WO2014129256A1 - System and method for synthesizing ammonia - Google Patents
System and method for synthesizing ammonia Download PDFInfo
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- WO2014129256A1 WO2014129256A1 PCT/JP2014/051289 JP2014051289W WO2014129256A1 WO 2014129256 A1 WO2014129256 A1 WO 2014129256A1 JP 2014051289 W JP2014051289 W JP 2014051289W WO 2014129256 A1 WO2014129256 A1 WO 2014129256A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0458—Separation of NH3
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- the present invention relates to an ammonia synthesis system and method for improving system efficiency.
- a part of product ammonia extracted from the synthesis loop system is used as a chiller refrigerant and used for cooling in the ammonia synthesis loop system.
- the refrigerant (gas ammonia) after use (after heat exchange) is compressed, cooled, reliquefied and circulated (Patent Documents 1 and 2).
- an object of the present invention is to provide an ammonia synthesis system and method capable of efficiently separating product ammonia.
- the first invention of the present invention for solving the above-mentioned problems is an ammonia synthesis tower for synthesizing an ammonia synthesis raw material, a first cooler for cooling a synthesis gas containing ammonia gas from the ammonia synthesis tower, An ammonia separation membrane device that separates only ammonia gas from the cooled synthesis gas, a second cooler that cools the membrane-separated ammonia gas into liquefied ammonia, and an unreacted source gas that has been membrane-separated, A raw material return line that returns to the ammonia synthesis tower side, a compressor that is interposed in the raw material return line and compresses the unreacted return gas that has been membrane-separated, and an unreacted return gas that has been membrane-separated A heat exchanger that exchanges heat with the return gas, and a third cooler that is interposed between the heat exchanger and the compressor of the raw material return line and cools the return gas after heat exchange. Equipped In ammonia synthesis system according
- an ammonia synthesis raw material is synthesized in an ammonia synthesis tower, the synthesis gas containing ammonia gas from the ammonia synthesis tower is cooled, and then only ammonia gas is separated from the synthesis gas by an ammonia separation membrane device.
- the separated ammonia gas is cooled to form liquefied ammonia, and when returning the unreacted raw material gas separated into the membrane to the ammonia synthesis tower side, the unreacted return gas separated from the membrane is compressed,
- heat is exchanged between the separated unreacted return gas and the compressed return gas, and the return gas after heat exchange is cooled before being introduced into the compressor.
- the membrane separation method by applying the membrane separation method, it is possible to efficiently separate ammonia by utilizing the self-pressure of the synthesis gas by ammonia synthesis, thereby reducing the refrigeration system power for producing liquefied ammonium. be able to.
- FIG. 1 is a schematic diagram of an ammonia synthesis system according to the present embodiment.
- FIG. 1 is a schematic diagram of an ammonia synthesis system according to the present embodiment.
- an ammonia synthesis system 10 according to this embodiment includes a first ammonia synthesis tower 11 that synthesizes an ammonia synthesis raw material, and a synthesis gas 13 that includes an ammonia gas 12G from the ammonia synthesis tower 11.
- a raw material introduction line L 4 for the raw material gas 20 for synthesis is connected to the ammonia synthesis tower 11 for the makeup of the synthesis system.
- symbol L 1 indicates a synthesis gas supply line
- L 3 indicates a liquefied ammonia line
- L 5 indicates a gas extraction line.
- the synthesis gas 13 obtained in the ammonia synthesis tower 11 contains ammonia gas 12G and unreacted raw material gas 20.
- the ammonia gas 12 ⁇ / b> G is subjected to membrane separation by the ammonia separation membrane device 15.
- the membrane-separated ammonia gas 12G is cooled by the second cooler 16, it becomes liquefied ammonia (liquid) 12L and is stored in the primary storage tank 21.
- the liquefied ammonia (liquid) 12L is used, for example, in the urea plant 22 as a raw material for chemical production such as urea.
- the ammonia separation membrane used in the ammonia separation membrane device 15 is not particularly limited as long as it is a known separation membrane. Examples thereof include a separation membrane made of a synthetic resin, a carbon separation membrane, and the like. Examples of the ammonia separation membrane include a porous silica membrane and a carbon membrane.
- the unreacted raw material gas 20 after the ammonia gas 12G is separated by the ammonia separation membrane device 15 passes through the heat exchanger 18 and the third cooler 19, and is compressed by the compressor 17, and then returned gas. 20b is returned to the ammonia synthesis tower 11, where ammonia synthesis is performed again.
- the return gas 20b compressed by the compressor 17 is heat-exchanged by the heat exchanger 18 with the unreacted return gas 20a separated by membrane.
