Decarbonized Olefins Production using Process Intensification

Abstract

A mixed metal oxide Selective Oxygen Carrier (SOC) suitable for the selective oxidation of hydrogen comprising bismuth oxides, rare earth oxides, and a dopant of Ti, Zr, and Hf and is characterizable by a high level of oxygen carrying capacity, selectivity and stability. The SOC can be synthesized using a sol gel procedure, co-precipitating salts, or the incipient wetness method. The invention includes a process of dehydrogenating a paraffin over a SOC. A SOC can also be used to catalytically crack hydrocarbons.

Claims

1. A mixed metal oxide Selective Oxygen Carrier (SOC) suitable for the selective oxidation of hydrogen at elevated temperatures in the presence of hydrocarbons and steam with a composition of the general formula (AC) (ST) (DP) wherein a) the Active Carrier (AC) represents oxides of bismuth, b) the active carrier stabilizer (ST) represents oxides of Rare Earth metals selected from the group of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb), and yttrium (Y) or mixtures thereof, and c) the Dopant (DP) represents oxides of Group 4 metals Titanium (Ti), Zirconium (Zr), Hafnium (Hf) or mixtures thereof; and characterizable by OC, the oxygen carrying capacity >20 kg 02/ton carrier, Selectivity Parameter ?0.1 and a stability parameter ?0.0025 using a test where the SOC is loaded in a fixed-bed reactor such that the 50>dT/dP>10 (diameter of tube to diameter of SOC particles) and 200>L/dP>50 (length of SOC bed to diameter of SOC particles) and 2>dP>0.5 mm exposed to a feed stream of a 1:1 molar mixture of propylene-to-hydrogen at a temperature of 550? C., 0.05 atm pressure and a feed rate of 0.5 hr.sup.?1 weight hourly space velocity and subjected to cycles of reaction for 9 minutes followed by 9 minutes of air regeneration with nitrogen purges of 5 minutes between reaction and air regeneration.

2. The SOC composition according to claim 1 wherein the AC (active carrier) species makes up 1 to 75 wt % of the total weight of the SOC, where weight includes the transition metals and associated oxygen needed to balance the oxidation state of the transition metals.

3. The SOC composition according to claim 1 wherein the active carrier (AC) species makes up 1 to 50 wt % of the total weight of the SOC.

4. The SOC composition according to claim 1 wherein the active carrier (AC) species makes up 1 to 40 wt % of the total weight of the SOC.

5. The SOC composition according to claim 1 wherein the DP (dopant) makes up 1 to 15 wt % of the total weight of the SOC.

6. The SOC composition according to claim 1 wherein the DP (dopant) makes up 1 to 10 wt % of the total weight of the SOC.

7. The SOC composition according to claim 1 wherein the DP (dopant) makes up 1 to 5 wt % of the total weight of the SOC.

8. The SOC composition according to claim 1 wherein ST (the SOC stabilizer) makes up 1 to 50 wt % of the total weight of the SOC.

9. The SOC composition according to claim 1 wherein ST (the SOC stabilizer) makes up 1 to 35 wt % of the total weight of the SOC.

10. The SOC composition according to claim 1 wherein ST (the SOC stabilizer) makes up 1 to 15 wt % of the total weight of the SOC.

11. The SOC composition according to claim 1, wherein said SOC composition has less than 2% by weight of either Copper (Cu) or Manganese (Mn) or Magnesium (Mg).

12. (canceled)

13. A method making the SOC of claim 1, wherein the SOC is synthesized using inorganic salts comprising the steps of: a) dissolving appropriate salts of the AC, ST and DP or mixtures thereof in water; b) coprecipitating the salts using a precipitating agent such as Ammonium Hydroxide; c) drying and calcining the resultant precipitate to produce the SOC d) adding a carrier support CS to the SOC to form the particle.

14. A method making the SOC of claim 1, wherein the SOC is synthesized using a sol gel procedure comprising the steps of a) dissolving an organic alkoxide, acetate of AC, ST and DP or mixtures thereof in an organic solvent; b) hydrolyzing the organic alkoxide, acetate solution, preferably in the presence of an acid or base catalyst, to produce a gel; c) drying and calcining the resultant gel to produce the SOC. d) adding a carrier support CS to the SOC to form the particle.

