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Title:
HYDROCARBON RAFFINATE STREAM PROCESSING
Document Type and Number:
WIPO Patent Application WO/2015/050635
Kind Code:
A1
Abstract:
A method to process a hydrocarbon raffinate stream to reduce sulfur and halogen contents. The raffinate stream is hydroprocessed in the presence of a catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide, the hydrogen sulfide and hydrogen halide are removed from the hydroprocessed stream, and a hydrocarbon product stream of reduced sulfur and halogen contents is recovered.

Inventors:
NADLER, Kirk, C. (2518 Coastal Oak Drive, Houston, TX, 77059, US)
BARBEE, Thomas, R. (2819 Evergreen Cliff Trail, Kingwood, TX, 77345, US)
DEAN, Timothy, P. (7522 Wimbledon Avenue, Baton Rouge, LA, 70810, US)
FALTA, Rachel, L. (777 Dunlavy Street #8212, Houston, TX, 77019, US)
ARSENEAUX, Carrie, B. (13375 Cypress Lake Avenue, Gonzales, LA, 70737, US)
Application Number:
US2014/050990
Publication Date:
April 09, 2015
Filing Date:
August 14, 2014
Export Citation:
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Assignee:
EXXONMOBIL CHEMICAL PATENTS INC. (5200 Bayway Drive, Baytown, TX, 77520-2101, US)
International Classes:
C10G45/02; C08F36/04; C10G45/04; C10G45/06; C10G45/08; C10G65/06; C10G69/12
Domestic Patent References:
Foreign References:
US4849095A
US5013424A
US20120165586A1
EP0389119A2
US20130240405A1
US6755963B2
US5171793A
US4629766A
US4328090A
EP0240253A2
EP0082726A2
US4530917A
US7407909B2
Other References:
"Hydrocarbon Resins, Kirk-Othmer Encyclopedia of Chemical Technology", vol. 13, 1995, J. WILEY & SONS, pages: 717 - 743
"Encycl. of Poly. Sci. and Eng.", vol. 7, 1987, J. WILEY & SONS, pages: 758 - 782
"Encycl. of Poly. Sci. and Eng.", vol. 14, 1988, JOHN WILEY & SONS, pages: 438 - 452
"Kirk-Othmer Encycl. of Chem. Tech.", vol. 17, 1968, JOHN WILEY & SON, pages: 475 - 478
"Handbook of Pressure-Sensitive Adhesive Technology", 1982, VAN NOSTRAND REINHOLD CO., pages: 353 - 356
Attorney, Agent or Firm:
PRASAD, Priya, G. et al. (Exxonmobil Chemical Company Law Technology, P.O. Box 2149Baytown, TX, 77522-2149, US)
Download PDF:
Claims:
CLAIMS;

We Claim:

1. A method to reduce sulfur and halogen contents from a hydrocarbon raffinate stream containing organic sulfide and organohalide, the raffinate stream comprising at least 30 ppmw sulfur and at least 30 ppmw halogen by weight of the raffinate stream, comprising: hydroprocessing the raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide; removing the hydrogen sulfide and hydrogen halide from the hydroprocessed stream; and

recovering a hydrocarbon product stream of reduced sulfur and halogen contents.

2. The method of claim 1, further comprising (a) polymerizing a diolefin-containing feed stream with a halide catalyst to form a resin-containing stream and (b) steam-stripping the resin-containing stream to recover the raffinate stream for the hydroprocessing.

3. The method of claim 1, wherein the raffinate stream comprises unreacted monomer or light oligomer components from polymerization of diolefins with a catalyst selected from aluminum trichloride, boron trifluoride or a combination thereof.

4. The method of claim 1, wherein the raffinate stream comprises 100 to 1000 ppmw sulfur (preferably 200 to 600 ppmw) and 100 to 1000 ppmw halogen (preferably 200 to 600 ppmw).

5. The method of claim 1, wherein the heterogeneous catalyst retains hydroprocessing activity in the presence of halogen.

6. The method of claim 1, wherein the heterogeneous catalyst is relatively more selective for hydrogenation of sulfur and halogen compounds and relatively less selective for mono-olefin conversion to saturated compounds.

7. The method of claim 1, wherein the heterogeneous catalyst comprises nickel, cobalt, molybdenum, tungsten or a combination thereof.

8. The method of claim 1, wherein the hydroprocessing and halide removal are effected in equipment resistant to hydrohalide corrosion.

9. The method of claim 1, wherein the removing comprises stripping the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream.

10. The method of claim 1, wherein the removing comprises washing the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream or from an off-gas stripped from the hydroprocessed stream. 1 1. The method of claim 1, further comprising neutralizing the hydrogen sulfide, hydrogen halide or a combination thereof in the hydroprocessed stream or in an off-gas stripped from the hydroprocessed stream.

12. The method of claim 1, wherein the recovered hydrocarbon product stream has a sulfur content less than 30 ppmw sulfur by weight of the hydrocarbon product stream.

13. The method of claim 1, wherein the recovered hydrocarbon product stream has a sulfur content less than 10 ppmw by weight of the hydrocarbon product stream.

14. A method to produce hydrocarbon resin and low sulfur raffinate, comprising:

polymerizing a hydrocarbon feed stream comprising olefins and diolefins in the presence of a halogen-containing catalyst to form a crude polymer stream; removing at least a portion of residual catalyst from the crude polymer stream to form a catalyst-lean stream;

fractionating at least a portion of the catalyst-lean stream to form a resin stream and a raffinate stream;

hydroprocessing at least a portion of the raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide;

removing at least a portion of the hydrogen sulfide and hydrogen halide from said portion of the hydroprocessed stream; and

recovering a hydrocarbon product stream of reduced sulfur and halogen contents.

15. The method of claim 14, wherein the halogen-containing catalyst comprises aluminum trichloride.

16. The method of claim 14, wherein the residual catalyst removal comprises washing with an aqueous solution of alkali, ammonia or sodium carbonate.

17. The method of claim 14, wherein the residual catalyst removal comprises adding an alcohol and filtration.

18. The method of claim 14, wherein the fractionation comprises steam stripping, vacuum distillation or a combination thereof.

19. The method of claim 14, further comprising hydrogenating the resin stream to produce a hydrogenated resin stream.

20. The method of claim 14, wherein the raffinate stream comprises 100 to 1000 ppmw sulfur (preferably 200 to 600 ppmw) and 100 to 1000 ppmw halide (preferably 200 to 600 ppmw). 21. The method of claim 14, wherein the heterogeneous catalyst comprises nickel, cobalt, molybdenum, tungsten or a combination thereof.

22. The method of claim 14, wherein the removing at least a portion of the hydrogen sulfide and hydrogen halide comprises stripping the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream.

23. The method of claim 14, wherein the recovered hydrocarbon product stream has a sulfur content less than 30 ppmw sulfur (preferably less than 20 ppmw) by weight of the hydrocarbon product stream.

24. The method of claim 14, wherein the recovered hydrocarbon product stream has a halogen content less than 10 ppmw halogen (preferably less than 5 or less than 1 ppmw) by weight of the hydrocarbon product stream.

