AU2005304604B2 - Treatment of high molar mass hydrocarbon streams - Google Patents
Treatment of high molar mass hydrocarbon streams Download PDFInfo
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- AU2005304604B2 AU2005304604B2 AU2005304604A AU2005304604A AU2005304604B2 AU 2005304604 B2 AU2005304604 B2 AU 2005304604B2 AU 2005304604 A AU2005304604 A AU 2005304604A AU 2005304604 A AU2005304604 A AU 2005304604A AU 2005304604 B2 AU2005304604 B2 AU 2005304604B2
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- Australia
- Prior art keywords
- stream
- wax
- aqueous fluid
- wax stream
- mass
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- 239000004215 Carbon black (E152) Substances 0.000 title claims description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000012530 fluid Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000010977 unit operation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 239000001993 wax Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 propanoic acetic Chemical compound 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- 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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
Landscapes
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
WO 2006/053350 PCT/ZA2005/000167 TREATMENT OF HIGH MOLAR MASS HYDROCARBON STREAMS Field of the Invention 5 The invention relates to the treatment of high molar mass hydrocarbon streams for the removal of contaminants therefrom. These streams might comprise synthetic waxes such as those produced from synthesis gas via the Fischer-Tropsch reaction. 10 Background to the Invention F-T derived product streams, such as waxes, contain oxygenates and to a certain extent metals and/or metal species. Ketones, aldehydes, alcohols, esters and carboxylic acids are the main constituents of the oxygenate 15 fraction. Carboxylic acids and alcohols are able to form under appropriate conditions carboxylate and/or alkoxide complexes and/or metalloxanes with the metals and/or metal species present. These metal carboxylates and/or alkoxides and/or metalloxanes may form deposits in processing equipment and catalyst beds. In addition, fine particulates of less than 1 pm in diameter 20 may be stabilized by surface-active compounds (such as the oxygenates) allowing them to remain in suspension. However, when this surface layer is disrupted, the particulates precipitate forming deposits. Eventually the deposits in the catalyst beds may grow to such an extent that shutdowns of reactors are inevitable. 25 Metals that might be part of the metal species of concern comprise aluminium, and/or silicon, and/or titanium, and/or zirconium, and/or cobalt, and/or iron, and/or alkaline earth elements such as calcium and barium etc. 30 The identified problem may be summarized as the plugging of downstream processing catalyst by a constituent of said product streams or a reaction product of a constituent of said product streams.
2 In this specification, whenever the terms contaminate contaminant, or related words are used, it is intended to convey the concept of an undesired constituent or a reaction product thereof and not necessarily an external impurity, unless the contrary is clearly indicated by the context. 5 Summary of the Invention The invention provides a process as defined in claim 1 for the removal of contaminants from a high molar mass hydrocarbon stream in hydrocarbon processing. The method includes at least two distinct steps: formation and growth of particles which include contaminant, said particles being 10 of sufficient size to facilitate removal thereof, said formation and growth being promoted by treating said hydrocarbon stream with an aqueous fluid including an acid; and removal of at least some of the particles from the process stream by one or more particle removal unit operations. 15 The particle removal unit operations may be filtration. The process includes maintaining the contaminated hydrocarbon stream with the aqueous fluid at conditions of elevated temperature. The aqueous fluid is admixed with said hydrocarbon stream. The high molar mass hydrocarbon stream is a synthetic wax and might be a 20 synthetic wax such as that produced from synthesis gas via the Fischer-Tropsch reaction. The aqueous fluid may be a water stream. The water stream may be a process water stream. The aqueous fluid is mixed with the hydrocarbon stream so that water 25 constitutes from 0.25 mass% to 2 mass% of the hydrocarbon stream and the acid constitutes from 0.005 mass% to 0.5 mass% of the hydrocarbon stream.
3 Preferably the acid may constitute 0.01 mass% of the hydrocarbon stream and water may constitute 0.5 mass% of the hydrocarbon stream. The acid may be an organic acid. 5 The aqueous fluid may include water and an organic acid. The aqueous fluid may include water and maleic acid. 10 The aqueous fluid may be pumped into the hydrocarbon stream. The hydrocarbon stream with admixed aqueous fluid is passed through a mixer to homogenize the stream. The mixer is an in line mixer. 15 The temperature of the hydrocarbon with admixed aqueous fluid is maintained at a level above at least 160 0 C, typically around 170 0 C. Operation at higher temperatures is also possible. The hydrocarbon stream with admixed aqueous fluid is maintained at elevated 20 temperature for from 10 minutes to 30 minutes to allow for the formation and growth of the particles prior to filtration. The hydrocarbon stream with admixed aqueous fluid is passed into a mixing vessel which allows the correct residence time for the particle generation to take 25 place while inhibiting settling or breaking up of formed particles. The pressure in the system is maintained for particle generation and filtration to prevent water from vapourising and forming a two-phase mixture anywhere in the system, even across the filter. The minimum pressure is therefore set by the 30 operating temperature of the system. The pressure is maintained at a minimum of 6 bar and may be as high as 9 bar or even higher.