- a gas extraction line L 5 is installed in the downstream line of the ammonia separation membrane device 15 so as to extract a certain amount of gas from the synthesis loop system for the purpose of removing the inert component (unreacted component) 32. I have to.
- the synthesis pressure of the ammonia synthesis tower 11 is about 18 MPa, for example, by applying a membrane separation method, efficient ammonia separation can be performed using the self-pressure of synthesis gas by ammonia synthesis. Refrigerating system power in the second cooler 16 for ammonia production can be reduced.
- the ammonia concentration at the inlet to the ammonia synthesis tower is for chiller equipment performance and purge gas (inert component (unreacted component) removal purpose)
- the ammonia concentration at the inlet to the ammonia synthesis tower is for chiller equipment performance and purge gas (inert component (unreacted component) removal purpose)
- it is about 4%, although it varies depending on the amount of gas extracted from the synthetic loop system. Therefore, since the upper limit of the amount of ammonia generated by the ammonia synthesis reaction is determined in terms of reaction equilibrium, the lower the inlet ammonia concentration, the more advantageous.
- ammonia synthesis reactor with an internal heat exchanger
- the ammonia gas is separated from the synthesis gas by using an ammonia separation membrane, and “increase the membrane area” or “lower the pressure on the membrane permeation (secondary side)” is performed.
- the ammonia concentration from the synthesis loop system can be reduced to zero (practically 0.5% to 1.0% at the ammonia synthesis tower inlet), and the following effects are expected.
- the compressor power can be reduced and the size can be reduced by the "flow rate reduction” and “loop pressure loss reduction” associated with the effects A) and B).
- the compression ratio is 190 / (190-10) versus 190 / (190-10) when liquefied using a conventional chiller facility. -8), and the power is reduced by the ratio 180/182.
- the ammonia concentration at the ammonia synthesis tower inlet is preferably 2.0% or less, more preferably. Is preferably not more than 1.0%, more preferably in the range of 0.5% to 1.0%.
- the ammonia concentration at the inlet to the ammonia synthesis tower 11 is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.5% to 1.0%.
- the compressor power can be reduced and downsized by “reducing the flow rate” and “reducing the loop pressure loss”, thereby reducing the site area of the synthetic loop system. Specifically, when applied to an actual machine, the site area can be reduced by about 20% to 25% of the conventional system using chiller equipment.
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Abstract
The present invention is provided with: an ammonia synthesis column (11) for synthesizing a raw material for ammonia synthesis; a first cooler (14) for cooling a synthesis gas (13) including ammonia gas (12G) from the ammonia synthesis column (11); an ammonia separation membrane device (15) for separating only the ammonia gas (12G) from the cooled synthesis gas (13); a second cooler (16) for cooling the membrane-separated ammonia gas (12G) to form liquefied ammonia (12L); a raw material return line (L2) for returning, to an ammonia synthesis column (11) side, a membrane-separated unreacted raw material gas (20); a compressor (17) for compressing a membrane-separated unreacted return gas (20a), the compressor (17) intervening in the raw material return line (L2); a heat exchanger (18) for exchanging heat between the membrane-separated unreacted return gas (20a) and the compressed return gas (20b); and a third cooler (19) for cooling the heat-exchanged return gas (20a), the third cooler (19) intervening between the compressor (17) and the heat exchanger (18) in the return gas line (L2).
Description
本発明は、システム効率の向上を図ったアンモニア合成システム及び方法に関するものである。
The present invention relates to an ammonia synthesis system and method for improving system efficiency.
例えば、従来のアンモニア合成プロセスにおいては、天然ガスを用いてアンモニア合成塔でアンモニアを合成した場合、アンモニア合成ループ系からアンモニアと合成ガスを分離し、製品アンモニアを取り出す際に、一般的には冷却プロセスが使用されている。
For example, in the conventional ammonia synthesis process, when natural gas is used to synthesize ammonia in an ammonia synthesis tower, it is generally cooled when ammonia and synthesis gas are separated from the ammonia synthesis loop system and product ammonia is taken out. The process is in use.
例えば合成ループ系から抜き出された製品アンモニアの一部を、チラー冷媒として使用し、アンモニア合成ループ系での冷却に使用している。この使用後(熱交換後)の冷媒(ガスアンモニア)は、圧縮、冷却、再液化され循環されている(特許文献1、2)。
For example, a part of product ammonia extracted from the synthesis loop system is used as a chiller refrigerant and used for cooling in the ammonia synthesis loop system. The refrigerant (gas ammonia) after use (after heat exchange) is compressed, cooled, reliquefied and circulated (Patent Documents 1 and 2).