25. A method to reduce sulfur and halogen contents from a hydrocarbon raffinate stream containing organic sulfide and organohalide, the raffinate stream comprising diolefins, at least 30 ppmw sulfur and at least 30 ppmw halogen by weight of the raffinate stream, comprising:

hydroprocessing the raffinate stream in a diolefin saturator to form a diolefin-lean raffinate stream;

separating gum formers from at least a portion of the diolefin-lean raffinate stream; gas-phase hydroprocessing a portion of the diolefin-lean raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide;

separating an effluent from the gas-phase hydroprocessed raffinate stream to recover vapor and liquid streams;

recirculating a first portion of the recovered vapor stream to the gas-phase hydroprocessing;

purging a second portion of the recovered vapor stream as a first off-gas stream; recirculating a first portion of the recovered liquid stream to the diolefin saturator; passing a second portion of the recovered liquid stream to a stripper to separate a second off-gas stream and recover a hydrocarbon product stream of reduced sulfur and halogen contents; and

treating the first and second off-gas streams to remove acid gases therefrom.

Description:
HYDROCARBON RAFFINATE STREAM PROCESSING CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 61/886,203, filed October 3, 2013 and European Application No. 13196245.8 filed December 9, 2013, the disclosures of which are fully incorporated herein by reference.

FIELD OF INVENTION

[0002] This invention is in the field of hydrocarbon raffinate stream processing.

BACKGROUND

[0003] Feedstocks for making hydrocarbon resins may comprise C5 to C9 steam cracker products including diolefins, olefins, paraffins and aromatic compounds, which are catalyzed with metal or boron halide catalysts such as aluminum trichloride and/or boron trifluoride. The highly reactive monomers are mostly incorporated into the resin product, and the less reactive monomers which are not incorporated into the resin product are separated by steam stripping and recovered in a raffinate stream. The steam cracker products typically contain sulfur compounds and thus sulfur compounds may also be present in the raffinate stream at high levels, e.g., more than 30 ppmw. The raffinate stream may also contain halogenated organics, e.g., organohalides, which may form by reaction with the catalyst or catalyst residues. The raffinate stream is sometimes similar in characteristics to light cat naphtha, except that it contains high sulfur and halogen contents.

[0004] The presence of sulfur and halogen compounds together in a hydrocarbon stream is undesirable and may severely limit the potential uses of the raffinate stream. For example, treatment of such raffinate streams has not been practical owing to the presence of halogen, which may form corrosive hydrogen halide acids and foulant salts in the process equipment. The art is desirous of a way to treat raffinate streams to make them, or obtain such raffinate streams that are, suitable for a wider number of applications requiring low sulfur and/or halogen content.

SUMMARY

[0005] According to some embodiments of the invention, a hydrocarbon raffinate stream is processed to reduce sulfur and halogen contents.

[0006] According to some embodiments of the invention, the raffinate stream is hydroprocessed in the presence of a catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide. The hydrogen sulfide and hydrogen halide are removed from the hydroprocessed stream, and a hydrocarbon product stream of reduced sulfur and halogen contents is recovered.

[0007] According to some embodiments of the invention, a method to produce hydrocarbon resin and low sulfur raffinates comprises polymerizing a hydrocarbon feed stream comprising olefins and diolefins in the presence of a halogen-containing catalyst to form a crude polymer stream, removing residual catalyst from the crude polymer stream to form a catalyst-lean stream, fractionating the catalyst-lean stream to form a resin stream and a raffinate stream, hydroprocessing the raffinate stream in the presence of a catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide, removing the hydrogen sulfide and hydrogen halide from the hydroprocessed stream, and recovering a hydrocarbon product stream of reduced sulfur and halogen contents.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 shows a process flow diagram for hydroprocessing a raffinate stream according to an embodiment of the invention.

[0009] FIG. 2 shows a process flow diagram to produce hydrocarbon resin and low sulfur raffinate according to an embodiment of the invention.

[0010] FIG. 3 shows a process flow diagram to produce low sulfur raffinate from a raffinate stream according to an embodiment of the invention.

DETAILED DESCRIPTION

[0011] According to some embodiments of the invention herein, a method to reduce sulfur and halogen contents from a hydrocarbon raffinate stream containing organic sulfide and organohalide, comprises hydroprocessing the raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide, removing hydrogen sulfide and hydrogen halide from the hydroprocessed stream and recovering a hydrocarbon product stream of reduced sulfur and halogen contents.

[0012] With reference to Fig. 1, the raffinate stream 10 is hydroprocessed in hydrogenation unit 12. Hydroprocessed stream 14 is treated in removal unit 16 to remove sulfur and/or halogen compounds in stream 18. A product stream 20 is obtained which in embodiments according to the invention may be similar in properties to low sulfur naphtha.

[0013] According to embodiments of the invention, the raffinate stream 10 comprises at least 30 ppmw sulfur or at least 100 ppmw sulfur, for example, 100 to 1000 ppmw sulfur or 200 to 600 ppmw sulfur, and/or at least 30 ppmw halogen or at least 100 ppmw halogen, for example, 100 to 1000 ppmw halogen or 200 to 600 ppmw halogen, all by weight of the raffinate stream. According to embodiments of the invention, the recovered hydrocarbon product stream 20 has a sulfur content less than 30 ppmw sulfur, for example, less than 10 ppmw sulfur, and a halogen content less than 20 ppmw halogen by weight, for example, less than 5 ppmw halogen or less than 1 ppmw halogen, all by weight of the hydrocarbon product stream.

[0014] According to embodiments of the invention, the heterogeneous catalyst may retain hydroprocessing activity in the presence of the halogens which may be present in the raffinate stream 10, such as fluorine, chlorine, bromine, iodine or a combination thereof. According to embodiments of the invention, the heterogeneous catalyst may be relatively more selective for hydrogenation of sulfur and halogen compounds and relatively less selective for mono- olefin conversion to saturated compounds. As used herein, a catalyst is more selective for hydrogenation of sulfur and halogen compounds and relatively less selective for mono-olefin conversion to saturated compounds if the hydroprocessed stream 14 contains at least 5 percent of the olefins supplied in raffinate stream 10 by weight of the olefins in raffinate stream 10. According to embodiments of the invention, the heterogeneous catalyst may comprise nickel, cobalt, molybdenum, tungsten or the like, or a combination thereof.

[0015] According to embodiments of the invention, the hydroprocessing is effected in equipment in hydrogenation unit 12 that is resistant to hydrohalide corrosion.

[0016] According to embodiments of the invention, the hydrogen sulfide and hydrogen halide removal from the hydroprocessed stream 14 comprises stripping the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream; washing the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream, e.g., caustic scrubbing; neutralizing the hydrogen sulfide, hydrogen halide or a combination thereof in the hydroprocessed stream; or the like, including combinations thereof. In embodiments according to the invention, the hydrogen halide removal from the hydroprocessed stream 14 is effected in equipment in removal unit 16 resistant to hydrohalide corrosion.

[0017] According to embodiments of the invention, the raffinate processing described herein may be a part of a process to produce hydrocarbon resins. According to embodiments of the invention, a method comprises polymerizing a hydrocarbon feed stream in the presence of a halogen-containing catalyst to form a crude polymer stream, removing residual catalyst from the crude polymer stream to form a catalyst-lean stream, and fractionating the catalyst- lean stream to form a resin stream and the raffinate stream. [0018] With reference to Fig. 2, wherein like items from Fig. 1 are referred to with like reference numerals, a hydrocarbon feed stream 30 is polymerized in the presence of catalyst 32 in polymerization unit 34.

