CN105396583A

CN105396583A - Propane dehydrogenation propylene preparation catalyst, preparation method and applications thereof

Info

Publication number: CN105396583A
Application number: CN201410461255.8A
Authority: CN
Inventors: 金立; 王国清; 杜志国; 鲁树亮; 黄龙; 石莹
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2014-09-11
Filing date: 2014-09-11
Publication date: 2016-03-16
Anticipated expiration: 2034-09-11
Also published as: CN105396583B

Abstract

The present invention discloses a propane dehydrogenation propylene preparation catalyst, a preparation method and applications thereof. According to the catalyst, alumina is adopted as a carrier, a platinum group metal is adopted as an active component, carbon and tin are adopted as auxiliary agents, and by adopting the catalyst mass as the reference, the mass percentage of the platinum metal element is 0.001-5%, the mass percentage of the tin metal element is 0.001-5%, and the mass percentage of the carbon element is 0.001-1%. The preparation method comprises: carrying out immersing loading of an active component and auxiliary agents on an alumina carrier, carrying out a baking treatment in a H2 and C2H4 mixing atmosphere, and finally reducing to prepare the final catalyst. According to the present invention, the prepared propane dehydrogenation propylene preparation catalyst has characteristics of improved activity stability, improved propylene selectivity, and improved propylene yield.

Description

A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application

Technical field

The present invention relates to a kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application.Relate in particular to and be a kind ofly applicable to catalyst for preparing propylene with propane dehydrogenation of fixed bed gas solid catalytic reaction and its preparation method and application, belong to catalyst and the Synthesis and applications technology thereof of Industrial Catalysis technical field.

Background technology

Propane is a kind of important Organic Chemicals, is widely used in the chemical products such as polypropylene, polyacrylonitrile, expoxy propane, acetone.At present, propylene is mainly derived from the catalytic cracking process of naphtha steam cracking ethene and petroleum refining.But, in recent years, along with the large-scale application of U.S.'s shale gas, the raw material of cracking of ethylene factory is turned to by the naphtha of high price and utilizes cheap ethane, cause byproduct propylene amount significantly to reduce; The propane that in U.S.'s shale gas, by-product is a large amount of, obtains having the propylene compared with high added value by the method highly selective of propane catalytic dehydrogenation, has important Research Significance.At present, dehydrogenating propane technology is industrialized is in the world the Oleflex technique of UOP and the Catofin technique of LUMMUS.Both at home and abroad built or at the dehydrogenating propane device built all from above-mentioned two kinds of techniques.

Uop Inc. adopts platinum metal catalyst, and LUMMUS adopts chromium metallic catalyst, catalyst all easily carbon distribution and inactivation is fast.UOP adopts Continuous Moving Bed to solve above-mentioned catalyst problem, and LUMMUS then adopts multiple parallel reactor to switch mutually and solves the problem, but plant investment cost is high, and operating cost is high.

The key realizing Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technology is to develop the new catalyst with high activity, high stability, high selectivity.Current, propane dehydrogenation catalyst mainly with aluminium oxide or molecular sieve supported chromium system or platinum group catalyst for major metal active component, and add the performance that various auxiliary agent attempts to improve catalyst.

CN1155451A discloses a kind of by IVA race metallic element, platinum group, alkali metal, halogen and element sulphur order are impregnated into aluminium oxide, silica, spinelle or molecular sieve are the catalyst of carrier, and need to process with water vapour in platinum group and IVA race metallic element.This catalyst is used for the reaction of C2 ~ C5 dehydrating alkanes, has higher conversion ratio and selective.

CN101003458A discloses a kind of ordered structure carrier and the coating coating containing matrix, dehydrogenation active component on this carrier with parallel empty island, and the sectional area of thick coating stomidium is not less than 10% of carrier hole sectional area.Utilize the method to carry out dehydrogenating propane reaction and can obtain higher conversion of propane and propene yield.

CN101380587A and CN101972664A then individually discloses to relate to and a kind ofly contains with skeleton the Catalysts and its preparation method that rare earth elemental metals or the bimetallic molecular sieve of SnAl are carrier, be major catalyst respectively with platinum group, with IVA race metallic element, IA race or IIA race metal for auxiliary agent, halogen is modifier, take high-temperature inorganic oxide as the shaping catalyst of binding agent.This catalyst has good conversion of propane, Propylene Selectivity and anti-carbon performance under high temperature, lower pressure.