しかしながら、製品アンモニアを分離する際に、冷媒の圧縮・冷却に伴う動力が大きく、しかも設備も大がかりであることから、プラントコスト及び運転費が嵩む、という問題がある。
However, when the product ammonia is separated, there is a problem that the power associated with the compression and cooling of the refrigerant is large and the equipment is large, which increases the plant cost and operation cost.
よって、アンモニア合成塔から得られる合成ガス中の製品アンモニアを効率的に分離できる、アンモニア合成システムの出現が切望されている。
Therefore, the emergence of an ammonia synthesis system that can efficiently separate the product ammonia in the synthesis gas obtained from the ammonia synthesis tower is highly desired.
本発明は、前記問題に鑑み、製品アンモニアを効率的に分離できる、アンモニア合成システム及び方法を提供することを課題とする。
In view of the above problems, an object of the present invention is to provide an ammonia synthesis system and method capable of efficiently separating product ammonia.
上述した課題を解決するための本発明の第1の発明は、アンモニア合成原料を合成するアンモニア合成塔と、前記アンモニア合成塔からのアンモニアガスを含む合成ガスを冷却する第1の冷却器と、冷却後の合成ガスからアンモニアガスのみを分離するアンモニア分離膜装置と、膜分離されたアンモニアガスを冷却して液化アンモニアとする第2の冷却器と、膜分離された未反応の原料ガスを、前記アンモニア合成塔側へ戻す原料戻しラインと、前記原料戻しラインに介装され、膜分離された未反応の戻りガスを圧縮する圧縮機と、膜分離された未反応の戻りガスと、圧縮された戻りガスとを熱交換する熱交換器と、前記原料戻しラインの前記熱交換器と前記圧縮機との間に介装され、熱交換後の戻りガスを冷却する第3の冷却器とを具備することを特徴とするアンモニア合成システムにある。
The first invention of the present invention for solving the above-mentioned problems is an ammonia synthesis tower for synthesizing an ammonia synthesis raw material, a first cooler for cooling a synthesis gas containing ammonia gas from the ammonia synthesis tower, An ammonia separation membrane device that separates only ammonia gas from the cooled synthesis gas, a second cooler that cools the membrane-separated ammonia gas into liquefied ammonia, and an unreacted source gas that has been membrane-separated, A raw material return line that returns to the ammonia synthesis tower side, a compressor that is interposed in the raw material return line and compresses the unreacted return gas that has been membrane-separated, and an unreacted return gas that has been membrane-separated A heat exchanger that exchanges heat with the return gas, and a third cooler that is interposed between the heat exchanger and the compressor of the raw material return line and cools the return gas after heat exchange. Equipped In ammonia synthesis system according to claim Rukoto.
第2の発明は、アンモニア合成原料をアンモニア合成塔で合成し、前記アンモニア合成塔からのアンモニアガスを含む合成ガスを冷却した後、合成ガスからアンモニアガスのみをアンモニア分離膜装置により分離し、膜分離されたアンモニアガスを冷却して液化アンモニアとすると共に、膜分離された未反応の原料ガスを、前記アンモニア合成塔側へ戻す際に、膜分離された未反応の戻りガスを圧縮し、膜分離された未反応の戻りガスと、圧縮された戻りガスとを熱交換しつつ、熱交換後の戻りガスを圧縮機へ導入する前に冷却することを特徴とするアンモニア合成方法にある。
According to a second aspect of the present invention, an ammonia synthesis raw material is synthesized in an ammonia synthesis tower, the synthesis gas containing ammonia gas from the ammonia synthesis tower is cooled, and then only ammonia gas is separated from the synthesis gas by an ammonia separation membrane device. The separated ammonia gas is cooled to form liquefied ammonia, and when returning the unreacted raw material gas separated into the membrane to the ammonia synthesis tower side, the unreacted return gas separated from the membrane is compressed, In the ammonia synthesizing method, heat is exchanged between the separated unreacted return gas and the compressed return gas, and the return gas after heat exchange is cooled before being introduced into the compressor.
本発明によれば、膜分離法を適用することで、アンモニア合成による合成ガスの自圧を利用して効率的なアンモニア分離が可能となるため、液化アンモニウム製造用の冷凍系動力の削減を図ることができる。
According to the present invention, by applying the membrane separation method, it is possible to efficiently separate ammonia by utilizing the self-pressure of the synthesis gas by ammonia synthesis, thereby reducing the refrigeration system power for producing liquefied ammonium. be able to.
