US20150053589A1 - Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream - Google Patents
Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream Download PDFInfo
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- US20150053589A1 US20150053589A1 US13/972,096 US201313972096A US2015053589A1 US 20150053589 A1 US20150053589 A1 US 20150053589A1 US 201313972096 A US201313972096 A US 201313972096A US 2015053589 A1 US2015053589 A1 US 2015053589A1
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- Prior art keywords
- gas oil
- hydrocarbon
- hydrocarbon stream
- vacuum
- coker
- Prior art date
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Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 74
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 74
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 22
- 239000003463 adsorbent Substances 0.000 claims abstract description 48
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 19
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- KBOBQLJBYKKAPN-UHFFFAOYSA-N 2-chloro-2-methylhexane Chemical compound CCCCC(C)(C)Cl KBOBQLJBYKKAPN-UHFFFAOYSA-N 0.000 description 1
- NXXHAWKBICGUCK-UHFFFAOYSA-N 2-chloro-2-methylpentane Chemical compound CCCC(C)(C)Cl NXXHAWKBICGUCK-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 but not limited to Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Definitions
- Organic chloride content is not an intrinsic property of crude oil, but originates from accidental or unintentional contamination thereof. That is, the amount of organic chlorides found in the crude is not related to the location from which the crude originated or other physical properties of the crude oil. Accordingly, historic crude assays do not provide a reliable indication of future chloride levels. Thus, newly selected crude oils are always viewed as posing a high risk for chloride contamination in a hydrotreating device.
- SCC chloride stress corrosion cracking
- One aspect of the invention is a method for processing hydrocarbons, the method including providing a hydrocarbon stream including chlorides from a crude, vacuum and/or coker column.
- the provided hydrocarbon stream is contacted with an adsorbent capable of adsorbing the chlorides from the hydrocarbon stream.
- the dechlorinated hydrocarbon stream is then provided to a hydrotreater reactor.
- Another aspect of the invention is a hydrocarbon hydrotreating device having: a crude, vacuum and/or coker column; an adsorbent bed is disposed downstream of the crude, vacuum and/or coker column and in fluid communication therewith to contact a hydrocarbon stream from the crude, vacuum and/or coker column with an adsorbent in the adsorbent bed.
- the adsorbent bed is capable of adsorbing chlorides.
- a hydrotreater reactor is disposed downstream of the adsorbent bed and in fluid communication with the adsorbent bed to treat the hydrocarbon stream.
- the FIGURE illustrates one embodiment of the chloride adsorption process of the present invention before entering a hydrocarbon hydrotreating device.
- a process has been developed to remove organic and inorganic chlorides from a hydrocarbon stream before the stream enters a hydrotreater reactor.
- a hydrotreater process including chloride adsorption is generally designated 10 .
- a hydrocarbon stream containing organic and inorganic chlorides is provided from one or more of a vacuum column, a crude column, and a coker column through a line 12 .
- the hydrocarbon stream preferably includes one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light, light coker gas oil, vacuum column overhead, cracked naphtha, and straight run naphtha.
- One example hydrocarbon stream includes light vacuum gas oil, heavy vacuum gas oil, heavy coker gas oil and naphtha.
- the hydrocarbon stream leaving the column typically has a chloride content up to 40 parts per million, by weight.
- the line 12 is preferably split.
- a tankage line 14 allows the stream to be cooled using a cooling device 16 , such as a fin-fan as shown in the FIGURE, and routed to tankage (not shown) when the downstream hydrotreater device is in shutdown mode.
- a cracking line 18 optionally allows the stream to be routed to a cracker unit (not shown), bypassing the hydrotreater device.
- a hydrotreater line 20 routes the hydrocarbon stream to a hydrotreater device. Prior to entering the hydrotreater device, chloride content of the hydrocarbon stream should be mitigated to help prevent chloride buildup within the hydrotreater.
- an adsorbent bed 22 Downstream of the vacuum column, crude column, and/or coker column, and connected to the hydrotreater line 20 , an adsorbent bed 22 is provided.
- the adsorbent bed 22 contains an adsorbent material that is preferably selected to adsorb both organic and inorganic chloride compounds.
