WO2005113425A1 - Recovery of waste water originating from synthesis processes - Google Patents

Recovery of waste water originating from synthesis processes Download PDF

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Publication number
WO2005113425A1
WO2005113425A1 PCT/ZA2005/000068 ZA2005000068W WO2005113425A1 WO 2005113425 A1 WO2005113425 A1 WO 2005113425A1 ZA 2005000068 W ZA2005000068 W ZA 2005000068W WO 2005113425 A1 WO2005113425 A1 WO 2005113425A1
Authority
WO
WIPO (PCT)
Prior art keywords
wastewater
water
synthesis gas
methanol
production unit
Prior art date
Application number
PCT/ZA2005/000068
Other languages
French (fr)
Other versions
WO2005113425B1 (en
Inventor
Desmond Johann Clur
Gareth David Huntley Shaw
Original Assignee
The Petroleum Oil And Gas Corporation Of South Africa (Pty) Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Petroleum Oil And Gas Corporation Of South Africa (Pty) Ltd. filed Critical The Petroleum Oil And Gas Corporation Of South Africa (Pty) Ltd.
Publication of WO2005113425A1 publication Critical patent/WO2005113425A1/en
Publication of WO2005113425B1 publication Critical patent/WO2005113425B1/en

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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
    • 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
    • C01B2203/061—Methanol production
    • 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 wastewater from Gas to Liquids (GTL) synthesis processes.
  • Synthesis gas carbon monoxide and hydrogen
  • Methanol plant for conversion into methanol
  • 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 Methanol Plant is to convert synthesis gas from the Synthesis Gas Production Unit into methanol.
  • the methanol is converted to propylene in a Methanol to Propylene (MTP) reactor.
  • MTP Methanol to Propylene
  • the propylene is then converted to distillates in a Catalytic Conversion of Olefins to Distillates (COD) plant.
  • 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 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 wastewater derived from a process selected from a group comprising a Methanol production process and a Methanol to Propylene (MTP) process which method includes the step of conducting the wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
  • MTP Methanol to Propylene
  • the 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 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.
  • 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.
  • 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.
  • the gas leaves the column 14 at the top and is water-saturated.
  • Circulation water 16 enters at the top of the saturator column 14
  • 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 Methanol Production Plant or Methanol to Propylene (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 wastewater 36 from the Methanol Plant 1 and / or the MTP Plant 2 in stead of routing the wastewater to a wastewater treatment plant 38 thereby freeing process condensate as surplus process condensate 40 for other uses.
  • Process equipment associated with the biological treatment of 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;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The invention provides a method of utilising wastewater derived from a process selected from a group comprising a Methanol production process and a Methanol to Propylene (MTP) process, which method includes the step of conducting the 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 Waste Water Originating from Synthesis Processes
Field of the Invention
The invention relates to the recovery of wastewater from Gas to Liquids (GTL) 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 Methanol plant for conversion into methanol.
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 Methanol Plant is to convert synthesis gas from the Synthesis Gas Production Unit into methanol.
The methanol is converted to propylene in a Methanol to Propylene (MTP) reactor. The propylene is then converted to distillates in a Catalytic Conversion of Olefins to Distillates (COD) plant.
Significant quantities of wastewater are generated in the Methanol and Methanol to Propylene (MTP) processes. Component
Methanol Ethanol C3-alcohols Aldehydes and Ketones Total organic acids Total hydrocarbons Carbon monoxide and -dioxide Nitrogen and Argon
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:
Figure imgf000004_0001
The applicant has found that the above listed contaminants have no negative impact on the synthesis gas process or catalyst. Traces of catalyst 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 wastewater derived from a process selected from a group comprising a Methanol production process and a Methanol to Propylene (MTP) process, which method includes the step of conducting the wastewater to a saturator column of a Synthesis Gas Production Unit for saturating a hydrocarbon gas stream of the Synthesis Gas Production Unit.
The 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.
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 the wastewater and substituting synthesis gas process condensate with 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. The gas leaves the column 14 at the top and is water-saturated.
Circulation water 16 enters at the top of the saturator column 14 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 Methanol Production Plant or Methanol to Propylene (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 wastewater 36 from the Methanol Plant 1 and / or the MTP Plant 2 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 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 wastewater directly to the saturator column without first being treated in a primary distillation section.