[0019] The hydrocarbon feed stream 30 may comprise one or a mixture of various streams containing polymerizable olefins and diolefins, for example, petroleum distillates, cracked petroleum distillates, refinery streams, steam cracking effluents, coal tar, turpentine fractions and a variety of pure monomers and the like, containing C5 and/or Ce olefin and/or diolefins, and/or Cs/Cg aromatic olefins, e.g., styrene, vinyl benzene, indene and the like. Suitable feed materials for forming hydrocarbon resins may include both aromatic and non- aromatic components. Differences in the hydrocarbon resins obtained are largely due to the olefins in the feedstock from which the hydrocarbon resin components are derived. Polymerization feedstreams are derived from hydrocarbon refining and cracking streams via various known means and methods of fractionation. For a description of feedstream derivation, monomer composition, methods of polymerization and hydrogenation, reference may be made to Hydrocarbon Resins, Kirk-Othmer Encyclopedia of Chemical Technology, v. 13, pp. 717-743 (J. Wiley & Sons, 1995); Encycl. of Poly. Sci. and Eng., vol. 7, pp. 758- 782 (J. Wiley & Sons, 1987).

[0020] The feed stream 30 may contain hydrocarbons giving rise to "aliphatic" derivatives in the polymer which have a hydrocarbon chain formed from C4-C6 fractions containing variable quantities of piperylene, isoprene, amylenes, mono-olefins, and cyclic components. Such hydrocarbon resins are based on pentene, butene, isoprene, piperylene, cyclopentadiene, dicyclopentadiene, etc. Piperylenes are generally a distillate cut or synthetic mixture of C5 diolefins, which include, but are not limited to, cis- l ,3-pentadiene, trans- 1 ,3- pentadiene, and mixed 1,3-pentadiene. Cyclics are generally a distillate cut or synthetic mixture of C5 and Ce cyclic olefins, diolefins, and dimers therefrom. Cyclics include, but are not limited to, cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1 ,3- cycylohexadiene, and 1,4-cyclohexadiene. The dicyclopentadiene may be in either the endo or exo form. The cyclics may or may not be substituted. Substituted cyclics include cyclopentadienes and dicyclopentadienes substituted with a Ci to C4 0 linear, branched, or cyclic alkyl group, for example, one or more methyl groups.

[0021] The hydrocarbon feed stream 30 may also contain "aromatic" hydrocarbon structures, such as benzene, styrene, xylene, toluene, ethyl benzene, a-methylstyrene, β- methylstyrene, vinyl toluene, indene, methylindene, their derivatives and the like. Also present in the feed stream 30 are non-polymerizable paraffinic and/or aromatic compounds. These non-polymerizable compounds, which may be used as a solvent, and any or all of the monomers which are unreacted in the polymerization unit 34, as well as any added solvent, may be present in the hydrogenated raffinate stream 14.

[0022] Polymerization in unit 34 may be in one or more reactor vessels with a Friedel- Crafts or Lewis acid catalyst. AICI 3 is generally used according to some embodiments, in an amount from 0.25 to 3.0 wt%, e.g., 0.5 to 1.5 wt%, based on the weight of the mixture to be polymerized. The optimum concentration depends on the nature of the solvent, which may determine the solubility of the catalyst, as well as on the stirring efficiency and other reactor design and operation parameters. Other catalysts which may be used according to embodiments of the invention include titanium, tri- or tetra-chloride, tin tertrachloride, boron trifluoride, complexes of boron trifluoride with organic ethers, phenols or acids, or acidic clays, or the like, or combinations thereof.

[0023] According to embodiments of the invention, the polymerization in unit 34 may be conducted at a temperature between -20°C and 200°C, for example, between -20°C and 100°C or between 30°C and 80°C. According to embodiments of the invention, the polymerization in unit 34 may be batchwise or continuous mode. Continuous polymerization may be accomplished in a single stage or in multiple stages. According to embodiments of the invention, thermal catalytic polymerization may also be utilized.

[0024] The term hydrocarbon resin as used in the specification and claims include the known high molecular weight polymers, low molecular weight polymers and oligomers derived from cracked petroleum distillates, coal tar, turpentine fractions and a variety of pure monomers. According to embodiments of the invention, the number average molecular weight is usually below 10,000 or below 2000, although higher molecular weights are also possible, and physical forms at ambient conditions range from thin or thick viscous liquids to hard, brittle solids. Oligomers refer to dimers, trimers, tetramers, pentamers, hexamers, octamers and the like, including combinations thereof, of olefinic monomers, e.g., olefins and diolefins.

[0025] Hydrogenated raffinate products, which may be made with the process described herein, specifically include raffinates separated from hydrocarbon resins suitable as tackifiers for adhesive compositions, particularly adhesive compositions comprising polymeric base polymer systems of either natural or synthetic elastomers, including such synthetic elastomers as those from styrene block copolymers, olefinic rubbers, olefin derived elastomers or plastomers, and various copolymers having elastomeric characteristics, e.g., ethylene-vinyl ester copolymers. Such adhesive compositions find particular utility in hot melt adhesive and pressure sensitive adhesive applications such as those for adhesive tapes, diaper tabs, envelopes, note pads, and the like.

[0026] Following polymerization in unit 34, the resin-containing stream 36 from the reactor system is supplied to catalyst removal unit 38 to remove any residual catalyst, for example, by contact with a wash fluid or precipitant added via stream 40. Wash fluids according to embodiments of the invention may include alkali, ammonia or sodium carbonate, for example precipitants may include alcohols such as methanol or other compounds that form an insoluble reaction product with the catalyst residue which can be removed by filtration in the catalyst removal unit 38. In addition to washing and/or filtration, catalyst removal may include any other operation by which the catalyst residue is removed from the resin-containing stream. Catalyst residue 42 is separated in the wash fluid, which may be regenerated for reuse or recycle, or as the filtrate.

[0027] According to embodiments of the invention, the resulting resin-containing, catalyst-lean stream 44 may be supplied to fractionation unit 46 where steam stripping or vacuum distillation may be used to separate the raffinate stream 10 from the resin stream 48. According to some embodiments of the invention, the resin stream 48 may optionally be hydrogenated in hydrogenation unit 50 to obtain a finished resin product 52.

[0028] Raffinate hydrogenation unit 12 may, in some embodiments of the invention include a reactor system used to hydrogenate the raffinate stream 10 and thereby convert the sulfur and halogen compounds therein to more volatile or reactive forms which may be removed in removal unit 16 by one or more of various treatments such as stripping, washing, and the like, to obtain the low-sulfur raffinate 20.

[0029] The hydrogenation reactor system in unit 12, in some embodiments herein may comprise one or more reactor vessels housing a catalyst bed, for example a moving, fluidized or, preferably, a fixed bed. In embodiments, any raffinate feedstream comprising hydrocarbons and sulfur and halogen compounds together may be hydrogenated to at least partially reduce the sulfur and/or halogen contents. As used herein, an "unsaturated hydrocarbon" is one containing carbon-carbon double bonds, and includes mono- and di- olefinic compounds. In an embodiment, the fixed catalyst bed comprises porous catalyst particles comprising a supported metal catalyst structure comprising an internal pore volume with interstitial surfaces. [0030] In an embodiment, a method to hydroprocess the raffinate, comprises passing the liquid hydrocarbon raffinate stream 10 through a catalyst bed under hydrogenation conditions. The catalyst referred to herein is generally useful in a process for hydrogenating or hydrotreating (used interchangeably herein) a raffinate stream containing sulfur and/or halogen compounds in the presence of the catalyst. Any of the various catalysts and/or processes for catalytically hydrogenating hydrocarbon streams can be modified in accordance with the present disclosure by substituting the catalyst system and/or processing steps, in particular the processes and metal catalysts of US 6,755,963, US 5, 171,793, US 4,629,766, US 4,328,090, EP 0 240 253, EP 0 082 726, WO 95/12623 and WO 99/03578 are suitable, each of which is referred to and incorporated herein by reference in their entireties for all purposes. "Metal" in the context of the catalyst does not necessarily mean the metal in its metallic form but present in any metal compound, such as the metal component as initially applied or as present in a bulk or supported catalyst composition, e.g., metal oxides and/or especially in the active state as metal sulfide.