- the adsorbent material contained in the bed 22 allows for physical adsorption and/or chemisorption.
- Example materials for use in the bed 22 include adsorbents containing one or more of alumina, alumino-silicate, and a mixture thereof.
- adsorbents are capable of adsorbing chloride compounds including, but not limited to, hydrochloric acid (HCl), ammonium chloride (NH 4 Cl), sodium chloride (NaCl), calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), polychlorinated biphenyls (PCBs), 1-chloroheptane, 2-chloro-2-methyl hexane, and 2-chloro-2-methyl pentane.
- the adsorbent material preferably has an equilibrium chloride capacity of up to about 20 wt %, and more preferably in a range of about 10 wt % to about 20 wt %.
- a temperature of the hydrocarbon stream is preferably adjusted if necessary to enhance the effectiveness of the adsorbent. That is, the temperature of the hydrocarbon stream may be controlled by adding an optional heating or cooling device to the hydrotreater line 20 so that the hydrocarbon stream entering the bed 22 has a temperature in a range from as low as ambient room temperature (e.g., approximately 20° C.) to approximately 130° C. More preferably, the temperature of the hydrocarbon stream is approximately 125° C. when the hydrocarbon stream enters the bed 22 and contacts the adsorbent. Those of skill in the art will recognize that other temperatures may be used with different adsorbent materials without departing from the scope of the invention.
- the adsorbent bed 22 is preferably sized to provide a reasonable service life and to allow for sufficient flow of the hydrocarbon stream through the bed. For example, a bed having a volume of approximately 66 m 3 is expected to have a service life of approximately 12 months. Additionally, the bed preferably accommodates a hydrocarbon stream flow rate of approximately 120 m 3 per hour. Those of skill in the art will recognize that the bed size may be varied to accommodate differing flow rates and/or service lifetimes without departing from the scope of the invention.
- the organic and inorganic chloride content of hydrocarbon stream is greatly reduced.
- the chloride content of the hydrocarbon stream exiting the adsorbent bed 22 is less than 1 part per million, by weight. Even more preferably, the chloride content is less than 0.1 part per million, by weight. This chloride content advantageously mitigates SCC phenomena caused by the chlorides.
- the adsorbent may be replaced.
- the used adsorbent may be regenerated, disposed of, or used in other capacities as is known in the art.
- the dechlorinated hydrocarbon stream Downstream of the adsorbent bed 22 , the dechlorinated hydrocarbon stream is provided to the hydrotreater device.
- the dechlorinated stream is preferably routed through line 24 to be joined with a combined gas oil stream 26 to form a joined stream 32 .
- the combined gas oil stream 26 includes hydrocarbons from other sources, including a hot feed 28 and a cold feed 30 that is warmed using a heat exchanger 31 , each of which may include one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light light coker gas oil, vacuum column overhead, cracked naphtha, and straight run naphtha.
- the heat exchanger 31 used to warm the cold feed 30 preferably receives high pressure steam (HPS) as an input 31 a. Because the HPS cools within the heat exchanger 31 , and exits the heat exchanger as high pressure condensate (HPC) 31 b . The mixing of the dechlorinated stream in line 24 and the combined gas oil stream 26 forms the joined stream 32 . The joined stream 32 is then provided through one or more filters 34 to a feed surge drum 36 as is known in the art.
- HPS high pressure steam
- HPC high pressure condensate
- the output of the feed surge drum 36 passes through a charge pump 38 and one or more preheaters 40 to a combined feed heater 42 . Then, after heating, the stream is routed to a reactor 44 .
- the reactor effluent is routed through the preheaters 40 to provide heat to the hydrocarbon stream.
- the preheaters 40 are preferably heat exchangers. Thus, in addition to heating the stream entering the combined feed heater, the preheaters 40 also help to cool the reactor effluent.
- the reactor effluent is then provided to a further cooling unit 46 , such as an air cooler, and provided to a high pressure separator 48 to separate the liquid and gaseous portions of the stream.
- the gaseous portion of the hydrocarbon stream exits the separator 48 and is provided to a recycle gas scrubber 50 for removal of impurities.
