Catalyst and hydrocarbon conversion process utilizing the catalyst

Abstract

The present invention relates to a hydrocarbon conversion catalyst comprising i) a catalyst, in oxidic form, metals M1, M2, M3 and M4, wherein: M1 is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is selected from W, Mo, Re and mixtures thereof; M4 is selected from Sn, K, Y, Yb and mixtures thereof; and ii) a hydrogen scavenger selected from at least one alkali and/or alkaline earth metal derivative, preferably in metallic, hydride, salt, complex or alloy form; as well as a hydrocarbon conversion process utilizing this catalyst.

Claims

1. A process for conversion of a hydrocarbon feed comprising saturated hydrocarbon compounds to olefin products comprising contacting the hydrocarbon feed with a hydrocarbon conversion catalyst comprising: i) metals M1, M2, M3 and M4, wherein: M1 is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is W; M4 is selected from Sn, K, Y, Yb, and mixtures thereof wherein a mass fraction of M1 is in the range of 0.1 to 0.8; a mass fraction of M2 is in the range of 0.001 to 0.2; a mass fraction of M3 is in the range of 0.001 to 0.2; a mass fraction of M4 is in the range of 0.0001 to 0.2; and a mass fraction of oxygen is in the range of 0.1 to 0.8; and ii) at least one alkali metal and/or alkaline earth metal in a metallic, hydride, salt, complex, or alloy form.

2. The process of claim 1, wherein the at least one alkali metal and/or alkaline earth metal is selected from Li, Na, K, Mg, Ca, and mixtures thereof.

3. The process of claim 2, wherein the at least one alkali metal and/or alkaline earth metal is Na or Mg.

4. The process of claim 1, wherein a weight ratio of catalyst i) said metals M1, M2, M3 and M14 and ii) said alkali metal and/or alkaline earth metal, is from 1-99 to 99-1.

5. The process of claim 1, wherein M2 is Pt and M3 is W.

6. The process according to claim 1, wherein the hydrocarbon feed comprises at least one paraffin having 2 to 5 carbon atoms.

7. The process of claim 6, wherein the hydrocarbon feed comprises propane, n-butane, or a mixture thereof.

8. The process of claim 7, wherein the hydrocarbon feed comprises propane and wherein the olefin products comprise ethylene and butene, resulting from the conversion of the propane.

9. The process according to claim 1, additionally comprising a regeneration step of the hydrocarbon conversion catalyst comprising heating the hydrocarbon conversion catalyst with an oxidizing agent at a temperature of about 200-700 C.

10. The process according to claim 9, wherein the oxidizing agent comprises air or oxygen.

11. The process of claim 1, wherein said metals M1, M2, M3, and M4 are in oxide forms.

12. The process of claim 1, wherein the catalyst further comprises metal M5 in oxide form, wherein M5 is selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

13. The process of claim 12, wherein said metal M1 is in oxide form, and further wherein said oxide form of M1 and said oxide form of M5 are obtained by heat treatment of corresponding precursor forms of M1 and M5, said corresponding precursor forms independently selected from the group consisting of a halide form, an alkoxide form, a nitrate form, a carbonate form, a formate form, an oxalate form, an amine form, and a hydroxide form.

14. The process of claim 13, wherein said corresponding precursor forms are independently selected from the group consisting of the carbonate form and the hydroxide form.

15. A process for conversion of a hydrocarbon feed comprising saturated hydrocarbon compounds to olefin products comprising contacting the hydrocarbon feed with a hydrocarbon conversion catalyst comprising: i) metals M1, M2, M3 and M4, wherein: M1 is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is W; M4 is selected from Sn, K, Y, Yb, and mixtures thereof wherein a mass fraction of M1 is in the range of 0.1 to 0.8; a mass fraction of M2 is in the range of 0.001 to 0.2; a mass fraction of M3 is in the range of 0.001 to 0.2; a mass fraction of M4 is in the range of 0.0001 to 0.2; and a mass fraction of oxygen is in the range of 0.1 to 0.8; and ii) at least one alkali metal and/or alkaline earth metal selected from the group consisting of Li, Na, Mg, Ca, and mixtures thereof, wherein the hydrocarbon feed comprises propane and wherein the olefin products comprise ethylene and butene, resulting from the conversion of the propane.

16. The process of claim 15, wherein said metals M1, M2, M3, and M4 are in oxide forms.

17. The process of claim 15, wherein said catalyst further comprises metal M5 in an oxide form, wherein M5 is selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

18. The process of claim 17, wherein said metal M1 is in oxide form, and further wherein said oxide form of M1 and said oxide form of M5 are obtained by heat treatment of corresponding precursor forms of M1 and M5, said corresponding precursor forms independently selected from the group consisting of a halide form, an alkoxide form, a nitrate form, a carbonate form, a formate form, an oxalate form, an amine form, and a hydroxide form.

