Method of processing sulfur-bearing wastes from refineries and upgraders
10850229 ยท 2020-12-01
Assignee
Inventors
- James Seamans (The Woodlands, TX, US)
- Terence McHugh (Post Falls, ID, US)
- Brian Visioli (Houston, TX, US)
Cpc classification
Y02A50/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01D53/1481
PERFORMING OPERATIONS; TRANSPORTING
B01D53/34
PERFORMING OPERATIONS; TRANSPORTING
B01D53/8615
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
The methods and systems are disclosed which leverage sulfur abatement resources present at most refineries or other hydrocarbon processing plants, such as natural gas processing plants to capture and treat sulfur-containing byproducts, such as SO.sub.2, generated during the regeneration of spent HDP catalysts. Thus, the disclosed methods and systems allow for converting hazardous waste spent catalyst to a salable product at it source while simultaneously capturing the sulfur oxides removed from the catalyst and converting them to a useful product instead of a resultant waste stream requiring management and/or disposal. Thus, spent sulfur bearing refinery wastes, such as HDP catalyst, can be roasted or regenerated at the refinery site to convert the hazardous sulfur-bearing wastes into one or more salable products.
Claims
1. A method of treating a sulfur-bearing waste, the method comprising: heating the sulfur-bearing waste to produce a first gas stream, wherein the first gas stream comprises sulfur dioxide (SO.sub.2), providing at least a portion of the first gas stream to a sulfur treatment process (STP), providing a second gas stream to the STP, wherein the second gas stream comprises hydrogen sulfide (H.sub.2S), providing a third gas stream to the STP, wherein the third gas stream comprises oxygen (O.sub.2), and adjusting an amount of the third gas stream provided to the STP to maintain a reaction between SO.sub.2 and H.sub.2S.
2. The method of claim 1, wherein the STP is an STP of a hydrocarbon processing plant.
3. The method of claim 2, wherein the hydrocarbon processing plant is a hydrocarbon refining plant, a hydrocarbon upgrader, or a natural gas treatment plant.
4. The method of claim 2, wherein the second gas stream comprises one or more gas streams derived from a hydrocarbon processing operation of the hydrocarbon processing plant.
5. The method of claim 4, wherein the second gas stream is selected from the group consisting of an acid gas stream, an amine gas stream, and a sour water stripping off-gas stream.
6. The method of claim 3, wherein the hydrocarbon processing plant is a hydrocarbon refining plant and wherein the sulfur-bearing waste comprises spent hydroprocessing (HDP) catalyst derived from the hydrocarbon refining plant.
7. The method of claim 4, wherein the sulfur-bearing waste comprises tank sludge.
8. The method of claim 4, wherein the sulfur-bearing waste comprises sulfur trap catalyst.
9. The method of claim 4, further comprising separating the sulfur-bearing waste from a mixture of oil and the sulfur-bearing waste before heating the sulfur-bearing waste.
10. The method of claim 1, wherein the first gas stream further comprises one or more components selected from the group consisting of carbon dioxide (CO.sub.2), water (H.sub.2O), and nitrogen (N.sub.2) and wherein providing a portion of the first gas stream to the STP comprises treating the first gas stream to provide an SO.sub.2-enriched gas stream and providing the SO.sub.2-enriched gas stream to the STP.
11. The method of claim 10, wherein treating the first gas stream to provide an SO.sub.2-enriched gas stream comprises: contacting the first gas stream with a lean SO.sub.2-adsorbing medium to yield an SO.sub.2-enriched SO.sub.2-adsorbing medium and an SO.sub.2-depleted gas, and stripping gaseous SO.sub.2-from the SO.sub.2-enriched SO.sub.2-adsorbing medium to yield the SO.sub.2-enriched gas stream.
12. The method of claim 11, wherein the lean SO.sub.2-adsorbing medium comprises a solvent comprising an amine.
13. The method of claim 1, wherein adjusting the amount of the third gas stream provided to the STP comprises: determining a feed rate of the at least a portion of the first gas stream to the STP, determining a feed rate of the second gas stream to the STP, and adjusting an amount of the third gas stream provided to the STP based on the determined feed rates.
14. The method of claim 13, wherein adjusting an amount of the third gas stream provided to the STP based on the determined feed rates comprises decreasing the amount of the third gas stream to the STP if the feed rate of the at least a portion of the first gas stream to the STP increases relative to the feed rate of the second gas stream to the STP.