- the scrubbed gas is then routed to a compressor 52 , and recycled as inputs to both the combined feed heater 42 and the reactor 44 .
- the high pressure separator also produces, as a byproduct, sour water, which exits the separator 48 through line 49 .
- the sour water is wastewater containing waste products such as hydrogen sulfide and ammonia.
- the liquid portion of the hydrocarbon stream exits the high pressure separator 48 and enters a stripper 54 to further separate liquid and gaseous components.
- Gaseous components are removed from the stripper 54 as off-gas 55 , and liquid stripper effluent is routed to fractionator 56 , to divide the hydrocarbon stream into various hydrocarbon outputs, including naphtha 56 a, kerosene 56 b, diesel 56 c, and/or vacuum gas oil bottoms 56 d. That is, low pressure steam enters the fractionator 56 through input line 57 , and the input hydrocarbon stream is divided into its various component outputs 56 a - 56 d based upon their differing boiling points, as is known in the art.
- the naphtha output 56 a of the fractionator 56 is cooled before entering a receiver 58 , and the output hydrocarbon liquid is then divided so that a portion is recycled into the fractionator, and a portion is output as a hydrocarbon output. Sour water is removed from the receiver 58 through line 59 .
- the reduction in chlorides in the hydrotreater allows for reduction in the amount of wash water used throughout the hydrotreating process. In particular, less wash water is required in upstream and downstream process line of air cooler 46 . This leads to a commensurate reduction in the amount of sour water produced during hydrotreating.
- LVGO Light vacuum gas oil
- the LVGO stream is the primary target for chloride adsorption, as is shown in the FIGURE.
- this chloride adsorption process can be adapted for use on other hydrocarbon streams either in place of or in addition to its use on the LVGO stream, without departing from the scope of this invention.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method for processing hydrocarbons includes providing a hydrocarbon stream including chlorides from one or more of a crude, vacuum or coker column and contacting the provided hydrocarbon stream with an adsorbent capable of adsorbing the chlorides from the hydrocarbon stream. The dechlorinated hydrocarbon stream is then provided to a hydrotreater reactor.
Description
- Incremental shifts in crude oil demands have caused increases in diesel and jet fuel production, leading refiners to run their units in distillate mode and increasing demand for hydrotreaters. However, crude contaminants must be dealt with before the hydrotreating process. In particular, chloride contaminants including organic and inorganic chlorides must be mitigated.
- Organic chloride content is not an intrinsic property of crude oil, but originates from accidental or unintentional contamination thereof. That is, the amount of organic chlorides found in the crude is not related to the location from which the crude originated or other physical properties of the crude oil. Accordingly, historic crude assays do not provide a reliable indication of future chloride levels. Thus, newly selected crude oils are always viewed as posing a high risk for chloride contamination in a hydrotreating device.
- Conventionally, it is possible to run hydrotreaters that possess targeted halide removal systems. However, such hydrotreaters are expensive to operate and/or to maintain. Thus their operation is impractical. Other mitigation measures, including metallurgical upgradation and wash water, have limitations which prevent widespread use.
- Spot sample analysis of crude oil received at certain refineries reflects a salt content that ranges from a PTB (Pounds per thousand barrels) of 10 to 300 (34 to 1,024 parts per million, by weight). In spite of desalter operations, most refinery data shows considerable quantities of both organic and inorganic chlorides in side cuts of crude, coker and/or vacuum column, particularly in light vacuum gas oil (LVGO) from the vacuum column and light coker gas oil (LCGO) from the coker column. Thus, while the chloride content of the individual side cuts of these columns is relatively high, the typical chloride limit in most hydrotreating devices is relatively low, with an upper bound set at about 1 part per million, by weight.
- Excess chlorides can lead to catastrophic failures, including chloride stress corrosion cracking (SCC). Presence of SCC phenomena can be somewhat mitigated through selection of materials during hydrotreater construction and/or reinforcing the pipes used throughout the hydrotreater. However, SCC-resistant materials are typically more expensive to purchase and maintain. Accordingly, there is a need for a relatively low cost process for removing both organic and inorganic chlorides from crude, coker and/or vacuum column distillates.
