WO2014042042A1 - 改質装置及び改質方法、改質装置を備えた化成品の製造装置及び化成品の製造方法 - Google Patents
改質装置及び改質方法、改質装置を備えた化成品の製造装置及び化成品の製造方法 Download PDFInfo
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- 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
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Definitions
- the present invention relates to a reformer for reforming natural gas using natural gas as fuel for a reformer for reforming natural gas or the like, and a chemical product manufacturing apparatus having the reformer.
- reformed gas obtained by reforming natural gas or the like with a reformer is used (for example, see Patent Documents 1 and 2).
- a part of the natural gas is extracted and used as a reformer fuel before supplying the natural gas to the reformer.
- the supplied natural gas is reformed.
- the present invention has been made in view of the above, a reforming apparatus and a reforming method capable of improving the thermal efficiency when reforming natural gas, a chemical product manufacturing apparatus equipped with the reforming apparatus, and The purpose is to provide a method of chemical products.
- 1st invention which solves the subject mentioned above is 1st compression part which compresses raw material gas containing hydrocarbon and sulfur, 1st heat exchange part which heats the compressed said raw material gas, and said heated raw material a desulfurization unit for removing sulfur contained in the gas, the hydrocarbon of the raw material gas reforming to either or both of H 2 and CO and CO 2, and H 2 and CO and CO 2
- a reforming unit that generates a reformed gas containing one or both of the above, and either the upstream side or the downstream side of the desulfurization unit of the compressed source gas with respect to the flow direction of the source gas, or
- a raw material gas branch line that is partially extracted from both and supplied as combustion fuel used for heating in the reforming section, and a combustion exhaust gas that exhausts combustion exhaust gas generated by combustion in the reforming section from the reforming section
- a combustion line used for heating in the discharge line and the reforming section A second heat exchanging part for exchanging heat with the flue gas exhausted by the first heat exchanging part, the first heat ex
- the reforming section supplies water vapor to the raw material gas, and the hydrocarbon in the raw material gas is changed to any one of H 2 and CO and CO 2 or Using the first reforming section that undergoes primary reforming in both, combustion air and the compressed source gas supplied from the source gas branch line, the first reforming section after the primary reforming And a second reforming section that secondarily reforms the hydrocarbon in the source gas into one or both of H 2 and CO and CO 2 to form a reformed gas.
- the reformer supplies water vapor to the raw material gas, and the hydrocarbon in the raw material gas is changed to any one of H 2 and CO and CO 2 or Using the first reforming section that undergoes primary reforming in both, combustion air and the compressed source gas supplied from the source gas branch line, the first reforming section after the primary reforming And a second reforming section that secondarily reforms the hydrocarbon in the source gas into one or both of H 2 and CO and CO 2 to form a reformed gas.
- the reformer supplies water vapor to the raw material
- the supply water supplied to the steam generating section is heat-exchanged with the combustion exhaust gas between the first heat exchanging section and the second heat exchanging section.
- the reformer is characterized by having a heat exchanger.
- the compressed raw material gas which is provided in the raw material gas branch line and is introduced into the first heat exchange section, is heated with a part of the branched raw material gas and heat.
- the reformer has a fourth heat exchanger to be replaced.
- a fifth aspect of the present invention is the combustion exhaust gas generated in the reforming unit, provided between the reforming unit and the heat exchange unit of the combustion exhaust gas discharge line in any one of the first to fourth inventions.
- removal and denitrification unit for removing NOx contained the provided on the downstream side of the heat exchanger to the flow direction of the combustion exhaust gas of the combustion exhaust gas discharge line, a CO 2 contained in the combustion exhaust gas in the
- the reformer is characterized by having either or both of a CO 2 recovery section.
- a reforming apparatus according to any one of the first to fifth aspects, and a chemical product generating unit that manufactures a chemical product using the reformed gas. It is in the product manufacturing equipment.
- the chemical product manufacturing apparatus according to the sixth aspect, wherein the chemical product generation unit is an ammonia synthesis unit that synthesizes ammonia using the reformed reformed gas. is there.
- the eighth invention is the chemical product manufacturing apparatus according to the seventh invention, wherein the chemical product production unit is a urea synthesis unit that synthesizes urea using the obtained ammonia.
- a ninth invention is the chemical product manufacturing apparatus according to the sixth invention, wherein the chemical product production unit is a methanol synthesis unit that synthesizes methanol using the reformed reformed gas. .
- a tenth aspect of the invention includes a first heat exchange step for heating a raw material gas containing compressed hydrocarbons and sulfur, a desulfurization step for removing a sulfur content contained in the heated raw material gas, and the raw material gas the hydrocarbon reforming in one or both of H 2 and CO and CO 2 in the reforming step to produce a reformed gas containing one or both of H 2 and CO and CO 2
- a second heat exchange step for exchanging heat with the combustion exhaust gas heat-exchanged in the first heat exchange step for the combustion air used for heating in the reforming step, and the compressed source gas is converted into the source gas Extracted from either or both of the upstream side and downstream side of the desulfurization process with respect to the flow direction of the gas, supplied as combustion fuel used for heating in the reforming process, and generated by combustion in the reforming process Combustion exhaust gas is discharged from the reforming process.
- the combustion exhaust gas is used as a heating medium for the compressed raw material gas to perform a first heat exchange, and after the heat exchange of the compressed raw material gas, the remaining heat of the fuel exhaust gas is used as the combustion air.
- the second heat exchange is performed as a heating medium.
- a third heat exchange is performed between the first heat exchange step and the second heat exchange step so that the supply water supplied to the steam generating means exchanges heat with the combustion exhaust gas. It is in the modification
- the compressed raw material gas provided in the raw material gas branch line and introduced into the first heat exchange step is heat exchanged with a part of the branched raw material gas.
- the reforming method includes a fourth heat exchange step.
- a thirteenth invention is characterized by comprising the reforming step according to any one of the tenth to twelfth inventions, and a chemical product production step for producing a chemical product using the reformed gas. It is in the manufacturing method of the product.
- a fourteenth invention is the chemical product manufacturing method according to the thirteenth invention, wherein the chemical product producing step is an ammonia synthesis step of synthesizing ammonia using the reformed reformed gas. is there.
- the fifteenth invention is the chemical product manufacturing method according to the fourteenth invention, wherein the chemical product production step is a urea synthesis step of synthesizing urea using the obtained ammonia.
- the chemical product production step is a methanol synthesis step of synthesizing methanol using the reformed reformed gas. is there.
- the amount of heat recovered from the heat medium to the natural gas can be improved, so that the thermal efficiency when reforming the natural gas can be improved.
- FIG. 1 is a schematic view of a reforming apparatus according to the first embodiment of the present invention.
- FIG. 2 is a schematic view of the reformer according to the first embodiment of the present invention.
- FIG. 3 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 4 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 5 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 6 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 7 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 8 is a schematic view of another reformer according to the first embodiment of the present invention.
- FIG. 1 is a schematic view of a reforming apparatus according to the first embodiment of the present invention.
- FIG. 2 is a schematic view of the reformer according to the first embodiment of the present invention.
- FIG. 3 is a schematic view of another
- FIG. 9 is a diagram showing an example of a system configuration of the reformer shown in FIG.
- FIG. 10 is a diagram showing an example of the system configuration of the reformer shown in FIG.
- FIG. 11 is a schematic view of a chemical product manufacturing apparatus including a reformer according to the second embodiment of the present invention.
- FIG. 12 is a schematic view of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 13 is a schematic view of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 14 is a schematic view of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 15 is a schematic diagram of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 16 is a schematic view of a chemical product manufacturing apparatus including another reforming apparatus according to the second embodiment of the present invention.
- FIG. 17 is a schematic view of a chemical product manufacturing apparatus including another reformer according to the second embodiment of the present invention.
- FIG. 18 is a schematic view of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 19 is a schematic view of a chemical product manufacturing apparatus provided with another reforming apparatus according to the second embodiment of the present invention.
- FIG. 1 is a schematic view of a reforming apparatus according to the first embodiment of the present invention.
- a reformer 10 includes a compressor (compressor) 11, a first heat exchanger (heat exchanger) 12, a desulfurizer (desulfurizer) 13, and a reformer (reformer). Part) 14, a denitration device (denitration part) 15, a second heat exchanger 16, a cooling device 17, a CO 2 recovery device (CO 2 recovery part) 18, a raw material gas branch line L11, and combustion exhaust gas discharge Line L12.
- the natural gas 21 is used as the raw material gas containing hydrocarbons and sulfur.
- the present invention is not limited to this, and any raw material gas containing hydrocarbons may be used.
- Gas Liquid Petroleum Gas: LPG
- synthetic gas obtained from other hydrocarbons such as butane or naphtha
- natural gas liquid Natural Gas Liquid: NGL
- methane hydrate produced with the production of crude oil and natural gas Etc.
- the compressor 11 compresses the natural gas 21 and raises the natural gas 21 to a predetermined pressure.