Claims

Claims
1. A method of utilising wastewater derived from a process selected from a Methanol production process or a Methanol to Propylene process, which method includes the step of conducting the 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 wastewater is used for saturation with any other water source.
3. A method as claimed in Claim 1 or Claim 2, wherein the 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 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 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 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 wastewater substantially as described and claimed herein.
PCT/ZA2005/000068 2004-05-20 2005-05-17 Recovery of waste water originating from synthesis processes WO2005113425A1 (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US57355104P 2004-05-20 2004-05-20
ZA2004/3895 2004-05-20
US60/573,551 2004-05-20
ZA200403895 2004-05-20
US65540205P 2005-02-23 2005-02-23
US60/655,402 2005-02-23
ZA2005/1586 2005-02-23
ZA200501586 2005-02-23

Publications (2)

Publication Number Publication Date
WO2005113425A1 true WO2005113425A1 (en) 2005-12-01
WO2005113425B1 WO2005113425B1 (en) 2005-12-22

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795684A (en) * 2012-08-29 2012-11-28 庞玉学 Treatment method of organic waste water of coal-to-liquids
EP2681292A1 (en) * 2011-03-03 2014-01-08 SRI International Gasification of a carbonaceous material
WO2016050722A1 (en) * 2014-09-30 2016-04-07 Shell Internationale Research Maatschappij B.V. Saturator and method for reusing water from a fischer-tropsch reactor

Citations (9)

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Publication number Priority date Publication date Assignee Title
US4048250A (en) * 1975-04-08 1977-09-13 Mobil Oil Corporation Conversion of natural gas to gasoline and LPG
US4587008A (en) * 1983-11-15 1986-05-06 Shell Oil Company Process comprising reforming, synthesis, and hydrocracking
US5053581A (en) * 1988-06-27 1991-10-01 Exxon Research & Engineering Company Process for recycling and purifying condensate from a hydrocarbon or alcohol synthesis process
US5500449A (en) * 1986-05-08 1996-03-19 Rentech, Inc. Process for the production of hydrocarbons
WO1997012118A1 (en) * 1995-09-25 1997-04-03 Den Norske Stats Oljeselskap A/S Method and system for the treatment of a well stream from an offshore oil field
EP0989093A2 (en) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products
WO2001060773A1 (en) * 2000-02-15 2001-08-23 Syntroleum Corporation System and method for preparing a synthesis gas stream and converting hydrocarbons
WO2003048035A1 (en) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Process and apparatus for steam-methane reforming
WO2004103896A1 (en) * 2003-05-21 2004-12-02 Davy Process Technology Limited Process comprising a synthesis gas formation and a hydrocarbon product formation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048250A (en) * 1975-04-08 1977-09-13 Mobil Oil Corporation Conversion of natural gas to gasoline and LPG
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
US5053581A (en) * 1988-06-27 1991-10-01 Exxon Research & Engineering Company Process for recycling and purifying condensate from a hydrocarbon or alcohol synthesis process
WO1997012118A1 (en) * 1995-09-25 1997-04-03 Den Norske Stats Oljeselskap A/S Method and system for the treatment of a well stream from an offshore oil field
EP0989093A2 (en) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products
WO2001060773A1 (en) * 2000-02-15 2001-08-23 Syntroleum Corporation System and method for preparing a synthesis gas stream and converting hydrocarbons
WO2003048035A1 (en) * 2001-12-05 2003-06-12 Gtl Microsystems Ag Process and apparatus for steam-methane reforming
WO2004103896A1 (en) * 2003-05-21 2004-12-02 Davy Process Technology Limited Process comprising a synthesis gas formation and a hydrocarbon product formation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2681292A1 (en) * 2011-03-03 2014-01-08 SRI International Gasification of a carbonaceous material
CN103842476A (en) * 2011-03-03 2014-06-04 斯坦福国际咨询研究所 Gasification of a carbonaceous material
EP2681292A4 (en) * 2011-03-03 2014-11-12 Stanford Res Inst Int Gasification of a carbonaceous material
CN102795684A (en) * 2012-08-29 2012-11-28 庞玉学 Treatment method of organic waste water of coal-to-liquids
WO2016050722A1 (en) * 2014-09-30 2016-04-07 Shell Internationale Research Maatschappij B.V. Saturator and method for reusing water from a fischer-tropsch reactor
EA035027B1 (en) * 2014-09-30 2020-04-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Saturator and method for reusing water from a fischer-tropsch reactor

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