15. The method of claim 1, wherein adjusting the amount of the third gas stream provided to the STP comprises: determining a composition of a tail gas of the STP, and adjusting the amount of the third gas stream provided to the STP based on the determined composition.
16. The method of claim 15, wherein determining the composition of a tail gas of the STP comprises determining a ratio of H.sub.2S to SO.sub.2 in the tail gas.
17. The method of claim 16, wherein adjusting the amount of the third gas stream provided to the STP based on the determined composition comprises increasing the amount of the third gas stream provided to the STP if the ratio of H.sub.2S to SO.sub.2 increases.
18. The method of claim 1, wherein providing at least a portion of the first gas stream to the STP comprises treating the first gas stream to remove particulates from the first gas stream.
19. The method of claim 1, wherein the STP comprises a Claus process.
20. The method of claim 1, wherein the STP comprises a sulfuric acid plant.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
DETAILED DESCRIPTION
(5) As mentioned above, HDP catalysts become spent during use and must be removed from the HDP units of the refinery. Handling of the spent catalyst poses several problems. The spent catalyst typically contains catalytic and contaminant metals in the sulfide form as well as liquid hydrocarbons and hydrocarbon deposits (i.e., coke). Such contaminants increase the weight of the catalyst material and, in many cases, may render the spent catalyst hazardous and/or self-heating, which increases the costs of handling and transporting the spent catalyst.
(6) Thermal stripping/oxidation technologies exist that can render the spent catalyst non-self-heating and/or convert it to a hazardous product rather than a waste. However, such oxidation processes convert the sulfur and sulfur-containing compounds present on the spent catalyst into sulfur dioxide (SO.sub.2), which must be captured or treated using a sulfur abatement technology. Such sulfur abatement equipment and processing add a significant cost to treating the spent catalyst.
(7) The methods and systems described in this disclosure leverage the sulfur abatement resources that are present at treating facilities such as refineries and gas processing plants to capture and treat sulfur-containing byproducts, such as SO.sub.2, that are generated during the regeneration of sulfur-bearing wastes, such as spent HDP catalysts. These sulfur abatement resources at the treating facility, e.g., the Claus sulfur recovery process, recover elemental sulfur as a product that can be used in fertilizer or other valuable products. To date, the removal of sulfur compounds from spent catalyst (by roasting or regeneration in an oxygen containing gas) has not been successfully integrated into the treating facility's Claus sulfur recovery system. The subject disclosure describes how this may be successfully done, thus converting the hazardous waste spent catalyst to a salable product at its source while simultaneously capturing the sulfur oxides removed from the catalyst and converting them to a useful product instead of a resultant waste stream requiring management and/or disposal. Thus, spent HDP catalyst can be roasted or regenerated at the refinery site or other treating facility that incorporates sulfur abatement.
(8)
(9) Again, it should be emphasized that HDP units 102 and 104 are only exemplary. A working refinery likely contains many different HDP units and such units may employ a variety of configurations, as is known in the art, such as fixed beds, moving beds, expanded or ebullated beds, and slurry beds.
(10) Generally, spent catalyst derived from the treatment of atmospheric distillation products and light products (such as in HDP unit 102) may be regenerated/reclaimed for reuse. Contrarily, spent catalyst derived from the treatment of residual oil and other heavy feeds (such as in HDP unit 104) may be too contaminated with metal-containing materials to be reused as catalyst even after such catalysts are treated to remove the accumulate deposits of hydrocarbon, other carbonaceous materials, sulfur-containing materials. Thus, the value in treating such spent catalyst is primarily to reclaim/recycle the component metals. However, it should be noted that these generalities may not always apply. For example, top beds of light feed treatments (i.e., HDP unit 102) may produce spent catalyst that is too poisoned for regeneration/reuse. Likewise, spent catalyst from the treatment of some resids and other heavy products (i.e., HDP unit 104) may still be suitable for regeneration and reuse. The point is that the catalyst treatment/regeneration methods and systems described herein may be used either for catalyst regeneration/reuse and/or for metals reclamation.
