PROCESS FOR THE SYNTHESIS GAS PRODUCTION OF A HYDROCARBIDE RAW MATERIAL, METHOD OF USING A PROCESS,

专利摘要:
process to reform hydrocarbons. the invention relates to the production of synthesis gas particularly by means of a series arrangement of heat exchange reforming stages and autothermal reforming stages, in which the heat required for the reforming reactions in the heat exchange reforming stage is supplied by hot effluent synthesis gas from the autothermal reforming stage. more particularly, the invention relates to optimizing the operation and control of an arrangement of reforming stages by heat exchange and autothermal reforming and introducing an additional waste heat boiler.
公开号:BR112014032213B1
申请号:R112014032213-9
申请日:2013-06-12
公开日:2021-08-10
发明作者:Martin Frahm Jensen；Lari Bjerg Knudsen
申请人:Haldor Tops0E A/S；
IPC主号:

专利说明:

[001] The present invention refers to a process and a plant for the production of gas rich in hydrogen and carbon monoxide, particularly synthesis gas for the production of ammonia, methanol, dimethyl ether (DME), hydrogen and hydrocarbons by synthesis of Fischer-Tropsch (FT). The invention further relates to the production of synthesis gas particularly by means of a series arrangement of heat exchange and autothermal reforming stages in which the heat required for reforming reactions in the heat exchange reforming stage is supplied by synthesis gas hot effluent from the autothermal reforming stage. More particularly, the invention relates to optimizing the operation and control of an arrangement, particularly a series arrangement, of heat exchange reforming stages and autothermal reforming stages and introducing an additional waste heat boiler.
[002] The use of a product reformed gas stream as a heat source in heat exchange reforming is known in the art. Thus, documents no. EP-A-0033128 and no. EP-A-0334540 deal with parallel arrangements in which a hydrocarbon feed is introduced in parallel to a tubular reformer and a heat exchanger reformer. The partially reformed gas from the tubular reformer is then used as a heat source for the reforming reactions in the heat exchanger reformer.
[003] Other parallel arrangements combine heat exchange reforming and autothermal reforming. Documents no. EP-A-0983963, no. EP-A-1106570 and no. EP-A-0504471 deal with processes in which a hydrocarbon feed is introduced in parallel to a heat exchanger reformer and autothermal reformer. The hot product synthesis gas from the autothermal reformer is used as the heat exchange medium for the reforming reactions that take place in the heat exchanger reformer. In particular, Figure 1 of document no. EP-A-1106570 discloses an embodiment in which the hot product synthesis gas from the autothermal reformer is used as a heat exchange medium for the reforming reactions taking place in heat exchanger reformers arranged in parallel. There is no disclosure of a heat exchanger such as a waste heat boiler or steam superheater arranged in parallel with a heat exchanger reformer.
[004] Document no. EP-A-0440258 discloses a process in which the hydrocarbon feed is first passed through a first heat exchanger reformer to supply a partially reformed stream. The partially reformed stream is then introduced in parallel to a tubular reformer and a second heat exchanger reformer. Product streams from both reformers are combined and fed into an autothermal reformer. Product gas from the autothermal reformer is used as a heat source in the second heat exchanger reformer, while the product gas from said second heat exchanger reformer is used as a heat source in the first heat exchanger reformer.
[005] Serial arrangements are also known in the art. Patent no. US 4,824,658 and Patent no. US 6,296,679 (Figure 2 in both references) discloses a process in which the entire hydrocarbon feed is first introduced to a heat exchanger reformer, then passed to a tubular reformer and finally to an autothermal reformer. The product gas from the autothermal reformer is used as a heat source in the heat exchanger reformer.
[006] Document no. US 4,376,717 and document no. US 2009/0184293 discloses a process in which a hydrocarbon feed is first passed through a tubular reformer; the partially reformed gas is then subjected to heat exchange reforming and finally autothermal reforming. The product gas from the posterior is used as a heat source in heat exchange reformation.
[007] Patent no. DK 148882 discloses a process for producing synthesis gas in which the hydrocarbon feed is passed through a heat exchange reformer and an autothermal reformer and where the product gas from the later is used as a heat source in the heat exchanger reformer. heat.
[008] Documents no. WO-A-03/051771, no. US 6,296,679 and no. WO-A-00/09441 also disclose a serial arrangement. In particular, document no. WO-A-00/09441 discloses a heat exchanger reformer arranged in series with an autothermal reformer where the hot effluent gas (synthesis gas) from the autothermal reformer is used as a heat exchange medium to drive the reformer's reforming reactions heat exchanger. Synthesis gas cooled in this way is then passed through a heat exchanger such as a steam lift boiler (waste heat boiler). There is no disclosure of a heat exchanger such as a waste heat boiler or steam superheater arranged in parallel with the heat exchanger reformer.
[009] The use of heat exchanger reformers in the production of synthetic fuels by Fischer-Tropsch synthesis has significant benefits. Potential benefits compared to other technologies include reduced oxygen consumption, lower capital cost per unit of product, and greater carbon and energy efficiency. In plants for the production of chemicals such as methanol, the use of heat exchange reformers has similar advantages.
[010] In co-pending patent application no. PCT/EP2011/006179 (WO-A-2012/084135), a process is disclosed in which a hydrocarbon feed is passed through a heat exchanger reformer and an autothermal reformer and where the product flow from the posterior is used as a heat source in the heat exchanger reformer. A residual gas from the FT synthesis is added after the heat exchanger reformer and before the autothermal reformer. The addition of tail gas is adjusted to give the desired stoichiometric ratio of H2/CO equal to about 2 in the effluent stream from the autothermal reformer. A steam is added downstream to the autothermal reformer to reduce the aggressiveness of the gas passed to the heat exchanger reformer with respect to metal powder.
[011] A specific modality also disclosed in document no. PCT/EP2011/006179 (WO-A-2012/084135) is where part of the hydrocarbon feedstock bypasses the heat exchanger reformer and is routed directly to the autothermal reformer. This reduces overall plant efficiency and increases oxygen consumption compared to no-shift mode.
[012] It is generally preferable to direct the entire product flow from the autothermal reformer to the heat exchanger reformer. If only part of the flux is used as a heating medium, the size of the heat exchanger reformer needs to be increased to compensate for a lower driving force (smaller temperature difference) for heat transfer.
[013] Heat exchange reformers can also be similarly coupled with other partial oxidation reactors. In addition to autothermal reforming (ATR), such reactors include non-catalytic partial oxidation (POX) as gasifiers and catalytic partial oxidation (CPO), although autothermal reforming (ATR) is preferred. ATR and CPO are provided with a fixed bed of catalyst. As used in this document, the term autothermal reforming (ATR) also encompasses a secondary reform.
[014] However, for many processes like those mentioned above, specifically for large scale plants comprising a heat exchanger reformer and an autothermal reformer, it may be preferable to operate with a low steam to carbon ratio. This, for example, is the case when the produced synthesis gas is to be used for subsequent hydrocarbon synthesis via Fischer-Tropsch (FT) synthesis. Operating at high steam to carbon ratios means higher flow rates due to the increased amount of steam in the feed. In other words, operating at high steam to carbon ratios means that the capital cost of using larger equipment can be prohibitively large, specifically for large scale plants. Furthermore, a high vapor to carbon ratio means that more carbon dioxide is formed in the process. This is, in many cases, a disadvantage, for example, in plants for the production of synthetic fuels by low-temperature Fischer-Tropsch synthesis. In low-temperature Fischer-Tropsch synthesis, a carbon dioxide is considered to be an inert and not a reactant.
[015] Still, operating at low steam to carbon ratios in plants comprising a heat exchanger reformer also creates numerous challenges. One such challenge is the risk of carbon formation in the catalyst in the heat exchanger reformer: CH4 ^ C + 2H2 (1)
[016] A carbon in the catalyst can also be formed from higher hydrocarbons (hydrocarbons with two or more carbon atoms in the molecule) or carbon monoxide according to reactions similar to those described in the literature.
[017] The formed carbon can lead to a catalyst deactivation and/or catalyst disintegration and pressure drop buildup. This is unwanted.
[018] The risk of carbon formation is linked to the catalyst temperature and the ratio of steam to carbon. For a given composition and pressure of a feed gas, the vapor to carbon ratio in the feed gas needs to be increased if the catalyst temperature is increased. As a higher steam to carbon ratio may not be economical as described above, it is important to be able to control the temperature in the heat exchange reformer catalyst to prevent the addition of excess steam. Temperature control thus allows operation closer to the carbon limit without exceeding it. In most cases, the catalyst temperature reaches its maximum at the exit of the heat exchanger reformer.
[019] Another challenge for the use of heat exchanger reformers is metal dust corrosion. In many cases, specifically at low vapor to carbon ratios, the prevention or minimization of metal dust requires the use of superior alloy and/or special materials in the reactor itself. Such alloys are generally expensive and therefore it is generally desirable to minimize the size and heat transfer surface of the heat exchanger reformer reactor itself.
[020] In the processes mentioned above comprising an upstream heat exchanger reformer and in series with an autothermal reformer, the simultaneous control of the catalyst exit temperature of the heat exchanger reformer and the production and quality of synthesis gas (by For example, obtaining the desired H2/CO ratio of about 2 for the production of synthesis gas for the FT synthesis) is not simple. This is particularly the case when it is considered that the synthesis gas production unit is required to operate under different conditions such as part load and with different natural gas feed and waste gas compositions. Furthermore, the production of the plant must remain unchanged even in the case of progressive incrustation of the heat exchanger reformer itself. Fouling is known in the industry and in the art and in this case has the consequence that the heat transferred from the effluent of the autothermal reformer to the catalyst side of the heat exchanger reformer is reduced.
[021] In several of the processes described above, the hydrocarbon feed is passed through a heat exchanger reformer and then an autothermal reformer and the product stream from the later is used as a heat source in the heat exchanger reformer.
[022] Fouling is known to the person skilled in the art as unwanted material that accumulates on the surface of heat exchange equipment. This material creates extra resistance to heat exchange. In a heat exchanger reformer, the consequence will be that the heat transferred from the effluent of the autothermal reformer to the catalyst side of the heat exchanger reformer is reduced.
