparation method and applications thereof
CN101676025B (en) Palladium-based catalyst for selective hydrogenation of acetylene
CN103420769B (en) The method of dehydrogenating low-carbon alkane producing light olefins
CN105582979B (en) A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof
CN104107718B (en) Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof
CN102614870B (en) Vinylacetylene hydrogenation catalyst and preparation method thereof
CN103418376B (en) Anti-sintering dehydrogenating low-carbon alkane producing light olefins Catalysts and its preparation method
CN103055857A (en) Catalyst for low-carbon alkane dehydrogenation and preparation method thereof
CN101623633A (en) Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof
CN106582629B (en) A kind of catalyst of preparing propylene by dehydrogenating propane and its preparation method and application
CN105363484B (en) Catalyst for dehydrogenating low-carbon alkane producing light olefins and its application
CN105396582B (en) A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application
CN106588544B (en) Method for preparing propylene by propane dehydrogenation
CN103801331B (en) A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin
CN104549219A (en) Supported catalyst for preparing olefin by dehydrogenating isobutane and application of supported catalyst
CN107537486A (en) The catalyst and its application method of low-carbon alkene are prepared for dehydrogenating low-carbon alkane
CN103418442A (en) Preparation method of precious metal-containing low-carbon alkane dehydrogenation catalyst carrier
CN105689013A (en) Regeneration method and application of low-alkane dehydrogenation catalyst
CN104549415B (en) Catalyst and its application method for manufacturing olefin by low-carbon alkane dehydrogenation
CN106607105B (en) Activation method of platinum-containing low-carbon alkane dehydrogenation catalyst
CN104549260B (en) Catalyst for preparing olefin through dehydrogenation of isobutene and preparation method of catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180105

RJ01 Rejection of invention patent application after publication