15. (canceled)

16. A method making the SOC of claim 1, wherein the SOC is synthesized using inorganic salts comprising the steps of a) dissolving appropriate salts of the AC, ST and DP or mixtures thereof in water; b) impregnating the carrier support CS with the salt solution; c) drying and calcining the resultant precipitate preferably at 550-800? C. and most preferably at 550-650? C. for 2-6 hrs in an oxygen containing atmosphere, preferably air to produce the SOC particle

17. The SOC composition according to claim 1 wherein particle size of the mixed-metal oxide SOC is 30-3000 microns (?m).

18. A process of dehydrogenating a paraffin, comprising contacting the paraffin with the SOC of claim 1 and a suitable Dehydrogenating catalyst in a reaction chamber under conditions sufficient to dehydrogenate the paraffin and resulting in an olefin.

19. A process for continuous dehydrogenating of paraffins having 2-8 carbon atoms, comprising: contacting said paraffins with the SOC composition according to claim 1 and a suitable Dehydrogenating catalyst at a reaction temperature of 500-800? C., a space velocity of 0.1-60 hr.sup.?1 and a pressure of 0.01-0.2 MPa and a SOC to Dehydrogenating catalyst ratio of 0.1 to 10 wt/wt for a reaction period in the range of 0.05 second to 10 minutes; regenerating the SOC and the Dehydrogenating catalyst with an oxygen-containing gas wherein said regeneration is performed at a reaction temperature of 500-800? C., a pressure of 0.01-0.2 MPa and a regeneration period ranging from 0.05 second to 10 minutes.

20. The process of claim 19 wherein said contacting is carried out in a fluidized bed reactor or a fixed-bed swing reactor.

21. A process for cracking hydrocarbons, comprising: contacting the hydrocarbon having 4-40 carbon atoms with the SOC of claim 1 and a suitable cracking catalyst in a reaction chamber under conditions sufficient to crack the hydrocarbon into smaller molecules.

22. A process for cracking hydrocarbons, comprising: contacting the hydrocarbon having 4-40 carbon atoms with the SOC of claim 1 and a suitable cracking catalyst in a reaction chamber under conditions sufficient to crack the hydrocarbon into smaller molecules contacting said hydrocarbons with the SOC composition according to claim 1 and a suitable cracking catalyst at a reaction temperature of 500-800? C., a space velocity of 0.1-60 hr.sup.1 and a pressure of 0.01-0.2 MPa, a steam concentration of 0-30 wt %, and a SOC to cracking catalyst ratio of 0.1 to 10 wt/wt for a reaction period in the range of 0.05 second to 10 minutes; regenerating the SOC and the cracking catalyst with an oxygen-containing gas wherein said regeneration is performed at a reaction temperature of 500-800? C., a pressure of 0.01-0.2 MPa and a regeneration period ranging from 0.05 second to 10 minutes.

23. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0048] FIG. 1 shows the effect of Bismuth loading on SOC capacity using yttria as the support. Estimates based on gas flow rates show that the Bi.sub.2O.sub.3-based SOC has an available oxygen-carrying capacity between 20-90 kg oxygen/ton SOC. Our research indicates that both the support and bismuth loading affect SOC capacity.

[0049] FIG. 2. Combined PDH selective hydrogen combustion using Zr-YDB SOC. Hydrogen conversion and propylene selectivity are shown as a function of propane conversion.

EXAMPLES

Example 1

[0050] The solid oxygen carrier (SOC) was prepared by dispersing 6 ml of 15% bismuth nitrate solution on 17 gm of zirconia via incipient wetness technique, followed by drying overnight at 120? C. and calcining at 450? C. for 4 hours. This SOC is designated as SOC A.

Example 2

[0051] The SOC used was as in Example 1, with the only difference being the support was silica instead of zirconia. This SOC is designated as SOC B.

Example 3

[0052] The SOC used was as in Example 1, with the only difference being the support was titania instead of zirconia. This SOC is designated as SOC C.