以下に添付図面を参照して、本発明の好適な実施例を詳細に説明する。なお、この実施例により本発明が限定されるものではなく、また、実施例が複数ある場合には、各実施例を組み合わせて構成するものも含むものである。
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited by this Example, Moreover, when there exists multiple Example, what comprises combining each Example is also included.
図1は、本実施例に係るアンモニア合成システムの概略図である。
図1に示すように、本実施例に係るアンモニア合成システム10は、アンモニア合成原料を合成するアンモニア合成塔11と、アンモニア合成塔11からのアンモニアガス12Gを含む合成ガス13を冷却する第1の冷却器14と、冷却後の合成ガス13からアンモニアガス12Gのみを分離するアンモニア分離膜装置15と、膜分離されたアンモニアガス12Gを冷却して液化アンモニア12Lとする第2の冷却器16と、膜分離された未反応の原料ガス20を、アンモニア合成塔11側へ戻す原料戻しラインL2と、原料戻しラインL2に介装され、膜分離された未反応の戻りガス20aを圧縮する圧縮機17と、膜分離された未反応の戻りガス20aと、圧縮された戻りガス20bとを熱交換する熱交換器18と、戻りガスラインL2の熱交換器18と圧縮機17との間に介装され、熱交換後の戻りガス20aを冷却する第3の冷却器19とを具備するものである。ここで、アンモニア合成塔11には、合成系のメイクアップ用に合成用の原料ガス20の原料導入ラインL4が接続されている。
なお、図1中、符号L1は合成ガス供給ライン、L3は液化アンモニアライン、L5はガス抜出しラインを図示する。 FIG. 1 is a schematic diagram of an ammonia synthesis system according to the present embodiment.
As shown in FIG. 1, anammonia synthesis system 10 according to this embodiment includes a first ammonia synthesis tower 11 that synthesizes an ammonia synthesis raw material, and a synthesis gas 13 that includes an ammonia gas 12G from the ammonia synthesis tower 11. A cooler 14, an ammonia separation membrane device 15 for separating only the ammonia gas 12G from the cooled synthesis gas 13, a second cooler 16 for cooling the membrane-separated ammonia gas 12G into liquefied ammonia 12L, The raw material return line L 2 for returning the membrane-reacted unreacted source gas 20 to the ammonia synthesis tower 11 side and the compression for compressing the membrane-reacted unreacted return gas 20 a interposed in the source return line L 2 a machine 17, a return gas 20a unreacted that are membrane separation, and the compressed return gas 20b and the heat exchanger 18 for heat exchange, the return gas line L 2 Is interposed between the exchanger 18 and the compressor 17 is for and a third cooler 19 for cooling the return gas 20a after the heat exchange. Here, a raw material introduction line L 4 for the raw material gas 20 for synthesis is connected to the ammonia synthesis tower 11 for the makeup of the synthesis system.
In FIG. 1, symbol L 1 indicates a synthesis gas supply line, L 3 indicates a liquefied ammonia line, and L 5 indicates a gas extraction line.
図1に示すように、本実施例に係るアンモニア合成システム10は、アンモニア合成原料を合成するアンモニア合成塔11と、アンモニア合成塔11からのアンモニアガス12Gを含む合成ガス13を冷却する第1の冷却器14と、冷却後の合成ガス13からアンモニアガス12Gのみを分離するアンモニア分離膜装置15と、膜分離されたアンモニアガス12Gを冷却して液化アンモニア12Lとする第2の冷却器16と、膜分離された未反応の原料ガス20を、アンモニア合成塔11側へ戻す原料戻しラインL2と、原料戻しラインL2に介装され、膜分離された未反応の戻りガス20aを圧縮する圧縮機17と、膜分離された未反応の戻りガス20aと、圧縮された戻りガス20bとを熱交換する熱交換器18と、戻りガスラインL2の熱交換器18と圧縮機17との間に介装され、熱交換後の戻りガス20aを冷却する第3の冷却器19とを具備するものである。ここで、アンモニア合成塔11には、合成系のメイクアップ用に合成用の原料ガス20の原料導入ラインL4が接続されている。
なお、図1中、符号L1は合成ガス供給ライン、L3は液化アンモニアライン、L5はガス抜出しラインを図示する。 FIG. 1 is a schematic diagram of an ammonia synthesis system according to the present embodiment.
As shown in FIG. 1, an
In FIG. 1, symbol L 1 indicates a synthesis gas supply line, L 3 indicates a liquefied ammonia line, and L 5 indicates a gas extraction line.