(11) Referring again to
(12) The HDP catalyst recovery unit 120 is referred to herein as a reuse catalyst recovery unit, because generally, the purpose of the reuse catalyst recovery unit 120 is to treat (i.e., regenerate) a spent HDP catalyst for reuse. The HDP catalyst recovery unit 130 is referred to herein as a reclaim catalyst recovery unit, because generally, the purpose of the reclaim catalyst recovery unit 130 is to render the spent HDP catalyst safe (e.g., non-self-heating) for further reclamation of the catalyst components, such as metals within the catalyst. The illustration is intended to show that the reuse catalyst recovery unit 120 may typically be used to treat catalyst derived from hydrotreating processes that operate on lighter materials whereas the reclaim catalyst recovery unit 130 may typically be used to treat catalyst derived from hydrotreating processes that operate on heavier materials, such as residuum. As mentioned above, embodiments of the disclosed system may include one of or both types of HDP treatment units.
(13) As mentioned above, the purpose of the reuse catalyst recovery unit 120 is to recover and treat spent HDP catalyst that has low levels of contaminants generated by refinery processes such as naphtha hydrotreaters, kerosene or jet hydrotreaters, distillate hydrotreaters, and other reactors, or certain beds in reactors, that have low levels of contaminants when the catalyst is removed from the reactors. According to some embodiments, the reuse catalyst recovery unit 120 can comprise a first stage for stripping free hydrocarbons from the spent catalyst, if any significant levels are present, and a second stage for regeneration of the spent catalyst in an oxygen-containing gas to remove coke on the catalyst and convert the catalyst metal sulfides to their oxide form. The first stage, i.e., stripping free hydrocarbons from the spent catalyst, may comprise thermal desorption of the hydrocarbons from the spent catalyst. Alternatively, or in addition, hydrocarbons may be removed by washing the spent catalyst with an organic solvent or with an aqueous medium that comprises surfactants and/or detergents. Equipment used for the reuse catalyst recovery unit 120 may include a moving belt regenerator, a fluidized bed, a rotolouver, a rotary calciner, or other equipment known in the art. For clarity, auxiliary equipment associated with the reuse catalyst recovery unit 120 has been omitted from
(14) According to some embodiments, spent catalyst from the (one or more) HDP unit(s) 102 are transported to the reuse catalyst recovery unit 120. Typically, the spent catalyst may comprise one or more Group VIII (Groups 8-10, IUPAC) metals, such as cobalt (Co) or nickel (Ni) and one or more Group VIB (Group 6, IUPAC) metals, such as molybdenum (Mo) or tungsten (W) supported on a carrier material, such as alumina (Al.sub.2O.sub.3), silica alumina, zeolite, or combinations thereof. The spent catalyst may be contaminated with hydrocarbon and carbonaceous contaminants from the HDP process. The spent catalyst may be heated in the reuse catalyst recovery unit 120 to strip those contaminants from the catalyst and to regenerate the spent catalyst. For example, the spent catalyst may be heated within a temperature range of about 500 F. to about 900 F. According to some embodiments, the reuse catalyst recovery unit 120 may employ multiple heating stages. For example, in a first stage the spent catalyst may be heated within a temperature range of about 500 F. to about 700 F. to strip the contaminants from the catalyst. Alternatively (or additionally) the spent catalyst may be washed with organic solvent and/or with an aqueous medium that may contain one or more surfactants and/or detergents. Then a second stage may be employed whereby the stripped catalyst is heated in an oxygen-containing atmosphere at a temperature of about 750 F. to about 900 F. to remove coke on the catalyst and convert the catalyst metal sulfides to their oxide form (i.e., to regenerate the catalyst). The oxygen-containing gas may be air or oxygen-enriched air, for example.
(15) Heating the spent catalyst during the stripping and/or regeneration stages yields an exhaust gas that typically comprises SO.sub.2, CO.sub.2, H.sub.2O, and N.sub.2. For example, the exhaust gas may comprise about 65% to about 85% N.sub.2, about 10% to about 20% O.sub.2, about 0.1% to about 0.4% CO.sub.2, and about 0.05% to about 0.2% SO.sub.2. As explained in more detail below, the exhaust from the reuse catalyst recovery unit 120 can be provided to the refinery's sulfur recovery unit (SRU) 106.
(16) Referring again to
(17) Referring again to
(18)
(19) The sulfur recovery unit (SRU) 106 of a typical refinery uses a process, referred to as the Claus Process, to convert hydrogen sulfide from the amine gas stream 202 and/or the sour water stripping stream 204 to elemental sulfur. The process involves a multistage catalytic process whereby hydrogen sulfide is oxidized to elemental sulfur according to the overall reaction:
2H.sub.2S+O.sub.22/xS.sub.x+2H.sub.2O
(20) Note that the stoichiometry of the above reaction is exemplary only and may change due to modifications in the particulars of the Claus reactions. Each catalytic stage of the sulfur recovery unit 106 typically includes a gas reheater, a catalyst reactor, and a sulfur condenser.