- the natural gas 21 is supplied to the compressor 11 through the raw material gas supply line L13-1.
- the natural gas 21 is raised to a predetermined pressure by the compressor 11 and heated to a high temperature, and then supplied to the first heat exchanger 12 through the raw material gas supply line L13-2.
- the first heat exchanger 12 heats the compressed natural gas 21.
- the first heat exchanger 12 is provided in the combustion exhaust gas discharge line L12.
- the first heat exchanger 12 has the duct side as the secondary side, the combustion exhaust gas 22 is circulated in the duct, and the tube (heat transfer tube) side of the first heat exchanger 12 is the primary side. Then, as described later, the combustion exhaust gas 22 discharged from the reformer 14 is circulated in the duct as a heating medium.
- the first heat exchanger 12 heats the natural gas 21 by using the combustion exhaust gas 22 supplied to the outer periphery of the heat transfer tube as a heat source and circulating the natural gas 21 in the heat transfer tube.
- the 1st heat exchanger 12 is not limited to a convection coil type heat exchanger, What is necessary is just to be able to indirectly heat-exchange the natural gas 21 and the combustion exhaust gas 22.
- FIG. 1st heat exchanger 12 is not limited to a convection coil type heat exchanger, What is necessary is just to be able to indirectly heat-exchange the natural gas 21 and the combustion exhaust gas 22.
- the natural gas 21 is heat-exchanged with the combustion exhaust gas 22 by the first heat exchanger 12 and heated, and then supplied to the desulfurization apparatus 13 through the raw material gas supply line L13-3.
- the desulfurization device 13 is for removing sulfur content (S content) such as hydrogen sulfide (H 2 S) and organic sulfur compounds contained in the heated natural gas 21.
- S content sulfur content
- a conventionally known desulfurization apparatus 13 is used, and either a wet type or a dry type can be used.
- the desulfurization apparatus 13 uses, for example, lime slurry (an aqueous solution in which limestone powder is dissolved in water) as the alkali absorption liquid.
- the temperature in the column is adjusted to about 30 to 80 ° C.
- the lime slurry is supplied to the bottom of the desulfurizer 13.
- the lime slurry supplied to the tower bottom of the desulfurization apparatus 13 is sent to a plurality of nozzles in the desulfurization apparatus 13 via an absorption liquid supply line and the like, and is ejected from the nozzle toward, for example, the tower top side of the absorption tower. .
- the S content in the natural gas 21 is absorbed by the lime slurry and separated from the natural gas 21. Removed.
- the S content in the natural gas 21 causes a reaction represented by the following formula (1) with the lime slurry.
- the lime slurry that has absorbed the S component in the natural gas 21 is oxidized by air (not shown) supplied to the bottom of the desulfurizer 13, and reacts with the air by the following formula (2). Arise. In this way, the S content in the natural gas 21 is captured in the form of gypsum CaSO 4 .2H 2 O in the desulfurization apparatus 13.
- the natural gas 21 purified by the lime slurry is discharged from the tower top side of the desulfurization apparatus 13. Thereafter, the natural gas 21 is supplied into the reformer 14 through the raw material gas supply line L13-4.
- the source gas supply line L13-4 is connected to the water vapor supply line L14.
- the water vapor 24 is supplied into the raw material gas supply line L13-4 through the water vapor supply line L14 and mixed with the natural gas 21.
- the natural gas 21 is supplied into the reformer 14 after the steam 24 is mixed in the steam supply line L14.
- Reformer 14 the hydrocarbons in the natural gas 21, modified in either or both of H 2 and CO and CO 2, including one or both of H 2 and CO and CO 2
- the reformed gas 23 is generated.
- the reformer 14 includes a main body 14a, a catalyst reaction tube 14b, and a burner 14c.
- the catalyst reaction tube 14b is provided inside the main body 14a, and the catalyst reaction tube 14b includes a reforming catalyst layer including a reforming catalyst.
- the burner 14c is provided inside the main body 14a, burns the combustion air 26, generates combustion exhaust gas 22, and heats the catalyst reaction tube 14b.
- the burner 14c is connected to the air supply line L15.
- the combustion air 26 is supplied to the burner 14c through the air supply line L15.
- the combustion air 26 is heat-exchanged with the combustion exhaust gas 22 in the second heat exchanger 16 and heated, and then supplied to the reformer 14.
- the catalyst reaction tube 14b is heated by the combustion exhaust gas 22, and the natural gas 21 contacts the reforming catalyst when passing through the reforming catalyst layer of the catalyst reaction tube 14b. ),
- the hydrocarbons in the natural gas 21 are reformed to H 2 and CO and CO 2 .
- the reformed gas 23 containing one or both of H 2 and CO and CO 2 is generated.
- the gas temperature of the reformed gas 23 is in the range of 400 ° C. to 1000 ° C., for example.
- the raw material gas branch line L11 connects the downstream side of the desulfurization apparatus 13 and the air supply line L15.
- the raw material gas branch line L11 extracts a part of the natural gas 21 as a branch gas 21a from the downstream side of the desulfurizer 13 with respect to the flow direction of the natural gas 21 from the natural gas 21 compressed by the compressor 11, and an air supply line It mixes with the combustion exhaust gas 22 which passes L15.
- this branched branch gas 21a the S content contained in the natural gas 21 is removed by the desulfurization device 13, so the natural gas 21 not containing the S content is supplied to the air supply line L15.
- the reformed gas 23 generated in the reformer 14 is used as a raw material gas for synthesizing hydrogen, liquid hydrocarbon, methanol, ammonia, or the like. Further, the combustion exhaust gas 22 discharged from the reformer 14 is supplied to the denitration device 15 through the combustion exhaust gas discharge line L12.
- the combustion exhaust gas discharge line L12 is a line for discharging the combustion exhaust gas 22 generated by burning the fuel including the natural gas 21 extracted to the raw material gas branch line L11 for fuel using the combustion air 26 in the reformer 14. is there.
- the combustion exhaust gas discharge line L12 includes a denitration device 15 in the middle thereof, and a reducing agent injector 28 on the upstream side of the denitration device 15.
- the reducing agent 29 is supplied from the reducing agent injector 28 to the combustion exhaust gas 22 while the combustion exhaust gas 22 passing through the combustion exhaust gas discharge line L ⁇ b> 12 is supplied to the denitration device 15.
- the reducing agent 29 for example, ammonia (NH 3 ), urea (NH 2 (CO) NH 2 ), ammonium chloride (NH 4 Cl), or the like is used.
- the reducing agent 29 is supplied to the combustion exhaust gas discharge line L12 as a solution or gas containing the reducing agent 29.
- the solution containing the reducing agent 29 is supplied to the combustion exhaust gas discharge line L12, the droplets of the solution containing the reducing agent 29 are evaporated and vaporized by the high-temperature ambient temperature of the combustion exhaust gas 22.
- the combustion exhaust gas 22 is supplied to the denitration device 15 through the combustion exhaust gas discharge line L12 while containing the reducing agent 29.
- the denitration device 15 is provided between the reformer 14 and the first heat exchanger 12 of the combustion exhaust gas discharge line L12, and nitrogen oxide (NOx) contained in the combustion exhaust gas 22 generated by the reformer 14 Is to be removed.
- a conventionally known denitration device 15 is used.
- the denitration device 15 includes a denitration catalyst layer in which a denitration catalyst for removing NOx in the combustion exhaust gas 22 is filled.
- the combustion exhaust gas 22 supplied into the NOx removal device 15 comes into contact with the NOx removal catalyst filled in the NOx removal catalyst layer, so that NOx in the combustion exhaust gas 22 on the NOx removal catalyst is reduced as shown in the following formula (5).
- the reduction reaction proceeds with 29 and is reduced and decomposed and removed into nitrogen gas (N 2 ) and water (H 2 O). 4NO + 4NH 3 + O 2 ⁇ 4N 2 + 6H 2 O (5)
- the combustion exhaust gas 22 is supplied to the first heat exchanger 12 after NOx in the combustion exhaust gas 22 is removed by the denitration device 15.
- the combustion exhaust gas 22 is heat-exchanged with the natural gas 21 to heat the natural gas 21 as described above. Thereafter, the combustion exhaust gas 22 is supplied from the first heat exchanger 12 to the second heat exchanger 16 through the combustion exhaust gas discharge line L12.
- the second heat exchanger 16 heats the combustion air 26. Similar to the first heat exchanger 12, the second heat exchanger 16 is provided in the combustion exhaust gas discharge line L12. As the second heat exchanger 16, a convection coil heat exchanger is used as in the first heat exchanger 12. The second heat exchanger 16 circulates the combustion exhaust gas 22 in the duct with the duct side as the secondary side and the combustion air 26 in the heat transfer tube with the tube (heat transfer tube) side as the primary side. The second heat exchanger 16 uses the combustion exhaust gas 22 supplied to the outside of the heat transfer tube as a heat source, causes the combustion air 26 to flow through the heat transfer tube, and heats the combustion air 26.
