Process to make olefins from organics with reduced side reactions
The present invention is a process for making an olefin product from an oxygen-containing organic feedstock comprising: providing a mixture of said oxygen-containing feedstock, an hydrocarbon and optionally an inert diluent, contacting said mixture in a reaction zone having an inner surface (the MTO reactor) with a zeolitic catalyst at conditions effective to convert at least a part of the oxygen-containing organic feedstock to olefin products (the MTO reactor effluent), recovering a reactor effluent comprising light olefins, a heavy hydrocarbon fraction and undesired by-products, wherein: at least a part of the inner surface is passivated such that the undesired by-products are reduced by comparison with a non passivated inner surface and/or one or more sulphur compound is co-injected with the said oxygen-containing feedstock and the hydrocarbon and said sulphur compound is capable to reduce the undesired by-products by comparison with a non injection of sulphur compound. The present invention is of high interest for the catalyst of the ZSM type such as ZSM-5 optionally containing phosphorus and regenerated in the MTO reactor.
1. A process for making an olefin product from an oxygen-containing organic feedstock comprising:
contacting an oxygen-containing organic feedstock, ethylene, and a sulphur compound in a reactor comprising a passivated inner surface with a zeolitic catalyst at conditions effective to convert at least a part of the oxygen-containing organic feedstock to olefin products,
wherein the sulphur compound is present in an amount ranging from 10 vppm to 1000 vppm, and wherein the sulphur compound comprises a thiol, dimethyldisulphide, or an aromatic heterocycle, wherein the ethylene and is present in the reactor at a ratio of oxygen-containing organic feedstock to ethylene ranging from 10:1 to 1:10.
2. The process according to claim 1 wherein a portion of the olefin products is sent to a fractionation section to separate light olefins from a heavy hydrocarbon fraction; wherein a portion of said heavy hydrocarbon fraction is recycled in the reactor as a portion of the hydrocarbon.
3. The process according to claim 1 wherein said olefin products are fractionated to form a stream comprising essentially ethylene and said stream in whole or in part is recycled in the reactor as a portion of the hydrocarbon.
4. The process according to claim 1 wherein the reactor comprises a plurality of reactors connected in series.
5. The process according to claim 1 wherein the reactor is further defined as a non-circulated fluidized bed reactor.
6. The process according to claim 1 wherein the reactor is further defined as a fluidized bed reactor.
7. The process according to claim 1 wherein the zeolitic catalyst comprises an MFI type zeolitic catalyst.
8. The process according to claim 7 wherein the MFI type zeolitic catalyst is further defined as a ZSM-5 optionally containing phosphorus.
9. The process according to claim 1 wherein the zeolitic catalyst is regenerated in the reactor.
10. The process according to claim 1 wherein the zeolitic catalyst is of the MFI type zeolitic catalyst with Si/Al ratio at least 60.
11. The process according to claim 1 wherein the zeolitic catalyst is selected from a group consisting of MEL, MIT, MWW, TON, EUO, and MFS.
12. The process according to claim 1 , wherein the sulphur compound is present in an amount ranging from 50 vppm to 800 vppm.
13. The process according to claim 1 , wherein the sulphur compound comprises the thiol.
14. The process according to claim 1 , wherein the sulphur compound comprises the aromatic heterocycle.
15. The process according to claim 1 , wherein the sulphur compound is introduced into the reactor prior to the ethylene.
16. The process according to claim 14 , wherein the aromatic heterocycle is selected from a group consisting of thiophene, benzothiophene, substituted thiophenes and combinations thereof.
17. The process according to claim 1 , wherein the ethylene is a reactive co-feed and is present in the reactor at a ratio of oxygen-containing organic feedstock to ethylene ranging from 30:1 to 1:30.
18. The process of claim 1 , wherein the ethylene is present in the reactor at a ratio of oxygen-containing organic feedstock to ethylene ranging from 10:1 to 1:5.
19. A process for making an olefin product from an oxygen-containing organic feedstock comprising:
providing a mixture of the oxygen containing organic feedstock, ethylene, and optionally an inert diluent;
contacting the mixture in a reaction zone having an inner surface with a zeolitic catalyst at conditions effective to convert at least a part of the oxygen-containing organic feedstock to olefin products;
recovering a reactor effluent comprising light olefins, a heavy hydrocarbon fraction, and by-products;
wherein:
at least a part of the inner surface is passivated;
one or more sulphur compounds are co-injected with the oxygen-containing organic feedstock and the ethylene;
wherein the sulphur compound is present in an amount ranging from 10 vppm to 1000 vppm; and
wherein the ethylene is present in the reactor at a ratio of oxygen-containing organic feedstock to ethylene ranging from 10:1 to 1:10.