- One aspect of the invention is a method for processing hydrocarbons, the method including providing a hydrocarbon stream including chlorides from a crude, vacuum and/or coker column. The provided hydrocarbon stream is contacted with an adsorbent capable of adsorbing the chlorides from the hydrocarbon stream. The dechlorinated hydrocarbon stream is then provided to a hydrotreater reactor.
- Another aspect of the invention is a hydrocarbon hydrotreating device having: a crude, vacuum and/or coker column; an adsorbent bed is disposed downstream of the crude, vacuum and/or coker column and in fluid communication therewith to contact a hydrocarbon stream from the crude, vacuum and/or coker column with an adsorbent in the adsorbent bed. The adsorbent bed is capable of adsorbing chlorides. A hydrotreater reactor is disposed downstream of the adsorbent bed and in fluid communication with the adsorbent bed to treat the hydrocarbon stream.
- The FIGURE illustrates one embodiment of the chloride adsorption process of the present invention before entering a hydrocarbon hydrotreating device.
- A process has been developed to remove organic and inorganic chlorides from a hydrocarbon stream before the stream enters a hydrotreater reactor.
- Referring now to the FIGURE, a hydrotreater process including chloride adsorption is generally designated 10. A hydrocarbon stream containing organic and inorganic chlorides is provided from one or more of a vacuum column, a crude column, and a coker column through a
line 12. The hydrocarbon stream preferably includes one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light, light coker gas oil, vacuum column overhead, cracked naphtha, and straight run naphtha. One example hydrocarbon stream includes light vacuum gas oil, heavy vacuum gas oil, heavy coker gas oil and naphtha. The hydrocarbon stream leaving the column typically has a chloride content up to 40 parts per million, by weight. Theline 12 is preferably split. Atankage line 14 allows the stream to be cooled using acooling device 16, such as a fin-fan as shown in the FIGURE, and routed to tankage (not shown) when the downstream hydrotreater device is in shutdown mode. Additionally, acracking line 18 optionally allows the stream to be routed to a cracker unit (not shown), bypassing the hydrotreater device. However, during normal operation, ahydrotreater line 20 routes the hydrocarbon stream to a hydrotreater device. Prior to entering the hydrotreater device, chloride content of the hydrocarbon stream should be mitigated to help prevent chloride buildup within the hydrotreater. - Downstream of the vacuum column, crude column, and/or coker column, and connected to the
hydrotreater line 20, anadsorbent bed 22 is provided. Theadsorbent bed 22 contains an adsorbent material that is preferably selected to adsorb both organic and inorganic chloride compounds. Preferably, the adsorbent material contained in thebed 22 allows for physical adsorption and/or chemisorption. Example materials for use in thebed 22 include adsorbents containing one or more of alumina, alumino-silicate, and a mixture thereof. In particular, adsorbents are capable of adsorbing chloride compounds including, but not limited to, hydrochloric acid (HCl), ammonium chloride (NH4Cl), sodium chloride (NaCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), polychlorinated biphenyls (PCBs), 1-chloroheptane, 2-chloro-2-methyl hexane, and 2-chloro-2-methyl pentane. The adsorbent material preferably has an equilibrium chloride capacity of up to about 20 wt %, and more preferably in a range of about 10 wt % to about 20 wt %. A temperature of the hydrocarbon stream is preferably adjusted if necessary to enhance the effectiveness of the adsorbent. That is, the temperature of the hydrocarbon stream may be controlled by adding an optional heating or cooling device to thehydrotreater line 20 so that the hydrocarbon stream entering thebed 22 has a temperature in a range from as low as ambient room temperature (e.g., approximately 20° C.) to approximately 130° C. More preferably, the temperature of the hydrocarbon stream is approximately 125° C. when the hydrocarbon stream enters thebed 22 and contacts the adsorbent. Those of skill in the art will recognize that other temperatures may be used with different adsorbent materials without departing from the scope of the invention. - The
adsorbent bed 22 is preferably sized to provide a reasonable service life and to allow for sufficient flow of the hydrocarbon stream through the bed. For example, a bed having a volume of approximately 66 m3 is expected to have a service life of approximately 12 months. Additionally, the bed preferably accommodates a hydrocarbon stream flow rate of approximately 120 m3 per hour. Those of skill in the art will recognize that the bed size may be varied to accommodate differing flow rates and/or service lifetimes without departing from the scope of the invention. - After exiting the