アンモニア合成塔11で得られた合成ガス13は、アンモニアガス12Gと未反応の原料ガス20とを含んでいる。この合成ガス13を第1の冷却器14で冷却した後、アンモニア分離膜装置15にてアンモニアガス12Gを膜分離する。膜分離されたアンモニアガス12Gは、第2の冷却器16で冷却された後、液化アンモニア(液体)12Lとなり、一次貯留タンク21で貯留される。そして、液化アンモニア(液体)12Lは、例えば尿素等の化学製造原料として、例えば尿素プラント22にて使用される。
The synthesis gas 13 obtained in the ammonia synthesis tower 11 contains ammonia gas 12G and unreacted raw material gas 20. After the synthesis gas 13 is cooled by the first cooler 14, the ammonia gas 12 </ b> G is subjected to membrane separation by the ammonia separation membrane device 15. After the membrane-separated ammonia gas 12G is cooled by the second cooler 16, it becomes liquefied ammonia (liquid) 12L and is stored in the primary storage tank 21. The liquefied ammonia (liquid) 12L is used, for example, in the urea plant 22 as a raw material for chemical production such as urea.
アンモニア分離膜装置15で用いるアンモニア分離膜は、公知の分離膜であれば、特に限定されるものではない。例えば合成樹脂からなる分離膜、炭素分離膜等を挙げることができる。
アンモニア分離膜としては、例えば多孔質シリカ膜や炭素膜等を挙げることができる。 The ammonia separation membrane used in the ammoniaseparation membrane device 15 is not particularly limited as long as it is a known separation membrane. Examples thereof include a separation membrane made of a synthetic resin, a carbon separation membrane, and the like.
Examples of the ammonia separation membrane include a porous silica membrane and a carbon membrane.
アンモニア分離膜としては、例えば多孔質シリカ膜や炭素膜等を挙げることができる。 The ammonia separation membrane used in the ammonia
Examples of the ammonia separation membrane include a porous silica membrane and a carbon membrane.
また、アンモニア分離膜装置15でアンモニアガス12Gを分離した後の未反応の原料ガス20は、熱交換器18及び第3の冷却器19を通過し、圧縮機17で圧縮された後、戻りガス20bとしてアンモニア合成塔11に戻され、ここで再度アンモニア合成がなされる。
The unreacted raw material gas 20 after the ammonia gas 12G is separated by the ammonia separation membrane device 15 passes through the heat exchanger 18 and the third cooler 19, and is compressed by the compressor 17, and then returned gas. 20b is returned to the ammonia synthesis tower 11, where ammonia synthesis is performed again.
圧縮機17で圧縮された戻りガス20bは、膜分離された未反応の戻りガス20aと、熱交換器18で熱交換されている。
また、アンモニア分離膜装置15の後流ラインにおいて、ガス抜出しラインL5が設置されており、イナート成分(未反応成分)32の除去目的のために、合成ループ系から一定量のガスを抜き取るようにしている。 Thereturn gas 20b compressed by the compressor 17 is heat-exchanged by the heat exchanger 18 with the unreacted return gas 20a separated by membrane.
In addition, a gas extraction line L 5 is installed in the downstream line of the ammoniaseparation membrane device 15 so as to extract a certain amount of gas from the synthesis loop system for the purpose of removing the inert component (unreacted component) 32. I have to.
また、アンモニア分離膜装置15の後流ラインにおいて、ガス抜出しラインL5が設置されており、イナート成分(未反応成分)32の除去目的のために、合成ループ系から一定量のガスを抜き取るようにしている。 The
In addition, a gas extraction line L 5 is installed in the downstream line of the ammonia
アンモニア合成塔11では、その合成圧が例えば18MPa程度であるので、膜分離法を適用することで、アンモニア合成による合成ガスの自圧を利用して効率的なアンモニア分離が可能となるため、液化アンモニア製造用の第2の冷却器16における冷凍系動力の削減を図ることができる。
Since the synthesis pressure of the ammonia synthesis tower 11 is about 18 MPa, for example, by applying a membrane separation method, efficient ammonia separation can be performed using the self-pressure of synthesis gas by ammonia synthesis. Refrigerating system power in the second cooler 16 for ammonia production can be reduced.
ここで、従来技術におけるチラー設備を用いての冷却分離をベースとするアンモニア合成プロセスでの、アンモニア合成塔への入口アンモニア濃度は、チラー設備性能及びパージガス(イナート分(未反応成分)除去目的で合成ループ系から一定量のガスを抜き取る)の量によっても変わるが、一般的に4%前後である。
よって、アンモニア合成反応によって生じるアンモニア量は反応平衡上、上限が決まっているため、入口アンモニア濃度が低いほど有利である。 Here, in the ammonia synthesis process based on the cooling separation using the chiller equipment in the prior art, the ammonia concentration at the inlet to the ammonia synthesis tower is for chiller equipment performance and purge gas (inert component (unreacted component) removal purpose) Generally, it is about 4%, although it varies depending on the amount of gas extracted from the synthetic loop system.
