NIELSEN RASMUS MUNKSGÅRD (DK)
LEMUS-YEGRES LIVED J (DK)
JACOBSEN JOACHIM HARTEG (DK)
| WO2013126210A1 | 2013-08-29 | |||
| WO2010107591A1 | 2010-09-23 | |||
| WO2015094655A1 | 2015-06-25 |
| US20180057422A1 | 2018-03-01 | |||
| EP0637578A1 | 1995-02-08 | |||
| US20100236985A1 | 2010-09-23 | |||
| US20040259727A1 | 2004-12-23 | |||
| EP0637578A1 | 1995-02-08 | |||
| US5308822A | 1994-05-03 | |||
| US7235706B2 | 2007-06-26 | |||
| US20150202601A1 | 2015-07-23 | |||
| US9776170B2 | 2017-10-03 |
| Claims : 1. A catalyst for the dehydrogenation of alkanes, where lower alkanes are dehydrogenated to the corresponding al kenes according to the reaction in which n is an integer from 2 to 5, by feeding the alkane to a catalyst-containing dehydrogenation reactor, said catalyst consisting of platinum, gallium and option ally potassium on an alumina carrier, wherein silica has been added as a promotor for the performance of the cata lyst. 2. Catalyst according to claim 1, which contains Si02 in an amount of 1-40 wt%. 3. Catalyst according to claim 2, wherein the Si02 con tent is 1-30 wt%, preferably 2-10 wt%. 4. Catalyst according to any of the claims 1-3, which preferably contains 0.5-1.5 wt% Ga, 1-100 ppm Pt and 0.05- 0.5 wt% K2O . 5. Process for the dehydrogenation of alkanes to the cor responding alkenes according to the reaction <-> CnPhn + ¾ in which n is an integer from 2 to 5 in the presence of a catalyst according to any one of claims 1 to 4. 6. The process of claim 5, wherein the catalyst is ar- ranged in a fixed bed. 7. The process of claim 5 or 6 comprising periodic cycles of sequential oxidative regeneration steps and said dehy drogenation steps, optionally separated by vacuum or flush- ing steps, but without a separate reduction step, such as a step in which hydrogen is fed to the catalyst. |
Basically, the catalytic dehydrogenation of lower alkanes is a simple, but yet important reaction, which can be il- lustrated by the dehydrogenation of propane to propene in accordance with the reaction:
C 3 H 8 <-> C 3 H 6 + ¾ With the ever growing demand for light olefins, i.e. lower aliphatic open-chain hydrocarbons having a carbon-carbon double bond, catalytic dehydrogenation is growing in im portance. Especially the dehydrogenation of propane and isobutane are important reactions, which are used commer- dally for the production of propylene and isobutylene, re spectively. Propylene is an important fundamental chemical building block for plastics and resins, and the worldwide demand for propylene has been growing steadily for decades. It is expected that the demand growth for propylene will soon be equal to or even higher than that for ethylene. For isobutylene, one of the major applications is that it can be used as feedstock in the manufacture of methyl-tert-bu- tyl ether (MTBE) .
The process shown above is endothermic and requires about 125 kJ/mole in heat of reaction. Thus, in order to achieve a reasonable degree of conversion, the dehydrogenation pro cess is taking place at a temperature around 600°C. The de hydrogenation of isobutene is similar to that of propene in every respect, apart from requiring a lower temperature.
Today there are 4 major processes for alkane dehydrogena tion in commercial use: The Catofin process, the Oleflex process, the STAR process and the Snamprogetti-Yarzintez process. The differences between these processes primarily deal with the supply of the heat of reaction. The important Catofin process is characterized by the heat of reaction being supplied by pre-heating of the catalyst. The Catofin process is carried out in 3 to 8 fixed-bed adiabatic reac tors, using a chromium oxide/alumina catalyst containing around 20 wt% chromium oxide. The catalyst may be supple mented with an inert material having a high heat capacity, or alternatively with a material which will selectively combust or react with the hydrogen formed, the so-called heat generating material (HGM) . Promoters such as potassium may be added. During regeneration, coke is burned by con tacting the catalyst with an air flow. Simultaneous to the coke combustion, there is usually oxidation of the Cr cata lyst, which needs to be reduced again before the dehydro genation cycle can start again.
Conventional catalyst regeneration processes often do not sufficiently restore the catalytic activity of platinum- gallium based alkane dehydrogenation catalysts to a level equalling that of such catalysts when they are fresh. Thus, skilled persons who practise alkane dehydrogenation, espe cially PDH, know that decreasing activity of the catalyst inevitably leads to decreasing alkene production, eventu ally to a point where process economics dictate replacement of the deactivated catalyst with fresh catalyst. Therefore, means and methods to restore catalyst activity more fully are desirable.