adsorbent bed 22, the organic and inorganic chloride content of hydrocarbon stream is greatly reduced. Preferably, the chloride content of the hydrocarbon stream exiting theadsorbent bed 22 is less than 1 part per million, by weight. Even more preferably, the chloride content is less than 0.1 part per million, by weight. This chloride content advantageously mitigates SCC phenomena caused by the chlorides. - Once the service life of the adsorbent in the
adsorbent bed 22 has elapsed, the adsorbent may be replaced. The used adsorbent may be regenerated, disposed of, or used in other capacities as is known in the art. - Downstream of the
adsorbent bed 22, the dechlorinated hydrocarbon stream is provided to the hydrotreater device. In particular, the dechlorinated stream is preferably routed throughline 24 to be joined with a combinedgas oil stream 26 to form a joinedstream 32. The combinedgas oil stream 26 includes hydrocarbons from other sources, including ahot feed 28 and acold feed 30 that is warmed using aheat exchanger 31, each of which may include one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light light coker gas oil, vacuum column overhead, cracked naphtha, and straight run naphtha. Theheat exchanger 31 used to warm thecold feed 30 preferably receives high pressure steam (HPS) as aninput 31 a. Because the HPS cools within theheat exchanger 31, and exits the heat exchanger as high pressure condensate (HPC) 31 b. The mixing of the dechlorinated stream inline 24 and the combinedgas oil stream 26 forms the joinedstream 32. The joinedstream 32 is then provided through one ormore filters 34 to afeed surge drum 36 as is known in the art. - The output of the
feed surge drum 36 passes through acharge pump 38 and one or more preheaters 40 to a combinedfeed heater 42. Then, after heating, the stream is routed to areactor 44. The reactor effluent is routed through thepreheaters 40 to provide heat to the hydrocarbon stream. Thepreheaters 40 are preferably heat exchangers. Thus, in addition to heating the stream entering the combined feed heater, thepreheaters 40 also help to cool the reactor effluent. The reactor effluent is then provided to afurther cooling unit 46, such as an air cooler, and provided to ahigh pressure separator 48 to separate the liquid and gaseous portions of the stream. - The gaseous portion of the hydrocarbon stream exits the
separator 48 and is provided to arecycle gas scrubber 50 for removal of impurities. The scrubbed gas is then routed to acompressor 52, and recycled as inputs to both the combinedfeed heater 42 and thereactor 44. The high pressure separator also produces, as a byproduct, sour water, which exits theseparator 48 throughline 49. The sour water is wastewater containing waste products such as hydrogen sulfide and ammonia. - The liquid portion of the hydrocarbon stream exits the
high pressure separator 48 and enters astripper 54 to further separate liquid and gaseous components. Gaseous components are removed from thestripper 54 as off-gas 55, and liquid stripper effluent is routed tofractionator 56, to divide the hydrocarbon stream into various hydrocarbon outputs, includingnaphtha 56 a,kerosene 56 b,diesel 56 c, and/or vacuumgas oil bottoms 56 d. That is, low pressure steam enters thefractionator 56 throughinput line 57, and the input hydrocarbon stream is divided into itsvarious component outputs 56 a-56 d based upon their differing boiling points, as is known in the art. Thenaphtha output 56 a of thefractionator 56 is cooled before entering areceiver 58, and the output hydrocarbon liquid is then divided so that a portion is recycled into the fractionator, and a portion is output as a hydrocarbon output. Sour water is removed from thereceiver 58 throughline 59. - The reduction in chlorides in the hydrotreater allows for reduction in the amount of wash water used throughout the hydrotreating process. In particular, less wash water is required in upstream and downstream process line of
air cooler 46. This leads to a commensurate reduction in the amount of sour water produced during hydrotreating. - Light vacuum gas oil (LVGO) is the component of the hydrotreating process that is most vulnerable to chloride contamination. Accordingly, it follows that the LVGO stream is the primary target for chloride adsorption, as is shown in the FIGURE. However, those of skill in the art will recognize that this chloride adsorption process can be adapted for use on other hydrocarbon streams either in place of or in addition to its use on the LVGO stream, without departing from the scope of this invention.