[023] In the period of initial operation, fouling is generally very low. However, over time, surface fouling of the heat exchanger reformer can occur, which reduces the heat transferred from the effluent stream of the autothermal reformer to the catalyst side of the heat exchanger reformer. This means that the exit temperature of the catalyst side of the heat exchanger reformer will drop if no action is taken. The exit temperature of the autothermal reformer will, as a consequence of the lower exit temperature of the heat exchanger reformer, also decrease, which again will lead to a further drop in the exit temperature of the heat exchanger reformer and so on. This feed and effluent relationship between the autothermal reformer and the heat exchanger reformer means that the fouling effect is amplified, so a small decrease in the heat exchanger reformer's ability to transfer heat can lead to a large decrease in the output temperature of the heat exchanger reformer.
[024] This, in turn, leads to reduced plant efficiency and/or reduced production and/or increased oxygen consumption per unit of synthesis gas produced.
[025] To maintain the hydrocarbon feedstock conversion and maintain production, several measures can be considered. The first is to preheat the raw material for the heat exchanger reformer to a higher temperature. However, this requires the import of additional fuel and reduces the plant's overall energy efficiency. Another alternative is to accept the lowest exit temperature (and thus the lowest hydrocarbon feedstock conversion) of the heat exchanger reformer and increase the conversion in the autothermal reformer. However, this requires additional oxygen and thus increases the capital cost associated with the expensive air separation unit (ASU) used to produce the oxygen. Also, plant efficiency will usually drop.
[026] An alternative would be to design the size of the heat exchanger reformer to take into account the reduction in heat transfer due to fouling. However, in this case, the temperature at the exit of the heat exchanger reformer on the catalyst side during the initial operating period (before any significant fouling has occurred) could become too high, which increases the risk of carbon formation in the catalyst .
[027] As described above, in one embodiment of the above-filed patent application no. PCT/EP2011/006179 (WO-A-2012/084135), part of the hydrocarbon feedstock bypasses the heat exchanger reformer and is directed to the autothermal reformer. In such an embodiment, the fraction of hydrocarbon feedstock that bypasses the heat exchanger reformer can be used to control the temperature outside the heat exchanger reformer. The heat exchanger reformer can, for example, be designed for a specific deviation during the start of operation (before fouling has occurred). As fouling occurs, the fraction of flow bypassing the heat exchanger reformer can be increased to maintain the catalyst exit temperature from the heat exchanger reformer. Production can be maintained by increasing the hydrocarbon feedstock stream. However, plant efficiency will also drop in this case.
[028] It is therefore an object of the present invention to provide a process for producing synthesis gas comprising a heat exchanger reformer and an autothermal reformer where the exit temperature of the heat exchanger reformer and the production of synthesis gas can be maintained during operation with no or very limited loss of effectiveness and no or very limited increase in oxygen consumption.
[029] These and other goals are solved by the present invention.
[030] The preferred arrangement of a plant for the production of synthesis gas is an upstream heat exchanger reformer and in series with an autothermal reformer as shown in Figures 1 to 5.
[031] According to the present invention, a process for the production of synthesis gas from a hydrocarbon feedstock is provided. The method comprises the first step of:a. reforming at least a portion of said hydrocarbon feedstock in an endothermic reforming stage in a heat exchanger reformer and extracting from the heat exchanger reformer an effluent stream of primary reformed gas.
[032] By the term "hydrocarbon feedstock" is meant a stream fed to the process that comprises hydrocarbons. In the broadest sense, hydrocarbons are organic compounds comprising hydrogen and carbon. Hydrocarbons can be as simple as, for example, CH4 methane and can comprise more complex molecules. In addition, for hydrocarbons, a hydrocarbon feedstock may comprise water and/or CO2. The process according to the invention may optionally comprise an additional step of adding water and/or CO2 to hydrocarbons to provide the hydrocarbon feedstock prior to the reforming step (step a.).
[033] The term "at least a portion" may comprise the entire hydrocarbon feedstock or simply a portion thereof. By "indirect heat exchange" it is understood that there is no direct contact between the catalyst and the heating medium and thus between the flow passing through the catalyst and the heating medium because they are separated by a metal wall , that is, the wall of the tube containing the catalyst.
[034] Hydrocarbons (eg desulfurized natural gas) are mixed with steam and/or carbon dioxide and the resulting hydrocarbon feedstock is directed to the catalyst side of the heat exchanger reformer. In the heat exchanger reformer, the gas is then steam reformed according to the following reactions: CH4+ H2O θ CO + 3H2 (2)CO + H2O θ CO2+ H2 (3)
[035] Reactions similar to reaction (2) can occur for any higher hydrocarbon present in the raw material. "Higher hydrocarbons" are hydrocarbons with 2 or more carbon atoms in the molecule (eg, ethane, propane, etc.). The gas leaving the heat exchanger reformer is close to chemical equilibrium for reactions (2) and (3) above. Typically, the outlet temperature is 600 to 850°C, preferably 675 to 775°C and more preferably 700 to 750°C.
[036] Step (b) of the process of the invention involves: b. pass the primary reformed gas from the heat exchanger reformer through an autothermal reforming (ATR) stage, catalytic partial oxidation (CPO) stage or partial oxidation (POX) stage and extract a stream of hot effluent synthesis gas.
[037] Autothermal reforming is described extensively in the technique and in open literature. Typically, the autothermal reforming reactor comprises a burner, a fuel chamber and a catalyst disposed in a fixed bed, all of which are contained in a refractory lined pressure hull.
[038] Autothermal reformation is, for example, described in Chapter 4 in "Studies in Surface Science and Catalysis", Vol. 152 (2004) edited by Andre Steynberg and Mark Dry. As used herein, the term autothermal reformation (ATR) also encompasses secondary reformation. Secondary reform is a reform conducted in a reformer under the addition of air or oxygen and in which the reformer is fed by primary reformed gas, ie reactors that use as a hydrocarbon feed a reformed gas from a primary reformer such as a reformer. half steam (SMR) or heat exchanger reformer.
[039] It will be understood by the person skilled in the art that ATR and POx imply the use of a burner at the top of the reactor. ATR and CPO use a bed of catalyst below the combustion zone. CPO means a catalytic reactor or catalytic gasifier that does not always require the use of a burner, but rather a mixer. Additionally, in a POx (aerator) there is no use of a catalyst.
[040] The partially reformed gas leaving the heat exchanger reformer is thus passed to the autothermal reformer. In the autothermal reformer, oxidizing gas as a gas that contains at least 90% by volume of oxygen and, in some cases, a vapor is added. A synthesis gas ("syngas") is formed by a combination of steam reforming and partial oxidation in the autothermal reformer.
[041] By the term "oxidizing gas" is meant a stream that comprises oxygen, preferably more than 75% by volume and more preferably more than 85% by volume oxygen. Examples of oxidizing gas are air, oxygen, mixture of oxygen and steam, and oxygen enriched air.
[042] The gas leaving the ATR is free of oxygen and, in general, reactions (2) and (3) above are close to chemical equilibrium. The temperature of this hot ATR effluent synthesis gas is between 950 and 1,100°C, typically between 1,000 and 1,075°C.
[043] The hot effluent synthesis gas leaving the autothermal reformer or CPO or POx comprises carbon monoxide, hydrogen, carbon dioxide, steam, residual methane and various other components including nitrogen and argon.
[044] The hot effluent synthesis gas from a step (b) is then divided into at least a first and a second synthesis gas stream wherein said first synthesis gas stream is used as a heating medium in indirect heat exchange in the one-stage heat exchanger reformer (a). Consequently, the first stream of synthesis gas is passed to the non-catalytic side (hereinafter also called "hull side") of the heat exchanger reformer. This first stream of synthesis gas is cooled by supplying heat to the catalytic side of the heat exchanger reformer by indirect heat exchange to produce a first stream of cooled synthesis gas. The exit temperature on the hull side of the heat exchanger reformer would normally be in the range of 450 to 800°C.
[045] The second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange to produce a second stream of cooled synthesis gas. Preferably, said second heat exchanger is a Waste Heat Boiler (WHB) for the production of steam. Consequently, the second heat exchanger is a heat exchanger in which at least a portion, preferably a main portion, particularly 50% or more like 90% or more preferably 100% of that second stream of synthesis gas is used to heat a stream. for which no reformation reaction takes place. Preferably, the second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange with a stream for which no reforming reaction takes place. Preferably, said stream is a stream other than said hydrocarbon feedstock as a stream of boiling feed water to raise steam. Preferably, said second heat exchanger is a waste heat boiler or steam superheater. Additionally, such heat exchangers can be arranged in parallel or in series with said second heat exchanger.
[046] Preferably, after leaving the heat exchanger reformer, the first stream of cooled synthesis gas is further cooled in a third heat exchanger to produce an additional first stream of cooled synthesis gas. Preferably, the third heat exchanger is a Waste Heat Boiler (WHB) for steam production.
[047] The additional cooled first syngas stream may be mixed with the second cooled syngas stream from the second heat exchanger to provide a raw syngas product stream as shown in Figures 2 to 5.
[048] This raw syngas product stream obtained from the combination of the second cooled syngas stream and the additional cooled first syngas stream can be further cooled in one or several additional heat exchangers. This cooling can bring the synthesis gas stream below the dew point temperature. Some or all of the water can thus be removed by condensation to produce a final synthesis gas stream which is directed to the plant's synthesis section, eg Fischer-Tropsch synthesis section.
[049] Alternatively, the first and second streams of synthesis gas can be used separately.
[050] In cases where synthesis gas is required for a Fischer-Tropsch synthesis unit, a residual gas from the Fischer-Tropsch synthesis unit can be added either upstream or downstream to the catalytic side of the heat exchanger reformer . Preferably, the tail gas is added upstream to the autothermal reforming reactor and downstream to the catalytic side of the heat exchange reforming reactor, ie the tail gas is added to the primary reformed gas (see Figure 4). Waste gas contains carbon monoxide, carbon dioxide, hydrogen, various hydrocarbons including olefins and paraffins, and a range of other components.
