Bifunctional catalyst comprising evenly distributed phosphorous

Patent metadata

Field	Value
Publication number	US-2019076830-A1
Application number	US-201615768916-A
Country	US
Kind code	A1
Filing date	Nov 30, 2016
Priority date	Nov 30, 2015
Publication date	Mar 14, 2019
Grant date	—

Abstract

A bifunctional catalyst for conversion of oxygenates, said bifunctional catalyst comprising zeolite, alumina binder, Zn and P, wherein P is evenly distributed across the catalyst.

First claim

1 . A bifunctional catalyst comprising zeolite, alumina binder, Zn and P, wherein the P is present throughout the catalyst, the P concentration at the catalyst center is above 0.1 wt %, and the Zn concentration at the catalyst center is above 3 wt %.

2 . Bifunctional catalyst according to claim 1 , wherein the catalyst is a bifunctional catalyst for conversion of oxygenates.

3 . Bifunctional catalyst according to claim 1 , wherein the P concentration at the catalyst edge is between 0.1 wt %-10 wt %.

4 . Bifunctional catalyst according to claim 1 , wherein the ratio of P concentration at the catalyst center to the P concentration at the catalyst edge (wt % P catalyst center: wt % P catalyst edge) is 1:20.

5 . Bifunctional catalyst according to claim 1 , wherein Zn is present at least partly as ZnAl 2 O 4 .

6 . Bifunctional catalyst according to claim 1 , wherein the catalyst is an extruded or pelletized catalyst.

7 . Bifunctional catalyst according to claim 1 , wherein the zeolite is ZSM-5 or ZSM-11.

8 . Bifunctional catalyst according to claim 1 , comprising 30-80 wt % zeolite, 1-40 wt % ZnAl 2 O4, 0-40% AlPO4, 0-40 wt % Al 2 O 3 , 0-10 wt % ZnO.

9 . Bifunctional catalyst according to claim 1 , wherein Zn is present in both zeolite and alumina binder.

10 . Bifunctional catalyst according to claim 1 , wherein the molar ratio of P/Zn is 0.02-5.

11 . Bifunctional catalyst according to claim 1 , wherein the molar ratio of P/Zn is at least substantially the same at the catalyst edge and the catalyst center.

12 . Bifunctional catalyst according to claim 1 , wherein the alumina binder further comprises silica.

13 . Bifunctional catalyst according to claim 1 , wherein the catalyst, by X-ray diffraction, does not contain free ZnO in the binder.

14 . Bifunctional catalyst according to claim 1 , wherein the Zn concentration is 3-25 wt % in the catalyst.

15 . Bifunctional catalyst according to claim 1 , wherein Zn is present in the binder as mainly ZnAl 2 O 4 .

16 . Bifunctional catalyst according to claim 1 , wherein the molar amount of Zn present in the binder phase as ZnAl 2 O 4 constitutes at least 50% of the total amount of Zn in the binder phase.

17 . Bifunctional catalyst according to claim 1 , wherein the molar amount of Zn present in the binder phase as ZnAl 2 O 4 constitutes at least 96% of the total amount of Zn present in the binder phase.

18 . Bifunctional catalyst according to claim 1 , wherein the molar amount of Zn present in the binder phase as ZnO corresponds to up to 10% ZnO relative to the total amount of Zn present in the binder phase.

19 . Bifunctional catalyst according to claim 1 , wherein Zn in the zeolite is present as ZnO, Zn(OH)+ and/or Zn++ in ion exchange positions.

20 . Bifunctional catalyst according to claim 1 , wherein the total Zn content in the catalyst is 8-15 wt % Zn.

21 . Bifunctional catalyst according to claim 1 , wherein zinc in the binder in said catalyst is partly or fully spinelized.

22 . Bifunctional catalyst according to claim 1 , wherein the Zn content is substantially the same in its partly spinelized and fully spinelized form.

