Title:
THE USE OF METAL DITHIOLENE COMPLEXES IN SELECTIVE OLEFIN RECOVERY
Document Type and Number:
WIPO Patent Application WO/2000/061527
Kind Code:
A2
Abstract:
Enhanced synthesis of transition metal dithiolene complexes is described. [1,2-bis(Trifluoromethyl)ethylene-1,2-dithiolato]nickel selectively and reversibly binds olefins (C¿2? to C¿6?). Under the same conditions, the complex does not react with H¿2?O, C¿2?H¿2?, CO, and H¿2?, and only slowly reacts with H¿2?S at high concentrations. The compositions are useful for selective removal and recovery of olefins from process streams containing contaminants such as CO and H¿2?S.
Inventors:
WANG KUN
STIEFEL EDWARD IRA
STIEFEL EDWARD IRA
Application Number:
PCT/US2000/009453
Publication Date:
October 19, 2000
Filing Date:
April 07, 2000
Export Citation:
Assignee:
EXXONMOBIL RES & ENG CO (US)
International Classes:
B01D53/14; B01D11/04; C02F1/54; C07C7/152; C07C11/04; C07C11/06; C07C11/08; C07C11/107; C07C319/12; C07C323/05; C07F15/04; (IPC1-7): C07C7/152; C07C319/02
Foreign References:
| US5414194A | 1995-05-09 |
Other References:
See also references of EP 1169286A2
Attorney, Agent or Firm:
Scuorzo, Linda M. (NJ, US)
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Claims:
CLAIMS:
| 1. | A method for separating olefins from olefincontaining streams, comprising: contacting an olefincontaining stream with a metal dithiolene compound selected from compounds represented by the formulas M [S2C2 (RaRb)] 2 and MIS2C6 (RIR2R3R4) 12 at conditions sufficient to form an adduct of the olefin with the metal dithiolene compound, wherein M is a transition metal Ra and Rb and R1, R2, R3, and R4 are independently selected and may be the same or different and are selected from hydrogen, electron withdrawing groups and unsubstituted and electron withdrawing group substituted hydrocarbyl groups. |
| 2. | The process of claim 1 wherein the olefincontaining stream contains at least one of paraffins, H2, CO, C, 7H2, H2S, H20, C02, and alkynes. |
| 3. | The process of claim 1 further comprising dissociating the olefin from the complex to recover the olefin. |
| 4. | The process of claim 1 wherein contacting is carried out at a temperature of from about60°C to 150°C. |
| 5. | The process of claim 1 wherein the metal dithiolene compound represented by the formula M [S2C2 (RaRb)] 2 is produced by the process of : (a) contacting RaC =CRb with sulfur at conditions sufficient to form a mixture of compounds represented by the formula [(RaRb) C2S2] n wherein the mixture contains compound corresponding to n = 2 in combination with the compounds corresponding to n = 1 and n > 2; (b) contacting the [(RaRb) C2S2] n prepared in (a) with metal powder at conditions sufficient to form M [S2C2 (RaRb)] 2 wherein Ra and Rb are independently selected and may be the same or different and are selected from hydrogen, electron withdrawing groups and substituted and unsubstituted hydrocarbyl groups. |
| 6. | The process of claim 1 or 5 wherein the electron withdrawing groups are selected from halo, heterocyclo, cyano, carboxylate, carboxylic ester, keto, nitro and sulfonyl groups. |
| 7. | The process of claim 1 or 5 wherein Ra, Rb, R1, R2, R3, and R4 are independently selected from CF3 and CN. |
| 8. | The process of claim 1 or 5 wherein M is selected from Ni, Pd and Pt. |
| 9. | The process of claim 1 further comprising the step of recovering the complex from the feed stream. |
| 10. | The process of claim 3 wherein dissociating is carried out by addition of a suitable solvent. |
| 11. | The process of claim 3 wherein dissociating is carried out by and effective change in at least one of temperature or pressure. |
| 12. | A method for making a metal dithiolene compound represented by the formula M [S2C2 (RaRb)] 2, comprising: (a) contacting RaC =CRb with sulfur at conditions sufficient to form a mixture of compounds represented by the formula [(RaRb) C2S2] n wherein the mixture contains compound corresponding to n = 2 in combination with the compounds corresponding to n = 1 and n > 2; (b) contacting the [(RaRb) C2S2] n prepared as in (a) with metal powder at conditions sufficient to form M [S2C2 (RaRb)] 2 wherein Ra and Rb are independently selected and may be the same or different and are selected from hydrogen, electron withdrawing groups and substituted and unsubstituted hydrocarbyl groups. |