[051] The by-pass ratio (defined as the flow ratio of the second stream of synthesis gas to the total flow of the hot effluent synthesis gas from the autothermal reformer) is typically between 1% and 30% or between 1 and 35%, preferably between 1% and 20% such as 4 or 16%, more preferably between 1% and 12%.
[052] A plant would normally be designed for a given deviation ratio at the start of operation, eg 12%. As operation proceeds, the outer surface of the tube heat exchanger reformer may become encrusted, which leads to less heat transferred. The actual drift ratio when the plant is in operation will then be adjusted to achieve certain objectives such as a target catalyst exit temperature from the heat exchanger reformer. Reducing the drift ratio from, for example, 12% to, for example, 1% will increase the difference between the stream temperature on the hull side and the temperature on the catalyst side of the heat exchanger reformer. The greater temperature difference will increase the heat transferred, which compensates for the fouling effect. Consequently, in one embodiment of the invention, as the process proceeds, the deviation ratio is reduced over time.
[053] If hydrocarbon feedstock input is reduced, the flow through the heat exchanger reformer and the autothermal reformer is also reduced. In such a partial load situation, the reformer heat exchanger can be too large, which in turn can lead to an unwanted increase in the temperature at the catalyst outlet of the heat exchanger reformer. In that case, the deviation ratio can be increased during this period of "low load" operation to reduce the heat transferred and thus reduce the catalyst exit temperature. Such a case is, for example, an initialization situation of a synthesis section downstream as a Fischer-Tropsch synthesis unit as is further described below in which an operation, for example, takes place with a reduced amount of raw material from hydrocarbon, i.e. reduced charge, for example, about 50% of the natural gas feed rate.
[054] The adjustment of the by-pass ratio can be conveniently done by the appropriate valves located downstream on the side of the heat exchanger reformer hull (preferably, downstream of the third heat exchanger) and also downstream of the second heat exchanger used for cool the second stream of synthesis gas.
[055] An optional third step in the process involves: c. adding a stream comprising steam either to said hot effluent synthesis gas from a step (b) or to said first stream of synthesis gas.
[056] The addition of steam reduces the thermodynamic potential for metal dust corrosion. Preferably, the stream comprising steam consists of greater than 99% steam. For reasons of economy, steam is preferably added to the first stream of synthesis gas. Additional details can be gained by co-pending order no. PCT/EP2011/006179 (WO-A-2012/084135).
[057] In one aspect of the invention, a small amount of the hydrocarbon feedstock bypasses the heat exchanger reformer and is directed to the autothermal reformer. This small amount is, in this modality, less than 25%, preferably less than 10% and more preferably less than 5%.
[058] In another preferred aspect of the invention, the hydrocarbon feedstock is subjected to a pre-reformation step, preferably adiabatic pre-reformation before being directed to the heat exchanger reformer. In the adiabatic pre-reformer, most or all of the higher hydrocarbons (hydrocarbon compounds with 2 or more carbon atoms) are converted according to the following reactions: CnHm + nH2O θ (^m+n)H2 + nCO ( 4)3H2+ CO θ CH4+ H2O (5)CO + H2O θ H2+ CO2 (6)
[059] Reactions (5) and (6) are normally close to equilibrium at the output of the pre-reformer.
[060] In another aspect, the process and plant of the invention are also particularly useful during plant operation without waste gas recycling of the Fischer-Tropsch synthesis section or during startup of the Fischer-Tropsch synthesis section in a plant to produce hydrocarbons. In this situation, no residual gas is available for recycling from the Fischer-Tropsch section as this section is not yet in operation. In a plant based on heat exchange reform followed by series autothermal reform, the ratio of H2/CO that can be generated without waste gas recycling may not be low enough to allow the start-up or operation of the Fischer-section. Tropsch.
[061] To obtain a ratio of H2/CO as low as possible, preferably a molar ratio of H2/CO of 2.5 or below such as 2.4 or 2.3 or 2.2 or 2.1 or 2.0 and, as required by the Fischer-Tropsch synthesis section, recycling part or all of the synthesis gas produced by cooling the hot effluent gas from the autothermal reforming can be performed. Typically, this recycling is done after most of the water has been removed by condensation as described previously.
[062] The recycling of the ATR synthesis gas during the start-up of a downstream synthesis section as a Fischer-Tropsch unit will be done to a point downstream to the catalytic side of the heat exchanger reformer and upstream to the ATR. This means that as recycling increases (to bring the H2/CO ratio down), the flow to the side of the heat exchanger reformer hull also increases. This occurs without a similar increase in flow to the catalytic side of the heat exchanger reformer. In such a situation, the reformer heat exchanger catalyst exit temperature may become undesirably high as more flow is added to the hull side but not to the tube side of the heat exchanger reformer, which thus increases the heat input to the tube side (catalytic side). This can result in carbon formation on the catalyst in the heat exchange reformer as described above. By dividing the ATR hot effluent synthesis gas into a first and second syngas stream, as per the present invention, a gas flow can be bypassed from the hull side of the heat exchanger reformer (first syngas stream ) for the second stream of synthesis gas. This allows for a corresponding reduction in heat input to the hull side of the heat exchanger reformer and will also reduce the H2/CO ratio (H2/CO molar ratio) of the gas leaving the autothermal reformer. This is an advantage for Fischer-Tropsch section initialization.
[063] Consequently, the invention also encompasses a process for initializing the hydrocarbon synthesis section of a gas-to-liquid process which comprises: d. reforming at least a portion of a hydrocarbon feedstock in an endothermic reforming stage in a heat exchanger reformer and extracting from the heat exchanger reformer an effluent stream of primary reformed gas; e. pass the primary reformed gas from the heat exchanger reformer through an autothermal reforming stage (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) and extract a stream of hot effluent synthesis gas; characterized by the fact that the process further comprises the step of dividing the hot effluent synthesis gas into at least a first synthesis gas stream and a second synthesis gas stream wherein said first synthesis gas stream is used as a heating means in indirect heat exchange in the one-step heat exchanger reformer (a); wherein said second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange to produce a second cooled synthesis gas stream; and wherein the process comprises an additional step after the first synthesis gas stream has passed the heat exchanger reformer de: cooling the first synthesis gas stream to a temperature low enough for steam to condense, separating the synthesis gas from said condensate and recycling part or all of this synthesis gas to the ATR, CPO or POx.
[064] As described above, the second heat exchanger is a heat exchanger in which at least a portion, preferably a main portion, particularly 50% or more like 90% or more preferably 100% of that second syngas stream is used to heat a current for which no reforming reaction takes place. Preferably, the second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange with a stream for which no reforming reaction takes place. Preferably, said stream is a stream other than said hydrocarbon feedstock as a stream of boiling feed water to raise steam. Preferably, said second heat exchanger is a waste heat boiler or steam superheater. Additionally, such heat exchangers can be arranged in parallel or in series with said second heat exchanger.
[065] Preferably, this process further comprises adding the second stream of synthesis gas to the first stream of synthesis gas after it has passed through the heat exchanger reformer. Thus, the combined stream is subsequently further cooled to a temperature low enough to allow steam to condense, separate the synthesis gas from the water and preferably recycle some of the synthesis gas to the ATR, CPO or POX. The portion of the synthesis gas that is not recycled is preferably directed to the hydrocarbon synthesis section, eg Fischer-Tropsch synthesis.
[066] In one modality of this process, the deviation ratio, being the ratio of the flow of the second stream of synthesis gas to the flow of the effluent stream of the ATR or CPO or POx is between 10% and 40%, preferably between 20% and 35%, more preferably 30% or 35%.
[067] In another mode of this process for initialization, as the process proceeds, the deviation ratio is constant with time.
[068] In one embodiment, hydrocarbon is a Fischer-Tropsch synthesis section.
[069] As the process proceeds and the amount of synthesis gas recycled to the ATR, CPO or POX is increased, the H2/CO molar ratio of the synthesis gas is reduced with time to a value below 2.5 or 2.4, preferably below 2.3 or 2.2, more preferably below 2.1.
[070] The start-up process allows for a significant reduction in the synthesis gas recycle flow needed to obtain the desired H2/CO molar ratio for a downstream process such as 2.3 or below for a gas to liquid process such as synthesis of Fischer-Tropsch. Reduced recycling translates to smaller, cheaper recycling equipment that requires less compression power. Additionally, irrespective of the lower load used during startup, the invention allows to obtain a lower catalyst exit temperature from the heat exchanger reformer; therefore, the initialization operation can be conducted with a large margin for carbon boundary formation, that is, with less risk of carbon formation.
[071] In yet another aspect and in the case where the produced synthesis gas is for a Fischer-Tropsch process or other downstream process in which the produced tail gas contains olefins, the tail gas is subjected to a hydrogenation step before be directed to the autothermal reformer. In the hydrogenation step, part or all of the unsaturated hydrocarbons such as olefins are converted to paraffins according to the following reaction (given for olefins); CnH2n+ H2 θ CnH2n+2 (for n>2) (7)
[072] The hydrogenation of olefins reduces the potential for carbon settling.
[073] The splitting of the hot effluent gas stream leaving the autothermal reformer seems contradictory to optimizing the process from a capital cost point of view. The heat exchanger reformer itself becomes larger because the current flow on the hull side is reduced. This reduces the difference between the temperature on the hull side and on the catalyst side of the heat exchanger reformer. This means that to transfer a specified amount of heat, the heat transfer area of the heat exchanger reformer needs to be increased. Furthermore, an additional heat exchanger (preferably a waste heat boiler) is introduced, which adds an additional cost.
[074] However, it has been found that the above disadvantages are overcome by the possibility of ensuring that the maximum catalyst temperature outside the heat exchanger reformer is not exceeded and specifically by the improved possibility of maintaining production and plant efficiency over time regardless of the scale, charge and different compositions of natural gas and/or waste gas.
