WO2005113426A1 - Recovery of water originating from low temperature fischer-tropsch synthesis processes - Google Patents
Recovery of water originating from low temperature fischer-tropsch synthesis processes Download PDFInfo
- Publication number
- WO2005113426A1 WO2005113426A1 PCT/ZA2005/000069 ZA2005000069W WO2005113426A1 WO 2005113426 A1 WO2005113426 A1 WO 2005113426A1 ZA 2005000069 W ZA2005000069 W ZA 2005000069W WO 2005113426 A1 WO2005113426 A1 WO 2005113426A1
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- WO
- WIPO (PCT)
- Prior art keywords
- low temperature
- water
- wastewater
- synthesis gas
- fisher
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using 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
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0888—Methods of cooling by evaporation of a fluid
- C01B2203/0894—Generation of steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
Definitions
- the invention relates to the recovery of water from Low Temperature Fischer Tr ⁇ psch Synthesis processes.
- Synthesis gas carbon monoxide and hydrogen
- a Low Temperature Fischer-Tropsch Synthesis Unit for conversion into liquid products.
- One of the process steps in the Synthesis Gas Production Unit entails the saturation of pre-treated natural gas feedstock with water. This is achieved in a packed column in which the gas is contacted countercurrently with water. Steam is added to the gas to ensure that the correct steam/carbon ratio is maintained for the production of synthesis gas in the downstream reactor section.
- synthesis gas process condensate water recovered from the synthesis gas cooldown section of the Synthesis Gas Production Unit is used for saturation.
- Such process condensate water is relatively good quality water.
- the purpose of the Low Temperature Fischer-Tr ⁇ psch Synthesis Unit is to convert synthesis gas from the Synthesis Gas Unit into liquid Fischer-Tropsch synthetic crude components.
- the overall chemistry of the process can be described by the following chemical equation:
- Products from the Low Temperature Fischer-Tropsch Synthesis process include hydrocarbons symbolised by the term "( - CH 2 - )" and consists of heavy- and light oil, wax and water. Tailgas including unconverted synthesis gas is recycled to the process, while the hydrocarbon products are normally further refined to naphtha and automotive diesel.
- the majority of the alcohols and organic material contained in the water is removed in a primary distillation tower, before being further treated in a biological wastewater treatment plant. This is done to reduce the organic load on the biological treatment plant and therefore to reduce the size and cost of a suitable plant as far as possible.
- the typical composition of treated water from the distillation column i.e the quality of the water being fed to the biological wastewater treatment plant is as follows:
- Traces of cobalt, rhenium and aluminium may be present in the water. It may be necessary in some instances to remove these traces or mitigate the effect of the traces on the synthesis gas catalyst.
- the purpose of the biological wastewater treatment plant is to treat the water to a quality suitable for re-use or disposal into a receiving water body.
- a method of utilising Low Temperature Fisher-Tropsch wastewater which method includes the step of conducting Low Temperature Fisher-Tropsch wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
- the Low Temperature Fisher-Tropsch wastewater may be used for saturation with any other water source, if needed, preferably synthesis gas process condensate recovered from the synthesis gas cooldown section of the Synthesis Gas Production Unit.
- the Low Temperature Fischer Tr ⁇ psch (LTFT) process may use a slurry bubble reactor with a suspended cobalt catalyst.
- the water may be routed directly to the saturator column in the Synthesis Gas Production Unit.
- the water may be routed from a primary distillation section to the saturator column. In another embodiment, the water may be routed from upstream the primary distillation section to the saturator column.
- water may be taken from both before the primary distillation section and from the primary distillation section to the saturator column.
- Synthesis gas process condensate recovered from the Synthesis Gas cooldown section of the plant is of a better quality than Low Temperature Fisher- Tr ⁇ psch wastewater and substituting synthesis gas process condensate with Fischer Tropsch wastewater has apparent advantages.
- the water recovered from the condensate may thus be used for a number of uses such as boiler feed water, agricultural water or the like.
- the condensate water may be demineralised prior to use as boiler feed water.
- Natural gas 10 is pre treated at a pre treatment unit 12 enters the bottom of the saturator column 14 at a temperature and pressure of 104 C C and 40500 kPag respectively.
- the gas leaves the column 14 at the top and is water-saturated at a temperature and pressure of 199 °C and 3900 kPag respectively.