Therefore, since the upper limit of the amount of ammonia generated by the ammonia synthesis reaction is determined in terms of reaction equilibrium, the lower the inlet ammonia concentration, the more advantageous.
よって、アンモニア合成反応によって生じるアンモニア量は反応平衡上、上限が決まっているため、入口アンモニア濃度が低いほど有利である。 Here, in the ammonia synthesis process based on the cooling separation using the chiller equipment in the prior art, the ammonia concentration at the inlet to the ammonia synthesis tower is for chiller equipment performance and purge gas (inert component (unreacted component) removal purpose) Generally, it is about 4%, although it varies depending on the amount of gas extracted from the synthetic loop system.
Therefore, since the upper limit of the amount of ammonia generated by the ammonia synthesis reaction is determined in terms of reaction equilibrium, the lower the inlet ammonia concentration, the more advantageous.
ここで、仮に、アンモニア合成塔11として、内部熱交換器設置型アンモニア合成反応器を用いた場合、合成塔出口ではアンモニア濃度が約17%及びガス温度が450℃付近で平衡に達する(ここで、圧力は100-140kg/cm2Gと想定する。)。よって、17%-4% =13%分のアンモニアが正味の生産分となる(「%」は容量%である。以下、同様。)。
そこで、アンモニア合成塔11への入口アンモニア濃度が、ほぼ0%近傍となれば、最大17%-0%=17%分のアンモニア生成が可能となる。 Here, if an ammonia synthesis reactor with an internal heat exchanger is used as theammonia synthesis tower 11, the ammonia concentration reaches about 17% and the gas temperature reaches about 450 ° C. at the synthesis tower outlet (here, The pressure is assumed to be 100-140 kg / cm 2 G). Therefore, 17% -4% = 13% of ammonia is the net production (“%” is volume%. The same applies hereinafter).
Therefore, if the concentration of ammonia at the inlet to theammonia synthesis tower 11 is approximately 0%, ammonia can be generated up to 17% -0% = 17%.
そこで、アンモニア合成塔11への入口アンモニア濃度が、ほぼ0%近傍となれば、最大17%-0%=17%分のアンモニア生成が可能となる。 Here, if an ammonia synthesis reactor with an internal heat exchanger is used as the
Therefore, if the concentration of ammonia at the inlet to the
そこで、本発明では、合成ガス中からのアンモニアガスの分離を、アンモニア分離膜を用いることとし、「膜面積を増やす」もしくは「膜透過(2次側)の圧力を下げる」等を実施することで、合成ループ系からのアンモニア濃度を限りなくゼロ(現実的にはアンモニア合成塔入口で0.5%~1.0%)に下げることが可能となり、以下の効果が見込まれる。
Therefore, in the present invention, the ammonia gas is separated from the synthesis gas by using an ammonia separation membrane, and “increase the membrane area” or “lower the pressure on the membrane permeation (secondary side)” is performed. Thus, the ammonia concentration from the synthesis loop system can be reduced to zero (practically 0.5% to 1.0% at the ammonia synthesis tower inlet), and the following effects are expected.
A)合成ループ循環流量の低減(又は合成ループ系循環量ベースでのアンモニア生産量増加)は、従来の循環流量の79%~81%となる。
B)合成ループ中の熱交換器の一部が不要となる。
チラー熱交換器が不要となる。一般的なアンモニアプラントでは、チラーは2段階の温度レベルとしており、この両方の熱交換器が不要となる。 A) The reduction of the synthetic loop circulation flow rate (or the increase of the ammonia production amount on the basis of the synthetic loop system circulation amount) is 79% to 81% of the conventional circulation flow rate.
B) A part of the heat exchanger in the synthesis loop becomes unnecessary.
No chiller heat exchanger is required. In a general ammonia plant, the chiller has two temperature levels, and both heat exchangers are unnecessary.
B)合成ループ中の熱交換器の一部が不要となる。
チラー熱交換器が不要となる。一般的なアンモニアプラントでは、チラーは2段階の温度レベルとしており、この両方の熱交換器が不要となる。 A) The reduction of the synthetic loop circulation flow rate (or the increase of the ammonia production amount on the basis of the synthetic loop system circulation amount) is 79% to 81% of the conventional circulation flow rate.