[075] Primary reformed gas can be mixed with tail gas from a Fischer-Tropsch synthesis stage or other downstream process for the production of hydrocarbons as a tail gas (off-gas) from a process for the production of gasoline from methanol and dimethyl ether as, for example, disclosed in document no. US 4,520,216 and no. US 4,481,305.
[076] The addition of such tail gas to the synthesis gas production section allows sufficient carbon dioxide to exist during the reformation to obtain the desired H2/CO molar ratio, typically around 2.0, particularly for the synthesis of Fischer-Tropsch.
[077] As used herein, "waste gas" means effluent gas from the Fischer-Tropsch synthesis stage for diesel production or downstream process for the production of gasoline that is not reused in said stage.
[078] A split stream rich in CO2, ie with at least 90% by volume of CO2 can be added to the primary reformed gas or upstream to the heat exchanger reformer. In one aspect, therefore, the process according to the invention comprises mixing the primary reformed gas or hydrocarbon feedstock with a gas stream comprising at least 90% by volume of CO 2 .
[079] The design heat exchanger reformer can be selected from any heat exchanger arrangement that can transfer heat from the effluent of the autothermal reformer to the process gas. This includes: shell and tube heat exchanger with segmental baffles, dual segment baffles, disc & toroidal baffles, rod baffles, single spiral, double spiral, expanded metal baffle or any other suitable baffle configuration that includes no baffles; double tube reactor with catalyst disposed inside the double tubes, a catalyst disposed outside the double tubes, and/or a catalyst is disposed outside and inside the double tubes.
[080] Suitably, the process of the invention further comprises the step of converting the separated synthesis gas into ammonia synthesis gas, methanol synthesis gas, dimethyl ether (DME) synthesis gas, synthesis gas for hydrocarbon production by Fischer-Tropsch synthesis or synthesis gas for the production of hydrogen and further conversion of said synthesis gas to the respective product in the form of ammonia, methanol, DME, liquid hydrocarbons or hydrogen.
[081] In a particular embodiment of the invention, a portion of the hydrocarbon feedstock bypasses the heat exchanger reformer to form a bypass stream. A tail gas is added to this bypass stream in case the resulting synthesis gas is used for the Fischer-Tropsch synthesis or downstream process for gasoline production as described above.
[082] A portion of the hydrocarbon feedstock may be added as a by-pass stream to the primary reformed gas to form a combined stream prior to entering the ATR, CPO or POX. In a particular embodiment, a tail gas is added to this bypass stream and the stream thus formed is combined with the primary reformed gas in case the resulting synthesis gas is used for the Fischer-Tropsch synthesis or downstream process for the gasoline production as described above.
[083] During the process, the pressure measured at the output of the ATR is suitably between 1,500 to 8,000 kPa (15 to 80 bar), preferably between 2,000 to 5,000 kPa (20 to 50 bar).
[084] In the process according to the invention, the steam to process carbon ratio (S/Cprocess) is suitably in the range from 0.4 to 3.0, preferably from 0.5 to 1.2, more preferably from 0.50 to 1.00. In particular, when synthesis gas is used for the Fischer-Tropsch synthesis, the steam to process carbon ratio (S/Cprocess) is between 0.4 and 1.3, preferably between 0.6 and 1.1 .
[085] The steam to process carbon ratio, S/Cprocess, means the number of moles of steam divided by the number of moles of hydrocarbon carbon. The number of moles of steam includes all steam added to the hydrocarbon feedstock, eg natural gas, upstream to the heat exchanger reformer. Hydrocarbon carbon includes hydrocarbons present in the raw material. The S/Cprocess ratio is measured upstream to the heat exchanger reformer or upstream to the pre-reformer (if present).
[086] Suitably, for a Fischer-Tropsch process, the molar ratio of H2/CO in the cooled synthesis gas stream in the first synthesis gas stream is in the range of 1.7 to 2.3, preferably in the range of 1.9 to 2.1.
[087] In the case of methanol synthesis, the following molar ratio of synthesis gas components is between 1.7 and 2.3, preferably between 1.9 and 2.1:H2 — CO2CO + CO2
[088] In a specific modality, the process comprises using valves installed immediately downstream of said heat exchangers, preferably waste boilers, to cool the first and second stream of synthesis gas to control the deviation ratio.
[089] In a particular embodiment of the invention, two or more heat exchanger reformers are operated in parallel. This can provide advantages over the ease of fabrication of large diameter containers containing hundreds of reformer tubes and can allow fine control of the process as well as easier maintenance. hydrocarbon is reformed in an endothermic reforming stage in a second heat exchanger reformer and a second primary reformed gas effluent stream is extracted from said second heat exchanger reformer;- said second primary reformed gas effluent stream is combined with the stream primary reformed gas effluent obtained from the reforming of the first portion of said hydrocarbon feedstock; - the combined primary reformed gases from the heat exchanger reformers are passed through an autothermal reforming (ATR) stage, catalytic partial oxidation stage ( CPO) or partial oxidation stage (POX), and a stream of synthesis gas effluents hot effluent is extracted; - the hot effluent synthesis gas from the autothermal reforming stage (ATR), the catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) is divided into at least a first stream of synthesis gas , a second syngas stream and a third syngas stream,
[090] As before, the first stream of synthesis gas is used as the heating medium in indirect heat exchange in the one-stage heat exchanger reformer (a); and said second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange to produce a second stream of cooled synthesis gas. In addition, the third syngas stream is used as the heating medium in indirect heat exchange in the second heat exchanger reformer.
[091] Also as described above, the second heat exchanger is a heat exchanger in which at least a portion, preferably a main portion, particularly 50% or more as 90% or more preferably 100% of that second stream of synthesis gas it is used to heat a current for which no reforming reaction takes place. Preferably, the second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange with a stream for which no reforming reaction takes place. Preferably, said stream is a stream other than said hydrocarbon feedstock as a stream of boiling feed water to raise steam. Preferably, said second heat exchanger is a waste heat boiler or steam superheater. Additionally, such heat exchangers can be arranged in parallel or in series with said second heat exchanger. The invention also provides a plant for the production of synthesis gas from a hydrocarbon feedstock as illustrated schematically in Figures 1 to 5.
[092] The plant comprises an arrangement of: - at least one heat exchanger reformer to produce a primary reformed gas by reforming at least a portion of said hydrocarbon feedstock, - an autothermal reformer (ATR) or oxidation apparatus catalytic partial (CPO) or a partial oxidation (POX) apparatus for producing said hot effluent synthesis gas from at least a portion of the primary reformed gas from said heat exchanger reformer; hot effluent synthesis, which thus forms said mixing stream, - means for dividing the hot effluent mixing/synthesis stream into at least a first synthesis gas stream and a second synthesis gas stream, - means for supplying the first stream of synthesis gas on the hull side of the heat exchanger reformer, and a second heat exchanger through which the second stream of synthesis gas is fed.
[093] Preferably, said second heat exchanger is a waste heat boiler or a steam superheater.
[094] In a specific modality, the plant also comprises a first heat exchanger, preferably a waste heat boiler, for additional cooling of the first synthesis gas after passing through the heat exchanger reformer.
[095] In another specific modality, the plant also comprises valves installed immediately downstream of said first and said second heat exchanger. Such valves are advantageously used to control the deviation ratio.
[096] As mentioned above, preferably said first and said second heat exchanger are a waste heat boiler.
[097] Suitably, the plant additionally comprises an adiabatic pre-reformer upstream to the heat exchanger reformer.
[098] In Figure 1, a hydrocarbon feedstock 10 is formed in a pre-reformer 15 from a stream of hydrocarbon 11 and steam 12. The hydrocarbon feedstock 10 is passed to the heat exchanger reformer. 25 where it is catalytically reformed by steam, thereafter it leaves the heat exchanger reformer as a stream 30. The primary reformed gas 30 is fed to an autothermal reformer 75 which is also supplied with an oxidizer 80. The primary reformed gas is partially combusted and equilibrated over the reforming catalyst in the autothermal reformer 75. The hot effluent synthesis gas 90 from the autothermal reformer 75 is divided into a first 111 and a second 112 syngas streams. A heat is recovered from the first synthesis gas stream 111 by passing it to the heat exchanger reformer 25. This first synthesis gas stream 111 is cooled by heat exchange with the reforming gas over the catalyst in the reformer heat exchanger 25. A cooled first syngas stream 111 thus leaves the heat exchanger reformer as stream 121. A second syngas stream 112 is passed through a waste heat boiler 115 to produce a second stream of cooled synthesis gas 122 through heat exchange. In the embodiment shown in Figure 1, a second cooled synthesis gas stream 122 and a cooled first synthesis gas stream 121 are not combined.
[099] In Figure 2, a hydrocarbon feedstock 10 is formed in a pre-reformer 15 from a hydrocarbon stream 11 and a steam 12. A hydrocarbon feedstock 10 is passed to the heat exchanger reformer. heat 25 where it is catalytically reformed by steam and thereafter leaves the heat exchanger reformer as a stream 30. A primary reformed gas stream 30 is fed to an autothermal reformer 75 to which an oxidizer 80 is also supplied. The primary reformed gas stream 30 is partially combusted and balanced over the reforming catalyst in the autothermal reformer 75. The hot effluent synthesis gas 90 from the autothermal reformer 75 is divided into a first 111 and a second 112 synthesis gas stream. A heat is recovered from the first synthesis gas stream 111 by passing it to the heat exchanger reformer 25. This first synthesis gas stream 111 is cooled by heat exchange with the reforming gas over the catalyst in the heat exchanger reformer 25. The first cooled syn gas stream thus leaves the heat exchanger reformer as a stream 121. The first cooled syn gas stream 121 is then further cooled in a third heat exchanger 116 (e.g. a waste heat boiler) to supply an additional cooled first syngas stream 131. The second syngas stream 112 is passed through a waste heat boiler 115 to produce steam via heat exchange . As shown in Figure 2, the second cooled synthesis gas stream 122 then joins the additional cooled first synthesis gas stream 131 downstream of the heat exchanger reformer 25 and the third heat exchanger 131 to form a combined stream of synthesis gas 120.