Example 4

[0053] The SOC used was as in Example 1, with the only difference being the support was ceria instead of zirconia. This SOC is designated as SOC D.

Example 5

[0054] The SOC was prepared by dispersing alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 55 ml of DI water for 30 minutes, followed by mixing Bi2O3 powder from Sigma Aldrich to the dispersed Dispal for 30 minutes. The excess water was evaporated by heating to obtain paste form. The paste was dried overnight at 120? C., followed by calcination at 800? C. for 5 hours. The ratio of Bi2O3 to Al.sub.2O.sub.3 in the mixture targeted to be 50/50 (wt/wt). This SOC is designated as SOC E.

Example 6

[0055] The SOC was prepared as in Example 5 with the only difference being the ratio of Bi2O3 to Al.sub.2O.sub.3 in the mixture targeted to be 45/55 (wt/wt). This SOC is designated as SOC F.

Example 7

[0056] The SOC was prepared as in Example 5 with the only difference being the ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 35/65 (wt/wt). This SOC is designated as SOC G.

Example 8

[0057] The SOC was prepared by dispersing alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 55 ml of DI water for 30 minutes, followed by mixing Bi.sub.2O.sub.3 powder from Sigma Aldrich to the dispersed Dispal for 30 minutes. The excess water was evaporated by heating to obtain paste form. The paste was dried overnight at 120? C. An aqueous solution consisting of 1 wt % CaO and 1 wt % MgO alkaline earth metal (AEM) oxides in forms of nitrate salts was dispersed on the dried SOC via incipient wetness technique, followed by calcination at 800? C. for 5 hours. The ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 80/20 (wt/wt). This SOC is designated as SOC H.

Example 9

[0058] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi2O3 to Al.sub.2O.sub.3 in the mixture targeted to be 70/30 (wt/wt). This SOC is designated as SOC I.

Example 10

[0059] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi2O3 to Al.sub.2O.sub.3 in the mixture targeted to be 60/40 (wt/wt). This SOC is designated as SOC J.

Example 11

[0060] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 50/50 (wt/wt). This SOC is designated as SOC K.

Example 12

[0061] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 40/60 (wt/wt). This SOC is designated as SOC L.

Example 13

[0062] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 30/70 (wt/wt). This SOC is designated as SOC M.

Example 14

[0063] The SOC was prepared as in Example 8 with the only difference being the ratio of Bi.sub.2O.sub.3 to Al.sub.2O.sub.3 in the mixture targeted to be 20/80 (wt/wt). This SOC is designated as SOC N.

Example 15

[0064] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 2 wt % CaO and 2 wt % MgO. This SOC is designated as SOC 0.

Example 16

[0065] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 3 wt % CaO and 3 wt % MgO. This SOC is designated as SOC P.

Example 17

[0066] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 4 wt % CaO and 4 wt % MgO. This SOC is designated as SOC Q.

Example 18

[0067] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 5 wt % CaO and 5 wt % MgO. This SOC is designated as SOC R.

Example 19

[0068] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 7.5 wt % CaO and 7.5 wt % MgO. This SOC is designated as SOC S.

Example 20

[0069] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 10 wt % CaO and 10 wt % MgO. This SOC is designated as SOC T.

Example 21

[0070] The SOC was prepared as in Example 13 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consists of 0 wt % CaO and 4 wt % MgO. This SOC is designated as SOC U.

Example 22

[0071] The SOC was prepared by adding AEM to the commercial bismuth aluminate hydrate from Sigma Aldrich. An aqueous solution consisting of 3 wt % CaO and 3 wt % MgO alkaline earth metal (AEM) oxides in forms of nitrate salts was dispersed on commercial bismuth aluminate via incipient wetness technique, followed by drying overnight at 120? C., and calcining at 550? C. for 4 hours. This SOC is designated as SOC V.

Example 23

[0072] The SOC was prepared as in Example 22 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 7.5 wt % CaO and 7.5 wt % MgO. This SOC is designated as SOC W.

Example 24

[0073] The SOC was prepared as in Example 22 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 10 wt % CaO and 10 wt % MgO. This SOC is designated as SOC X.