B) A part of the heat exchanger in the synthesis loop becomes unnecessary.
No chiller heat exchanger is required. In a general ammonia plant, the chiller has two temperature levels, and both heat exchangers are unnecessary.
この結果、上記効果A)及び効果B)に伴う「流量減少」及び「ループ圧損の低減」による圧縮機動力の低減・小型化を図ることができる。
As a result, the compressor power can be reduced and the size can be reduced by the "flow rate reduction" and "loop pressure loss reduction" associated with the effects A) and B).
以上より、従来のループ圧損は10kg/cm2程度とすると、「ループ圧損の低減」により従来のループ圧損の80%程度となり、約8kg/cm2まで低減することとなる。この効果に加えて、「流量減少」に伴う影響を加味すると、圧縮機動力は、従来の79%程度となり、小型化を図ることができる。
From the above, assuming that the conventional loop pressure loss is about 10 kg / cm 2 , “reduction of the loop pressure loss” is about 80% of the conventional loop pressure loss, and is reduced to about 8 kg / cm 2 . In addition to this effect, taking into account the effect associated with “flow rate reduction”, the compressor power is about 79% of the conventional one, and the size can be reduced.
ここで、仮にアンモニア合成塔11での合成圧を例えば190kg/cm2とした場合、圧縮比は従来のチラー設備を用いて液化する場合、190/(190-10)に対して190/(190-8)となり、その比180/182分動力が低減する。
また流量についても71~81%低減(平均して80%)する。
よって、180/182×0.8=79%となる。 Here, if the synthesis pressure in theammonia synthesis tower 11 is, for example, 190 kg / cm 2 , the compression ratio is 190 / (190-10) versus 190 / (190-10) when liquefied using a conventional chiller facility. -8), and the power is reduced by the ratio 180/182.
The flow rate is also reduced by 71 to 81% (80% on average).
Therefore, 180/182 × 0.8 = 79%.
また流量についても71~81%低減(平均して80%)する。
よって、180/182×0.8=79%となる。 Here, if the synthesis pressure in the
The flow rate is also reduced by 71 to 81% (80% on average).
Therefore, 180/182 × 0.8 = 79%.
ここで、アンモニア合成塔11でのアンモニア濃度を限りなくゼロにすることは、実機適用する場合には、困難であるので、アンモニア合成塔入口でアンモニア濃度が好ましくは2.0%以下、より好ましくは1.0%以下、さらに好ましくは0.5%~1.0%の範囲に規定することが好ましい。
Here, since it is difficult to make the ammonia concentration in the ammonia synthesis tower 11 to zero as much as possible when applied to an actual machine, the ammonia concentration at the ammonia synthesis tower inlet is preferably 2.0% or less, more preferably. Is preferably not more than 1.0%, more preferably in the range of 0.5% to 1.0%.
以上より、アンモニア合成塔11への入口でアンモニア濃度が好ましくは2.0%以下、より好ましくは1.0%以下、さらに好ましくは0.5%~1.0%の範囲に規定することにより、「流量減少」及び「ループ圧損の低減」による圧縮機動力の低減・小型化を図ることができ、これにより、合成ループ系の敷地面積を縮小することができる。
具体的には、実機適用する場合に、チラー設備を用いた従来システムの約20%~25%の敷地面積削減効果を図ることができる。 From the above, the ammonia concentration at the inlet to theammonia synthesis tower 11 is preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.5% to 1.0%. The compressor power can be reduced and downsized by “reducing the flow rate” and “reducing the loop pressure loss”, thereby reducing the site area of the synthetic loop system.
Specifically, when applied to an actual machine, the site area can be reduced by about 20% to 25% of the conventional system using chiller equipment.
具体的には、実機適用する場合に、チラー設備を用いた従来システムの約20%~25%の敷地面積削減効果を図ることができる。 From the above, the ammonia concentration at the inlet to the
Specifically, when applied to an actual machine, the site area can be reduced by about 20% to 25% of the conventional system using chiller equipment.
以上より、従来技術の製品アンモニアを冷却分離する場合には、圧縮機が必要の為、かかる動力は大きく、プラント運転費(製品原単位)の悪化要因の一つであったが、膜分離法を適用することで、合成圧(約18~19MPa)の自圧を利用した効率的なアンモニア分離が可能となるため、冷凍系動力の約10%の削減を図ることができる。
From the above, when cooling and separating the product ammonia of the prior art, since a compressor is necessary, this power is large, which was one of the causes of deterioration of plant operating cost (product basic unit). By applying this, it becomes possible to efficiently separate ammonia using the self-pressure of the synthetic pressure (about 18 to 19 MPa), so that it is possible to reduce the refrigeration system power by about 10%.
本システム例では、尿素プラントを併設した場合を説明したが、アンモニア製造単独プラント、アンモニア及び尿素製造一体型プラント、メタノール合成併産型アンモニア合成プラント、メタノール併産型アンモニア、尿素一体型プラント等に適用することができる。
In this system example, a case where a urea plant is also provided has been described. However, an ammonia production single plant, an ammonia and urea production integrated plant, a methanol synthesis combined ammonia synthesis plant, a methanol combined production ammonia, a urea integrated plant, etc. Can be applied.
10 アンモニア合成システム
11 アンモニア合成塔
12G アンモニアガス
12L 液化アンモニア
13 合成ガス
14 第1の冷却器
15 アンモニア分離膜装置
16 第2の冷却器
17 圧縮機
18 熱交換器
19 第3の冷却器
20 原料ガス DESCRIPTION OFSYMBOLS 10 Ammonia synthesis system 11 Ammonia synthesis tower 12G Ammonia gas 12L Liquefied ammonia 13 Syngas 14 1st cooler 15 Ammonia separation membrane apparatus 16 2nd cooler 17 Compressor 18 Heat exchanger 19 3rd cooler 20 Source gas
11 アンモニア合成塔
12G アンモニアガス
12L 液化アンモニア
13 合成ガス
14 第1の冷却器
15 アンモニア分離膜装置
16 第2の冷却器
17 圧縮機
18 熱交換器
19 第3の冷却器
20 原料ガス DESCRIPTION OF
Claims (2)
- アンモニア合成原料を合成するアンモニア合成塔と、
前記アンモニア合成塔からのアンモニアガスを含む合成ガスを冷却する第1の冷却器と、
冷却後の合成ガスからアンモニアガスのみを分離するアンモニア分離膜装置と、
膜分離されたアンモニアガスを冷却して液化アンモニアとする第2の冷却器と、
膜分離された未反応の原料ガスを、前記アンモニア合成塔側へ戻す原料戻しラインと、
前記原料戻しラインに介装され、膜分離された未反応の戻りガスを圧縮する圧縮機と、
膜分離された未反応の戻りガスと、圧縮された戻りガスとを熱交換する熱交換器と、
前記原料戻しラインの前記熱交換器と前記圧縮機との間に介装され、熱交換後の戻りガスを冷却する第3の冷却器とを具備することを特徴とするアンモニア合成システム。 An ammonia synthesis tower for synthesizing an ammonia synthesis raw material;
A first cooler that cools the synthesis gas containing ammonia gas from the ammonia synthesis tower;
An ammonia separation membrane device for separating only ammonia gas from the cooled synthesis gas;
A second cooler that cools the membrane-separated ammonia gas into liquefied ammonia;
A raw material return line for returning the unreacted raw material gas separated into the membrane to the ammonia synthesis tower side,
A compressor that compresses unreacted return gas that is interposed in the raw material return line and separated by membrane;
A heat exchanger for exchanging heat between the membrane-reacted unreacted return gas and the compressed return gas;
An ammonia synthesis system comprising a third cooler interposed between the heat exchanger of the raw material return line and the compressor and cooling the return gas after heat exchange. - アンモニア合成原料をアンモニア合成塔で合成し、
前記アンモニア合成塔からのアンモニアガスを含む合成ガスを冷却した後、合成ガスからアンモニアガスのみをアンモニア分離膜装置により分離し、
膜分離されたアンモニアガスを冷却して液化アンモニアとすると共に、
膜分離された未反応の原料ガスを、前記アンモニア合成塔側へ戻す際に、膜分離された未反応の戻りガスを圧縮し、膜分離された未反応の戻りガスと、圧縮された戻りガスとを熱交換しつつ、熱交換後の戻りガスを圧縮機へ導入する前に冷却することを特徴とするアンモニア合成方法。 Synthesize ammonia synthesis raw material in ammonia synthesis tower,
After cooling the synthesis gas containing ammonia gas from the ammonia synthesis tower, only ammonia gas is separated from the synthesis gas by an ammonia separation membrane device,
While the membrane-separated ammonia gas is cooled to liquefied ammonia,
When returning the unreacted raw material gas separated into the membrane to the ammonia synthesis tower side, the unreacted return gas separated from the membrane is compressed, and the unreacted return gas separated from the membrane and the compressed return gas are compressed. The ammonia synthesis method is characterized in that the return gas after the heat exchange is cooled before being introduced into the compressor.
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