Description:
inte: ational applicationNo. INTERNATIONALSEARCHREPORTPCT/US00/09453 BoxIObservationswherecertainclaimswerefoundunsearchable(Cont
inuationofitem1offirstsheet) ThisInternationalSearchReporthasnotbeenestablishedinrespecto
fcertainclaimsunderArticle17(2)(a)forthefolfowingreasons: 1.0 ClaimsNos.: becausetheyrelatetosubjectmatternotrequiredtobesearchedbythi
sAuthority,namely: 2.EClaims Nos. : becausetheyrelatetopartsoftheInternationalApplicationthatdon
otcomplywiththeprescribedrequirementstosuch anextentthatnomeaningfulInternationalSearchcanbecarriedout,s
pecifically: seeFURTHERINFORMATIONsheetPCT/ISA/210 3.Claims Nos.: becausetheyaredependentclaimsandarenotdraftedinaccordancewit
hthesecondandthirdsentencesofRule6.4(a). Box 11Observationswhereunityofinventionislacking(Continuationofi
tem2offirstsheet) ThisInternationalSearchingAuthorityfoundmultipleinventionsin
thisinternationalapplication,asfollows: 1. 1 As allrequiredadditionalsearchfeesweretimelypaidbytheapplicant,
thisInternationalSearchReportcoversall searchable claims. 2.as aïsearchableclaimscouldbesearchedwithouteffortjustifyingana
dditionalfee,thisAuthoritydidnotinvitepayment ofanyadditionalfee. 3. 0Asonlysomeoftherequiredadditionalsearchfeesweretimelypaidby
theapplicant,thisInternationalSearchReport covers onlythoseclaimsforwhichfeeswerepaid,specificallyclaimsNos.: 4.\/Norequiredadditionalsearchfeesweretimelypaidbytheapplica
nt.Consequently,thisInternationalSearchReportis restrictedtotheinventionfirstmentionedintheclaims;itiscovere
dbyclaimsNos.: 1-11 RemarkonProtestTheadditionalsearchfeeswereaccompaniedbytheap
plicant'sprotest. u Noprotestaccompaniedthepaymentofadditionalsearchfees. u FURTHER INFORMATION CONTINUED FROM PCT/ISA/210 1. Claims: 1-11 A process for the separation of olefins 2. Claim: 12 A process for the preparation of metal dithiolenes FURTHER INFORMATION CONTINUED FROM PCT/ISA/210 Continuation of Box 1.2 Present claims 1 to 11 relate to the use of an extremely large number of possible compounds. Support within the meaning of Article 6 PCT and/or disclosure within the meaning of Article 5 PCT is to be found, however, for only a very small proportion of the compounds for which the use is claimed. In the present case, the claims so lack support, and the application so lacks disclosure, that a meaningful search over the whole of the claimed scope is impossible. Consequently, the search has been carried out for those parts of the claims which appear to be supported and disclosed, namely those parts relating to the use or preparation of the compounds for which the substituents are cyano or halo substituted alkyl groups (see the sentence bridging pages 6 and 7).
Insofar as can be said at this moment, claim 12 appears to present similar defects as the preparation of the same range of products is claimed in this claim.
The applicant's attention is drawn to the fact that claims, or parts of claims, relating to inventions in respect of which no international search report has been established need not be the subject of an international preliminary examination (Rule 66.1 (e) PCT). The applicant is advised that the EPO policy when acting as an International Preliminary Examining Authority is normally not to carry out a preliminary examination on matter which has not been searched. This is the case irrespective of whether or not the claims are amended following receipt of the search report or during any Chapter II procedure. INTERNATIONALSEARCHREPORT j------------------ ! International Application No I : nation on patent family members PCT,_00/09453 PatentdocumentPublicationPatentfamily Publication citedinsearchreportdatemember(s)date US5414194A09-05-1995US5391791A21-02-1995 US5430225A04-07-1995