- While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment is merely an example, and is not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those of skill in the art with a convenient road map for implementing an exemplary embodiment of the invention. It will be understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.
Claims (20)
1. A method for processing hydrocarbons, the method comprising:
providing a hydrocarbon stream including chlorides from one or more of a crude, vacuum or coker column;
contacting the provided hydrocarbon stream with an adsorbent capable of adsorbing the chlorides from the hydrocarbon stream; and
providing the dechlorinated hydrocarbon stream to a hydrotreater reactor.
2. The method of claim 1 , wherein the provided hydrocarbon stream comprises one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light light coker gas oil, vacuum column overhead, cracked naphtha, straight run naphtha, and mixtures thereof.
3. The method of claim 2 , wherein the hydrocarbon stream comprises light vacuum gas oil, heavy vacuum gas oil, heavy coker gas oil and naphtha.
4. The method of claim 1 , wherein the provided hydrocarbon stream has a chloride content up to 40 parts per million by weight, and the de-chlorinated stream has a chloride content in a range of less than 1 part per million, by weight.
5. The method of claim 1 , wherein said adsorbent includes one or more of alumina, alumino-silicate, and a mixture thereof.
6. The method of claim 1 , wherein said step of contacting comprises contacting the provided hydrocarbon stream with the adsorbent while the hydrocarbon stream is at a temperature greater than or equal to ambient room temperature and up to 130° C.
7. The method of claim 6 , wherein said temperature is approximately 125° C.
8. The method of claim 1 , where the hydrocarbon stream includes organic chlorides and inorganic chlorides.
9. A hydrocarbon hydrotreating device comprising:
a crude, vacuum and/or coker column;
an adsorbent bed disposed downstream of said crude, vacuum and/or coker column and in fluid communication with said crude, vacuum and/or coker column to contact a hydrocarbon stream from said crude, vacuum and/or coker column with an adsorbent in said adsorbent bed, said adsorbent bed capable of adsorbing chlorides; and
a hydrotreater reactor disposed downstream of said adsorbent bed and in fluid communication with said adsorbent bed.
10. The hydrocarbon hydrotreating device of claim 9 , wherein the hydrocarbon stream includes one or more of light vacuum gas oil, heavy vacuum gas oil, heavy atmospheric gas oil, heavy coker gas oil, light coker gas oil, light light coker gas oil, vacuum column overhead, cracked naphtha, straight run naphtha, and mixtures thereof.
11. The hydrocarbon hydrotreating device of claim 9 , wherein the hydrocarbon stream includes light vacuum gas oil, heavy vacuum gas oil, heavy coker gas oil and naphtha.
12. The hydrocarbon hydrotreating device of claim 9 , wherein the downstream of said adsorbent bed is combined with a gas oil combined feed prior to entering said hydrotreater reactor.
13. The hydrocarbon hydrotreating device of claim 9 , wherein said adsorbent bed contains an adsorbent including one or more of alumina, alumino-silicate and a mixture thereof.
14. The hydrocarbon hydrotreating device of claim 9 , wherein the hydrocarbon stream enters said adsorbent bed having a chloride content up to 40 parts per million by weight, and leaves said adsorbent bed having a chloride content in a range of less than 1 part per million, by weight.
15. The hydrocarbon hydrotreating device of claim 9 , wherein the hydrocarbon stream enters said adsorbent bed at a temperature equal to or greater than ambient room temperature and up to 130° C.
16. The hydrocarbon hydrotreating device of claim 15 , wherein said temperature is approximately 125° C.
17. The hydrocarbon hydrotreating device of claim 9 , where the hydrocarbon stream includes organic chlorides and inorganic chlorides.
18. A hydrocarbon hydrotreating device comprising:
a crude, vacuum and/or coker column;
an adsorbent bed containing an adsorbent including one or more of alumina, alumino-silicate and a mixture thereof and disposed downstream of said crude, vacuum and/or coker column, so that said adsorbent contacts a hydrocarbon stream from said crude, vacuum, and/or coker column; and
a hydrotreater reactor disposed downstream of said adsorbent bed and in fluid communication with said adsorbent bed.