[0031] Catalysts employed for the hydrogenation of sulfur/halogen containing hydrocarbons may be supported monometallic, bimetallic or multimetallic catalyst systems based on elements from Group 6, 8, 9, 10, or 11 of the Periodic Table of Elements. Bulk multimetallic catalysts in an embodiment are comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10: 1 to about 1 : 10, e.g., a nickel molybdotungstate catalyst, as described in US 6,755,963. In one embodiment, the catalyst is supported, e.g., on an inert material such as metal oxide such as alumina (e.g., gamma-alumina), silica or the like, which may function as a binder to hold the metal catalyst compounds at the interstitial surfaces of the pores. In another embodiment the catalyst is unsupported, i.e. a bulk catalyst prepared without a binder.

[0032] The Group VIB metal in one embodiment comprises chromium, molybdenum, tungsten, or mixtures thereof. Group VIII non-noble metals in one embodiment are, e.g., iron, cobalt, nickel, or mixtures thereof. In an embodiment, the catalyst comprises a combination of metal components comprising nickel, molybdenum and tungsten or nickel, cobalt, molybdenum and tungsten. In an embodiment, nickel components used to prepare the catalyst may comprise water-insoluble nickel components such as nickel carbonate, nickel hydroxide, nickel phosphate, nickel phosphite, nickel formate, nickel sulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloys such as nickel-molybdenum alloys, Raney nickel, or mixtures thereof.

[0033] In an embodiment, molybdenum components used to prepare the catalyst may comprise water-insoluble molybdenum components such as molybdenum (di- and tri) oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid (e.g. H2M0O4), molybdenum sulfide, or mixtures thereof; or water-soluble nickel components, e.g. nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, or mixtures thereof.

[0034] In an embodiment, tungsten components used to prepare the catalyst may comprise tungsten di- and trioxide, tungsten sulfide (WS 2 and WS 3 ), tungsten carbide, tungstic acid (e.g. H2WO4-H 2 O, H2W4O1 3 -9H 2 O), tungsten nitride, aluminum tungstate (also meta-, or polytungstate) or mixtures thereof.

[0035] In an embodiment, the catalyst may be made from and/or contain water-soluble molybdenum and tungsten components such as alkali metal or ammonium molybdate (also peroxo-, di-, tri-, terra-, hepta-, octa-, or tetradecamolybdate), Mo-P heteropolyanion compounds, Wo-Si heteropolyanion compounds, W-P heteropolyanion compounds, W-Si heteropolyanion compounds, Ni-Mo-W heteropolyanion compounds, Co-Mo-W heteropolyanion compounds, alkali metal or ammonium tungstates (also meta-, para-, hexa-, or polytungstate), or mixtures thereof. In an embodiment, combinations of metal components comprising the catalyst are nickel carbonate, tungstic acid and molybdenum oxide; or nickel carbonate, ammonium dimolybdate and ammonium metatungstate.

[0036] According to embodiments of the invention, the hydrogenation catalyst is generally comprised of porous metal and/or support components having a suitable pore volume and pore size, such as, for example, a pore volume of 0.05-5 ml/g, or of 0.1-4 ml/g, or of 0.1-3 ml/g or of 0.1-2 ml/g determined by nitrogen adsorption. Pores with a diameter smaller than 1 nm may be but are generally not present. Further, the catalysts may generally have a surface area of at least 10 m 2 /g, or at least 50 m 2 /g or at least 100 m 2 /g, determined via the Brunaur-Emmett-Teller (B.E.T.) method. For instance, nickel carbonate has a total pore volume of 0.19-0.39 ml/g or of 0.24-0.35 ml/g determined by nitrogen adsorption and a surface area of 150-400 m 2 /g or of 200-370 m 2 /g determined by the B.E.T. method. Furthermore, the catalyst particles may have a median particle diameter of at least 50 nm, or at least 100 nm, or not more than 5 mm or not more than 3 mm. According to embodiments of the invention, the catalyst particles are generally cylindrical, trilobite, quadrilobate or the like and prepared by cutting an extrudate of the desired profile, e.g., from 1 to 6 mm in diameter and from 2 to 12 mm in length, such as 4 mm long and 2 mm in diameter. According to embodiments of the invention, the median particle diameter may be in the range of 0.1-50 microns or in the range of 0.5-50 microns.

[0037] According to embodiments of the invention, a bulk catalyst composition may be prepared by reacting in a reaction mixture a Group VIII non-noble metal component in solution and a Group VIB metal component in solution or wherein one or both of the metal components are partly in the solid state. The bulk catalyst composition can generally be directly shaped into hydroprocessing particles. If the amount of liquid of the bulk catalyst composition is so high that it cannot be directly subjected to a shaping step, a solid liquid separation can be performed before shaping. Optionally the bulk catalyst composition, either as such or after solid liquid separation, can be calcined before shaping. The median diameter of the bulk catalyst particles is at least 50 nm, more preferably at least 100 nm, and preferably not more than 5 mm and more preferably not more than 3 mm. Even more preferably, the median particle diameter may be in the range of 0.1-50 μιη and most preferably in the range of 0.5-50 μιη.

[0038] If a binder material is used in the preparation of the supported catalyst composition it can be any suitable binder material. Examples include silica, silica-alumina, such as conventional silica-alumina, silica-coated alumina and alumina-coated silica, alumina such as (pseudo)boehmite, or gibbsite, titania, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titanic, zirconia, or mixtures thereof. These binders may be applied as such or after peptization. According to embodiments of the invention, it is also possible to apply precursors of these binders that, before or during the process of the invention are converted into any of the above-described binders. Suitable precursors are, e g., alkali metal aluminates (to obtain an alumina binder), water glass (to obtain a silica binder), a mixture of alkali metal aluminates and water glass (to obtain a silica alumina binder), a mixture of sources of a di-, tri-, and/or tetravalent metal such as a mixture of water-soluble salts of magnesium, aluminum and/or silicon (to prepare a cationic clay and/or anionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.

[0039] In an embodiment, the binder material may be composited with a Group VIB metal and/or a Group VIII non-noble metal, alternatively or additionally to being composited with the bulk catalyst composition and/or prior to being added during the preparation thereof. Compositing the binder material with any of these metals may be carried out by impregnation of the solid binder with these materials. The person skilled in the art knows suitable impregnation techniques. If the binder is peptized, it is also possible to carry out the peptization in the presence of Group VIB and/or Group VIII non-noble metal components. If alumina is applied as binder, the surface area preferably may be in the range of 100-400 m 2 /g, or 150-350 m 2 /g, measured by the B.E.T. method. The pore volume of the alumina in one embodiment is in the range of 0.5-1.5 ml/g measured by nitrogen adsorption.

[0040] In one embodiment, the binder material may have less catalytic activity than the bulk catalyst composition or no catalytic activity at all. Consequently, by adding a binder material, the activity of the bulk catalyst composition may be reduced. Therefore, the amount of binder material present may depend on the desired activity of the final catalyst composition. Binder amounts from 0-95 wt% of the total composition can be present, or in the range of 0.5-75 wt% of the total catalyst composition.