- the combustion exhaust gas 22 is heat-exchanged with the combustion air 26 by the second heat exchanger 16 and then supplied to the cooling device 17.
- the combustion air 26 is heated by exchanging heat with the combustion exhaust gas 22 in the second heat exchanger 16 and then supplied to the reformer 14.
- the cooling device 17 cools the combustion exhaust gas 22.
- the cooling device 17 is a cooling tower in which the cooling water 30 circulates inside and outside.
- the cooling water 30 is supplied from the tower top side, and the combustion exhaust gas 22 supplied into the tower is brought into gas-liquid contact with the cooling water 30 to be cooled.
- the cooling device 17 is not limited to a device that cools the combustion exhaust gas 22 by directly contacting the combustion exhaust gas 22 with the cooling water 30, and cools the combustion exhaust gas 22 by indirectly exchanging heat with the cooling water 30. You may do it.
- the combustion exhaust gas 22 is cooled by the cooling device 17 and then supplied to the CO 2 recovery device 18.
- the CO 2 recovery device 18 is for removing CO 2 contained in the combustion exhaust gas 22.
- the CO 2 recovery device 18 is provided downstream of the second heat exchanger 16 with respect to the flow direction of the combustion exhaust gas 22 in the combustion exhaust gas discharge line L12.
- CO 2 recovery device 18 a conventionally known one can be used.
- CO 2 absorbs CO 2 in the the CO 2 absorbing solution of amine and the flue gas 22 by gas-liquid contact in a CO 2 absorption combustion in fluid exhaust 22 tower absorption it can be used and towers, and the like apparatus and a regenerator which dissipates CO 2 absorbed by the CO 2 absorbing solution in the column to reproduce the CO 2 absorbing liquid.
- the combustion exhaust gas 22 is contacted CO 2 absorbing solution and gas-liquid in a CO 2 absorption tower, CO 2 in the combustion exhaust gas 22 is absorbed by the CO 2 absorbing solution, the CO 2 in the combustion exhaust gas 22 is removed.
- the combustion exhaust gas 22 is released into the atmosphere as a purified gas after the CO 2 contained in the combustion exhaust gas 22 is removed by the CO 2 recovery device 18.
- the raw material gas branch line L11 connects the downstream side of the desulfurization device 13 and the air supply line L15, and the natural gas 21 compressed by the compressor 11 is downstream of the desulfurization device 13 with respect to the flow direction of the natural gas 21. It is extracted from the side and mixed with the combustion exhaust gas 22 passing through the air supply line L15. Since the S content contained in the natural gas 21 is removed by the desulfurization device 13, the natural gas 21 not containing the S content can be supplied to the air supply line L15. As a result, the combustion exhaust gas 22 discharged from the reformer 14 does not contain S. As a result, the amount of S in the combustion exhaust gas 22 becomes extremely small, so that the acid dew point temperature itself is lowered. Accordingly, the exhaust gas temperature can be further lowered and the amount of heat recovered from the exhaust gas can be increased, so that the fuel in the reformer 14 can be reduced.
- the amount of natural gas 21 used as fuel in the reformer 14 can be reduced by, for example, about 0.7% to 8.5%.
- the temperature of the flue gas becomes lower than the dew point temperature of the acid of S such as anhydrous sulfuric acid contained in the flue gas, and the sulfur contained in the flue gas combines with moisture and sulfuric acid (H 2 SO 4 ) Condensates and corrodes metal. Therefore, it is necessary to use acid-resistant steel having high corrosion resistance against acids such as sulfuric acid as a material for piping through which combustion exhaust gas passes.
- the combustion exhaust gas 22 discharged from the reformer 14 does not contain S, the combustion exhaust gas 22 exchanges heat with the combustion air 26 in the second heat exchanger 16, and the combustion exhaust gas.
- the material of the combustion exhaust gas discharge line L12 is not limited to acid-resistant steel, and other materials can be used, and the application range can be expanded.
- the heat exchange in the second heat exchanger 16 is, for example, 175 ° C. in consideration of the acid dew point, but can be lowered to the lower limit of 120 ° C.
- the lower limit of 120 ° C. is the exhaust gas temperature determined in consideration of the dew point of water.
- a reducing agent 29 such as ammonia is supplied into the flue, but methanol conventionally used as in Patent Documents 1 and 2, etc.
- unreacted ammonia also referred to as leaked ammonia
- Ammonium sulfate may be deposited on heat transfer tubes and coils in a heat exchanger that exchanges heat between combustion exhaust gas and natural gas, and may block the pipe through which combustion exhaust gas passes to increase pressure loss.
- Ammonium hydrogen sulfate may cause corrosion in a heat exchanger that exchanges heat between combustion exhaust gas and natural gas, a material that forms a pipe through which the combustion exhaust gas passes, and the like.
- a reducing agent 29 such as ammonia is added to the combustion exhaust gas discharge line L12 upstream of the denitration device 15. Even if it supplies in, it can suppress that reducing agent 29, such as unreacted ammonia, and S component react, and ammonium sulfate, ammonium hydrogen sulfate, etc. are produced
- ammonium sulfate, ammonium hydrogen sulfate, and the like are deposited in the combustion exhaust gas discharge line L12 to suppress an increase in pressure loss in the combustion exhaust gas discharge line L12, corrosion in the passage of the combustion exhaust gas discharge line L12, and the like. Can do.
- a CO 2 recovery device 18 is provided to remove CO 2 contained in the combustion exhaust gas 22, which has been conventionally used as in Patent Documents 1 and 2, for example.
- a desulfurization device is provided upstream of the CO 2 recovery device in the gas flow direction of the combustion exhaust gas, and the sulfur concentration in the combustion exhaust gas at the inlet of the CO 2 recovery device is set to a predetermined value (for example, 1 ppm). ) It is necessary to do the following.
- the number of apparatuses to be installed increases as much as the desulfurization apparatus is provided, and the place where each apparatus is disposed is limited and the equipment cost increases.
- the reformer 10 has the first heat exchanger 12 and the second heat exchanger 16 interposed in the combustion exhaust gas discharge line L12.
- the present invention is not limited to this.
- a plurality of heat exchangers for exchanging heat with the combustion exhaust gas 22 may be provided.
- FIG. 2 is a diagram illustrating an example of another configuration of the reforming apparatus 10.
- the combustion exhaust gas discharge line L ⁇ b> 12 has a third heat exchanger (heat exchange part) 19 interposed between the first heat exchanger 12 and the second heat exchanger 16.
- the third heat exchanger 19 is a heat exchanger that preheats the supply water 75 supplied to the steam generation unit 70.
- a fourth heat exchanger (heat exchange section) 20 is provided between the compressor 11 and the first heat exchanger 12 of the raw material gas supply line L13-2, and branches after desulfurization.
- the natural gas 21a supplied to the first heat exchanger 12 is preheated by the natural gas 21a.
- the fourth heat exchanger 20 for exchanging heat between the natural gases 21 further heat-exchanges the natural gas 21 introduced into the first heat exchanger 12 in advance as compared with the system shown in FIG.
- the amount of heat recovered from the subsequent combustion exhaust gas 22 can be reduced, and the amount of heat recovered in the third heat exchanger 19 can be increased.
- the temperature difference of the fluid to be heat exchanged can be improved, and the heat transfer area of the third heat exchanger 19 can be reduced.
- the reformer 10 includes only one reformer 14, but the present invention is not limited to this, and a plurality of reformers 14 may be provided.
- FIG. 4 is a diagram illustrating an example of another configuration of the reforming apparatus 10. As shown in FIG. 4, the reformer 14 may include a first reformer 14-1 and a second reformer 14-2.
- the first reformer 14-1 supplies water vapor 24 to the desulfurized compressed natural gas 21, and the hydrocarbons in the natural gas 21 are any of H 2, CO, and CO 2. One or both of these are subjected to primary reforming.
- the first reformer 14-1 has the same configuration as the first reformer 14 shown in FIG. 1, and includes a main body 14a (not shown in FIG. 4), a catalyst reaction tube 14b (not shown in FIG. 4), And a burner 14c (not shown in FIG. 4).
- the catalytic reaction tube 14b is heated by the combustion exhaust gas 22 generated by combustion in the burner 14c, and the introduced natural gas 21 comes into contact with the reforming catalyst when passing through the reforming catalyst layer of the catalyst reaction tube 14b.
- the hydrocarbons in the natural gas 21 are steam reformed to H 2 and / or one of CO and CO 2 .
- Natural gas 21 is primarily reformed by the first reformer 14-1, and then supplied to the second reformer 14-2.
- the second reformer 14-2 supplies air (oxygen) to the reformed gas 23, and secondarily reforms the hydrocarbons in the reformed gas 23 using a partial oxidation reaction.
- the second reformer 14-2 introduces combustion air 26 heated from the outside, and the hydrocarbons in the reformed gas 23 undergo secondary reforming to H 2 and / or CO and CO 2. Is done.