19. A process for conversion of a hydrocarbon feed comprising saturated hydrocarbon compounds to olefin products comprising contacting the hydrocarbon feed with a hydrocarbon conversion catalyst comprising: i) metals M1, M2, M3, and M4, wherein: said metals M1, M2, M3, and M4 are in oxide forms; M1 is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is selected from W, Mo, Re and mixtures thereof; M4 is selected from Sn, K, Y, Yb, and mixtures thereof; wherein a mass fraction of M1 is in the range of 0.1 to 0.8; a mass fraction of M2 is in the range of 0.001 to 0.2; a mass fraction of M3 is in the range of 0.001 to 0.2; a mass fraction of M4 is in the range of 0.0001 to 0.2; and a mass fraction of oxygen is in the range of 0.1 to 0.8; and ii) at least one alkali metal and/or alkaline earth metal selected from the group consisting of Li, Na, Mg, Ca, and mixtures thereof, wherein the hydrocarbon feed comprises propane and wherein the olefin products comprise ethylene and butene, resulting from conversion of the propane.

20. The process of claim 19, wherein said catalyst further comprises metal M5 in an oxide form, wherein M5 is selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

21. The process of claim 20, wherein said metal M1 is in oxide form, and further wherein said oxide form of M1 and said oxide form of M5 are obtained by heat treatment of corresponding precursor forms of M1 and M5, said corresponding precursor forms independently selected from the group consisting of a halide form, an alkoxide form, a nitrate form, a carbonate form, a formate form, an oxalate form, an amine form, and a hydroxide form.

Description

EXPERIMENTAL RESULTS

(1) In the examples section below, the conversion of propane into olefins, preferably ethylene and butene, has been investigated using hydrocarbon conversion catalysts according to the present invention and comparative catalysts.

Example A

(2) Each example catalyst was pretreated by contacting with air at approximately 500 C. for 30 minutes and with hydrogen at approximately 500 C. for 90 minutes before contacted with C3H8 at approximately 500 C., 0.1 bar gauge, and WHSV of 0.2 h.sup.1. The results were measured at time on stream for approximately 60-65 hours. Effluents from the reaction were directed to a gas chromatography apparatus to measure their chemical composition. The measured compositions of effluents were used to calculate conversion and selectivity. Percent C3H8 conversion was calculated from the weight of C3H8 converted during reaction divided by weight of C3H8 in feed stream and then multiplied by 100. Percent selectivity of each other product was calculated also from the weight of that specific product produced from the reaction divided by weight of all products produced from the reaction and then multiplied by 100. The composition of catalyst was calculated from the amount of precursor used to prepare the catalyst. The mass fraction can be calculated from the weight percentage divided by 100.

(3) TABLE-US-00001 Result C3H8 Selectivity (% wt) Catalyst Conversion Total Example (% wt) (% wt) Olefins CH4 C2H4 C2H6 C3H6 C4H8 C4H10 C5+ 1 (compare) 0.811 Al 10.858 77.279 6.038 8.505 14.252 54.499 13.243 2.429 1.032 1.792 Mg 50.495 O 0.501 Pt 42.526 Si 3.396 W 0.076 Yb 0.403 Zr 2 (compare) 0.649 Al 10.481 86.695 4.854 2.902 6.837 78.846 4.946 0.907 0 6.977 B 3.903 H 1.433 Mg 9.040 N 40.438 O 0.401 Pt 34.058 Si 2.716 W 0.061 Yb 0.323 Zr 3 0.649 Al 11.451 84.668 4.172 9.877 8.216 53.427 19.648 1.075 1.715 (inventive) 1.433 Mg 3.283 N 5.388 Na 51.687 O 0.401 Pt 34.058 Si 2.716 W 0.061 Yb 0.323 Zr 4 0.725 Al 14.783 79.676 6.146 9.675 12.457 53.146 15.526 1.716 1.327 (inventive) 1.600 Mg 1.800 N 2.955 Na 51.143 O 0.445 Pt 37.873 Si 3.032 W 0.068 Yb 0.358 Zr 5 0.722 Al 10.695 84.389 5.830 9.803 8.688 59.617 13.965 1.091 1.003 (inventive) 4.306 K 1.594 Mg 1.543 N 50.156 O 0.444 Pt 37.787 Si 3.021 W 0.068 Yb 0.358 Zr

Example 1 (Comparative)

(4) A catalyst sample containing 0.811 wt % of Al, 1.792 wt % of Mg, 50.495 wt % of O, 0.501 wt % of Pt, 42.526 wt % of Si, 3.396 wt % of W, 0.076 wt % of Yb, and 0.403 wt % Zr was calcined at 550 C. for 3 hours in air before subjected to the reaction test.

(5) This catalyst is a standard catalyst for conversion of paraffins into olefins without adding hydrogen scavenger.

Example 2 (Comparative)

(6) The catalyst sample was prepared by: 1) Providing a powder catalyst containing 0.810 wt % of Al, 1.789 wt % of Mg, 50.497 wt % of O, 0.5 wt % of Pt, 42.53 wt % of Si, 3.391 wt % of W, 0.076 wt % of Yb, and 0.403 wt % of Zr. 2) Calcining the powder catalyst in step 1) at 550 C. for 3 hours in air. 3) Calcining NH3BH3 at 550 C. for 3 hours in air. 4) Physically mixing 80 wt % of the calcined catalyst from step 2) with 20 wt % of calcined NH3BH3 from step 3).