[0041] The catalyst and any binder can be formed into cylindrical pellets in one embodiment. The pellets may have any suitable length and diameter, e.g., in one embodiment a diameter from 2 to 12 mm and a length of from 2 to 12 mm.

[0042] In one embodiment, a basic promoter may be used in the catalyst with the metal compounds, particularly if improved halogen resistance is sought. Promoters include metals from Groups 1-3, including the lanthanide and actinide series, of the periodic table of elements. The promoters in one embodiment are lanthanum, potassium or a combination thereof. The basic promoters may be used in amounts of 0.25% to 10% by weight of the total catalyst, preferably 1% to 3% by weight.

[0043] According to embodiments of the invention, a metal catalyst useful for hydrogenating the raffinate may be sulfided ex situ, passivated and optionally stored for later use. If desired, the metal raffinate hydrogenation catalyst may comprise a pore volume at least partially filled with an organic compound which may passivate the presulfided catalyst and inhibit fines formation from handling the catalyst prior to and/or during loading, and/or the catalyst may be contacted with an organic liquid to partially fill a pore volume, and the partially filled catalyst is thereafter loaded into a hydrogenation reactor, wherein the catalyst may be sulfided before, during or after contact with the organic liquid and passivated prior to the catalyst loading into the reactor, or alternatively or additionally the catalyst may be sulfided in situ after the catalyst is loaded into the reactor. The presulfided catalyst may be loaded into the hydrogenation reactor and is immediately ready for use without any further sulfidation operation in situ. [0044] In one embodiment the catalyst is presulfided ex situ. Catalyst in the metallic or oxide form can be made as described above, or purchased commercially from a catalyst supplier. The catalyst is sulfided ex situ in a suitable reactor(s) other than the hydrogenation reactor(s) to convert the oxide and/or metallic forms of the catalyst metal compounds to their active sulfide forms. The sulfiding reactor(s) can be located nearby the hydrogenation reactor(s), or it can be remote. At the sulfiding facility, a sulfiding process is used to convert the catalyst to its active sulfide form. In the case of nickel and tungsten oxides according to some embodiments of the invention, the sulfiding process converts nickel and tungsten oxides to their active sulfide forms using a sulfiding agent in the presence of hydrogen according to the following exemplary reactions:

3 NiO + 2 H 2 S + H 2 → Ni 3 S 2 + 3 H 2 0 (1)

W0 3 + 2 H 2 S + H 2 → WS 2 + 3 H 2 0 (2)

[0045] The sulfur compounds that can be used as the sulfiding agent include H 2 S, carbon disulfide, methyl disulfide, ethyl disulfide, propyl disulfide, isopropyl disulfide, butyl disulfide, tertiary butyl disulfide, thianaphthene, thiophene, secondary dibutyl disulfide, thiols, sulfur containing hydrocarbon oils and sulfides such as methyl sulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, butyl sulfide, secondary dibutyl sulfide, tertiary butyl sulfide, dithiols and sulfur-bearing gas oils. Any other organic sulfur source that can be converted to H 2 S over the catalyst in the presence of hydrogen can be used. The catalyst may also be activated by an organo sulfur process as described in US 4,530,917 and other processes described therein and this description is incorporated by reference into this specification.

[0046] The active catalyst sulfide is sensitive to oxygen (from air), which can re-oxidize the catalyst and render it inactive. Therefore, the sulfided catalyst may be protected from contact with air or passivated. As used herein, passivated catalyst has been protected sufficiently against air oxidation to make reactor loading under air possible. Whether passivated or especially if it is not otherwise passivated, prior to loading, the catalyst is to the extent feasible handled under an inert atmosphere such as nitrogen and kept in sealed, inert gas-purged bins or drums during storage and shipment. As used herein, an inert gas is one which does not react to an appreciable extent with the sulfided catalyst, e.g., nitrogen.

[0047] In an embodiment, the porous catalyst is impregnated with an organic compound which is a liquid at the impregnation conditions and which at least partially fills the void space inside in the catalyst particles. This fill liquid provides a diffusion barrier to prevent oxygen from air from penetrating the catalyst and deactivating it. The liquid fill passivation technique may be used alone, in combination with an inert shipping/storage atmosphere, and/or in combination with another passivation technique that may involve treatment of the catalyst before or after liquid impregnation, e.g., as disclosed in US 7,407,909, which is hereby incorporated herein by reference in its entirety.

[0048] In one embodiment, the liquid used to protect the catalyst from premature oxidation is a hydrocarbon resin (including oligomers) or a normally liquid olefinic monomer or a normally liquid raffinate. Normally liquid monomers refer to polymerizable monomers, e.g., olefins and diolefins, having a vapor pressure of less than 1 atmosphere at 25°C. In another embodiment the hydrocarbon resin may be the same resin or the same type of resin from which the raffinate is obtained. The hydrocarbon resin used to passivate the catalyst, where the organic liquid is a hydrocarbon resin, is referred to herein as the fill resin. The fill resin may be a hydrogenated resin with a low unsaturation content, e.g., less than 1 mole percent olefinic hydrogens based on the total hydrogen content of the fill resin. For example, the fill resin may be obtained under the trade designation ESCOREZ™, e.g., 1102, 1102F, 1102RM, 1304, 1310LC, 1315, 1401, 2203LC, 2394, 2520, 5300, 5320, 5340, 5380, 5400, 5415, 5490, 5600, 5615, 5620, 5637 and 5690. For purposes of convenience and clarity, the fill material is referred to herein as the fill hydrocarbon resin as an example, but the fill liquid is not necessarily limited thereto.

[0049] In another embodiment, the hydrocarbon used for passivation may be the same raffinate or the same type of raffinate to be hydrogenated with the catalyst in the hydrotreating reactor(s). The fill material may be a hydrogenated raffinate with a low unsaturation content, e.g., less than 1 mole percent olefinic hydrogens based on the total hydrogen content of the fill material.

[0050] The fill hydrocarbon resin and/or the raffinate may have a viscosity that facilitates introduction onto and impregnating the sulfide catalyst. In an embodiment, fill hydrocarbon resins have melt viscosity of from 300 to 800 centipoise (cPs) at 160°C, or from 350 to 650 cPs at 160°C. In an embodiment, the hydrocarbon resin melt viscosity is from 375 to 615 cPs at 160°C, or from 475 to 600 cPs at 160°C. The melt viscosity may be measured by a Brookfield viscometer with a type "J" spindle, ASTM D6267.

[0051] According to embodiments of the invention, the fill hydrocarbon resins may have a weight average molecular weight (Mw) greater than about 300 g/mole, or greater than 600 g/mole or greater than about 1000 g/mole. In at least one embodiment, hydrocarbon resins have a weight average molecular weight (Mw) of from 300 to 10,000 g/mole, or from 300 to 3000 g/mole, or from 300 to 2000 g/mole. The hydrocarbon resin in one embodiment may have a number average molecular weight (Mn) of from 450 to 700 g/mole. The hydrocarbon resin may have a z-average molecular weight (Mz) of from 5000 to 10,000 g/mole, or from 6000 to 8000 g/mole. Mw, Mn, and Mz may be determined by gel permeation chromatography (GPC).

[0052] According to embodiments of the invention, the fill hydrocarbon resin may have a polydispersion index ("PDI", PDI=Mw/Mn) of 4 or less. In an embodiment, the hydrocarbon resin has a PDI of from 2.6 to 3.1.