- FIG. 5 is a diagram showing an example of another configuration of the reformer 10.
- the reformer 14 may include a pre-reformer 14-3, a first reformer 14-1, and a second reformer 14-2.
- the pre-reformer 14-3 supplies steam 24 to the natural gas 21, and primarily reforms hydrocarbons in the natural gas 21 into H 2, CO, and / or CO 2. .
- the pre-reformer 14-3 includes a main body and a reforming catalyst layer including a reforming catalyst therein. Further, the pre-reformer 14-3 is connected to the steam supply line L14.
- the steam 24 is supplied into the pre-reformer 14-3 through the steam supply line L 14 and mixed with the natural gas 21.
- the natural gas 21 is supplied to the reforming catalyst layer after the water vapor 24 is mixed in the main body.
- the natural gas 21 comes into contact with the reforming catalyst when passing through the reforming catalyst layer in the pre-reformer 14-3, so that the natural gas 21 is in the natural gas 21 as shown in the above formulas (3) and (4). Is primarily reformed into H 2 and / or CO and CO 2 .
- the first reformer 14-1 is discharged.
- Part or all of the combustion exhaust gas 22 may be used as a heating medium for heating the reforming catalyst layer of the pre-reformer 14-3.
- FIGS 6 to 8 are diagrams showing modifications of other configurations of the reforming apparatus 10.
- the source gas branch line L11 is provided so as to be connected to the air supply line L15, and the natural gas 21 is supplied together with the combustion air 26 into the reformer 14 through the air supply line L15.
- the present invention is not limited to this.
- the raw gas branch line L11 is directly connected to the reformer 14, and the natural gas 21 and the combustion air 26 are separately supplied to the reformer 14. You may make it supply in.
- the raw material gas branch line L11 is provided so as to be connected to the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21, but is not limited thereto.
- a raw material gas branch line L ⁇ b> 21 connecting the upstream side of the desulfurization apparatus 13 and the air supply line L ⁇ b> 15 is provided. You may make it extract from the upstream of the desulfurization apparatus 13 with respect to a flow direction.
- source gas branch lines L ⁇ b> 11 and L ⁇ b> 21 are provided, and a part 21 a of the natural gas 21 is extracted from the upstream side and the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21. Also good.
- the reformer 10 includes the denitration device 15, but is not limited thereto, and the denitration device 15 may not be provided.
- the reformer 10 includes the cooling device 17 and the CO 2 recovery device 18, but is not limited to this, and the recovery of CO 2 contained in the combustion exhaust gas 22 is not limited thereto. These devices may not be provided when unnecessary.
- the reformer 10 since the reformer 10 has the above-described characteristics, it can be used for the manufacture of chemical products using the reformed gas 23 obtained by the reformer 10.
- the chemical product include ammonia, methanol, urea, hydrogen, liquid fuels of liquid hydrocarbons such as wax, light oil, kerosene, and gasoline by FT synthesis.
- the reformer 10 by applying the reformer 10 to an ammonia and methanol production system or a urea and methanol production system, it is possible to improve the production efficiency of methanol and ammonia or the production efficiency of urea and methanol.
- FIG. 9 and 10 are diagrams showing an example of the system configuration of the reformer shown in FIG. 1 and the reformer shown in FIG.
- FIG. 9 is an example of a system configuration corresponding to the reformer shown in FIG. 1, and the combustion exhaust gas 22 introduced into the combustion exhaust gas discharge line L12 from the reformer 14 includes a plurality of gas exhausts provided in the gas flue. Heat is exchanged at the heat exchange section.
- the heated natural gas 21 passes through the desulfurization section 13, is further heat-exchanged by a heat exchanger (not shown), and is introduced to the reformer 14 side.
- FIG. 10 shows an example of a system configuration corresponding to the reformer shown in FIG.
- heat is exchanged.
- T 2 290 ° C.
- T 3 160 ° C.
- T 31 130 ° C.
- T 32 260 ° C.
- the heated supply water 75 is introduced into the steam generation unit 70.
- the reforming system of FIG. 10 increases the amount of steam generation water 75 to be introduced into the steam generator 70, so that the amount of steam generated is compared to that of the reforming system of FIG. This is an improvement of about 20 t / h, and a reduction of 1.9% can be achieved in the ammonia product basic unit (Gcal / ton-NH 3 ) including the installation of an auxiliary boiler.
- the chemical product manufacturing apparatus includes a reformer 10 and a chemical product generator that manufactures a chemical product using the reformed gas 23 obtained by the reformer 10.
- This embodiment demonstrates the case where ammonia, methanol, or urea is manufactured as a chemical product.
- FIG. 11 is a schematic view of a chemical product manufacturing apparatus including a reformer according to the second embodiment of the present invention.
- a reformer having a two-stage configuration shown in FIG. 4 is used.
- the overlapping description is abbreviate
- the reformer is configured such that the primary reformer 14 includes the primary reformer 14-1 and the second reformer 14-2, but the present invention is not limited to this. . As shown in FIG.
- a chemical product manufacturing apparatus 40 that manufactures ammonia includes a reformer 10, a steam generation unit 70, a CO shift reaction device (CO shift reaction unit) 41, and a carbon dioxide gas removal device (carbon dioxide gas).
- the CO shift reaction device 41, the carbon dioxide gas removal device 42, the methanation device 43, the compressors 44-1 and 44-2, the hydrogen separation device 45, and the ammonia synthesis unit 46 are converted into chemical product production units. To do.
- first and second preheating units 76-1 and 76-2 for preheating the feed water 75 supplied to the steam generation unit 70 include a CO shift reaction device (CO shift reaction unit) 41, carbon dioxide gas It is interposed between the removal device (carbon dioxide gas removal unit) 42 and between the ammonia synthesis unit 46 and the cooling unit 72.
- reference numeral 80 denotes a steam header that supplies the water vapor obtained by the steam generation unit 70.
- steam from an auxiliary boiler or the like is also introduced into the steam header so that a necessary amount of steam is sent to each steam supply destination.
- the steam generation unit 70 supplies the steam 24 to the steam header 80 in the system.
- the steam generation unit 70 includes a waste heat recovery boiler (WHB) that recovers waste heat of the reformed gas 23 and a superheater. After heating the supply water 75 with waste heat and obtaining heated steam, Further, the steam 24 is sent to the steam header 80 by being heated by a superheater.
- a waste heat recovery boiler may be further installed on the downstream side of the passage line of the reformed gas 23 and the downstream side of the ammonia synthesis unit 46 to recover heat, but this is omitted in this embodiment. is doing.
- the CO shift reaction device 41 converts (shifts) CO in the reformed gas 23 to CO 2 to generate a shift gas 51 containing CO 2 .
- a CO shift reactor including a packed portion filled with a catalyst for CO shift reaction that converts (shifts) CO into CO 2 is used.
- the reformed gas 23 obtained by reforming the natural gas 21 with the reformer 10 is discharged from the reformer 10 and supplied to the CO shift reactor 41.
- the CO in the reformed gas 23 is converted to CO 2, to produce a shifted gas 51 containing CO 2.
- the gas temperature of the shift gas 51 is in the range of 150 ° C. to 1000 ° C., for example.
- the shift gas 51 generated in the CO shift reaction device 41 is discharged from the CO shift reaction device 41 and supplied to the carbon dioxide gas removal device 42.
- the carbon dioxide removal device 42 removes carbon dioxide (CO 2 ) in the shift gas 51.
- the carbon dioxide gas removing device 42 include a device that removes CO 2 in the shift gas 51 using a chemical adsorption using a CO 2 absorbing solution such as an amine solvent, a device that includes a catalyst that removes CO 2 , or a shift gas.
- a membrane separation device provided with a separation membrane for separating CO 2 in 51 is used.
- the carbon dioxide removal device 42 removes CO 2 from the shift gas 51 to produce a CO 2 removal gas 52 from which CO 2 has been removed.
- the gas temperature of the CO 2 removal gas 52 is about 50 ° C., for example.
- the carbon dioxide removal device 42 separates CO 2 from the shift gas 51.
- the separated CO 2 may be used as a gas for methanol synthesis.
- the CO 2 removal gas 52 discharged from the carbon dioxide removal device 42 is supplied to the methanation device 43.
- Methanation apparatus 43 is for methanation of CO 2 in the CO 2 reducing gas 52 from which CO 2 has been removed by the carbon dioxide gas removing unit 42.
- the methanator 43 for example, a methanation reactor (methanator) provided with a catalyst part filled with a methanation catalyst is used.
- the reaction temperature (methanation temperature) in the catalyst part is preferably 220 ° C. or higher and 450 ° C. or lower, more preferably 290 ° C. or higher and 350 ° C. or lower, from the viewpoint of the limit temperature at which the methanation catalyst can be used.
- the CO 2 removal gas 53 discharged from the methanator 43 is supplied to the compressor 44.