(21) The Claus process involves using a thermal reactor, such as a furnace, to oxidize a portion, for example one-third, of the H.sub.2S in an oxygen-containing atmosphere to form SO.sub.2, according to the following reaction:
2H.sub.2S+3O.sub.22SO.sub.2+2H.sub.2O
(22) The combustion gases, which comprise primarily H.sub.2S, SO.sub.2, H.sub.2O, and N.sub.2 are sent to a condenser whereby elemental sulfur is condensed and separated from the process gases, and the cooled gases exiting the condenser are then sent to the catalytic converters. In each stage, the remaining uncombusted portion of the H.sub.2S reacts with SO.sub.2 in the catalytic converters to form elemental sulfur, as follows:
2H.sub.2S+SO.sub.23/xS.sub.x+2H.sub.2O
(23) Claus Process-based sulfur recovery units are well known in the art and need not be described here in detail. But what is important to note is that sulfur dioxide (SO.sub.2) is a reactant in the Claus Process chemistry. Under typical Claus operation, the SO.sub.2 is produced via the oxidation of H.sub.2S in the thermal reactor. Embodiments of the disclosed methods introduce SO.sub.2-containing gas streams that are the exhaust combustion gas streams from the catalyst recovery units 120 and/or 130 into the Claus SRU, as illustrated in
(24) The SRU 106 illustrated in
(25) As some amount of SO.sub.2 is introduced into the SRU 106 via stream(s) 201, the operation of the thermal reactor can be adjusted to compensate for that additional SO.sub.2. In other words, the thermal reactor of the retrofitted SRU is not responsible for generating all of the SO.sub.2 for the Claus chemistry as some of the SO.sub.2 is provided from the catalyst recovery unit exhaust stream(s) 201. The thermal reactor conditions are compensated by adjusting the O.sub.2 (air) flow to the thermal reactor. The illustrated SRU 106 includes meters 301, 302, and 304 that measure the flow and/or compositions of streams 201, 202, and 204 respectively. Readings from those meters can be used to adjust the amount O.sub.2 provided to the thermal reactor based on the flow and/or composition of the streams 201, 202, and 204. For example, the amount of O.sub.2 provided to the thermal reactor can be decreased if a greater amount of SO.sub.2 is being provided to the thermal reactor, thereby decreasing the amount of SO.sub.2 that is generated by oxidizing H.sub.2S. Likewise, the SRU 106 may include one or more analyzers 306, for example to analyze the composition of the tail gas and to adjust the amount of O.sub.2 provided to the thermal reactor accordingly. For example, the analyzer 306 may determine the relative amounts of H.sub.2S and SO.sub.2 in the tail gas. If the amount of H.sub.2S is too high, then more O.sub.2 may be provided to the thermal reactor.
(26) The above discussion and
(27) Likewise, according to some embodiments, the exhaust gases from the catalyst recovery units 120/130 may be at elevated temperatures and therefore may need to be cooled before being provided to the SRU 106. For example, the reclaim catalyst recovery unit 130 typically operates at temperatures of 1000 F. to about 2000 F., for example 1800 F., as described above. Consequently, the exhaust gas exiting the reclaim catalyst recovery unit 130 may have a temperature of about 1800 F. According to some embodiments, the effluent gases are compressed before they are provided to the SRU. If the gases are to be compressed, they should be cooled, for example, to a temperature below about 400 F. Thus, embodiments of the disclosed retrofit HDP catalyst recovery system 110 and associated methods include one or more processes and associated equipment for cooling the exhaust gases. According to some embodiments, the exhaust gas may be cooled using a water quench, a heat exchanger, or the like. Such treatment of the exhaust streams of the catalyst recovery units 120/130 will be implementation specific and within the ability of a person of skill in the art.