4 The level of contaminants in the hydrocarbon stream can be as high as 100 ppm but typically is around 60 ppm. The level of contaminants in the treated hydrocarbon stream is typically below 2 ppm and more often below 1 ppm. 5 Although an aqueous phase consisting essentially of water does lead to particle generation, far more rapid blocking of the filter material is observed than when acid is present. Specific Description of the Invention 10 The invention will now be described, by way of non-limiting example only, with reference to the following example with reference to the flowsheet of Figure 1. In the process of the example, a contaminated hydrocarbon stream 1 from 15 storage is heated in a preheater 11 to a temperature above 160 0 C, typically to approximately 170"C or even higher. An aqueous fluid 2 is pumped into the hydrocarbon stream while maintaining said process temperature. The resultant stream 3 then passes through a mixer 12, which is an in-line mixer, before entering a mixing vessel 13. 20 The heated mix of hydrocarbon with admixed aqueous fluid stream 3 is maintained in the mixing vessel 13 at a temperature above 160*C, preferably around 170"C, for a residence time of from 10 minutes to 30 minutes, preferably around 30 minutes, to allow for the formation and growth of the particles. The 25 mixing conditions in the mixing vessel 13 are selected to inhibit settling and to avoid breaking up of formed particles. The aqueous fluid may consist of water and an organic acid, preferably maleic acid. 30 The aqueous fluid may be mixed with the hydrocarbon stream so that water constitutes from 0.25 mass% to 2 mass% of the admixed hydrocarbon stream and the maleic acid constitutes from 0.005 mass% to 0.5 mass% of the WO 2006/053350 PCT/ZA2005/000167 admixed hydrocarbon stream. Preferably the maleic acid constitutes approximately 0.01 mass% of the admixed hydrocarbon stream and aqueous fluid constitutes approximately 0.5 mass% of the admixed hydrocarbon stream. 5 Other organic acids or short chain oxygenates which may be used include methanol, ethanol, oxalic acid, acetic acid, propanoic acetic, salicylic acid, succinic acid, tartaric acid, lactic acid, malonic acid, glycine acid, citric acid, carbonic acid, fumaric acid, phthalic acid, the anhydrides of these acids (e.g. 10 maleic anhydride) and thermal decomposition products of these acids, Also included are solid acids such as silica-alumina and/or other mixed oxide systems that possess Bronsted acidity. Although an aqueous phase consisting essentially of water does lead to 15 particle generation, the size of the solid particle generated is substantially smaller causing clogging of the filter material which blocks far more rapidly than when the selected acid is present. After treatment of the stream with the maleic acid and water mixture, the 20 stream exiting the mixing vessel 13 is filtered using a pressure leaf filter 14. Usually the method makes use, of at least two filters 14 in parallel that are operated alternately to allow the process to run continually. The filters 14 may be precoated with a suitable material such as cellulose or 25 diatomaceous earth. Filter cycle times may be improved by adding body feed (filtration aid) from the body feed tank to the hydrocarbon stream prior to filtration. It is convenient to express the Al content of the feed as the equivalent mass of AI(OH) 3 . For 30 cases where the main contaminant in the feed is Al, the body feed rate may be between 0.5 and 3 kg of body feed / kg AI(OH) 3 in the untreated hydrocarbon, more preferably around 1.5 kg of body feed / kg AI(OH) 3 in the contaminated hydrocarbon. 5 6 The system pressure is maintained at levels to ensure that there is no water flashing at any point in the process, especially across the filter medium. The pressure is maintained at above 6 bar and may be above 9 bar or even higher, depending on the system temperature. 5 Velocities in the pipes, especially those down stream of the body feed addition point, are maintained such that deposition does not occur as this could lead to blockages, but must not be so high that the formed particles break up. 10 Break up of particles causes finer particles to be caught on the filter and results in filter cycle times being drastically reduced. Example I - Treatment of Fischer-Tropsch Wax 15 Untreated Al-contaminated wax from storage was heated to 170 0 C. An aqueous fluid was pumped into the heated untreated wax so that the mixture contained 0.01 mass% maleic acid and 0.5 mass% water. The mixture was homogenized using an in-line mixer and the homogenized mixture was hereafter maintained at 170*C in a mixing tank with a 30 minute residence time. A body feed rate of 1.5 20 kg body feed/kg AI(OH) 3 complex in the untreated wax was added to the wax leaving the mixing tank. Filtration was performed using an 80 micron screen filter mesh precoated with 1 kg/m 2 of cellulose material (Arbocel (RTM) BWB 40). A filter flux of 0.5 25 m 3 /(m 2 .hr) was maintained for the duration of the run. The run length was determined by measuring the time it took for the pressure drop across the filter to exceed 1 bar at this set filter flux rate. Feed metal levels in the untreated wax feed was 24.7ppm Al in solution with 30 other metals below detection limits. The average level of Al in the treated wax over a run length of 27.6hr was 0.74 ppm at which time the pressure drop across the filter exceeded 1 bar. The average process efficiency was calculated as 97%.