- the compressor 44 compresses the CO 2 removal gas 53.
- CO 2 stripping gas 53 After raising the pressure of CO 2 stripping gas 53 in the compressor 44, CO 2 stripping gas 53 is supplied to the hydrogen separator 45.
- ammonia synthesizer 46 produces ammonia (NH 3 ) 55 after methanation of CO 2 in the CO 2 removal gas 53 by the methanator 43.
- ammonia synthesizing unit 46 those conventionally used in general can be used, and examples thereof include an ammonia synthesis reactor in which a catalyst is arranged on one or more beds in the reactor. A method of synthesizing ammonia by flowing a CO 2 removal gas 53 as a synthesis gas containing nitrogen (N 2 ) and hydrogen is used in this ammonia synthesis reactor.
- the ammonia synthesized product obtained in the ammonia synthesizing unit 46 passes through the second preheating unit 76-2, is then cooled in the cooling unit 72, and the target ammonia 55 is separated in the separating unit 73.
- the chemical product manufacturing apparatus 40 that manufactures ammonia can improve the thermal efficiency when reforming the natural gas 21 by including the reforming apparatus 10 described above, and the process of treating the combustion exhaust gas 22. It is possible to suppress the occurrence of corrosion in the passage of the combustion exhaust gas discharge line L12. Therefore, according to the chemical product manufacturing apparatus 40 which manufactures ammonia, while being able to produce ammonia 55 stably, the production efficiency of ammonia 55 can be improved.
- the temperature of the combustion exhaust gas 22 after heat exchange can be lowered to 120 ° C., and heat exchange in the second heat exchanger 16 of the combustion exhaust gas discharge line L12. Efficiency can be increased. That is, conventionally, since the sulfur content is not removed, the temperature of the combustion exhaust gas 22 can only be lowered to about 175 ° C., and the amount of branch fuel introduced is increased correspondingly, resulting in the production of reformed gas. The amount was decreasing.
- the temperature of the combustion air 26 to be introduced into the reformer 14 can be raised, so that the natural gas 21 to be branched into the reformer 14 is branched.
- the amount can be reduced.
- the production amount of the reformed gas can be increased, so that the production amount of ammonia can be increased.
- the amount of the natural gas 21 introduced into the reformer 14 is 8.5%. It becomes an improvement. As a result, the efficiency of the entire plant can be reduced by 1.1% in terms of the product basic unit (Gcal / ton-NH 3 ).
- FIG. 12 is a schematic view of a chemical product manufacturing apparatus including the reforming apparatus shown in FIG. 3 according to the second embodiment of the present invention.
- the reformer 14 has one stage, but in this example, the reformer has a two-stage structure as shown in FIG.
- the third heat exchanger 19 is interposed between the first heat exchanger 12 and the second heat exchanger 16 interposed in the combustion exhaust gas discharge line L12. Is intervening.
- a steam superheater 89 for exchanging heat of the steam 24 from the steam generating unit 70 is further provided in the combustion exhaust gas discharge line L12.
- the temperature of the steam can be set to a higher temperature (for example, 515 ° C.).
- a separate auxiliary boiler is provided to cover the steam with the auxiliary boiler.
- the amount of water vapor generated is greatly increased, so that no auxiliary boiler is required or the auxiliary boiler can be greatly reduced in size.
- the chemical product manufacturing apparatus 40 that manufactures ammonia can improve the thermal efficiency when the natural gas 21 is reformed by including the reforming apparatus 10, and in the process of processing the combustion exhaust gas 22, the combustion exhaust gas 22 Corrosion can be prevented from occurring in the passage of the discharge line L12. Therefore, according to the chemical product manufacturing apparatus 40 of this embodiment, the ammonia 55 can be stably produced and the production efficiency of the ammonia 55 can be improved.
- FIG. 13 is a schematic view of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- FIG. 13 is a schematic diagram of a urea and methanol production system according to the second embodiment of the present invention.
- the chemical product manufacturing apparatus 40 for manufacturing urea is the same as the chemical product manufacturing apparatus 40 shown in FIG. 12, but further includes a urea synthesis unit 61 and a carbon dioxide branch supply line L33.
- the urea synthesis unit 61 is provided on the downstream side of the ammonia synthesis unit 46 in the ammonia flow direction.
- the urea synthesis unit 61 synthesizes urea 62 using the ammonia 55 obtained by the ammonia synthesis unit 46.
- the urea synthesizing unit 61 those conventionally used in general can be used, and examples thereof include a urea synthesizing tube that reacts ammonia and CO 2 in a tube.
- the carbon dioxide branch supply line L ⁇ b > 33 is a line for introducing CO 2 removed by the carbon dioxide removal device 42 into the urea synthesis unit 61.
- the ammonia 55 obtained by the ammonia synthesis unit 46 is supplied to the urea synthesis unit 61. Further, the carbon dioxide is removed from the carbon dioxide removing device 42 and supplied from the carbon dioxide supply line L33 to the urea synthesizer 61.
- ammonia 55 obtained in the ammonia synthesizing unit 46 and CO 2 separated by the carbon dioxide removing device 42 react as shown in the following reaction formula (9), and urea (NH 2 ( CO) NH 2 ) is synthesized.
- urea NH 2 ( CO) NH 2
- the chemical product manufacturing apparatus 40 for manufacturing urea manufactures urea 62 using the ammonia 55 obtained by the ammonia synthesizing unit 46 and the CO 2 separated by the carbon dioxide gas removing apparatus 42 during the ammonia synthesis. can do.
- the chemical product manufacturing apparatus 40 that manufactures urea is provided with the reforming apparatus 10 of the first embodiment, so that the chemical product manufacturing apparatus 40 that manufactures ammonia according to the second embodiment is natural. It is possible to improve the thermal efficiency when reforming the gas 21 and to suppress the occurrence of corrosion in the passage of the combustion exhaust gas discharge line L12 in the process of processing the combustion exhaust gas 22. Therefore, according to the chemical product manufacturing apparatus 40 which manufactures urea, the urea 62 can be stably produced and the production efficiency of the urea 62 can be improved.
- FIG. 14 is a schematic view of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- a chemical product manufacturing apparatus 40 that manufactures ammonia and methanol includes a reformer 10, a CO shift reaction apparatus (CO shift reaction section) 41, and a carbon dioxide removal apparatus (carbon dioxide removal section) 42.
- a methanol synthesis unit 47 is installed on the upstream side of the methanator 43.
- the compressor 44 is provided with a first compressor 44-1 between the carbon dioxide removing device 42 and the methanol synthesizer 47, and a second compressor 44 between the methanator 43 and the ammonia synthesizer 46. -2 is installed.
- the compressor 44 has a two-stage configuration, but may further have a plurality of stages such as a three-stage configuration of a low-pressure compressor, an intermediate-pressure compressor, and a high-pressure compressor.
- the methanol synthesizer 47 synthesizes methanol 56 using carbon dioxide and hydrogen in the reformed gas 23 obtained by the reformer 10 as raw materials.
- the methanol synthesizing unit 47 those conventionally used in general can be used.
- a methanol synthesizing apparatus having a catalytic reactor is used.
- the carbon dioxide in the reformed gas 23, which is a methanol production raw material is a bypass line L35 provided with open / close valves V 1 and V 2 that partially bypass the CO shift reaction device 41 and the carbon dioxide gas removal device 42, By providing L36, the content is adjusted.
- the chemical product manufacturing apparatus 40 for manufacturing ammonia and methanol can obtain the ammonia 55 obtained in the ammonia synthesis unit 46 and the methanol 56 obtained in the methanol synthesis unit 47. Can be manufactured simultaneously in parallel.
- the chemical product manufacturing apparatus 40 that manufactures ammonia and methanol includes the reforming apparatus 10 of the first embodiment, so that the chemical product manufacturing apparatus 40 that manufactures ammonia according to the second embodiment and Similarly, it is possible to improve the thermal efficiency when reforming the natural gas 21 and to suppress the occurrence of corrosion in the passage of the combustion exhaust gas discharge line L12 in the process of processing the combustion exhaust gas 22. Therefore, according to the chemical product manufacturing apparatus 40 which manufactures urea, while being able to produce ammonia 55 and methanol 56 stably, those production efficiencies can be improved.
- FIG. 15 is a schematic diagram of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- ammonia and methanol are manufactured.
- an apparatus capable of manufacturing urea using ammonia as a raw material and simultaneously manufacturing methanol as a chemical product manufacturing apparatus is provided.
- the ammonia 55 obtained in the ammonia synthesis unit 46 is further introduced into the urea synthesis unit 61 to produce urea.
- the chemical product manufacturing apparatus 40 that manufactures urea and methanol can obtain urea 62 that is a raw material of the ammonia 55 obtained by the ammonia synthesis unit 46 and methanol 56 obtained by the methanol synthesis unit 47. 62 and methanol 56 can be produced simultaneously in parallel.