CN101884922A discloses a kind of sol-gal process that adopts and tin component is introduced Alumina gel, is used as the catalyst of Supported Pt Nanoparticles component and other metal promoters after drying and moulding again.This catalyst well solves tin component under hot operation condition and easily reduces precipitation, affects the problem of catalytic performance.

In sum, although be that the relevant research of the catalyst for preparing propylene with propane dehydrogenation system of active component achieves larger progress with platinum group in prior art, but fundamentally do not solve platinum group catalyst system easy in inactivation, conversion ratio and selective lower technical problem.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application.The activity stability of catalyst for preparing propylene with propane dehydrogenation prepared by the method, the selective and productivity of propylene of propylene are all improved.

One of the object of the invention is to provide a kind of catalyst for preparing propylene with propane dehydrogenation.Described catalyst is carrier with aluminium oxide, take platinum group metal as active component, with carbon and tin for auxiliary agent; Take catalyst quality as benchmark, platinum element mass content is 0.001 ~ 5%, preferably 0.1 ~ 1%, more preferably 0.3 ~ 0.5%, tin metal element mass content is 0.001% ~ 5%, preferably 0.1 ~ 3%, more preferably 0.5 ~ 2.5%, carbon mass content is 0.001 ~ 1%, is preferably 0.01 ~ 0.5%, more preferably 0.1 ~ 0.5%.

In above-mentioned catalyst, described platinum group metal is at least the one in ruthenium, rhodium, palladium, osmium, iridium or platinum, preferred platinum.

Two of the object of the invention is to provide a kind of preparation method of catalyst for preparing propylene with propane dehydrogenation, comprises the steps:

(1) take aluminium oxide as carrier, adopt infusion process supporting platinum-group metals and tin;

(2) aluminium oxide of step (1) load active component and auxiliary agent is at H ₂and C ₂h ₄mixed atmosphere under carry out roasting, wherein H ₂and C ₂h ₄volume ratio be 1:1 ~ 1:30, sintering temperature is 300 ~ 500 DEG C, and roasting time is 3 ~ 15min;

(3) material after step (2) roasting is obtained catalyst for preparing propylene with propane dehydrogenation after reduction.

In said method, adopt total immersion stain supporting platinum-group metals and tin, comprise drying and roasting process after dipping, preferably adopt rotary evaporation dry, sintering temperature is 450 ~ 650 DEG C.

Three of the object of the invention is to provide the application of catalyst for preparing propylene with propane dehydrogenation described in more than one, take propane as raw material, the temperature of reactor inlet 400 ~ 650 DEG C, preferably 540 ~ 620 DEG C; Volume space velocity 300 ~ 2000h ^-1, preferably 500 ~ 1500h ^-1; Reaction pressure is the highest is no more than 0.05Mpa (gauge pressure).

Propane dehydrogenation catalyst prepared by the present invention take platinum group metal as active component, with tin and carbon for auxiliary agent.Described catalyst conversion of propane, selective, anti-carbon performance are improved, and therefore have good prospects for commercial application.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is further described in detail, but the present invention is not by the restriction of these embodiments.Following % content is as being mass content without special records.

Embodiment 1

Take 60g γ-Al ₂o ₃, at 75 DEG C, impregnated in 0.03mol/LH ₂ptCl ₆and 0.2mol/LSnCl ₂total immersion stain 0.5h in the aqueous solution, wherein liquor capacity measures according to catalytic component mass content, obtains dry presoma and be placed into Muffle furnace, roasting 3h in the air of 450 DEG C after 75 DEG C of rotary evaporations.Take out catalyst and be placed in tube furnace, at H ₂and C ₂h ₄volume ratio is roasting 15min in the mixed atmosphere of 1:1, sintering temperature 500 DEG C.Finally obtain Pt-Sn-C propane dehydrogenation catalyst 1 at hydrogen reducing 1h at 580 DEG C, wherein the mass content of platinum is 0.5%, Sn mass content is 1.5%, and carbon mass content is 0.1%.

