Method for synthesising a mercaptan by adding hydrogen sulfide to an olefin

Abstract

The invention relates to a method for synthesising a mercaptan from a terminal olefin and hydrogen sulphide which comprises the following consecutive steps: Acatalytic addition of hydrogen sulphide to a terminal olefin catalysed by an acid catalyst; Bseparation of the products of the addition reaction into a light fraction including the surplus hydrogen sulphide and the olefins, and into a heavy fraction including at least one mercaptan and optionally one or more thioethers; Ca finishing step of passing the light fraction obtained in step B over an acid catalyst; then Dseparation of the products of the finishing step into a fraction that is rich in hydrogen sulphide and into a fraction that is rich in additives; and finally Erecirculation of the fraction that is rich in hydrogen sulphide to the catalytic addition step A. The invention also relates to the facility for implementing said method.

Claims

1. A process for synthesis of a mercaptan starting from a terminal olefin and hydrogen sulphide comprising at least the following successive steps: Acatalytically adding hydrogen sulphide to a terminal olefin catalysed by an acid catalyst, then Bseparating the products of the addition reaction into a light fraction comprising the excess hydrogen sulphide and the olefins, and a heavy fraction comprising at least one mercaptan and optionally one or more thioethers, Cin a finishing step, passing the light fraction obtained from step B over an acid catalyst, then Dseparating the products from the finishing step into a fraction rich in hydrogen sulphide and a fraction rich in addition products and then Erecycling the fraction rich in hydrogen sulphide to step A.

2. A process according to claim 1, wherein the mercaptan synthesized is a secondary mercaptan.

3. A process according to claim 1, wherein the catalyst used in the addition step is a catalyst comprising Lewis acid sites.

4. A process according to claim 1, wherein the addition reaction in step A and/or step C is or are heterogeneous catalyses using a solid acid catalyst.

5. A process according to claim 3, wherein the catalyst comprising Lewis acid sites is selected from the group consisting of oxides of molybdenum, oxides of cobalt, oxides of chromium, cobalt molybdate, phosphotungstic acids deposited on supports selected from activated carbon, alumina, zirconia, silica, thorium oxide, pumice stone or silica-alumina compositions.

6. A process according to claim 1, wherein the terminal olefin is of the following general formula (1):
R.sub.1R.sub.2CCH.sub.2(1), in which R.sub.1 denotes a hydrogen atom, and R.sub.2 represents an alkyl radical with from 1 to 20 carbon atoms, linear, branched or cyclic.

7. A process according to claim 6, wherein the terminal olefin is 1-butene.

8. A process according to claim 1, wherein the catalyst used for the finishing step is an acid catalyst that has strong acid sites.

9. A process according to claim 1, wherein the process comprises the following additional step: Fcombining and then purifying the heavy fraction obtained from ,separation step B and the fraction rich in addition products obtained from separation step D, to provide one or more light fractions comprising one or more mercaptans and a heavy fraction comprising the sulphides.

10. A process according to claim 9, wherein the process comprises the following additional step: Grecycling the heavy fraction from the purification step F to the finishing step C.

11. An installation for carrying out the process as defined in claim 1 comprising: an addition reactor, supplied with hydrogen sulphide and with olefin via a first pipeline and a second pipeline, a third pipeline, connected to an outlet of the addition reactor , which supplies a first separating device with a stream of crude reaction mixture, a fourth pipeline, connected to an outlet of the first separating device, which supplies a finishing reactor with the light fraction comprising the excess hydrogen sulphide and the olefins, a fifth pipeline, connected to an outlet of the finishing reactor, which supplies a second separating device with all of the reaction mixture from the finishing reactor, a sixth pipeline located at an outlet of the second separating device which recycles the fraction rich in hydrogen sulphide to the addition reactor, additional pipelines coming from the first and second separating devices which recover the heavy fraction comprising at least one mercaptan and optionally one or more thioethers and the fraction rich in addition products, and a single pipeline combining the heavy fraction comprising at least one mercaptan and optionally one or more thioethers and the fraction rich in addition products.