WO 2006/053350 PCT/ZA2005/000167 Example 2 - Treatment of Fischer-Tropsch Wax A contaminated wax with an Al level of between 23 and 120 ppm and a Co level of between 1.8 and 6.5 ppm was continuously treated using the same 5 process described in Example 1. The wax was treated at 167 0 C using an aqueous solution of maleic acid (2 wt % concentration). The treatment performance is reported in Table 1. 7 2784073.1 -8 Table 1 Performance in Successive Treatment Cycles Cycle 1 2 3 4 Contaminated Wax e Al, ppm 23 57 83 120 " Co, ppm 1.8 2.0 6.5 2.6 Treated Wax * Al, ppm 0.31 0.34 <0.23 <0.23 " Co, ppm :0.55 <0.55 <0.55 <0.55 Al removal efficiency, % 98.7 99.4 >99.7 >99.8 Cycle Length, h 16.5 4.7 6.7 8.7 It is clear that the process matter of this invention can produce sustained results. The Al 5 separation efficiency increases with an increase in the Al content in the contaminated wax feed. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will 10 be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or 15 admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.
Claims (16)
1. A process for the removal of contaminants from a synthetic wax stream in hydrocarbon processing, said method including at least two distinct steps: -- formation and growth of particles which include contaminant, said particles being of sufficient size to facilitate filtration thereof, said formation and growth being promoted by treating said wax stream with an aqueous fluid including an acid; and - removal of at least some of the particles from the synthetic wax stream by one or more particle removal unit operations; wherein the aqueous fluid is admixed with said wax stream so that water constitutes from 0.25 mass% to 2 mass% of the wax stream and the acid constitutes from 0.005 mass% to 0.5 mass% of the wax stream, and the wax stream with admixed aqueous fluid is passed through an in-line mixer to homogenize the stream whereafter the wax stream with admixed aqueous fluid is passed into a mixing vessel wherein the temperature is maintained at above 160 0 C and the pressure at above 6 Bar for from 10 minutes to 30 minutes to allow for the formation and growth of the particles prior to filtration while inhibiting settling or breaking up of formed particles as well as to prevent water from vapourising and forming a two-phase mixture anywhere in the system, even across the filter.
2. A process as claimed in claim 1, wherein the particle removal unit operation is filtration.
3. A process as claimed in claims or claim 2, which process includes maintaining the contaminated wax stream with the aqueous fluid at conditions of elevated temperature above 1600C.
4. A process as claimed in claim 1, wherein the synthetic wax is produced from synthesis gas via the FIscher-Tropsch reaction.
5. A process as claimed in any one of the preceding claims, wherein the aqueous fluid is a water stream. 10
6. A process as claimed in claim 5, wherein the water stream is a process water stream.
7. A process as claimed in any one of the preceding claims, wherein the 5 acid constitutes 0.01 mass% of the wax stream and water constitutes 0.5 mass% of the wax stream.
8. A process as claimed in any one of the preceding claims, wherein the aqueous fluid includes water and an organic acid. 10
9. A process as claimed in any one of the preceding claims, wherein the aqueous fluid includes water and maleic acid.
10. A process as claimed in any one of the preceding claims, wherein the 15 aqueous fluid is pumped into the wax stream.
11. A process as claimed in any one of the preceding claims, wherein the temperature of the wax with admixed aqueous fluid is maintained at a level above at least 160*C. 20
12. A process as claimed in claim 11, wherein the temperature is maintained around 170*C.
13. A process as claimed in any one of the preceding claims, wherein the 25 wax stream with aqueous fluid is maintained at elevated temperature for a minimum of 1 minute.
14. A process as claimed in any one of the preceding claims, wherein the level of contaminants in the wax stream is as high as 100 ppm and in the treated 30 wax stream is below 2 ppm.