Embodiment 2

Take 60g γ-Al ₂o ₃, at 75 DEG C, impregnated in 0.03mol/LH ₂ptCl ₆and 0.2mol/LSnCl ₂total immersion stain 0.5h in the aqueous solution, wherein liquor capacity measures according to catalytic component mass content, obtains dry presoma and be placed into Muffle furnace, roasting 3h in the air of 650 DEG C after 75 DEG C of rotary evaporations.Take out catalyst and be placed in tube furnace, at H ₂and C ₂h ₄volume ratio is roasting 3min in the mixed atmosphere of 1:30, sintering temperature 300 DEG C.Finally obtain Pt-Sn-C propane dehydrogenation catalyst 2 at hydrogen reducing 1h at 580 DEG C, wherein wherein the mass content of platinum is 0.3%, Sn content to catalyst 2 is 0.5%, and carbon content is 0.5%.

Embodiment 3 ~ 6

Preparation method is identical with embodiment 1, but catalyst activity component is different with the mass content of auxiliary agent, obtained catalyst 3 ~ 6.The mass percentage of catalyst 3 platinum is 0.2%, Sn content is 0.6%, and carbon content is 0.025%.The mass percentage of catalyst 4 platinum is 0.2%, Sn content is 0.6%, and carbon content is 0.1%.Wherein the mass percentage of platinum is 0.1%, Sn content to catalyst 5 is 2.5%, and carbon content is 0.1%.Wherein the mass percentage of platinum is 0.5%, Sn content to catalyst 6 is 0.3%, and carbon content is 0.1%.

Catalyst prepared by said method completes on fixed bed reactors for dehydrogenating propane experiment.Wherein catalyst filling volume 30ml, propane volume space velocity 500 ~ 1500h ^-1, reaction pressure is normal pressure, and reactor inlet temperature is 540 ~ 620 DEG C, and dehydrogenating propane product adopts HP7890 gas-chromatography to analyze, and the experimental result that experimental period reaches 3 hours refers to table 1.

Table 1

As can be seen from Table 1, the single reaction time reaches 3 hours, and catalyst still has good activity and selectivity, has good prospects for commercial application.

Claims

1. a catalyst for preparing propylene with propane dehydrogenation, is characterized in that: described catalyst is carrier with aluminium oxide, take platinum group metal as active component, with carbon and tin for auxiliary agent; Take catalyst quality as benchmark, platinum element mass content is 0.001 ~ 5%, and tin metal element mass content is 0.001% ~ 5%, and carbon mass content is 0.001 ~ 1%.

2. catalyst according to claim 1, is characterized in that: platinum element mass content is 0.1 ~ 1%, and tin metal element mass content is 0.1 ~ 3%, and carbon mass content is 0.01 ~ 0.5%.

3. catalyst according to claim 1, is characterized in that: platinum element mass content is 0.3 ~ 0.5%, and tin metal element mass content is 0.5 ~ 2.5%, and carbon mass content is 0.1 ~ 0.5%.

4. catalyst according to claim 1, is characterized in that: described platinum group metal is at least the one in ruthenium, rhodium, palladium, osmium, iridium or platinum.

5. catalyst according to claim 4, is characterized in that: described platinum group metal is platinum.

6. the preparation method of the arbitrary described catalyst of claim 1 to 5, is characterized in that: comprise the steps:

7. method according to claim 6, is characterized in that: adopt total immersion stain supporting platinum-group metals and tin, comprise drying and roasting process after dipping.

8. method according to claim 7, is characterized in that: the dry rotary evaporation that adopts is dry, and sintering temperature is 450 ~ 650 DEG C.

9. the application of the arbitrary described catalyst of claim 1 to 5 in preparing propylene by dehydrogenating propane, is characterized in that: take propane as raw material, reactor inlet temperature 400 ~ 650 DEG C, volume space velocity 300 ~ 2000h ^-1, reaction pressure is the highest is no more than 0.05Mpa (gauge pressure).

10. application according to claim 9, is characterized in that: reactor inlet temperature 540 ~ 620 DEG C, volume space velocity 500 ~ 1500h ^-1.