To regenerate platinum-gallium based catalysts for alkane dehydrogenation, an oxidation treatment is required. Typi cally, high temperatures and long reaction times (up to 2 hours) are needed to fully reactivate the catalysts.
Pt/Ga propane dehydrogenation catalysts supported by AI 2 O 3 are deactivated very fast during the dehydrogenation proce dure. The subsequent regeneration process is not capable of fully recovering the catalyst activity, and therefore a gradual catalyst deactivation is observed from the first regeneration cycle to subsequent regeneration cycles.
It has now surprisingly turned out that the use of a
SiCy/A^Cy combination instead of using AI2O3 alone as a catalyst carrier leads to a markedly decreased catalyst de activation, not only within a single regeneration cycle, but also from the first regeneration cycle to subsequent regeneration cycles. Optimal Si0 2 contents furthermore lead to
- increased catalyst activity
- improved selectivity and - decreased formation of higher hydrocarbons and coke.
A catalyst based on Pt/Ga also has the advantage of not needing an extra reduction step after regeneration, which is an economic advantage due to the reduction of total cy cle time.
Platinum-gallium based catalysts for alkane dehydrogenation are known in the art. Thus, catalysts containing 0.5-2.5 wt% Ga 2 0 3 , 5-50 ppm Pt, 0.1-1.0 wt% K 2 0 and 0.08-3 wt% Si0 2 are known from EP 0 637 578 Al, US 5.308.822 A (not con taining Pt) and US 7.235.706 A.
In Angew. Chem. Int. Ed. 53, 9251-9256 (2014), a platinum- promoted Ga/Al20 3 catalyst is described, which is a highly active, selective and stable propane dehydrogenation cata lyst consisting of 1000 ppm Pt, 3 wt% Ga and 0.25 wt% K supported on alumina. A synergy between Ga and Pt is ob served, and a bifunctional active phase is proposed, in which coordinately unsaturated Ga 3+ species are the active species, and where Pt functions as a promoter.
WO 2010/107591 Al discloses a supported alkane dehydrogena tion catalyst with a slightly broader composition range: 0.5-5 wt% Ga or Ga 2 0 3 , 500 ppm Pt, 0.2 wt% K 2 0 and 5 wt%
Si0 2 .
In the above patent documents, the Pt/Ga catalysts are con sidered to be mostly suited for fluidized bed reactors and not suitable for use in the fixed-bed Catofin process. WO 2015/094655 A1 describes how to manage sulfur present in a hydrocarbon feed stream while effecting dehydrogenation of hydrocarbons, e.g. propane, present in the feed stream to their corresponding olefins. This is done by using a fluidizable dehydrogenation catalyst that also works as a desulfurant, comprising gallium and platinum on an alumina or alumina-silica support and optionally also an alkali metal such as potassium. US 2015/0202601 A1 discloses a catalyst and a reactivation process useful for alkane dehydrogenation. The catalyst comprises a group IIIA metal such as gallium, a group VIII noble metal such as platinum, at least one dopant and an optional promotor metal on a support selected from silica, alumina and silica-alumina composites.
A heterogeneous catalyst suitable for alkane dehydrogena tion is described in US 9.776.170 B2. It has an active layer that includes alumina and gallia, which is dispersed on a support such as optionally silica-modified alumina.
The present invention presents a solution to the problem of catalyst deactivation during light alkane dehydrogenation, especially Pt/Ga propane dehydrogenation catalysts. So far, Pt/Ga propane dehydrogenation catalysts have not been used commercially for any processes, the main reason for that being that Pt/Ga catalysts simply deactivate too fast.
Thus, improving the stability of a Pt/Ga catalyst would al low it to compete with the Cr-based catalysts that are cur- rently used for light alkane dehydrogenation in the Catofin process . Thus, the present invention concerns a catalyst for the de hydrogenation of alkanes, where lower alkanes are dehydro genated to the corresponding alkenes according to the reac tion in which n is an integer from 2 to 5, by feeding the alkane to a catalyst-containing dehydrogenation reactor, said catalyst consisting of platinum, gallium and option ally potassium on an alumina carrier, wherein silica has been added as a promotor for the performance of the cata lyst.
Such catalysts are meant specifically for a fixed-bed pro cess rather than a fluidized bed process.
The catalyst also has the advantage of not needing a reduc tion step after regeneration (as opposed to the Cr-based catalyst counterpart) , which makes the total cycle time shorter .