- the chemical product manufacturing apparatus 40 that manufactures urea and methanol is similar to the chemical product manufacturing apparatus 40 that manufactures ammonia according to the second embodiment by including the reforming device 10 of the first embodiment.
- FIG. 16 is a schematic view of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- methanol is manufactured by the reformed gas 23.
- carbon dioxide gas and hydrogen are separated from the reformed gas 23 and a methanol synthesis unit is separately provided.
- a hydrogen separator 45 is provided between the first compressor 44-1 and the second compressor 44-2.
- the hydrogen separator 45 is a membrane separator provided with a hydrogen permeable functional membrane.
- the hydrogen permeable functional membrane is a membrane for separating at least a part of hydrogen (H 2 ) contained in the gas.
- the hydrogen-permeable functional membrane it is preferable to use, for example, a polymer membrane such as a palladium (Pd) membrane, polysulfone, polyamide, polyimide, or a bundle of many hollow fibers.
- a polymer membrane such as a palladium (Pd) membrane, polysulfone, polyamide, polyimide, or a bundle of many hollow fibers.
- the hydrogen permeable functional membrane can be appropriately designed based on the material, use conditions, lifetime, hydrogen permeability coefficient, and selectivity.
- the CO 2 removal gas 53 passes through the hydrogen permeable functional membrane, so that the hydrogen contained in the CO 2 removal gas 53 is separated by the hydrogen permeable functional membrane.
- the CO 2 removal gas 53 from which hydrogen has been separated by the hydrogen separator 45 is discharged from the hydrogen separator 45.
- the hydrogen separator 45 is connected to the hydrogen supply line L32, and a part of the hydrogen (H 2 ) separated from the shift gas 51 in the hydrogen separator 45 is supplied to the methanol synthesis unit 47 through the hydrogen supply line L32. And used as a gas for methanol synthesis.
- a membrane separator provided with a hydrogen permeable functional membrane is used as the hydrogen separator 45.
- the present invention is not limited to this, and for example, a pressure swing adsorption device (PSA) or the like is used. Any apparatus that can separate at least a part of hydrogen contained in the CO 2 removal gas 53 can be used.
- PSA pressure swing adsorption device
- the CO 2 removal gas 53 discharged from the hydrogen separator 45 is supplied to the second compressor 44-2. After the pressure of the CO 2 stripping gas 53 is appropriately adjusted to a suitable pressure to the ammonia synthesis in the second compressor 44-2, CO 2 stripping gas 53 is supplied to the ammonia synthesis unit 46. The hydrogen separated by the hydrogen separator 45 is supplied to the methanol synthesis unit 47 through the hydrogen supply line L32.
- the hydrogen separated by the hydrogen separator 45 passes through the hydrogen supply line L32, and the CO 2 separated by the carbon dioxide remover 42 passes through the carbon dioxide supply line L31 to remove hydrogen and carbon dioxide separated by the hydrogen separator 45.
- Carbon dioxide (CO 2 ) separated by the device 42 is supplied to the methanol synthesis unit 47.
- the methanol synthesizing unit 47 synthesizes the methanol 56 using the carbon dioxide separated by the carbon dioxide removing device 42 and the hydrogen separated by the hydrogen separating device 45 as raw materials.
- the methanol synthesizing unit 47 those conventionally used in general can be used.
- a methanol synthesizing apparatus having a catalytic reactor is used.
- the chemical product manufacturing apparatus 40 that manufactures the ammonia 55 and the methanol 56 includes the ammonia 55 obtained by the ammonia synthesis unit 46, the carbon dioxide separated by the carbon dioxide removal device 42, and the hydrogen separated by the hydrogen separation device 45. Can be used to obtain methanol 56, and ammonia 55 and methanol 56 can be simultaneously produced in parallel.
- the ammonia and methanol production system 40 can improve the thermal efficiency when reforming the natural gas 21 by including the reformer 10, and at the same time, process the combustion exhaust gas 22 in the process of treating the combustion exhaust gas 22. Corrosion can be prevented from occurring in the passage of L12. Therefore, according to the ammonia and methanol production system 40, the ammonia 55 and the methanol 56 can be stably produced, and the production efficiency of the ammonia 55 and the methanol 56 can be improved.
- a hydrogen separation device 45 is provided between the first compressor 44-1 and the second compressor 44-2, and all of the CO 2 removal gas 53 separated by the hydrogen separation device 45 is included.
- the present invention is not limited to this, and only a part of the CO 2 removal gas 53 separated by the first compressor 44-1 or the second compressor 44-2 is separated into hydrogen.
- the hydrogen may be supplied to the separator 45 and the hydrogen in the CO 2 removal gas 53 may be separated by the hydrogen separator 45.
- FIG. 17 is a schematic view of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- ammonia 55 and methanol 56 are manufactured, but in this embodiment, an apparatus capable of manufacturing urea from the obtained ammonia 55 by the urea synthesis unit 61 is provided as a chemical product manufacturing apparatus.
- the ammonia 55 obtained by the ammonia synthesis unit 46 in the chemical product manufacturing apparatus 40 of FIG. Is manufacturing.
- the chemical product manufacturing apparatus 40 that manufactures urea and methanol according to the present embodiment can obtain urea 62 that is a raw material of ammonia 55 obtained by the ammonia synthesis unit 46 and methanol 56 obtained by the methanol synthesis unit 47.
- the urea 62 and the methanol 56 can be simultaneously manufactured in parallel.
- the chemical product manufacturing apparatus 40 that manufactures urea and methanol includes the reforming apparatus 10 of the first embodiment, so that the chemical product manufacturing apparatus 40 that manufactures ammonia according to the second embodiment described above and Similarly, it is possible to improve the thermal efficiency when reforming the natural gas 21 and to suppress the occurrence of corrosion in the passage of the combustion exhaust gas discharge line L12 in the process of processing the combustion exhaust gas 22. Therefore, according to the chemical product manufacturing apparatus 40 that manufactures urea, the urea 62 and the methanol 56 can be stably produced and their production efficiency can be improved.
- [Methanol production example] 18 and 19 are schematic views of a chemical product manufacturing apparatus including a reforming apparatus according to the second embodiment of the present invention.
- an apparatus for manufacturing methanol alone is provided as the chemical product manufacturing apparatus.
- the chemical product manufacturing apparatus 40 that manufactures methanol includes the reformer 10, a steam generation unit 70, a compressor 44, and a methanol synthesis unit 47.
- the chemical product manufacturing apparatus 40 of this embodiment synthesizes methanol 56 using carbon dioxide and hydrogen in the reformed gas 23 obtained by the reformer 10 as raw materials.
- the methanol synthesizing unit 47 those conventionally used in general can be used. For example, a methanol synthesizing apparatus having a catalytic reactor is used.
- the reformer 14 has a two-stage configuration
- the first reformer 14-1 has the reformer configuration of FIG. 1
- the second reformer 14-2 has the autothermal modification.
- oxygen is supplied instead of air to obtain a reformed gas 23 having a gas composition suitable for methanol synthesis.
- ammonia, methanol or urea is produced alone or in combination.
- the second embodiment is not limited to this, but ammonia or urea. And other hydrocarbons and the like can be used in the same manner in parallel production.
- the reformer 10 can also be used in a hydrogen production system that produces hydrogen, a system that produces liquid hydrocarbon liquid fuel by FT synthesis, and the like. Moreover, you may make it manufacture combining these chemical products in multiple numbers.