- Circulation water 16 enters at the top of the saturator column 14 at a temperature and pressure of 220 °C and 4500 kPag respectively.
- the temperature and pressure of the water leaving the column 14 at the bottom is 134 °C and 4100 kPag respectively.
- Water 18 from the bottom of the column 14 is supplemented and mixed with synthesis gas process condensate 20, which is recovered from the synthesis gas cooldown section 22 of the plant.
- Synthesis gas 24 is routed to the Low Temperature Fisher- Tr ⁇ psch plant (not shown).
- the combined water stream 26 is then pumped to the top of the saturator column 14.
- Surplus water 28 from the column 14 is treated in a process condensate stripping section 30, before being routed to the Demineralisation Unit 32 of the plant.
- Purified water 34 from the Demineralisation Unit 32 is used for the production of boiler feed water and steam.
- circulation water 16 is supplemented by Low Temperature Fisher- Tr ⁇ psch wastewater 36 from a primary distillation section 37 in stead of routing the wastewater to a wastewater treatment plant 38 thereby freeing process condensate as surplus process condensate 40 for other uses.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method of utilising Low Temperature Fisher-Tropsch wastewater, which method includes the step of conducting Low Temperature Fisher-Tropsch wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
Description
Recovery of Water Originating from Low Temperature Fischer-Trδpsch Synthesis Processes
Field of the Invention
The invention relates to the recovery of water from Low Temperature Fischer Trόpsch Synthesis processes.
Background to the Invention
Presently, natural gas is converted to synthesis gas in a Synthesis Gas Production Unit.
Synthesis gas (carbon monoxide and hydrogen) is required as feedstock to a Low Temperature Fischer-Tropsch Synthesis Unit for conversion into liquid products.
One of the process steps in the Synthesis Gas Production Unit entails the saturation of pre-treated natural gas feedstock with water. This is achieved in a packed column in which the gas is contacted countercurrently with water. Steam is added to the gas to ensure that the correct steam/carbon ratio is maintained for the production of synthesis gas in the downstream reactor section.
Normally, synthesis gas process condensate water recovered from the synthesis gas cooldown section of the Synthesis Gas Production Unit is used for saturation. Such process condensate water is relatively good quality water.
The purpose of the Low Temperature Fischer-Trδpsch Synthesis Unit is to convert synthesis gas from the Synthesis Gas Unit into liquid Fischer-Tropsch synthetic crude components. The overall chemistry of the process can be described by the following chemical equation:
2H2 + CO ( - CH2 - ) + H2O
Products from the Low Temperature Fischer-Tropsch Synthesis process include hydrocarbons symbolised by the term "( - CH2 - )" and consists of heavy- and light oil,
wax and water. Tailgas including unconverted synthesis gas is recycled to the process, while the hydrocarbon products are normally further refined to naphtha and automotive diesel.
Significant quantities of wastewater are also generated in the Low Temperature Fischer- Tropsch process. The typical composition of wastewater originating from the Low Temperature Fischer Trδpsch Synthesis process, is as follows:
The majority of the alcohols and organic material contained in the water is removed in a primary distillation tower, before being further treated in a biological wastewater treatment plant. This is done to reduce the organic load on the biological treatment plant and therefore to reduce the size and cost of a suitable plant as far as possible.
The typical composition of treated water from the distillation column i.e the quality of the water being fed to the biological wastewater treatment plant, is as follows:
The applicant has found that the above listed contaminants have no negative impact on the synthesis gas process or catalyst.
Traces of cobalt, rhenium and aluminium may be present in the water. It may be necessary in some instances to remove these traces or mitigate the effect of the traces on the synthesis gas catalyst.
The purpose of the biological wastewater treatment plant is to treat the water to a quality suitable for re-use or disposal into a receiving water body.
Summary of the Invention
According to the invention, there is provided a method of utilising Low Temperature Fisher-Tropsch wastewater, which method includes the step of conducting Low Temperature Fisher-Tropsch wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
The Low Temperature Fisher-Tropsch wastewater may be used for saturation with any other water source, if needed, preferably synthesis gas process condensate recovered from the synthesis gas cooldown section of the Synthesis Gas Production Unit.
The Low Temperature Fischer Trόpsch (LTFT) process may use a slurry bubble reactor with a suspended cobalt catalyst.
In one embodiment, the water may be routed directly to the saturator column in the Synthesis Gas Production Unit.
In another embodiment the water may be routed from a primary distillation section to the saturator column.