[100] Figure 3 illustrates a development of the embodiment of Figure 2. Figure 3 also shows the step in which hot effluent synthesis gas 90 from autothermal reformer 75 is mixed with a stream of H2O 100 to form a combined stream 105 before to be divided into a first 111 and a second 112 stream of synthesis gas. In addition, Figure 3 shows the step in which the combined stream of synthesis gas 120 is further cooled in series cooling and separating units 125 and separated into product synthesis gas 130 and process condensate 140.
[101] Figure 4 illustrates a development of the embodiment of Figure 3 in which the primary reformed gas 30 is mixed with Fischer-Tropsch 60 tail gas which forms the ATR 70 feed stream. The primary reformed gas 30 is mixed with gas residual 60 (which contains CH4, higher hydrocarbons, olefins, etc.) and other gases (H2, CO, CO2, N2, etc.). This supply stream 70 is fed to the ATR 75 where it is partially burned and further catalytically reformed for balance. Figure 4 also shows the optional step in which hot effluent synthesis gas 90 from autothermal reformer 75 is mixed with a stream of H2O 100 to form a combined stream 105 before being split into a first 111 and a second 112 gas stream. of synthesis. Finally, in Figure 4, the cooled synthesis gas 120 leaving the heat exchanger reformer 25 is further cooled in series cooling and separation units 125 to a low temperature, eg 40 to 80°C and separated as synthesis gas 130 of the condensate, i.e. water and dissolved gases. Heat can be used for steam and pre-heating purposes.
[102] The embodiment of Figure 5 is based on that of Figure 4. The hydrocarbon feedstock 10 is divided into two streams 20 and 40. The first stream 20 is fed to the heat exchanger reformer 25 where it is catalytically reformed by steam and thereafter leaves the heat exchanger reformer as primary reformed gas 30. The second stream 40 is preheated in a heat exchanger 45 to provide preheated stream 50. The preheated stream 50 and the gas Primary reformer 30 are mixed together with Fischer-Tropsch 60 tail gas which forms the ATR feed stream 70. The ATR feed stream is fed to the autothermal reformer 75 to which oxidizer 80 is also supplied. The ATR feed stream is partially combusted and is balanced over reforming catalyst in autothermal reformer 75. The hot effluent synthesis gas 90 from autothermal reformer 75 is divided into a first 111 and a second 112 syngas stream. Heat is recovered from the first synthesis gas stream 111 by passing it to the heat exchanger reformer 25. This first synthesis gas stream 111 is cooled by heat exchange with the reforming gas over the catalyst in the reformer heat exchanger 25. The first cooled syn gas stream thus leaves the heat exchanger reformer as stream 121. The first cooled syn gas stream 121 is then further cooled in a third heat exchanger 116 (by example, a waste heat boiler) to supply a further cooled first syngas stream 131. The second syngas stream 112 is passed through a waste heat boiler 115 to produce steam through heat exchange. As shown in Figure 2, the second cooled syngas stream 122 then joins the additional cooled first syngas stream 131 downstream of the heat exchanger reformer 25 and the third heat exchanger 131 to form a combined stream. of syngas 120. In addition, Figure 5 shows the step in which the combined syngas stream 120 is further cooled in the cooling series and in the separation units 125 and separated into the product syngas 130 and the condensate of process 140.
[103] In Figures 2 to 5, valves downstream of heat exchangers 115 and 116 are indicated. It is preferred that one or both of these valves are installed and used to control the deviation ratio.
[104] In a further aspect, the invention provides a parallel arrangement of heat exchanger reformer and autothermal reformer (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX). In this way, a process for the production of synthesis gas from a hydrocarbon feedstock is provided which comprises the steps of: a. splitting the hydrocarbon feedstock into at least a first and a second hydrocarbon feedstock stream; b. reforming said first hydrocarbon feedstock stream in an endothermic reforming stage in one or more heat exchanger reformers and extracting from the heat exchanger reformer an effluent stream of reformed gas; c. pass the second hydrocarbon feedstock stream through an autothermal reforming stage (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) and extract a stream of hot effluent synthesis gas; characterized by fact that the process comprises the step of dividing said hot effluent synthesis gas into at least a first synthesis gas stream and a second synthesis gas stream, wherein said first synthesis gas stream is used as a heating means in indirect heat exchange in the one-stage heat exchanger reformer (b); and wherein said second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange to produce a second stream of cooled synthesis gas.
[105] Also as before, the second heat exchanger is a heat exchanger in which at least a portion, preferably a main portion, particularly 50% or more like 90% or more preferably 100% of that second stream of synthesis gas it is used to heat a current for which no reforming reaction takes place. Preferably, the second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange with a stream for which no reforming reaction takes place. Preferably, said stream is a stream other than said hydrocarbon feedstock as a stream of boiling feed water to raise steam. Preferably, said second heat exchanger is a waste heat boiler or steam superheater. Additionally, such heat exchangers can be arranged in parallel or in series with said second heat exchanger. In a particular embodiment according to this further aspect of the invention, the first stream of synthesis gas may be combined with reformed gas from the heat exchanger reformer before delivering heat to said heat exchanger reformer.
[106] The plant for the production of synthesis gas from a hydrocarbon feedstock in a parallel arrangement comprises an arrangement of: - means for dividing the hydrocarbon feedstock into at least a first and a second material stream - hydrocarbon feedstock; - at least one heat exchanger reformer arranged to reform said first hydrocarbon feedstock stream in an endothermic reforming stage to provide an effluent stream of reformed gas; - an autothermal reforming stage ( ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) arranged to pass the second hydrocarbon feedstock stream through it so as to provide a hot effluent synthesis gas stream; - optionally, means to add steam to said hot effluent synthesis gas, which thus forms a mixing stream; means for dividing the hot effluent mixing/synthesis stream into powder. at least one first syngas stream and at least one second syngas stream; - means for supplying the first syngas stream on the hull side of the heat exchanger reformer, and - a second heat exchanger through the which the second stream of synthesis gas is fed.
[107] In a specific modality, the plant also comprises a third heat exchanger arranged downstream to the hull side of the heat exchanger reformer for additional cooling of the first synthesis gas after passing it through the heat exchanger reformer. It will be understood that such third heat exchanger is arranged in series with the heat exchanger reformer.
[108] In another specific modality, the plant comprises means to combine the cooled second synthesis gas from the second heat exchanger with the additional cooled first synthesis gas from the third heat exchanger.
[109] In yet another specific modality, the plant also comprises means to adjust the deviation ratio, preferably valves installed or arranged downstream, more preferably immediately downstream of said second and said third heat exchangers. Preferably, said second and said third heat exchanger are a waste heat boiler.
[110] Suitably, the plant additionally comprises an adiabatic pre-reformer upstream to the heat exchanger reformer.
[111] In yet another aspect, the invention as recited in claim 22 also encompasses the use of the process according to any one of claims 1 to 16 or the plant according to any one of claims 17 to 21 during the initialization of the section of Fischer-Tropsch synthesis in a plant to produce hydrocarbons or downstream process for gasoline production.
[112] The present invention is not to be limited by the above description and enclosed figures. Instead, the person skilled in the art will be able to combine resources of various modalities while remaining within the scope of the claims. In particular, some embodiments show that a steam is added to the hot effluent synthesis gas 90 from the ATR and that the first 121 and second 122 streams of cooled synthesis gas are combined, these steps are optional.
[113] A process using the bypass current of the present invention as shown in Figure 4 is shown in this example (as New Disposition). This is compared to a process where the bypass current of the present invention is not used (Reference Arrangement).
[114] It is shown that it is possible by the implementation of the present invention to cancel the influence of heat exchanger surface fouling in a heat exchanger reformer by controlling the amount of hot effluent synthesis gas from an autothermal reformer sent to the side. hull of the heat exchanger reformer, thus obtaining constant performance from the plant.
[115] The feed gas (not shown in Figure 4) is mixed with hydrogen and desulfurized to form a stream 11. It is mixed with steam (stream 12 in Figure 4) and sent to an adiabatic pre-reformer (15 ). The effluent from the pre-reformer (stream 10) is sent to the process side of a heat exchanger reformer (25). The effluent from the heat exchanger reformer (stream 30) is mixed with waste gas (stream 60) and sent to an autothermal reformer (75) where it is partially burned and reformed to equilibrium, which produces a hot effluent stream (stream 90) ). No steam (100 stream) is mixed into the hot effluent stream.
[116] Four cases are shown: Case 1.1. Execution Start Reference Arrangement (SOR Ref). The heat exchanger reformer is descaled and all the gas from the autothermal reformer is sent to the heat exchanger reformer, ie the deviation ratio = 0.Case 1.2. End of Execution Reference Arrangement (EOR Ref). The heat exchanger reformer is encrusted and all the gas from the autothermal reformer is sent to the heat exchanger reformer, ie the deviation ratio = 0.Case 1.3. New Execution Start disposition (New SOR). The heat exchanger reformer is descaled and 88% of the gas from the autothermal reformer is sent to the heat exchanger reformer. 12% are diverted (diversion ratio) through the current 112.Case 1.4. New End of Execution disposition (New EOR). The heat exchanger reformer is encrusted and 99% of the gas from the autothermal reformer is sent to the heat exchanger reformer. 1% is bypassed (shift ratio) via current 112.
[117] The performance of the heat exchanger reformer in the 4 cases is summarized in Table 1.1
[118] It is observed that it is possible to have the same performance of the heat exchanger reformer at the Start of Execution and at the End of Execution with the use of the new arrangement according to the present invention. Exit temperature and transfer rate are the same under SOR and EOR conditions. The transferred rate is the amount of energy that is transferred per unit of time from the flowing gas hull side to the flowing gas tube side in the heat exchanger reformer. By gradually adjusting the amount of gas from the autothermal reformer over the operating period from descaled to encrusted conditions, it is possible to maintain the same performance at any time.
[119] This is not the case in the Reference Arrangement (no bypass current). Performance is lower under EOR conditions compared to SOR. The outlet temperature under EOR conditions is 15°C lower and the transfer rate is 8.1 Gcal/h lower corresponding to 7%.TABLE 1.1 DECALOR EXCHANGE REFORMER PERFORMANCE.