The catalysts according to the invention preferably contain 0.5-1.5 wt% Ga, 1-100 ppm Pt, 0.05-0.5 wt% K 2 0 and Si0 2 in an amount of 3-40 wt%, preferably 3-30 wt% and most prefer ably 5-10 wt%.
The use of Si02/Al20 3 as a carrier for Pt/Ga catalysts for light alkane dehydrogenation markedly decreases the cata lyst deactivation during the dehydrogenation procedure. This improvement allows the catalysts according to the in- vention to compete with the carcinogenic Cr-based catalysts that are currently used for light alkane dehydrogenation in the Catofin process.
The invention is described n further detail in the experi- mental section which follow
Experimental
SiCy has been identified as a promotor for the performance of Pt/Ga catalysts supported on AI2O3. The following proce dure was used:
All carriers were impregnated according to the process as described below. AI2O3 with different contents of SiCy were used as carriers .
Preparation of impregnation solution:
4.0 g of a 5 wt% Ga solution, 0.20 g of a 0.5 wt% Pt solu tion and 0.10 g KNO 3 are dissolved with 11 ml water. This solution is used to impregnate 20 g of the selected sup port. The sample is rolled for 1 hour to ensure complete pore volume impregnation, dried at 100 °C overnight and then calcined at 700°C for 2 h with a 4 h heating ramp.
The support materials were the following: 1. A1 2 0 3 , no Si0 2
2. AI2O3, 5 wt% Si0 2 , low surface area (SA)
3. AI 2 O 3 , 5 wt% Si0 2 , medium SA
4. AI 2 O 3 , 5 wt% Si0 2 , higher SA
5. AI2O3, 10 wt% Si0 2 , high SA
6. AI 2 O 3 , 20 wt% Si0 2 , high SA
7. AI 2 O 3 , 30 wt% Si0 2 , high SA
Catalyst performance :
The reactor used was an isothermal quartz reactor with a quartz thermal pocket over the thermocouple. The outlet gas stream was analyzed using a gas chromatograph with an FID and TCD detector. The gas chromatograph analyzes the Cl to C4 hydrocarbons. Conversion and selectivity are based on the analyzed product mixture. Catalyst performances are evaluated by loading 1.5 gram of catalyst with a sieve fraction of 0.3-0.5 mm into the reactor, and then exposing the catalyst to five cycles of the following sequence of gas flows and temperatures: 200 ml/min of 10% propane in nitrogen for 14 mins at 570°C, followed by 200 ml/min ni trogen flush for 60 mins while heating to 630°C, followed by regeneration with 50 ml/min 2% Oxygen in nitrogen for 30 mins at 630°C, followed by cooling in 50 ml/min 2% Oxygen in nitrogen for 30 mins to 570°C, followed by 200 ml/min nitrogen flush for 3 mins at 570°C. The dehydrogenation cy cle is then started again, without including a reduction step. The tests were performed at a pressure of 5 bar.
The results appear from the figures, where: Fig. 1 (a-c) show the steady-state catalytic performance
(5 th cycle) regarding activity (Fig. la), selectivity (Fig. lb) and 'oil' formation as indicated by the formation of 1- butene (Fig. lc) of 1.5 g (0.3-0.5 mm) catalyst at a tem- perature of 570°C, a 12 Nl/h flow of 10% propane and a pressure of 5 bar, and
Fig. 2 shows the TPO (temperature-programmed oxidation) of spent catalysts after testing.
It can be seen in Fig. la that all SiCy-containing cata lysts have a higher performance after 11 minutes on stream than the corresponding reference catalyst without SiCy. Two of the catalysts with 5 wt% SiCy furthermore also have a higher initial activity after 1 minute on stream. It is thus seen that SiCy is able to improve both the activity and the stability of the catalyst.
The catalytic activity of the catalyst seems to correlate very well with the Lewis acidity of the carriers
(http : //www . sasolgermany . de/fileadmin/doc/alumina/0271. SAS- BR-Inorganics_Siral_Siralox_WEB.pdf). The by-product for mation (selectivity) , the oil formation and the coke for mation all seem to correlate with the Br0nsted acidity of the carrier. Furthermore, the higher the SiCy loading is, the harder the coke becomes (Fig. 2) . It thus requires in creasingly higher temperatures to remove the coke. In con clusion, Lewis acid sites introduced by SiCy appear to be beneficial for the catalyst, whereas Br0nsted acid sites cause side reactions. The optimum catalyst performance seems to be obtained with the 5 wt% SiCy carrier.