In another embodiment, the water may be routed from upstream the primary distillation section to the saturator column.
Yet further, water may be taken from both before the primary distillation section and from the primary distillation section to the saturator column.
The advantages of each of the abovementioned embodiments will depend on the specifics of the synthesis gas and LTFT process used. The advantages will relate to cost savings.
Synthesis gas process condensate recovered from the Synthesis Gas cooldown section of the plant is of a better quality than Low Temperature Fisher- Trόpsch wastewater and substituting synthesis gas process condensate with Fischer Tropsch wastewater has apparent advantages.
The water recovered from the condensate may thus be used for a number of uses such as boiler feed water, agricultural water or the like.
The condensate water may be demineralised prior to use as boiler feed water.
Specific Description of the Invention
The description that follows, together with Figure 1 associated therewith, is intended to illustrate the invention only and not to limit the scope of the invention in any way whatsoever.
Natural gas 10 is pre treated at a pre treatment unit 12 enters the bottom of the saturator column 14 at a temperature and pressure of 104 CC and 40500 kPag respectively. The gas leaves the column 14 at the top and is water-saturated at a temperature and pressure of 199 °C and 3900 kPag respectively.
Circulation water 16 enters at the top of the saturator column 14 at a temperature and pressure of 220 °C and 4500 kPag respectively. The temperature and pressure of the water leaving the column 14 at the bottom is 134 °C and 4100 kPag respectively. Water 18 from the bottom of the column 14 is supplemented and mixed with synthesis gas
process condensate 20, which is recovered from the synthesis gas cooldown section 22 of the plant. Synthesis gas 24 is routed to the Low Temperature Fisher- Trδpsch plant (not shown). The combined water stream 26 is then pumped to the top of the saturator column 14. Surplus water 28 from the column 14 is treated in a process condensate stripping section 30, before being routed to the Demineralisation Unit 32 of the plant. Purified water 34 from the Demineralisation Unit 32 is used for the production of boiler feed water and steam.
In one embodiment of the invention, circulation water 16 is supplemented by Low Temperature Fisher- Trόpsch wastewater 36 from a primary distillation section 37 in stead of routing the wastewater to a wastewater treatment plant 38 thereby freeing process condensate as surplus process condensate 40 for other uses.
The advantages of the treatment system of the embodiment described above, compared to existing systems, are as follows:
Process equipment associated with the biological treatment of Fischer Trδpsch wastewater can be eliminated, as the water will be routed directly to the saturator column in the Synthesis Gas Unit. This will result in substantial savings in capital costs. Also, the operating costs associated with biological treatment of wastewater will be significantly reduced, primarily due to savings in the costs of chemicals required;
Significant quantities of water of a very good quality (process condensate) will become available for use elsewhere e.g. for purposes of irrigation, recreational use, integration into the utility networks of neighbouring companies etc. This is not only a huge advantage to arid- and semi-arid countries, but water from the Gas to Liquids complex is now available as a saleable product, which will generate additional income;
The requirement for make-up water from the Raw Water Treatment Plant to the Demineralisation Unit will under normal operating conditions be eliminated, as the demand for water will be supplied from process condensate from the Synthesis Gas Unit. This implies that the design capacity of the Raw Water
Treatment Plant can be reduced, which will result in further savings in capital costs;
Further savings in capital costs may be realised by routing the Fischer Trδpsch wastewater directly to the saturator column without first being treated in a primary distillation section.
Claims
1. A method of utilising Low Temperature Fisher-Tropsch wastewater, which method includes the step of conducting Low Temperature Fisher-Tropsch wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
2. A method as claimed in Claim 1, wherein the Low Temperature Fisher-Trδpsch wastewater is used for saturation with any other water source.
3. A method as claimed in Claim 1 or Claim 2, wherein the Low Temperature Fisher-Trδpsch wastewater is routed directly to the saturator column in the Synthesis Gas Production Unit.
4. A method as claimed in Claim 1 or Claim 2, wherein the Low Temperature Fisher-Trδpsch wastewater is routed from a primary distillation section to the saturator column.
5. A method as claimed in Claim 1 or Claim 2, wherein the Low Temperature Fisher-Tropsch wastewater is routed from upstream a primary distillation section to the saturator column.
6. A method as claimed in Claim 1 or Claim 2, wherein the Low Temperature Fisher-Trδpsch wastewater is routed from both before a primary distillation section and from the primary distillation section to the saturator column.