23 . Bifunctional catalyst according to claim 1 , wherein a fully spinelized form is obtained by heating a partly spinelized form at 300-550° C. in an atmosphere comprising steam.

24 . A method for producing a bifunctional catalyst comprising an alumina binder, zeolite, P and Zn, said method comprising the steps of:
impregnating an alumina/zeolite catalyst with a P and/or Zn-containing aqueous solution, at least partly spinelizing the Zn impregnated alumina/zeolite catalyst by heating the impregnated alumina/zeolite catalyst to 300-650° C. for 0.25-7 h.

25 . Method for producing a bifunctional catalyst comprising an alumina binder, zeolite, P and Zn, said method comprising the steps of:
applying a P and/or Zn compound or a solution of a P and/or Zn compound onto a zeolite or alumina/zeolite by mixing, shaping said mixture by extrusion or palletization, at least partly spinelizing the Zn in the impregnated alumina/zeolite catalyst by heating the impregnated alumina/zeolite catalyst to 300-650° C. for 0.25-7 h.

26 . Method according to claim 24 , wherein the P and/or Zn compounds are applied in at least two separate steps by mixing and/or impregnation.

27 . Method according to claim 24 , wherein the P is applied first.

28 . Method according to claim 24 , wherein the zeolite is a ZSM preferably H-ZSM-5.

29 . Method according to claim 24 wherein the Zn aqueous solution is a Zn nitrate solution or a Zn acetate solution and/or where P is applied by use of ammoniumdihydrogenphosphate.

30 . Method according to claim 24 , wherein Zn impregnation and calcination and/or spinelization results in a total Zn content of 3 wt % Zn.

31 . Method according to claim 24 , wherein the Zn concentration is higher in the binder phase than in the zeolite phase.

32 . Method according to claim 24 , wherein the catalyst is further or fully spinelized by heating a partly spinelized form at 300-550° C. in an atmosphere comprising steam.

33 . A bifunctional catalyst according to claim 1 , used in a methanol conversion process comprising:
a conversion step wherein a feed stream comprising oxygenates such as methanol and/or DME is converted into a hydrocarbon stream rich in aromatics in presence of said bifunctional catalyst, a separation step wherein the hydrocarbon stream rich in aromatics is separated into at least an aromatics rich product stream, a stream comprising water and a recycle stream.

34 . A catalyst and method according to claim 1 , where the selectivity to aromatics of the catalyst is 30-80%, as determined at 420° C., 20 bar, 10 mol % methanol and a WHSV of 1.6.

35 . A catalyst and method according to claim 1 , where the selectivity of the catalyst to CO x is 0-10% as determined at 420° C., 20 bar, 10 mol % methanol and a WHSV of 1.6.

36 . A process for conversion of a feed stream comprising methanol and/or DME to a aromatics rich hydrocarbon stream in presence of an at least partially spinelized bifunctional catalyst comprising Zn and P, wherein the aromatics rich hydrocarbon stream is separated into at least an aromatics rich product stream, a process condensate stream and an off gas stream, and where at least part of said off gas stream is recycled to the conversion reactor.

37 . Process according to claim 36 wherein H 2 is at least partly removed from the off gas recycle.

38 . Process according to claim 36 further comprising an initial step of in situ further or fully spinelizing said at least partially spinelized bifunctional catalyst, preferably by steaming at 300-550° C. in an atmosphere comprising 1-100% steam.

39 . Process according to claim 36 , wherein the bifunctional catalyst or comprises zeolite, alumina binder, Zn and P, wherein the P is present throughout the catalyst, the P concentration at the catalyst center is above 0.1 wt %, and the Zn concentration at the catalyst center is above 3 wt %.

Assignees

• Haldor Topsoe As

Inventors

• Joensen Finn
• Vie Uffe

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C10G2400/30

  Aromatics · CPC title

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• B01J23/06

  of zinc, cadmium or mercury · CPC title