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Abstract
Description
<改質装置>
本発明の第1の実施形態に係る改質装置について、図面を参照して説明する。図1は、本発明の第1の実施形態に係る改質装置の概略図である。図1に示すように、改質装置10は、圧縮機(圧縮部)11と、第1熱交換器(熱交換部)12と、脱硫装置(脱硫部)13と、改質器(改質部)14と、脱硝装置(脱硝部)15と、第2熱交換器16と、冷却装置17と、CO2回収装置(CO2回収部)18と、原料ガス分岐ラインL11と、燃焼排ガス排出ラインL12と、を有するものである。
CaCO3 + SO2 + 0.5H2O → CaSO3・0.5H2O + CO2 ・・・(1)
CaSO3・0.5H2O + 0.5O2 + 1.5H2O → CaSO4・2H2O ・・・(2)
CH4 + H2O → CO + 3H2 ・・・(3)
CH4 + 2H2O → CO2 + 4H2 ・・・(4)
4NO+4NH3+O2 → 4N2+6H2O・・・(5)
ここで、第2熱交換器16での熱交換は、酸露点を考慮すると例えば175℃であったものが、下限値120℃まで低下させることができる。なお、下限値の120℃は水の露点を考慮して決定される排ガス温度である。
この第3熱交換器19は、蒸気発生部70に供給する供給水75を余熱する熱交換器である。この第3熱交換器19を第1熱交換器12と、第2熱交換器16との間に備えることにより、蒸気発生部70に供給する供給水75の水量及び熱量の増大を図ることができる。
本実施形態においては、原料ガス分岐ラインL11は、空気供給ラインL15と接続するように設け、天然ガス21を燃焼空気26と共に空気供給ラインL15を通って改質器14内に供給するようにしているが、これに限定されるものではなく、図6に示すように、原料ガス分岐ラインL11を改質器14に直接接続して天然ガス21と燃焼空気26とをそれぞれ別々に改質器14内に供給するようにしてもよい。
図9は、図1に示す改質装置に対応するシステム構成の一例であり、改質器14からの燃焼排ガス排出ラインL12に導入される燃焼排ガス22は、ガス煙道内に設けられた複数の熱交換部で熱交換されている。
<化成品の製造装置>
次に、上記図1に示す第1の実施形態に係る改質装置10を化成品の製造装置に適用した場合の一例について、図面を参照して説明する。化成品の製造装置は、改質装置10と、改質装置10で得られる改質ガス23を用いて化成品を製造する化成品生成部とを有するものである。本実施形態では、化成品としてアンモニア、メタノール又は尿素を製造する場合について説明する。
図11は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。本実施形態においては、図4に示す2段構成の改質装置を用いている。なお、上記図4に示す第1の実施形態に係る改質装置と同様の構成については同一であるため、重複した説明は省略する。本実施例では、改質器は一次改質器14が一次改質器14-1と第2改質器14-2とからなる構成としているが、本発明はこれに限定されるものではない。
図11に示すように、アンモニアを製造する化成品製造装置40は、改質装置10と、蒸気発生部70と、COシフト反応装置(COシフト反応部)41と、炭酸ガス除去装置(炭酸ガス除去部)42と、メタン化装置(メタン化部)43と、圧縮機44と、水素分離装置(水素分離部)45と、アンモニア合成部46と、冷却部72と、分離部73とを有するものである。なお、本実施形態では、COシフト反応装置41、炭酸ガス除去装置42、メタン化装置43と、圧縮機44-1、44-2、水素分離装置45、アンモニア合成部46を化成品生成部とする。
また、蒸気発生部70に供給する供給水75を予備加熱する2つの第1及び第2予備加熱部76-1、76-2が、COシフト反応装置(COシフト反応部)41と、炭酸ガス除去装置(炭酸ガス除去部)42との間と、アンモニア合成部46と冷却部72との間に介装されている。なお、図11中、符号80は蒸気発生部70で得られた水蒸気を供給するスチームヘッダを図示する。なお、このスチームヘッダには補助ボイラ等からの水蒸気も導入され、ここから各水蒸気供給先に水蒸気を必要量送られるようにしている。
蒸気発生部70は、システム内のスチームヘッダ80に水蒸気24を供給するものである。蒸気発生部70は、改質ガス23の廃熱を回収する廃熱回収ボイラ(WHB)と過熱器とを備えており、供給水75を廃熱により熱加熱し、加熱蒸気を得たのち、さらに過熱器により過熱させてスチームヘッダ80に水蒸気24を送っている。なお、本システムでは、改質ガス23の通過ラインの下流側及びアンモニア合成部46の下流側に、さらに廃熱回収ボイラを設置して熱回収するようにしてもよいが、本実施例では省略している。
COシフト反応装置41は、改質ガス23中のCOをCO2に転化(シフト)し、CO2を含むシフトガス51を生成するものである。COシフト反応装置41は、例えば、COをCO2に転化(シフト)するCOシフト反応用触媒を充填した充填部を備えるCOシフト反応器などが用いられる。
CO + H2O → CO2 + H2 ・・・(6)
炭酸ガス除去装置42は、シフトガス51中の炭酸ガス(CO2)を除去するものである。炭酸ガス除去装置42としては、例えば、アミン溶剤などCO2吸収液を用いて化学吸着を利用してシフトガス51中のCO2を除去する装置、CO2を除去する触媒を備えた装置、又はシフトガス51中のCO2を分離する分離膜を備えた膜分離装置などが用いられる。炭酸ガス除去装置42で、シフトガス51中のCO2を除去して、CO2が除去されたCO2除去ガス52とを生成する。また、CO2除去ガス52のガス温度は、例えば50℃程度である。
メタン化装置43は、炭酸ガス除去装置42でCO2が除去されたCO2除去ガス52中のCO2をメタン化するものである。メタン化装置43としては、例えば、内部にメタネーション触媒を充填した触媒部を備えたメタネーション反応器(メタネータ)などが用いられる。前記触媒部での反応温度(メタネーション温度)は、メタネーション触媒が使用できる限界温度の観点から、220℃以上450℃以下であることが好ましく、より好ましくは290℃以上350℃以下である。
CO2 + 4H2 → CH4 + 2H2O ・・・(7)
圧縮機44は、CO2除去ガス53を圧縮するものである。
アンモニア合成部46は、メタン化装置43でCO2除去ガス53中のCO2をメタン化した後、アンモニア(NH3)55を製造するものである。アンモニア合成部46は、従来より一般的に用いられているものを用いることができ、例えば、反応器内の1つ以上の床に触媒を配置したアンモニア合成反応器などが挙げられる。このアンモニア合成反応器に、窒素(N2)および水素を含有する合成ガスとしてCO2除去ガス53を流してアンモニアを合成する方法などが用いられる。
N2 + 3H2 → 2NH3 ・・・(8)
図12に示す化成品製造装置40の改質装置10では、燃焼排ガス排出ラインL12に介装された第1熱交換器12と第2熱交換器16との間に、第3熱交換器19を介装している。これにより、蒸気発生部70へ供給する供給水75を第3熱交換器19で加熱することができるので、水蒸気発生量が大幅に上昇する。また、図12に示す改質装置10では、さらに燃焼排ガス排出ラインL12に蒸気発生部70からの水蒸気24を熱交換する蒸気過熱機89を介装している。これにより、スチームヘッダ80に供給する水蒸気24を、高温(例えば890℃)の燃焼排ガス22により過熱しているので、水蒸気の温度をより高温(例えば515℃)とすることができる。
図13は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。
図13は、本発明の第2の実施形態に係る尿素およびメタノールの製造システムの概略図である。図13に示すように、尿素を製造する化成品製造装置40は、図12に示す化成品製造装置40において、さらに尿素合成部61と、炭酸ガス分岐供給ラインL33とを備えたものである。
2NH3+CO2→NH2(CO)NH2+H2 ・・・(9)
図14は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。前述の実施形態では、アンモニア又は尿素を単独で製造していたが、本実施形態では、化成品製造装置として、アンモニアのみならず、メタノールも同時に製造できる装置を提供する。
図14に示すように、アンモニア及びメタノールを製造する化成品製造装置40は、改質装置10と、COシフト反応装置(COシフト反応部)41と、炭酸ガス除去装置(炭酸ガス除去部)42と、メタン化装置(メタン化部)43と、第1及び第2圧縮機44-1、44-2、アンモニア合成部(アンモニア合成部)46と、メタノール合成部47とを有するものである。
本実施形態の化成品製造装置40は、メタン化装置43の上流側にメタノール合成部47を設置している。また、圧縮機44を炭酸ガス除去装置42とメタノール合成部47との間に第1圧縮機44-1を設置すると共に、メタン化装置43とアンモニア合成部46との間に第2圧縮機44-2を設置している。なお、本実施例では、圧縮機44を2段構成としているが、さらに、低圧圧縮機と中圧圧縮機と高圧圧縮機との三段構成とするなど複数段としてもよい。
メタノール合成部47は、改質装置10で得られた改質ガス23中の二酸化炭素と水素とを原料としてメタノール56を合成するものである。メタノール合成部47は、従来より一般的に用いられているものを用いることができ、例えば、触媒反応器を有するメタノール合成装置などが用いられる。
ここで、メタノール製造原料である改質ガス23中の二酸化炭素は、COシフト反応装置41及び炭酸ガス除去装置42とを一部バイパスする開閉弁V1、V2を各々備えたバイパスラインL35、L36を設けることで、その含有量を調整するようにしている。