[0053] According to embodiments of the invention, the fill hydrocarbon resins may have a glass transition temperature (Tg) of from about -30°C to about 100°C, or from about 0°C to 80°C, or from about 40-60°C. Differential scanning calorimetry (DSC) may be used to determine the Tg of the hydrocarbon resin.

[0054] According to embodiments of the invention, natural resins can also be used as the fill resin. The natural resins are traditional materials documented in the literature, see for example, Encycl. of Poly. Sci. and Eng., vol. 14, pp. 438-452 (John Wiley & Sons, 1988).

[0055] The rosins capable of impregnating the catalyst and/or hydrotreating with the filled catalyst in accordance herewith include any of those known in the art to be suitable as tackifying agents, specifically including the esterified rosins. The principal sources of the rosins include gum rosins, wood rosin, and tall oil rosins which typically have been extracted or collected from their known sources and fractionated to varying degrees. Additional background can be obtained from technical literature, e.g., Kirk-Othmer Encycl. of Chem. Tech., vol. 17, pp. 475-478 (John Wiley & son, 1968) and Handbook of Pressure-Sensitive Adhesive Technology, ed. by D. Satas, pp. 353-356 (Van Nostrand Reinhold Co., 1982).

[0056] The catalyst particles may be filled by contacting the catalyst particles with the fill resin or other liquid under conditions wherein the fill material is liquid. Fill resins or other fill material which have a low softening point or melting point and a low melt viscosity may be used at ambient or elevated temperatures, e.g., up to 140°C, or up to 120°C, or up to 100°C, or up to 80°C, or up to 60°C, or up to 40°C. According to embodiments of the invention, the temperature should be sufficiently low so as to avoid excessive catalytic activity or denaturing of the catalyst. The contact may be in a tumbler, conveyor or other suitable apparatus in one embodiment by spraying the liquid onto the catalyst particles at a sufficient rate until the liquid is sufficiently absorbed into the pores of the catalyst particles. According to embodiments of the invention, the tumbler apparatus may be sufficiently gentle so as to avoid the formation of catalyst fines. In one embodiment the pore volume of the catalyst is only partially filled so as to maintain a dry character of the catalyst, which allows free catalyst flow and avoids agglomeration. In an embodiment the fill resin fills from 50 to 100% of the pore volume of the catalyst particles, or from 60 to 99%, or from 70 to 98%, or from 80 to 95%, or from 90 to 95% of the pore volume of the catalyst particles. The filling process may be operated batchwise, semi-batch or continuously.

[0057] The partially filled catalyst particles may be optionally screened to remove fines. However, in one embodiment the partially filled catalyst particles have improved (reduced) attrition and fines formation, and screening to remove fines may not be needed. In embodiments, the catalyst particles, which may optionally be presulfided and/or partially filled catalyst particles, are loaded, e.g., from the storage and/or shipping containers, into hydrogenation reactor(s) using conventional catalyst loading equipment and techniques.

[0058] In an embodiment, the catalyst bed in hydrogenation unit 12 may be used to hydrogenate the raffinate stream 10 comprising sulfo and/or halo compounds. The raffinate stream 10 is obtained from the reactor effluent 36 from the polymerization of any of the hydrocarbon resins discussed above that are used to impregnate the presulfided catalyst. In one embodiment, the fill hydrocarbon resin, when employed, and the hydrocarbon resin from which the raffinate 10 is separated for hydrogenation, are the same, and in another embodiment they are different.

[0059] According to embodiments of the invention, raffinate hydrogenation unit 12 treating conditions include a temperature of about 100°C - 350°C and a pressure of between 5 atm (506 kPa) and 300 atm (30.4 MPa) hydrogen, for example, 10 to 275 atm (1.01 MPa to 27.6 MPa). In one embodiment the temperature is in the range including 160°C and 320°C and the pressure is in the range including 15.2 MPa and 20.3 MPa hydrogen. According to embodiments of the invention, the hydrogen to feed volume ratio to the reactor under standard conditions (25°C, 1 atm pressure) may be in the range from 20-200, for example, 100-200.

[0060] According to embodiments of the invention, hydrogen may be recirculated in a recompression loop through the hydrogenation reactor(s) in the raffinate hydrogenation unit 12, with appropriate hydrogen separation from the reactor effluent and with makeup hydrogen resupplied to the loop as needed. Similarly, if present, hydrogen may be recirculated in a recompression loop through the hydrogenation reactor(s) in the resin hydrogenation unit 50, with appropriate hydrogen separation from the reactor effluent and with makeup hydrogen also resupplied to the resin hydrogenation loop as needed. According to embodiments of the invention, a common serial recompression loop may be employed to recirculate hydrogen through the respective hydrogenation reactors in units 12, 50, serially first to the higher pressure reactor(s), then to the lower pressure reactor(s) and back to the compression unit; or parallel compression loops through the respective hydrogenation reactors in units 12, 50 may employ a common compressor. In a similar manner, according to some embodiments, the units 12, 50 may if desired, also share integrated or partially integrated sulfiding equipment, sulfur/halogen removal equipment, wash effluent regeneration equipment, filtrate recovery or treatment equipment, and so on.

[0061] Accordingly, the invention provides the following embodiments:

El. A method to reduce sulfur and halogen contents from a hydrocarbon raffinate stream containing organic sulfide and organohalide, comprising: hydroprocessing the raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide; removing hydrogen sulfide and hydrogen halide from the hydroprocessed stream; and recovering a hydrocarbon product stream of reduced sulfur and halogen contents.

E2. The method of Embodiment El wherein the raffinate stream comprises at least 100 ppmw sulfur.

E3. The method of Embodiment El or Embodiment E2 wherein the raffinate stream comprises at least 100 ppmw halogen by weight of the raffinate stream.

E4. The method of any one of Embodiments El to E3 wherein the raffinate stream comprises 100 to 1000 ppmw sulfur.

E5. The method of any one of Embodiments El to E4 wherein the raffinate stream comprises 200 to 600 ppmw sulfur.

E6. The method of any one of Embodiments El to E5 wherein the raffinate stream comprises 100 to 1000 ppmw halogen.

E7. The method of any one of Embodiments El to E6 wherein the raffinate stream comprises 200 to 600 ppmw halogen.

E8. The method of any one of Embodiments El to E7 comprising polymerizing a diolefin-containing feed stream with a halide catalyst to form a resin-containing stream and steam-stripping the resin-containing stream to recover the raffinate stream for the hydroprocessing. E9. The method of any one of Embodiments El to E8 wherein the raffinate stream comprises unreacted monomer or light oligomer components from polymerization of diolefins with a catalyst selected from aluminum trichloride, boron trifluoride or a combination thereof.

E10. The method of any one of Embodiments El to E9 comprising polymerizing a hydrocarbon feed stream comprising olefins and diolefins in the presence of a halogen- containing catalyst to form a crude polymer stream, removing residual catalyst from the crude polymer stream to form a catalyst-lean stream, and fractionating the catalyst-lean stream to form a resin stream and the raffinate stream.

El l . The method of Embodiment E10, wherein the halogen-containing catalyst comprises aluminum trichloride.

E12. The method of Embodiment E10 or Embodiment El l, wherein the residual catalyst removal comprises washing with an aqueous solution of alkali, ammonia or sodium carbonate.

E13. The method of any one of Embodiments E10 to E12, wherein the residual catalyst removal comprises adding an alcohol.