(7) Using of this catalyst shows higher olefins selectivity, however it seems NH3BH3 suppressed metathesis activity of W and therefore ethylene and butylene selectivity were significantly lowered.

Example 3

(8) The catalyst sample was prepared by: 1) Providing a powder catalyst containing 0.811 wt % of Al, 1.791 wt % of Mg, 50.448 wt % of O, 0.501 wt % of Pt, 42.573 wt % of Si, 3.395 wt % of W, 0.076 wt % of Yb, and 0.403 wt % of Zr. 2) Calcining the powder catalyst in step 1) at 550 C. for 3 hours in air. 3) Calcining Na(NO3) at 550 C. for 3 hours in air. 4) Physically mixing 80 wt % of the calcined catalyst from step 2) with 20 wt % of calcined Na(NO3) from step 3).

(9) Use of this catalyst can suppress hydrogenation side reaction. This is evidenced by higher C2H4 and C4H8 selectivity but lower C2H6 and C4H10 selectivity compared to the standard catalyst in Example 1.

Example 4

(10) The catalyst sample was prepared by the same steps as Example 3, but 10 wt % of Na(NO3) was used.

(11) Use of this catalyst can suppress hydrogenation side reaction. This is evidenced by higher C2H4 and C4H8 selectivity but lower C2H6 and C4H10 selectivity compared to the standard catalyst in Example 1.

Example 5

(12) The catalyst sample was prepared by the same steps as the Example 3, but 10 wt % of K(NO3) was used instead of Na(NO3).

(13) Use of this catalyst can suppress hydrogenation side reaction. This is evidenced by higher C2H4 and C4H8 selectivity but lower C2H6 and C4H10 selectivity compared to the standard catalyst in Example 1.

Example B

(14) Each example catalyst was pretreated by contacting with air at approximately 500 C. for 30 minutes and with hydrogen at approximately 500 C. for 90 minutes before contacted with C3H8 at approximately 550 C., 0.05-0.1 bar gauge, and WHSV of approximately 0.4-0.7 h-1. The results were measured at time on stream approximately 155-160 hours.

(15) TABLE-US-00002 Result C3H8 Selectivity (% wt) Catalyst Conversion Total Example (% wt) (% wt) Olefins CH4 C2H4 C2H6 C3H6 C4H8 C4H10 C5+ 6 0.324 Al 27.719 75.199 1.519 6.934 17.655 44.806 20.063 3.512 3.394 (compare) 0.715 Mg 49.624 O 4.277 Pt 42.700 Si 1.355 W 0.390 Yb 0.641 Zr 7 0.649 Al 24.276 93.554 1.311 8.276 3.353 69.419 14.841 0.722 1.016 (inventive) 6.093 B 11.294 Ca 2.272 H 1.432 Mg 39.375 O 2.159 Pt 33.131 Si 2.715 W 0.574 Yb 0.307 Zr 8 0.753 Al 27.504 86.788 1.874 14.874 7.912 46.881 20.795 1.474 4.402 (inventive) 2.518 B 0.939 H 4.492 Mg 45.930 O 2.531 Pt 38.654 Si 3.151 W 0.673 Yb 0.360 Zr

Example 6 (Comparative)

(16) A catalyst sample containing 0.324 wt % of Al, 0.715 wt % of Mg, 49.624 wt % of O, 4.277 wt % of Pt, 42.700 wt % of Si, 1.355 wt % of W, 0.390 wt % of Yb, 0.641 wt % Zr was calcined at 550 C. for 3 hours in air before subjected to the reaction test.

Example 7

(17) The catalyst sample was prepared by:

(18) 1) Providing a powder catalyst containing 0.801 wt % of Al, 1.782 wt % of Mg, 49.009 wt % of O, 2.687 wt % of Pt, 41.237 wt % of Si, 3.379 wt % of W, 0.714 wt % of Yb, and 0.382 wt % of Zr.

(19) 2) Calcining the powder catalyst in step 1) at 550 C. for 3 hours in air.

(20) 3) Calcining Ca(BH.sub.4).sub.2 at 550 C. for 3 hours in air.

(21) 4) Physically mixing 80 wt % of the calcined catalyst from step 2) with 20 wt % of calcined Ca(BH4)2 from step 3).

(22) Use of this catalyst can suppress hydrogenation side reaction. This is evidenced by lower C2H6 and C4H10 selectivity compared to the standard catalyst in Example 6.

Example 8

(23) The catalyst sample was prepared by the same steps as the Example 7, but 6.5 wt % of Mg(BH4)2 was used instead of Ca(BH4)2.

(24) Use of this catalyst can suppress hydrogenation side reaction. This is evidenced by lower C2H6 and C4H10 selectivity compared to the standard catalyst in Example 6.

(25) The features disclosed in the foregoing description and in the claims may, both separately and in any combination thereof, be material for realizing the invention in diverse forms.