15. A process as claimed in any one of the preceding claims, wherein the level of contaminants in the wax stream is 60 ppm and in the treated wax stream is below 1 ppm. -11
16. A process as claimed in claim I substantially as hereinbefore described with reference to the accompanying drawings.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ZA200409084 | 2004-11-10 | ||
ZA2004/9084 | 2004-11-10 | ||
PCT/ZA2005/000167 WO2006053350A1 (en) | 2004-11-10 | 2005-11-08 | Treatment of high molar mass hydrocarbon streams |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2005304604A1 AU2005304604A1 (en) | 2006-05-18 |
AU2005304604B2 true AU2005304604B2 (en) | 2010-04-22 |
Family
ID=35789143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2005304604A Ceased AU2005304604B2 (en) | 2004-11-10 | 2005-11-08 | Treatment of high molar mass hydrocarbon streams |
Country Status (7)
Country | Link |
---|---|
AU (1) | AU2005304604B2 (en) |
BR (1) | BRPI0516430A (en) |
GB (1) | GB2434589B (en) |
NO (1) | NO20072339L (en) |
RU (1) | RU2388792C2 (en) |
WO (1) | WO2006053350A1 (en) |
ZA (1) | ZA200703773B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US20100249485A1 (en) * | 2007-06-18 | 2010-09-30 | Masikana Millan Mdleleni | Removal of ultra-fine particles from a Fischer Tropsch Stream |
US20130306522A1 (en) * | 2012-05-16 | 2013-11-21 | General Electric Company | Use of acid buffers as metal and amine removal aids |
DE102013106439A1 (en) | 2013-06-20 | 2014-12-24 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for removing metals from high boiling hydrocarbon fractions |
DE102013106441A1 (en) | 2013-06-20 | 2014-12-24 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for removing metals from high boiling hydrocarbon fractions |
DE102014107374A1 (en) | 2014-05-26 | 2015-11-26 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for removing metals from high boiling hydrocarbon fractions |
DE102014107375A1 (en) | 2014-05-26 | 2015-11-26 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for removing metal from high-boiling hydrocarbon fractions |
CA2974405A1 (en) | 2015-01-20 | 2016-07-28 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude (Air Liquide Sa) | Ltft catalyst fines removal |
Citations (2)
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WO2002007883A2 (en) * | 2000-07-24 | 2002-01-31 | Sasol Technology (Proprietary) Limited | Production of hydrocarbons from a synthesis gas |
WO2003012008A2 (en) * | 2001-07-27 | 2003-02-13 | Sasol Technology (Proprietary) Limited | Production of fischer-tropsch synthesis produced wax |
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US2661362A (en) * | 1947-11-26 | 1953-12-01 | Standard Oil Dev Co | Removal of oxygenated organic compounds from hydrocarbons |
US7150823B2 (en) * | 2003-07-02 | 2006-12-19 | Chevron U.S.A. Inc. | Catalytic filtering of a Fischer-Tropsch derived hydrocarbon stream |
US8022108B2 (en) * | 2003-07-02 | 2011-09-20 | Chevron U.S.A. Inc. | Acid treatment of a fischer-tropsch derived hydrocarbon stream |
BRPI0512754B1 (en) * | 2004-07-06 | 2016-03-29 | Sasol Tech Pty Ltd | hydrocarbon treatment |
US7416656B2 (en) * | 2004-07-07 | 2008-08-26 | Chevron U.S.A. Inc. | Process for removing aluminum contaminants from Fischer-Tropsch feed streams using dicarboxylic acid |
-
2005
- 2005-11-08 WO PCT/ZA2005/000167 patent/WO2006053350A1/en active Application Filing
- 2005-11-08 RU RU2007117197/04A patent/RU2388792C2/en active
- 2005-11-08 BR BRPI0516430-3A patent/BRPI0516430A/en not_active IP Right Cessation
- 2005-11-08 GB GB0710985A patent/GB2434589B/en not_active Expired - Fee Related
- 2005-11-08 AU AU2005304604A patent/AU2005304604B2/en not_active Ceased
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2007
- 2007-05-07 NO NO20072339A patent/NO20072339L/en not_active Application Discontinuation
- 2007-05-10 ZA ZA200703773A patent/ZA200703773B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2002007883A2 (en) * | 2000-07-24 | 2002-01-31 | Sasol Technology (Proprietary) Limited | Production of hydrocarbons from a synthesis gas |
WO2003012008A2 (en) * | 2001-07-27 | 2003-02-13 | Sasol Technology (Proprietary) Limited | Production of fischer-tropsch synthesis produced wax |
Also Published As
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GB2434589A (en) | 2007-08-01 |
GB2434589B (en) | 2009-02-25 |
RU2007117197A (en) | 2008-12-20 |
NO20072339L (en) | 2007-06-21 |
GB0710985D0 (en) | 2007-07-18 |
ZA200703773B (en) | 2008-06-25 |
RU2388792C2 (en) | 2010-05-10 |
AU2005304604A1 (en) | 2006-05-18 |
BRPI0516430A (en) | 2008-09-02 |
WO2006053350A1 (en) | 2006-05-18 |
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