US20170233661A1 - Conversion of oxgenates in purge from raw methanol evaporator - Google Patents
Conversion of oxgenates in purge from raw methanol evaporator Download PDFInfo
- Publication number
- US20170233661A1 US20170233661A1 US15/519,049 US201515519049A US2017233661A1 US 20170233661 A1 US20170233661 A1 US 20170233661A1 US 201515519049 A US201515519049 A US 201515519049A US 2017233661 A1 US2017233661 A1 US 2017233661A1
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- United States
- Prior art keywords
- stream
- methanol
- purge
- conversion step
- conversion
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 238000010926 purge Methods 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 23
- 239000003502 gasoline Substances 0.000 claims description 22
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 229940032007 methylethyl ketone Drugs 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- -1 LPG Chemical compound 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010457 zeolite 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- 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
- C10G2300/1011—Biomass
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the invention relates to an improved preparation process of hydrocarbons useful as gasoline compounds from a feed comprising methanol.
- Gasoline can be produced by conversion of raw methanol, pure methanol and/or dimethyl ether.
- the raw methanol is evaporated before being mixed with a recycle gas from the conversion process and send to the gasoline reactor.
- the raw methanol contains impurities in form of water and various oxygenates such as ketones, aldehydes and higher alcohols. It has surprisingly been shown that these oxygenates are concentrated in the evaporator/boiler to a degree where it effects methanol evaporation due to an increased boiling temperature. This lowers the vaporization effectivity in the evaporator/boiler/reboiler and thus decreases the methanol flow from the evaporator/boiler/reboiler.
- the oxygenates and other compounds are removed from the evaporator or similar by the purge thereby ensuring that the boiling point in the evaporator is kept within acceptable levels in order to ensure a desired flow of the gas phase methanol rich stream.
- the purge is then added to the conversion step thereby maximizing the product generation in the conversion loop as at least some of the purge oxygenates are converted. I.e. by the present process a purge is removed from the evaporator/boiler/reboiler without wasting the oxygenates in the purge, as this purge is sent to the conversion step.
- this process configuration also has the benefit of enabling the use of raw methanol as feed, thereby avoiding costly purification.
- the purge may be removed continuously or on/off for example in periodic or otherwise predetermined intervals.
- the amount and/or frequency of the purge may in some embodiments be controlled based on the need in order to maintain the flow of the gas phase methanol rich stream at a desired level.
- the conversion step can be a gasoline conversion step in which case the methanol rich stream is converted in presence of a catalyst into hydrocarbons stream which in several embodiments is within the gasoline range, such as predominantly C3-C10 hydrocarbons and water.
- the conversion of oxygenates in the methanol rich stream is carried out in a reactor in the presence of a catalyst being active in the reaction of oxygenates to hydrocarbons, preferably C 5+ hydrocarbons.
- a preferred catalyst for the conversion reaction may be a zeolite based catalyst such as ZSM-5 or similar
- more than one conversion reactor is used.
- the multiple reactors are preferably arranged in parallel.
- the raw product from the converter in form of a gasoline reactor may comprise hydrocarbons in the range from C1 to C13 water and carbon dioxide.
- a liquid phase of water and a liquid phase comprising a mix of gasoline and light petroleum gas (LPG) is obtained, referred to as raw gasoline.
- the raw gasoline and water may be separated from a tail gas comprising Methane, Ethane, LPG, CO 2 , CO, H 2 and/or C5+, part of which is recycled to the converter.
- the tail gas further may comprise inerts, light hydrocarbons such as methane, ethane, etc. and carbon dioxide which e.g. may be used as fuel gas.
- the raw gasoline may be further processed by conventional means to obtain a lower-boiling gasoline fraction and a fraction of LPG.
- LPG may often be regarded as mainly C3 and C4.
- the recycle gas may be recycled and re-introduced into the converter.
- the recycle stream may be compressed and/or at one or more points during the flow from the separator to the converter be heated, preferably by heat exchange utilizing the heat from the effluent from the converter.
- the gas phase methanol rich stream is preferably mixed into the recycle stream thereby creating a mixed stream which is introduced to the converter.
- the oxygenates in the liquid purge may comprise ketones, aldehydes and/or alcohols including higher alcohols.
- the liquid purge may e.g. comprise water, CO 2 , Dimethyl ether (DME), Acetone, Propanol, Ethanol, Butanol, one or more higher alcohols, Formaldehyde, Acetaldehyde, methyl ethyl ketone and methanol.
- the liquid purge is added to the recycle from the conversion step. As the recycle is heated the liquid purge will evaporate when e.g. sprayed into the recycle stream at points after heating of the recycle.
- the liquid purge can be added to the recycle from the conversion step up- and/or downstream the point where the methanol rich stream is mixed with the recycle from the conversion step.
- the heat from the recycle stream can be optimally used to ensure evaporation of the liquid purge when entering the recycle stream and/or mixed stream (recycle+methanol rich stream). I.e. it may be advantageous to add the purge to the recycle stream and/or mixed stream where the temperature is high, such as above 180° C.
- the liquid purge can be added to the gas phase methanol rich stream upstream and preferably close to the methanol mixing point in order to utilize the heat from the hot recycle stream.
- the liquid purge may be added to the recycle from the conversion step by quenching such as via a spray nozzle to evaporate the liquid in the recycle stream.
- the improved process described in this invention allows to run on raw methanol as opposed to pure (grade AA) methanol.
- a set of distillation steps are required after the methanol synthesis.
- This separation is highly energy intensive due to the inherent difficulty in separating water and methanol and/or other oxygenates like ketones, aldehydes, higher alcohols, etc. Therefore, a process modification which allows producing gasoline from a raw methanol feedstock is of great advantage because it makes possible to remove the distillation steps and thus significantly reduce the investment cost.
- the energy demand is greatly reduced.
- the energy required for the methanol purification is equivalent to half the energy demand in the gasoline synthesis loop.
- the raw methanol may also comprise aldehydes, methyl-ethyl-ketone and/or C3+ alcohols, which are not included in the specifications.
- the present process is preferably carried out in a plant comprising an evaporator, reboiler or boiler, a conversion loop, at least one methanol mixing point for adding the gas phase methanol rich stream upstream the converter and at least one purge mixing point for adding the liquid purge to the recycle or mixed stream of recycle/methanol rich stream.
- One or more of the purge mixing point may e.g. be arranged up-stream and/or downstream the methanol mixing point.
- the position of the methanol and purge mixing points may be chosen based on various parameters temperature, flow and/or pressure considerations as discussed above.
- the methanol rich mixing point(s) may advantageously be arranged to mix the gas phase methanol rich stream into the hot recycle stream upstream a final heating of the stream to the conversion step in order to maintain optimal temperature control of the conversion feed.
- the purge mixing point(s) may preferably be arranged to ensure full evaporation of the purge to avoid purge droplets in the system.
- the purge mixing point(s) is arranged where the recycle stream and/or mixed stream is hot.
- one or more purge mixing points can be arranged to mix liquid purge into the methanol rich stream a stage close to the methanol mixing point. I.e. the purge can be added to the methanol rich stream just before the methanol rich stream is heated as it is mixed with hot recycle.
- the conversion loop may comprise a conversion step, a separator and means for returning a recycle stream to the conversion step.
- the conversion loop may further comprise one or more heaters for heating the recycle stream, one or more coolers and/or one or more condensers for condensing the converter effluent.
- Temperature 140-180° C., preferably 160° C.
- Pressure 18-30 barg, preferably 24.1 barg
- Temperature 160-205° C., preferably 182° C.
- Pressure 18-30 barg, preferably 23.8 barg
- Temperature 160-205° C., preferably 182° C.
- Pressure 18-30 barg, preferably 23.8 barg
- Temperature 160-205° C., preferably 182° C.
- Pressure 18-30 barg, preferably 23.8 barg
- Temperature 290-450° C., preferably [340-410° C.] ° C.
- Temperature 290-450° C., preferably 340-410° C. ° C.
- Temperature 320-480° C., preferably 340-410° C. ° C.
- Pressure 18-30 barg, preferably 20.0 barg
- FIG. 1 shows a simplified diagram of the process and plant.
- FIG. 2 shows a diagram of the process and plant indicating some options for the process and plant.
- FIG. 1 shows a principle diagram of the present process and plant.
- the diagram shows an evaporator 1 receiving a feed 2 in form of raw methanol. From the evaporator a gas phase methanol rich stream 3 and a liquid purge 4 are withdrawn.
- the methanol rich stream and the liquid purge is mixed into a gasoline conversion loop comprising a conversion step 5 in which at least the methanol rich stream is converted into at converted mixture (converter effluent) comprising raw gasoline.
- the converted mixture is separated into at least a recycle stream 6 and a raw gasoline stream 7 . At least part of the recycle is returned to the conversion step and the raw gasoline may be send to further treatment, use and/or storage.
- FIG. 2 shows options for various embodiments of the present process and plant.
- the base process is the same as described in FIG. 1 and for like parts like numbers are used.
- the mixing point 8 where the methanol rich stream is mixed with the recycle is here arranged up-steam a heater 9 which helps ensure a desired temperature of the stream to the converter 5 .
- several converters may be arranged in parallel. The number of converters may e.g. depend on the flow in the system.
- the parallel converts may be worked one or more at a time while one or more converters are being regenerated.
- the purge mixing point 10 is here arranged downstream a heat exchanger 11 heating the recycle stream and upstream the methanol mixing point 8 , thus vaporizing the totality of the liquid purge.
- Alternative positions 10 a , 10 b 10 c for the purge mixing point are indicated by dotted lines. If point 10 a is used, insufficient vaporization may under disadvantageous parameters lead to a second phase. If point 10 b is used, a similar result to that in alternative 10 is obtained, being the difference that a higher gas/liquid ratio goes through the nozzle. If point 10 c is used, several nozzles are required (one per converter) which may increase the operation complexity due to parallel flow but may still be a functional and relevant alternative.
- Processes and plants comprising more than one methanol mixing point and/or more than purge mixing point are also possible setups where e.g. temperature or flow conditions renders it advantageous.
- FIG. 2 is also indicated how the effluent 12 from the converter 5 is preferably cooled by at least a cooler 13 before being separated in a separator 14 into the recycle stream 6 , the raw gasoline stream 7 and process water 15 .
- a purge 16 can be taken e.g. from the recycle stream in order to reduce the amount of inerts etc. in the system.
- a pump 17 for the liquid purge from the evaporator 1 and a compressor 18 for the recycle stream is also indicated in the figure.
- one or more of the heat exchangers 9 and 11 utilize the heat in the converter effluent 12 whereby the (mixed) feed to the converter is heated while the effluent from the converter is cooled before condensing and separation.
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- Engineering & Computer Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a processes comprising the steps of: in an evaporator forming a gas phase methanol rich stream from a feed stream; withdrawing a liquid purge stream from the evaporator, said liquid purge stream comprising oxygenates and water; providing the gas phase methanol rich stream to a conversion step; and adding at least part of said liquid purge stream upstream the conversion step.
Description
- The invention relates to an improved preparation process of hydrocarbons useful as gasoline compounds from a feed comprising methanol.
- Gasoline can be produced by conversion of raw methanol, pure methanol and/or dimethyl ether. In known setups the raw methanol is evaporated before being mixed with a recycle gas from the conversion process and send to the gasoline reactor. The raw methanol contains impurities in form of water and various oxygenates such as ketones, aldehydes and higher alcohols. It has surprisingly been shown that these oxygenates are concentrated in the evaporator/boiler to a degree where it effects methanol evaporation due to an increased boiling temperature. This lowers the vaporization effectivity in the evaporator/boiler/reboiler and thus decreases the methanol flow from the evaporator/boiler/reboiler.
- Thus there is a need for a process and a plant enabling a steady gas flow from the evaporator/boiler/reboiler.
- In a first aspect of the present invention is provided a process for running on raw methanol by avoiding building up of too high concentrations of oxygenates with higher boiling point than methanol.
- In a second aspect of the present invention is provided a process which increases the utilization of the oxygenates in the gasoline synthesis loop.
- These and other advantages are achieved by a process comprising the steps of:
- an evaporator, boiler, reboiler or similar forming a gas phase methanol rich stream from a feed stream,
- withdrawing a liquid purge from the evaporator, boiler, reboiler or similar said liquid purge comprising oxygenates and water,
- providing the gas phase methanol rich stream to a conversion step, and
- adding at least part of said liquid purge upstream the conversion step.
- Thus the oxygenates and other compounds are removed from the evaporator or similar by the purge thereby ensuring that the boiling point in the evaporator is kept within acceptable levels in order to ensure a desired flow of the gas phase methanol rich stream. The purge is then added to the conversion step thereby maximizing the product generation in the conversion loop as at least some of the purge oxygenates are converted. I.e. by the present process a purge is removed from the evaporator/boiler/reboiler without wasting the oxygenates in the purge, as this purge is sent to the conversion step. Moreover, this process configuration also has the benefit of enabling the use of raw methanol as feed, thereby avoiding costly purification.
- The purge may be removed continuously or on/off for example in periodic or otherwise predetermined intervals. The amount and/or frequency of the purge may in some embodiments be controlled based on the need in order to maintain the flow of the gas phase methanol rich stream at a desired level.
- For example the conversion step can be a gasoline conversion step in which case the methanol rich stream is converted in presence of a catalyst into hydrocarbons stream which in several embodiments is within the gasoline range, such as predominantly C3-C10 hydrocarbons and water. The conversion of oxygenates in the methanol rich stream is carried out in a reactor in the presence of a catalyst being active in the reaction of oxygenates to hydrocarbons, preferably C5+ hydrocarbons.
- A preferred catalyst for the conversion reaction may be a zeolite based catalyst such as ZSM-5 or similar
- In various setups more than one conversion reactor is used. In these setups the multiple reactors are preferably arranged in parallel.
- The raw product from the converter in form of a gasoline reactor may comprise hydrocarbons in the range from C1 to C13 water and carbon dioxide.
- By cooling and condensation of the effluent from the converter a liquid phase of water and a liquid phase comprising a mix of gasoline and light petroleum gas (LPG) is obtained, referred to as raw gasoline. The raw gasoline and water may be separated from a tail gas comprising Methane, Ethane, LPG, CO2, CO, H2 and/or C5+, part of which is recycled to the converter. The tail gas further may comprise inerts, light hydrocarbons such as methane, ethane, etc. and carbon dioxide which e.g. may be used as fuel gas. The raw gasoline may be further processed by conventional means to obtain a lower-boiling gasoline fraction and a fraction of LPG. LPG may often be regarded as mainly C3 and C4.
- The recycle gas may be recycled and re-introduced into the converter. The recycle stream may be compressed and/or at one or more points during the flow from the separator to the converter be heated, preferably by heat exchange utilizing the heat from the effluent from the converter.
- The gas phase methanol rich stream is preferably mixed into the recycle stream thereby creating a mixed stream which is introduced to the converter.
- The oxygenates in the liquid purge may comprise ketones, aldehydes and/or alcohols including higher alcohols. The liquid purge may e.g. comprise water, CO2, Dimethyl ether (DME), Acetone, Propanol, Ethanol, Butanol, one or more higher alcohols, Formaldehyde, Acetaldehyde, methyl ethyl ketone and methanol.
- In various embodiments the liquid purge is added to the recycle from the conversion step. As the recycle is heated the liquid purge will evaporate when e.g. sprayed into the recycle stream at points after heating of the recycle.
- The liquid purge can be added to the recycle from the conversion step up- and/or downstream the point where the methanol rich stream is mixed with the recycle from the conversion step. Depending on where the liquid purge is added the heat from the recycle stream can be optimally used to ensure evaporation of the liquid purge when entering the recycle stream and/or mixed stream (recycle+methanol rich stream). I.e. it may be advantageous to add the purge to the recycle stream and/or mixed stream where the temperature is high, such as above 180° C. Alternatively or in combination the liquid purge can be added to the gas phase methanol rich stream upstream and preferably close to the methanol mixing point in order to utilize the heat from the hot recycle stream.
- The liquid purge may be added to the recycle from the conversion step by quenching such as via a spray nozzle to evaporate the liquid in the recycle stream.
- The improved process described in this invention allows to run on raw methanol as opposed to pure (grade AA) methanol. Typically, in order to produce pure methanol, a set of distillation steps are required after the methanol synthesis. This separation is highly energy intensive due to the inherent difficulty in separating water and methanol and/or other oxygenates like ketones, aldehydes, higher alcohols, etc. Therefore, a process modification which allows producing gasoline from a raw methanol feedstock is of great advantage because it makes possible to remove the distillation steps and thus significantly reduce the investment cost. Moreover, the energy demand is greatly reduced. By way of example, the energy required for the methanol purification is equivalent to half the energy demand in the gasoline synthesis loop.
- It is known that in the grade AA methanol specification, there are maximum values for acetone and ethanol. Nonetheless if no purification step is included, the raw methanol may also comprise aldehydes, methyl-ethyl-ketone and/or C3+ alcohols, which are not included in the specifications.
- The present process is preferably carried out in a plant comprising an evaporator, reboiler or boiler, a conversion loop, at least one methanol mixing point for adding the gas phase methanol rich stream upstream the converter and at least one purge mixing point for adding the liquid purge to the recycle or mixed stream of recycle/methanol rich stream. One or more of the purge mixing point may e.g. be arranged up-stream and/or downstream the methanol mixing point. The position of the methanol and purge mixing points may be chosen based on various parameters temperature, flow and/or pressure considerations as discussed above.
- For example, the methanol rich mixing point(s) may advantageously be arranged to mix the gas phase methanol rich stream into the hot recycle stream upstream a final heating of the stream to the conversion step in order to maintain optimal temperature control of the conversion feed. The purge mixing point(s) may preferably be arranged to ensure full evaporation of the purge to avoid purge droplets in the system. For example the purge mixing point(s) is arranged where the recycle stream and/or mixed stream is hot. Alternatively one or more purge mixing points can be arranged to mix liquid purge into the methanol rich stream a stage close to the methanol mixing point. I.e. the purge can be added to the methanol rich stream just before the methanol rich stream is heated as it is mixed with hot recycle.
- The conversion loop may comprise a conversion step, a separator and means for returning a recycle stream to the conversion step.
- The conversion loop may further comprise one or more heaters for heating the recycle stream, one or more coolers and/or one or more condensers for condensing the converter effluent.
- Below are exemplary parameters for conditions and compositions in the present plant and process. The values are exemplary and serve to illustrate the present invention and are not to be construed as limiting to the invention.
- Temperature=140-180° C., preferably 160° C.
- Pressure=18-30 barg, preferably 24.1 barg
-
Compound wt % Water 11.6 Carbon Dioxide 0.3 Dimethyl Ether 563 wtppm Acetone 56 wtppm Propanol 2046 wtppm Butanol 824 wtppm Ethanol 1249 wtppm Higher alcohols 821 wtppm Methyl Ethyl Ketone 44 wtppm Methanol balance - Temperature=160-205° C., preferably 182° C.
- Pressure=18-30 barg, preferably 23.8 barg
- Temperature=160-205° C., preferably 182° C.
- Pressure=18-30 barg, preferably 23.8 barg
-
Compound wt % Water 18.7 Carbon Dioxide 6.59E−03 Dimethyl Ether 142 wtppm Acetone 38 wtppm Propanol 2459 wtppm Butanol 1230 wtppm Ethanol 1266 wtppm Higher alcohols 1483 wtppm Methyl Ethyl Ketone 33 wtppm Methanol balance - Temperature=160-205° C., preferably 182° C.
- Pressure=18-30 barg, preferably 23.8 barg
-
Compound wt % Water 11.4 Carbon Dioxide 0.3 Dimethyl Ether 576 wtppm Acetone 57 wtppm Propanol 2033 wtppm Butanol 812 wtppm Ethanol 1249 wtppm Higher alcohols 800 wtppm Methyl Ethyl Ketone 44 wtppm Methanol balance - Temperature=290-450° C., preferably [340-410° C.] ° C.
- Pressure=18-30 barg, preferably 21.3 barg
-
Compound wt % Hydrogen 0.5 Water 1.7 Carbon Monoxide 9.2 Carbon Dioxide 15.7 Methane 27.6 Ethane 500 wtppm LPG 24.140 Ethanol 100 wtppm Methanol 10.480 Dimethyl Ether 100 wtppm Acetone <0 wtppm Propanol 200 wtppm Butanol 100 wtppm Higher alcohols 100 wtppm Methyl Ethyl Ketone <0 wtppm C5+ balance - Temperature=290-450° C., preferably 340-410° C. ° C.
- Pressure=18-30 barg, preferably 21.3 barg
- Temperature=320-480° C., preferably 340-410° C. ° C.
- Pressure=18-30 barg, preferably 20.0 barg
-
-
Compound wt % Hydrogen 0.5 Water 7.6 Carbon Monoxide 9.2 Carbon Dioxide 15.7 Methane 27.7 Ethane 473 wtppm LPG 25.1 Ethanol 100 wtppm Methanol <0 wtppm Dimethyl Ether 100 wtppm Acetone <0 wtppm Propanol 200 wtppm Butanol 100 wtppm Higher alcohols <0 wtppm Methyl Ethyl Ketone <0 wtppm C5+ balance - In the following the process and plant is further describe by reference to the figures. The embodiments in the figures are exemplary and are not to be construed as limiting to the invention.
-
FIG. 1 shows a simplified diagram of the process and plant. -
FIG. 2 shows a diagram of the process and plant indicating some options for the process and plant. -
FIG. 1 shows a principle diagram of the present process and plant. The diagram shows anevaporator 1 receiving afeed 2 in form of raw methanol. From the evaporator a gas phase methanolrich stream 3 and a liquid purge 4 are withdrawn. The methanol rich stream and the liquid purge is mixed into a gasoline conversion loop comprising a conversion step 5 in which at least the methanol rich stream is converted into at converted mixture (converter effluent) comprising raw gasoline. The converted mixture is separated into at least a recycle stream 6 and araw gasoline stream 7. At least part of the recycle is returned to the conversion step and the raw gasoline may be send to further treatment, use and/or storage. -
FIG. 2 shows options for various embodiments of the present process and plant. The base process is the same as described inFIG. 1 and for like parts like numbers are used. The mixing point 8 where the methanol rich stream is mixed with the recycle is here arranged up-steam a heater 9 which helps ensure a desired temperature of the stream to the converter 5. As indicated by dotted lines several converters may be arranged in parallel. The number of converters may e.g. depend on the flow in the system. The parallel converts may be worked one or more at a time while one or more converters are being regenerated. - The
purge mixing point 10 is here arranged downstream a heat exchanger 11 heating the recycle stream and upstream the methanol mixing point 8, thus vaporizing the totality of the liquid purge.Alternative positions 10 a, 10 b 10 c for the purge mixing point are indicated by dotted lines. Ifpoint 10 a is used, insufficient vaporization may under disadvantageous parameters lead to a second phase. If point 10 b is used, a similar result to that inalternative 10 is obtained, being the difference that a higher gas/liquid ratio goes through the nozzle. If point 10 c is used, several nozzles are required (one per converter) which may increase the operation complexity due to parallel flow but may still be a functional and relevant alternative. - Processes and plants comprising more than one methanol mixing point and/or more than purge mixing point are also possible setups where e.g. temperature or flow conditions renders it advantageous.
- In
FIG. 2 is also indicated how the effluent 12 from the converter 5 is preferably cooled by at least a cooler 13 before being separated in aseparator 14 into the recycle stream 6, theraw gasoline stream 7 and process water 15. A purge 16 can be taken e.g. from the recycle stream in order to reduce the amount of inerts etc. in the system. - A pump 17 for the liquid purge from the
evaporator 1 and a compressor 18 for the recycle stream is also indicated in the figure. - In several embodiments one or more of the heat exchangers 9 and 11 utilize the heat in the
converter effluent 12 whereby the (mixed) feed to the converter is heated while the effluent from the converter is cooled before condensing and separation.
Claims (14)
1. A processes comprising the steps of:
in an evaporator forming a gas phase methanol rich stream from a feed stream,
withdrawing a liquid purge stream from the evaporator, said liquid purge stream comprising oxygenates and water,
providing the gas phase methanol rich stream to a conversion step, and
adding at least part of said liquid purge stream upstream the conversion step.
2. A process according to claim 1 , wherein the conversion step is a gasoline conversion step.
3. A process according to claim 1 , wherein the feed stream comprises raw methanol.
4. A process according to claim 1 , wherein the oxygenates comprises ketones, aldehydes and/or higher alcohols.
5. A process according to claim 1 , wherein the liquid purge stream is added to a recycle stream from the conversion step.
6. A process according to claim 1 , wherein the liquid purge stream is added to the recycle stream from the conversion step up- and/or downstream a point where the gas phase methanol rich stream is added to the recycle stream from the conversion step.
7. A process according to claim 1 , wherein the liquid purge stream is added to the recycle stream from the conversion step by quenching.
8. A plant comprising an evaporator or boiler, a conversion loop, at least one methanol mixing point and at least one purge mixing point.
9. A plant according to claim 8 wherein the conversion loop comprises a conversion step, a separator and means for returning a recycle stream to the conversion step.
10. Plant according to claim 8 wherein the conversion loop further comprises one or more heaters for heating the recycle stream, one or more coolers and condensers for condensing the converter effluent.
11. Plant according to claim 8 , wherein one or more purge mixing points are arranged up-steam and/or downstream the methanol mixing point.
12. A plant comprising an evaporator or boiler, a conversion loop, at least one methanol mixing point and at least one purge mixing point, arranged to carry out the process according to claim 1 .
13. Gasoline product produced according to the process of claim 1 .
14. Gasoline product produced by the plant of claim 8 .
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DKPA201400634 | 2014-10-31 | ||
DKPA201400634 | 2014-10-31 | ||
PCT/EP2015/075276 WO2016066813A1 (en) | 2014-10-31 | 2015-10-30 | Conversion of oxygenates in purge from raw methanol evaporator |
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US20170233661A1 true US20170233661A1 (en) | 2017-08-17 |
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US15/519,049 Abandoned US20170233661A1 (en) | 2014-10-31 | 2015-10-30 | Conversion of oxgenates in purge from raw methanol evaporator |
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US (1) | US20170233661A1 (en) |
CN (1) | CN107075386A (en) |
AU (1) | AU2015340496B2 (en) |
BR (1) | BR112017008677A2 (en) |
CA (1) | CA2966087A1 (en) |
EA (1) | EA201790927A1 (en) |
MX (1) | MX2017005429A (en) |
WO (1) | WO2016066813A1 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5008088A (en) * | 1983-04-13 | 1991-04-16 | Mobil Oil Corporation | Methanol-gas saturator for catalytic conversion system |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US3931349A (en) * | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
US4035430A (en) * | 1976-07-26 | 1977-07-12 | Mobil Oil Corporation | Conversion of methanol to gasoline product |
US4851606A (en) * | 1988-04-25 | 1989-07-25 | Mobil Oil Corporation | Control of waste water chemical oxygen demand in an oxygenate to hydrocarbon conversion process |
BRPI0614813B1 (en) * | 2005-08-18 | 2016-05-31 | Haldor Topsoe As | processes for converting oxygenated compounds into hydrocarbons and for preparing hydrocarbons |
US7763765B2 (en) * | 2006-03-31 | 2010-07-27 | Exxonmobil Chemical Patents Inc. | Method of high pressure and high capacity oxygenate conversion with catalyst exposure cycle |
CA2783154C (en) * | 2006-12-13 | 2014-08-12 | Haldor Topsoee A/S | Process for the synthesis of hydrocarbon constituents of gasoline |
CN101568620B (en) * | 2006-12-13 | 2014-03-12 | 赫多特普索化工设备公司 | Process for synthesis of hydrocarbon constituents of gasoline |
US20130178676A1 (en) * | 2012-01-05 | 2013-07-11 | Uop Llc | Methods for producing light olefins |
WO2014063758A1 (en) * | 2012-10-23 | 2014-05-01 | Haldor Topsøe A/S | Process for the preparation of hydrocarbons |
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- 2015-10-30 EA EA201790927A patent/EA201790927A1/en unknown
- 2015-10-30 AU AU2015340496A patent/AU2015340496B2/en active Active
- 2015-10-30 MX MX2017005429A patent/MX2017005429A/en unknown
- 2015-10-30 BR BR112017008677A patent/BR112017008677A2/en not_active Application Discontinuation
- 2015-10-30 US US15/519,049 patent/US20170233661A1/en not_active Abandoned
- 2015-10-30 CA CA2966087A patent/CA2966087A1/en not_active Abandoned
- 2015-10-30 WO PCT/EP2015/075276 patent/WO2016066813A1/en active Application Filing
- 2015-10-30 CN CN201580058415.7A patent/CN107075386A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5008088A (en) * | 1983-04-13 | 1991-04-16 | Mobil Oil Corporation | Methanol-gas saturator for catalytic conversion system |
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MX2017005429A (en) | 2017-08-16 |
AU2015340496B2 (en) | 2019-11-21 |
CA2966087A1 (en) | 2016-05-06 |
CN107075386A (en) | 2017-08-18 |
AU2015340496A1 (en) | 2017-05-25 |
BR112017008677A2 (en) | 2018-06-19 |
EA201790927A1 (en) | 2017-09-29 |
WO2016066813A1 (en) | 2016-05-06 |
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