E14. The method of any one of Embodiments E10 to E13, wherein the residual catalyst removal comprises filtration.

E15. The method of any one of Embodiments E10 to El 4, wherein the fractionation comprises steam stripping, vacuum distillation or a combination thereof.

E16. The method of any one of Embodiments E10 to E15, further comprising hydrogenating the resin stream to produce a hydrogenated resin stream.

El 7. The method of any one of Embodiments El to El 6 wherein the first heterogeneous catalyst retains hydroprocessing activity in the presence of chlorine.

El 8. The method of any one of Embodiments El to El 7 wherein the first heterogeneous catalyst is relatively more selective for hydrogenation of sulfur and halogen compounds and relatively less selective for mono-olefin conversion to saturated compounds.

El 9. The method of any one of Embodiments El to El 8 wherein the first heterogeneous catalyst comprises nickel, cobalt, molybdenum, tungsten or a combination thereof.

E20. The method of any one of Embodiments El to El 9 wherein the hydroprocessing is effected in equipment resistant to hydrohalide corrosion. E21. The method of any one of Embodiments El to E20 wherein the hydrogen halide removal from the hydroprocessed stream is effected in equipment resistant to hydrohalide corrosion.

E22. The method of any one of Embodiments El to E21 wherein the hydrogen sulfide and hydrogen halide removal from the hydroprocessed stream comprises stripping the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream.

E23. The method of any one of Embodiments El to E22 wherein the hydrogen sulfide and hydrogen halide removal from the hydroprocessed stream comprises washing the hydrogen sulfide, hydrogen halide or a combination thereof from the hydroprocessed stream or from an off-gas stripped from the hydroprocessed stream.

E24. The method of any one of Embodiments El to E23 further comprising neutralizing the hydrogen sulfide, hydrogen halide or a combination thereof in the hydroprocessed stream or in an off-gas stripped from the hydroprocessed stream.

E25. The method of any one of Embodiments El to E24 wherein the recovered hydrocarbon product stream has a sulfur content less than 30 ppmw sulfur by weight of the hydrocarbon product stream.

E26. The method of any one of Embodiments El to E24 wherein the recovered hydrocarbon product stream has a sulfur content less than 10 ppmw sulfur by weight of the hydrocarbon product stream.

E27. The method of any one of Embodiments El to E26 wherein the recovered hydrocarbon product stream has a halogen content less than 20 ppmw halogen by weight of the hydrocarbon product stream.

E28. The method of any one of Embodiments El to E26 wherein the recovered hydrocarbon product stream has a halogen content less than 5 ppmw halogen by weight of the hydrocarbon product stream.

E29. The method of any one of Embodiments El to E26 wherein the recovered hydrocarbon product stream has a halogen content less than 1 ppmw halogen by weight of the hydrocarbon product stream.

E30. The method of any one of Embodiments El to E29 wherein the raffinate stream hydroprocessing comprises passing the raffinate stream through a diolefin saturation zone to remove diolefins and form a diolefin-lean raffinate stream. E31. The method of Embodiment E30 wherein the diolefin saturation zone comprises a liquid phase reactor(s) comprising a second heterogeneous catalyst, which may be the same as or different than the first heterogeneous catalyst.

E32. The method of Embodiment E31 wherein the second heterogeneous catalyst comprises nickel, cobalt, molybdenum, tungsten or a combination thereof.

E33. The method of any one of Embodiments E30 to E32 wherein the hydroprocessing comprises vaporizing the diolefin-lean raffinate stream and passing the vaporized diolefin- lean raffinate stream through a hydrodesulfurization zone in the presence of the first heterogeneous catalyst.

E34. The method of Embodiment E33, further comprising separating gum formers from the diolefin-lean raffinate stream.

E35. The method of Embodiment E33 or Embodiment E34, further comprising cooling an effluent from the hydrodesulfurization zone to partially condense the effluent.

E36. The method of Embodiment E35, further comprising separating the partially condensed effluent into vapor and liquid streams.

E37. The method of Embodiment E36, further comprising recirculating at least a portion of the separated vapor stream to the hydrodesulfurization zone.

E38. The method of Embodiment E37, further comprising supplying at least a portion of the separated liquid stream to a stripping unit to strip an off-gas from the separated liquid stream.

E39. The method of Embodiment E38, wherein the stripping unit is bottoms reboiled and condensate refluxed overhead.

E40. The method of Embodiment E38 or Embodiment E39, further comprising passing the off-gas to an off-gas treatment unit to remove acid gases therefrom.

E41. The method of Embodiment E40, wherein the off-gas treatment unit comprises a scrubber to contact the off-gas with a solvent.

E42. The method of Embodiment E41, wherein the solvent is aqueous,

further comprising passing a fraction of the separated vapor stream.

E43. The method of any one of Embodiments E40 to E42, further comprising passing a portion of the vapor stream separated from the partially condensed hydrodesulfurization zone effluent to the off-gas treatment unit. E44. The method of any one of Embodiments E36 to E43, further comprising recirculating a portion of the liquid stream separated from the partially condensed hydrodesulfurization zone effluent to the diolefin saturation zone.

E45. A method to produce hydrocarbon resin and low sulfur raffinate, comprising:

polymerizing a hydrocarbon feed stream comprising olefins and diolefins in the presence of a halogen-containing catalyst to form a crude polymer stream; removing residual catalyst from the crude polymer stream to form a catalyst-lean stream;

fractionating the catalyst-lean stream to form a resin stream, an optional resin fill stream, and a raffinate stream;

hydroprocessing the raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide; removing the hydrogen sulfide and hydrogen halide from the hydroprocessed stream; and

recovering a hydrocarbon product stream of reduced sulfur and halogen contents. E46. A method to reduce sulfur and halogen contents from a hydrocarbon raffinate stream containing organic sulfide and organohalide, the raffinate stream comprising diolefins, at least 30 or at least 100 ppmw sulfur and at least 30 or at least 100 ppmw halogen by weight of the raffinate stream, comprising:

hydroprocessing the raffinate stream in a diolefin saturator to form a diolefin-lean raffinate stream;

separating gum formers from the diolefin-lean raffinate stream;

gas-phase hydroprocessing the diolefin-lean raffinate stream in the presence of a heterogeneous catalyst at hydrogenation conditions to form hydrogen sulfide and hydrogen halide;

separating an effluent from the gas-phase hydroprocessing to recover vapor and liquid streams;

recirculating a first portion of the recovered vapor stream to the gas-phase hydroprocessing;

purging a second portion of the recovered vapor stream as a first off-gas stream; recirculating a first portion of the recovered liquid stream to the diolefin saturator; passing a second portion of the recovered liquid stream to a stripper to separate a second off-gas stream and recover a hydrocarbon product stream of reduced sulfur and halogen contents; and

treating the first and second off-gas streams to remove acid gases therefrom.

EXAMPLES

[0062] Example 1 - With reference to Fig. 3, one example of a hydroprocessing and sulfur/halogen removal process 100 according to the present invention is shown. In this example, the raffinate from tank 102 is supplied at a rate of, e.g., 5220 kg/h (1 1,500 lbs/h) via pump 104 into line 106, mixed with hydrogen from line 108 at 181 kg/h (400 lbs/h), the mixture preheated in exchanger 1 10, which may be a cross exchanger with another process stream or heated with a suitable heat transfer medium such as steam, for example, and fed with, e.g., 20,900 kg/h (46,000 lbs/h) raffinate from recycle line 112 into diolefin saturator 1 14. The raffinate from tank 102 in this example may contain up to 1000 ppmw sulfur and up to 1000 ppmw chlorine, e.g., 500 ppmw sulfur and/or 600 ppmw chlorine. The hydrogen may be 85 to 95% pure, for example 90%, with the balance as methane and other inerts, for example.