[120] Table 1.2 shows the overall performance of the syngas mill for the 4 cases. It is observed that, in the new arrangement using the present invention, the same amount of syngas and CO is produced under conditions of EOR as compared to those of SOR. The amount of CO produced by unitary natural gas and unitary oxygen is also constant over the entire operating period from scale to scale conditions.
[121] In the Reference Arrangement, the amount of syngas and CO produced under EOR condition is smaller under EOR conditions compared to SOR. The amount of CO produced is 1,213 Nm3/h less corresponding to 0.7%. The amount of CO produced by unitary natural gas and unitary oxygen is also smaller, by unitary oxygen, the quantity is 2.3% smaller.TABLE 1.2. GENERAL PROCESS PERFORMANCE

[122] In summary, this example shows that the performance of a heat exchanger reformer and a syngas plant can sustain constant performance by using an arrangement that includes a by-pass current in accordance with the present invention. If the bypass current of the invention is not used and all the gas from the autothermal reformer is sent to the heat exchanger reformer, the result will be a gradual decrease in performance.
[123] A process using the present invention as shown in Figure 3 (no addition of tail gas) is presented in this example (as a new arrangement). This is compared to the Reference Arrangement which is a process where the present invention is not used, ie all the gas (stream 111 in Figure 3) is sent from the hull side of the heat exchanger reformer.
[124] It is shown that it is possible, by the implementation of the present invention, to cancel the influence of heat exchanger surface fouling in a heat exchanger reformer by controlling the amount of hot effluent synthesis gas from an autothermal reformer sent to the side of the hull of the heat exchanger reformer.
[125] With reference to Figure 3. The feed gas (not shown in Figure 3) is mixed with hydrogen and desulfurized to form a stream 11. It is mixed with steam (stream 12) and is sent to a pre-reformer adiabatic (15). The effluent from the pre-reformer (stream 10) is sent to the process side of a heat exchanger reformer (25). The effluent from the heat exchanger reformer (stream 30) is sent to an autothermal reformer (75) where it is partially burned and formed to equilibrium producing a hot effluent stream (stream 90). No steam (100 stream) is mixed into the hot effluent stream. No residual gas is mixed in the heat exchanger reformer effluent (stream 30).
[126] Four cases are shown:126.1. Execution Start Reference Arrangement (SOR Ref). The heat exchanger reformer is descaled and all the gas from the autothermal reformer is sent to the heat exchanger reformer via stream 111, ie the deviation ratio = 0.126.2. End of Execution Reference Disposition (EOR Ref). The heat exchanger reformer is encrusted and all the gas from the autothermal reformer is sent to the heat exchanger reformer via stream 111, ie the deviation ratio = 0.126.3. New Start of Execution arrangement (New SOR).The heat exchanger reformer is descaled and 84% of the gas from the autothermal reformer is sent to the heat exchanger reformer (stream 111). 16% are bypassed through current 112, ie, the deviation ratio = 16%.126.4. New End of Execution disposition (New EOR). The heat exchanger reformer is encrusted and 96% of the gas from the autothermal reformer is sent to the heat exchanger reformer (stream 111). 4% are bypassed through current 112, ie, the deviation ratio = 4%.
[127] The performance of the heat exchanger reformer in the 4 cases is summarized in Table 2.1. It is observed that it is possible to have the same performance of the heat exchanger reformer at Start of Run and End of Run with the use of the new arrangement with the present invention. Exit temperature and transfer rate are the same under SOR and EOR conditions. The transferred rate is the amount of energy that is transferred per unit of time from the flowing gas hull side to the flowing gas tube side in the heat exchanger reformer. By gradually adjusting the amount of gas from the autothermal reformer throughout the entire operating period from descaled to encrusted conditions, it is possible to maintain the same performance at any time.
[128] This is not the case in the Reference Provision. Performance is lower under EOR conditions compared to SOR. The outlet temperature under EOR conditions is 19°C lower and the transferred rate is 8.5 Gcal/h lower corresponding to 10%.TABLE 2.1. DECALOR EXCHANGE REFORMER PERFORMANCE