12. An installation according to claim 11, wherein the installation comprises a purification device, connected to the single pipeline, the purification device being able to isolate a secondary mercaptan in a first line, a linear mercaptan in a second line and to discharge a heavy fraction comprising the sulphides and other by-products in a third line.

13. An installation according to claim 12, wherein the installation comprises a fourth line, connected to the outlet of the purification device, conveying the sulphides and other by-products, the fourth line supplying the finishing reactor.

14. A process according to claim 3, wherein the catalyst comprising Lewis acid sites is chromium oxide supported on alumina.

15. A process according to claim 6, wherein R.sub.2 represents an alkyl radical with from 2 to 12 carbon atoms, linear, branched or cyclic.

16. A process according to claim 1, wherein the catalyst used for the finishing step is selected from the group consisting of cation exchange resins and zeolites, whether exchanged or not.

Description

EXAMPLES OF LABORATORY IMPLEMENTATION OF THE CATALYTIC ADDITION OF HYDROGEN SULPHIDE TO A TERMINAL OLEFIN

Example 1

Process According to the Invention

(1) The step of addition of hydrogen sulphide to a butene-1 is carried out in the following conditions: 1First fixed-bed catalytic reactor charged with 200 cm.sup.3 of catalyst (19% Cr.sub.2O.sub.3/Alumina):

(2) Butene-1: 75 g/h

(3) H.sub.2S: 92 NL/h, corresponding to a molar ratio H.sub.2S/butene=2

(4) Average temperature of the catalyst bed=245 C.

(5) P=1.4 MPa

(6) LHSV=60 h.sup.1 The results obtained for this addition step are as follows:

(7) Conversion: 83%

(8) Selectivities: 81/14/5 (SBM/NBM/thioethers) The unconverted butenes then have the following molar composition: 10% butene-1/45% butene-2 cis/45% butene-2 trans The fraction of unconverted butenes goes into the finishing reactor according to the following conditions: 2Fixed-bed finishing reactor charged with 100 cm.sup.3 of sulphonic resin A36 dry (DOW)

(9) Butenes: 7.3 NL/h

(10) H.sub.2S: 120 NL/h

(11) LHSV=120 h.sup.1

(12) No solvent. The results obtained for this finishing step are as follows:

(13) Conversion: 97.5%

(14) Selectivities: 87% SBM, 13% thioethers These two steps thus lead to a conversion of 99.5% of butene-1 and the following selectivity:

(15) SBM: 81.6%

(16) NBM: 11.6%

(17) Sulphides: 6.2% with a supply of butenes of: 99.5% butene-1/0.5% butenes-2.

Example 2

Comparative Process

(18) The first step of the process is identical to that of example 1. 1Fixed-bed catalytic reactor charged with 200 cm.sup.3 of catalyst (19% Cr.sub.2O.sub.3/Alumina):

(19) Butene-1: 75 g/h

(20) H.sub.2S: 92 NL/h corresponding to a molar ratio H.sub.2S/butene=2

(21) Average temperature of the catalyst bed=245 C.

(22) P=1.4 MPa

(23) LHSV=60 h.sup.1 Performance:

(24) Conversion: 83%

(25) Selectivities: 81/14/5 (SBM/NBM/thioethers) The unconverted butenes then have the following molar composition: 10% butene-1/45% butene-2 cis/45% butene-2 trans The fraction of unconverted butenes is recycled to the catalytic reactor according to the following conditions: Supply of butenes: 75 g/h with 20% butenes-2 in butene-1

(26) H.sub.2S: 92 NL/h corresponding to a molar ratio H.sub.2S/butene=2

(27) Average temperature of the catalyst bed=245 C.

(28) P=1.4 MPa

(29) LHSV=80 h.sup.1

(30) These steps of addition and recycling lead to a conversion of 60% and a selectivity of 82/12/6 (SBM/NBM/thioethers).

(31) The butenes-2, not reacting, lead to a drop in productivity and accumulate in the recycling, finally making the process inoperative.