7. A method as claimed in any one of claims 1 to 6, which includes the step of recovering water from synthesis condensate for use as boiler feed water.
8. A method of utilising Low Temperature Fisher-Tropsch wastewater substantially as described and claimed herein.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57355104P | 2004-05-20 | 2004-05-20 | |
| US60/573,551 | 2004-05-20 | ||
| ZA2004/3895 | 2004-05-20 | ||
| ZA200403895 | 2004-05-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2005113426A1 true WO2005113426A1 (en) | 2005-12-01 |
| WO2005113426B1 WO2005113426B1 (en) | 2005-12-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ZA2005/000069 WO2005113426A1 (en) | 2004-05-20 | 2005-05-17 | Recovery of water originating from low temperature fischer-tropsch synthesis processes |
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| Country | Link |
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| WO (1) | WO2005113426A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069581A1 (en) | 2008-12-19 | 2010-06-24 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| WO2010086182A1 (en) | 2009-01-30 | 2010-08-05 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| ITMI20090769A1 (en) * | 2009-05-06 | 2010-11-07 | Eni Spa | PROCESS FOR THE PURIFICATION OF AN AQUEOUS CURRENT COMING FROM THE FISCHER-TROPSCH REACTION |
| ITMI20091718A1 (en) * | 2009-10-08 | 2011-04-09 | Eni Spa | PROCESS FOR THE PURIFICATION OF AN AQUEOUS CURRENT COMING FROM THE FISCHER-TROPSCH REACTION |
| DE102014006996A1 (en) * | 2014-05-13 | 2015-11-19 | CCP Technology GmbH | Process and apparatus for the production of synthetic hydrocarbons |
| US9365765B2 (en) | 2013-03-15 | 2016-06-14 | Velocys, Inc. | Generation of hydrocarbon fuels having a reduced environmental impact |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10260005B2 (en) | 2016-08-05 | 2019-04-16 | Greyrock Technology LLC | Catalysts, related methods and reaction products |
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| US4587008A (en) * | 1983-11-15 | 1986-05-06 | Shell Oil Company | Process comprising reforming, synthesis, and hydrocracking |
| US5500449A (en) * | 1986-05-08 | 1996-03-19 | Rentech, Inc. | Process for the production of hydrocarbons |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069581A1 (en) | 2008-12-19 | 2010-06-24 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| WO2010086182A1 (en) | 2009-01-30 | 2010-08-05 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| CN102458620A (en) * | 2009-05-06 | 2012-05-16 | 艾尼股份公司 | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| WO2010127773A1 (en) * | 2009-05-06 | 2010-11-11 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| ITMI20090769A1 (en) * | 2009-05-06 | 2010-11-07 | Eni Spa | PROCESS FOR THE PURIFICATION OF AN AQUEOUS CURRENT COMING FROM THE FISCHER-TROPSCH REACTION |
| CN102458620B (en) * | 2009-05-06 | 2015-01-14 | 艾尼股份公司 | Process for the purification of an aqueous stream coming from the fischer-tropsch reaction |
| US9296628B2 (en) | 2009-05-06 | 2016-03-29 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the Fischer-Tropsch reaction |
| ITMI20091718A1 (en) * | 2009-10-08 | 2011-04-09 | Eni Spa | PROCESS FOR THE PURIFICATION OF AN AQUEOUS CURRENT COMING FROM THE FISCHER-TROPSCH REACTION |
| WO2011042806A1 (en) | 2009-10-08 | 2011-04-14 | Eni S.P.A. | Process for the purification of an aqueous stream coming from the fischer tropsch reaction |
| CN102666395A (en) * | 2009-10-08 | 2012-09-12 | 艾尼股份公司 | Process for the purification of an aqueous stream coming from the Fischer-Tropsch reaction |
| US9365765B2 (en) | 2013-03-15 | 2016-06-14 | Velocys, Inc. | Generation of hydrocarbon fuels having a reduced environmental impact |
| US9994763B2 (en) | 2013-03-15 | 2018-06-12 | Velocys, Inc. | Generation of hydrocarbon fuels having a reduced environmental impact |
| DE102014006996A1 (en) * | 2014-05-13 | 2015-11-19 | CCP Technology GmbH | Process and apparatus for the production of synthetic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005113426B1 (en) | 2005-12-22 |
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