[0063] The diolefin saturator 1 14 may remove (hydroprocess, e.g., hydrogenate) diolefins to protect the hydrodesulfurization catalyst from fouling. Diolefin saturator 1 14 in this example preferably operates as a liquid phase reactor with a nickel-molybdenum catalyst at an average temperature of from about 120°C to about 177°C (about 250°F to about 350°F), for example, 150°C (302°F) or an inlet temperature of 135°C (275°F) and an outlet temperature of 153°C (308°F); a pressure of 2.07 - 2.41 MPa (300 - 350 psig); a space velocity of 2 - 8 h "1 , for example 4 h "1 (volumes feed/h-volume catalyst bed) and a hydrogen/raffinate ratio of 90 to 270 m 3 /m 3 (500 - 1500 SCF/42-gal. bbl), for example, 178 m 3 /m 3 (1000 SCF/bbl). The conditions in the diolefin saturator 114 are preferably selected so as to avoid excessive vapor formation and premature organosulfur reaction. The effluent from the diolefin saturator 1 14 may be treated to remove compounds which may foul downstream equipment, e.g., combined with recycle hydrogen from line 116 and fed via line 118 to heavies knock-out drum 120 to separate gum-forming compounds via line 122, and thus inhibit fouling in downstream equipment. The overhead 124 is heated in heater 126, which may be a fired heater, a cross exchanger or heated with a suitable heat transfer medium, and fed to hydrodesulfurization (HDS) reactor 128. [0064] HDS reactor 128 may convert sulfur compounds including organosulfur to hydrogen sulfide and halogen compounds including organohalides to hydrogen halide, e.g., hydrogen chloride. The HDS reactor 128 in this example operates as a gas phase reactor with a nickel-molybdenum catalyst, which may be the same or different with respect to the catalyst in diolefin saturator 1 14, at an average temperature of from about 230°C to about 315°C (about 450°F to about 600°F), for example, 260°C (500°F) or an inlet temperature of 250°C (482°F) and an outlet temperature of 290°C (555°F); a pressure of 1.72 - 2.41 MPa (250 up to 350 psig), for example 1.96 MPa (285 psig); a space velocity of 3 - 15 h "1 , for example 7 h "1 and a hydrogen/raffinate ratio of 90 to 215 m 3 /m 3 (500 - 1200 SCF/bbl), for example, 178 m 3 /m 3 (1000 SCF/bbl). The conditions in the HDS reactor 128 are preferably selected to maintain a vapor phase, e.g., 22°C (40°F) above the dew point. Effluent stream 130 is cooled in exchanger 132, which may be a cross exchanger with another process stream or cooled with a suitable heat transfer medium such as chilled water, for example, and fed to high pressure separator 134 to separate hydrogen treat gas from the liquid raffinate. The high pressure separator may be sized for the desired reactor holdup. A portion (e.g., 136 kg (300 lbs)) or all of the hydrogen-rich overhead vapor from the high pressure separator 134 may be withdrawn via line 138 for off-gas processing, and any remainder may be recycled to the HDS reactor 128 with make-up hydrogen 140 as needed via knock-out drum 142, compressor 144 and line 116 as described above.

[0065] Hydrogen-lean liquid from the high pressure separator 134 is fed via bottoms stream 146 to recycle pump 148 and stripper 150. Recycle pump 148 recirculates raffinate to the diolefin saturator 114 via line 112 as described above in this example at a rate, for example, of 20,900 kg/h (46,000 lbs/h). Any remaining raffinate from line 146 is fed to stripper 150 as previously mentioned.

[0066] Stripper 150 removes gases, such as hydrogen sulfide and hydrogen halide, from the product, and in this example may have approximately 5-10, e.g., 8 theoretical stages, depending on the amount of hydrogen sulfide in the feed and the level of hydrogen sulfide desired in the product. Overhead vapor is cooled in exchanger 152, which may be a cross exchanger with another process stream or cooled with a suitable heat transfer medium such as chilled water or air as in a fin-fan exchanger, for example. Condensate is collected in drum 154, vapor is recovered via line 156, and the liquid is gravity separated into water draw 158 and raffinate reflux stream 160 which is returned to the stripper 150. Bottoms stream 162 is circulated by pump 164 through reboiler 166 and split between bottoms return line 168 and treated raffinate product line 170.

[0067] Off-gas (hydrogen tail gas containing acid gases, hydrocarbons and inerts) from lines 138 and 156 in this example may be processed in off-gas treater 172 which may be a scrubber configured to contact the off-gas with an absorption solvent such as water or caustic, for example, which may be introduced via line 174, and preferentially absorb the hydrogen sulfide and/or hydrogen halide from the hydrogen tail gas, producing a lean tail gas stream 176 recovered overhead and a hydrogen sulfide-rich solvent stream 178.

[0068] According to this example, the raffinate product stream 170 has a sulfur content less than 30 ppmw sulfur or less than 10 ppmw sulfur.

[0069] Example 2 - With reference to Fig. 3, another example of a hydroprocessing and sulfur/halogen removal process 100 according to the present invention is shown. To simulate the process 100 on a commercial scale, a pilot plant test was conducted. To model the two- reactor system of the present invention, the first reactor (diolefin saturator 1 14) was tested first and the product from the diolefin saturator 1 14 was then fed into the second reactor (HDS reactor 128) for testing. To model the recycle the raffinate feed was diluted in a 5: 1 ratio with heptane. KL8233, a nickel-molybdenum catalyst available from Criterion, was loaded into both the diolefin saturator 114 and the HDS reactor 128 and sulfided in-situ by methods generally known in the art. The space velocity reported in Table 1 is based on the undiluted raffinate feed.

[0070] The diolefin saturator 1 14 was evaluated with three run conditions, as listed below in Table 1 as Examples 2A, 2B, and 2C. The reactor pressure for all runs was maintained at 2.3 MPa (335 psig).

TABLE 1

[0071] All of the examples of Table 1 show favorable diolefin removal at varying reactor temperature and space velocity conditions, indicating sufficient protection of the downstream HDS catalyst from fouling. Specifically, Example 2A and Example 2C had a 92% diolefin conversion and Example 2B had an 88% diolefin conversion.

[0072] The HDS reactor 128 was evaluated with two run conditions, as listed below in Table 2 as Examples 3 A and 3B. The reactor pressure for both runs was maintained at 1.97 MPa (285 psig) and the reactor temperature for both runs was maintained at 270°C (518°F), with only the space velocity changing.

TABLE 2

[0073] Both examples of Table 2 show favorable sulfur and halogen removal at varying space velocity conditions. Specifically, Example 3A had a 97% sulfur conversion to H2S and a 98% conversion of halogen conversion to HC1 and Example 3B had an 88% sulfur conversion and a 96% halogen conversion. While the higher space velocity of Example 3B as compared to Example 3A resulted in a slightly lower sulfur and halogen conversion, the product sulfur and halogen content of Example 3B was still well within the target less than 30 ppmw sulfur and less than 20 ppmw halogen.

[0074] All documents described herein are incorporated by reference herein, including any patent applications and/or testing procedures to the extent that they are not inconsistent with this application and claims. The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.