2H2 + CO → CH3OH ・・・(10)
3H2 + CO2 → CH3OH+H2O・・・(11)
図15は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。前述の実施形態では、アンモニア及びメタノールを製造していたが、本実施形態では、化成品製造装置として、アンモニアを原料として尿素を製造すると共にメタノールも同時に製造できる装置を提供する。
図14の化成品製造装置40において、さらにアンモニア合成部46で得られたアンモニア55を尿素合成部61に導入して、尿素を製造している。
図16は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。図14の実施形態では、メタノールの製造を改質ガス23により製造していたが、本実施形態では、化成品製造装置として、改質ガス23から炭酸ガス及び水素を分離して別途メタノール合成部により、メタノールを製造できる装置を提供する。
図16に示すように、第1圧縮機44-1と第2圧縮機44-2との間に、水素分離装置45を設けている。
第1圧縮機44-1と第2圧縮機44-2との間に設けられる水素分離装置45は、CO2除去ガス53からCO2除去ガス53に含まれる一部の水素(H2)を分離するものである。水素分離装置45は、水素透過性機能膜を備えた膜分離装置である。なお、本実施形態において、水素透過性機能膜とは、ガス中に含まれる少なくとも一部の水素(H2)を分離するための膜である。
メタノール合成部47は、炭酸ガス除去装置42で分離された二酸化炭素と水素分離装置45で分離された水素とを原料としてメタノール56を合成するものである。メタノール合成部47は、従来より一般的に用いられているものを用いることができ、例えば、触媒反応器を有するメタノール合成装置などが用いられる。
図17は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。図16の実施形態では、アンモニア55及びメタノール56を製造していたが、本実施形態では、化成品製造装置として、得られたアンモニア55から尿素合成部61により、尿素を製造できる装置を提供する。
図17に示すように、本実施形態の化成品製造装置40では、図14の化成品製造装置40において、さらにアンモニア合成部46で得られたアンモニア55を尿素合成部61に導入して、尿素を製造している。
図18及び図19は、本発明の第2の実施形態に係る改質装置を備えた化成品製造装置の概略図である。前述の実施形態では、化成品製造装置としてメタノール単独の製造装置を提供する。
図18に示すように、メタノールを製造する化成品製造装置40は、改質装置10と、蒸気発生部70と、圧縮機44と、メタノール合成部47とを有するものである。
本実施形態の化成品製造装置40は、改質装置10で得られた改質ガス23中の二酸化炭素と水素とを原料としてメタノール56を合成するものである。メタノール合成部47は、従来より一般的に用いられているものを用いることができ、例えば、触媒反応器を有するメタノール合成装置などが用いられる。
11 圧縮機(第1圧縮部)
12 第1熱交換器(熱交換部)
13 脱硫装置(脱硫部)
14 改質器(改質部)
14a 本体
14b 触媒反応管
14c バーナ
14-1 第1改質器
14-2 第2改質器
14-3 プレ改質器
15 脱硝装置(脱硝部)
16 第2熱交換器(熱交換部)
17 冷却装置
18 CO2回収装置(CO2回収部)
19 第3熱交換器(熱交換部)
20 第4熱交換器(熱交換部)
21 天然ガス
22 燃焼排ガス
23 改質ガス
24 水蒸気
26 燃焼空気
28 還元剤注入器
29 還元剤
30 冷却水
40 化成品製造装置
41 COシフト反応装置(COシフト反応部)
42 炭酸ガス除去装置(炭酸ガス除去部)
43 メタン化装置(メタン化部)
44、44-1、44-2 圧縮機
45 水素分離装置
46 アンモニア合成部
47 メタノール合成部
51 シフトガス
52、53 CO2除去ガス
55 アンモニア
56 メタノール
61 尿素合成部
62 尿素
L11、L21 原料ガス分岐ライン
L12 燃焼排ガス排出ライン
L13-1~L13-4 原料ガス供給ライン
L14 水蒸気供給ライン
L15 空気供給ライン
L31 炭酸ガス供給ライン
L32 水素供給ライン
L33 炭酸ガス分岐供給ライン
Claims (16)
- 炭化水素、硫黄を含む原料ガスを圧縮する第1圧縮部と、
圧縮された前記原料ガスを加熱する第1熱交換部と、
加熱された前記原料ガス中に含まれる硫黄分を除去する脱硫部と、
前記原料ガス中の前記炭化水素をH2及びCOとCO2との何れか一方又は両方に改質し、H2及びCOとCO2との何れか一方又は両方を含む改質ガスを生成する改質部と、
圧縮された前記原料ガスを前記原料ガスの流れ方向に対して前記脱硫部の上流側と下流側との何れか一方又は両方から一部を抜き出して、前記改質部で加熱に用いる燃焼用燃料として供給する原料ガス分岐ラインと、
前記改質部で燃焼により発生した燃焼排ガスを、前記改質部から排出する燃焼排ガス排出ラインと、
前記改質部で加熱に用いる燃焼空気を前記第1熱交換部で熱交換した前記燃焼排ガスと熱交換させる第2熱交換部と、を有し、
前記第1熱交換部が前記燃焼排ガス排出ラインに設けられ、前記燃焼排ガスは圧縮された前記原料ガスの加熱媒体として用いられると共に、
前記第2熱交換部が前記燃焼排ガス排出ラインの前記第1熱交換部の下流側に設けられ、前記第1熱交換部で熱交換した余熱で前記燃焼空気の加熱媒体として用いられることを特徴とする改質装置。 - 請求項1において、
前記改質部が、
前記原料ガスに水蒸気を供給して、前記原料ガス中の前記炭化水素をH2及びCOとCO2との何れか一方又は両方に一次改質する第1の改質部と、
燃焼空気と前記原料ガス分岐ラインから供給される圧縮された前記原料ガスとを用いて、前記第1の改質部で一次改質後の前記原料ガス中の前記炭化水素をH2及びCOとCO2との何れか一方又は両方に二次改質して改質ガスとする第2の改質部と、
を有することを特徴とする改質装置。 - 請求項1又は2において、
前記第1熱交換部と前記第2熱交換部との間に、蒸気発生部に供給する供給水を前記燃焼排ガスと熱交換させる第3熱交換器を有することを特徴とする改質装置。 - 請求項3において、
前記原料ガス分岐ラインに設けられ、前記第1熱交換部に導入する前の圧縮された前記原料ガスを、分岐した前記原料ガスの一部と熱交換させる第4熱交換器を有することを特徴とする改質装置。 - 請求項1乃至4のいずれか一つにおいて、
前記燃焼排ガス排出ラインの前記改質部と前記熱交換部との間に設けられ、前記改質部で生成された燃焼排ガス中に含まれるNOxを除去する脱硝部と、
前記燃焼排ガス排出ラインの前記燃焼排ガスの流れ方向に対して前記熱交換部よりも下流側に設けられ、前記燃焼排ガス中に含まれるCO2を除去するCO2回収部と、
の何れか一方又は両方を有することを特徴とする改質装置。 - 請求項1乃至5の何れか一つに記載の改質装置と、
前記改質ガスを用いて化成品を製造する化成品生成部と、
を有することを特徴とする化成品の製造装置。 - 請求項6において、
前記化成品生成部が、改質された前記改質ガスを用いてアンモニアを合成するアンモニア合成部であることを特徴とする化成品の製造装置。 - 請求項7において、
前記化成品生成部が、得られた前記アンモニアを用いて尿素を合成する尿素合成部であることを特徴とする化成品の製造装置。 - 請求項6において、
前記化成品生成部が、改質された改質ガスを用いてメタノールを合成するメタノール合成部であることを特徴とする化成品の製造装置。 - 圧縮された炭化水素、硫黄を含む原料ガスを加熱する第1熱交換工程と、
加熱された前記原料ガス中に含まれる硫黄分を除去する脱硫工程と、
前記原料ガス中の前記炭化水素をH2及びCOとCO2との何れか一方又は両方に改質し、H2及びCOとCO2との何れか一方又は両方を含む改質ガスを生成する改質工程と、
前記改質工程で加熱に用いる燃焼空気を前記第1熱交換工程で熱交換した前記燃焼排ガスと熱交換させる第2熱交換工程と、を有し、
圧縮された前記原料ガスを前記原料ガスの流れ方向に対して前記脱硫工程の上流側と下流側との何れか一方又は両方から抜き出して、前記改質工程で加熱に用いる燃焼用燃料として供給し、
前記改質工程で燃焼により発生した燃焼排ガスを、前記改質工程から排出すると共に、該燃焼排ガスを、圧縮された前記原料ガスの加熱媒体として用いて第1の熱交換をし、前記圧縮された前記原料ガスを熱交換した後の余熱の前記燃料排ガスを、前記燃焼空気の加熱媒体として第2の熱交換をすることを特徴とする改質方法。 - 請求項10において、
前記第1熱交換工程と前記第2熱交換工程との間に、蒸気発生手段に供給する供給水を前記燃焼排ガスと熱交換させる第3熱交換工程を有することを特徴とする改質方法。 - 請求項11において、
前記原料ガス分岐ラインに設けられ、前記第1熱交換工程に導入する圧縮された前記原料ガスを、前記分岐した原料ガスの一部と熱交換させる第4熱交換工程を有することを特徴とする改質方法。 - 請求項10乃至12の何れか一つに記載の改質工程と、
前記改質ガスを用いて化成品を製造する化成品生成工程と、
を有することを特徴とする化成品の製造方法。 - 請求項13において、
前記化成品生成工程が、改質された前記改質ガスを用いてアンモニアを合成するアンモニア合成工程であることを特徴とする化成品の製造方法。 - 請求項14において、
前記化成品生成工程が、得られた前記アンモニアを用いて尿素を合成する尿素合成工程であることを特徴とする化成品の製造方法。 - 請求項13において、
前記化成品生成工程が、改質された前記改質ガスを用いてメタノールを合成するメタノール合成工程であることを特徴とする化成品の製造方法。
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