19. The hydrocarbon hydrotreating device of claim 18 , wherein the hydrocarbon stream includes organic chlorides and inorganic chlorides, and enters said adsorbent bed at a temperature equal to or greater than ambient room temperature and up to 130° C.
20. The hydrocarbon hydrotreating device of claim 18 , wherein the downstream of said adsorbent bed is combined with a gas oil combined feed prior to entering said hydrotreater reactor.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/972,096 US20150053589A1 (en) | 2013-08-21 | 2013-08-21 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
CN201480049553.4A CN105518106A (en) | 2013-08-21 | 2014-08-13 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
PCT/US2014/050840 WO2015026592A1 (en) | 2013-08-21 | 2014-08-13 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
RU2016109057A RU2016109057A (en) | 2013-08-21 | 2014-08-13 | INSTALLATION OF HYDRO-CLEANING OF HYDROCARBONS AND METHOD FOR REMOVING CHLORIDES FROM HYDROCARBON FLOW |
EP14838207.0A EP3036310A4 (en) | 2013-08-21 | 2014-08-13 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/972,096 US20150053589A1 (en) | 2013-08-21 | 2013-08-21 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
Publications (1)
Publication Number | Publication Date |
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US20150053589A1 true US20150053589A1 (en) | 2015-02-26 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US13/972,096 Abandoned US20150053589A1 (en) | 2013-08-21 | 2013-08-21 | Hydrocarbon hydrotreating device and method for removing chloride from a hydrocarbon stream |
Country Status (5)
Country | Link |
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US (1) | US20150053589A1 (en) |
EP (1) | EP3036310A4 (en) |
CN (1) | CN105518106A (en) |
RU (1) | RU2016109057A (en) |
WO (1) | WO2015026592A1 (en) |
Cited By (3)
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WO2018025103A1 (en) | 2016-08-01 | 2018-02-08 | Sabic Global Technologies, B.V. | Dechlorination of mixed plastics pyrolysis oils using devolatilization extrusion and chloride scavengers |
CN109694737A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of dechlorination method of alkylate oil |
US20220010213A1 (en) * | 2020-07-10 | 2022-01-13 | Uop Llc | Process for pvc-containing mixed plastic waste pyrolysis |
Families Citing this family (2)
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EP4058536A1 (en) * | 2019-11-13 | 2022-09-21 | Topsoe A/S | Halides removal washing system for a hydrocarbon stream |
US20230287282A1 (en) | 2020-04-07 | 2023-09-14 | Totalenergies Onetech Belgium | Purification of waste plastic based oil with a high temperature hydroprocessing |
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2013
- 2013-08-21 US US13/972,096 patent/US20150053589A1/en not_active Abandoned
-
2014
- 2014-08-13 WO PCT/US2014/050840 patent/WO2015026592A1/en active Application Filing
- 2014-08-13 EP EP14838207.0A patent/EP3036310A4/en not_active Withdrawn
- 2014-08-13 CN CN201480049553.4A patent/CN105518106A/en active Pending
- 2014-08-13 RU RU2016109057A patent/RU2016109057A/en not_active Application Discontinuation
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Cited By (4)
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WO2018025103A1 (en) | 2016-08-01 | 2018-02-08 | Sabic Global Technologies, B.V. | Dechlorination of mixed plastics pyrolysis oils using devolatilization extrusion and chloride scavengers |
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CN109694737A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of dechlorination method of alkylate oil |
US20220010213A1 (en) * | 2020-07-10 | 2022-01-13 | Uop Llc | Process for pvc-containing mixed plastic waste pyrolysis |
Also Published As
Publication number | Publication date |
---|---|
WO2015026592A1 (en) | 2015-02-26 |
RU2016109057A3 (en) | 2018-05-22 |
RU2016109057A (en) | 2017-09-18 |
EP3036310A4 (en) | 2017-03-22 |
EP3036310A1 (en) | 2016-06-29 |
CN105518106A (en) | 2016-04-20 |
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