Example 25

[0074] The SOC was prepared as in Example 22 with the only difference being the aqueous solution of CaO and MgO alkaline earth metal (AEM) oxides consisting of 15 wt % CaO and 15 wt % MgO. This SOC is designated as SOC Y

Example 26

[0075] The SOC was prepared by dispersing alumina binder in the form of acidic Dispal (T25N4-80) from Sasol in 25 ml of DI water for 30 minutes, followed by mixing 50 wt % Bi.sub.2O.sub.3 and 50 wt % Y.sub.2O.sub.3 powders from Sigma Aldrich, and Alfa Aesar to the dispersed Dispal for 30 minutes. The excess water was evaporated by heating to obtain paste form. The paste was dried overnight at 120? C. and calcined at 800? C. for 5 hours. The ratio of Bi.sub.2O.sub.3 and Y.sub.2O.sub.3 combined to Al.sub.2O.sub.3 in the mixture targeted to be 80/20 (wt/wt). This SOC is designated as SOC Z.

Example 27

[0076] The SOC was prepared as in Example 26 with the only difference being the ratio of Bi.sub.203 and Y.sub.2O.sub.3 combined to Al.sub.2O.sub.3 in the mixture targeted to be 70/30 (wt/wt). This SOC is designated as SOC AA.

Example 28

[0077] The SOC was prepared via precipitation method. An aqueous solution of 3M nitric acid was prepared by mixing 54 ml of 70% nitric acid in 146 ml of DI water, followed by dissolving yttrium nitrate, zirconium oxy nitrate and bismuth nitrate salts at room temperature. Water insoluble precipitates of bismuth, zirconia and yttrium hydroxides were obtained by adding 2M NH.sub.4OH dropwise until the pH of solution became to 8 and filtration. The precipitate was dried overnight at 120? C. and calcined at 800? C. for 5 hours. The ratio of Bi.sub.2O.sub.3 and Y.sub.2O.sub.3 in the mixture targeted to be 25/75 (wt/wt). This SOC is designated as SOC AB.

Example 29

[0078] The SOC was prepared as in Example 28 with the only difference being the ratio of Bi.sub.203 and Y.sub.2O.sub.3 in the mixture targeted to be 50/50 (wt/wt). This SOC is designated as SOC AC.

Example 30

[0079] The SOC was prepared as in Example 28 with the only difference being the ratio of Bi.sub.203 and Y.sub.2O.sub.3 in the mixture targeted to be 75/25 (wt/wt). This SOC is designated as SOC AD.

[0080] SOC Tests The SOCs from examples 28-30 were tested as follows: SOC was loaded in a packed bed reactor with reactor to such that d.sub.T/d.sub.p>10 and L/d.sub.p>50. The SOC was activated by flowing air at 550? C. for 4 hours. Experiments were carried out in a fixed-bed reactor at temperatures of 550? C. and a GHSV of 5000/hr, which are typical conditions for dehydrogenation processes.

Combined PDH+SOC Test

[0081] The SOC from Example 29 was combined with the ExOlt dehydrogenation catalyst (4:1 wt/wt ratio) to run the reaction coupled with selective hydrogen oxidation under commercial reactor conditions, Exelus used its patented ExOlt dehydrogenation catalyst (U.S. patent Ser. No. 11/478,778). Results are shown in FIG. 5. The tests show high conversion of propane (>45%) with a high propylene selectivity (>85%) and low COx formation (SP<0.1). TCD measurements showed that for propane conversion to about 45%, 100% of hydrogen evolved during the dehydrogenation reaction was consumed. This suggests that the SOC was effective under PDH reaction conditions without excessive combustion of hydrocarbons.

[0082] While there have been many studies in the literature.sup.(1) (2) to couple selective hydrogen combustion with PDH reaction, none of them have demonstrated the coupled reaction at temperatures greater than 500? C. and/or obtained high propane conversions with high propylene selectivity. Our experiments also show that the SOC is selective to hydrogen combustion not just in the presence of propane but also with large amounts of propylene. To the best of our knowledge, this is the first time a chemical looping-based catalyst system has been successfully applied to obtain high conversions (>45%) at high propylene selectivity (>90 mole %).

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