(28)
(29) Examples of sulfur dioxide scrubbing systems are well known in the art and need not be described here in detail. Exemplary sulfur dioxide scrubbing systems provide for contacting the SO.sub.2-containing feed (i.e., the exhaust gases) with an SO.sub.2-adsorbing medium, such as an amine-containing solvent, for example. According to some embodiments, the exhaust gases are contacted with the SO.sub.2-absorbing medium, for example, in a counter-current absorption column. SO.sub.2 is preferentially absorbed in the SO.sub.2-absorbing medium to yield an SO.sub.2-enriched absorbing medium and a SO.sub.2-depeleted gaseous phase, which is enriched in the non-SO.sub.2 components (e.g., CO.sub.2, H.sub.2O, and/or N.sub.2). The SO.sub.2 is then stripped from the SO.sub.2-enriched absorbing medium to regenerate lean SO.sub.2-absorbing medium and to yield a gas stream that is enriched in SO.sub.2, which can be provided to the SRU. An example of an SO.sub.2 scrubbing system is described in U.S. Pat. No. 7,214,358, issued May 8, 2007.
(30) It should be noted that some refineries may not use a Claus-based process for sulfur recovery, and instead may treat the acid gas streams using other technology such as a sulfuric acid plant. According to some such processes, the H.sub.2S of the acid gas is incinerated to make SO.sub.2, which can then be catalytically converted to SO.sub.3 and used to produce sulfuric acid. Such sulfur-treating processes of the refinery can also be leveraged to treat the SO.sub.2-containing combustion gases from the reuse catalyst recovery unit 120 and/or the reclaim catalyst recovery unit 130, as described above. For example, the combustion gases may be fed to the incinerator and/or to the catalytic converter of a sulfuric acid plant. As used in this disclosure, the term sulfur recovery unit (SRU) refers to sulfur abatement technologies based on Claus processes, as well as sulfur abatement technologies based on other processes, such as sulfuric acid plants. Sulfur abatement process, such as, but not limited to, Claus processes, sulfuric acid plants, and the like, are also referred to herein as sulfur treatment processes (STPs).
(31) A person of skill in the art will appreciate that methods and systems of treating sulfur-bearing wastes have been disclosed herein. The disclosure focuses primarily on treating sulfur-bearing spent catalysts used in hydrotreating process. However, the methods and systems described herein can be applied to other sulfur-bearing wastes in a refinery setting. For example, the catalyst recovery units 120 and/or 130 can be used for combusting organics on other wastes such as storage tank sludges and sulfur traps (typically containing Ni and Zn-based catalysts). Thus, while units 120 and 130 are referred to herein as catalyst recovery units, it should be appreciated that their use is not so limited. In other words, units 120 and 130 may be used to treat any sulfur-bearing waste derived within a hydrocarbon processing plant, a hydrocarbon upgrading process, a natural gas plant, or the like, and to leverage the sulfur-treatment equipment of such processing plants to abate the generated SO.sub.2. Thus, throughout this specification, the term catalyst recovery unit may be substituted with terms such as sulfur waste treating unit, sulfur waste heating unit, sulfur waste oxidation unit, or the like. Depending on the nature and composition of the sulfur-bearing waste, the waste may be treated before providing it to the treatment unit(s) 120 and/or 130. For example, tank bottoms (or sludge) may comprise solids and oil. Such waste may be treated to separate the oil from the solids so that the oil can be sold or reprocessed, and the solids can be treated using the treatment unit(s) 120 and/or 130. For example, the waste may be treated using one or more mechanical methods, such as centrifugation to separate solid and liquid components of the waste.
(32) The above discussion primarily focuses on embodiments wherein catalyst recovery systems are implemented in a refinery setting and particularly wherein such systems leverage the refinery's sulfur-treatment equipment to abate the SO.sub.2 produced during catalyst recovery. However other embodiments can be implemented in settings other than refineries that include sulfur-treatment. For example, natural gas processing plants typically include Claus and/or other sulfur abatement facilities and such facilities can be leveraged to treat SO.sub.2 produced during catalyst recovery, as described above. For example, spent catalyst from processes such as oil sands/bitumen upgrading may be regenerated at a natural gas processing plant and the plant's sulfur-treatment facilities used to treat the produced SO.sub.2.
(33) Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges may appear in one or more claims below. All numerical values are about or approximately the indicated value, and take into account numerical error and variations that would be expected by a person having ordinary skill in the art. Unless otherwise noted, about may be interpreted to imply plus or minus 10 percent. The use of the word a or an when used in conjunction with the term comprising in the claims or the specification means one or more than one, unless the context dictates otherwise. The use of the term or in the claims is used to mean and/or unless explicitly indicated to refer to alternatives only or if the alternatives are mutually exclusive. The terms comprise, have, include and contain (and their variants) are open-ended linking verbs and allow the addition of other elements when used in a claim.
(34) While the invention herein disclosed has been described in terms of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims.