CA3009530C - Method for the production and use of a hydrocarbon mixture - Google Patents
Method for the production and use of a hydrocarbon mixture Download PDFInfo
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- CA3009530C CA3009530C CA3009530A CA3009530A CA3009530C CA 3009530 C CA3009530 C CA 3009530C CA 3009530 A CA3009530 A CA 3009530A CA 3009530 A CA3009530 A CA 3009530A CA 3009530 C CA3009530 C CA 3009530C
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- reformer
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- hydrocarbon mixture
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- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- 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
- C10G2300/1022—Fischer-Tropsch products
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- 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
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- 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
Abstract
The invention relates to a method for the production and use of a hydrocarbon mixture from natural gases (3) for crude oil refineries. The method is characterized in that the hydrocarbon mixture is anhydrous and is produced from natural gas using the following method steps: converting the natural gas to a methanol/water mixture (crude methanol) (14) without subsequent distillation; catalytic conversion of the crude methanol (14) to a dimethyl ether/methanol/water mixture; conversion of the dimethyl ether/methanol/water mixture to a hydrous hydrocarbon mixture, predominantly consisting of paraffins, C6+ olefins, and aromatics, in particular such as toluene and xylene; degassing and dehydration of the hydrocarbon mixture. The resulting hydrocarbon mixture is supplied to a refinery (25) processing crude oil, where the hydrocarbon mixture is converted to in particular specification-compliant products.
Description
, Method for the production and use of a hydrocarbon mixture The invention relates to a method for the production and use of a hydrocarbon mixture made from natural gas for crude oil refineries. The hydrocarbon mixture can be supplied without further processing for use in a crude oil processing refinery.
It is generally known that natural gas, once broken down into the components hydrogen, carbon monoxide, and carbon dioxide, can be converted via catalytic synthesis steps into ammonia and methanol, but also petrochemical products, such as gasoline, diesel, or olefins. Already at the beginning of the 20th century the scientific and technical foundations were generated for the Fischer-Tropsch synthesis, which converts synthesis gases of most various origins (coal, natural gas, oil, wood) into liquid hydrocarbons. The method was further developed in many steps, implemented on an industrial scale, and is still protected today by a plurality of new patents. An essential disadvantage of the modern methods is the fact that, according to the Fischer-Tropsch synthesis, a mixture of different hydrocarbons is accrued, including a high percentage of waxes, which must be subjected to comprehensive refining. Only with the implementation of such intense post processing, which is extremely expensive with regards to investments and costs, can market-conform products be produced, such as diesel, gasoline, or kerosene.
In connection with the first oil crisis in the middle of the seventies of the last century, an alternative method to the Fischer-Tropsch synthesis was developed; the catalytic conversion of synthesis gases into methanol and the subsequent catalytic conversion (dehydration) of methanol into gasoline. This method, called "methanol to gasoline" was also used on an industrial scale (as MtG
technology) and was/is used globally in various arrangements. It allows the production of standardized gasoline with an octane rating exceeding 92, which fulfills the specifications of the major markets in the U.S.A., Europe, and Asia. After dehydration of methanol, this method requires a refining/distillation/hydration process, without which the required qualities of gasoline cannot be achieved. Therefore, any arrangement of earlier systems for the conversion of synthesis gas into gasoline, via the intermediate product methanol, was forced to integrate this refining step ,
It is generally known that natural gas, once broken down into the components hydrogen, carbon monoxide, and carbon dioxide, can be converted via catalytic synthesis steps into ammonia and methanol, but also petrochemical products, such as gasoline, diesel, or olefins. Already at the beginning of the 20th century the scientific and technical foundations were generated for the Fischer-Tropsch synthesis, which converts synthesis gases of most various origins (coal, natural gas, oil, wood) into liquid hydrocarbons. The method was further developed in many steps, implemented on an industrial scale, and is still protected today by a plurality of new patents. An essential disadvantage of the modern methods is the fact that, according to the Fischer-Tropsch synthesis, a mixture of different hydrocarbons is accrued, including a high percentage of waxes, which must be subjected to comprehensive refining. Only with the implementation of such intense post processing, which is extremely expensive with regards to investments and costs, can market-conform products be produced, such as diesel, gasoline, or kerosene.
In connection with the first oil crisis in the middle of the seventies of the last century, an alternative method to the Fischer-Tropsch synthesis was developed; the catalytic conversion of synthesis gases into methanol and the subsequent catalytic conversion (dehydration) of methanol into gasoline. This method, called "methanol to gasoline" was also used on an industrial scale (as MtG
technology) and was/is used globally in various arrangements. It allows the production of standardized gasoline with an octane rating exceeding 92, which fulfills the specifications of the major markets in the U.S.A., Europe, and Asia. After dehydration of methanol, this method requires a refining/distillation/hydration process, without which the required qualities of gasoline cannot be achieved. Therefore, any arrangement of earlier systems for the conversion of synthesis gas into gasoline, via the intermediate product methanol, was forced to integrate this refining step ,
2 in the overall equipment, with approx. 20% of the total investment costs allocated to this processing step. Further, in this MtG-method, in order to yield the specified octane rating in gasoline, the dwell time in the reactor for converting the dim4hyl ether /
methanol / water ¨
mixture is largely determined with fixed parameters, and therefore allows hardly any or only minor variability.
An essential disadvantage of the above-stated solutions is the considerable expense for converting the initially obtained crude gasoline into a market-conform product, which must be generated in a methanol synthesis that meets highest standards.
The objective of the invention is to provide a simplified method for converting natural gas into hydrocarbon mixtures, which allows feeding the generated mixtures without any further processing for use in a refinery processing crude oil. Here it shall be possible to adapt individual components of the hydrocarbon mixture, based on the respective goals of the refinery, in their volumetric portions according to the specific requirements of the respective refinery.
According to the invention it has been recognized that natural gas can be converted into a crude methanol as an intermediate product using a simplified process. This crude methanol can then be converted catalytically into a dimethyl ether ¨ methanol ¨ water mixture and then, also in a simplified method, into a hydrocarbon mixture which preferably is free from sulfur and benzene, and after dehydration and degassing is fed to a refinery processing crude oil, where it is preferably converted into products such as gasoline and/or aromatics meeting certain specifications. The term "crude oil refinery" shall here be understood as a refinery processing crude oil.
WO 201,6/102533
methanol / water ¨
mixture is largely determined with fixed parameters, and therefore allows hardly any or only minor variability.
An essential disadvantage of the above-stated solutions is the considerable expense for converting the initially obtained crude gasoline into a market-conform product, which must be generated in a methanol synthesis that meets highest standards.
The objective of the invention is to provide a simplified method for converting natural gas into hydrocarbon mixtures, which allows feeding the generated mixtures without any further processing for use in a refinery processing crude oil. Here it shall be possible to adapt individual components of the hydrocarbon mixture, based on the respective goals of the refinery, in their volumetric portions according to the specific requirements of the respective refinery.
According to the invention it has been recognized that natural gas can be converted into a crude methanol as an intermediate product using a simplified process. This crude methanol can then be converted catalytically into a dimethyl ether ¨ methanol ¨ water mixture and then, also in a simplified method, into a hydrocarbon mixture which preferably is free from sulfur and benzene, and after dehydration and degassing is fed to a refinery processing crude oil, where it is preferably converted into products such as gasoline and/or aromatics meeting certain specifications. The term "crude oil refinery" shall here be understood as a refinery processing crude oil.
WO 201,6/102533
3 By modifying the reaction parameters, such as pressure, temperature, or dwell time during the conversion process of the dimethyl ether ¨ methanol ¨ water mixture into a hydrocarbon mixture, here individual components (aromatics, paraffins, olefins) can be increased or reduced in their volumetric ratio according to the specific requirements of the respective refinery.
The method according to the invention and use of a hydrocarbon mixture made from natural gas for crude oil refineries is characterized in that the hydrocarbon mixture is anhydrous. Preferably the hydrocarbon mixture is free from oxygenated compounds.
According to the invention the hydrocarbon mixture made from natural gas is produced using the following production steps: a) converting the natural gas into a methanol water mixture (here and in the following called "crude methanol") without subsequent distillation. The method according to the invention further comprises b) the catalytic conversion of the crude methanol of step a) into a dimethyl ether ¨ methanol ¨ water mixture, and then c) the conversion, preferably by way of dehydration, of the dimethyl ether ¨ methanol ¨ water mixture of step b) into an aqueous hydrocarbon mixture, which primarily comprises paraffins, C6+ olefins, and aromatics, particularly methylated benzenes, such as toluene or xylene. It is preferred that the aqueous hydrocarbon mixtures are free from sulfur and/or benzene. The method according to the invention further comprises d) the degassing and dehydration of the hydrocarbon mixture, with the hydrocarbon mixture yielded with the above-stated processing steps a) to d) now being anhydrous.
According to the invention, the hydrocarbon mixture yielded with the above-stated processing steps a) to d) is then fed to a refinery, particularly a nearby one processing crude oil, particularly supplied by way of pumping, and here converted in particular into products, preferably gasoline and/or aromatics meeting certain specifications.
The term "products meeting certain specifications" shall here and in the following be understood as particularly such petrochemical products which, such as gasoline for example, meet qualities standards which have been set by the industry or public supervisory authorities. The fuel standards "DIN EN 228" for gasoline and "DIN EN 590" are defined as the minimum requirements for the most important quality features, as well as the octane rating:
The method according to the invention and use of a hydrocarbon mixture made from natural gas for crude oil refineries is characterized in that the hydrocarbon mixture is anhydrous. Preferably the hydrocarbon mixture is free from oxygenated compounds.
According to the invention the hydrocarbon mixture made from natural gas is produced using the following production steps: a) converting the natural gas into a methanol water mixture (here and in the following called "crude methanol") without subsequent distillation. The method according to the invention further comprises b) the catalytic conversion of the crude methanol of step a) into a dimethyl ether ¨ methanol ¨ water mixture, and then c) the conversion, preferably by way of dehydration, of the dimethyl ether ¨ methanol ¨ water mixture of step b) into an aqueous hydrocarbon mixture, which primarily comprises paraffins, C6+ olefins, and aromatics, particularly methylated benzenes, such as toluene or xylene. It is preferred that the aqueous hydrocarbon mixtures are free from sulfur and/or benzene. The method according to the invention further comprises d) the degassing and dehydration of the hydrocarbon mixture, with the hydrocarbon mixture yielded with the above-stated processing steps a) to d) now being anhydrous.
According to the invention, the hydrocarbon mixture yielded with the above-stated processing steps a) to d) is then fed to a refinery, particularly a nearby one processing crude oil, particularly supplied by way of pumping, and here converted in particular into products, preferably gasoline and/or aromatics meeting certain specifications.
The term "products meeting certain specifications" shall here and in the following be understood as particularly such petrochemical products which, such as gasoline for example, meet qualities standards which have been set by the industry or public supervisory authorities. The fuel standards "DIN EN 228" for gasoline and "DIN EN 590" are defined as the minimum requirements for the most important quality features, as well as the octane rating:
4 regular gasoline mm. 91 octane, premium min. 95 octane, premium plus mm. 98 octane. In Germany, fuels may only be sold if they meet the respective standard. In the present case, the term "crude oil" and "crude oil processing" are used synonymously with "petroleum"
and/or "petroleum processing".
The terms "free from sulfur" and "free from benzene" as well as "free from oxygenated compounds" and "anhydrous" are preferably understood such that the product may still show a very low residual content of these compounds mentioned, however no further cleaning process is required to this regard in order to allow subsequent use thereof The term "nearby refinery processing crude oil" is here and in the following understood such that the refinery processing crude oil is arranged in the proximity of the location of the execution of at least one of the processing steps a) to d), preferably all of these processing steps. In particular it shall be understood that the refinery processing crude oil is arranged at a distance of maximally 20 km from the location of execution of one or more of the processing steps a) to d).
It is preferred that the hydrocarbon mixture yielded according to the processing steps a) to d) is pumped via a pipeline to a refinery processing crude oil and here, depending on the configuration of said refinery, is either added to the crude oil and/or suitable cleavage products, e.g., from "Fluidized Catalytic Cracking" (FCC). During the subsequent treatment of the hydrocarbon mixture, preferably in a hydro-treater, the produced quantity of gasoline and/or gasoline and aromatics is increased by the quantity of hydrocarbons comprising the hydrocarbon mixture yielded according to the processing steps a) to d).
A major Advantage, economically and regarding processing technology on the one hand, is the simplification of the technology for producing crude methanol, namely particularly the omission of the distillation of the crude methanol and the reduction of requirements to the methanol synthesis connected thereto, and on the other hand the complete omission of the refining of the developing hydrocarbon mixture in connection with the methanol production. For example, the investment costs for converting natural gas into petrochemical products can be reduced by up to 35%, and the technical requirements for implementing the method are diminished. Due to the fact that the production capacity of a refinery processing crude oil is usually much larger than the volume of hydrocarbon mixture developed from the method according to the invention, here such a refinery processing crude oil can also be used according to the invention for processing the hydrocarbon mixture without any increase of the refinery capacity being required. Thus, existing infrastructure can be used without this, considerably changing the capacity utilization, and the expensive erection of a refinery station, especially for the hydrocarbon mixture, can be waived.
The distillation of the crude methanol in the MtG-method known from prior art is expensive since a thermal method must be used for the crude methanol in order to allow separating water from the homogenous crude methanol. In the method according to the invention the removal of the water can be waived until the hydrocarbon mixture has been yielded. Then, this removal can occur by simple deposition, since the water is then present in a separate phase. This simplification more than compensates the now required entraining of water through the intermediate processing steps, particularly since the water ratio is not excessively high.
Another considerable advantage arises here in the sense that according to the respective configuration of the accepting refinery processing crude oil the product ratios (paraffins, aromatics, olefins) can be adjusted to the particular requirements of the refinery processing crude oil. This adjustment is easily possible by modifying the dwell time in the reactor for converting the dimethyl ether ¨ methanol ¨ water mixture into the initially aqueous hydrocarbon mixture.
Here, preferably dwell times are set from 10 minutes to one hour. This is not possible with the previous the MtG-method because the dwell times are already predetermined by the fact that a certain octane rating shall be achieved. The method according to the invention is not subject to this limitation, but rather allows adjustment of the dwell times to the individual conditions of the refinery processing crude oil.
For example, in such relatively short dwell times of two to three minutes, after complete conversion of the dimethyl ether ¨ methanol mixture, a composition of the hydrocarbon mixture can be yielded having approx. 19 % by weight C2-05-olefins, approx. 14 % by weight paraffin, and C6+ olefin as well as approx. 9 % by weight aromatics, in addition to water. At relatively long dwell times from half an hour to one hour the portion of C2-05-olefins drops and the respective ratio of paraffin and C6+ olefins as well as aromatics increase. The ratio of water remains here essentially unchanged. At a dwell time of approx. one hour, here for example a distribution of hydrocarbons of approx. 1 % by weight C2-05-olefin, approx. 17-18 % by weight aromatics, and approx. 22 % by weight paraffins, and C6+ olefins can be yielded, with the remainder being water.
In other words, with the method according to the invention, by selecting the dwell time, the fraction of C2-05-olefins can be either adjusted as a preferred fraction or as a by-product with a low ratio of approx. 1 % by weight. Respective ratios therebetween can also be adjusted, here.
The term "C6+ olefins" shall here and in the following represent particularly alkenes, which are either branched or unbranched, and show 6 or more than 6 carbon atoms, preferably ranging from 6 to 20 carbon atoms, particularly from 6 to 15 carbon atoms. Accordingly, the term "C2-05 olefins" shall represent particularly alkenes, which are either branched or unbranched and comprise from 2 to 5 carbon atoms.
Further, the method according to the invention allows that the hydrocarbon mixture yielded by the method is fed in another intermediate step to the crude oil processing of the refinery. The hydrocarbon mixture therefore does not need to run necessarily through all processing steps of crude oil to be processed, but can "skip" some of these processing steps. This way the additional workload of the refinery processing the crude oil is even lower by the hydrocarbon mixture provided according to the invention than is currently the case.
Another advantage results for the accepting refinery in the sense that the method according to the invention produces a hydrocarbon mixture preferably free from sulfur and benzene, which contributes by its processing in a refinery to a reduction of the sulfur and/or benzene content, particularly in gasoline. The hydrocarbon mixture is preferably also free from oxygenated compounds.
Natural gas is a flammable, gas found in nature, which is obtained from underground deposits. It is frequently found together with crude oil, since it develops in a similar process. Natural gas comprises primarily methane; however it is distinguished by additional chemical compounds and varies considerably, depending on place of origin. Frequently natural gas also comprises major portions of ethane (frequently from 1 % to 15 % of the molar fraction), propane (frequently from 1% to 10 % of the molar fraction), and butane. Additional secondary components are hydrosulfide, nitrogen, carbon dioxide, and water vapor, in addition thereto helium and perhaps elementary sulfur and mercury.
According to the invention, the respectively yielded crude methanol is subjected to no further distillation. In particular it is preferred that the methanol ¨ water mixture (crude methanol) yielded without any intermediate distillation, is converted particularly directly in the processing step b) into a dimethyl ether ¨ methanol ¨ water mixture, which then is converted in the processing step c) into the aqueous hydrocarbon mixture.
This hydrocarbon mixture shows for example the following composition:
- 57 % by weight water
and/or "petroleum processing".
The terms "free from sulfur" and "free from benzene" as well as "free from oxygenated compounds" and "anhydrous" are preferably understood such that the product may still show a very low residual content of these compounds mentioned, however no further cleaning process is required to this regard in order to allow subsequent use thereof The term "nearby refinery processing crude oil" is here and in the following understood such that the refinery processing crude oil is arranged in the proximity of the location of the execution of at least one of the processing steps a) to d), preferably all of these processing steps. In particular it shall be understood that the refinery processing crude oil is arranged at a distance of maximally 20 km from the location of execution of one or more of the processing steps a) to d).
It is preferred that the hydrocarbon mixture yielded according to the processing steps a) to d) is pumped via a pipeline to a refinery processing crude oil and here, depending on the configuration of said refinery, is either added to the crude oil and/or suitable cleavage products, e.g., from "Fluidized Catalytic Cracking" (FCC). During the subsequent treatment of the hydrocarbon mixture, preferably in a hydro-treater, the produced quantity of gasoline and/or gasoline and aromatics is increased by the quantity of hydrocarbons comprising the hydrocarbon mixture yielded according to the processing steps a) to d).
A major Advantage, economically and regarding processing technology on the one hand, is the simplification of the technology for producing crude methanol, namely particularly the omission of the distillation of the crude methanol and the reduction of requirements to the methanol synthesis connected thereto, and on the other hand the complete omission of the refining of the developing hydrocarbon mixture in connection with the methanol production. For example, the investment costs for converting natural gas into petrochemical products can be reduced by up to 35%, and the technical requirements for implementing the method are diminished. Due to the fact that the production capacity of a refinery processing crude oil is usually much larger than the volume of hydrocarbon mixture developed from the method according to the invention, here such a refinery processing crude oil can also be used according to the invention for processing the hydrocarbon mixture without any increase of the refinery capacity being required. Thus, existing infrastructure can be used without this, considerably changing the capacity utilization, and the expensive erection of a refinery station, especially for the hydrocarbon mixture, can be waived.
The distillation of the crude methanol in the MtG-method known from prior art is expensive since a thermal method must be used for the crude methanol in order to allow separating water from the homogenous crude methanol. In the method according to the invention the removal of the water can be waived until the hydrocarbon mixture has been yielded. Then, this removal can occur by simple deposition, since the water is then present in a separate phase. This simplification more than compensates the now required entraining of water through the intermediate processing steps, particularly since the water ratio is not excessively high.
Another considerable advantage arises here in the sense that according to the respective configuration of the accepting refinery processing crude oil the product ratios (paraffins, aromatics, olefins) can be adjusted to the particular requirements of the refinery processing crude oil. This adjustment is easily possible by modifying the dwell time in the reactor for converting the dimethyl ether ¨ methanol ¨ water mixture into the initially aqueous hydrocarbon mixture.
Here, preferably dwell times are set from 10 minutes to one hour. This is not possible with the previous the MtG-method because the dwell times are already predetermined by the fact that a certain octane rating shall be achieved. The method according to the invention is not subject to this limitation, but rather allows adjustment of the dwell times to the individual conditions of the refinery processing crude oil.
For example, in such relatively short dwell times of two to three minutes, after complete conversion of the dimethyl ether ¨ methanol mixture, a composition of the hydrocarbon mixture can be yielded having approx. 19 % by weight C2-05-olefins, approx. 14 % by weight paraffin, and C6+ olefin as well as approx. 9 % by weight aromatics, in addition to water. At relatively long dwell times from half an hour to one hour the portion of C2-05-olefins drops and the respective ratio of paraffin and C6+ olefins as well as aromatics increase. The ratio of water remains here essentially unchanged. At a dwell time of approx. one hour, here for example a distribution of hydrocarbons of approx. 1 % by weight C2-05-olefin, approx. 17-18 % by weight aromatics, and approx. 22 % by weight paraffins, and C6+ olefins can be yielded, with the remainder being water.
In other words, with the method according to the invention, by selecting the dwell time, the fraction of C2-05-olefins can be either adjusted as a preferred fraction or as a by-product with a low ratio of approx. 1 % by weight. Respective ratios therebetween can also be adjusted, here.
The term "C6+ olefins" shall here and in the following represent particularly alkenes, which are either branched or unbranched, and show 6 or more than 6 carbon atoms, preferably ranging from 6 to 20 carbon atoms, particularly from 6 to 15 carbon atoms. Accordingly, the term "C2-05 olefins" shall represent particularly alkenes, which are either branched or unbranched and comprise from 2 to 5 carbon atoms.
Further, the method according to the invention allows that the hydrocarbon mixture yielded by the method is fed in another intermediate step to the crude oil processing of the refinery. The hydrocarbon mixture therefore does not need to run necessarily through all processing steps of crude oil to be processed, but can "skip" some of these processing steps. This way the additional workload of the refinery processing the crude oil is even lower by the hydrocarbon mixture provided according to the invention than is currently the case.
Another advantage results for the accepting refinery in the sense that the method according to the invention produces a hydrocarbon mixture preferably free from sulfur and benzene, which contributes by its processing in a refinery to a reduction of the sulfur and/or benzene content, particularly in gasoline. The hydrocarbon mixture is preferably also free from oxygenated compounds.
Natural gas is a flammable, gas found in nature, which is obtained from underground deposits. It is frequently found together with crude oil, since it develops in a similar process. Natural gas comprises primarily methane; however it is distinguished by additional chemical compounds and varies considerably, depending on place of origin. Frequently natural gas also comprises major portions of ethane (frequently from 1 % to 15 % of the molar fraction), propane (frequently from 1% to 10 % of the molar fraction), and butane. Additional secondary components are hydrosulfide, nitrogen, carbon dioxide, and water vapor, in addition thereto helium and perhaps elementary sulfur and mercury.
According to the invention, the respectively yielded crude methanol is subjected to no further distillation. In particular it is preferred that the methanol ¨ water mixture (crude methanol) yielded without any intermediate distillation, is converted particularly directly in the processing step b) into a dimethyl ether ¨ methanol ¨ water mixture, which then is converted in the processing step c) into the aqueous hydrocarbon mixture.
This hydrocarbon mixture shows for example the following composition:
- 57 % by weight water
- 5 % by weight propane - 38 % by weight hydrocarbons, primarily ranging from C4 to C14.
The hydrocarbons comprise paraffins, olefins, and aromatics.
It is preferred that the conversion of the natural gas into the crude methanol comprises in the above-mentioned processing step a) the following processing steps:
a') desulfurizing, b') saturating with process condensate and steam to form a processing gas saturated with water, c') converting the processing gas into synthesis gas, namely a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide, d') cooling the synthesis gas, preferably in a waste heat boiler system, and compressing the synthesis gas via a compressor, e') yielding methanol by catalytic conversion of the synthesis gas from the processing step d') within the scope of a two-stage methanol synthesis in a reactor arrangement, particularly in a water-cooled reactor and a gas-cooled reactor, and f) yielding the crude methanol by the subsequent multi-stage condensation of methanol.
As already indicated above, natural gas comprises, depending on the location of the deposit and/or the source, a ratio of up to 15 % nitrogen and a ratio of noble gases of up to 1 %. The respective nitrogen ratio and the respective portion of noble gases is entrained during the conversion of the natural gas into the crude methanol according to the above-stated processing step a) as well as in the processing gas, in the respective synthesis gas, in the cracked gas mentioned in the following, and in all other gaseous mixtures of the processing step a) without this being explicitly mentioned each time in the following. To this regard, the above-mentioned compositions are to be understood always in consideration of this potential nitrogen ratio and the potential ratio of noble gases. In addition to this nitrogen portion and this portion of noble gases, the synthesis gas may also comprise, in addition to hydrogen, carbon dioxide, and carbon monoxide, very minute quantities of uncracked methane, for example.
A preferred further development provides that the conversion of the processing gas into synthesis gas comprises in the processing step c') the pre-cracking of at least a portion of the processing gas in a pre-reformer into a cracked gas with methane, hydrogen, carbon dioxide, and carbon monoxide. In particular, this cracked gas may consist entirely or essentially of methane, hydrogen, carbon dioxide, and carbon monoxide. By such a use of a pre-reformer for pre-cracking here the oxygen consumption can be reduced in the method according to the invention.
Here it is further preferred that the conversion of the processing gas into synthesis gas in the processing step c') comprises a catalytic conversion of a processing gas flow, preformed downstream the pre-reformer, which processing gas flow comprises a cracked gas, under elevated temperature in an auto-thermal reformer into the synthesis gas for the processing step d') with addition of preheated oxygen. Here the term "processing gas flow" shall be understood as any arbitrary gas flow in the procedural sense, in the process suggested, which is given based on the processing gas or its processing and which is given in the processing step c'). According to this preferred embodiment this processing gas flow comprises the cracked gas. The processing gas flow may also include the processing gas and particularly essentially comprise the processing gas and the cracked gas.
According to a preferred embodiment essentially the entire processing gas from the processing step b") is fed to the pre-reformer for pre-cracking, and the cracked gas from the pre-reformer to the auto-thermal reformer. A preferred variant provides that the cracked gas is fed from the pre-reformer, essentially in its entirety, to the auto-thermal reformer.
Preferably then the catalytic conversion occurs in the auto-thermal reformer at a pressure of at least 50 bar.
According to another preferred variant it is provided that the conversion of the processing gas into synthesis gas in the processing step c') comprises a conversion of the cracked gas in a steam reformer into another synthesis gas performed procedurally dovvnstream the pre-reformer. This additional synthesis gas is here also a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide. The additional synthesis gas may also, in principle, show other ratios of these components than the synthesis gas developing by conversion in the auto-thermal reformer.
Preferably the additional synthesis gas is fed to the compressor, particularly via the waste heat boiler system, as the synthesis gas for the processing step d').
According to a first variant, this steam reformer may be arranged parallel to the auto-thermal reformer and procedurally downstream the pre-reformer. Accordingly, it is preferred that the cracked gas from the pre-reformer is divided into a first cracked gas flow, which is fed to the auto-thermal reformer, and a second cracked gas flow, which is fed to the steam reformer. In order to execute the subsequent cooling and compression it is preferably provided that the additional synthesis gas from the steam reformer and the synthesis gas of the auto-thermal reformer are combined in order to yield the synthesis gas for the processing step d').
It is preferred that a partial flow of the processing gas is branched out for feeding the pre-reformer, the cracked gas from the pre-reformer is preferably fed in its entirety to the steam reformer, the additional synthesis gas is returned from the steam reformer to the remaining processing gas for mixing, and then it is fed to the auto-thermal reformer. Preferably the catalytic conversion occurs in the auto-thermal reformer at a pressure of at least 30 bar.
According to a preferred embodiment, in case of a two-stage methanol synthesis, in a processing step e') a first portion of reactor exhaust gas is branched out, the first portion of the reactor exhaust is circulated, and here in another compressor compressed to an operating pressure for the two-stage methanol synthesis. The term "reactor exhaust gas" shall here and in the following be understood as the gas mixture which develops in the reactor arrangement in the two-stage methanol synthesis.
Additionally, in the two-stage methanol synthesis in the processing step e') a second portion of reactor gas can be branched out and fed to a pressure-swing arrangement (PSA), in which hydrogen is separated from the second portion, with the separated hydrogen being fed to the compressor of the processing step d') at its suction side. Such a pressure-swing arrangement is also called pressure-swing-adsorption arrangement or pressure-change adsorption arrangement, and is characterized by providing a physical method for separating gas mixtures under pressure by way of adsorption.
To this regard, it is further preferred that the synthesis gas - particle flow is branched off after compression via the compressor and also fed to the pressure swing arrangement.
The pressure swing arrangement therefore serves to compensate the hydrogen balance in the two-stage methanol synthesis. In particular it is provided that in the pressure swing arrangement hydrogen is separated from the partial flow of the synthesis gas, and that the separated hydrogen is fed to the compressor of the processing step d') on the suction side.
WO 201,6/102533 According to a preferred embodiment, the conversion of the crude methanol into the dimethyl ether / methanol / water mixture of the processing step b) occurs in a fixed bed reactor. It is also preferred that the conversion of the dimethyl ether / methanol / water mixture into the aqueous hydrocarbon mixture of the processing step c) occurs in at least one additional adiabatically operating reactor at a temperature range from 300 C to 450 C.
It is also preferred that the dimethyl ethyl ¨ methanol ¨ water mixture developing in the fixed bed reactor is mixed with recycle gas for temperature adjustment, namely preferably in the additional adiabatically operating reactors.
The term "recycle gas" is here, and in the following, understood as a recycled gas component, particularly a gas component essentially comprising hydrocarbons, from a processing step procedurally arranged downstream, particularly from degassing according to the processing step d).
The hydrocarbon mixture, initially still containing water, is now after degassing and dehydration transported to a refinery processing crude oil, preferably pumped, namely particularly via a pipeline and here added, depending on the configuration of the refinery, either to the crude oil or to suitable by-products.
Here it is preferably provided, on the one hand, that the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery procedurally upstream the hydro-treater. In particular, it can be added directly before a hydro-treater of the refinery.
This hydro-treater may represent on the one hand a hydro-treater which is located upstream a "fluidized catalytic cracking"
(FCC)-unit, particularly procedurally directly upstream thereof. Such a hydro-treater, procedurally located upstream the FCC-unit, may be arranged directly following the crude oil distillation.
On the other hand, the hydro-treater may represent a hydro-treater which is procedurally arranged downstream the FCC-unit, particularly directly following it. The hydro-treater procedurally arranged downstream the FCC-unit is preferably arranged procedurally upstream a gasoline mixing in a gasoline pool of the refinery, namely preferably directly in front thereof.
On the other hand, it is preferably provided that the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery procedurally upstream the crude oil distillation.
In particular, it may be added to the refinery directly upstream such a crude oil distillation.
According to another preferred exemplary embodiment it is provided that the hydrocarbon mixture yielded via the processing steps a) to d) is moved for feeding to the refinery. This moved shall be understood as a separating for pumping and can particularly represent shipping in which the hydrocarbon mixture yielded is therefore moved for shipping to water crafts, e.g., transportation barges. Alternatively or additionally the hydrocarbon mixture yielded can also be loaded onto land vehicles, particularly trucks for the purpose of transportation.
The suggested method for the production and use of a hydrocarbon mixture from natural gas for crude oil refineries can alternatively also be described as a method for using natural gas, converted into a hydrocarbon mixture, in crude oil refineries or as a method for utilizing natural gas by converting it into a hydrocarbon mixture for crude oil refineries.
In the following, the invention is explained in greater detail based on two exemplary embodiments.
The drawing shows in Fig. I a flow chart of a first exemplary embodiment of the suggested method, Fig. 2 a flow chart of a second exemplary embodiment of the suggested method, and Fig. 3 an illustration of measured components of the aqueous hydrocarbon mixture from the conversion of the dimethyl ether methanol ¨ water mixture as a function of the dwell time.
A natural gas (350,000 Nm3/h) with the following composition - nitrogen 1.5 % by volume - methane 92 % by volume - ethane 3.5 % by volume - propane 1.5 % by volume - higher hydrocarbons 1.0 % by volume - sulfur 50 ppm is converted in a chemical plant, erected nearby a refinery 25 processing crude oil, which as described in greater detail in the following based on two exemplary embodiments, into a hydrocarbon mixture as follows:
Exemplary embodiment 1:
Fig. 1 shows for the first exemplary embodiment a central oil processing 1 for crude oil originating in various well heads 2. The above-mentioned natural gas 3 is obtained here as a by-product of crude oil. This natural gas 3 is initially desulfurized at a temperature of 375 C and a pressure of 70 bar via a zinc-oxide bed (desulfurizing unit 4), then saturated with process condensate and steam to a process gas saturated with water (saturator 5), and after adjustment to a steam/carbon ratio of 1.0 in the pre-reformer 6, an adiabatically operating catalytic reactor, pre-cracked at 480 C into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide.
After further heating to 630 to 650 C the cracked gas is fed to an auto-thermal reformer 7. The auto-thermal reformer 7 represents also an adiabatically operating catalytic reactor in which by adding oxygen 9, preheated to 230 C yielded in an air separation unit 8, a synthesis gas 10 is generated at 1030 C, which comprises hydrogen, carbon monoxide, and carbon dioxide and only comprises a minute quantity of uncracked methane. This synthesis gas 10 is cooled in a waste heat boiler system 11.
Via various stages, which are used for steam generation and/or heating of several gas/product flows, now compression occurs with synthesis gas, applied at 55 bar and cooled, to 75 bar using a compressor 12. Subsequently, in a dual system comprising a reactor arrangement 13 with a water-cooled and a gas-cooled reactor, synthesis gas is catalytically converted into methane at a temperature range from 220 to 260 C and by condensation crude methanol 14 is yielded with the following composition:
- methanol 83 % by weight - carbon dioxide 3.6 % by weight - water 11.7 % by weight - methane 1.5 % by weight - higher hydrocarbons 0.1 % by weight - higher alcohols 0.1 % by weight During the methanol synthesis here a portion of the reactor exhaust gas 15 is circulated via a pipeline and here brought to the required pressure using another compressor 16.
Due to the contaminants included in the synthesis gas 10 a second portion of reactor exhaust gas 17 is branched off as purge gas and passed through via a pressure swing arrangement (PSA) 18. A
partial synthesis gas flow 19 is also fed to this PSA 18 at high pressure, branched off after pressure increase via the compressor 12. The hydrogen 20 generated in the PSA 18 is returned at the suction side of the compressor 12 into the synthesis gas flow.
The crude methanol 14 (503 t/h) is subsequently converted catalytically in a fixed bed reactor 21 (DME-reactor) into a DME (dimethyl ether / methanol I water) mixture. The reaction product from the DME-reactor is mixed with the recycled gas 22 for temperature adjustment, and then in additional adiabatically operating reactors 23, at a temperature range from 320 to 420 C and at a dwell time of 60 minutes, converted into an aqueous hydrocarbon mixture. From the 503 t/h methanol here 191 t hydrocarbons and 312 t water develop. This aqueous hydrocarbon mixture is then dehydrated in a post-processing unit 24 and degassed.
The dewatered and degassed hydrocarbon mixture (191 t/h) is pumped into a nearby refinery 25 processing crude oil. The procedurally relevant processing steps of this refinery 25 comprise, in the following sequence, a crude oil distillation 26, a first hydro-treater 27a, a FCC-unit 28, a second hydro-treater 27b, and a gasoline pool 29 for mixing the gasoline. In this exemplary embodiment the hydrocarbon mixture is added upstream the second hydro-treater 27b, which is arranged procedurally downstream the "Fluidized Catalytic Cracking" (FCC) unit 28. The advantage of this feeding comprises that the introduced hydrocarbons, as preferably sulfur and benzene-free components, improve the quality of the gasoline produced. Practically 100 % of the hydrocarbon mixture is ultimately converted into gasoline. This way, the hydrocarbons contained in the hydrocarbon mixture are added to the gasoline pool 29. The dwell time selected in the adiabatically operating reactors 23 lead here to a mixture comprising approx. 65 % paraffins and C6+ olefins as well as 35 % aromatics (primarily toluene and xylene).
Exemplary embodiment 2:
The second exemplary embodiment shown in Fig. 2 is generally equivalent to the above-stated one, however it is distinguished from the first exemplary embodiment described in reference to Fig. 1 in the following features:
After the saturator 5, via a first line 29, a first partial flow of approx. 40 % of the processing gas, saturated with water, desulfurized, and mixed with steam, is added at a temperature of approx. 480 C to the pre-reformer 6. Here, the processing gas is pre-cracked into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide.
After an additional heating to 520 C this cracked gas is converted in a steam reformer 30, particularly an externally heated pipe-reactor with a nickel catalytic converter, here into another synthesis gas 31, namely a mixture of hydrogen, carbon monoxide, and carbon dioxide.
This additional synthesis gas 31 is returned in a second line 32 in another partial flow (approx.
60%) of the processing gas, saturated with water, desulfurized, and mixed with steam, developing after the saturator 5, and fed at a mixed temperature of 670 C to the auto-thermal reformer 7.
In the auto-thermal reformer 7, an adiabatically operating catalytic reactor, the mixed gas is yielded by addition of oxygen 9, heated to 240 C, and obtained in an air separation device 8, completely converted at 980 C into a second synthesis gas 1 Oa, which comprises only minute amounts of uncracked methane. This second synthesis gas 10a is cooled in a waste heat boiler system 11.
The second synthesis gas 10a, applied with a pressure of 32 bar, is then further treated in a manner similar to the synthesis gas 10 of the first exemplary embodiment, as stated in example 1, in order to produce an anhydrous hydrocarbon mixture with the above-stated composition, with the difference that downstream the compressor 12 no partial synthesis gas flow 19 is branched off and fed to the pressure swing arrangement (PSA) 18.
With this method it is possible, compared to the procedure according to example 1, to reduce the gas consumption, particularly the oxygen consumption, by 10 % for the production of the hydrocarbon mixture.
Another difference of the second exemplary embodiment comprises that the dehydrated and degassed hydrocarbon mixture, after being pumped to the nearby refinery 25, is added upstream the first hydro-treater 27a and thus directly after the crude oil distillation 28. Here, the procedural point of adding the hydrocarbon mixture may also be switched between the first and the second exemplary embodiment.
Fig. 3 shows an illustration of measured components of the aqueous hydrocarbon mixture of the conversion of dimethyl ether ¨ methanol ¨ water mixture as a function of the dwell time. This illustration is based on the interpolation of individual measuring points. In particular, the dwell time is shown logarithmically in hours on the abscissa 33, while on the ordinate 34 the product selectivity is shown in % by weight. At the start of the process, exclusively dimethyl ether 35 and methanol 36 as well as minor portions of water 37 are present, while in later dwell times and thus continued conversion the portion of water 37 largely increases and the respective portions of the increasingly formed C2-05 olefins 38, paraffins, and C6+ olefins (here shown jointly) 39, as well as the aromatics 40 initially increase slowly. Similarly the portion of the reactants dimethyl ether 35 and methanol 36 reduces.
After converting approximately the entire dimethyl ether 35 and methanol 36 the portion of water 37 reaches a constant value and the portion of C2-05 olefins 38 reaches it maximum. In a dwell time exceeding this point of time of complete conversion 41 of the reactants the portion of the C2-05-olefins 38 reduces again in favor of the aromatics 40 as well as the paraffins, and the C6+
olefins 39. This trend continues to an almost complete conversion of the C2-05-olefins 38, thus the short-chained olefins, into aromatics 40 on the one hand as well as paraffins and C6+ olefins 39 on the other hand.
The hydrocarbons comprise paraffins, olefins, and aromatics.
It is preferred that the conversion of the natural gas into the crude methanol comprises in the above-mentioned processing step a) the following processing steps:
a') desulfurizing, b') saturating with process condensate and steam to form a processing gas saturated with water, c') converting the processing gas into synthesis gas, namely a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide, d') cooling the synthesis gas, preferably in a waste heat boiler system, and compressing the synthesis gas via a compressor, e') yielding methanol by catalytic conversion of the synthesis gas from the processing step d') within the scope of a two-stage methanol synthesis in a reactor arrangement, particularly in a water-cooled reactor and a gas-cooled reactor, and f) yielding the crude methanol by the subsequent multi-stage condensation of methanol.
As already indicated above, natural gas comprises, depending on the location of the deposit and/or the source, a ratio of up to 15 % nitrogen and a ratio of noble gases of up to 1 %. The respective nitrogen ratio and the respective portion of noble gases is entrained during the conversion of the natural gas into the crude methanol according to the above-stated processing step a) as well as in the processing gas, in the respective synthesis gas, in the cracked gas mentioned in the following, and in all other gaseous mixtures of the processing step a) without this being explicitly mentioned each time in the following. To this regard, the above-mentioned compositions are to be understood always in consideration of this potential nitrogen ratio and the potential ratio of noble gases. In addition to this nitrogen portion and this portion of noble gases, the synthesis gas may also comprise, in addition to hydrogen, carbon dioxide, and carbon monoxide, very minute quantities of uncracked methane, for example.
A preferred further development provides that the conversion of the processing gas into synthesis gas comprises in the processing step c') the pre-cracking of at least a portion of the processing gas in a pre-reformer into a cracked gas with methane, hydrogen, carbon dioxide, and carbon monoxide. In particular, this cracked gas may consist entirely or essentially of methane, hydrogen, carbon dioxide, and carbon monoxide. By such a use of a pre-reformer for pre-cracking here the oxygen consumption can be reduced in the method according to the invention.
Here it is further preferred that the conversion of the processing gas into synthesis gas in the processing step c') comprises a catalytic conversion of a processing gas flow, preformed downstream the pre-reformer, which processing gas flow comprises a cracked gas, under elevated temperature in an auto-thermal reformer into the synthesis gas for the processing step d') with addition of preheated oxygen. Here the term "processing gas flow" shall be understood as any arbitrary gas flow in the procedural sense, in the process suggested, which is given based on the processing gas or its processing and which is given in the processing step c'). According to this preferred embodiment this processing gas flow comprises the cracked gas. The processing gas flow may also include the processing gas and particularly essentially comprise the processing gas and the cracked gas.
According to a preferred embodiment essentially the entire processing gas from the processing step b") is fed to the pre-reformer for pre-cracking, and the cracked gas from the pre-reformer to the auto-thermal reformer. A preferred variant provides that the cracked gas is fed from the pre-reformer, essentially in its entirety, to the auto-thermal reformer.
Preferably then the catalytic conversion occurs in the auto-thermal reformer at a pressure of at least 50 bar.
According to another preferred variant it is provided that the conversion of the processing gas into synthesis gas in the processing step c') comprises a conversion of the cracked gas in a steam reformer into another synthesis gas performed procedurally dovvnstream the pre-reformer. This additional synthesis gas is here also a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide. The additional synthesis gas may also, in principle, show other ratios of these components than the synthesis gas developing by conversion in the auto-thermal reformer.
Preferably the additional synthesis gas is fed to the compressor, particularly via the waste heat boiler system, as the synthesis gas for the processing step d').
According to a first variant, this steam reformer may be arranged parallel to the auto-thermal reformer and procedurally downstream the pre-reformer. Accordingly, it is preferred that the cracked gas from the pre-reformer is divided into a first cracked gas flow, which is fed to the auto-thermal reformer, and a second cracked gas flow, which is fed to the steam reformer. In order to execute the subsequent cooling and compression it is preferably provided that the additional synthesis gas from the steam reformer and the synthesis gas of the auto-thermal reformer are combined in order to yield the synthesis gas for the processing step d').
It is preferred that a partial flow of the processing gas is branched out for feeding the pre-reformer, the cracked gas from the pre-reformer is preferably fed in its entirety to the steam reformer, the additional synthesis gas is returned from the steam reformer to the remaining processing gas for mixing, and then it is fed to the auto-thermal reformer. Preferably the catalytic conversion occurs in the auto-thermal reformer at a pressure of at least 30 bar.
According to a preferred embodiment, in case of a two-stage methanol synthesis, in a processing step e') a first portion of reactor exhaust gas is branched out, the first portion of the reactor exhaust is circulated, and here in another compressor compressed to an operating pressure for the two-stage methanol synthesis. The term "reactor exhaust gas" shall here and in the following be understood as the gas mixture which develops in the reactor arrangement in the two-stage methanol synthesis.
Additionally, in the two-stage methanol synthesis in the processing step e') a second portion of reactor gas can be branched out and fed to a pressure-swing arrangement (PSA), in which hydrogen is separated from the second portion, with the separated hydrogen being fed to the compressor of the processing step d') at its suction side. Such a pressure-swing arrangement is also called pressure-swing-adsorption arrangement or pressure-change adsorption arrangement, and is characterized by providing a physical method for separating gas mixtures under pressure by way of adsorption.
To this regard, it is further preferred that the synthesis gas - particle flow is branched off after compression via the compressor and also fed to the pressure swing arrangement.
The pressure swing arrangement therefore serves to compensate the hydrogen balance in the two-stage methanol synthesis. In particular it is provided that in the pressure swing arrangement hydrogen is separated from the partial flow of the synthesis gas, and that the separated hydrogen is fed to the compressor of the processing step d') on the suction side.
WO 201,6/102533 According to a preferred embodiment, the conversion of the crude methanol into the dimethyl ether / methanol / water mixture of the processing step b) occurs in a fixed bed reactor. It is also preferred that the conversion of the dimethyl ether / methanol / water mixture into the aqueous hydrocarbon mixture of the processing step c) occurs in at least one additional adiabatically operating reactor at a temperature range from 300 C to 450 C.
It is also preferred that the dimethyl ethyl ¨ methanol ¨ water mixture developing in the fixed bed reactor is mixed with recycle gas for temperature adjustment, namely preferably in the additional adiabatically operating reactors.
The term "recycle gas" is here, and in the following, understood as a recycled gas component, particularly a gas component essentially comprising hydrocarbons, from a processing step procedurally arranged downstream, particularly from degassing according to the processing step d).
The hydrocarbon mixture, initially still containing water, is now after degassing and dehydration transported to a refinery processing crude oil, preferably pumped, namely particularly via a pipeline and here added, depending on the configuration of the refinery, either to the crude oil or to suitable by-products.
Here it is preferably provided, on the one hand, that the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery procedurally upstream the hydro-treater. In particular, it can be added directly before a hydro-treater of the refinery.
This hydro-treater may represent on the one hand a hydro-treater which is located upstream a "fluidized catalytic cracking"
(FCC)-unit, particularly procedurally directly upstream thereof. Such a hydro-treater, procedurally located upstream the FCC-unit, may be arranged directly following the crude oil distillation.
On the other hand, the hydro-treater may represent a hydro-treater which is procedurally arranged downstream the FCC-unit, particularly directly following it. The hydro-treater procedurally arranged downstream the FCC-unit is preferably arranged procedurally upstream a gasoline mixing in a gasoline pool of the refinery, namely preferably directly in front thereof.
On the other hand, it is preferably provided that the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery procedurally upstream the crude oil distillation.
In particular, it may be added to the refinery directly upstream such a crude oil distillation.
According to another preferred exemplary embodiment it is provided that the hydrocarbon mixture yielded via the processing steps a) to d) is moved for feeding to the refinery. This moved shall be understood as a separating for pumping and can particularly represent shipping in which the hydrocarbon mixture yielded is therefore moved for shipping to water crafts, e.g., transportation barges. Alternatively or additionally the hydrocarbon mixture yielded can also be loaded onto land vehicles, particularly trucks for the purpose of transportation.
The suggested method for the production and use of a hydrocarbon mixture from natural gas for crude oil refineries can alternatively also be described as a method for using natural gas, converted into a hydrocarbon mixture, in crude oil refineries or as a method for utilizing natural gas by converting it into a hydrocarbon mixture for crude oil refineries.
In the following, the invention is explained in greater detail based on two exemplary embodiments.
The drawing shows in Fig. I a flow chart of a first exemplary embodiment of the suggested method, Fig. 2 a flow chart of a second exemplary embodiment of the suggested method, and Fig. 3 an illustration of measured components of the aqueous hydrocarbon mixture from the conversion of the dimethyl ether methanol ¨ water mixture as a function of the dwell time.
A natural gas (350,000 Nm3/h) with the following composition - nitrogen 1.5 % by volume - methane 92 % by volume - ethane 3.5 % by volume - propane 1.5 % by volume - higher hydrocarbons 1.0 % by volume - sulfur 50 ppm is converted in a chemical plant, erected nearby a refinery 25 processing crude oil, which as described in greater detail in the following based on two exemplary embodiments, into a hydrocarbon mixture as follows:
Exemplary embodiment 1:
Fig. 1 shows for the first exemplary embodiment a central oil processing 1 for crude oil originating in various well heads 2. The above-mentioned natural gas 3 is obtained here as a by-product of crude oil. This natural gas 3 is initially desulfurized at a temperature of 375 C and a pressure of 70 bar via a zinc-oxide bed (desulfurizing unit 4), then saturated with process condensate and steam to a process gas saturated with water (saturator 5), and after adjustment to a steam/carbon ratio of 1.0 in the pre-reformer 6, an adiabatically operating catalytic reactor, pre-cracked at 480 C into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide.
After further heating to 630 to 650 C the cracked gas is fed to an auto-thermal reformer 7. The auto-thermal reformer 7 represents also an adiabatically operating catalytic reactor in which by adding oxygen 9, preheated to 230 C yielded in an air separation unit 8, a synthesis gas 10 is generated at 1030 C, which comprises hydrogen, carbon monoxide, and carbon dioxide and only comprises a minute quantity of uncracked methane. This synthesis gas 10 is cooled in a waste heat boiler system 11.
Via various stages, which are used for steam generation and/or heating of several gas/product flows, now compression occurs with synthesis gas, applied at 55 bar and cooled, to 75 bar using a compressor 12. Subsequently, in a dual system comprising a reactor arrangement 13 with a water-cooled and a gas-cooled reactor, synthesis gas is catalytically converted into methane at a temperature range from 220 to 260 C and by condensation crude methanol 14 is yielded with the following composition:
- methanol 83 % by weight - carbon dioxide 3.6 % by weight - water 11.7 % by weight - methane 1.5 % by weight - higher hydrocarbons 0.1 % by weight - higher alcohols 0.1 % by weight During the methanol synthesis here a portion of the reactor exhaust gas 15 is circulated via a pipeline and here brought to the required pressure using another compressor 16.
Due to the contaminants included in the synthesis gas 10 a second portion of reactor exhaust gas 17 is branched off as purge gas and passed through via a pressure swing arrangement (PSA) 18. A
partial synthesis gas flow 19 is also fed to this PSA 18 at high pressure, branched off after pressure increase via the compressor 12. The hydrogen 20 generated in the PSA 18 is returned at the suction side of the compressor 12 into the synthesis gas flow.
The crude methanol 14 (503 t/h) is subsequently converted catalytically in a fixed bed reactor 21 (DME-reactor) into a DME (dimethyl ether / methanol I water) mixture. The reaction product from the DME-reactor is mixed with the recycled gas 22 for temperature adjustment, and then in additional adiabatically operating reactors 23, at a temperature range from 320 to 420 C and at a dwell time of 60 minutes, converted into an aqueous hydrocarbon mixture. From the 503 t/h methanol here 191 t hydrocarbons and 312 t water develop. This aqueous hydrocarbon mixture is then dehydrated in a post-processing unit 24 and degassed.
The dewatered and degassed hydrocarbon mixture (191 t/h) is pumped into a nearby refinery 25 processing crude oil. The procedurally relevant processing steps of this refinery 25 comprise, in the following sequence, a crude oil distillation 26, a first hydro-treater 27a, a FCC-unit 28, a second hydro-treater 27b, and a gasoline pool 29 for mixing the gasoline. In this exemplary embodiment the hydrocarbon mixture is added upstream the second hydro-treater 27b, which is arranged procedurally downstream the "Fluidized Catalytic Cracking" (FCC) unit 28. The advantage of this feeding comprises that the introduced hydrocarbons, as preferably sulfur and benzene-free components, improve the quality of the gasoline produced. Practically 100 % of the hydrocarbon mixture is ultimately converted into gasoline. This way, the hydrocarbons contained in the hydrocarbon mixture are added to the gasoline pool 29. The dwell time selected in the adiabatically operating reactors 23 lead here to a mixture comprising approx. 65 % paraffins and C6+ olefins as well as 35 % aromatics (primarily toluene and xylene).
Exemplary embodiment 2:
The second exemplary embodiment shown in Fig. 2 is generally equivalent to the above-stated one, however it is distinguished from the first exemplary embodiment described in reference to Fig. 1 in the following features:
After the saturator 5, via a first line 29, a first partial flow of approx. 40 % of the processing gas, saturated with water, desulfurized, and mixed with steam, is added at a temperature of approx. 480 C to the pre-reformer 6. Here, the processing gas is pre-cracked into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide.
After an additional heating to 520 C this cracked gas is converted in a steam reformer 30, particularly an externally heated pipe-reactor with a nickel catalytic converter, here into another synthesis gas 31, namely a mixture of hydrogen, carbon monoxide, and carbon dioxide.
This additional synthesis gas 31 is returned in a second line 32 in another partial flow (approx.
60%) of the processing gas, saturated with water, desulfurized, and mixed with steam, developing after the saturator 5, and fed at a mixed temperature of 670 C to the auto-thermal reformer 7.
In the auto-thermal reformer 7, an adiabatically operating catalytic reactor, the mixed gas is yielded by addition of oxygen 9, heated to 240 C, and obtained in an air separation device 8, completely converted at 980 C into a second synthesis gas 1 Oa, which comprises only minute amounts of uncracked methane. This second synthesis gas 10a is cooled in a waste heat boiler system 11.
The second synthesis gas 10a, applied with a pressure of 32 bar, is then further treated in a manner similar to the synthesis gas 10 of the first exemplary embodiment, as stated in example 1, in order to produce an anhydrous hydrocarbon mixture with the above-stated composition, with the difference that downstream the compressor 12 no partial synthesis gas flow 19 is branched off and fed to the pressure swing arrangement (PSA) 18.
With this method it is possible, compared to the procedure according to example 1, to reduce the gas consumption, particularly the oxygen consumption, by 10 % for the production of the hydrocarbon mixture.
Another difference of the second exemplary embodiment comprises that the dehydrated and degassed hydrocarbon mixture, after being pumped to the nearby refinery 25, is added upstream the first hydro-treater 27a and thus directly after the crude oil distillation 28. Here, the procedural point of adding the hydrocarbon mixture may also be switched between the first and the second exemplary embodiment.
Fig. 3 shows an illustration of measured components of the aqueous hydrocarbon mixture of the conversion of dimethyl ether ¨ methanol ¨ water mixture as a function of the dwell time. This illustration is based on the interpolation of individual measuring points. In particular, the dwell time is shown logarithmically in hours on the abscissa 33, while on the ordinate 34 the product selectivity is shown in % by weight. At the start of the process, exclusively dimethyl ether 35 and methanol 36 as well as minor portions of water 37 are present, while in later dwell times and thus continued conversion the portion of water 37 largely increases and the respective portions of the increasingly formed C2-05 olefins 38, paraffins, and C6+ olefins (here shown jointly) 39, as well as the aromatics 40 initially increase slowly. Similarly the portion of the reactants dimethyl ether 35 and methanol 36 reduces.
After converting approximately the entire dimethyl ether 35 and methanol 36 the portion of water 37 reaches a constant value and the portion of C2-05 olefins 38 reaches it maximum. In a dwell time exceeding this point of time of complete conversion 41 of the reactants the portion of the C2-05-olefins 38 reduces again in favor of the aromatics 40 as well as the paraffins, and the C6+
olefins 39. This trend continues to an almost complete conversion of the C2-05-olefins 38, thus the short-chained olefins, into aromatics 40 on the one hand as well as paraffins and C6+ olefins 39 on the other hand.
Claims (24)
1. A method for the production and use of a hydrocarbon mixture from natural gas (3) for crude oil refineries, wherein the hydrocarbon mixture is anhydrous and produced from natural gas with the following processing steps:
a) converting the natural gas into a methanol / water - mixture comprising crude methanol (14) without any subsequent distillation, b) catalytically converting the crude methanol (14) into a dimethyl ether /
methanol / water -mixture, c) converting the dimethyl ether / methanol / water - mixture into an aqueous hydrocarbon mixture, primarily comprising paraffins, C6+ olefins, and aromatics, d) degassing and dehydrating the hydrocarbon mixture, wherein the conversion of natural gas (3) into crude methanol (14) in processing step a) comprises the following processing steps:
a') desulfurizing the natural gas (3), b') saturation of the natural gas (3) with process condensate and steam to form a processing gas saturated with water, c') converting the processing gas into synthesis gas (10), which synthesis gas (10) is a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide, wherein the converting comprises the pre-cracking of at least a portion of the processing gas in a pre-reformer (6) into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide and the converting further comprising a catalytic conversion of a processing gas flow, procedurally arranged downstream the pre-reformer (6), which processing gas flow comprises the cracked gas, under elevated temperature in the auto-thermal reformer (7) into the synthesis gas (10) for step d') with the addition of pre-heated oxygen (9) d') cooling the synthesis gas (10) and compressing the synthesis gas (10) via a compressor (12), e') yielding methanol by catalytic conversion of the synthesis gas (10) from step d') within the scope of a two-stage methanol synthesis in a reactor arrangement (13) and f) yielding the crude methanol (14) by the subsequent multi-stage condensation of methanol and feeding the hydrocarbon mixture yielded according to the processing steps a) to d) to a refinery (25) processing crude oil and converting it into products meeting particular specifications.
a) converting the natural gas into a methanol / water - mixture comprising crude methanol (14) without any subsequent distillation, b) catalytically converting the crude methanol (14) into a dimethyl ether /
methanol / water -mixture, c) converting the dimethyl ether / methanol / water - mixture into an aqueous hydrocarbon mixture, primarily comprising paraffins, C6+ olefins, and aromatics, d) degassing and dehydrating the hydrocarbon mixture, wherein the conversion of natural gas (3) into crude methanol (14) in processing step a) comprises the following processing steps:
a') desulfurizing the natural gas (3), b') saturation of the natural gas (3) with process condensate and steam to form a processing gas saturated with water, c') converting the processing gas into synthesis gas (10), which synthesis gas (10) is a mixture essentially comprising hydrogen, carbon dioxide, and carbon monoxide, wherein the converting comprises the pre-cracking of at least a portion of the processing gas in a pre-reformer (6) into a cracked gas comprising methane, hydrogen, carbon dioxide, and carbon monoxide and the converting further comprising a catalytic conversion of a processing gas flow, procedurally arranged downstream the pre-reformer (6), which processing gas flow comprises the cracked gas, under elevated temperature in the auto-thermal reformer (7) into the synthesis gas (10) for step d') with the addition of pre-heated oxygen (9) d') cooling the synthesis gas (10) and compressing the synthesis gas (10) via a compressor (12), e') yielding methanol by catalytic conversion of the synthesis gas (10) from step d') within the scope of a two-stage methanol synthesis in a reactor arrangement (13) and f) yielding the crude methanol (14) by the subsequent multi-stage condensation of methanol and feeding the hydrocarbon mixture yielded according to the processing steps a) to d) to a refinery (25) processing crude oil and converting it into products meeting particular specifications.
2. A method according to claim 1, characterized by essentially the entire processing gas from the processing step b') is fed to the pre-reformer (6) for pre-cracking and the cracked gas from the pre-reformer (6) is fed to the auto-thermal reformer (7), with the catalytic conversion occurring in the auto-thermal reformer (7) being performed at a pressure of at least 50 bar.
3. A method according to claim 2, wherein the cracked gas from the pre-reformer (6) is fed to the auto-thermal reformer (7) essentially in its entirety.
4. A method according to any one of claims 1, 2 or 3, characterized in that the conversion of the processing gas into synthesis gas (10) comprises in the processing step c') a conversion of the cracked gas in a steam reformer (30) into another synthesis gas (31), procedurally downstream the pre-reformer (6).
5. A method according to claim 4, wherein the additional synthesis gas (31) is fed to the compressor (12).
6. The method according to claim 5, wherein the additional synthesis gas (31) is fed to the compressor (12) via the waste heat boiler system (11) as a synthesis gas for the processing step d').
7. A method according to claim 4, characterized by the cracked gas from the pre-reformer (6) is divided into a first cracked gas flow, which is fed to the auto-thermal reformer (7), and a second cracked gas flow, which is fed to the steam reformer (30).
8. A method according to claim 7, wherein the additional synthesis gas (31) from the steam reformer (30) and the synthesis gas (10) from the auto-thermal reformer (7) is combined, in order to yield the synthesis gas for the processing step d').
9. A method according to claim 4, characterized in that a partial flow of the processing gas is separated for feeding the pre-reformer (6).
10. A method according to claim 9, wherein the cracked gas of the pre-reformer (6) is fed to the steam reformer (30).
11. A method according to claim 10, wherein the cracked gas of the pre-reformer (6) is fed to the steam reformer (30) essentially in its entirety.
12. A method according to claim 11, wherein the additional synthesis gas (31) of the steam reformer (30) is returned to the remaining processing gas for the purpose of mixing, and then fed to the auto-thermal reformer (7).
13. A method according to claim 12, wherein the catalytic conversion occurring in the auto-thermal reformer (7) occurs at a pressure of at least 30 bar.
14. A method according to any one of claims 1 to 13, characterized by the two-stage methanol synthesis in the processing step e') a first portion of reactor exhaust gas (15) is separated, circulated, and here is compressed to an operating pressure for the two-stage methanol synthesis in another compressor (16).
15. A method according to any one of claims 1 to 14, characterized in that in a two-stage methanol synthesis in a processing step e') a second portion of the reaction exhaust gas (17) is separated and fed to a pressure swing arrangement (18), in which from the second portion of reactor exhaust gas (17) hydrogen is separated and that the separated hydrogen (20) is fed to the compressor (12) of the processing step d') at its suction side.
16. A method according to claim 15, characterized by a partial synthesis flow (19) is separated after compression with the compressor (12) and also fed to the pressure swing arrangement (18).
17. A method according to claim 16, wherein in the pressure swing arrangement (18) hydrogen is separated from the synthesis gas partial flow (19) and the separated hydrogen (20) is fed to the compressor (12) of the processing step d') on its suction side.
18. A method according to any one of claims 1 to 17, characterized by the conversion of the crude methanol (14) into the dimethyl ether / methanol / water - mixture of the processing step b) occurs in a fixed bed reactor (21).
19. A method according to claim 18, wherein the conversion of the dimethyl ether / methanol /
water - mixture occurs in the aqueous hydrocarbon mixture of the processing step c) in at least one additional, adiabatically operating reactor (23) at a temperature range from 300 °C to 450 °C.
water - mixture occurs in the aqueous hydrocarbon mixture of the processing step c) in at least one additional, adiabatically operating reactor (23) at a temperature range from 300 °C to 450 °C.
20. A method according to claim 18 or 19, characterized by the dimethyl ether / methanol / water - mixture developing in the fixed bed reactor (21) is mixed with recycled gas (22) for adjusting the temperature.
21. A method according to any one of claims 1 to 20, characterized by the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery (25) procedurally directly upstream of the hydro-treater (26).
22. A method according to any one of claims 1 to 21, characterized by the hydrocarbon mixture yielded according to the processing steps a) to d) is added in the refinery (25) procedurally directly upstream of the crude oil distillation (28).
23. A method according to any one of claims 1 to 22, characterized by the hydrocarbon mixture yield according to the processing steps a) to d) is moved in order to supply the refinery (25).
24. A method according to claim 23, wherein the hydrocarbon mixture yield according to the processing steps a) to d) is shipped to the refinery (25).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14200179.1A EP3037503B1 (en) | 2014-12-23 | 2014-12-23 | Method for the creation and use of a hydrocarbon mixture |
| EP14200179.1 | 2014-12-23 | ||
| PCT/EP2015/080918 WO2016102533A1 (en) | 2014-12-23 | 2015-12-22 | Method for the production and use of a hydrocarbon mixture |
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| CA3009530C true CA3009530C (en) | 2020-10-27 |
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| EP (1) | EP3037503B1 (en) |
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| WO (1) | WO2016102533A1 (en) |
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| CN114442185A (en) * | 2020-11-06 | 2022-05-06 | 中国石油天然气股份有限公司 | Method and device for determining natural gas geological resource amount, computer equipment and medium |
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| DK147705C (en) * | 1982-09-07 | 1985-05-13 | Haldor Topsoe As | METHOD FOR MANUFACTURING CARBON HYDRADES FROM SYNTHESE GAS |
| US4590176A (en) * | 1984-06-05 | 1986-05-20 | Shell Oil Company | Catalyst for dimethyl ether synthesis and a process for its preparation |
| WO2010107929A2 (en) * | 2009-03-17 | 2010-09-23 | Synch Energy Corp | Catalytic reactions using ionic liquids |
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| EP3037503B1 (en) | 2024-05-01 |
| EP3037503A1 (en) | 2016-06-29 |
| WO2016102533A1 (en) | 2016-06-30 |
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