[129] Table 2.2 shows the overall performance of the syngas unit for the 4 cases. It is observed that in the new arrangement, using the present invention, the SOR synthesis gas module is kept in EOR operation. Furthermore, the same amount of syngas and CO are produced under EOR conditions as compared to SOR.
[130] The amount of CO produced by unitary natural gas and unitary oxygen is also constant over the entire operating period from scale to scale conditions.
[131] In the Reference arrangement, the synthesis gas modulus was decreased by 1.5% in EOR compared to SOR. The amount of syngas and CO produced under EOR condition is less than under SOR conditions. The amount of CO produced is 342 Nm3/h lower, corresponding to 0.3%. The amount of CO produced by unitary natural gas and unitary oxygen is also smaller; the latter by 2.7%.TABLE 2.2. GENERAL PROCESS PERFORMANCE

[132] In summary, this example shows that the performance of the heat exchanger reformer in a syngas plant can sustain constant performance by using an arrangement of the present invention. If this invention is not used and all the gas from the autothermal reformer is sent to the heat exchanger reformer, a gradual decrease in performance will be the consequence.EXAMPLE 3. STARTUP
[133] A process using the present invention as shown in Figure 3 is shown in this example (as a New Disposition). This is compared to the Reference Arrangement which is a process where the present invention is not used, ie all the gas leaving the autothermal reformer is sent by the hull side of the heat exchanger reformer (drift ratio = 0).
[134] In this example it is shown that it is possible, by the implementation of the present invention, to cancel an excess temperature increase in the stream that leaves the process side of the heat exchanger reformer (stream 30) during an operation configuration in which part of the Synthesis gas (STM 130) is recycled to the autothermal reformer (75) to achieve an H2/CO ratio low enough to start up (or operate) a FT synthesis unit in the event that no residual gas is available. In the present example, the target H2/CO ratio was set to 2.3, but various TF syntheses will have varying requirements in many different cases of H2/CO = 2.3. Note that the recycling of part of the synthesis gas (STM 130) to the autothermal reformer (75) is not shown in Figure 3.
[135] In this case, the heat exchanger reformers are designed for normal operation with a feed flow of 150,000 Nm3/h of natural gas (see Example 1). Heat exchange reformers are designed to have a catalyst side exit temperature of 730°C during normal operation under descaled conditions. The unit in this example 3 operates with a natural gas feed rate of 75,000 Nm3/h. corresponding to 50% of the design flow rate.
[136] Referring to Figure 3; the feed gas (not shown in Figure 3) is mixed with hydrogen and desulfurized to form a stream 11. It is mixed with steam (stream 12) and is sent to an adiabatic pre-reformer (15). The effluent from the pre-reformer (stream 10) is sent to the process side of a heat exchanger reformer (25). The effluent from the heat exchanger reformer (stream 30) and a portion of the synthesis gas (stream 130) are combined and sent to the autothermal reformer (75) in which they are partially burned using oxygen (stream 80) and reformed to equilibrium, producing a hot effluent stream (stream 90). No steam (100 stream) is mixed into the hot effluent stream. No tail gas is mixed into the heat exchanger reformer effluent (stream 30) at this point of operation. In all three cases, the flow, feed gas composition, temperature, pressure, and vapor to carbon ratio have the same values. in the stream just upstream to the heat exchanger reformer (stream 10 in Figure 3). Three cases are shown:136.1. Reference Disposition (de-embedded). All gas from the autothermal reformer is sent to the heat exchanger reformer via stream 111. No flow in bypass steam 112, ie, the bypass ratio = 0.136.2. New layout (unincrusted). 70.1% of the gas from the autothermal reformer is sent to the heat exchanger reformer (stream 111). 29.9% are bypassed through current 112, ie, the deviation ratio = 30%.136.3. New layout (unincrusted). 64.6% of the gas from the autothermal reformer is sent to the heat exchanger reformer (stream 111). 35.4% is sent through stream 112, ie, the deviation ratio = 35%.
[137] The performances of the heat exchanger reformers in the 3 cases are summarized in Table 3.1.
[138] It is observed that it is possible to considerably reduce the transferred rate and the temperature of the exit process side of the heat exchanger reformer with the use of the new arrangement with the present invention. The transferred rate is the amount of energy that is transferred per unit of time from the flowing gas hull side to the flowing gas tube side in the heat exchanger reformer. By adjusting the amount of gas from the autothermal reformer to the hull side heat exchanger reformer, it is possible to maintain conditions without excessive temperatures at the catalyst output of the heat exchanger reformer also at reduced load and with recycling of part of the synthesis gas, by example, for initialization of the downstream Fischer-Tropsch synthesis unit.
[139] This is not the case in the Reference provision. The large transfer rate in case 3.1 results in a large gas temperature increase on the process side (stream 30) from 730°C in normal operation to 781°C, both in descaled condition.TABLE 3.1. DECALOR EXCHANGE REFORMER PERFORMANCE


[140] Table 3.2 shows the overall performance of the syngas unit for the 3 cases. It is observed that in the new arrangement, using the present invention, the required recycle flow of synthesis gas to obtain H2/CO = 2.3 in the synthesis gas decreases considerably (by 11.3% with a hull deviation of 29, 9%) compared to the Reference provision. This has a positive impact on recycling equipment that gets smaller and cheaper that gets smaller and cheaper and that requires less power. Furthermore, due to the lower temperature, the new arrangement using the present invention results in operation with a greater margin for carbon boundary formation (reaction according to equation 1) compared to the Reference arrangement. As indicated previously, for otherwise identical conditions, the margin for carbon formation increases with decreasing temperature. Catalyst temperature is substantially lower in the new arrangement compared to the Reference arrangement.TABLE 3.2. GENERAL PROCESS PERFORMANCE


[141] In summary, this example shows that, using an arrangement with the present invention, the output of excessive temperatures on the process side of the heat exchanger reformer during low load and process configuration for starting a Fischer-Tropsch unit to downstream can be avoided. Additionally, the required recycle flow of synthesis gas to achieve the desired H2CO ratio is smaller and the distance to the carbon threshold for decomposition to CH4 is greater than in the reference case.

权利要求:
Claims (28)
[0001]
1. Process for the production of synthesis gas from a hydrocarbon feedstock comprising the steps of: a. reforming at least a portion of said hydrocarbon feedstock in an endothermic reforming stage in a heat exchanger reformer and extracting from the heat exchanger reformer an effluent stream of primary reformed gas; b. pass the primary reformed gas from the heat exchanger reformer through an autothermal reforming stage (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) and extract a stream of hot effluent synthesis gas; characterized by fact that the process further comprises step (c) of dividing the hot effluent synthesis gas into at least a first synthesis gas stream and a second synthesis gas stream, wherein said first synthesis gas stream is used as a heating medium in an indirect heat exchange in the one-stage heat exchanger reformer (a) with an outlet temperature in the range of 450-800°C; and wherein said second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by an indirect heat exchange to produce a second stream of cooled synthesis gas.
[0002]
2. Process according to claim 1, characterized in that it further comprises the step of: adding a stream comprising steam to hot effluent from step (b) or to said first stream of synthesis gas.
[0003]
3. Process according to claim 1, characterized in that the hydrocarbon feedstock is subjected to a pre-reformation step, preferably adiabatic pre-reformation before being directed to the heat exchanger reformer.
[0004]
4. Process according to claim 1, characterized in that the process comprises an additional step after the first stream of synthesis gas has passed the heat exchanger reformer of: cooling the first stream of synthesis gas to a temperature low enough for the steam to condense and separate the synthesis gas from said condensate.
[0005]
5. Process according to claim 1, characterized in that it further comprises mixing the primary reformed gas with residual gas from a Fischer-Tropsch synthesis stage or downstream process for the production of gasoline.
[0006]
6. Process according to claim 1, characterized in that the diversion ratio of a second stream of synthesis gas to the flow of the effluent stream of the autothermal reformer is between 1% and 30%.
[0007]
7. Process according to claim 6, characterized in that, as the process proceeds, the deviation ratio is reduced over time.
[0008]
8. Process according to claim 1, characterized in that it comprises mixing the primary reformed gas or hydrocarbon feedstock with a gas stream comprising at least 90% by volume of CO2.
[0009]
9. Process according to claim 1, characterized in that the heat exchanger reformer is selected from a tube and shell heat exchanger and a double tube reactor with catalyst disposed inside the double tubes, catalyst disposed outside the double tubes and/or catalyst disposed outside and inside the double tubes.
[0010]
10. Process according to claim 1, characterized in that the primary reformed gas from the heat exchanger reformer is passed through an autothermal reforming (ATR) stage.
[0011]
11. Process according to claim 1, characterized in that it further comprises the step of converting the separated synthesis gas into ammonia synthesis gas, methanol synthesis gas, dimethyl ether synthesis gas (DME), synthesis gas for the production of hydrocarbons by Fischer-Tropsch synthesis or synthesis gas for the production of hydrogen and which additionally converts said synthesis gas into the respective product in the form of ammonia, methanol, DME, liquid hydrocarbons in a downstream process for the production of gasoline or hydrogen.
[0012]
12. Process according to claim 1, characterized in that a portion of the hydrocarbon feedstock is carried directly by a by-pass stream to the primary reformed gas to form a combined stream before entering the ATR, CPO or POX
[0013]
13. Process according to claim 1, characterized in that the steam to process carbon ratio (S/Cprocess) is in the range of 0.4 to 3.0.
[0014]
14. Process according to claim 1, characterized in that the ratio of H2/CO-molar in said stream of cooled synthesis gas in the first stream of synthesis gas is in the range of 1.7 to 2.3 .
[0015]
15. Process according to claim 1, characterized in that, after the heat exchanger reformer, cooled synthesis gas or additionally cooled synthesis gas, the first stream of cooled or additionally cooled synthesis gas and the second stream of cooled synthesis gas are mixed together to provide a raw synthesis gas product stream.
[0016]
16. Process according to claim 1, characterized in that: a. at least a second portion of said hydrocarbon feedstock is reformed in an endothermic reforming stage in at least one second heat exchanger reformer and a second primary reformed gas effluent stream is withdrawn from said second heat exchanger reformer;b. said second primary reformed gas effluent stream is combined with the primary reformed gas effluent stream of the hydrocarbon feedstock; c. the combined primary reformed gases from the heat exchanger reformers are passed through an autothermal reforming (ATR) stage, catalytic partial oxidation (CPO) stage or partial oxidation (POX) stage and a stream of hot effluent synthesis gas is extracted; d. the hot effluent synthesis gas from the autothermal reforming stage (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) is divided into at least a first synthesis gas stream, a second gas stream. synthesis gas and a third synthesis gas stream, and wherein said first synthesis gas stream is used as a heating medium in indirect heat exchange in the one-stage heat exchanger reformer (a) with an outlet temperature at range 450-800°C; and wherein said second stream of synthesis gas is directed to a second heat exchanger in which it is cooled by indirect heat exchange to produce a second stream of cooled synthesis gas; and wherein said third stream of synthesis gas is used as a heating medium in indirect heat exchange in the second heat exchanger reformer.
[0017]
17. Process according to claim 1, characterized in that it comprises the beginning of the Fischer-Tropsch synthesis to produce hydrocarbons or a downstream process for the production of gasoline.
[0018]
18. Process according to claim 1, characterized in that the first stream of synthesis gas is combined with reformed gas from the heat exchanger reformer before delivering heat to said heat exchanger reformer.
[0019]
19. A process for starting the hydrocarbon synthesis section of a gas-to-liquid process comprising: a. reforming at least a portion of a hydrocarbon feedstock in an endothermic reforming stage in a heat exchanger reformer and extracting an effluent stream of primary reformed gas from the heat exchanger reformer; b. pass the primary reformed gas from the heat exchanger reformer through an autothermal reforming stage (ATR), catalytic partial oxidation stage (CPO) or partial oxidation stage (POX) and extract a stream of hot effluent synthesis gas; characterized by fact that the process further comprises the step of dividing the hot effluent synthesis gas into at least a first synthesis gas stream and a second synthesis gas stream, wherein said first synthesis gas stream is used as a heating medium in indirect heat exchange in the one-stage heat exchanger reformer (a) with an outlet temperature in the range of 450-800°C; wherein said second stream of synthesis gas is directed to a second heat exchanger heat in which it is cooled by indirect heat exchange to produce a second stream of cooled synthesis gas; and wherein the process comprises an additional step after the first stream of synthetic gas if you have gone through the heat exchanger reformer to: cool the first stream of synthesis gas to a temperature low enough for steam to condense, separate the synthesis gas from said condensate and recycle some or all of this synthesis gas to the ATR, CPO or POx
[0020]
20. Process according to claim 19, characterized in that it further comprises adding the second stream of synthesis gas to the first stream of synthesis gas after it has passed through the heat exchanger reformer.
[0021]
21. Process according to claim 20, characterized in that the diversion ratio of the second stream of synthesis gas flow to the flow of the effluent stream of the ATR or CPO or POx is between 10% and 40%.
[0022]
22. Process according to claim 21, characterized in that, as the process proceeds, the deviation ratio is constant with time.
[0023]
23. Process according to claim 19, characterized in that the ratio of H2/CO-molar in the synthesis gas stream is reduced with time to a value below 2.5.
[0024]
24. Process according to claim 1, characterized in that the pre-reformation step comprises adiabatic pre-reformation before being directed to the heat exchanger reformer.
[0025]
25. Process according to claim 6, characterized in that the flow deviation ratio of the second stream of synthesis gas to the flow of the effluent stream of the autothermal reformer is between 1% and 12%.
[0026]
26. Process according to claim 13, characterized in that the ratio of steam to carbon is in the range of 0.5 to 1.0.
[0027]
27. Process according to claim 21, characterized in that the diversion ratio of the second stream of synthesis gas flow to the flow of the effluent stream of the ATR or CPO or POx is between 30% and 35%.
[0028]
28. Process according to claim 23, characterized in that the molar ratio of H2/CO of the synthesis gas is reduced with time to a value below 2.1.

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同族专利:

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公开号 | 公开日

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UA117459C2|2018-08-10|

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KR20150028311A|2015-03-13|

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US9434613B2|2016-09-06|

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US10029224B2|2018-07-24|

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US20160325253A1|2016-11-10|

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KR102060451B1|2020-02-11|

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EA030103B1|2018-06-29|

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US20150321913A1|2015-11-12|

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MX2014015216A|2015-03-05|

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EP2676924A1|2013-12-25|

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EA201590063A1|2015-05-29|

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US9156689B2|2015-10-13|

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CA2877165C|2019-07-23|

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US20130345324A1|2013-12-26|

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CN104411625A|2015-03-11|

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ZA201409403B|2016-08-31|

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AU2013279617A1|2015-01-22|

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AR091493A1|2015-02-11|

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MX349716B|2017-08-10|

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EP2864243A1|2015-04-29|

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AU2013279617B2|2016-11-24|

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CN104411625B|2017-05-17|

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WO2013189791A1|2013-12-27|

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BR112014032213A2|2017-06-27|

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CA2877165A1|2013-12-27|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-04-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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